Development of a new class of stable and adaptable free-standing fibre mats with high room-temperature hydroxide-ion conductivity.

For alkaline anion-exchange membrane electrolysers and fuel cells to become a technological reality, hydroxide-ion (OH-) conducting membranes that are flexible, robust, affording high OH- conductivity, and synthesised in a low-cost and scalable way must be developed. In this paper, we engineer a stable, self-supporting, and flexible fibre mat using a low-cost ZIF-8 metal-organic framework composited with ionic liquid tetrabutylammonium hydroxide and widely used polyacrylonitrile as polymeric backbone. We obtain mats with a high intrinsic OH- conductivity for a metal-organic framework-based material already at room temperature, without added ion-conductor polymers. This approach will contribute to the development of low-cost and tuneable ion-conducting membranes.

Disentangling water, ion and polymer dynamics in an anion exchange membrane.

Semipermeable polymeric anion exchange membranes are essential for separation, filtration and energy conversion technologies including reverse electrodialysis systems that produce energy from salinity gradients, fuel cells to generate electrical power from the electrochemical reaction between hydrogen and oxygen, and water electrolyser systems that provide H2 fuel. Anion exchange membrane fuel cells and anion exchange membrane water electrolysers rely on the membrane to transport OH- ions between the cathode and anode in a process that involves cooperative interactions with H2O molecules and polymer dynamics. Understanding and controlling the interactions between the relaxation and diffusional processes pose a main scientific and critical membrane design challenge. Here quasi-elastic neutron scattering is applied over a wide range of timescales (100-103 ps) to disentangle the water, polymer relaxation and OH- diffusional dynamics in commercially available anion exchange membranes (Fumatech FAD-55) designed for selective anion transport across different technology platforms, using the concept of serial decoupling of relaxation and diffusional processes to analyse the data. Preliminary data are also reported for a laboratory-prepared anion exchange membrane especially designed for fuel cell applications.

Capping 1,3-propanedithiol to boost the antibacterial activity of protein-templated copper nanoclusters.

We have prepared copper nanoclusters (Cu NCs) in the presence of bovine serum albumin (BSA) and 1,3-propanedithiol (PDT). The PDT/BSA-Cu NCs possess great activities against different types of bacteria, including non-multidrug-resistant bacteria (Escherichia coli, Salmonella Enteritidis, Pseudomonas aeruginosa, and Staphylococcus aureus) and multidrug-resistant bacteria (methicillin-resistant S. aureus). Their minimal inhibitory concentration (MIC) values are at least 242-fold and 10-fold lower than that of the free PDT and BSA-Cu NCs, respectively. The PDT/BSA-Cu NCs are strongly bound to the bacterial membrane, in which they induce the generation of ascorbyl (Asc) and perhydroxyl (HOO) radicals that result in disruption of their membrane integrity. At a concentration of 100-fold higher than their MIC for Escherichia coli, the PDT/BSA-Cu NCs exhibit negligible cytotoxicity towards the tested mammalian cells and show insignificant hemolysis. We have further demonstrated that low-cost PDT/BSA-Cu NCs-coated carbon fiber fabrics (CFFs) are effective against antibacterial growth, showing their great potential for antifouling applications.

Porous aluminum electrodes with 3D channels and zig-zag edges for efficient hydrogen evolution.

An eco-friendly electrochemical approach, including base and acid treatments, and anodization, has been developed for preparation of defect-rich porous aluminum electrodes for efficient hydrogen evolution. A small Tafel slope value of 43 mV dec-1 reveals improved reaction kinetics through the micropores, 3D channels, and zig-zag edges of the aluminum electrode. It exhibits an onset potential of 460 mV and an overpotential of 580 mV at the current density of 10 mA cm-2 due to the porous and edge structures that enhance the charge transfer and mass transport.

Parameters affecting the synthesis of carbon dots for quantitation of copper ions.

