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Experimental analysis and optimization of synthesized magnetic nanoparticles coated with PMAMPC-MNPs for bioengineering application
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St. Petersburg Polytechnical University Journal: Physics and Mathematics 3 (2017) 333–338 www.elsevier.com/locate/spjpm
Experimental analysis and optimization of synthesized magnetic nanoparticles coated with PMAMPC-MNPs for bioengineering application Adeyinka O.M. Adeoye, Joseph F. Kayode, Bankole I. Oladapo∗, Samuel O. Afolabi Department of Mechanical and Mechatronics Engineering, Afe Babalola University, Ado-Ekiti, Nigeria Available online 3 November 2017
Abstract Biomedical and biotechnological engineering applications of magnetic nanoparticles (MNPs) for sensors are found to be of great importance. MNPs have attracted a growing interest in the design and development of sensors and biosensors for other several fields of applications. This research dealt with a novel optimization of MNPs of precipitation method of Fe3+ in basic solution. Also, for a surface coat with a random poly [(methacrylic acid)-ran-(2-methacryloyloxyethyl phosphorylcholine)] (PMAMPC-MNPs) by the means of chelating carboxylic group in its structure. We proposed MNPs to be incorporated into the transducer materials used for (bio)sensor and be dispersed in the sample. These caused an attraction by an external magnetic field onto the active detection surface of the (bio)sensor. RPM AMD PC and iron atoms were used to find the optimum conditions needed to coat the surfaces of the sensor such as particle concentrations. Particle technique FT-IR and TEM techniques showed that the synthesized PMAMPC-MNPs were spherical in shape in the range of 10–60 nm coated with a polymer capable of enhancing dispersion and good stability. In addition, particles coated with polymers of this property remain stable as the catalysts in reactions allowed the colour changes. This would be able to enhance sensitivity and stability of sensors and biosensors. This can be applied to the PMAMPC-MNPs for biosensors measurement application. Copyright © 2017, St. Petersburg Polytechnic University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license. (http://creativecommons.org/licenses/by-nc-nd/4.0/) Keywords: Magnetic nanoparticles; (Bio)sensor; TEM; Biomedical engineering; PMAMPC-MNPs.
Introduction The nanoscale particles of iron oxide MNPs are particles that display magnetic properties. Magnets have the ability to respond to external magnetic fields faster. This has been an added advantage in many fields where it was applied, especially in the medical field, it has been so useful. Magnetic nanoparticles ∗
Corresponding author. E-mail address: [email protected] (B.I. Oladapo).
were applied in equipment delivery, controlled manufacturing of drugs and biomolecular techniques using known principles. This involved immunoglobulin and immunomagnetic separation (IMS) which works on the principle of using molecules as baits and also order measurement probes which immobilize particles [1–3]. In separating of biomolecules from samples, mixtures of biomolecules were observed to stick together and separated from the solution by providing a magnetic field using nano-sized particles. Iron oxide catalyst of high surface area to volume
https://doi.org/10.1016/j.spjpm.2017.10.003 2405-7223/Copyright © 2017, St. Petersburg Polytechnic University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license. (http://creativecommons.org/licenses/by-nc-nd/4.0/) (Peer review under responsibility of St. Petersburg Polytechnic University).
