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Nanomaterials as sorbents for sample preparation in bioanalysis: A review
Analytica Chimica Acta 958 (2017) 1e21
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Analytica Chimica Acta journal homepage: www.elsevier.com/locate/aca
Review
Nanomaterials as sorbents for sample preparation in bioanalysis: A review Mazaher Ahmadi a, b, Hatem Elmongy a, Tayyebeh Madrakian b, Mohamed Abdel-Rehim a, * a b
Department of Environmental and Analytical Chemistry, Stockholm University, SE10691 Stockholm, Sweden Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Nanomaterials are used as Nanosorbents in various sample preparations methods. Nanoparticles provide high surface area compared to microscale particles. Nano-materials have high sorption capacities compared to conventional microscale sorbents. The use of carbon nanotubes in sample preparation. Polymer based Nano-sorbents.
a r t i c l e i n f o
a b s t r a c t
Article history: Received 21 June 2016 Received in revised form 24 November 2016 Accepted 27 November 2016 Available online 7 December 2016
In recent years, application of nanomaterials as sorbent has gained the attention of researchers in bioanalysis. Different nanomaterials have been utilized as the sorbent in extraction techniques such as solid phase extraction, dispersive solid phase extraction, magnetic solid phase extraction, microextraction by packed sorbent, solid phase microextraction, dispersive m-solid phase extraction, and stir bar sorptive extraction. In the present review, different nanomaterials which have recently been utilized as sorbent for bioanalysis are classified into six main groups, namely metallic, metallic and mixed oxide, magnetic, carbonaceous, silicon, and polymer-based nanomaterials. Application of these nanomaterials in different extraction techniques for bioanalysis has been reviewed. This study shows that magnetic nanomaterials have gained significant attention owing to their magnetic separation ability. In addition, the present review shows that there is a lack in the application of nanomaterials for on-line analysis procedures, most probably due to some intrinsic properties of nanomaterials such as spontaneous agglomeration. © 2016 Elsevier B.V. All rights reserved.
Keywords: Nanomaterials Sorptive extraction Sample preparation Microextraction techniques Bioanalysis Review
Contents 1. 2.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Definition and classification of nanomaterials as nanosorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 2.1. Metallic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
* Corresponding author. Tel.: þ46707108122; fax: þ46709569894. E-mail addresses: [email protected], Mohamed.astra@gmail. com (M. Abdel-Rehim). http://dx.doi.org/10.1016/j.aca.2016.11.062 0003-2670/© 2016 Elsevier B.V. All rights reserved.
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2.2. 2.3. 2.4.
3.
4.
5. 6.
Metallic and mixed oxide nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Magnetic nanoparticles (MNPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Carbonaceous nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.4.1. Fullerenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.4.2. Carbon nanotubes (CNTs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.4.3. Graphene and graphene oxide (G and GO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.5. Silicon nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.6. Polymer-based nanosorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.6.1. Organic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.6.2. Inorganic and hybrid polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.6.3. Molecularly imprinted polymers (MIPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Sample preparation procedures for bioanalysis using nanomaterials as sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 3.1. In-solution methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 3.2. Headspace methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 Application of nanomaterials as sorbents for bioanalysis in sorptive extraction techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 4.1. Solid phase extraction (SPE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 4.2. Dispersive solid phase extraction (dSPE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 4.3. Magnetic solid phase extraction (MSPE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 4.4. Microextraction by packed sorbent (MEPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 4.5. Solid phase microextraction (SPME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 4.6. Dispersive m-solid phase extraction (dispersive m-SPE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 4.7. Stir bar sorptive extraction (SBSE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 4.8. Other methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 Application of nanomaterials in determination of biomolecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 Conclusions and perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Abbreviations AgNPs silver nanoparticles AuNPs gold nanoparticles BSA bovine serum albumin CE capillary electrophoresis CNTs carbon nanotubes CTAB cetyltrimethylammonium bromide CV-ETAAS cold vapor generation-electrothermal atomic absorption spectrometry Dispersive m-SPE dispersive m-solid phase extraction dSPE dispersive solid phase extraction EC-SPME electrochemically controlled SPME ETAAS electrothermal atomic absorption spectrometry FAAS flame atomic absorption spectroscopy FASS-OT-CEC field-amplified sample stacking open-tubular capillary electrochromatography FL spectrofluorometry G graphene GC-FID gas chromatography-flame ionization detector GC-MS gas chromatography-mass spectrometry GE gel electrophoresis GFAAS graphite furnace atomic absorption spectrometry GO graphene oxide HPLC high-performance liquid chromatography HSA human serum albumin ICP-MS inductively coupled plasma-mass spectrometry ICP-OES inductively coupled plasma optical emission spectrometry
IIP ion-imprinted polymer IMS ion mobility spectrometry LC-DAD liquid chromatography-diode array detector LC-FL liquid chromatography-florescence detection LC-MS liquid chromatography-mass spectrometry LC-MS/MS liquid chromatography tandem mass spectrometry LC-UV liquid chromatography-ultraviolet detection LDHs layered double hydroxides LOD limit of detection LOQ limit of quantification MALDI-TOF MS matrix-assisted laser desorption/ionizationtime of flight mass spectrometry MEPS microextraction by packed sorbent MIP molecularly imprinted polymers MNPs magnetic nanoparticles MOFs metal-organic frameworks MSPE magnetic solid phase extraction MWCNTs multi-wall carbon nanotubes PDMS polydimethylsiloxane PTFE polytetrafluoroethylene RGO reduced graphene oxide SBSE stir bar sorptive extraction SPE solid phase extraction SPME solid phase microextraction SWCNTs single-walled carbon nanotubes UFLC-MS/MS ultra-fast liquid chromatography-tandem mass spectrometry
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1. Introduction When R. Feynman first introduced the concept of nanotechnology in 1959 by his well-known sentence “there is a lot of space down there” [1], maybe he did not have any idea about how this technology would change the future of science as it has done. Nowadays, nanotechnology is widely used in many fields such as medicine [2], electronics [3], agriculture [4], food industries [5], and biotechnology [6] because of different chemical and physical properties of nanomaterials in comparison to microscale and bulk materials. These unexpected properties are mainly due to higher surface atoms fraction and surface energy of small particles in comparison to bulk materials [7]. One of the most interesting properties of nanomaterials is their high surface area to volume ratio because of their high surface atoms fraction. This means more active atoms are available to interact with free molecules, atoms, and ions. In general, due to the high surface area to volume ratio of nanomaterials in comparison to bulk and microscale materials, application of nanosorbents for sample preparation purposes provides some advantages such as high adsorption capacity and preconcentration factors in addition to their easy functionalization and reusability [8]. Many researchers have confirmed that nanomaterials provide higher efficiency in adsorption of various compounds in gaseous or liquid phases [9,10]. However there are some limitations in the application of nanomaterials as the sorbent originated from the high surface energy of small particles. Nanomaterials usually have higher surface energy and tend to agglomerate or adsorb other molecules to decrease their surface free energy. The agglomeration leads to diminishing of the sorbent specific surface area. Also, in the case of high operation flow rates, the sorbent compaction occurs because of the small particle size of the materials leading to reduction of the flow rate, increasing the extraction time and the column back pressure. In addition, in the case of high ionic strength samples (most biological samples), unwanted coagulation can also occur during the analytical procedure, resulting in a loss of nanoparticles efficiency. By far, different various nanomaterials with different compositions and morphologies have been employed as sorbents for sample preparation purposes, aiming for the enrichment of target analytes, cleanup of the samples, and signal enhancement [11]. Sample preparation is a crucial step in processing chemical, biological, material, and surface analysis. Especially in the case of biological matrices, sample preparation is the most critical step because of the complexity of the biological samples and the presence of multiple components in the samples at the same time [12e14]. Where quantitative measurement of drugs, metabolites, and biological molecules such as proteins and DNA in biological systems (blood, plasma, hair, saliva) are concerned (the subject of bioanalysis), sample preparation has two main functions: first, sample screening, cleanup, preconcentration, and subsequently signal enhancement. The second is enhancement of the method selectivity [15]. Usually, these two goals can be reached together by the employment of some advanced sorbents; however, they are usually in a balanced relationship regarding the final cost, the sample preparation technique, and the detection method. If the detection method already provides high selectivity itself, such as liquid or gas chromatography coupled mass spectrometry (LC-MS and GC-MS, respectively) or GC tandem mass spectrometry (GCMS/MS), simpler sorbents with lower selectivity and cost are more desirable. In these cases, the aim of sample preparation usually is screening the desired analyte(s), clean-up of common contaminants such as macromolecules and proteins and preconcentration of the analyte(s) for further separation and determination. However, when the detection method provides relatively low selectivity, such as UVevisible spectroscopy (UVevis) and fluorescence
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spectroscopy, the sorbent should provide high selectivity toward the target analyte. In both cases, application of nanomaterials could be helpful because there are lots of simple and cost-effective methods for synthesis of nanomaterials with high adsorption capacity and moderate selectivities such as sol-gel, co-precipitation, and electrodeposition [16]. Nevertheless, in recent years, application of nanomaterials in sample preparation has attracted the attention of many research groups. Khajeh et al. have discussed classification, preparation, and applications of different nanomaterials as sorbents for environmental analysis with emphasis on aqueous media [17]. Chen et al. have reviewed application of aptamer-conjugated nanomaterials in bioanalysis and biotechnology. The paper has discussed the features and properties of aptamers, application of aptamerconjugated nanomaterials as sensing platforms and delivery vehicles, and effect of aptamer-conjugated nanomaterials in the enhancement of sensitivity and selectivity of the methods [18]. Xu et al. have reviewed the applications of nanomaterials as a sorbent for different purposes [19]. This paper has emphasized on nanoparticles with different chemical compositions and porous structures and their respective applications in sample preparation of various matrices such as environmental, biological and food samples. The use of nanomaterial in microextraction techniques for bioanalysis was reported [20,21]. Furthermore, He et al. published a review of the magnetic separation techniques based on magnetic nanoparticles for biological analysis applications [22]. In addition, the application of polymer-nanoparticle composites in bioanalytical sample preparation was reported [23]. In another review, the preparation and application of nanoimprinting technology in sample preparation was presented [24]. This review paper will present a comprehensive study of recently published papers (2011 and onward) on the application of nanomaterials as sorbents for bioanalysis. Various frequently used nanomaterials will be classified, and application of these materials in different sorptive sample preparation methods such as SPE, MSPE, MEPS, SPME, SBSE, and dSPE for bioanalysis will be reviewed. Moreover, some applications of nanomaterials for the enrichment of biomolecules will be reviewed. It is shown that researchers are interested in the advantages of nanotechnology not only to improve the efficiency of the conventional sorptive extraction methods, but also to establish new innovative methods. Furthermore, it is shown that MSPE due to its easy operation steps has gained the highest interest from several research groups for different final goals in bioanalysis. 2. Definition and classification of nanomaterials as nanosorbents There are some definitions and classifications of nanomaterials based on dimension, and some based on composition. Based on dimension, any material with at least one dimension in the nanoscale (i.e. 1e100 nm) can be called “nanomaterial”. According to this definition, nanomaterials can be divided into (i) zero-dimensional (such as nanoparticles), in which all dimensions are in the nanoscale, (ii) one-dimensional (such as nanotubes, nanorods, and nanowires), in which only one dimension is not in the nanoscale, (iii) two-dimensional (such as nanofilms, nanolayers, and nanocoatings), in which two dimensions are not in the nanoscale, and (iv) three-dimensional, also known as bulk nanomaterials, which are not confined to the nanoscale in any dimension. These materials possess in common a nanocrystalline structure or involve the presence of features at the nanoscale [25]. It is notable that the 100 nm size boundary used in these definitions is nowadays being questioned [26]. However, researchers are still using the abovementioned definitions, and therefore, in this paper, the above-
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mentioned definitions will be embraced. On the other hand, based on composition, nanomaterials can be classified into metallic, metallic and mixed oxide, magnetic, carbonaceous, silicon, nanofibers and nanowires, and polymeric nanomaterials. All these sorts of nanomaterials are widely used as nanosorbents in various sample preparation methods, which we will provide a brief introduction of each in the following.
walled CNTs (SWCNTs) and more than one sheet in the case of multi-walled CNTs (MWCNTs), respectively) with a diameter between a few tenths to tens of nanometers and length up to centimeters. Their interesting properties as sorbents are the high surface area, high ability for p-p interactions, relatively lower price, wider accessibility, and easy functionalization [35]. These advantages have made CNTs one of the most used sorbents in the recent years [36e38].
2.1. Metallic nanoparticles Among metallic nanoparticles, only noble metal nanoparticles (e.g. gold, silver, platinum) have gained wide attention as sorbents because of their chemical stability [27]. One of the most interesting kinds of noble metal nanoparticles in bioanalysis is gold nanoparticles (AuNPs) because of their well-known specific interaction with thiol containing compounds. Biomolecules that contain thiol or amino groups can be adsorbed spontaneously onto AuNPs to generate well-organized and self-assembled monolayers [28].
2.4.3. Graphene and graphene oxide (G and GO) GO can be considered one graphite sheet containing a wide range of functional groups, such as carboxyl, hydroxyl, ketone, and epoxy functional groups [39]. It has gained the attention of researchers as an alternative sorbent because of its improved water dispersibility, high surface area, high mechanical strength, and versatile surface modification. G having most of the advantages of CNTs can be considered highly reduced graphene oxide (RGO). G application as a sorbent because of its lower water dispersibility has not gained great attention.
2.2. Metallic and mixed oxide nanoparticles 2.5. Silicon nanomaterials Metallic and mixed oxide nanoparticles, including a wide range of different inorganic nanoparticles, having unique properties, such as high surface area, high adsorption capacity, and higher chemical stability, have gained attention as sorbents for sample preparation. Among them, some nanoparticles such as Fe3O4, TiO2, Al2O3, ZrO2, MnO, and CeO2, in bare form or modified with different functional coatings, have gained more attention [7,13,29]. Moreover, layered double hydroxides (LDHs), synthetic two-dimensional inorganic nanostructured materials, have gained attention as ion exchange sorbents. The ion exchange property of these materials is attributed to the presence of a significant number of anions in the interlayer spaces.
Silicon nanomaterials, including silica dioxide nanoparticles (SiO2), core-shell layers, nanotubes and nanowires, and nanoporous materials, are widely used for the preparation of nanosorbents [40,41]. Silicon nanomaterials are easy to synthesize and modify by various functional groups on their surface, cheap, and highly biocompatible. Their core-shell form has wide applications in protecting various nanoparticles and grafting various organic ligands. On the other hand, their monolith form has gained much attention in on-line extraction procedures as extraction and separation column [42]. 2.6. Polymer-based nanosorbents
2.3. Magnetic nanoparticles (MNPs) Magnetic nanoparticles with the ability of to be separated from the medium using an external magnetic field (consisting of magnetic elements such as iron, nickel, cobalt and their oxides) comprise a relatively new class of nanosorbents. Their magnetic properties has made them one of the most interesting nanoparticles in solid phase extraction. These nanoparticles can be used as sorbents or magnetic carriers in core-shell nanoparticles. Among these nanoparticles, iron oxide nanoparticles (magnetite and maghemite) have gained greater attention due to ease of synthesis, low cost, and biocompatibility [30e32]. 2.4. Carbonaceous nanomaterials Application of carbon nanomaterials as nanosorbents began when fullerene C60 was discovered in 1985 [33]. The application of carbon nanomaterials as nanosorbents is mainly focused on CNTs, GO and G, and fullerenes [34]. 2.4.1. Fullerenes Fullerenes are polyhedral nanostructures with 5e6 membered carbon rings in the form of a hollow sphere, ellipsoid or tube [33]. Application of these nanomaterials is relatively limited due to their extreme insolubility in aqueous and organic media, high price, and lower accessibility. However, because of their lower aggregation tendency, there are some reports on their application as solid phase sorbents [34]. 2.4.2. Carbon nanotubes (CNTs) CNTs are rolled graphene sheets (one sheet in the case of single-
2.6.1. Organic polymers Organic polymers are considered among the sorbents of greatest interest and can be used as a matrix to embed inorganic nanomaterials into them, as core-shell layers, and as supporting materials to synthesize and immobilize nanoparticles for improving the nanocomposite chemical, thermal, mechanical and sorption properties, as well as biocompatibility. Among them, in recent years, conductive polymer nanofibers and nanofilms have gained more attention because of their capacity for electrochemical synthesis [43,44]. 2.6.2. Inorganic and hybrid polymers Inorganic and hybrid polymers including xerogels, metalorganic frameworks (MOFs), and core-shell layers have some interesting applications as nanosorbents. Xerogels and aerogels having relatively high surface area, porosity, and internal pore volume, have gained some attention as potential efficient sorbents. Among them, silica xerogel has gained the most attention [45,46]. Polysiloxanes are the most important inorganic polymers regarding their commercial applications as a coating for different extraction devices. Their applications range from medical to sealants, waterbarriers, and cosmetics. Polydimethylsiloxane (PDMS) or silicone rubber is the most widely used material in sample preparation techniques [47]. MOFs, hybrid organic-inorganic materials, can be constructed by strong coordination bond formation between metal ions as nodes and organic linkers as rods. These classes of materials have a super large surface area and their pore apertures can vary substantially; moreover, in recent years, they have been used as a sorbent for extraction of a wide range of analytes from small ions to high molecular weight proteins [48,49].
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Fig. 1. Summary of bioanalysis procedures using sorptive extraction techniques.
