Electrochemical based quantification of bacterial growth in media using square wave voltammetry and low cost screen printed electrodes.

A novel method for determining the yield of bacterial growth using square wave voltammetry and screen printed electrodes is described here. This procedure was shown to be a reliable and accurate way to quickly determine the level of bacterial growth within culturing media and these results suggest that the combination of such sensors and the application of square wave voltammetry is suitable for applications such as within a bioreactor where the rapid determination of bacterial growth may be necessary.

Metal Electrocatalysts for Hydrogen Production in Water Splitting.

The rising demand for fossil fuels and the resulting pollution have raised environmental concerns about energy production. Undoubtedly, hydrogen is the best candidate for producing clean and sustainable energy now and in the future. Water splitting is a promising and efficient process for hydrogen production, where catalysts play a key role in the hydrogen evolution reaction (HER). HER electrocatalysis can be well performed by Pt with a low overpotential close to zero and a Tafel slope of about 30 mV dec-1. However, the main challenge in expanding the hydrogen production process is using efficient and inexpensive catalysts. Due to electrocatalytic activity and electrochemical stability, transition metal compounds are the best options for HER electrocatalysts. This study will focus on analyzing the current situation and recent advances in the design and development of nanostructured electrocatalysts for noble and non-noble metals in HER electrocatalysis. In general, strategies including doping, crystallization control, structural engineering, carbon nanomaterials, and increasing active sites by changing morphology are helpful to improve HER performance. Finally, the challenges and future perspectives in designing functional and stable electrocatalysts for HER in efficient hydrogen production from water-splitting electrolysis will be described.

Understanding the bonding mechanisms of organic molecules deposited on graphene for biosensing applications.

Graphene is an ideal material for biosensors due to the large surface area for multiple bonding sites, the high electrical conductivity allowing for high sensitivity, and the high tensile strength providing durability in fabricated sensor devices. For graphene to be successful as a biosensing platform, selectivity must be achieved through functionalization with specific chemical groups. However, the device performance and sensor sensitivity must still be maintained after functionalization, which can be challenging. We compare phenyl amine and 1,5-diaminonaphthalene functionalization methods for chemical vapor deposition grown graphene, both used to obtain graphene modified with amine groups-which is required for surface attachment of highly selective antibody bio-receptors. Through atomic force microscopy (AFM), Raman spectroscopy, and time-of-flight secondary ion mass spectrometry imaging of co-located areas, the chemistry, thickness, and coverage of the functional groups bound to the graphene surface have been comprehensively analyzed. We demonstrate the modification of functionalized graphene using AFM, which unexpectedly suggests the removal of covalently bonded functional groups, resulting in a "recovered" graphene structure with reduced disorder, confirmed with Raman spectroscopy. This removal explains the decrease in the ID/IG ratio observed in Raman spectra from other studies on functionalized graphene after mechanical strain or a chemical reaction and reveals the possibility of reverting to the non-functionalized graphene structure. Through this study, preferred functionalization processes are recommended to maintain the performance properties of graphene as a biosensor.

MIL-101(Cr), an Efficient Heterogeneous Catalyst for One Pot Synthesis of 2,4,5-tri Substituted Imidazoles under Solvent Free Conditions.

A chromium-containing metal-organic framework (MOF), MIL-101 (Chromium(III) benzene-1,4-dicarboxylate), was used to catalyze the one pot, three component synthesis of some 2,4,5-trisubstituted imidazoles under solvent-free conditions. The advantages of using this heterogeneous catalyst include short reaction time, high yields, easy and quick isolation of catalyst and products, low amount of catalyst needed, and that the addition of solvent, salt, and additives are not needed. This catalyst is highly efficient and can be recovered at least 5 times with a slight loss of efficiency. The structure of the metal-organic frameworks (MOF) was confirmed by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (HNMR) were performed to confirm some of the synthesized products. Experimental data indicated that the optimum amount of catalyst was 5 mg for benzil (1 mmol), 4-chlorobenzaldehyde (1 mmol), and ammonium acetate (2.5 mmol), and the synthetic route to the various imidazoles is performed in 10 min by 95% yield, an acceptable result rivalling those of other catalysts.

Assessing Surface Coverage of Aminophenyl Bonding Sites on Diazotised Glassy Carbon Electrodes for Optimised Electrochemical Biosensor Performance.

Electrochemical biosensors using carbon-based electrodes are being widely developed for the detection of a range of different diseases. Since their sensitivity depends on the surface coverage of bioreceptor moieties, it necessarily depends on the surface coverage of amine precursors. Electrochemical techniques, using ferrocene carboxylic acid as a rapid and cheap assay, were used to assess the surface coverage of amino-phenyl groups attached to the carbon electrode. While the number of electrons transferred in the first step of diazotisation indicated a surface coverage of 8.02 ± 0.2 × l0-10 (mol/cm2), and those transferred in the second step, a reduction of nitrophenyl to amino-phenyl, indicated an amine surface coverage of 4-5 × l0-10 (mol/cm2), the number of electrons transferred during attachment of the amine coupling assay compound, ferrocene carboxylic acid, indicated a much lower available amine coverage of only 2.2 × l0-11 (mol/cm2). Furthermore, the available amine coverage was critically dependent upon the number of cyclic voltammetry cycles used in the reduction, and thus the procedures used in this step influenced the sensitivity of any subsequent sensor. Amine coupling of a carboxyl terminated anti-beta amyloid antibody specific to Aß(1-42) peptide, a potential marker for Alzheimer's disease, followed the same pattern of coverage as that observed with ferrocene carboxylic acid, and at optimum amine coverage, the sensitivity of the differential pulse voltammetry sensor was in the range 0-200 ng/mL with the slope of 5.07 µA/ng.mL-1 and R2 = 0.98.