A simple, eco-friendly, and low-cost electrochemical approach has been applied to the synthesis of carbon dots (C dots) from histidine hydrochloride in the absence or presence of halides (Cl, Br, and I) at various potentials up to 10 V. The as-formed C dots refer to C dots, Cl-C, Br-C, and I-C dots. The time-evolution UV-vis absorption and photoluminescence (PL) spectra provide more detailed information about the formation of C dots. Upon increasing the reaction time from 1 to 120 min, more and more C dots are formed, leading to increased PL intensity. The halides play two important roles in determining the formation of C dots; controlling the reaction rate and surface states. When compared to chloride and bromide, iodide has a greater effect on varying surface states and inducing PL quenching through intersystem crossing. The PL intensities of the four types of C dots all decrease upon increasing Cu2+, Hg2+, and Ag+ concentrations. In the presence of 0.8 mM I-, I-C dots compared to C dots, Cl-C dots, and Br-C dots are slightly better for quantitation of Cu2+. Fourier transform infrared spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and X-ray photoelectron spectroscopy results of I-C dots reveal the interactions of Cu2+ with the surface ligands (imidazole and histidine). The I-C dot probe in the presence of 0.8 mM I- is selective toward Cu2+ over the tested metal ions such as Hg2+ and Ag+. The assay provides a limit of detection of 0.22 µM for Cu2+ at a signal-to-noise ratio of 3. Practicality of this probe has been validated by the analyses of tap, lake, and sea water samples, with negligible matrix effects.

Smart app-based on-field colorimetric quantification of mercury via analyte-induced enhancement of the photocatalytic activity of TiO2-Au nanospheres.

We have devised a unique strategy for highly sensitive, selective, and colorimetric detection of mercury based on analyte-induced enhancement of the photocatalytic activity of TiO2-Au nanospheres (TiO2-Au NSs) toward degradation of methylene blue (MB). Through electrostatic interactions, Au nanoparticles are attached to poly-(sodium 4-styreneulfonate)/poly(diallyldimethylammonium chloride) modified TiO2 nanoparticles, which then form an Au shell on each TiO2 core through reduction of Au3+ with ascorbic acid. Notably, the deposition of Hg species (Hg2+/CH3Hg+) onto TiO2-Au NSs through strong Au-Hg aurophilic interactions speeds up catalytic degradation of MB. The first-order degradation rates of MB by TiO2-Au NSs and TiO2-Au-Hg NSs are 1.4 × 10-2 min-1 and 2.1 × 10-2 min-1, respectively. Using a commercial absorption spectrometer, the TiO2-Au NSs/MB approach provides linearity (R2 = 0.98) for Hg2+ over a concentration range of 10.0 to 100.0 nM, with a limit of detection (LOD) of 1.5 nM. On the other hand, using a low-cost smartphone app that records the color changes (ΔRGB) of MB solution based on the red-blue-green (RGB) component values, the TiO2-Au NSs/MB approach provides an LOD of 2.0 nM for Hg2+ and 5.0 nM for CH3Hg+, respectively. Furthermore, the smartphone app sensing system has been validated for the analyses of various samples, including tap water, lake water, soil, and Dorm II, showing its great potential for on-line analysis of environmental and biological samples. Graphical Abstract ᅟ.

Facet- and structure-dependent catalytic activity of cuprous oxide/polypyrrole particles towards the efficient reduction of carbon dioxide to methanol.