2.6.3. Molecularly imprinted polymers (MIPs) MIPs as artificial biomimetic receptors are well-known sorbents because of their high selectivity. MIPs are cross-linked synthetic polymers obtained by co-polymerization of a functional monomer and a cross-linker in the presence of a template molecule. By removing the template after the polymerization process, materials with MIPs cavities are produced. These cavities provide highly selective adsorption properties [45,50]. The MIPs formation mechanism can be a sol-gel process or free-radical polymerization such as bulk, emulsion, suspension, precipitation, and seed polymerization [51]. The functional monomer includes special functional groups which can form a complex with the template molecule via most commonly non-covalent or covalent interactions. The cross-linker's duty is to fix this complex inside of the copolymer matrix by the formation of cross-linked bonds. A particularly promising application of imprinted polymers is ion-imprinted polymers (IIPs) which is used for solid-phase extractive preconcentration and/or separation of target ion(s) from other coexisting ions or complex matrices.
3. Sample preparation procedures for bioanalysis using nanomaterials as sorbents The complete development of an analytical method using sorptive extraction techniques requires a number of intermediate steps between sample collection and the final report of the results including sample pretreatment, sorptive extraction, desorption, and detection. Fig. 1 depicts a summary of steps that are usually involved in bioanalysis using sorptive extraction procedures. The first step in these procedures is sample collection from a biosystem. The most popular samples are plasma and serum, urine, saliva, and some tissue sections like hair and nail. Usually, one or more pretreatment steps are necessary to introduce the sample to the sorptive extraction unit, mostly because of the complexity of biological samples [52]. In the case of liquid samples (i.e. urine, serum, and plasma), centrifugation and protein precipitation are the most popular methods to separate high molecular weight species such as proteins and enzymes. In the case of solid samples, a digestion step (such as acid hydrolysis and enzymatic digestion) is usually
sufficient. In the next step, the pretreated sample is exposed to the sorptive extraction unit. The aim of this step is to clean up and preconcentrate the sample in order to get higher selectivity and sensitivity with the following analytical steps. By far, many methods have been proposed to facilitate this step and to increase its efficiency and accuracy. To this end, various sorptive extraction methods have been developed such as SPE, MSPE, MEPS, SPME, SBSE, and dSPE. These methods can be chosen for a specific aim based on their advantages and disadvantages. Moein et al. have reviewed advantages and disadvantages of some of these methods as following: In the case of SPE, advantages are high sorptive capacity, chemical or physical mechanical stability, and high selectivity, while the disadvantages are a large volume of solvent and that the method is time-consuming. In the case of SPME, the advantages are that the method is solvent free, online, and suitable for volatile compounds. The disadvantages are losing and breakable fibers, desorption, and low sensitivity. In the case of SBSE, the advantages are high sensitivity, high extraction recovery, and a packed and coated sorbent. The disadvantages are loss of coating, drying, and desorption, on-line disability, and long equilibrium time. In the case of MEPS, the advantages are high throughout, sensitivity, rapidity and ease of use, and good extraction recovery. The disadvantages are blockage and carryover, as well as desorption [53]. Some of these methods are based on direct exposure of the sorptive materials to the samples (In-solution methods) while some of them are based on the sorptive extraction of volatile or semivolatile compounds from the headspace of the samples (Headspace methods). In both cases, application of nanomaterials has motivated researchers to increase the efficiency and selectivity of the sorptive extraction methods.
3.1. In-solution methods In these methods, the sorbent is in direct contact with the solution which contains the target analyte(s). An ideal sorbent should be able to separate all of the analytes in solution while releasing the other compounds of the matrix. In this regard, the sorbent should
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Fig. 2. Published papers on the application of nanomaterials as sorbent for bioanalysis since 2011 until May 2016 extracted from Scopus: (a) number of publications per year, and (b) pie chart of application of the nanosorbents in various sorptive sample preparation techniques.
Fig. 3. Schematic representation of some commercially available devices for sorptive extraction.
have enough sorption capacity to adsorb all of the analyte molecules or ions, and on the other hand, should have specific interaction with the target analyte. In the next step (desorption), elution by another solvent or increasing medium temperature should easily release the analyte completely before introduction to the detection method. However, this kind of sorbent is very rare, and in practice, researchers prefer selective sorbents instead of specific sorbents. Usually, in order to increase the overall method selectivity, one or more separation steps are used (Fig. 1). Furthermore, in order to increase overall sorption capacity, a higher amount of sorbent can be used. However, this idea has been made almost obsolete by the introduction of nanomaterials with high surface areas. Nowadays, nanosorbents are extensively used in bioanalysis because of their high sorption capacity, and in some cases high selectivity. 3.2. Headspace methods In these methods, the sample is placed into a vial with wellsealed equipment, and the sorbent material is exposed to the headspace of the sample (liquid, or solid) to extract the target
volatile or semivolatile analyte(s) which escapes the sample matrix. These methods potentially increase the overall selectivity because the number of volatile compounds in biological samples is relatively limited. The ideal sorbents for these methods are the same sorbents used in the in-solution methods. However, the desorption step in these methods is usually thermal desorption, and the sorbent should have high chemical and thermal stability at desorption temperatures. 4. Application of nanomaterials as sorbents for bioanalysis in sorptive extraction techniques A comprehensive study on the number of publications regarding the application of nanomaterials as sorbents since 2011 (Fig. 2a) shows that the interest in nanomaterials for sorption and enrichment of target analytes, clean-up and pretreatment of biological samples is increasing. Researchers have used nanotechnology to improve extraction capacity, selectivity, sensitivity, and to reduce matrix effect. This analysis (Fig. 2b) shows that researchers have become very interested in MSPE using nanosorbents for different final goals. In the case of other well-established sample preparation
Table 1 Recent applications of different nanomaterials as sorbent for bioanalysis. Type of modification
Analyte
Matrix
Extraction technique
Detection Extraction Operation Adsorption mode mode capacity (mg technique g1)
Ref.
Surface assembly of GO on SiO2 nanospheres
Electrostatic interactions H-bonding
Hemoglobin
Human blood
dSPE
Off-line
e
UVevis
[54]
Hemoglobin
Human blood
dSPE
Insolution Insolution
Off-line
122.3
UVevis
[55]
Human urine and water
dSPE
Off-line
56.58
ICP-OES
[56]
human plasma
MSPE
Insolution Insolution
Off-line
e
LC-MS/MS
[57]
Fe3O4- MWCNTs nanocomposite
Amide bond Al(III) formation Polymerization in the Nicotine presence of nanosupport e Doxorubicin
Rat tissues
MSPE
Off-line
e
LC-FL
[58]
Core-shell Fe3O4-SiO2 coated with Ni2þ
e
Peptides
Protein digests and human serum
MSPE
Off-line
e
Adsorption
Water, food, and biological samples
MSPE
Off-line
17.3e39.9
[60]
SDS coated Fe3O4
Electrostatic interaction Adsorption
Cu(II), Cd(II), Ni(II), and Cr(III) Fuoxetine
MALDI-TOF MS FAAS
[59]
Core-shell Fe3O4-SiO2 modified with salicylic acid
Water and urine samples
MSPE
Off-line
e
FL
[61]
Pb(II) and Cr(III)
water, food, and urine samples
SPE
Off-line
100
FAAS
[62]
Pharmaceutical and biological samples
SPE
Off-line
4.8
FL
[63]
Human plasma
SPE
Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution
Off-line
e
FL
[64]
Off-line
4.9
FAAS
[65]
Off-line
e
FL
[66]
Off-line
e
FL
[67]
Off-line
e
CE-UV
[68]
Off-line
e
FL
[69]
Off-line
578
UVevis
[70]
Off-line
e
LC-MS/MS
[71]
Off-line
e
LC-MS
[72]
Off-line
e
UVevis
[73]
Off-line
e
[74]
Off-line
67.6
MALDI-TOF MS e
[75]
Off-line
e
LC-DAD
[76]
Off-line
e
ICP-MS
[77]
Off-line
e
FAAS
[78]
N,N-bis[2-methylbutyl] imidazolium hexafluorophosphate ionic liquid modified TiO2 nanocomposites TiO2 eSiO2 composite modified with 4aminophenylarsonic acid Core-shell Fe3O4- strong cation exchange resin
SDS coated Al2O3 modified with 2,4dinitrophenylhydrazine Ni-Al LDHs
e
G
e
Salicylic Acid Glutathione
SDS coated Al2O3 modified with a Schiff base
Adsorption
Cd(II)
Water, food, and human hair and urine SPE
Nanostructured overoxidized polypyrrole film
MIP
Salicylate
Human urine and plasma
EC-SPME
Au nanoparticles
Adsorption
Human urine
In-capillary SPME
HSA-coated Au nanoparticles
Adsorption
Monohydroxypolycyclic aromatic hydrocarbons Lysozyme
Hen egg white and human tear
dSPE
Ni-Al LDHs
e
Dopamine
Human serum
dSPE
Cu(II) modified ethylene glycol dimethacrylatemethacryloylamidohistidine nano-copolymer MWCNTs
Adsorption
Immunoglobulin G
Human Plasma
dSPE
e
b2-agonists
Swine urine
dSPE
TiO2-MWCNTs nanocomposite
e
Phosphopeptides
Protein digest
dSPE
SDS coated Al2O3 modified with 2,4dinitrophenylhydrazine G-Ni nanoparticles hybride
Adsorption
Formaldehyde
Water, food, and urine
dSPE
e
Proteins and peptides
Water
MSPE
Fe3O4 modified with polyarginine
Adsorption
BSA
BSA-lysozyme mixture and Egg white
MSPE
Fe3O4-MWCNTs nanocomposite
e
Aconitines
Human serum
MSPE
MnFe2O4 nanoparticles
e
Metal ions
human urine
MSPE
SDS coated Fe3O4 modified with a Schiff base
Adsorption
Heavy metal ions
Water, food, and human hair
MSPE
Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
Nanomaterial
(continued on next page) 7
8
Table 1 (continued ) Nanomaterial
Type of modification
Analyte
poly(styrene-divinylbenzene) coated Fe3O4 nanoparticles Carboxymethyl-b-cyclodextrin modified Fe3O4 nanoparticles Polymer coated Fe3O4 nanoparticles
Polymerization in the Fenitrothion presence of nanosupport Amid bond formation Adenosine and guanosine MIP Catecholamines
Fe3O4-G-MWCNTs nanocomposites
e
Histidine modified MWCNTs
Extraction technique
Detection Extraction Operation Adsorption mode mode capacity (mg technique g1)
Ref.
Water, soil, urine and human plasma samples
MSPE
Insolution
Off-line
e
UVevis
[79]
e
MSPE
Off-line
e
UVevis
[80]
Human urine
MSPE
Insolution Insolution Insolution
Off-line
e
CE-DAD
[81]
Off-line
e
MALDI-TOF MS
[82]
On-line
4.85
ETAAS
[83]
Off-line
13 and 18
FAAS
[84]
Off-line
7.7
UVevis
[85]
Off-line
e
LC-FL
[86]
e e
GC-FID LC-MS/MS
[87] [88]
e
LC-MS
[89]
Off-line
153.84
LC-DAD
[90]
Off-line
e
LC-MS/MS
[91]
Off-line
e
[92]
Off-line
e
Off-line
e
Off-line
e
MALDI-TOF MS MALDI-TOF MS MALDI-TOF MS UVevis
Off-line
241.82
UVevis
[96]
Off-line
4.65
UVevis
[97]
Off-line
8.51
UVevis
[98]
Off-line
11.34
FL
[15]
Off-line
e
CE-UV
[99]
Human urine
MSPE
biological and environmental samples
SPE
MWCNTs modified with a Schiff base
Covalent bond formation Adsorption
Berberine, curcumin, luteoloside and chlorogenic acid V(v) Cu(II) and Pb(II)
Water samples, corn, and human hair
SPE
Ni-Al-Zr LDHs
e
Iodate
Food, Environmental, and human urine SPE
G
e
Rat brain
SPE
Nanostructured a-Carboxy polypyrrol Methacrylate-based monolith
e e
Glycine, gammaaminobutyrate and taurine Methadone Peptides
Human urine and plasma Tryptic digestion BSA
Tetraethylenepentamine modified Fe3O4 nanoparticles
Phenolic Environmental estrogens Haloperidol
Headspace Off-line InOn-line solution InOff-line solution
Nanopolymer
Polymerization in the presence of nanosupport MIP
SPME In-capillary SPME Dispersive mSPE
Human plasma and urine
dSPE
MWCNTs
e
Sulfonamides
Pork
dSPE
TiO2-MWCNTs nanocomposite
e
Phosphopeptides
Rat brain
dSPE
Amine-functionalized Fe3O4 nanoparticles
e
Tryptic digest of proteins
MSPE
Cu(II) immobilized polydopamine coated G- Fe3O4 nanocomposite Poly(acrylic acid) modified poly(glycidylmethacrylate)-grafted nanocellulose Fe3O4-nanocrystalline cellulose nanocomposite
e
Phosphopeptides and glycopeptides Peptides
Water
MSPE
Graft copolymerization
Hemoglobin
Water
dSPE
Insolution Insolution Insolution Insolution Insolution Insolution
e
Myoglobin
Water
MSPE
Polymer coated SiO2- Fe3O4 nanocomposite
MIP
Hemoglobin
Water
MSPE
Polymer coated SiO2- Fe3O4 nanocomposite
MIP
Tramadol
Human urine
MSPE
Polymer coated Fe3O4-MWCNTs nanocomposite
MIP
Naproxen
Human urine
MSPE
Fe3O4 nanoparticles
e
Human urine and Portulaca oleracea L. MSPE leaves
CTAB coated Fe3O4 nanoparticles
Electrostatic interactions
SDS coated g-Fe2O3 nanoparticles
Electrostatic interactions
Dopamine, noradrenaline, and adrenaline Amitriptyline, nortriptyline, imipramine, and doxepin Oxymetholone and mestanolone
Human blood
Insolution Insolution Insolution Insolution
Insolution Insolution Insolution Insolution Insolution
[93] [94] [95]
Water and human urine
MSPE
Insolution
Off-line
e
LC-UV
[100]
Human urine
MSPE
Insolution
Off-line
e
UVevis
[101]
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
Matrix
e
Pb(II)
Water and human serum
MSPE
Anthrax lethal factor coated SiO2-Fe3O4 nanocomposite Surface-oxidized nanodiamond
Amide bond formation Oxidation
Neutrophil peptides
Human serum, saliva, and tear
MSPE
Tryptic peptides
Membrane proteins
dSPE
Nanostructured polymer
IIP
Cu(II)
Human urine and serum
SPE
RGO-SiO2 nanocomposite
e
BSA digests
SPE
Alizarin red S modified TiO2 nanoparticles
Adsorption
Chlorophenols and peptides Cd(II) and Pb(II)
SPE
Polymer coated TiO2 nanoparticles
MIP
MWCNTs
e
Aspartic acid enantiomers Strychnine and brucine
Water samples, human hair and fingernail Human serum and lumbar CSF, and pharmaceutics Human urine
MWCNTs modified monolithic Nanostructured polypyrrole film ZN-Al LDHs-TiO2 nanosheet film
Oligomer matrixassisted dispersion e e
Hemoglobin and cytochrome c Urea Valproic acid
Fe3O4-MWCNTs nanocomposite
e
G-SiO2 nanocomposite
e
Lomefloxacin and ofloxacin Pb(II), Cd(II), and Cr(III
Water, human urine and saliva
Polymer coated Fe3O4-MWCNTs nanocomposite
IIP
Pb(II)
Water and human hair
Dispersive mSPE Dispersive mSPE MSPE
Polymer coated Fe3O4-SiO2-TiO2 nanocomposite
IIP
Co(II)
Water, food, and human urine
MSPE
Water and human hair
MSPE
Water and human urine
MSPE MSPE
g-mercaptopropyltrimethoxysilane modified Fe3O4- e
Whole human blood Dialysis human serum Human serum and pharmaceutical samples Human plasma and urine
SPME HF-SPME In capillarySPME SPME SPME
SiO2 nanocomposite Polymer coated Fe3O4-SiO2 nanocomposite
MIP
Hg(II) and methylmercury Tizanidine
GO-Fe3O4 nanocomposite
e
Pseudoephedrine
Human urine
Polymer coated Fe3O4-SiO2 nanocomposite
MIP
Diclofenac
Polymer coated Fe3O4-SiO2 nanocomposite
MIP
Codeine
Water samples, human blood serum and MSPE urine samples, and pharmaceutical ampoules Human urine MSPE
CdTe QDs
e e
Se(IV) Hg(II) and methylmercury Losartan and valsartan
g-mercaptopropyltrimethoxysilane modified Fe3O4-SiO2 nanocomposite Ni:Zn sulphide nanoparticles loaded activated carbon Polydopamine, Ag nanoparticles and polypyrrole nanocomposite 1,5-bis(di-2-pyridil)methylene thiocarbohydrazide modified Fe3O4-SiO2 nanocomposite Fe3O4-MWCNTs nanocomposite
Sol-gel e
e
Amitriptyline, imipramine, and citalopram Hg(II)
e
Cd(II)
Polymeric monolith modified with Au nanoparticles e Polyaniline-coated Fe3O4 nanoparticles
e
Nanohydroxyapatite
e
Mesoporous SiO2 particles
e
BSA, cytochrome c, and lectins Lorazepam and nitrazepam Volatile organic metabolites Endogenous peptides
Reference materials and human urine HepG2 cells Human urine and plasma
SPE Chip-based MSPE SBSE
Human urine
MEPS
Certified reference materials and water MSPE samples Human urine, water, and certified MSPE reference materials Water SPE
Human urine
Dispersive mSPE dSPE
Human urine
In-syringe dSPE
Human urine and plasma
Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Headspace Headspace Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Headspace Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution
Off-line
100
FAAS
[102]
Off-line
e
[103]
Off-line
e
Off-line
e
MALDI-TOF MS MALDI-TOF MS ICP-OES
[105]
Off-line
e
LC-UV
[106]
Off-line
10.7 and 19.2 FAAS
Off-line
0.0352
Voltammetric [108]
Off-line
e
LC-UV
[109]
On-line
e
UVevis
[110]
Off-line Off-line
e e
IMS GC-FID
[111] [112]
Off-line
e
FL
[113]
Off-line
e
ETAAS
[114]
Off-line
e
GFAAS
[115]
Off-line
35.21
FAAS
[116]
Off-line
e
ICP-MS
[117]
Off-line
e
UVevis
[118]
Off-line
e
LC-UV
[119]
Off-line
44.11 and 116.35
UVevis
[120]
Off-line
13.44
FL
[121]
Off-line On-line
e e
FL ICP-MS
[122] [123]
Off-line
e
LC-UV
[124]
Off-line
e
GC-MS
[125]
On-line
5.22 and 6.81 CV-ETAAS
[126]
On-line
3.67
GFAAS
[127]
Off-line
16.6
UVevis
[128]
Off-line
e
LC-UV
[129]
Off-line
e
GC-MS
[130]
Off-line
e
[104]
[107]
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
Amino-functionalized SiO2-Fe3O4 nanocomposite
[131] 9
(continued on next page)
Nanomaterial
10
Table 1 (continued ) Type of modification
Analyte
Matrix
Extraction technique
Adsorption
BSA
Water
MSPE
Precipitation
Phosphopeptides
BSA digest
MSPE
G and GO
e
DNA and RNA
Eukaryotic and Prokaryotic cells
dSPE
Polymer coated Fe3O4-SiO2 nanocomposite
MIP
Hemoglobin
Bovine calf serum
MSPE
Poly[N-isopropylacrylamide-co-1-(N,N-biscarboxymethyl)amino-3-allylglycerol] coated Fe3O4-SiO2 nanocomposite Polyethylene glycol-coated Fe3O4-MWCNTs nanocomposite Methylcellulose Fe3O4-SiO2 nanocomposite Polyethylene glycol modified Fe3O4-MWCNTs nanocomposite SDS coated Fe3O4 nanoparticles
Polymerization in the Fluvoxamine presence of nanosupport e Puerarin
Human plasma and urine, and tablet
MSPE
Rat plasma
MSPE
e
Sildenafil and its metabolite Methylprednisolone
Human urine and plasma
MSPE
Rat plasma
MSPE
Chlorpromazine
Water, human urine and plasma
MSPE
Human plasma and urine
MSPE
Cortex Phellodendri extract
MSPE
Human urine
MSPE
Human urine
MSPE
Human plasma and urine, and pharmaceutical formulations Saliva
SPE
Au nanoparticles coated Fe3O4 nanoparticles Polydopamine coated Fe3O4 nanoparticles
Adsorption Electrostatic interaction e
Nanostructured polymer
Progesterone and testosterone Polymerization in the Berberine presence of nanosupport e 5-hydroxy-3-indole acetic acid e Polycyclic aromatic hydrocarbon metabolites MIP Human insulin
Ni-Al LDHs
e
Thiocyanate
3-(1-methyl-1H-pyrrol-2-yl)-1H-pyrazole-5carboxylic acid modified GO Polymer coated GO
e
Mn(II) and Fe(III)
MIP
Dopamine
e
Water and human hair
b-cyclodextrin modified Fe3O4-SiO2 nanocomposite GO-Fe3O4 nanocomposite
Water samples, food samples, human urine and blood Human serum
Al-terephthalate MOFs modified polymeric monolith Ionic liquid coated TiO2 nanoparticle
e
G-polyaniline film MWCNTs coated SiO2 nanoparticles
e e
Nanostructured polymer
IIP
Ketoprofen, fenbufen, and ibuprofen Lorazepam, alprazolam, and diazepam Aldehydes Nucleobases and nucleosides Hg(II)
GO-polyethyleneglycol nanocomposite
e
Fluoroquinolones
Chicken muscle and liver
Bidentate Ag nanoparticles
e
Milk and human urine
Polypyrrole coated Fe3O4 nanoparticles
e
Cytochrome c and insulin Citalopram and sertraline Levodopa
e
Water and human urine Water, and human hair and urine Human exhaled breath condensate Human urine
Human urine and plasma Human urine
Insolution Insolution Insolution Insolution Insolution Insolution
Off-line
e
Off-line
e
Off-line
MALDI-TOF MS UVevis
Ref.
