Evolution of gluconic acid capped paramagnetic iron oxide nanoparticles

Nano-Structures & Nano-Objects 20 (2019) 100389

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Evolution of gluconic acid capped paramagnetic iron oxide nanoparticles Bamidele M. Amos-Tautua a,b , Olayemi J. Fakayode a,b , Sandile P. Songca c , ∗ Oluwatobi S. Oluwafemi a,b , a

Department of Chemical Sciences (formerly applied Chemistry), University of Johannesburg, P.O. Box 17011, Doornfontein 2028, Johannesburg, South Africa b Centre for Nanomaterials Science Research, University of Johannesburg, Johannesburg, South Africa c Department of Chemistry, University of Zululand, Private bag X1001, Kwadlangezwa, 3886, South Africa

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Article history: Received 1 July 2019 Received in revised form 27 July 2019 Accepted 27 August 2019 Keywords: Paramagnetism Iron oxide Gluconic acid Magnetic nanoparticles BET-surface area Mesoporous

a b s t r a c t Magnetic iron oxide nanomaterials are essential for many industrial, environmental and biomedical applications. While ferromagnetic and superparamagnetic iron oxide materials are known, paramagnetic iron oxide nanoparticles have not been significantly reported. In this study, we report the synthesis and characterization of the gluconic acid capped paramagnetic iron oxide nanoparticles (PIONs) using a simple green co-precipitation approach. The PIONs were characterized using Fourier Transform infrared spectroscopy, Scanning electron microscopy, X-ray diffractiometry, differential scanning calorimetry, thermogravimetry, Brunauer–Emmett–Teller (BET) and vibrating sample magnetometry (VSM). The material exhibited linear relationship between magnetization and the field, thus confirming its paramagnetic nature. Also, the as-synthesized PIONs showed a positive zeta potential (+29.7 mV), H2 type IV mesoporous characteristics (pore size = 3.09 nm) with a higher surface area (261.31 m2 /g) than some materials in the literature. The as-synthesized material, exhibited potentials for catalysis, organic synthesis, adsorption, environmental remediation and magnetic resonance T1 bio-imaging. © 2019 Elsevier B.V. All rights reserved.

1. Introduction Nanomaterials are established unique materials with at least one dimension less than or equal to 100 nm. The uniqueness of these materials lies under the fact that they exhibit many awesome characteristics than their bulk counterparts based on their relatively smaller particle sizes. These attributes include enhanced optical absorption and emission [1,2], catalysis [3] and magnetic properties [4] suitable for applications such as material synthesis, molecular extraction [5], environmental sensing [6], thermal conductivity [6,7], drug delivery [8,9], bio-molecular imaging [10] and biomedical therapies [8,11–13]. Among these properties, the magnetic property has the advantage of controlling the material’s behaviour using an applied external magnetic field through the placement of a physical magnet [11]. As a result, many magnetic nanomaterials have been used to achieve certain important accomplishments such as cancer targeting [8], thermal therapeutics [14], data storage and pollutant’s aggregation, degradation and separation from water matrix [15,16]. ∗ Corresponding author at: Department of Chemical Sciences (formerly applied Chemistry), University of Johannesburg, P.O. Box 17011, Doornfontein 2028, Johannesburg, South Africa. E-mail address: [email protected] (O.S. Oluwafemi). https://doi.org/10.1016/j.nanoso.2019.100389 2352-507X/© 2019 Elsevier B.V. All rights reserved.

Typically, magnetic properties of essential characteristics include ferromagnetism, paramagnetism and superparamagnetism which have different applications due to their different magnetization behaviour. For example, ferromagnetism can be identified based on the presence of hysteresis loop [17] while paramagnetism and superparamagnetism can be identified based on the absence of the hysteresis loop [16,18] on the magnetization curve (M-H). The manipulation of materials to exhibit different magnetic properties, i.e. ferromagnetism, paramagnetism and superparamagnetism, is essential in order to meet certain industrial, environmental and biomedical demands such as catalysis and organic synthesis [19,20], data storage (ferromagnets), thermal characteristics [7,21], water purification (ferromagnets and superparamagnets) [16,22], drug delivery (superparamagnets) [23,24] and clinical imaging (paramagnets and superparamagnets) [18]. While ferromagnets retain their magnetizations (evident by the presence of a hysteresis loop) [25], both paramagnets and superparamagnets lose their magnetizations(evident by the absence of a hysteresis loop) [18,26] after the magnetic field has been removed. In addition, ferromagnetic and superparamagnetic materials exhibit a non-linear dependence on magnetic fields while paramagnets show a linear dependence on magnetic fields [18, 27]. In the environmental and industrial water purifications, both ferromagnetic and superparamagnetic materials are employed for

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Fig. 1. Characterization of the PIONs. (a) Vibrating sample magnetometry; (b) FT-IR spectrum; (c) Zeta Potential; (d) hydrodynamic size spectrum.