The preparation of cost-effective, stable catalysts for the selective reduction of carbon dioxide (CO2) to C1 products such as methanol is extremely important because methanol can be used directly as a fuel or it can be converted into other value-added products. However, the catalysts currently used for the reduction of CO2 to methanol exhibit poor selectivity, poor stability and very low faradaic efficiency. Herein, we used low-cost, stable cuprous oxide/polypyrrole (Cu2O/Ppy) particles having structures of octahedra and icosahedra (microflowers) that were prepared on linen texture (LT) papers for the selective reduction of CO2 to form a value-added single C1 product, methanol. The Cu2O/Ppy particles possessing both octahedral and microflower shapes with exposed low-index (111) facets and high-index (311) and (211) facets are denoted as Cu2O(OL-MH)/Ppy particles. The as-prepared Cu2O(OL-MH)/Ppy particles exhibited high catalytic activity and selectivity towards the electrochemical reduction of CO2 at -0.85 V vs. RHE to form methanol, with a faradaic efficiency of 93 ± 1.2% and an average methanol formation rate of 1.61 ± 0.02 µmol m-2 s-1. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the pyrrolic nitrogen atoms present in the Ppy shell played a dominant role as active sites for CO2 molecules. The Raman bands of Ppy and Cu2O did not shift even after being subjected to electrolysis for several hours, suggesting superior stability of the Cu2O(OL-MH)/Ppy particles. The high resolution microscopic, spectroscopic, diffraction and electrochemical analysis results clearly revealed that the Ppy shell protected the Cu2O particles and avoided corrosion, dissolution, and structural and crystal facet changes, leading to greater stability. The low-cost, durable, flexible, and catalytically active Cu2O(OL-MH)/Ppy LT paper holds great potential for catalytic, photocatalytic and energy storage applications.

Polymer/reduced graphene oxide functionalized sponges as superabsorbents for oil removal and recovery.

Polyurethane dish-washing (PU-DW) sponges are functionalized sequentially with polyethylenimine (PEI) and graphene oxide (GO) to form PEI/reduced graphene oxide (RGO) PU-DW sponges. The PEI/RGO PU-DW sponge consists of PEI/RGO sheets having numerous pores, with diameters ranging from 236 to 254nm. To further enhance hydrophobicity and absorption capacity of oil, PEI/RGO PU-DW sponge is further coated with 20% phenyltrimethoxysilane (PTMOS). The PTMOS/PEI/RGO PU-DW sponge absorbs various oils within 20s, with maximum absorption capacity values of 880% and 840% for bicycle chain oil and motorcycle engine oil, respectively. The absorbed oils were released completely by squeezing or immersed in hexane. The PTMOS/PEI/RGO PU-DW sponge efficiently separates oil/water mixtures through a flowing system. Having the advantages of faster absorption rate, reusability, and low cost, the PTMOS/PEI/RGO PU-DW sponge holds great potential as a superabsorbent for efficient removal and recovery of oil spills as well as for the separation of oil/water mixtures.

Photoluminescent graphene quantum dots for in vivo imaging of apoptotic cells.

Apoptosis (programmed cell death) is linked to many incurable neurodegenerative, cardiovascular and cancer causing diseases. Numerous methods have been developed for imaging apoptotic cells in vitro; however, there are few methods available for imaging apoptotic cells in live animals (in vivo). Here we report a novel method utilizing the unique photoluminescence properties of plant leaf-derived graphene quantum dots (GQDs) modified with annexin V antibody (AbA5) to form (AbA5)-modified GQDs (AbA5-GQDs) enabling us to label apoptotic cells in live zebrafish (Danio rerio). The key is that zebrafish shows bright red photoluminescence in the presence of apoptotic cells. The toxicity of the GQDs has also been investigated with the GQDs exhibiting high biocompatibility as they were excreted from the zebrafish's body without affecting its growth significantly at a concentration lower than 2 mg mL(-1) over a period of 4 to 72 hour post fertilization. The GQDs have further been used to image human breast adenocarcinoma cell line (MCF-7 cells), human cervical cancer cell line (HeLa cells), and normal human mammary epithelial cell line (MCF-10A). These results are indispensable to further the advance of graphene-based nanomaterials for biomedical applications.

Carbon nanodots prepared from o-phenylenediamine for sensing of Cu(2+) ions in cells.

A simple hydrothermal method was applied to prepare carbon nanodots (C dots) from o-phenylenediamine (OPD). The C dots exhibit photoluminescence at 567 nm when excited at 420 nm. In the presence of Cu(2+) ions, the colour of C dots changes from yellow to orange, with an increased PL intensity as a result of the formation of Cu(OPD)2 complexes on the surfaces of C dots. The D-band to G-band ratios of C dots in the absence and presence of 80 nM Cu(2+) ions are 1.31 and 4.75, respectively. The C dots allow the detection of Cu(2+) ions with linearity over a concentration range of 2-80 nM, with a limit of detection of 1.8 nM at a signal-to-noise ratio of 3. The cell viability values of A549, MCF-10A, and MDA-MB-231 cells treated with 3 µg mL(-1) of C dots are all greater than 99%, showing their great biocompatibility. Having great water dispersibility, photostability, chemical stability (against NaCl up to 0.5 M), great selectivity, and biocompatibility, the C dots have been employed for the localization of Cu(2+) ions in the cancer cells (A549 cells) treated with 10 µM Cu(2+) ions.