[132] [133]
e
MALDI-TOF MS GE
Off-line
71
UVevis
[135]
Off-line
e
LC-UV
[136]
Insolution Insolution Insolution Insolution Insolution Insolution
Off-line
e
LC-DAD
[137]
Off-line
e
LC-DAD
[138]
Off-line
e
LC-UV
[139]
Off-line
e
LC-UV
[140]
Off-line
e
LC-UV
[141]
Off-line
e
LC-UV
[142]
Insolution Insolution
Off-line
e
FL
[143]
Off-line
e
LC-MS
[144]
On-line
460
LC-DAD
[145]
Off-line
86.8
GC-FID
[146]
Off-line
21.6 and 24.0 FAAS
[147]
Off-line
e
LC-DAD
[148]
Off-line
e
LC-DAD
[149]
Off-line
e
LC-UV
[150]
On-line Off-line
e e
LC-UV LC-DAD
[151] [152]
On-line
e
UVevis
[153]
Off-line
e
LC-FL
[154]
Off-line
e
[155]
Off-line
e
MALDI-TOF MS LC-UV
[156]
Off-line
e
UVevis
[157]
Insolution SPE Insolution SPE Insolution HF-SPME Insolution In-capillary InSPME solution HF-SPME Insolution In-tube SPME Headspace SPE Insolution SPE Insolution SBSE Insolution Single drop Inmicroextraction solution InDispersive mSPE solution dSPE
[134]
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Ionic liquids modified Fe3O4-SiO2 nanocomposite TiO2 coated Fe3O4-MWCNTs nanocomposite
Detection Extraction Operation Adsorption mode mode capacity (mg technique g1)
[160] LC-UV Off-line
e
[159] FL e Off-line
FAAS
dSPE
Al(III)
Vancomycin
Adsorption
e
Human plasma and urine
dSPE
11
techniques with commercially available devices such as SPME and MEPS (Fig. 3), researchers are using these techniques for the cleanup of samples prior to their introduction into the chromatographic separation systems. However, there are some reports on improvements in the efficiency of these techniques by the application of nanomaterials as sorbents instead of conventional microscale sorbents. Furthermore, some new procedures for sample preparation have been proposed based on the application of nanosorbents for on-line and fully automated analysis of biological samples to establish fast, cost-effective, simple, sensitive and selective methods for daily determination of targeted analytes. In addition, application of nanomaterials for the extraction and determination of macromolecules from biological samples is increasing. Table 1 shows the summary of application of some nanoparticles as sorbents for bioanalysis since 2011. This table contains some useful information about the nanomaterials used together with the extraction technique and the results obtained including type of modification, the investigated analyte, type of sample matrix, extraction technique, extraction mode (i.e. in-solution or headspace modes), operation mode (i.e. on-line or off-line modes), adsorption capacity, detection technique, and extraction efficiency. In the following, some of these nanomaterials together with the extraction techniques used and the results obtained have been reviewed in detail. 4.1. Solid phase extraction (SPE)
8-hydroxyquinoline modified SDS coated CoFe2O4 nanoparticles Polypyrrole coated G
Carboxymethyl-a-cyclodextrin polymer coated TiO2 nanoparticles Hydroxyapatite nanorods
e
Cu(II), Zn(II), and Pb(II)
Certified reference materials, water, food, and human blood, urine and hair Water and human serum
dSPE
Insolution Insolution Insolution Insolution
Off-line
e
[158]
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
SPE is an alternative sample preparation technique to liquidliquid extraction which can reduce the volume of solvents needed. It has been used for the preconcentration or clean-up of target analytes from various matrices for many years. In this technique, the sorbent is packed inside cartridges, syringe barrels, microcolumns or disks. SPE cartridges are commercially available (Fig. 3). Conventional sorbents for SPE are silica derived compounds such as C18-bonded silica. Nowadays, nanosorbents are extensively being used for SPE. Various types of nanoparticles and nanocomposites in bare form or modified with organic and inorganic ligands such as MIPs [145,161e164], IIPs [105,165], LDHs [63,146,166], CNTs [84,152,167], G and RGO [64,86,106], GO [147,168,169], TiO2 [107], and Al2O3 [62,65] have been used to extract, preconcentrate, and clean up biological samples (Table 1). In an interesting article, Liu et al. developed new sorbents by G and GO supporting on silica as versatile and high-performance sorbents for SPE [168]. Their results showed that the newly developed adsorbent can be efficiently used for SPE extraction of a wide range of analytes from small molecules to high molecular weight macromolecules such as proteins. Because of different polarity of G and GO, the adsorbent can be efficiently used for both reversed phase and normal phase extractions. In another interesting article, Luo et al. used a simple hydrothermal strategy for the preparation of RGO encapsulated SiO2 as a new SPE sorbent. The newly developed sorbent showed higher efficiency compared to the other conventional SPE sorbents [106]. The sorbent was successfully used for SPE extraction and enrichment of chlorophenols from water and peptides from BSA digests. Toward establishing an on-line method to determine human insulin in plasma and pharmaceutical formulations, Moein et al. developed MIP cartridges coupled with LC [145]. The MIP sorbent was prepared using methacrylic acid (the functional monomer), ethylene glycol dimethacrylate (the cross-linker), chloroform (the porogenic solvent), and insulin (the template). The results showed that fast and facile LC analysis of insulin was achievable with the good selectivity provided by the MIP sorbent. LOD and LOQ in ng mL1 levels were obtained in plasma and urine samples. Furthermore, the results showed that the method provided cleaner
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extraction and suppressed interfering peaks from the complicated biological samples. 4.2. Dispersive solid phase extraction (dSPE) In 2003, Anastassiades et al. introduced a new extraction technique named dSPE based on the dispersion of the solid sorbent inside of the sample solution containing the targeted analytes using magnetic stirring, vortex, and ultrasonication [170]. In dSPE, the sorbent can directly interact with the analytes and be separated from the solution usually using centrifugation, and then, subsequent desorption using a suitable eluent can be conducted. Because of the direct contact of the sorbent with the analytes, the extraction time and capacity can be improved. dSPE can be regarded as a batch mode of SPE, and all of the nanoparticles that are used in SPE can be used as sorbent for dSPE. In recent years, different nanoparticles and nanocomposites such as CNTs [91,171], G [160,172], GO-MOF and GO-SiO2 composites [173,174], MIPs [90,175e178], coated or grafted polymers [157,179,180], LDHs [69], MOFs [181], diamond nanopowder [182], TiO2 nanoparticles and aerogels [183,184], TiO2-CNTs nanocomposites [72,92], Al2O3 [73,185], and AuNPs [68,186] have been used as dSPE sorbents for extraction of target analytes and matrix clean-up in bioanalysis (Table 1). Recently, Ge et al. have proposed an interesting method to produce 3D porous graphene as a sorbent to extract proteins and peptides from some biofluids prior to MALDI-TOF MS analysis [172]. The sorbent was prepared by dissolving cuprous oxide microspheres as sacrificial templates in the composite of graphene and cuprous oxide microspheres using diluted nitric acid. The sorbent was successfully used for enrichment of low-abundance proteins and peptides prior to subsequent MALDI-TOF MS identification. Major features of the newly developed sorbent are a large surface area, 3D porous architecture, cost effectiveness, and satisfactory reproducibility. Chauhan et al. have proposed a MIP sorbent for simultaneous extraction of polycyclic aromatic hydrocarbon metabolites from urine samples prior to LC analysis [178]. In this regard, they have synthesized a nanostructured multi-template imprinted polymer to eliminate the need of individual MIPs for each metabolite. In another interesting work, Yeh et al. synthesized human serum albumin-coated AuNPs for selective extraction of lysozyme from hen egg white, human milk, and human tear samples prior to CE analysis [68]. The results showed that the protein coating layer on the AuNPs has negative charges and can be efficiently dispersed in high-ionic-strength solutions, and capture lysozyme through electrostatic attraction. The results showed that highly efficient analyte loading and extraction was achievable at pH 7 which closely resembles the biological pH. 4.3. Magnetic solid phase extraction (MSPE) MSPE is similar to dSPE in methodology except that the sorbent can be easily separated from the medium using an external magnetic field. To this end, magnetic nanoparticles (MNPs), usually iron oxide magnetic nanoparticles, in bare, core-shell, composite, and organic and inorganic ligand modified forms are used. This method has obtained heightened attention in sample preparation for bioanalysis because of its easy operation steps. Researchers have used many strategies to prepare magnetic nanosorbents for MSPE of various analytes to form different complex matrixes. Various nanocomposites such as CNT-MNPs [76,187,188], RGO-, GO- and G-MNPs [189,190], surfactant coated MNPs [61,100,101,191e193], MIP-coated MNPs [15,98,119, 121,135,194e199], IIP coated MNPs [115,116,200], polymer coated MNPs [79,139,142,201e205], amine functionalized MNPs
[81,102,206,207], TiO2-MNPs [133,208,209], ionic liquid coated MNPs [210e212], and cyclodextrin coated MNPs [143,213e215] have been used as sorbents in MSPE for bioanalysis (Table 1). In an interesting study, Shi et al. developed a method based MSPE and MALDI-TOF MS for determination of small molecules present in urine samples, by the elimination of the desorption step in MSPE [82]. In this regard, a magnetic composite of G with CNT was utilized as a novel adsorbent to enrich the targeted analytes and introduce the loaded analyte to MALDI-TOF MS analysis. In order to evaluate the benefits of the utilized magnetic composite, other possible magnetic sorbents including magnetic CNTs, magnetic G, and the mixture of them were also employed as sorbent as well as the functional matrixes. The results showed that the magnetic composite of G with CNT provided the highest efficiency in terms of the extraction process, signal enhancement, and facilitation of desorption/ionization process. In another study, Dramou et al. synthesized a novel amphiphilic magnetic MIP sorbent to extract gatifloxacin from human urine and serum samples prior to UVevis spectrophotometric determination [216]. To this end, a layer of the analyte imprinted polymer was coated on oleic acid and PVP coated MNPs. The sorbent solubility and dispersibility studies demonstrated sorbents with high amphiphilicity, an important factor for an efficient sorbent used in MSPE. In another interesting study, multicore MNPs doped with Cs and FITC dye for the extraction of the CA19-9 biomarker in serum for direct introduction to ICP-MS without analyte desorption was synthesized by Ko et al. [217]. The sorbent was used for nonspecific magnetic extraction of the investigated analyte from serum samples, after which the ratiometric measurement of the tagged particle was performed using the doped Cs as the internal standard. 4.4. Microextraction by packed sorbent (MEPS) In 2004, miniaturization of SPE cartridges led to the introduction of a new microextraction technique named MEPS by AbdelRehim [218]. In MEPS, the SPE cartridges have been replaced by microsyringes, and subsequently, the required sorbent amount has been decreased to a few milligrams. The sorbent can be packed into the syringe barrel as a plug, between the needle and the barrel, or inside of the needle as a cartridge (Fig. 3). This technique is specially designed for on-line fully-automated measurements. As other microextraction techniques, the required sample volume has been significantly reduced to a few microliters. Nowadays, MEPS syringes are commercially available from SGE (SGE Analytical Science Pty Ltd, Victoria, Australia). This method has as high a potential for on-line applications as any sorbent materials such as conventional SPE sorbents, and even more advanced sorbents can be packed and used for bioanalysis. Recently, Bagheri et al. have synthesized a nanocomposite consisting of polydopamine, AgNPs, and polypyrrole as a sorbent for MEPS that was used for simultaneous extraction of amitriptyline, imipramine, and citalopram antidepressant drugs from urine samples prior to GC-MS analysis [125]. They used a homemade MEPS syringe by packing 2 mg of the synthesized sorbent into a 1 mL syringe between two PTFE frits. The results of their work showed that the synthesized nanocomposite provides higher efficiency in extraction of the investigated analytes in comparison to bare polydopamine and polypyrrole sorbents. Zhu et al. used a nanostructured monolith sorbent for the effective enrichment of endogenous peptides from human plasma prior to MALDI-TOF MS analysis [219]. The monolith sorbent was prepared using carbohydrate-based sponge-like pomelo peel as the base material. Then, a mesostructured CTAB-SiO2 composite was deposited on the base material. After removing unstable compounds in pomelo peel and CTAB using acid treatment and calcination, a continuous
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skeleton, interconnecting macropores and ultra-high surface area sorbent was obtained. The sorbent was then packed inside a 1 mL syringe between two cotton layers. 4.5. Solid phase microextraction (SPME) Undoubtedly, SPME still is the most popular microextraction technique. Since Pawliszyn and Arthur proposed SPME and applied it in practice in 1990 [220], there have been many modifications made to this technique. In its conventional and commercially available form, the SPME device consists of a fused silica fiber uncoated or coated with a thin layer of extraction medium fixed inside of the needle of a syringe-like device (Fig. 3). The extraction process can be conducted either using in-solution or headspace extraction strategies from gaseous and liquid samples by immersing the fiber in the investigated solutions or placing it in the headspace of the samples. Researchers have used different strategies to improve SMPE extraction efficiency for bioanalysis by using nanomaterials such as nanomaterials coating capillary [67,221e223], MIPs coating silica fiber or capillary [108,224], nanostructured polymers electrodepositing conductive cores or tubes [66,87,111,151], nanomaterials coating fiber [225,226], and monoliths packing capillary [88,110,149,227e232] (Table 1). Guo et al. have prepared a fused silica capillary column coated with dimethylethanolamine aminated polychloromethyl styrene nano-latex for the extraction and enrichment of four tetracycline antibiotics from pig plasma prior to FASS-OT-CEC [233]. Their results showed that better separation of the investigated analytes could be obtained on the coated capillary column than that obtained on the bare fused silica capillary, and the method sensitivity could also be increased. In another interesting study, Liu et al. prepared TiO2 nanoparticle functionalized monolithic capillary for on-line microextraction of Gd ion and Gd-based contrast agents from human urine prior to ICP-MS determination [232]. In order to prepare the monolithic capillary, TiO2 nanoparticles were embedded in the poly(methacrylic acid-ethylene glycol dimethacrylate) framework. After optimizing extraction condition, they managed to determine the investigated analytes in mg L1 concentration levels with LODs in ng L1 levels. The developed on-line method is featured with high sensitivity, low sample consumption, and efficient separation ability and provides an attractive non-chromatography strategy for the speciation of Gd ion and Gd-based contrast agents in human urine. Toward establishing a method for on-line determination of aldehydes in human exhaled breath condensate, Li et al. synthesized a novel G-polyaniline coating [234]. The G-polyaniline composite was electrodeposited on the internal surface of a stainless steel tube, and the coated tube was used for the analysis of breath samples of healthy people and lung cancer patients. The results showed that in comparison to bare polyaniline coating, the G-polyaniline coating exhibited enhanced mechanical stability, large specific surface area, long lifespan, and good biocompatibility. Furthermore, on-line mode of the method provided faster analysis, higher enrichment efficiency, and higher automation level than its off-line mode. 4.6. Dispersive m-solid phase extraction (dispersive m-SPE) Dispersive m-SPE is a miniaturized form of dSPE that has recently been developed based on microextraction strategies such as reducing the required sorbent amount. In this technique, the solid sorbent is added to the solution and dispersed by shaking. Finally, the sorbent loaded with the investigated analytes is separated from the solution by centrifugation or other similar methods. In dispersive m-SPE, the quantity of the sorbent in comparison to dSPE has been significantly reduced, and therefore, the technique