Graphene based electrochemical immunosensor for the ultra-sensitive label free detection of Alzheimer's beta amyloid peptides Aß(1-42).

An immunosensor capable of high sensitivity detection of beta-amyloid peptides, shown to be a reliable biomarker for Alzheimer's disease, has been developed using screen printed graphene electrodes (SPGEs) modified with ultra-thin layers of polymerised 1,5-diaminonaphthalene (pDAN). Electropolymerization of 1,5-diaminonaphthalene (DAN) was performed to coat the graphene screen printed electrodes in a continuous polymer layer with controlled thickness. The surface characteristics of pristine graphene and polymer modified graphene electrodes were examined using Raman and X-ray photoelectron spectroscopy. The effects of polymer thickness on the electron transfer rates were investigated. An immunosensor for selective detection of beta amyloid peptides Aß(1-42) was developed via biofunctionalization of the pDAN modified SPGE with the anti-beta amyloid antibody used as the peptide bioreceptor. The immunosensor has been used for specific detection of Aß(1-42) with a linear range of 1 pg mL-1 to 1000 pg mL-1 and showed 1.4 pg mL-1 and 4.25 pg mL-1 detection and quantification limit, respectively. The biosensor was further validated for the analysis of spiked human plasma. The immunosensor enables rapid, accurate, precise, reproducible and highly sensitive detection of Aß(1-42) using a low-cost SPGE platform, which opens the possibilities for diagnostic ex vivo applications and research-based real time studies.

A Facile Method for the Non-Covalent Amine Functionalization of Carbon-Based Surfaces for Use in Biosensor Development.

Affinity biosensors based on graphene field-effect transistor (GFET) or resistor designs require the utilization of graphene's exceptional electrical properties. Therefore, it is critical when designing these sensors, that the electrical properties of graphene are maintained throughout the functionalization process. To that end, non-covalent functionalization may be preferred over covalent modification. Drop-cast 1,5-diaminonaphthalene (DAN) was investigated as a quick and simple method for the non-covalent amine functionalization of carbon-based surfaces such as graphene, for use in biosensor development. In this work, multiple graphene surfaces were functionalized with DAN via a drop-cast method, leading to amine moieties, available for subsequent attachment to receptor molecules. Successful modification of graphene with DAN via a drop-cast method was confirmed using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and real-time resistance measurements. Successful attachment of receptor molecules also confirmed using the aforementioned techniques. Furthermore, an investigation into the effect of sequential wash steps which are required in biosensor manufacture, on the presence of the DAN layer, confirmed that the functional layer was not removed, even after multiple solvent exposures. Drop-cast DAN is thus, a viable fast and robust method for the amine functionalization of graphene surfaces for use in biosensor development.

Adsorption of Lead Ions by a Green AC/HKUST-1 Nanocomposite.

A new nanocomposite consisting of activated carbon (AC) from the Cortaderia selloana flower and copper-based metal-organic framework (HKUST-1) was synthesized through a single-step solvothermal method and applied for the removal of lead ions from aqueous solution through adsorption. The nanocomposite, AC/HKUST-1, was characterized by Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR), and Energy-Dispersive X-ray Spectroscopy (EDX) methods. The SEM images of both HKUST-1 and AC/HKUST-1 contain octahedral crystals. Different factors affecting adsorption processes, such as solution pH, contact time, adsorbent dose, and initial metal pollution concentration, were studied. The adsorption isotherm was evaluated with Freundlich and Langmuir models, and the latter was fitted with the experimental data on adsorption of lead ion. The adsorption capacity was 249.4 mg g-1 for 15 min at pH 6.1, which is an excellent result rivalling previously reported lead adsorbents considering the conditions. These nanocomposites show considerable potential for use as a functional material in the ink formulation of lead sensors.

Ultrathin Functional Polymer Modified Graphene for Enhanced Enzymatic Electrochemical Sensing.

Grafting thin polymer layers on graphene enables coupling target biomolecules to graphene surfaces, especially through amide and aldehyde linkages with carboxylic acid and primary amine derivatives, respectively. However, functionalizing monolayer graphene with thin polymer layers without affecting their exceptional electrical properties remains challenging. Herein, we demonstrate the controlled modification of chemical vapor deposition (CVD) grown single layer graphene with ultrathin polymer 1,5-diaminonaphthalene (DAN) layers using the electropolymerization technique. It is observed that the controlled electropolymerization of DAN monomer offers continuous polymer layers with thickness ranging between 5⁻25 nm. The surface characteristics of pure and polymer modified graphene was examined. As anticipated, the number of surface amine groups increases with increases in the layer thickness. The effects of polymer thickness on the electron transfer rates were studied in detail and a simple route for the estimation of surface coverage of amine groups was demonstrated using the electrochemical analysis. The implications of grafting ultrathin polymer layers on graphene towards horseradish peroxidase (HRP) enzyme immobilization and enzymatic electrochemical sensing of H2O2 were discussed elaborately.