Sensitive and selective DNA probe based on "turn-on" photoluminescence of C-dots@RGO.

In this study, highly hydrophilic and photoluminescent sheets of reduced graphene oxide decorated with carbon dots (C-dots@RGO), methylene blue (MB), and a probe DNA have been used for the detection of DNA. The photoluminescence of C-dots@RGO is quenched by MB, which is restored in the presence of a target DNA. The combination of the C-dots@RGO, MB, and a DNA probe is selective for perfectly matched DNA over mismatched DNA, mainly because relative to single-stranded DNA, double-stranded DNA intercalates more strongly with MB, but interacts more weakly with RGO. In the presence of a target DNA, MB intercalates with the as-formed double-stranded DNA and is released from the surface of C-dots@RGO, leading to "turn-on" photoluminescence. The practicality of this assay has been validated by the determination of tumor suppressor gene BRCA1, with linearity over the concentration range from 25 to 250 nM and a limit of detection (LOD, at a signal-to-noise ratio of 3) of 14.6 nM. The C-dots@RGO probe provides higher specificity towards target DNA than towards common salts, carbohydrates, amino acids, and proteins found in real samples. Having the advantages of simplicity, cost-effectiveness, selectivity, and sensitivity, the DNA-P/C-dots@RGO-MB probe on microwells has been successfully employed for the detection of DNA, suggesting its potential for multiple analyses of DNA targets when various DNA probes are employed.

Synthesis of graphene-ZnO-Au nanocomposites for efficient photocatalytic reduction of nitrobenzene.

A simple hydrothermal method of preparing highly photocatalytic graphene-ZnO-Au nanocomposites (G-ZnO-Au NCs) has been developed. Zinc acetate and graphene oxide are reduced by catechin to form graphene-zinc oxide nanospheres (G-ZnO NSs; average diameter of (45.3 ± 3.7) nm) in the presence of ethylenediamine (EDA) as a stabilizing agent and gold nanorods (Au NRs) at 300 °C for 2 h. Then Au NRs are deposited onto as-formed G-ZnO NSs to form G-ZnO-Au NCs. Upon ultraviolet light activation, G-ZnO-Au NCs (4 mg mL(-1)) in methanol generates electron-hole pairs. Methanol (hydroxyl group) assists in trapping holes, enabling photogenerated electrons to catalyze reduction of nitrobenzene (NB) to aniline with a yield of 97.8% during a reaction course of 140 min. The efficiency of G-ZnO-Au NCs is 3.5- and 4.5-fold higher than those provided by commercial TiO2 and ZnO NSs, respectively. Surface assisted laser desorption/ionization mass spectrometry has been for the first time applied to detect the intermediates (nitrosobenzene and phenylhydroxylamine) and major product (aniline) of NB through photoelectrocatalytic or photocatalytic reactions. The result reveals that the reduction of NB to aniline is through nitrosobenzene to phenylhydroxylamine in the photoelectrocatalytic reaction, while via nitrosobenzene directly in the photocatalytic reaction. G-ZnO-Au NC photocatalyst holds great potential in removal of organic pollutants like NB and in the production of aniline.

Photoluminescent C-dots@RGO probe for sensitive and selective detection of acetylcholine.