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requires highly efficient sorbents to maintain or even improve the extraction and preconcentration efficiency. Therefore, application of nanosorbents with high surface area and sorption capacities is a suitable option to improve the efficiency of dispersive m-SPE. Different nanosorbents have been used for dispersive m-SPE of targeted analytes from biological samples such as MNPs-polymer nanocomposite [129,156], MNPs-CNTs nanocomposite [113], GO and G [235,236], G-silica hybrid [114], and modified MNPs [89,237] (Table 1). Asgharinezhad et al. synthesized a polyaniline-MNPs polymeric nanocomposite for dispersive m-SPE of benzodiazepines from human urine and plasma samples [129] (Table 1). They also synthesized polypyrrole-MNPs and polypyrrole/polyanilineMNPs and evaluated the extraction efficiencies of the three sorbents. The comparison of polyaniline-MNPs nanocomposite sorbent with polypyrrole-MNPs and polypyrrole/polyaniline-MNPs nanocomposite sorbents along with the bare MNPs demonstrated that the polyaniline-MNPs nanocomposite sorbent provides the highest extraction efficiency for the investigated analytes. They have reported that the coating of MNPs with polyaniline can increase the adsorption ability of the target analytes and also improve the stability of the MNPs and their dispersibility in aqueous media. In another study, Zhao et al. have used tetraethylenepentamineMNPs polymeric nanocomposite for simultaneous extraction of eight phenolic environmental estrogens in blood samples prior to UFLC-MS/MS determination [89] (Table 1). Their results showed that using the synthesized sorbent and protein precipitation technique, the level of phospholipids in plasma samples as the major contributing source of matrix effects in LC-MS/MS for analysis of plasma samples and, subsequently, the absolute matrix effects could be greatly reduced. 4.7. Stir bar sorptive extraction (SBSE) In 1999, Baltussen et al. introduced a novel extraction technique named SBSE [238]. The technique, in its original version, employs a PDMS coated stir bar as sorptive element (Fig. 3). The coated stir bar can be immersed in the sample solution or fastened in the headspace of the sample to extract the analytes of interest. Then, the stir bar can be transferred for desorption and determination of the extracted analytes. Nowadays, an automated version of the SBSE technique is commercially available and GERSTEL®MultiPurpose Sampler is a commercially available device to automate the whole SBSE extraction procedure. In recent years, many researchers have used different nanoparticles to increase the extraction efficiency of the SBSE technique. Fan et al. have used a GO-polyethyleneglycol polymeric nanocomposite coated stir bar for sorptive extraction of fluoroquinolones from chicken muscle and liver prior to LC-FL determination [154] (Table 1). GO was composited with polyethyleneglycol through intermolecular interactions to improve its stability and a stir bar was coated with it using the sol-gel technique. The results showed that the newly developed sorbent provides higher efficiency for extraction of the investigated analytes in comparison to GO-polyaniline composite and PDMS coated stir bar. In another study, Pebdani et al. used another nanosorbent to enhance conventional SBSE device extraction efficiency for losartan and valsartan extraction from urine and plasma matrices [124] (Table 1). In this instance, the stir bar was coated with nickel:zinc sulfide (Ni:ZnS) nanoparticles loaded onto activated carbon as well as 1-ethyl-3-methylimidazolium hexafluorophosphate ionic liquid using the sol-gel technique and was used for SBSE extraction of the investigated analytes prior to LC-UV determination. Their results showed that the synthesized coating provides much higher extraction efficiency than activated carbon coating. This behavior is attributed to the multi-elemental nature of the sorbent (Ni metallic
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site can interact with the investigated analytes via electrostatic interaction according to the hard-soft principle, S reactive site can react with p electrons of the analytes, and the Zn site can interact with the structures containing hydroxyl groups), as well as to the higher surface area of the nanomaterials.
4.8. Other methods In addition to the abovementioned techniques, other innovative or well-established methods have also been used for bioanalysis utilizing nanomaterials as sorbents. Various techniques such as pipette-tip extraction, microfluidic methods, electrochemical methods, and single drop microextraction have benefited from the interesting advantages of nanotechnology. In the following, some of the recent applications are being reviewed. Alwael et al. reported on the preparation of a pipette-tip packed by lectin modified AuNPs on a polymeric monolithic for selective extraction of glycoproteins prior to LC-UV determination [239]. In this regard, ethylene dimethacrylate porous polymer monolith was in situ prepared within a 20 mL polypropylene pipette tip bounded via surface grafted methacrylate anchor sites. AuNPs were then immobilized onto the monolith pore surface. The results showed that high capacity and selective extraction was achievable using the newly developed monolith because of the high surface area provided by the nanomaterials and lectin affinity phase, respectively. In an interesting study, Wu et al. developed a novel microfluidic method for in vivo fast equilibrium monitoring (2 min total extraction time) of pharmacokinetic profiles of desipramine in rabbits based on a biocompatible core-sheath electrospun nanofiber membrane sandwiched within the microfluidic unit as sorbent [240]. In order to prepare the membrane, polystyrenecollagen co-polymer was coaxially electrospun, and then strengthened with in situ glutaraldehyde cross-linking. The membrane showed high mechanical strength and stability in water and biomatrix resistance and provided high mass transfer rate and large extraction capacity. The membrane was embedded into the microfluidic device using a sandwich design, and the blood stream could be introduced in vivo into the microfluidic device to interact with the membrane repetitively. The authors managed to monitor free and total concentrations of desipramine in vivo with 10 min intervals almost without rabbit blood consumption using the innovative microfluidic device and the nanostructured sorbent. Wang et al. developed a chip-based open tubular capillary electrochromatography method for drugs, amino acids, and dipeptide enantiomers utilizing a series of magnetic MIP nanosorbents [241]. The magnetic nanosorbents were synthesized using MNPs as the support substrate, dopamine as the functional monomer, and the investigated enantiomers as the templates. The sorbents were then packed inside a PDMS microchannel and fixed inside of the column using an external magnetic field as a novel stationary phase for the enantioseparation of the targeted enantiomers. The synthesized sorbent exhibited high adsorption capacity, excellent selectivity, and high stability. Their results confirmed that the proposed method could distinguish and separate not only amino acid enantiomers but also dipeptides and drug enantiomers, which greatly expands the range of the design in bioanalytical applications. Madrakian et al. used a different design for selective and sensitive sorptive extraction of mefenamic acid from some real samples including human urine based on magnetic MIP nanoparticles [242]. In this regard, the magnetic MIPs nanoparticles were synthesized using MNPs-SiO2 core-shell nanoparticles (as the support material), methacrylamide (as the functional monomer), ethylene
glycol dimethacrylate (as the cross-linker), and 2-20 -azoisobutyronitrile (as the initiator). In order to extract the investigated analyte from the sample matrix, the nanosorbent was added to the solution, and after loading the analyte, it was collected on a homemade carbon paste electrode which included a permanent magnet inside of it. Then, the voltammetric determination was carried out. Their results showed that application of the selective MIP sorbent for extraction of the investigated analyte prior the electrochemical analysis could greatly improve the selectivity and sensitivity. Shastri et al. have synthesized bidentate AgNPs and evaluated the potential usage of the nanoparticles in single drop microextraction of proteins and peptides from biological samples prior to MALDI-TOF MS determination [155] (Table 1). The results showed that highly efficient extraction of the investigated analytes was achievable because of the high ability of the bidentate nanoparticles to interact with the investigated analytes. They could improve MALDI-TOF MS signal intensity of the investigated proteins and peptides 10e15 times by utilization of the bidentate AgNPs in single drop microextraction.
5. Application of nanomaterials in determination of biomolecules The high surface and surface functionality of nanomaterials provide a good degree of selectivity towards targeted biomolecules. For example, HSA modified AuNPs have been used for the selective extraction and enrichment of lysozymes prior to analysis by CE due to the electrostatic interaction between the HSA layer and the lysozymes [243]. AuNPs have high affinity towards thiol functional groups, which helps in the extraction of amino-thiols (biomarkers of Alzheimer's disease) through m-SPE [244]. Graphene templated magnetic nanocomposite was demonstrated to be highly selective for extraction and separation of low-concentration biomolecules from biological samples due to the size-selection property provided by the unique porous structure and the excellent affinity of the composite materials [245]. Moreover, customized molecular imprinted polymers could be immobilized on various nanoparticles to improve selectivity for different analytes [246]. AuNPs were integrated into liquid phase microextraction as extracting/preconcentrating probes for determination of methionine-encephalin and leucine-encephalin peptide mixture using MALDI-TOF MS [247]. The surfaces of AuNPs were functionalized with tetraalkylammonium bromide, which contains negative and positive charges. Furthermore, surface-modified AgNPs were used for microextraction of peptide mixtures from biological samples prior to MALDI-TOF MS [248]. AgNPs were functionalized with tetraoctylammonium bromide and the average size of the nanoparticles were found to be < 50 nm. Microextraction of bovine fibrinogen and BSA proteins from complex protein matrixes was carried out using PDMS fibers coated with MWCNTs and SWCNTs that were used as adsorbents in a SPME procedure. It was reported that BSA was more absorbed on the surface of SWCNTs as than on MWCNTs [249]. Single-drop microextraction using AuNPs in toluene as an extracting phase was utilized for the extraction of Met-enkephalin (Met-enk, H-Tyr-Gly-Gly-Phe-Met-OH) and Leu-enkephalin (Leuenk, H-Tyr-Gly-Gly-Phe-Leu-OH) peptides from aqueous and urine samples [250]. Liquid/liquid microextraction of hydrophobic proteins (valinomycin and gramicidin D) was carried out using oleic acid capped Mg(OH)2 nanoparticles as hydrophobic probes. The extracted proteins were determined by MALDI-TOF MS [251]. In addition to their application as sorbents, nanomaterials have gained some attention in the determination of biomolecules. The integration of nanomaterials with mass spectrometry has improved
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the determination of a wide variety of biomolecules [252e256]. Several nanoparticles have been utilized as matrices, extracting or preconcentrating probes for biomolecular determination using MALDI-TOF MS by manipulating surface functionality for better interaction with analyte molecules [257]. For example, nanoparticles were engineered to provide controlled interactions with biomolecules such as cell membrane lipids, proteins, and nucleic acids as they facilitated their ionization that improved their determination by MALDI-TOF MS. Subsequently, micron- or nanosized particles such as C10, Ag11,12, Au1317 and Si18 showed different degrees of success as desorption/ionization matrices. This led the application of nanomaterials to facilitate the mass spectral imaging of biomolecules of interest by their implantation into tissues, such as brain and plant leaf tissues [258]. 6. Conclusions and perspective By studying recently published papers on the application of nanomaterials as sorbents for bioanalysis, it can be concluded that researchers are interested in the advantages of nanotechnology to improve the efficiency of conventional sorptive extraction methods, and also establish new innovative methods. The most important feature of nanomaterials as sorbents is their high surface area which provides higher sorption capacities than conventional microscale sorbents. However, bioanalysis needs fully-automated on-line methods for the daily analysis of analytes of interest to obtain fast, cheap, simple, and at the same time, sensitive and accurate determinations. This aim requires on-line coupling of sample preparation devices to separation instruments such as LC and GC. The best sample preparation technique should provide selective, fast, cheap and green extractions. This can be achieved by using miniaturized techniques which use very low quantities of sorbent materials and also require low sample volumes. Lower quantities of sorbent mean lower sorption capacity. This problem can be resolved by application of nanosorbents with higher surface areas, but the application of nanosorbents should be carefully handled, not only because of their environmental and health impacts [259,260], but also because of the requirements of on-line coupling with chromatographic instruments. An on-line method requires fast extraction and fast desorption of the analytes of interest, and also highly stable materials to high-pressure injection of the mobile phase [261]. Nanomaterials usually have higher surface energy and tend to agglomerate or adsorb other molecules to decrease their surface free energy. This means that nanomaterials can strongly adsorb the analytes, so subsequently the desorption process should be slower and needs harsher conditions in comparison to microscale and bulk materials. Furthermore, the agglomeration leads to diminishing the sorbent specific surface area. Also, in the case of high operation flow rates, the sorbent compaction occurs because of the small particle size of the materials leading to reducing the flow rate, increasing the extraction time and the column back pressure. In addition, in the case of high ionic strength samples, unwanted coagulation can also occur during the analytical procedure, resulting in a loss of nanoparticles. Nevertheless, in the case of in vivo studies, the sorbents should have more features such as high biocompatibility and stability in biological systems which are under question in the case of many routine nanoparticles efficiency. References [1] J.R. Gribbin, M. Gribbin, Richard Feynman: a Life in Science, Penguin Books, New York, United States, 1997. [2] H.F. Tibbals, Medical Nanotechnology and Nanomedicine, CRC Press, 2010. [3] A. Korkin, P.S. Krsti c, J.C. Wells, Nanotechnology for Electronics, Photonics, and Renewable Energy, Springer, New York, 2010.
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Mazaher Ahmadi received his BSc degree in Applied Chemistry from Bu-Ali Sina University, Hamedan, Iran in 2009 and his MSc degree in Analytical Chemistry also from Bu-Ali Sina University in 2011. Currently, he is guest PhD student in Prof. Abdel-Rehim group at Stockholm University and he is working toward his PhD degree in Bu-Ali Sina University. His current research interests focus on benefits of nanotechnology in sample preparation for bioanalysis.
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21 Hatem Elmongy: Hatem Elmongy is a PhD candidate at Stockholm University working with Prof. Abdel-Rehim. His research work focus on drug analysis in biological fluids with emphasis on saliva as alternative specimen to blood for screening of drugs and biomarkers. He is also working on development of new extraction strategies of drugs from bio-samples
Tayyebeh Madrakian received her BSc degree in Chemistry from Shiraz University, Shiraz, Iran in 1989 and his MSc degree in Analytical Chemistry also from Bu-Ali Sina University in 1996. In 2000, she received her PhD in Analytical Chemistry from Razi University, Kermanshah, Iran. In the same year, she started working at Bu-Ali Sina University as an Assistance Professor. Now, she is a Professor of Analytical Chemistry at Bu-Ali Sina University. Her current research interests include method development for trace analysis of important organic and inorganic compounds in biological samples, electrochemical methods, and wastewater treatment.
21 Mohamed Abdel-Rehim: Mohamed Abdel-Rehim is a Professor in analytical and bioanalytical chemistry at Stockholm University. Abdel-Rehim obtained his PhD in pharmaceutical sciences from Uppsala University. He has long experience in drug discovery and development from big pharma AstraZeneca. He specialized in sample preparation and the analysis of drugs and metabolites in biological samples by GCeMS and LCeMSMS. He is the inventor of MEPS technique. He is also interested in the preparation of new sorbents for applications in bioanalysis.