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ratio was used. A proposition by [3,4] postulated that nanoparticles of magnesium tight (Fe3 O4 ) were better catalyst and changes the colour of the hydrogen peroxide substrate H2 O2 . The enzyme peroxidase horseradish peroxidase (HRP) caused changes in the colour of the hydrogen peroxide substrate to which it was applied. Biological sensors (biosensors) that can monitor the measurement of the analyte by easily tracking colour changes of the substrate [4–7] which is appropriate for magnetic nanoparticles’ applications. Magnetic nanoparticles can be modified to be suitable for surface coating with small molecules or polymers, but recent research found that magnetic properties and catalytic properties to change the substrate colour were most useful characteristics of magnetic nanoparticles. Magnetic nanoparticles also can be coated with the subsequent changes in species such as polyethylene glycol (PEG) and silicon dioxide (SiO2 ), these features were valuable and magnetic property can be reduced by an increase in the density and thickness of the enamel coating on the magnetic nanoparticle [6,7]. In addition, the development of magnetic nanoparticles for the detection of the specific target molecule is another important factor that affects the performance (efficiency), the specificity and the sensitivity of the sensor. A popular approach is predetermined to be used in the polymer thin film coating on the nanoparticles. Magnets were used in the fixation of biomolecules with the functional molecules for detection, called probes. The advantages of using polymers enable the design of the structure of the polymer to a particular functional group that is chemically stable. Organic molecules [8–10] attributed to the polymer have the volume and density of the functional groups in high doses. These made probe fixing or the number of moles of the probes on the area (mole of probes per unit area) in high doses possible as well as good measurement performance of the sensor (efficiency). The polymer was designed to have specific functional groups that can reduce the attraction between the probe and other substances different from the desired substance. Detection sensors can also help with the analysis of specific increase due to the use of a random copolymer of poly metallic acrylic acid and polymer. The design of the components of the polymer assumes the responsibility of fixing probes of PMA unit. The polymer truly helps to enhance the properties of biological compatibility (biocompatibility) and lower clamping is not the specific among phospholipid choline Enrile’s PMPC unit. The study found PMAMPC can help optimize measurement performance both in terms of
increasing the concentration in the latest developments of detecting (detection limit; LODs) target molecule and the ability to block the absorption without the specific [9–11]. The researchers therefore observed that the performance of PMAMPC copolymer can be used to improve the surface MNPs to be appropriate for the PM. The application is a sensor that can detect biological target molecule with the specific measurements and can be observed with the naked eye. The aim is to study the surface modification with a coating of MNPs with PMAMPC through the gelatin carboxylic group that is in the structure of PMAMPC. Atoms of iron were used to find the optimum conditions for the coating [10–12]. The main objective of this research is to propose a novel optimization of MNPs by precipitation method of Fe3+ in basic solution. To have a surface coat with a random poly[(methacrylic acid)-ran-(2-methacryloyloxyethyl phosphorylcholine)] (PMAMPC-MNPs) by the means of chelating carboxylic group in its structure. This help to integrate MNPs into the transducer materials use for (bio)sensor and be dispersed in the sample. These caused an attraction by an external magnetic field into the active detection surface of the (bio)sensor. RPM AMD PC and iron atoms were used to find the optimum conditions needed for coating surfaces of the sensor such as particle concentrations. Particle technique FT-IR and TEM techniques showed that the synthesized PMAMPC-MNPs were spherical in shape coated with a polymer capable of enhancing dispersion and good stability. This particle was analysed by Fourier transformed infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) to check the stability and the colour change of the substrate particles coated with the PMAMPC. These factors can prove the success of the coating of PMAMPC surface. Material and methods A PMAMPC synthetic polymer with a reactive process was available through a radical reaction mechanism. That is reversible; the addition fragmentation chain transfer (RAFT) of MA monomer and MPC (the ratio of the light alumni, 50:50) with 4cyanopentanoic acid thiobenzoate (CPD) and 4,4 azobis (4-cyanovaleric acid) (ACVA) as a chain transfer agent in (CTA) and radical initiator respectively. Weighing FeCl3 ·6H2 O 8.00 g and FeCl2 ·4H2 O 3.60 g ratio of 2:1 by melted water poured into 150 mL of distilled water filled to bottleneck and then connected to a condenser and agitation speed is 750 rpm. This
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Fig. 1. Operation of the process for deposition to result.