We have developed a sensitive and selective photoluminescence (PL) quenching assay for the detection of acetylcholine (ACh) that uses reduced graphene oxide decorated with carbon dots (C-dots@RGO). The highly stable C-dots@RGO synthesized from catechin and graphene oxide through a hydrothermal reaction displays excitation-wavelength dependence of PL. Acetylcholinesterase (AChE) converts ACh to choline, which in turn is oxidized by choline oxidase (ChOx) to produce betaine and H2O2 that generates the reactive oxygen species (ROS). The as-produced ROS induces PL quenching of the C-dots@RGO through an etching process. With respect to sensitivity, the optimal reaction/sensing temperature and pH are 37 °C and 9.0, respectively, using C-dots@RGO (0.4 mg·mL(-1)) and AChE and ChOx at the activities of 0.5 and 0.1 unit·mL(-1), respectively. The PL intensity (excitation/emission wavelengths 365/440 nm) of the C-dots@RGO is inversely proportional to the concentration of ACh over a range of 0.05-10 nM (r = 0.997), with a limit of detection (signal-to-noise ratio 3) of 30 pM. We have validated this assay by determination of concentrations of ACh in plasma and blood samples, with results of 2.6 ± 0.8 nM (n = 5) and 6.8 ± 0.4 nM (n = 5), respectively. Our study opens an avenue for the detection of various analytes by use of C-dots@RGO in conjunction with different enzymes, substrates, and/or inhibitors.

Preparation and characterization of bismuth oxide nanoparticles-multiwalled carbon nanotube composite for the development of horseradish peroxidase based H2O2 biosensor.

In this work, preparation and characterization of a novel nanocomposite containing bismuth oxide (Bi(2)O(3)) nanoparticles and multiwalled carbon nanotubes (MWCNTs) was presented. Powder X-ray diffraction (XRD) studies revealed that as-synthesized Bi(2)O(3) nanoparticles are crystalline and belong to α-phase with monoclinic symmetry. Field emission scanning electron microscopy (FESEM) study results showed that the size of Bi(2)O(3) nanoparticles is 50 nm. Energy-dispersive X-ray (EDX) spectra of as-prepared Bi(2)O(3)-MWCNT nanocomposite displayed characteristic Bi and C peaks which confirmed the incorporation of Bi(2)O(3) with MWCNT. The prepared Bi(2)O(3)-MWCNT was also characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM) studies. The direct electron transfer of horseradish peroxidase (HRP) has been revealed at Bi(2)O(3)-MWCNT modified glassy carbon electrode (GCE). In order to firmly anchor the HRP molecules onto Bi(2)O(3)-MWCNT matrix, a thin layer of 1% nafion (NF) solution was coated as a binder. The fabricated NF/HRP/Bi(2)O(3)-MWCNT/GCE exhibits well defined quasi-reversible redox peaks at a formal potential (E(0)') of -0.326V vs. Ag/AgCl reference electrode in 0.05M phosphate buffer solution (PBS), pH 7. NF/HRP/Bi(2)O(3)-MWCNT film remarkably lowers the over potential for H(2)O(2) reduction than MWCNT, Bi(2)O(3)-MWCNT and unmodified GCEs. The proposed composite film exhibits quick amperometric i-t response (5s) towards H(2)O(2) in the linear range of 8.34-28.88mM with a sensitivity of 26.54 µA µM(-1)cm(-2). The developed NF/HRP/Bi(2)O(3)-MWCNT biosensor has a good operational stability and high selectivity towards H(2)O(2).

Multiwalled carbon nanotubes dispersed in carminic acid for the development of catalase based biosensor for selective amperometric determination of H(2)O(2) and iodate.

We report the preparation of stable dispersion of multiwalled carbon nanotubes (MWCNTs) using carminic acid (CA) as a dispersing agent. The transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM) results confirmed that MWCNT is well dispersed in CA aqueous solution and CA has been well adsorbed at MWCNT walls. Fourier transform infrared (FTIR) and UV-vis absorption spectra results also confirmed the adsorption of CA at MWCNT. To develop a highly selective amperometric biosensor for H(2)O(2) and iodate, the model enzyme catalase (CAT) was immobilized at CACNT modified glassy carbon electrode surface. The immobilized CAT exhibits well defined quasi reversible redox peaks at a formal potential (E°') of -0.559V in 0.05M pH 7 phosphate buffer solution (PBS). The proposed CAT/CACNT biosensor exhibits excellent amperometric response towards H(2)O(2) and iodate in the linear concentration range between 10µM to 3.2mM and 0.01-2.16mM. The sensitivity values are 287.98µAmM(-1)cm(-2) and 0.253mAmM(-1)cm(-2), respectively. Moreover, the developed CAT biosensor exhibits high affinity for H(2)O(2) and iodate with good selectivity.