Contents lists available at ScienceDirect
Analytica Chimica Acta journal homepage: www.elsevier.com/locate/aca
Review
Nanomaterials as sorbents for sample preparation in bioanalysis: A review Mazaher Ahmadi a, b, Hatem Elmongy a, Tayyebeh Madrakian b, Mohamed Abdel-Rehim a, * a b
Department of Environmental and Analytical Chemistry, Stockholm University, SE10691 Stockholm, Sweden Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Nanomaterials are used as Nanosorbents in various sample preparations methods. Nanoparticles provide high surface area compared to microscale particles. Nano-materials have high sorption capacities compared to conventional microscale sorbents. The use of carbon nanotubes in sample preparation. Polymer based Nano-sorbents.
a r t i c l e i n f o
a b s t r a c t
Article history: Received 21 June 2016 Received in revised form 24 November 2016 Accepted 27 November 2016 Available online 7 December 2016
In recent years, application of nanomaterials as sorbent has gained the attention of researchers in bioanalysis. Different nanomaterials have been utilized as the sorbent in extraction techniques such as solid phase extraction, dispersive solid phase extraction, magnetic solid phase extraction, microextraction by packed sorbent, solid phase microextraction, dispersive m-solid phase extraction, and stir bar sorptive extraction. In the present review, different nanomaterials which have recently been utilized as sorbent for bioanalysis are classified into six main groups, namely metallic, metallic and mixed oxide, magnetic, carbonaceous, silicon, and polymer-based nanomaterials. Application of these nanomaterials in different extraction techniques for bioanalysis has been reviewed. This study shows that magnetic nanomaterials have gained significant attention owing to their magnetic separation ability. In addition, the present review shows that there is a lack in the application of nanomaterials for on-line analysis procedures, most probably due to some intrinsic properties of nanomaterials such as spontaneous agglomeration. © 2016 Elsevier B.V. All rights reserved.
Keywords: Nanomaterials Sorptive extraction Sample preparation Microextraction techniques Bioanalysis Review
Contents 1. 2.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Definition and classification of nanomaterials as nanosorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 2.1. Metallic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
* Corresponding author. Tel.: þ46707108122; fax: þ46709569894. E-mail addresses: [email protected], Mohamed.astra@gmail. com (M. Abdel-Rehim). http://dx.doi.org/10.1016/j.aca.2016.11.062 0003-2670/© 2016 Elsevier B.V. All rights reserved.
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2.2. 2.3. 2.4.
3.
4.
5. 6.
Metallic and mixed oxide nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Magnetic nanoparticles (MNPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Carbonaceous nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.4.1. Fullerenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.4.2. Carbon nanotubes (CNTs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.4.3. Graphene and graphene oxide (G and GO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.5. Silicon nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.6. Polymer-based nanosorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.6.1. Organic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.6.2. Inorganic and hybrid polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.6.3. Molecularly imprinted polymers (MIPs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Sample preparation procedures for bioanalysis using nanomaterials as sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 3.1. In-solution methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 3.2. Headspace methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 Application of nanomaterials as sorbents for bioanalysis in sorptive extraction techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 4.1. Solid phase extraction (SPE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 4.2. Dispersive solid phase extraction (dSPE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 4.3. Magnetic solid phase extraction (MSPE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 4.4. Microextraction by packed sorbent (MEPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 4.5. Solid phase microextraction (SPME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 4.6. Dispersive m-solid phase extraction (dispersive m-SPE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 4.7. Stir bar sorptive extraction (SBSE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 4.8. Other methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 Application of nanomaterials in determination of biomolecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 Conclusions and perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Abbreviations AgNPs silver nanoparticles AuNPs gold nanoparticles BSA bovine serum albumin CE capillary electrophoresis CNTs carbon nanotubes CTAB cetyltrimethylammonium bromide CV-ETAAS cold vapor generation-electrothermal atomic absorption spectrometry Dispersive m-SPE dispersive m-solid phase extraction dSPE dispersive solid phase extraction EC-SPME electrochemically controlled SPME ETAAS electrothermal atomic absorption spectrometry FAAS flame atomic absorption spectroscopy FASS-OT-CEC field-amplified sample stacking open-tubular capillary electrochromatography FL spectrofluorometry G graphene GC-FID gas chromatography-flame ionization detector GC-MS gas chromatography-mass spectrometry GE gel electrophoresis GFAAS graphite furnace atomic absorption spectrometry GO graphene oxide HPLC high-performance liquid chromatography HSA human serum albumin ICP-MS inductively coupled plasma-mass spectrometry ICP-OES inductively coupled plasma optical emission spectrometry
IIP ion-imprinted polymer IMS ion mobility spectrometry LC-DAD liquid chromatography-diode array detector LC-FL liquid chromatography-florescence detection LC-MS liquid chromatography-mass spectrometry LC-MS/MS liquid chromatography tandem mass spectrometry LC-UV liquid chromatography-ultraviolet detection LDHs layered double hydroxides LOD limit of detection LOQ limit of quantification MALDI-TOF MS matrix-assisted laser desorption/ionizationtime of flight mass spectrometry MEPS microextraction by packed sorbent MIP molecularly imprinted polymers MNPs magnetic nanoparticles MOFs metal-organic frameworks MSPE magnetic solid phase extraction MWCNTs multi-wall carbon nanotubes PDMS polydimethylsiloxane PTFE polytetrafluoroethylene RGO reduced graphene oxide SBSE stir bar sorptive extraction SPE solid phase extraction SPME solid phase microextraction SWCNTs single-walled carbon nanotubes UFLC-MS/MS ultra-fast liquid chromatography-tandem mass spectrometry
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1. Introduction When R. Feynman first introduced the concept of nanotechnology in 1959 by his well-known sentence “there is a lot of space down there” [1], maybe he did not have any idea about how this technology would change the future of science as it has done. Nowadays, nanotechnology is widely used in many fields such as medicine [2], electronics [3], agriculture [4], food industries [5], and biotechnology [6] because of different chemical and physical properties of nanomaterials in comparison to microscale and bulk materials. These unexpected properties are mainly due to higher surface atoms fraction and surface energy of small particles in comparison to bulk materials [7]. One of the most interesting properties of nanomaterials is their high surface area to volume ratio because of their high surface atoms fraction. This means more active atoms are available to interact with free molecules, atoms, and ions. In general, due to the high surface area to volume ratio of nanomaterials in comparison to bulk and microscale materials, application of nanosorbents for sample preparation purposes provides some advantages such as high adsorption capacity and preconcentration factors in addition to their easy functionalization and reusability [8]. Many researchers have confirmed that nanomaterials provide higher efficiency in adsorption of various compounds in gaseous or liquid phases [9,10]. However there are some limitations in the application of nanomaterials as the sorbent originated from the high surface energy of small particles. Nanomaterials usually have higher surface energy and tend to agglomerate or adsorb other molecules to decrease their surface free energy. The agglomeration leads to diminishing of the sorbent specific surface area. Also, in the case of high operation flow rates, the sorbent compaction occurs because of the small particle size of the materials leading to reduction of the flow rate, increasing the extraction time and the column back pressure. In addition, in the case of high ionic strength samples (most biological samples), unwanted coagulation can also occur during the analytical procedure, resulting in a loss of nanoparticles efficiency. By far, different various nanomaterials with different compositions and morphologies have been employed as sorbents for sample preparation purposes, aiming for the enrichment of target analytes, cleanup of the samples, and signal enhancement [11]. Sample preparation is a crucial step in processing chemical, biological, material, and surface analysis. Especially in the case of biological matrices, sample preparation is the most critical step because of the complexity of the biological samples and the presence of multiple components in the samples at the same time [12e14]. Where quantitative measurement of drugs, metabolites, and biological molecules such as proteins and DNA in biological systems (blood, plasma, hair, saliva) are concerned (the subject of bioanalysis), sample preparation has two main functions: first, sample screening, cleanup, preconcentration, and subsequently signal enhancement. The second is enhancement of the method selectivity [15]. Usually, these two goals can be reached together by the employment of some advanced sorbents; however, they are usually in a balanced relationship regarding the final cost, the sample preparation technique, and the detection method. If the detection method already provides high selectivity itself, such as liquid or gas chromatography coupled mass spectrometry (LC-MS and GC-MS, respectively) or GC tandem mass spectrometry (GCMS/MS), simpler sorbents with lower selectivity and cost are more desirable. In these cases, the aim of sample preparation usually is screening the desired analyte(s), clean-up of common contaminants such as macromolecules and proteins and preconcentration of the analyte(s) for further separation and determination. However, when the detection method provides relatively low selectivity, such as UVevisible spectroscopy (UVevis) and fluorescence
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spectroscopy, the sorbent should provide high selectivity toward the target analyte. In both cases, application of nanomaterials could be helpful because there are lots of simple and cost-effective methods for synthesis of nanomaterials with high adsorption capacity and moderate selectivities such as sol-gel, co-precipitation, and electrodeposition [16]. Nevertheless, in recent years, application of nanomaterials in sample preparation has attracted the attention of many research groups. Khajeh et al. have discussed classification, preparation, and applications of different nanomaterials as sorbents for environmental analysis with emphasis on aqueous media [17]. Chen et al. have reviewed application of aptamer-conjugated nanomaterials in bioanalysis and biotechnology. The paper has discussed the features and properties of aptamers, application of aptamerconjugated nanomaterials as sensing platforms and delivery vehicles, and effect of aptamer-conjugated nanomaterials in the enhancement of sensitivity and selectivity of the methods [18]. Xu et al. have reviewed the applications of nanomaterials as a sorbent for different purposes [19]. This paper has emphasized on nanoparticles with different chemical compositions and porous structures and their respective applications in sample preparation of various matrices such as environmental, biological and food samples. The use of nanomaterial in microextraction techniques for bioanalysis was reported [20,21]. Furthermore, He et al. published a review of the magnetic separation techniques based on magnetic nanoparticles for biological analysis applications [22]. In addition, the application of polymer-nanoparticle composites in bioanalytical sample preparation was reported [23]. In another review, the preparation and application of nanoimprinting technology in sample preparation was presented [24]. This review paper will present a comprehensive study of recently published papers (2011 and onward) on the application of nanomaterials as sorbents for bioanalysis. Various frequently used nanomaterials will be classified, and application of these materials in different sorptive sample preparation methods such as SPE, MSPE, MEPS, SPME, SBSE, and dSPE for bioanalysis will be reviewed. Moreover, some applications of nanomaterials for the enrichment of biomolecules will be reviewed. It is shown that researchers are interested in the advantages of nanotechnology not only to improve the efficiency of the conventional sorptive extraction methods, but also to establish new innovative methods. Furthermore, it is shown that MSPE due to its easy operation steps has gained the highest interest from several research groups for different final goals in bioanalysis. 2. Definition and classification of nanomaterials as nanosorbents There are some definitions and classifications of nanomaterials based on dimension, and some based on composition. Based on dimension, any material with at least one dimension in the nanoscale (i.e. 1e100 nm) can be called “nanomaterial”. According to this definition, nanomaterials can be divided into (i) zero-dimensional (such as nanoparticles), in which all dimensions are in the nanoscale, (ii) one-dimensional (such as nanotubes, nanorods, and nanowires), in which only one dimension is not in the nanoscale, (iii) two-dimensional (such as nanofilms, nanolayers, and nanocoatings), in which two dimensions are not in the nanoscale, and (iv) three-dimensional, also known as bulk nanomaterials, which are not confined to the nanoscale in any dimension. These materials possess in common a nanocrystalline structure or involve the presence of features at the nanoscale [25]. It is notable that the 100 nm size boundary used in these definitions is nowadays being questioned [26]. However, researchers are still using the abovementioned definitions, and therefore, in this paper, the above-
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mentioned definitions will be embraced. On the other hand, based on composition, nanomaterials can be classified into metallic, metallic and mixed oxide, magnetic, carbonaceous, silicon, nanofibers and nanowires, and polymeric nanomaterials. All these sorts of nanomaterials are widely used as nanosorbents in various sample preparation methods, which we will provide a brief introduction of each in the following.
walled CNTs (SWCNTs) and more than one sheet in the case of multi-walled CNTs (MWCNTs), respectively) with a diameter between a few tenths to tens of nanometers and length up to centimeters. Their interesting properties as sorbents are the high surface area, high ability for p-p interactions, relatively lower price, wider accessibility, and easy functionalization [35]. These advantages have made CNTs one of the most used sorbents in the recent years [36e38].
2.1. Metallic nanoparticles Among metallic nanoparticles, only noble metal nanoparticles (e.g. gold, silver, platinum) have gained wide attention as sorbents because of their chemical stability [27]. One of the most interesting kinds of noble metal nanoparticles in bioanalysis is gold nanoparticles (AuNPs) because of their well-known specific interaction with thiol containing compounds. Biomolecules that contain thiol or amino groups can be adsorbed spontaneously onto AuNPs to generate well-organized and self-assembled monolayers [28].
2.4.3. Graphene and graphene oxide (G and GO) GO can be considered one graphite sheet containing a wide range of functional groups, such as carboxyl, hydroxyl, ketone, and epoxy functional groups [39]. It has gained the attention of researchers as an alternative sorbent because of its improved water dispersibility, high surface area, high mechanical strength, and versatile surface modification. G having most of the advantages of CNTs can be considered highly reduced graphene oxide (RGO). G application as a sorbent because of its lower water dispersibility has not gained great attention.
2.2. Metallic and mixed oxide nanoparticles 2.5. Silicon nanomaterials Metallic and mixed oxide nanoparticles, including a wide range of different inorganic nanoparticles, having unique properties, such as high surface area, high adsorption capacity, and higher chemical stability, have gained attention as sorbents for sample preparation. Among them, some nanoparticles such as Fe3O4, TiO2, Al2O3, ZrO2, MnO, and CeO2, in bare form or modified with different functional coatings, have gained more attention [7,13,29]. Moreover, layered double hydroxides (LDHs), synthetic two-dimensional inorganic nanostructured materials, have gained attention as ion exchange sorbents. The ion exchange property of these materials is attributed to the presence of a significant number of anions in the interlayer spaces.
Silicon nanomaterials, including silica dioxide nanoparticles (SiO2), core-shell layers, nanotubes and nanowires, and nanoporous materials, are widely used for the preparation of nanosorbents [40,41]. Silicon nanomaterials are easy to synthesize and modify by various functional groups on their surface, cheap, and highly biocompatible. Their core-shell form has wide applications in protecting various nanoparticles and grafting various organic ligands. On the other hand, their monolith form has gained much attention in on-line extraction procedures as extraction and separation column [42]. 2.6. Polymer-based nanosorbents
2.3. Magnetic nanoparticles (MNPs) Magnetic nanoparticles with the ability of to be separated from the medium using an external magnetic field (consisting of magnetic elements such as iron, nickel, cobalt and their oxides) comprise a relatively new class of nanosorbents. Their magnetic properties has made them one of the most interesting nanoparticles in solid phase extraction. These nanoparticles can be used as sorbents or magnetic carriers in core-shell nanoparticles. Among these nanoparticles, iron oxide nanoparticles (magnetite and maghemite) have gained greater attention due to ease of synthesis, low cost, and biocompatibility [30e32]. 2.4. Carbonaceous nanomaterials Application of carbon nanomaterials as nanosorbents began when fullerene C60 was discovered in 1985 [33]. The application of carbon nanomaterials as nanosorbents is mainly focused on CNTs, GO and G, and fullerenes [34]. 2.4.1. Fullerenes Fullerenes are polyhedral nanostructures with 5e6 membered carbon rings in the form of a hollow sphere, ellipsoid or tube [33]. Application of these nanomaterials is relatively limited due to their extreme insolubility in aqueous and organic media, high price, and lower accessibility. However, because of their lower aggregation tendency, there are some reports on their application as solid phase sorbents [34]. 2.4.2. Carbon nanotubes (CNTs) CNTs are rolled graphene sheets (one sheet in the case of single-
2.6.1. Organic polymers Organic polymers are considered among the sorbents of greatest interest and can be used as a matrix to embed inorganic nanomaterials into them, as core-shell layers, and as supporting materials to synthesize and immobilize nanoparticles for improving the nanocomposite chemical, thermal, mechanical and sorption properties, as well as biocompatibility. Among them, in recent years, conductive polymer nanofibers and nanofilms have gained more attention because of their capacity for electrochemical synthesis [43,44]. 2.6.2. Inorganic and hybrid polymers Inorganic and hybrid polymers including xerogels, metalorganic frameworks (MOFs), and core-shell layers have some interesting applications as nanosorbents. Xerogels and aerogels having relatively high surface area, porosity, and internal pore volume, have gained some attention as potential efficient sorbents. Among them, silica xerogel has gained the most attention [45,46]. Polysiloxanes are the most important inorganic polymers regarding their commercial applications as a coating for different extraction devices. Their applications range from medical to sealants, waterbarriers, and cosmetics. Polydimethylsiloxane (PDMS) or silicone rubber is the most widely used material in sample preparation techniques [47]. MOFs, hybrid organic-inorganic materials, can be constructed by strong coordination bond formation between metal ions as nodes and organic linkers as rods. These classes of materials have a super large surface area and their pore apertures can vary substantially; moreover, in recent years, they have been used as a sorbent for extraction of a wide range of analytes from small ions to high molecular weight proteins [48,49].
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
5
Fig. 1. Summary of bioanalysis procedures using sorptive extraction techniques.