takes 1h under a nitrogen atmosphere, with 15 M NH added. 4 OH (pH 11) with the volume 80 mL of and with the temperature at 50 °C were then added. The agitation continued for 6 h under a nitrogen atmosphere. Sediments were washed with distilled water and neutralized and with ethanol. Using magnetic particles separated from the solution and baked to dry at room temperature 55 °C for 24 h [12,13], the powder has a solid colour of MNPs and was characterized by FT-IR technique and TEM. The summary of the operation of the process for better understanding can be seen in Fig. 1. Surface coating of MNPs with PMAMPC The number of particles, 10 mg/mL were dispersed in distilled water and then filled with ultrasonic PMAMPC. The amount prescribed were 5, 10, 20 and 40 mg and the time required to sonicate is 15, 30, 45 and 60 min for each milligram. Particles were washed with distilled water several times with ultrasonic and magnetic particle separation in a vacuum. From the dried solution and identification [13], PMAMPC-MNPs were prepared by Technicians FTIR and TEM. The particles of MNPs and PMAMPCMNPs were analysed by preparing particles of concentrations 50 g/mL in NaOAc buffer solution of 0.1 M
and pH 3.5, TMB (5 (L, 10 mg/mL) and 30% H2 O2 of 1.9 L were added on the left. This was done at room temperature for 30 min in the solution. Measurement of absorption of light at a wavelength of 652 nm with UV–visible spectrophotometer using NaOAc solution is blank. Identification techniques with Fourier transform infrared spectroscopy (FT-IR) This was prepared by weighing with the weight of MNPs PMAMPC-MNPs mixture being 2 mg in a KBr solution of 200 mg. The mixture was crushed and compressed into a thin sheet and analysed with an infrared spectrometer FT-IR model gives the wave number 400–4000 cm−1 (128 scans). Results and discussion MNPs synthesized by co-precipitation (coprecipitation method) between Fe2+ and Fe3+ in a solution of NH4 OH and by the morphological analysis showed that the particles using TEM MNPs are spherical and their size is in the range of 10–50 nm as shown in Fig. 2. The analysis of the functional groups with technical FT-IR signal bond Fe–O (bending) with the
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A.O.M. Adeoye et al. / St. Petersburg Polytechnical University Journal: Physics and Mathematics 3 (2017) 333–338 Table 1 The transmittance intensity ratio of different concentrations of PMAMPC. Concentrated solution PMAMPC (mg/mL) 5 10 20 40 Table 2 The transmittance intensity PMAMPC 10 mg/mL. Time (min) Fig. 2. TEM images of MNPs [11].
Fig. 3. TEM images of PMAMPC-MNPs [12].
wave number of about 560 cm−1 and OH (stretching) with wave number around 3500 cm−1 . The surface coating of MNPs with PMAMPC relies on the surface of the metal chelating carboxylic groups and Al-(COOH) within the structure of PMAMPC. After analysis techniques, the TEM is shown in Fig. 3. These particles have been revealed to be spherical and are not different from the particles before coating which shows PMAMPC coated. The MNPs surface of a thin film, considering FT-IR spectra of PMAMPCMNPs will appear. Signal at position 1708 cm−1 represents C = O (stretching) and 1086 cm−1 represents PO (stretching) of the group. The function of the structure of PMAMPC and found signs of CH
15 30 45 60
Transmittance intensity ratio [C = O (str) of PMAMPC/Fe–O (str)] 0.59 0.78 0.67 0.64
ratio
at
various
concentrations
Transmittance intensity ratio [C = O (str) of PMAMPC/Fe–O (str)] 0.76 0.79 0.85 0.85
(stretching) are around a wave number 2930 cm−1 and show the –CH2– in the chain of the polymer. There were also signs that appeared at about 1566 cm−1 and 1400 cm−1 which shows bond CO (symmetric and asymmetric stretching), which demonstrated the chelation (bidentate bonding) between the squad car and the surface of magnetic nanoparticles [14–16]. The study for optimum coating the surface of MNPs with PMAMPC found concentrations of soluble polymer affecting the ability of the coating. You can determine the intensity of the C = O signals at a position of 1708 cm−1 compared to the signal at position 1634 cm−1 . This is due to show in terms of the MNPs transmittance intensity ratio that the transmittance intensity ratio increases with the concentration shown to increase the amount of coating on the particle PMAMPC as shown in Table 1. However, when the concentration was greater than 10 mg/mL, the coating was reduced. This may be due to the chain polymer concentration. While increasing the time it took to collate has little effect as shown in Table 2. It was also found that PMAMPC-MNPs prepare a good dispersion and stable in water without sticking together into large cubes (aggregate) and no precipitation while the magnetic nanoparticles that were not coated with the polymer were in place. Precipitation exhibited instability in the distribution of water, the results of this trial show with PMAMPC that a