Electrocatalysis and simultaneous determination of catechol and quinol by poly(malachite green) coated multiwalled carbon nanotube film.

Electrochemically active composite film that contains multiwalled carbon nanotubes (MWCNTs), Nafion (NF), and poly(malachite green) (PMG) has been synthesized on glassy carbon electrode (GCE), gold, and indium tin oxide (ITO) electrodes by potentiodynamic method. The presence of MWCNTs in the composite film (MWCNT-NF-PMG) enhances the surface coverage concentration (Γ) of PMG by fivefold. Similarly, an electrochemical quartz crystal microbalance study revealed enhancement in the deposition of PMG at MWCNT-NF film when compared with bare and only NF modified electrodes. The surface morphology of the composite film was studied using atomic force microscopy, which revealed that the PMG incorporated on MWCNT-NF film. The composite film exhibited enhanced electrocatalytic activity toward the mixture of biochemical compounds catechol and quinol. The electrocatalytic responses of analytes at MWCNT-NF-PMG composite film were measured using both cyclic voltammetry (CV) and differential pulse voltammetry (DPV). From electrocatalysis studies, well-separated voltammetric peaks were obtained at the composite film for catechol and quinol with a peak separation of 147mV. The sensitivity values of the composite film toward catechol and quinol by the DPV technique were 0.4 and 3.2mAmM(-1)cm(-2), respectively, which are higher than the values obtained by the CV technique. Similarly, the above-mentioned values are better than the previously reported electroanalytical values for the same analytes.

Toluidine blue adsorbed on alcohol dehydrogenase modified glassy carbon electrode for voltammetric determination of ethanol.

A novel toluidine blue O (TBO) adsorbed alcohol dehydrogenase (ADH) biocomposite film have been prepared through simple adsorption technique with the help of electrostatic interaction between oppositely charged layers. Nafion (NF) coating was made on top of the biocomposite film modified glassy carbon electrode (GCE) to protect ADH from leaching. The fabricated ADH/TBO/NF biocomposite electrode remains highly stable in the pH range from 4 to 13. More facile electron transfer process occurs at ADH/TBO/NF biocomposite than at TBO/NF film, which is obvious from the six folds increase in k(s) value. Maximum surface coverage concentration (Γ) of TBO is noticed at ADH/TBO/NF film, which is 82% higher than at TBO/NF and 15% higher than at ADH/TBO film modified GCEs. Electrochemical impedance spectroscopy studies reveal that ADH has been well immobilized in the biocomposite film. Scanning electron microscopy studies confirm the discriminate surface morphology of various components present in the biocomposite film. Cyclic voltammetry studies validate that ADH/TBO/NF biocomposite film exhibits excellent electrocatalytic activity for ethanol oxidation at low over potential (I(pa)=-0.14 V). The same studies show biocomposite film possesses a good sensitivity of 7.91 µAM(-1)cm(-2) for ethanol determination. This above sensitivity value is 17.40% higher than the sensitivity obtained for TBO/NF film (6.74 µAM(-1)cm(-2)). Further, using differential pulse voltammetry, a sensitivity of 1.70 µAM(-1)cm(-2) has been achieved for ADH/TBO/NF biocomposite film.

Amperometric glucose sensor based on glucose oxidase immobilized on gelatin-multiwalled carbon nanotube modified glassy carbon electrode.