2.6.3. Molecularly imprinted polymers (MIPs) MIPs as artificial biomimetic receptors are well-known sorbents because of their high selectivity. MIPs are cross-linked synthetic polymers obtained by co-polymerization of a functional monomer and a cross-linker in the presence of a template molecule. By removing the template after the polymerization process, materials with MIPs cavities are produced. These cavities provide highly selective adsorption properties [45,50]. The MIPs formation mechanism can be a sol-gel process or free-radical polymerization such as bulk, emulsion, suspension, precipitation, and seed polymerization [51]. The functional monomer includes special functional groups which can form a complex with the template molecule via most commonly non-covalent or covalent interactions. The cross-linker's duty is to fix this complex inside of the copolymer matrix by the formation of cross-linked bonds. A particularly promising application of imprinted polymers is ion-imprinted polymers (IIPs) which is used for solid-phase extractive preconcentration and/or separation of target ion(s) from other coexisting ions or complex matrices.
3. Sample preparation procedures for bioanalysis using nanomaterials as sorbents The complete development of an analytical method using sorptive extraction techniques requires a number of intermediate steps between sample collection and the final report of the results including sample pretreatment, sorptive extraction, desorption, and detection. Fig. 1 depicts a summary of steps that are usually involved in bioanalysis using sorptive extraction procedures. The first step in these procedures is sample collection from a biosystem. The most popular samples are plasma and serum, urine, saliva, and some tissue sections like hair and nail. Usually, one or more pretreatment steps are necessary to introduce the sample to the sorptive extraction unit, mostly because of the complexity of biological samples [52]. In the case of liquid samples (i.e. urine, serum, and plasma), centrifugation and protein precipitation are the most popular methods to separate high molecular weight species such as proteins and enzymes. In the case of solid samples, a digestion step (such as acid hydrolysis and enzymatic digestion) is usually
sufficient. In the next step, the pretreated sample is exposed to the sorptive extraction unit. The aim of this step is to clean up and preconcentrate the sample in order to get higher selectivity and sensitivity with the following analytical steps. By far, many methods have been proposed to facilitate this step and to increase its efficiency and accuracy. To this end, various sorptive extraction methods have been developed such as SPE, MSPE, MEPS, SPME, SBSE, and dSPE. These methods can be chosen for a specific aim based on their advantages and disadvantages. Moein et al. have reviewed advantages and disadvantages of some of these methods as following: In the case of SPE, advantages are high sorptive capacity, chemical or physical mechanical stability, and high selectivity, while the disadvantages are a large volume of solvent and that the method is time-consuming. In the case of SPME, the advantages are that the method is solvent free, online, and suitable for volatile compounds. The disadvantages are losing and breakable fibers, desorption, and low sensitivity. In the case of SBSE, the advantages are high sensitivity, high extraction recovery, and a packed and coated sorbent. The disadvantages are loss of coating, drying, and desorption, on-line disability, and long equilibrium time. In the case of MEPS, the advantages are high throughout, sensitivity, rapidity and ease of use, and good extraction recovery. The disadvantages are blockage and carryover, as well as desorption [53]. Some of these methods are based on direct exposure of the sorptive materials to the samples (In-solution methods) while some of them are based on the sorptive extraction of volatile or semivolatile compounds from the headspace of the samples (Headspace methods). In both cases, application of nanomaterials has motivated researchers to increase the efficiency and selectivity of the sorptive extraction methods.
3.1. In-solution methods In these methods, the sorbent is in direct contact with the solution which contains the target analyte(s). An ideal sorbent should be able to separate all of the analytes in solution while releasing the other compounds of the matrix. In this regard, the sorbent should
6
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
Fig. 2. Published papers on the application of nanomaterials as sorbent for bioanalysis since 2011 until May 2016 extracted from Scopus: (a) number of publications per year, and (b) pie chart of application of the nanosorbents in various sorptive sample preparation techniques.
Fig. 3. Schematic representation of some commercially available devices for sorptive extraction.
have enough sorption capacity to adsorb all of the analyte molecules or ions, and on the other hand, should have specific interaction with the target analyte. In the next step (desorption), elution by another solvent or increasing medium temperature should easily release the analyte completely before introduction to the detection method. However, this kind of sorbent is very rare, and in practice, researchers prefer selective sorbents instead of specific sorbents. Usually, in order to increase the overall method selectivity, one or more separation steps are used (Fig. 1). Furthermore, in order to increase overall sorption capacity, a higher amount of sorbent can be used. However, this idea has been made almost obsolete by the introduction of nanomaterials with high surface areas. Nowadays, nanosorbents are extensively used in bioanalysis because of their high sorption capacity, and in some cases high selectivity. 3.2. Headspace methods In these methods, the sample is placed into a vial with wellsealed equipment, and the sorbent material is exposed to the headspace of the sample (liquid, or solid) to extract the target
volatile or semivolatile analyte(s) which escapes the sample matrix. These methods potentially increase the overall selectivity because the number of volatile compounds in biological samples is relatively limited. The ideal sorbents for these methods are the same sorbents used in the in-solution methods. However, the desorption step in these methods is usually thermal desorption, and the sorbent should have high chemical and thermal stability at desorption temperatures. 4. Application of nanomaterials as sorbents for bioanalysis in sorptive extraction techniques A comprehensive study on the number of publications regarding the application of nanomaterials as sorbents since 2011 (Fig. 2a) shows that the interest in nanomaterials for sorption and enrichment of target analytes, clean-up and pretreatment of biological samples is increasing. Researchers have used nanotechnology to improve extraction capacity, selectivity, sensitivity, and to reduce matrix effect. This analysis (Fig. 2b) shows that researchers have become very interested in MSPE using nanosorbents for different final goals. In the case of other well-established sample preparation
Table 1 Recent applications of different nanomaterials as sorbent for bioanalysis. Type of modification
Analyte
Matrix
Extraction technique
Detection Extraction Operation Adsorption mode mode capacity (mg technique g1)
Ref.
Surface assembly of GO on SiO2 nanospheres
Electrostatic interactions H-bonding
Hemoglobin
Human blood
dSPE
Off-line
e
UVevis
[54]
Hemoglobin
Human blood
dSPE
Insolution Insolution
Off-line
122.3
UVevis
[55]
Human urine and water
dSPE
Off-line
56.58
ICP-OES
[56]
human plasma
MSPE
Insolution Insolution
Off-line
e
LC-MS/MS
[57]
Fe3O4- MWCNTs nanocomposite
Amide bond Al(III) formation Polymerization in the Nicotine presence of nanosupport e Doxorubicin
Rat tissues
MSPE
Off-line
e
LC-FL
[58]
Core-shell Fe3O4-SiO2 coated with Ni2þ
e
Peptides
Protein digests and human serum
MSPE
Off-line
e
Adsorption
Water, food, and biological samples
MSPE
Off-line
17.3e39.9
[60]
SDS coated Fe3O4
Electrostatic interaction Adsorption
Cu(II), Cd(II), Ni(II), and Cr(III) Fuoxetine
MALDI-TOF MS FAAS
[59]
Core-shell Fe3O4-SiO2 modified with salicylic acid
Water and urine samples
MSPE
Off-line
e
FL
[61]
Pb(II) and Cr(III)
water, food, and urine samples
SPE
Off-line
100
FAAS
[62]
Pharmaceutical and biological samples
SPE
Off-line
4.8
FL
[63]
Human plasma
SPE
Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution
Off-line
e
FL
[64]
Off-line
4.9
FAAS
[65]
Off-line
e
FL
[66]
Off-line
e
FL
[67]
Off-line
e
CE-UV
[68]
Off-line
e
FL
[69]
Off-line
578
UVevis
[70]
Off-line
e
LC-MS/MS
[71]
Off-line
e
LC-MS
[72]
Off-line
e
UVevis
[73]
Off-line
e
[74]
Off-line
67.6
MALDI-TOF MS e
[75]
Off-line
e
LC-DAD
[76]
Off-line
e
ICP-MS
[77]
Off-line
e
FAAS
[78]
N,N-bis[2-methylbutyl] imidazolium hexafluorophosphate ionic liquid modified TiO2 nanocomposites TiO2 eSiO2 composite modified with 4aminophenylarsonic acid Core-shell Fe3O4- strong cation exchange resin
SDS coated Al2O3 modified with 2,4dinitrophenylhydrazine Ni-Al LDHs
e
G
e
Salicylic Acid Glutathione
SDS coated Al2O3 modified with a Schiff base
Adsorption
Cd(II)
Water, food, and human hair and urine SPE
Nanostructured overoxidized polypyrrole film
MIP
Salicylate
Human urine and plasma
EC-SPME
Au nanoparticles
Adsorption
Human urine
In-capillary SPME
HSA-coated Au nanoparticles
Adsorption
Monohydroxypolycyclic aromatic hydrocarbons Lysozyme
Hen egg white and human tear
dSPE
Ni-Al LDHs
e
Dopamine
Human serum
dSPE
Cu(II) modified ethylene glycol dimethacrylatemethacryloylamidohistidine nano-copolymer MWCNTs
Adsorption
Immunoglobulin G
Human Plasma
dSPE
e
b2-agonists
Swine urine
dSPE
TiO2-MWCNTs nanocomposite
e
Phosphopeptides
Protein digest
dSPE
SDS coated Al2O3 modified with 2,4dinitrophenylhydrazine G-Ni nanoparticles hybride
Adsorption
Formaldehyde
Water, food, and urine
dSPE
e
Proteins and peptides
Water
MSPE
Fe3O4 modified with polyarginine
Adsorption
BSA
BSA-lysozyme mixture and Egg white
MSPE
Fe3O4-MWCNTs nanocomposite
e
Aconitines
Human serum
MSPE
MnFe2O4 nanoparticles
e
Metal ions
human urine
MSPE
SDS coated Fe3O4 modified with a Schiff base
Adsorption
Heavy metal ions
Water, food, and human hair
MSPE
Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
Nanomaterial
(continued on next page) 7
8
Table 1 (continued ) Nanomaterial
Type of modification
Analyte
poly(styrene-divinylbenzene) coated Fe3O4 nanoparticles Carboxymethyl-b-cyclodextrin modified Fe3O4 nanoparticles Polymer coated Fe3O4 nanoparticles
Polymerization in the Fenitrothion presence of nanosupport Amid bond formation Adenosine and guanosine MIP Catecholamines
Fe3O4-G-MWCNTs nanocomposites
e
Histidine modified MWCNTs
Extraction technique
Detection Extraction Operation Adsorption mode mode capacity (mg technique g1)
Ref.
Water, soil, urine and human plasma samples
MSPE
Insolution
Off-line
e
UVevis
[79]
e
MSPE
Off-line
e
UVevis
[80]
Human urine
MSPE
Insolution Insolution Insolution
Off-line
e
CE-DAD
[81]
Off-line
e
MALDI-TOF MS
[82]
On-line
4.85
ETAAS
[83]
Off-line
13 and 18
FAAS
[84]
Off-line
7.7
UVevis
[85]
Off-line
e
LC-FL
[86]
e e
GC-FID LC-MS/MS
[87] [88]
e
LC-MS
[89]
Off-line
153.84
LC-DAD
[90]
Off-line
e
LC-MS/MS
[91]
Off-line
e
[92]
Off-line
e
Off-line
e
Off-line
e
MALDI-TOF MS MALDI-TOF MS MALDI-TOF MS UVevis
Off-line
241.82
UVevis
[96]
Off-line
4.65
UVevis
[97]
Off-line
8.51
UVevis
[98]
Off-line
11.34
FL
[15]
Off-line
e
CE-UV
[99]
Human urine
MSPE
biological and environmental samples
SPE
MWCNTs modified with a Schiff base
Covalent bond formation Adsorption
Berberine, curcumin, luteoloside and chlorogenic acid V(v) Cu(II) and Pb(II)
Water samples, corn, and human hair
SPE
Ni-Al-Zr LDHs
e
Iodate
Food, Environmental, and human urine SPE
G
e
Rat brain
SPE
Nanostructured a-Carboxy polypyrrol Methacrylate-based monolith
e e
Glycine, gammaaminobutyrate and taurine Methadone Peptides
Human urine and plasma Tryptic digestion BSA
Tetraethylenepentamine modified Fe3O4 nanoparticles
Phenolic Environmental estrogens Haloperidol
Headspace Off-line InOn-line solution InOff-line solution
Nanopolymer
Polymerization in the presence of nanosupport MIP
SPME In-capillary SPME Dispersive mSPE
Human plasma and urine
dSPE
MWCNTs
e
Sulfonamides
Pork
dSPE
TiO2-MWCNTs nanocomposite
e
Phosphopeptides
Rat brain
dSPE
Amine-functionalized Fe3O4 nanoparticles
e
Tryptic digest of proteins
MSPE
Cu(II) immobilized polydopamine coated G- Fe3O4 nanocomposite Poly(acrylic acid) modified poly(glycidylmethacrylate)-grafted nanocellulose Fe3O4-nanocrystalline cellulose nanocomposite
e
Phosphopeptides and glycopeptides Peptides
Water
MSPE
Graft copolymerization
Hemoglobin
Water
dSPE
Insolution Insolution Insolution Insolution Insolution Insolution
e
Myoglobin
Water
MSPE
Polymer coated SiO2- Fe3O4 nanocomposite
MIP
Hemoglobin
Water
MSPE
Polymer coated SiO2- Fe3O4 nanocomposite
MIP
Tramadol
Human urine
MSPE
Polymer coated Fe3O4-MWCNTs nanocomposite
MIP
Naproxen
Human urine
MSPE
Fe3O4 nanoparticles
e
Human urine and Portulaca oleracea L. MSPE leaves
CTAB coated Fe3O4 nanoparticles
Electrostatic interactions
SDS coated g-Fe2O3 nanoparticles
Electrostatic interactions
Dopamine, noradrenaline, and adrenaline Amitriptyline, nortriptyline, imipramine, and doxepin Oxymetholone and mestanolone
Human blood
Insolution Insolution Insolution Insolution
Insolution Insolution Insolution Insolution Insolution
[93] [94] [95]
Water and human urine
MSPE
Insolution
Off-line
e
LC-UV
[100]
Human urine
MSPE
Insolution
Off-line
e
UVevis
[101]
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
Matrix
e
Pb(II)
Water and human serum
MSPE
Anthrax lethal factor coated SiO2-Fe3O4 nanocomposite Surface-oxidized nanodiamond
Amide bond formation Oxidation
Neutrophil peptides
Human serum, saliva, and tear
MSPE
Tryptic peptides
Membrane proteins
dSPE
Nanostructured polymer
IIP
Cu(II)
Human urine and serum
SPE
RGO-SiO2 nanocomposite
e
BSA digests
SPE
Alizarin red S modified TiO2 nanoparticles
Adsorption
Chlorophenols and peptides Cd(II) and Pb(II)
SPE
Polymer coated TiO2 nanoparticles
MIP
MWCNTs
e
Aspartic acid enantiomers Strychnine and brucine
Water samples, human hair and fingernail Human serum and lumbar CSF, and pharmaceutics Human urine
MWCNTs modified monolithic Nanostructured polypyrrole film ZN-Al LDHs-TiO2 nanosheet film
Oligomer matrixassisted dispersion e e
Hemoglobin and cytochrome c Urea Valproic acid
Fe3O4-MWCNTs nanocomposite
e
G-SiO2 nanocomposite
e
Lomefloxacin and ofloxacin Pb(II), Cd(II), and Cr(III
Water, human urine and saliva
Polymer coated Fe3O4-MWCNTs nanocomposite
IIP
Pb(II)
Water and human hair
Dispersive mSPE Dispersive mSPE MSPE
Polymer coated Fe3O4-SiO2-TiO2 nanocomposite
IIP
Co(II)
Water, food, and human urine
MSPE
Water and human hair
MSPE
Water and human urine
MSPE MSPE
g-mercaptopropyltrimethoxysilane modified Fe3O4- e
Whole human blood Dialysis human serum Human serum and pharmaceutical samples Human plasma and urine
SPME HF-SPME In capillarySPME SPME SPME
SiO2 nanocomposite Polymer coated Fe3O4-SiO2 nanocomposite
MIP
Hg(II) and methylmercury Tizanidine
GO-Fe3O4 nanocomposite
e
Pseudoephedrine
Human urine
Polymer coated Fe3O4-SiO2 nanocomposite
MIP
Diclofenac
Polymer coated Fe3O4-SiO2 nanocomposite
MIP
Codeine
Water samples, human blood serum and MSPE urine samples, and pharmaceutical ampoules Human urine MSPE
CdTe QDs
e e
Se(IV) Hg(II) and methylmercury Losartan and valsartan
g-mercaptopropyltrimethoxysilane modified Fe3O4-SiO2 nanocomposite Ni:Zn sulphide nanoparticles loaded activated carbon Polydopamine, Ag nanoparticles and polypyrrole nanocomposite 1,5-bis(di-2-pyridil)methylene thiocarbohydrazide modified Fe3O4-SiO2 nanocomposite Fe3O4-MWCNTs nanocomposite
Sol-gel e
e
Amitriptyline, imipramine, and citalopram Hg(II)
e
Cd(II)
Polymeric monolith modified with Au nanoparticles e Polyaniline-coated Fe3O4 nanoparticles
e
Nanohydroxyapatite
e
Mesoporous SiO2 particles
e
BSA, cytochrome c, and lectins Lorazepam and nitrazepam Volatile organic metabolites Endogenous peptides
Reference materials and human urine HepG2 cells Human urine and plasma
SPE Chip-based MSPE SBSE
Human urine
MEPS
Certified reference materials and water MSPE samples Human urine, water, and certified MSPE reference materials Water SPE
Human urine
Dispersive mSPE dSPE
Human urine
In-syringe dSPE
Human urine and plasma
Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Headspace Headspace Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution Headspace Insolution Insolution Insolution Insolution Insolution Insolution Insolution Insolution
Off-line
100
FAAS
[102]
Off-line
e
[103]
Off-line
e
Off-line
e
MALDI-TOF MS MALDI-TOF MS ICP-OES
[105]
Off-line
e
LC-UV
[106]
Off-line
10.7 and 19.2 FAAS
Off-line
0.0352
Voltammetric [108]
Off-line
e
LC-UV
[109]
On-line
e
UVevis
[110]
Off-line Off-line
e e
IMS GC-FID
[111] [112]
Off-line
e
FL
[113]
Off-line
e
ETAAS
[114]
Off-line
e
GFAAS
[115]
Off-line
35.21
FAAS
[116]
Off-line
e
ICP-MS
[117]
Off-line
e
UVevis
[118]
Off-line
e
LC-UV
[119]
Off-line
44.11 and 116.35
UVevis
[120]
Off-line
13.44
FL
[121]
Off-line On-line
e e
FL ICP-MS
[122] [123]
Off-line
e
LC-UV
[124]
Off-line
e
GC-MS
[125]
On-line
5.22 and 6.81 CV-ETAAS
[126]
On-line
3.67
GFAAS
[127]
Off-line
16.6
UVevis
[128]
Off-line
e
LC-UV
[129]
Off-line
e
GC-MS
[130]
Off-line
e
[104]
[107]
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
Amino-functionalized SiO2-Fe3O4 nanocomposite
[131] 9
(continued on next page)
Nanomaterial
10
Table 1 (continued ) Type of modification
Analyte
Matrix
Extraction technique
Adsorption
BSA
Water
MSPE
Precipitation
Phosphopeptides
BSA digest
MSPE
G and GO
e
DNA and RNA
Eukaryotic and Prokaryotic cells
dSPE
Polymer coated Fe3O4-SiO2 nanocomposite
MIP
Hemoglobin
Bovine calf serum
MSPE
Poly[N-isopropylacrylamide-co-1-(N,N-biscarboxymethyl)amino-3-allylglycerol] coated Fe3O4-SiO2 nanocomposite Polyethylene glycol-coated Fe3O4-MWCNTs nanocomposite Methylcellulose Fe3O4-SiO2 nanocomposite Polyethylene glycol modified Fe3O4-MWCNTs nanocomposite SDS coated Fe3O4 nanoparticles
Polymerization in the Fluvoxamine presence of nanosupport e Puerarin
Human plasma and urine, and tablet
MSPE
Rat plasma
MSPE
e
Sildenafil and its metabolite Methylprednisolone
Human urine and plasma
MSPE
Rat plasma
MSPE
Chlorpromazine
Water, human urine and plasma
MSPE
Human plasma and urine
MSPE
Cortex Phellodendri extract
MSPE
Human urine
MSPE
Human urine
MSPE
Human plasma and urine, and pharmaceutical formulations Saliva
SPE
Au nanoparticles coated Fe3O4 nanoparticles Polydopamine coated Fe3O4 nanoparticles
Adsorption Electrostatic interaction e
Nanostructured polymer
Progesterone and testosterone Polymerization in the Berberine presence of nanosupport e 5-hydroxy-3-indole acetic acid e Polycyclic aromatic hydrocarbon metabolites MIP Human insulin
Ni-Al LDHs
e
Thiocyanate
3-(1-methyl-1H-pyrrol-2-yl)-1H-pyrazole-5carboxylic acid modified GO Polymer coated GO
e
Mn(II) and Fe(III)
MIP
Dopamine
e
Water and human hair
b-cyclodextrin modified Fe3O4-SiO2 nanocomposite GO-Fe3O4 nanocomposite
Water samples, food samples, human urine and blood Human serum
Al-terephthalate MOFs modified polymeric monolith Ionic liquid coated TiO2 nanoparticle
e
G-polyaniline film MWCNTs coated SiO2 nanoparticles
e e
Nanostructured polymer
IIP
Ketoprofen, fenbufen, and ibuprofen Lorazepam, alprazolam, and diazepam Aldehydes Nucleobases and nucleosides Hg(II)
GO-polyethyleneglycol nanocomposite
e
Fluoroquinolones
Chicken muscle and liver
Bidentate Ag nanoparticles
e
Milk and human urine
Polypyrrole coated Fe3O4 nanoparticles
e
Cytochrome c and insulin Citalopram and sertraline Levodopa
e
Water and human urine Water, and human hair and urine Human exhaled breath condensate Human urine
Human urine and plasma Human urine
Insolution Insolution Insolution Insolution Insolution Insolution
Off-line
e
Off-line
e
Off-line
MALDI-TOF MS UVevis
Ref.