A.O.M. Adeoye et al. / St. Petersburg Polytechnical University Journal: Physics and Mathematics 3 (2017) 333–338
polymer with properties like water (hydrophilic polymer) will improve the taste of water to its property [18,19]. The MNPs particles made the particles well dispersed and ensure a stable dispersion, in water or in a medium that can store terminals of the particles in the solution of a long period of time [15–17], but when an external magnetic field, the particles PMAMPCMNPs can be easily separated from the solution. The MNPs and PMAMPC-MNPs particle concentration was 0.1 mg/mL under (a) set aside at room temperature 0 min, (b) left at room temperature for 120 min and (c) the magnetic field from the outside. PMAMPC-MNPs particles that showed their property as a catalyst to change the colour of substrates which can be TMB solution which changes colour from a colourless solution to the colour of water that can be observed with the naked eye. With the appropriate solution to measure the absorbance at 652 nm wavelength using UV-visible spectroscopy techniques, we have discovered that the ability to change the colour of TMB substrate particles PMAMPC-MNPs decreased about 22% for MNPs
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compared to the particles shown in Fig. 4, which was expected, due to the particles being coated with MNPs [18]. PMAMPC may cause obstruction to the surface of the iron oxide nanoparticles on the skin which accelerates the oxidation reaction. TMB’s study of concentrations showed minimum catalyst particles that can change the colour of TMB substrates found. This experimental conditions at the concentration of 12.5 g/mL concentration were lowest at the MNPs and PMAMPC-MNPs can. Colour substrates have a signal to Noise ratio of 1. The colour of TMB substrate after the addition of 50 g/mL of particles MNPs and PMAMPC-MNPs. Conclusion The surface modification coating of magnetic nanoparticles with magnetic properties PMAMPC adds water to taste. With magnetic nanoparticle, the offer was dispersed well in water and stabilized with
Fig. 4. Absorption of the solution TMB at a wavelength of 652 nm.
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conducting separate particles removed from the solution with an external magnetic field. A novel optimization of MNPs of precipitation method of Fe3 + in basic solution was done. The particles were coated with a polymer with specifically still feature as a catalyst to change the colour of TMB substrates and this yielded results close to the MNPs particles that were not coated. This technique helped to shorten the detection time through rapid transfer of the material to the MNPs for quick sensing. Also, higher sensitivity of the material corresponded to the great amount of MNPs that was deposited on the PMAMPC. All trials demonstrated that the surfaces modified with magnetic particles can be employed by PMAMPC development. References [1] L.K. Quynh, B.D. Tu, D.X. Dang, D.Q. Viet, L.T. Hien, D.T. Huong Giang, N.H. Doc, Detection of magnetic nanoparticles using simple AMR sensors in Wheatstone bridge, J. Sci. Adv. Mater. Devices 1 (2016) 98–102. [2] P.P. Freitas, H.A. Ferreira, D.L. Graham, L.A. Clarke, M.D. Amaral, V. Martins, L. Fonseca, J.S. Cabral, Magnetoelectronics, in: M. Johnson (Ed.), Elsevier, Amsterdam, 2004. [3] H. Kim, V. Reddy, K. Woo Kim, I. Jeong, X.H. Hu, C.G. Kim, Single magnetic bead detection in a microfluidic chip using planar hall effect sensor, J. Magn. 19 (2014) 10. [4] E. Tully, S.P. Higson, R. O’Kennedy, The development of a ‘labeless’ immunosensor for the detection of Listeria monocytogenes cell surface protein, Internalin B, Biosens. Bioelectron. 23 (2008) 906. [5] T. Laochai, M. Mooltongchun, Siriwan Teepoo Design and construction of magnetic nanoparticles incorporated with a chitosan and poly (vinyl) alcohol cryogel and its application for immobilization of horseradish peroxidase, Energy Procedia 89 (2016) 248–254. [6] E. Graf, J.T. Penniston, Method for determination of hydrogen peroxide with its application illustrated by glucose assay, Clin. Chem. 26 (1980) 658–660. [7] A.C. Patel, S. Li, J. Yuan, Y. Wei, In situ encapsulation of horseradish peroxidase in electrospun porous silica fibers for potential biosensor applications, Nano Lett. 6 (2006) 1042–1046.