the removal of pollutants from water while in clinical imaging, both paramagnetic and superparamagnetic materials are used as contrast agents under different relaxation modes. For example, paramagnetic gadolinium complex and superparamagnetic iron oxide nanoparticles are employed under the T1 and T2 relaxation modes respectively [18]. However, paramagnetic gadolinium complexes are limited by short circulation causing the disappearance of images over time. Traditionally, functionalized iron oxide nanoparticles exhibit long circulation and thus paramagnetic iron oxide nanoparticles may be used as alternative materials for T1 imaging. To the best of our knowledge, no report has made reference to the production of gluconic acid capped paramagnetic iron oxide nanoparticles in the literature. In this study, we report the synthesis and characterization of gluconic acid capped paramagnetic iron oxide nanoparticles (PIONs) as potential materials for magnetic resonance imaging and environmental water purification. 2. Materials and method 2.1. Materials All chemicals (Sigma Aldrich) were analytical grades and used without further purification.

a brown colloidal solution. The resulting solution was heated to 65 ◦ C for 40 min and afterwards cooled to room temperature. The black-brown colloidal solution was washed three times with 40 mL of distilled water, dried and stored until further analysis. 2.3. Characterization of the as-synthesized PIONs The PIONs were characterized using Ultraviolet–Visible spectrophotometry, Fourier Transform infrared spectroscopy (FT-IR) (Spectrum two UATR spectrometer, Perkin Elmer, UK), scanning electron microscopy (SEM, Tescan Vega 3XMU, Japan, 20 KV), Xray diffractiometry (XRD, Bruker Advance), Micrometrics ASAP 2010 (for Surface Area and Porosity; N2 , −196 ◦ C, P /P o from 0.05 to 1), SQUID magnetometer (for magnetic measurement; PPMS, Quantum Design Inc., San Diego, CA, USA; 300 K, H: −20 000– 20 000), TGA (Hitachi STA 7200RV-TGA (Japan); 900 ◦ C, 10 ◦ C/min in N2 gas flow), Zeta and Dynamic light scattering (DLS, Anton Paar, Litesizer 500 (Austria) with conductivity value of 14.62 mS/cm at 25 ◦ C. The PIONs’ were ground to powder in a mortar with pestle before loading on the respective instrumentations. 3. Results and discussion 3.1. Synthesis and characterization of PIONs

2.2. Synthesis of paramagnetic iron oxide nanoparticles A mixture of glucose (50 mL, 0.003M) and ferric chloride (25 mL, 0.022M; hexahydrate) solutions was heated to 87 ◦ C for 40 min. Afterwards, the mixture (2.4 mL) was allowed to cool for 15 min. The cooled solution was then added to a preheated ammonium hydroxide solution (50 mL, 1M; 55 ◦ C) dropwise to form

The PIONs evolved as brown black nano-crystal materials. The magnetization characterization showed a linear response with magnetic field, indicating that they were paramagnetic in nature (Fig. 1a) [4]. Furthermore, FTIR analysis showed the presence of carboxylic acid OHstr , C–Hstr , C==Ostr , O–Hbend and C–Ostr groups at 3748–2400, 2882, 1644, 1433 and 1106,1093 (bimodal) cm−1 ,

B.M. Amos-Tautua, O.J. Fakayode, S.P. Songca et al. / Nano-Structures & Nano-Objects 20 (2019) 100389

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Fig. 2. Morphology, crystallinity, thermal stability and surface area characterizations of the PIONs. (a) Scanning electron microscopy; (b) X-ray diffractiometry; (c) DTG and TGA; (d) BET.

Table 1 Comparison of pore and surface area properties of PIONs with some literature materials. Material

Pore size (nm)

Magnetism

XRDSize (nm)

Particle size DBET (nm)

BET surface area (m2 /g)

Isotherm type

Reference

Maghemite nanoparticles Magnetite nanoparticles BiOCl catalyst Akaganeite nanorod PIONs

NA NA 6–13 NA 3.09

Superparamagnetic Superparamagnetic Non-magnetic Non-magnetic Paramagnetic

17 58 39.6 NA 8.14

16 85.1 NA NA 5.37

74.8 14.1 40 111.7 261.31

NA NA IV IV IV

[15] [16] [17] [18] Present work

respectively, confirming the presence of gluconic acid on the surface of the PIONs. In addition, the presence of Fe-Ostr group was confirmed at 448, 585 cm−1 for maghemite and 700, 858 cm−1 for akaganeite respectively (Fig. 1b) [6]. The results from the Zeta potential and DLS analyses showed that the materials exhibited positive surface charge (+29.7 mV) and hydrodynamic size of 0.625 µm respectively (Fig. 1c, d). The SEM image of the as-synthesized PIONs revealed a monodispersed system with isometric face-centred cubic (fcc) octahedral geometry (Fig. 2a). Powder X-ray diffractiometry evaluation showed diffractions at 2θ crystallographic planes of (111), (220), (311), (400), (422), (511) and (440) for cubic inverse spinel maghemite (JCPDS card no 89–5892) and (310) and (301) for a few traces of akaganeite (Fig. 2b) [7]. The nano-crystallite size of the PIONs was estimated to be 8.14 nm using the Debye– Scherrer’s relation (Eq. (1)).