[132] [133]
e
MALDI-TOF MS GE
Off-line
71
UVevis
[135]
Off-line
e
LC-UV
[136]
Insolution Insolution Insolution Insolution Insolution Insolution
Off-line
e
LC-DAD
[137]
Off-line
e
LC-DAD
[138]
Off-line
e
LC-UV
[139]
Off-line
e
LC-UV
[140]
Off-line
e
LC-UV
[141]
Off-line
e
LC-UV
[142]
Insolution Insolution
Off-line
e
FL
[143]
Off-line
e
LC-MS
[144]
On-line
460
LC-DAD
[145]
Off-line
86.8
GC-FID
[146]
Off-line
21.6 and 24.0 FAAS
[147]
Off-line
e
LC-DAD
[148]
Off-line
e
LC-DAD
[149]
Off-line
e
LC-UV
[150]
On-line Off-line
e e
LC-UV LC-DAD
[151] [152]
On-line
e
UVevis
[153]
Off-line
e
LC-FL
[154]
Off-line
e
[155]
Off-line
e
MALDI-TOF MS LC-UV
[156]
Off-line
e
UVevis
[157]
Insolution SPE Insolution SPE Insolution HF-SPME Insolution In-capillary InSPME solution HF-SPME Insolution In-tube SPME Headspace SPE Insolution SPE Insolution SBSE Insolution Single drop Inmicroextraction solution InDispersive mSPE solution dSPE
[134]
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Ionic liquids modified Fe3O4-SiO2 nanocomposite TiO2 coated Fe3O4-MWCNTs nanocomposite
Detection Extraction Operation Adsorption mode mode capacity (mg technique g1)
[160] LC-UV Off-line
e
[159] FL e Off-line
FAAS
dSPE
Al(III)
Vancomycin
Adsorption
e
Human plasma and urine
dSPE
11
techniques with commercially available devices such as SPME and MEPS (Fig. 3), researchers are using these techniques for the cleanup of samples prior to their introduction into the chromatographic separation systems. However, there are some reports on improvements in the efficiency of these techniques by the application of nanomaterials as sorbents instead of conventional microscale sorbents. Furthermore, some new procedures for sample preparation have been proposed based on the application of nanosorbents for on-line and fully automated analysis of biological samples to establish fast, cost-effective, simple, sensitive and selective methods for daily determination of targeted analytes. In addition, application of nanomaterials for the extraction and determination of macromolecules from biological samples is increasing. Table 1 shows the summary of application of some nanoparticles as sorbents for bioanalysis since 2011. This table contains some useful information about the nanomaterials used together with the extraction technique and the results obtained including type of modification, the investigated analyte, type of sample matrix, extraction technique, extraction mode (i.e. in-solution or headspace modes), operation mode (i.e. on-line or off-line modes), adsorption capacity, detection technique, and extraction efficiency. In the following, some of these nanomaterials together with the extraction techniques used and the results obtained have been reviewed in detail. 4.1. Solid phase extraction (SPE)
8-hydroxyquinoline modified SDS coated CoFe2O4 nanoparticles Polypyrrole coated G
Carboxymethyl-a-cyclodextrin polymer coated TiO2 nanoparticles Hydroxyapatite nanorods
e
Cu(II), Zn(II), and Pb(II)
Certified reference materials, water, food, and human blood, urine and hair Water and human serum
dSPE
Insolution Insolution Insolution Insolution
Off-line
e
[158]
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
SPE is an alternative sample preparation technique to liquidliquid extraction which can reduce the volume of solvents needed. It has been used for the preconcentration or clean-up of target analytes from various matrices for many years. In this technique, the sorbent is packed inside cartridges, syringe barrels, microcolumns or disks. SPE cartridges are commercially available (Fig. 3). Conventional sorbents for SPE are silica derived compounds such as C18-bonded silica. Nowadays, nanosorbents are extensively being used for SPE. Various types of nanoparticles and nanocomposites in bare form or modified with organic and inorganic ligands such as MIPs [145,161e164], IIPs [105,165], LDHs [63,146,166], CNTs [84,152,167], G and RGO [64,86,106], GO [147,168,169], TiO2 [107], and Al2O3 [62,65] have been used to extract, preconcentrate, and clean up biological samples (Table 1). In an interesting article, Liu et al. developed new sorbents by G and GO supporting on silica as versatile and high-performance sorbents for SPE [168]. Their results showed that the newly developed adsorbent can be efficiently used for SPE extraction of a wide range of analytes from small molecules to high molecular weight macromolecules such as proteins. Because of different polarity of G and GO, the adsorbent can be efficiently used for both reversed phase and normal phase extractions. In another interesting article, Luo et al. used a simple hydrothermal strategy for the preparation of RGO encapsulated SiO2 as a new SPE sorbent. The newly developed sorbent showed higher efficiency compared to the other conventional SPE sorbents [106]. The sorbent was successfully used for SPE extraction and enrichment of chlorophenols from water and peptides from BSA digests. Toward establishing an on-line method to determine human insulin in plasma and pharmaceutical formulations, Moein et al. developed MIP cartridges coupled with LC [145]. The MIP sorbent was prepared using methacrylic acid (the functional monomer), ethylene glycol dimethacrylate (the cross-linker), chloroform (the porogenic solvent), and insulin (the template). The results showed that fast and facile LC analysis of insulin was achievable with the good selectivity provided by the MIP sorbent. LOD and LOQ in ng mL1 levels were obtained in plasma and urine samples. Furthermore, the results showed that the method provided cleaner
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extraction and suppressed interfering peaks from the complicated biological samples. 4.2. Dispersive solid phase extraction (dSPE) In 2003, Anastassiades et al. introduced a new extraction technique named dSPE based on the dispersion of the solid sorbent inside of the sample solution containing the targeted analytes using magnetic stirring, vortex, and ultrasonication [170]. In dSPE, the sorbent can directly interact with the analytes and be separated from the solution usually using centrifugation, and then, subsequent desorption using a suitable eluent can be conducted. Because of the direct contact of the sorbent with the analytes, the extraction time and capacity can be improved. dSPE can be regarded as a batch mode of SPE, and all of the nanoparticles that are used in SPE can be used as sorbent for dSPE. In recent years, different nanoparticles and nanocomposites such as CNTs [91,171], G [160,172], GO-MOF and GO-SiO2 composites [173,174], MIPs [90,175e178], coated or grafted polymers [157,179,180], LDHs [69], MOFs [181], diamond nanopowder [182], TiO2 nanoparticles and aerogels [183,184], TiO2-CNTs nanocomposites [72,92], Al2O3 [73,185], and AuNPs [68,186] have been used as dSPE sorbents for extraction of target analytes and matrix clean-up in bioanalysis (Table 1). Recently, Ge et al. have proposed an interesting method to produce 3D porous graphene as a sorbent to extract proteins and peptides from some biofluids prior to MALDI-TOF MS analysis [172]. The sorbent was prepared by dissolving cuprous oxide microspheres as sacrificial templates in the composite of graphene and cuprous oxide microspheres using diluted nitric acid. The sorbent was successfully used for enrichment of low-abundance proteins and peptides prior to subsequent MALDI-TOF MS identification. Major features of the newly developed sorbent are a large surface area, 3D porous architecture, cost effectiveness, and satisfactory reproducibility. Chauhan et al. have proposed a MIP sorbent for simultaneous extraction of polycyclic aromatic hydrocarbon metabolites from urine samples prior to LC analysis [178]. In this regard, they have synthesized a nanostructured multi-template imprinted polymer to eliminate the need of individual MIPs for each metabolite. In another interesting work, Yeh et al. synthesized human serum albumin-coated AuNPs for selective extraction of lysozyme from hen egg white, human milk, and human tear samples prior to CE analysis [68]. The results showed that the protein coating layer on the AuNPs has negative charges and can be efficiently dispersed in high-ionic-strength solutions, and capture lysozyme through electrostatic attraction. The results showed that highly efficient analyte loading and extraction was achievable at pH 7 which closely resembles the biological pH. 4.3. Magnetic solid phase extraction (MSPE) MSPE is similar to dSPE in methodology except that the sorbent can be easily separated from the medium using an external magnetic field. To this end, magnetic nanoparticles (MNPs), usually iron oxide magnetic nanoparticles, in bare, core-shell, composite, and organic and inorganic ligand modified forms are used. This method has obtained heightened attention in sample preparation for bioanalysis because of its easy operation steps. Researchers have used many strategies to prepare magnetic nanosorbents for MSPE of various analytes to form different complex matrixes. Various nanocomposites such as CNT-MNPs [76,187,188], RGO-, GO- and G-MNPs [189,190], surfactant coated MNPs [61,100,101,191e193], MIP-coated MNPs [15,98,119, 121,135,194e199], IIP coated MNPs [115,116,200], polymer coated MNPs [79,139,142,201e205], amine functionalized MNPs
[81,102,206,207], TiO2-MNPs [133,208,209], ionic liquid coated MNPs [210e212], and cyclodextrin coated MNPs [143,213e215] have been used as sorbents in MSPE for bioanalysis (Table 1). In an interesting study, Shi et al. developed a method based MSPE and MALDI-TOF MS for determination of small molecules present in urine samples, by the elimination of the desorption step in MSPE [82]. In this regard, a magnetic composite of G with CNT was utilized as a novel adsorbent to enrich the targeted analytes and introduce the loaded analyte to MALDI-TOF MS analysis. In order to evaluate the benefits of the utilized magnetic composite, other possible magnetic sorbents including magnetic CNTs, magnetic G, and the mixture of them were also employed as sorbent as well as the functional matrixes. The results showed that the magnetic composite of G with CNT provided the highest efficiency in terms of the extraction process, signal enhancement, and facilitation of desorption/ionization process. In another study, Dramou et al. synthesized a novel amphiphilic magnetic MIP sorbent to extract gatifloxacin from human urine and serum samples prior to UVevis spectrophotometric determination [216]. To this end, a layer of the analyte imprinted polymer was coated on oleic acid and PVP coated MNPs. The sorbent solubility and dispersibility studies demonstrated sorbents with high amphiphilicity, an important factor for an efficient sorbent used in MSPE. In another interesting study, multicore MNPs doped with Cs and FITC dye for the extraction of the CA19-9 biomarker in serum for direct introduction to ICP-MS without analyte desorption was synthesized by Ko et al. [217]. The sorbent was used for nonspecific magnetic extraction of the investigated analyte from serum samples, after which the ratiometric measurement of the tagged particle was performed using the doped Cs as the internal standard. 4.4. Microextraction by packed sorbent (MEPS) In 2004, miniaturization of SPE cartridges led to the introduction of a new microextraction technique named MEPS by AbdelRehim [218]. In MEPS, the SPE cartridges have been replaced by microsyringes, and subsequently, the required sorbent amount has been decreased to a few milligrams. The sorbent can be packed into the syringe barrel as a plug, between the needle and the barrel, or inside of the needle as a cartridge (Fig. 3). This technique is specially designed for on-line fully-automated measurements. As other microextraction techniques, the required sample volume has been significantly reduced to a few microliters. Nowadays, MEPS syringes are commercially available from SGE (SGE Analytical Science Pty Ltd, Victoria, Australia). This method has as high a potential for on-line applications as any sorbent materials such as conventional SPE sorbents, and even more advanced sorbents can be packed and used for bioanalysis. Recently, Bagheri et al. have synthesized a nanocomposite consisting of polydopamine, AgNPs, and polypyrrole as a sorbent for MEPS that was used for simultaneous extraction of amitriptyline, imipramine, and citalopram antidepressant drugs from urine samples prior to GC-MS analysis [125]. They used a homemade MEPS syringe by packing 2 mg of the synthesized sorbent into a 1 mL syringe between two PTFE frits. The results of their work showed that the synthesized nanocomposite provides higher efficiency in extraction of the investigated analytes in comparison to bare polydopamine and polypyrrole sorbents. Zhu et al. used a nanostructured monolith sorbent for the effective enrichment of endogenous peptides from human plasma prior to MALDI-TOF MS analysis [219]. The monolith sorbent was prepared using carbohydrate-based sponge-like pomelo peel as the base material. Then, a mesostructured CTAB-SiO2 composite was deposited on the base material. After removing unstable compounds in pomelo peel and CTAB using acid treatment and calcination, a continuous
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skeleton, interconnecting macropores and ultra-high surface area sorbent was obtained. The sorbent was then packed inside a 1 mL syringe between two cotton layers. 4.5. Solid phase microextraction (SPME) Undoubtedly, SPME still is the most popular microextraction technique. Since Pawliszyn and Arthur proposed SPME and applied it in practice in 1990 [220], there have been many modifications made to this technique. In its conventional and commercially available form, the SPME device consists of a fused silica fiber uncoated or coated with a thin layer of extraction medium fixed inside of the needle of a syringe-like device (Fig. 3). The extraction process can be conducted either using in-solution or headspace extraction strategies from gaseous and liquid samples by immersing the fiber in the investigated solutions or placing it in the headspace of the samples. Researchers have used different strategies to improve SMPE extraction efficiency for bioanalysis by using nanomaterials such as nanomaterials coating capillary [67,221e223], MIPs coating silica fiber or capillary [108,224], nanostructured polymers electrodepositing conductive cores or tubes [66,87,111,151], nanomaterials coating fiber [225,226], and monoliths packing capillary [88,110,149,227e232] (Table 1). Guo et al. have prepared a fused silica capillary column coated with dimethylethanolamine aminated polychloromethyl styrene nano-latex for the extraction and enrichment of four tetracycline antibiotics from pig plasma prior to FASS-OT-CEC [233]. Their results showed that better separation of the investigated analytes could be obtained on the coated capillary column than that obtained on the bare fused silica capillary, and the method sensitivity could also be increased. In another interesting study, Liu et al. prepared TiO2 nanoparticle functionalized monolithic capillary for on-line microextraction of Gd ion and Gd-based contrast agents from human urine prior to ICP-MS determination [232]. In order to prepare the monolithic capillary, TiO2 nanoparticles were embedded in the poly(methacrylic acid-ethylene glycol dimethacrylate) framework. After optimizing extraction condition, they managed to determine the investigated analytes in mg L1 concentration levels with LODs in ng L1 levels. The developed on-line method is featured with high sensitivity, low sample consumption, and efficient separation ability and provides an attractive non-chromatography strategy for the speciation of Gd ion and Gd-based contrast agents in human urine. Toward establishing a method for on-line determination of aldehydes in human exhaled breath condensate, Li et al. synthesized a novel G-polyaniline coating [234]. The G-polyaniline composite was electrodeposited on the internal surface of a stainless steel tube, and the coated tube was used for the analysis of breath samples of healthy people and lung cancer patients. The results showed that in comparison to bare polyaniline coating, the G-polyaniline coating exhibited enhanced mechanical stability, large specific surface area, long lifespan, and good biocompatibility. Furthermore, on-line mode of the method provided faster analysis, higher enrichment efficiency, and higher automation level than its off-line mode. 4.6. Dispersive m-solid phase extraction (dispersive m-SPE) Dispersive m-SPE is a miniaturized form of dSPE that has recently been developed based on microextraction strategies such as reducing the required sorbent amount. In this technique, the solid sorbent is added to the solution and dispersed by shaking. Finally, the sorbent loaded with the investigated analytes is separated from the solution by centrifugation or other similar methods. In dispersive m-SPE, the quantity of the sorbent in comparison to dSPE has been significantly reduced, and therefore, the technique
13