We investigated the direct electrochemistry of glucose oxidase (GOx) at gelatin-multiwalled carbon nanotube (GCNT) modified glassy carbon electrode (GCE). GOx was covalently immobilized onto GCNT modified GCE through the well known glutaraldehyde (GAD) chemistry. The immobilized GOx showed a pair of well-defined reversible redox peaks with a formal potential (E(0)') of -0.40V and a peak to peak separation (ΔE(p)) of 47mV. The surface coverage concentration (Г) of GOx in GCNT/GOx/GAD composite film modified GCE was 3.88×10(-9)mol cm(-2) which indicates the high enzyme loading. The electron transfer rate constant (k(s)) of GOx immobilized onto GCNT was 1.08s(-1) which validates a rapid electron transfer processes. The composite film shows linear response towards 6.30 to 20.09mM glucose. We observed a good sensitivity of 2.47µA mM(-)(1)cm(-2) for glucose at the composite film. The fabricated biosensor displayed two weeks stability. Moreover, it shows no response to 0.5mM of ascorbic acid (AA), uric acid (UA), acetaminophen (AP), pyruvate (PA) and lactate (LA) which shows its potential application in the determination of glucose from human serum samples. The composite film exhibits excellent recovery for glucose in human serum at physiological pH with good practical applicability.

Poly(malachite green) at nafion doped multi-walled carbon nanotube composite film for simple aliphatic alcohols sensor.

Conductive composite film which contains nafion (NF) doped multi-walled carbon nanotubes (MWCNTs) along with the incorporation of poly(malachite green) (PMG) has been synthesized on glassy carbon electrode (GCE), gold and indium tin oxide (ITO) electrodes by potentiostatic methods. The presence of MWCNTs in the composite film (MWCNTs-NF-PMG) enhances surface coverage concentration (Gamma) of PMG to approximately 396%, and increases the electron transfer rate constant (k(s)) to approximately 305%. Similarly, electrochemical quartz crystal microbalance study reveals the enhancement in the deposition of PMG at MWCNTs-NF film. The surface morphology of the composite film deposited on ITO electrode has been studied using scanning electron microscopy (SEM) and scanning tunneling microscopy (STM). These two techniques reveal that the PMG incorporated on MWCNTs-NF film. The MWCNTs-NF-PMG composite film also exhibits promising enhanced electrocatalytic activity towards the simple aliphatic alcohols such as methanol, ethanol and propanol. The electroanalytical responses of analytes at NF-PMG and MWCNTs-NF-PMG films were measured using both cyclic voltammetry (CV) and differential pulse voltammetry (DPV). From electroanalytical studies, well defined voltammetric peaks have been obtained at MWCNTs-NF-PMG composite film for methanol, ethanol and propanol at Epa=609, 614 and 602mV respectively. The sensitivity of MWCNTs-NF-PMG composite film towards methanol, ethanol and propanol in CV technique are 0.59, 0.36 and 0.92microAmM(-1)cm(-2) respectively, which are higher than NF-PMG film. Further, the sensitivity values obtained using DPV are higher than the values obtained using CV technique.

Nanomaterials - acetylcholinesterase enzyme matrices for organophosphorus pesticides electrochemical sensors: a review.

Acetylcholinesterase (AChE) is an important cholinesterase enzyme present in the synaptic clefts of living organisms. It maintains the levels of the neurotransmitter acetylcholine by catalyzing the hydrolysis reaction of acetylcholine to thiocholine. This catalytic activity of AChE is drastically inhibited by trace amounts of organophosphorus (OP) pesticides present in the environment. As a result, effective monitoring of OP pesticides in the environment is very desirable and has been done successfully in recent years with the use of nanomaterial-based AChE sensors. In such sensors, the enzyme AChE has been immobilized onto nanomaterials like multiwalled carbon nanotubes, gold nanoparticles, zirconia nanoparticles, cadmium sulphide nano particles or quantum dots. These nanomaterial matrices promote significant enhancements of OP pesticide determinations, with the thiocholine oxidation occurring at much lower oxidation potentials. Moreover, nanomaterial-based AChE sensors with rapid response, increased operational and long storage stability are extremely well suited for OP pesticide determination over a wide concentration range. In this review, the unique advantages of using nanomaterials as AChE immobilization matrices are discussed. Further, detection limits, sensitivities and correlation coefficients obtained using various electroanalytical techniques have also been compared with chromatographic techniques.