The results of the evaluation of the thermal stability of the as-synthesized PIONs showed four derivative peaks in the DTG curve (Fig. 2c), representing four stages of weight loss (TGA curve, Fig. 2c), corresponding to loss of water (27–145 ◦ C, 11%), gluconic acid (145–251 ◦ C, 8%), akaganeite (251–431 ◦ C, 10%) [8] and remaining akaganeite (431–650 ◦ C, 2%) respectively, together with topo tactical transformation of maghemite to haematite between 650–831 ◦ C) (Fig. 2c) [8,9]. In addition, the material exhibited characteristic Type IV isotherm with H2 hysteresis loop, making it mesoporous in nature [10,11]. Mesoporous materials are essential adsorbents for the removal of pollutants from the environment [12]. Furthermore, the as-synthesized PIONs exhibited higher surface area than some materials reported in the literature (Table 1). Higher surface area materials are required for applications such as chemical sensing [13] and catalysis [14].

DXRD = λ/β cosθ

4. Conclusion

(1)

where DXRD is the crystallite mean size, λ is the wavelength of the radiation, β is the full width at half-maximum (FWHM) and θ is the Bragg’s angle.

Gluconic acid capped paramagnetic iron oxide nanoparticles have been synthesized and characterized. The materials were

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B.M. Amos-Tautua, O.J. Fakayode, S.P. Songca et al. / Nano-Structures & Nano-Objects 20 (2019) 100389

found to be mesoporous with high surface area characteristics. These features show that the as-synthesized nanomaterials may be utilized for applications such as magnetic resonance imaging, adsorption and catalysis. Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgements The authors will like to thank National Research Foundation (NRF), South Africa under the Nanotechnology Flagship Programme (Grant no: 97983), Competitive Programme for Rated Researchers, South Africa (Grant no: 106060), DST/NRF Collaborative Postgraduate Training programme, South Africa (Grant no: 92553), the University of Johannesburg, South Africa, Faculty of Science Research Committee, and University research Committee, South Africa for financial support. References [1] Y. Al-Douri, N.I. Badi, C.H. Voon, Synthesis of carbon - based quantum dots from starch extracts: Optical investigations, Luminescence 33 (2018) 260–266. [2] M.L. Liu, B. Bin Chen, M.C. Li, C.Z. Huang, Carbon dots: synthesis formation mechanism fluorescence origin and sensing applications, Green Chem. 21 (2019) 449–471. [3] H. Wang, Z. Wei, H. Matsui, S. Zhou, Fe3 O4 /carbon quantum dots hybrid nanoflowers for highly active and recyclable visible-light driven photocatalyst, J. Mater. Chem. A 2 (2014) 15740–15745. [4] M. Starowicz, P. Starowicz, J. Zukrowski, J. Przewoźnik, A. Lemański, C. Kapusta, J. Banaś, Electrochemical synthesis of magnetic iron oxide nanoparticles with controlled size, J. Nanoparticle Res. 13 (2011) 7167–7176. [5] D. Yang, X. Li, D. Meng, Y. Yang, Carbon quantum dots-modified ferrofluid for dispersive solid-phase extraction of phenolic compounds in water and milk samples, J. Molecular Liquids 261 (2018) 155–161. [6] J. Hong, K.-H. Kim, N. Raza, A. Azzouz, E. Ballesteros, K.Y. Goud, S.-E. Lee, A. Deep, Nanomaterial-based electrochemical sensors for the detection of neurochemicals in biological matrices, Trends Anal. Chem. 110 (2018) 15–34. [7] D.X. Song, W.G. Ma, X. Zhang, Anisotropic thermal conductivity in ferrofluids induced by uniform cluster orientation and anisotropic phonon mean free path, Int. J. Heat Mass Transfer 138 (2019) 1228–1237. [8] O.J. Fakayode, C.A. Kruger, S.P. Songca, H. Abrahamse, O.S. Oluwafemi, Photodynamic therapy evaluation of methoxypolyethyleneglycol-thiolSPIONs-gold-meso-tetrakis(4-hydroxyphenyl) porphyrin conjugate against breast cancer cells, Mater. Sci. Eng. C 92 (2018) 737–744. [9] A.J. Wagstaff, S.D. Brown, M.R. Holden, G.E. Craig, J. a. Plumb, R.E. Brown, N. Schreiter, W. Chrzanowski, N.J. Wheate, Cisplatin drug delivery using gold-coated iron oxide nanoparticles for enhanced tumour targeting with external magnetic fields, Inorg. Chim. Acta 393 (2012) 328–333.

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