[8] H. Xu, L. Cui, N. Tong, H. Gu, Development of high magnetization Fe3O4/ polystyrene/silica nanospheres via combined miniemulsion/emulsion polymerization, J. Am. Chem. Soc. 128 (2006) 15582–15583. [9] H. Jia, F. Huang, Z. Gao, C. Zhong, H. Zhou, M. Jiang, P. Wei, Immobilization of v-transaminase by magnetic PVA-Fe3O4 nanoparticles, Biotechnol. Rep. 10 (2016) 49–55. [10] D. Zhang, A.B. Karki, D. Rutman, D.P. Young, A. Wang, D. Cocke, T.H. Ho, Z.H. Guo, Electrospun polyacrylonitrile nanocomposite fibers reinforced with Fe3O4 nanoparticles: fabrication and property analysis, Polymer 50 (2009) 4189–4198. [11] Z.Y. Ma, Y.P. Guan, H.Z. Liu, Synthesis and characterization of micron-sized monodisperse superparamagnetic polymer particles with amino groups, J. Polym. Sci. A 43 (2005) 3433–3439. [12] K.S. Atia, A.I. El-Batal, Preparation of glucose oxidase immobilized in different carriers using radiation polymerization, J. Chem. Technol. Biotechnol. 80 (2005) 805–811. [13] F. Kartal, A. Akkaya, A. Kilinc, Immobilization of porcine pancreatic lipase on glycidyl methacrylate grafted poly vinyl alcohol, J. Mol. Catal. B 57 (2009) 55–61. [14] C.T. Dung, L.M. Quynh, N.P. Linh, N.H. Nam, N.H. Luong, Synthesis of ZnS:MneFe3O4 bifunctional nanoparticles by inverse microemulsion method, J. Sci. Adv. Mater. Devices 1 (2016) 200–203. [15] T. Tajiri, N. Terashita, K. Hamamoto, H. Deguchi, M. Mito, Y. Morimoto, K. Konishi, A. Kohno, J. Magn. Magn. Mater. 345 (2013) 288. [16] T. Tajiri1, Y. Ando, H. Deguchi, M. Mito, A. Kohno, Magnetic properties and crystal structure of DyMn2O5 Nanoparticles embedded in mesoporous silica, Phys. Procedia 75 (2015) 1181–1186. [17] C.A. Demarchi, A. Debrassi, F.C. Buzzi, N. Nedelko, A.S. Waniewska, P.D. Dłuzewski, J.D. Magro, J. Scapinello, C.A. Rodrigues, Adsorption of the dye Remazol Red 198 (RR198) by O-carboxymethylchitosan-N-lauryl/c-Fe2O3 magnetic nanoparticles, Arabian J. Chem. (2015) (in press), doi:10. 1016/j.arabjc.2015.08.028. [18] R. Hushiarian, N.A. Yusof, A.H. Abdullah, S.A.A. Ahmad, S.W. Dutse, Facilitating the indirect detection of genomic DNA in an electrochemical DNA biosensor using magnetic nanoparticles and DNA ligase, Anal. Chem. Res. 6 (2015) 17–25. [19] S. Mukdasai, N. Butwong, C. Thomas, S. Srijaranai, S. Srijaranai, A sensitive and selective spectrophotometric method for 2-chlorophenol based on solid phase extraction with mixed hemimicelle magnetic nanoparticles, Arabian J. Chem. 9 (2016) 463–470.
St. Petersburg Polytechnical University Journal: Physics and Mathematics 3 (2017) 333–338 www.elsevier.com/locate/spjpm
Experimental analysis and optimization of synthesized magnetic nanoparticles coated with PMAMPC-MNPs for bioengineering application Adeyinka O.M. Adeoye, Joseph F. Kayode, Bankole I. Oladapo∗, Samuel O. Afolabi Department of Mechanical and Mechatronics Engineering, Afe Babalola University, Ado-Ekiti, Nigeria Available online 3 November 2017
Abstract Biomedical and biotechnological engineering applications of magnetic nanoparticles (MNPs) for sensors are found to be of great importance. MNPs have attracted a growing interest in the design and development of sensors and biosensors for other several fields of applications. This research dealt with a novel optimization of MNPs of precipitation method of Fe3+ in basic solution. Also, for a surface coat with a random poly [(methacrylic acid)-ran-(2-methacryloyloxyethyl phosphorylcholine)] (PMAMPC-MNPs) by the means of chelating carboxylic group in its structure. We proposed MNPs to be incorporated into the transducer materials used for (bio)sensor and be dispersed in the sample. These caused an attraction by an external magnetic field onto the active detection surface of the (bio)sensor. RPM AMD PC and iron atoms were used to find the optimum conditions needed to coat the surfaces of the sensor such as particle concentrations. Particle technique FT-IR and TEM techniques showed that the synthesized PMAMPC-MNPs were spherical in shape in the range of 10–60 nm coated with a polymer capable of enhancing dispersion and good stability. In addition, particles coated with polymers of this property remain stable as the catalysts in reactions allowed the colour changes. This would be able to enhance sensitivity and stability of sensors and biosensors. This can be applied to the PMAMPC-MNPs for biosensors measurement application. Copyright © 2017, St. Petersburg Polytechnic University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license. (http://creativecommons.org/licenses/by-nc-nd/4.0/) Keywords: Magnetic nanoparticles; (Bio)sensor; TEM; Biomedical engineering; PMAMPC-MNPs.