requires highly efficient sorbents to maintain or even improve the extraction and preconcentration efficiency. Therefore, application of nanosorbents with high surface area and sorption capacities is a suitable option to improve the efficiency of dispersive m-SPE. Different nanosorbents have been used for dispersive m-SPE of targeted analytes from biological samples such as MNPs-polymer nanocomposite [129,156], MNPs-CNTs nanocomposite [113], GO and G [235,236], G-silica hybrid [114], and modified MNPs [89,237] (Table 1). Asgharinezhad et al. synthesized a polyaniline-MNPs polymeric nanocomposite for dispersive m-SPE of benzodiazepines from human urine and plasma samples [129] (Table 1). They also synthesized polypyrrole-MNPs and polypyrrole/polyanilineMNPs and evaluated the extraction efficiencies of the three sorbents. The comparison of polyaniline-MNPs nanocomposite sorbent with polypyrrole-MNPs and polypyrrole/polyaniline-MNPs nanocomposite sorbents along with the bare MNPs demonstrated that the polyaniline-MNPs nanocomposite sorbent provides the highest extraction efficiency for the investigated analytes. They have reported that the coating of MNPs with polyaniline can increase the adsorption ability of the target analytes and also improve the stability of the MNPs and their dispersibility in aqueous media. In another study, Zhao et al. have used tetraethylenepentamineMNPs polymeric nanocomposite for simultaneous extraction of eight phenolic environmental estrogens in blood samples prior to UFLC-MS/MS determination [89] (Table 1). Their results showed that using the synthesized sorbent and protein precipitation technique, the level of phospholipids in plasma samples as the major contributing source of matrix effects in LC-MS/MS for analysis of plasma samples and, subsequently, the absolute matrix effects could be greatly reduced. 4.7. Stir bar sorptive extraction (SBSE) In 1999, Baltussen et al. introduced a novel extraction technique named SBSE [238]. The technique, in its original version, employs a PDMS coated stir bar as sorptive element (Fig. 3). The coated stir bar can be immersed in the sample solution or fastened in the headspace of the sample to extract the analytes of interest. Then, the stir bar can be transferred for desorption and determination of the extracted analytes. Nowadays, an automated version of the SBSE technique is commercially available and GERSTEL®MultiPurpose Sampler is a commercially available device to automate the whole SBSE extraction procedure. In recent years, many researchers have used different nanoparticles to increase the extraction efficiency of the SBSE technique. Fan et al. have used a GO-polyethyleneglycol polymeric nanocomposite coated stir bar for sorptive extraction of fluoroquinolones from chicken muscle and liver prior to LC-FL determination [154] (Table 1). GO was composited with polyethyleneglycol through intermolecular interactions to improve its stability and a stir bar was coated with it using the sol-gel technique. The results showed that the newly developed sorbent provides higher efficiency for extraction of the investigated analytes in comparison to GO-polyaniline composite and PDMS coated stir bar. In another study, Pebdani et al. used another nanosorbent to enhance conventional SBSE device extraction efficiency for losartan and valsartan extraction from urine and plasma matrices [124] (Table 1). In this instance, the stir bar was coated with nickel:zinc sulfide (Ni:ZnS) nanoparticles loaded onto activated carbon as well as 1-ethyl-3-methylimidazolium hexafluorophosphate ionic liquid using the sol-gel technique and was used for SBSE extraction of the investigated analytes prior to LC-UV determination. Their results showed that the synthesized coating provides much higher extraction efficiency than activated carbon coating. This behavior is attributed to the multi-elemental nature of the sorbent (Ni metallic
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M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
site can interact with the investigated analytes via electrostatic interaction according to the hard-soft principle, S reactive site can react with p electrons of the analytes, and the Zn site can interact with the structures containing hydroxyl groups), as well as to the higher surface area of the nanomaterials.
4.8. Other methods In addition to the abovementioned techniques, other innovative or well-established methods have also been used for bioanalysis utilizing nanomaterials as sorbents. Various techniques such as pipette-tip extraction, microfluidic methods, electrochemical methods, and single drop microextraction have benefited from the interesting advantages of nanotechnology. In the following, some of the recent applications are being reviewed. Alwael et al. reported on the preparation of a pipette-tip packed by lectin modified AuNPs on a polymeric monolithic for selective extraction of glycoproteins prior to LC-UV determination [239]. In this regard, ethylene dimethacrylate porous polymer monolith was in situ prepared within a 20 mL polypropylene pipette tip bounded via surface grafted methacrylate anchor sites. AuNPs were then immobilized onto the monolith pore surface. The results showed that high capacity and selective extraction was achievable using the newly developed monolith because of the high surface area provided by the nanomaterials and lectin affinity phase, respectively. In an interesting study, Wu et al. developed a novel microfluidic method for in vivo fast equilibrium monitoring (2 min total extraction time) of pharmacokinetic profiles of desipramine in rabbits based on a biocompatible core-sheath electrospun nanofiber membrane sandwiched within the microfluidic unit as sorbent [240]. In order to prepare the membrane, polystyrenecollagen co-polymer was coaxially electrospun, and then strengthened with in situ glutaraldehyde cross-linking. The membrane showed high mechanical strength and stability in water and biomatrix resistance and provided high mass transfer rate and large extraction capacity. The membrane was embedded into the microfluidic device using a sandwich design, and the blood stream could be introduced in vivo into the microfluidic device to interact with the membrane repetitively. The authors managed to monitor free and total concentrations of desipramine in vivo with 10 min intervals almost without rabbit blood consumption using the innovative microfluidic device and the nanostructured sorbent. Wang et al. developed a chip-based open tubular capillary electrochromatography method for drugs, amino acids, and dipeptide enantiomers utilizing a series of magnetic MIP nanosorbents [241]. The magnetic nanosorbents were synthesized using MNPs as the support substrate, dopamine as the functional monomer, and the investigated enantiomers as the templates. The sorbents were then packed inside a PDMS microchannel and fixed inside of the column using an external magnetic field as a novel stationary phase for the enantioseparation of the targeted enantiomers. The synthesized sorbent exhibited high adsorption capacity, excellent selectivity, and high stability. Their results confirmed that the proposed method could distinguish and separate not only amino acid enantiomers but also dipeptides and drug enantiomers, which greatly expands the range of the design in bioanalytical applications. Madrakian et al. used a different design for selective and sensitive sorptive extraction of mefenamic acid from some real samples including human urine based on magnetic MIP nanoparticles [242]. In this regard, the magnetic MIPs nanoparticles were synthesized using MNPs-SiO2 core-shell nanoparticles (as the support material), methacrylamide (as the functional monomer), ethylene
glycol dimethacrylate (as the cross-linker), and 2-20 -azoisobutyronitrile (as the initiator). In order to extract the investigated analyte from the sample matrix, the nanosorbent was added to the solution, and after loading the analyte, it was collected on a homemade carbon paste electrode which included a permanent magnet inside of it. Then, the voltammetric determination was carried out. Their results showed that application of the selective MIP sorbent for extraction of the investigated analyte prior the electrochemical analysis could greatly improve the selectivity and sensitivity. Shastri et al. have synthesized bidentate AgNPs and evaluated the potential usage of the nanoparticles in single drop microextraction of proteins and peptides from biological samples prior to MALDI-TOF MS determination [155] (Table 1). The results showed that highly efficient extraction of the investigated analytes was achievable because of the high ability of the bidentate nanoparticles to interact with the investigated analytes. They could improve MALDI-TOF MS signal intensity of the investigated proteins and peptides 10e15 times by utilization of the bidentate AgNPs in single drop microextraction.
5. Application of nanomaterials in determination of biomolecules The high surface and surface functionality of nanomaterials provide a good degree of selectivity towards targeted biomolecules. For example, HSA modified AuNPs have been used for the selective extraction and enrichment of lysozymes prior to analysis by CE due to the electrostatic interaction between the HSA layer and the lysozymes [243]. AuNPs have high affinity towards thiol functional groups, which helps in the extraction of amino-thiols (biomarkers of Alzheimer's disease) through m-SPE [244]. Graphene templated magnetic nanocomposite was demonstrated to be highly selective for extraction and separation of low-concentration biomolecules from biological samples due to the size-selection property provided by the unique porous structure and the excellent affinity of the composite materials [245]. Moreover, customized molecular imprinted polymers could be immobilized on various nanoparticles to improve selectivity for different analytes [246]. AuNPs were integrated into liquid phase microextraction as extracting/preconcentrating probes for determination of methionine-encephalin and leucine-encephalin peptide mixture using MALDI-TOF MS [247]. The surfaces of AuNPs were functionalized with tetraalkylammonium bromide, which contains negative and positive charges. Furthermore, surface-modified AgNPs were used for microextraction of peptide mixtures from biological samples prior to MALDI-TOF MS [248]. AgNPs were functionalized with tetraoctylammonium bromide and the average size of the nanoparticles were found to be < 50 nm. Microextraction of bovine fibrinogen and BSA proteins from complex protein matrixes was carried out using PDMS fibers coated with MWCNTs and SWCNTs that were used as adsorbents in a SPME procedure. It was reported that BSA was more absorbed on the surface of SWCNTs as than on MWCNTs [249]. Single-drop microextraction using AuNPs in toluene as an extracting phase was utilized for the extraction of Met-enkephalin (Met-enk, H-Tyr-Gly-Gly-Phe-Met-OH) and Leu-enkephalin (Leuenk, H-Tyr-Gly-Gly-Phe-Leu-OH) peptides from aqueous and urine samples [250]. Liquid/liquid microextraction of hydrophobic proteins (valinomycin and gramicidin D) was carried out using oleic acid capped Mg(OH)2 nanoparticles as hydrophobic probes. The extracted proteins were determined by MALDI-TOF MS [251]. In addition to their application as sorbents, nanomaterials have gained some attention in the determination of biomolecules. The integration of nanomaterials with mass spectrometry has improved
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21
the determination of a wide variety of biomolecules [252e256]. Several nanoparticles have been utilized as matrices, extracting or preconcentrating probes for biomolecular determination using MALDI-TOF MS by manipulating surface functionality for better interaction with analyte molecules [257]. For example, nanoparticles were engineered to provide controlled interactions with biomolecules such as cell membrane lipids, proteins, and nucleic acids as they facilitated their ionization that improved their determination by MALDI-TOF MS. Subsequently, micron- or nanosized particles such as C10, Ag11,12, Au1317 and Si18 showed different degrees of success as desorption/ionization matrices. This led the application of nanomaterials to facilitate the mass spectral imaging of biomolecules of interest by their implantation into tissues, such as brain and plant leaf tissues [258]. 6. Conclusions and perspective By studying recently published papers on the application of nanomaterials as sorbents for bioanalysis, it can be concluded that researchers are interested in the advantages of nanotechnology to improve the efficiency of conventional sorptive extraction methods, and also establish new innovative methods. The most important feature of nanomaterials as sorbents is their high surface area which provides higher sorption capacities than conventional microscale sorbents. However, bioanalysis needs fully-automated on-line methods for the daily analysis of analytes of interest to obtain fast, cheap, simple, and at the same time, sensitive and accurate determinations. This aim requires on-line coupling of sample preparation devices to separation instruments such as LC and GC. The best sample preparation technique should provide selective, fast, cheap and green extractions. This can be achieved by using miniaturized techniques which use very low quantities of sorbent materials and also require low sample volumes. Lower quantities of sorbent mean lower sorption capacity. This problem can be resolved by application of nanosorbents with higher surface areas, but the application of nanosorbents should be carefully handled, not only because of their environmental and health impacts [259,260], but also because of the requirements of on-line coupling with chromatographic instruments. An on-line method requires fast extraction and fast desorption of the analytes of interest, and also highly stable materials to high-pressure injection of the mobile phase [261]. Nanomaterials usually have higher surface energy and tend to agglomerate or adsorb other molecules to decrease their surface free energy. This means that nanomaterials can strongly adsorb the analytes, so subsequently the desorption process should be slower and needs harsher conditions in comparison to microscale and bulk materials. Furthermore, the agglomeration leads to diminishing the sorbent specific surface area. Also, in the case of high operation flow rates, the sorbent compaction occurs because of the small particle size of the materials leading to reducing the flow rate, increasing the extraction time and the column back pressure. In addition, in the case of high ionic strength samples, unwanted coagulation can also occur during the analytical procedure, resulting in a loss of nanoparticles. Nevertheless, in the case of in vivo studies, the sorbents should have more features such as high biocompatibility and stability in biological systems which are under question in the case of many routine nanoparticles efficiency. References [1] J.R. Gribbin, M. Gribbin, Richard Feynman: a Life in Science, Penguin Books, New York, United States, 1997. [2] H.F. Tibbals, Medical Nanotechnology and Nanomedicine, CRC Press, 2010. [3] A. Korkin, P.S. Krsti c, J.C. Wells, Nanotechnology for Electronics, Photonics, and Renewable Energy, Springer, New York, 2010.
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Mazaher Ahmadi received his BSc degree in Applied Chemistry from Bu-Ali Sina University, Hamedan, Iran in 2009 and his MSc degree in Analytical Chemistry also from Bu-Ali Sina University in 2011. Currently, he is guest PhD student in Prof. Abdel-Rehim group at Stockholm University and he is working toward his PhD degree in Bu-Ali Sina University. His current research interests focus on benefits of nanotechnology in sample preparation for bioanalysis.
M. Ahmadi et al. / Analytica Chimica Acta 958 (2017) 1e21 Hatem Elmongy: Hatem Elmongy is a PhD candidate at Stockholm University working with Prof. Abdel-Rehim. His research work focus on drug analysis in biological fluids with emphasis on saliva as alternative specimen to blood for screening of drugs and biomarkers. He is also working on development of new extraction strategies of drugs from bio-samples
Tayyebeh Madrakian received her BSc degree in Chemistry from Shiraz University, Shiraz, Iran in 1989 and his MSc degree in Analytical Chemistry also from Bu-Ali Sina University in 1996. In 2000, she received her PhD in Analytical Chemistry from Razi University, Kermanshah, Iran. In the same year, she started working at Bu-Ali Sina University as an Assistance Professor. Now, she is a Professor of Analytical Chemistry at Bu-Ali Sina University. Her current research interests include method development for trace analysis of important organic and inorganic compounds in biological samples, electrochemical methods, and wastewater treatment.
21 Mohamed Abdel-Rehim: Mohamed Abdel-Rehim is a Professor in analytical and bioanalytical chemistry at Stockholm University. Abdel-Rehim obtained his PhD in pharmaceutical sciences from Uppsala University. He has long experience in drug discovery and development from big pharma AstraZeneca. He specialized in sample preparation and the analysis of drugs and metabolites in biological samples by GCeMS and LCeMSMS. He is the inventor of MEPS technique. He is also interested in the preparation of new sorbents for applications in bioanalysis.