Introduction The nanoscale particles of iron oxide MNPs are particles that display magnetic properties. Magnets have the ability to respond to external magnetic fields faster. This has been an added advantage in many fields where it was applied, especially in the medical field, it has been so useful. Magnetic nanoparticles ∗
Corresponding author. E-mail address: [email protected] (B.I. Oladapo).
were applied in equipment delivery, controlled manufacturing of drugs and biomolecular techniques using known principles. This involved immunoglobulin and immunomagnetic separation (IMS) which works on the principle of using molecules as baits and also order measurement probes which immobilize particles [1–3]. In separating of biomolecules from samples, mixtures of biomolecules were observed to stick together and separated from the solution by providing a magnetic field using nano-sized particles. Iron oxide catalyst of high surface area to volume
https://doi.org/10.1016/j.spjpm.2017.10.003 2405-7223/Copyright © 2017, St. Petersburg Polytechnic University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license. (http://creativecommons.org/licenses/by-nc-nd/4.0/) (Peer review under responsibility of St. Petersburg Polytechnic University).
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A.O.M. Adeoye et al. / St. Petersburg Polytechnical University Journal: Physics and Mathematics 3 (2017) 333–338
ratio was used. A proposition by [3,4] postulated that nanoparticles of magnesium tight (Fe3 O4 ) were better catalyst and changes the colour of the hydrogen peroxide substrate H2 O2 . The enzyme peroxidase horseradish peroxidase (HRP) caused changes in the colour of the hydrogen peroxide substrate to which it was applied. Biological sensors (biosensors) that can monitor the measurement of the analyte by easily tracking colour changes of the substrate [4–7] which is appropriate for magnetic nanoparticles’ applications. Magnetic nanoparticles can be modified to be suitable for surface coating with small molecules or polymers, but recent research found that magnetic properties and catalytic properties to change the substrate colour were most useful characteristics of magnetic nanoparticles. Magnetic nanoparticles also can be coated with the subsequent changes in species such as polyethylene glycol (PEG) and silicon dioxide (SiO2 ), these features were valuable and magnetic property can be reduced by an increase in the density and thickness of the enamel coating on the magnetic nanoparticle [6,7]. In addition, the development of magnetic nanoparticles for the detection of the specific target molecule is another important factor that affects the performance (efficiency), the specificity and the sensitivity of the sensor. A popular approach is predetermined to be used in the polymer thin film coating on the nanoparticles. Magnets were used in the fixation of biomolecules with the functional molecules for detection, called probes. The advantages of using polymers enable the design of the structure of the polymer to a particular functional group that is chemically stable. Organic molecules [8–10] attributed to the polymer have the volume and density of the functional groups in high doses. These made probe fixing or the number of moles of the probes on the area (mole of probes per unit area) in high doses possible as well as good measurement performance of the sensor (efficiency). The polymer was designed to have specific functional groups that can reduce the attraction between the probe and other substances different from the desired substance. Detection sensors can also help with the analysis of specific increase due to the use of a random copolymer of poly metallic acrylic acid and polymer. The design of the components of the polymer assumes the responsibility of fixing probes of PMA unit. The polymer truly helps to enhance the properties of biological compatibility (biocompatibility) and lower clamping is not the specific among phospholipid choline Enrile’s PMPC unit. The study found PMAMPC can help optimize measurement performance both in terms of
increasing the concentration in the latest developments of detecting (detection limit; LODs) target molecule and the ability to block the absorption without the specific [9–11]. The researchers therefore observed that the performance of PMAMPC copolymer can be used to improve the surface MNPs to be appropriate for the PM. The application is a sensor that can detect biological target molecule with the specific measurements and can be observed with the naked eye. The aim is to study the surface modification with a coating of MNPs with PMAMPC through the gelatin carboxylic group that is in the structure of PMAMPC. Atoms of iron were used to find the optimum conditions for the coating [10–12]. The main objective of this research is to propose a novel optimization of MNPs by precipitation method of Fe3+ in basic solution. To have a surface coat with a random poly[(methacrylic acid)-ran-(2-methacryloyloxyethyl phosphorylcholine)] (PMAMPC-MNPs) by the means of chelating carboxylic group in its structure. This help to integrate MNPs into the transducer materials use for (bio)sensor and be dispersed in the sample. These caused an attraction by an external magnetic field into the active detection surface of the (bio)sensor. RPM AMD PC and iron atoms were used to find the optimum conditions needed for coating surfaces of the sensor such as particle concentrations. Particle technique FT-IR and TEM techniques showed that the synthesized PMAMPC-MNPs were spherical in shape coated with a polymer capable of enhancing dispersion and good stability. This particle was analysed by Fourier transformed infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) to check the stability and the colour change of the substrate particles coated with the PMAMPC. These factors can prove the success of the coating of PMAMPC surface. Material and methods A PMAMPC synthetic polymer with a reactive process was available through a radical reaction mechanism. That is reversible; the addition fragmentation chain transfer (RAFT) of MA monomer and MPC (the ratio of the light alumni, 50:50) with 4cyanopentanoic acid thiobenzoate (CPD) and 4,4 azobis (4-cyanovaleric acid) (ACVA) as a chain transfer agent in (CTA) and radical initiator respectively. Weighing FeCl3 ·6H2 O 8.00 g and FeCl2 ·4H2 O 3.60 g ratio of 2:1 by melted water poured into 150 mL of distilled water filled to bottleneck and then connected to a condenser and agitation speed is 750 rpm. This
A.O.M. Adeoye et al. / St. Petersburg Polytechnical University Journal: Physics and Mathematics 3 (2017) 333–338
335
Fig. 1. Operation of the process for deposition to result.
takes 1h under a nitrogen atmosphere, with 15 M NH added. 4 OH (pH 11) with the volume 80 mL of and with the temperature at 50 °C were then added. The agitation continued for 6 h under a nitrogen atmosphere. Sediments were washed with distilled water and neutralized and with ethanol. Using magnetic particles separated from the solution and baked to dry at room temperature 55 °C for 24 h [12,13], the powder has a solid colour of MNPs and was characterized by FT-IR technique and TEM. The summary of the operation of the process for better understanding can be seen in Fig. 1. Surface coating of MNPs with PMAMPC The number of particles, 10 mg/mL were dispersed in distilled water and then filled with ultrasonic PMAMPC. The amount prescribed were 5, 10, 20 and 40 mg and the time required to sonicate is 15, 30, 45 and 60 min for each milligram. Particles were washed with distilled water several times with ultrasonic and magnetic particle separation in a vacuum. From the dried solution and identification [13], PMAMPC-MNPs were prepared by Technicians FTIR and TEM. The particles of MNPs and PMAMPCMNPs were analysed by preparing particles of concentrations 50 g/mL in NaOAc buffer solution of 0.1 M
and pH 3.5, TMB (5 (L, 10 mg/mL) and 30% H2 O2 of 1.9 L were added on the left. This was done at room temperature for 30 min in the solution. Measurement of absorption of light at a wavelength of 652 nm with UV–visible spectrophotometer using NaOAc solution is blank. Identification techniques with Fourier transform infrared spectroscopy (FT-IR) This was prepared by weighing with the weight of MNPs PMAMPC-MNPs mixture being 2 mg in a KBr solution of 200 mg. The mixture was crushed and compressed into a thin sheet and analysed with an infrared spectrometer FT-IR model gives the wave number 400–4000 cm−1 (128 scans). Results and discussion MNPs synthesized by co-precipitation (coprecipitation method) between Fe2+ and Fe3+ in a solution of NH4 OH and by the morphological analysis showed that the particles using TEM MNPs are spherical and their size is in the range of 10–50 nm as shown in Fig. 2. The analysis of the functional groups with technical FT-IR signal bond Fe–O (bending) with the
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A.O.M. Adeoye et al. / St. Petersburg Polytechnical University Journal: Physics and Mathematics 3 (2017) 333–338 Table 1 The transmittance intensity ratio of different concentrations of PMAMPC. Concentrated solution PMAMPC (mg/mL) 5 10 20 40 Table 2 The transmittance intensity PMAMPC 10 mg/mL. Time (min) Fig. 2. TEM images of MNPs [11].
Fig. 3. TEM images of PMAMPC-MNPs [12].
wave number of about 560 cm−1 and OH (stretching) with wave number around 3500 cm−1 . The surface coating of MNPs with PMAMPC relies on the surface of the metal chelating carboxylic groups and Al-(COOH) within the structure of PMAMPC. After analysis techniques, the TEM is shown in Fig. 3. These particles have been revealed to be spherical and are not different from the particles before coating which shows PMAMPC coated. The MNPs surface of a thin film, considering FT-IR spectra of PMAMPCMNPs will appear. Signal at position 1708 cm−1 represents C = O (stretching) and 1086 cm−1 represents PO (stretching) of the group. The function of the structure of PMAMPC and found signs of CH
15 30 45 60
Transmittance intensity ratio [C = O (str) of PMAMPC/Fe–O (str)] 0.59 0.78 0.67 0.64
ratio
at
various
concentrations
Transmittance intensity ratio [C = O (str) of PMAMPC/Fe–O (str)] 0.76 0.79 0.85 0.85
(stretching) are around a wave number 2930 cm−1 and show the –CH2– in the chain of the polymer. There were also signs that appeared at about 1566 cm−1 and 1400 cm−1 which shows bond CO (symmetric and asymmetric stretching), which demonstrated the chelation (bidentate bonding) between the squad car and the surface of magnetic nanoparticles [14–16]. The study for optimum coating the surface of MNPs with PMAMPC found concentrations of soluble polymer affecting the ability of the coating. You can determine the intensity of the C = O signals at a position of 1708 cm−1 compared to the signal at position 1634 cm−1 . This is due to show in terms of the MNPs transmittance intensity ratio that the transmittance intensity ratio increases with the concentration shown to increase the amount of coating on the particle PMAMPC as shown in Table 1. However, when the concentration was greater than 10 mg/mL, the coating was reduced. This may be due to the chain polymer concentration. While increasing the time it took to collate has little effect as shown in Table 2. It was also found that PMAMPC-MNPs prepare a good dispersion and stable in water without sticking together into large cubes (aggregate) and no precipitation while the magnetic nanoparticles that were not coated with the polymer were in place. Precipitation exhibited instability in the distribution of water, the results of this trial show with PMAMPC that a
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polymer with properties like water (hydrophilic polymer) will improve the taste of water to its property [18,19]. The MNPs particles made the particles well dispersed and ensure a stable dispersion, in water or in a medium that can store terminals of the particles in the solution of a long period of time [15–17], but when an external magnetic field, the particles PMAMPCMNPs can be easily separated from the solution. The MNPs and PMAMPC-MNPs particle concentration was 0.1 mg/mL under (a) set aside at room temperature 0 min, (b) left at room temperature for 120 min and (c) the magnetic field from the outside. PMAMPC-MNPs particles that showed their property as a catalyst to change the colour of substrates which can be TMB solution which changes colour from a colourless solution to the colour of water that can be observed with the naked eye. With the appropriate solution to measure the absorbance at 652 nm wavelength using UV-visible spectroscopy techniques, we have discovered that the ability to change the colour of TMB substrate particles PMAMPC-MNPs decreased about 22% for MNPs
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compared to the particles shown in Fig. 4, which was expected, due to the particles being coated with MNPs [18]. PMAMPC may cause obstruction to the surface of the iron oxide nanoparticles on the skin which accelerates the oxidation reaction. TMB’s study of concentrations showed minimum catalyst particles that can change the colour of TMB substrates found. This experimental conditions at the concentration of 12.5 g/mL concentration were lowest at the MNPs and PMAMPC-MNPs can. Colour substrates have a signal to Noise ratio of 1. The colour of TMB substrate after the addition of 50 g/mL of particles MNPs and PMAMPC-MNPs. Conclusion The surface modification coating of magnetic nanoparticles with magnetic properties PMAMPC adds water to taste. With magnetic nanoparticle, the offer was dispersed well in water and stabilized with
Fig. 4. Absorption of the solution TMB at a wavelength of 652 nm.
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