Solvent dependent dimercaptothiadiazole monolayers on gold electrode for the simultaneous determination of uric acid and ascorbic acid

Dimercaptothiadiazole compound, 2,5-dimercapto-1,3,4-thiadiazole (DMcT) forms ‘thin’ monolayers on Au electrode when it was adsorbed from methanol, ethanol or DMSO solutions while it forms ‘thick’ layers on Au electrode from an aqueous solution under identical experimental conditions. Thick DMcT layers formed from aqueous solution effectively blocks the redox reaction of couple in contrast to thin DMcT monolayers. The monolayer thickness did not vary when structurally related DMcT compounds, 5-methyl-1,3,4-thiadiazole-2-thiol or 5-amino-1,3,4-thiadiazole-2-thiol was adsorbed from aqueous and non-aqueous solutions. This indicates that the presence of two thiol groups in DMcT plays a crucial role in the formation of thick and thin DMcT layers on Au electrode when it was adsorbed from aqueous and non-aqueous solutions. Methanol, ethanol, or DMSO solution of DMcT is considered as strong acid because these solvents are able to deprotonate DMcT into DMcT⁻ and thus thin monolayers formed on Au electrode. The deprotonating ability of these solvents was further verified from the observed absorption spectrum characteristic of DMcT⁻ species. On the other hand, an aqueous solution of DMcT is less acidic due to weak deprotonation of DMcT by water and thus DMcT forms thick layer on Au electrode. Interestingly, thin DMcT monolayers formed from non-aqueous solvents separates the voltammetric signals of uric acid and ascorbic acid while thick DMcT layers formed from aqueous solution fails to separate them.     

Comments on “Crystal growth,spectral, optical,and thermal characterization of glycyl-l-alanine hydrochloride (GLAH) single crystal”

The authors of the title paper (J Therm Anal Calorim 2012,110:873–878) report to have grown a dipeptide hydrochloride crystal namely glycyl-l-alanine hydrochloride by the slow evaporation of an aqueous solution containing stoichiometric amounts of l-alanine and glycine and an excess of hydrochloric acid. In this letter, we prove that no such dipeptide hydrochloride can be crystallized simply by mixing two amino acids in aqueous hydrochloric acid.     

Nanostructured electropolymerized film of 5-amino-2-mercapto-1,3,4-thiadiazole on glassy carbon electrode for the selective determination of l-cysteine

We report the electropolymerization of 5-amino-2-mercapto-1,3,4-thiadiazole (AMT) in 0.1 M H₂SO₄ on glassy carbon electrode (GCE) and utilization of the resulting polymer film for the selective determination of l-cysteine (CY) at physiological pH for the first time. The electropolymerized film was characterized by cyclic voltammetry (CV), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). AFM image shows a homogeneous film containing spherical structure with a thickness of ～25 nm for p-AMT deposited by 15 cycles. The binding energies at 163.5, 400.2 and 398.8 eV in the XPS corroborate that the p-AMT was linked by S–S, HN–NH and NN groups. The p-AMT film successfully separates the voltammetric signals of CY and ascorbic acid (AA) with a potential difference of 480 mV which is higher than the previous reports.     

Electrocatalysis of a Europium-Dependent Bacterial Methanol Dehydrogenase with Its Physiological Electron-Acceptor Cytochrome cGJ

We report the first electrochemical study of a lanthanoid-dependent methanol dehydrogenase (Eu-MDH) from the acidophilic verrucomicrobial methanotroph Methylacidiphilum fumariolicum SolV with its own physiological cytochrome c_GJ electron acceptor. Eu-MDH harbours a redox active 2,7,9-tricarboxypyrroloquinoline quinone (PQQ) cofactor which is non-covalently bound but coordinates trivalent lanthanoid elements including Eu³⁺. Eu-MDH and the cytochrome were co-adsorbed with the biopolymer chitosan and cast onto a mercaptoundecanol (MU) monolayer modified Au working electrode. Cyclic voltammetry of cytochrome c_GJ reveals a well-defined quasi-reversible Fe^III/II redox couple at +255 mV vs. NHE at pH 7.5 and this response is pH independent. The reversible one-electron response of the cytochrome c_GJ transforms into a sigmoidal catalytic wave in the presence of Eu-MDH and its substrates (methanol or formaldehyde). The catalytic current was pH-dependent and pH 7.3 was found to be optimal. Kinetic parameters (pH dependence, activation energy) obtained by electrochemistry show the same trends as those obtained from an artificial phenazine ethosulfate/dichlorophenol indophenol assay.     

“Click” Silica-Supported Sulfonic Acid Catalysts with Variable Acid Strength and Surface Polarity

Solid acid catalysts are central in our chemical industry and are major players in the valorization of bioresources. However, there is still a need to develop solid acid catalysts with enhanced acid strength and improved, or tunable, physicochemical profile to enhance the efficiency and sustainability of chemical processes. Here, a modular approach to tune the acid strength and surface polarity of silica-supported sulfonic acid catalysts, based on a versatile copper-catalyzed azide–alkyne cycloaddition (CuAAC)-based anchoring scheme, is presented. The CuAAC-formed triazole link was used to enhance the activity of the grafted sulfonic acids and to pair the acid sites with secondary hydrophobic functions. The beneficial effects of both the triazolium link and the paired hydrophobic site, as well as the optimal positioning of the sulfonic moiety on the triazole ring, are discussed in model esterification reactions.     

Charge-transfer interaction of aromatic thiols with 2,3-dichloro-5,6-dicyano-p-benzoquinone: spectral and quantum mechanical studies

Charge-transfer (CT) complexes formed between aromatic thiol donors (thiophenol (TP), benzene-1,4-dithiol (BDT), p-aminothiophenol (ATP), p-hydroxythiophenol (HTP), and p-toluenethiol (TTP)) and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) as an acceptor were studied spectrophotometrically in dichloromethane. Addition of aromatic thiols in dichloromethane to DDQ leads to the formation of colored solutions that exhibit a very broad absorption band in the range 440-800 nm and a band in the region 300-400 nm. On the basis of the energies of LUMO and HOMO from quantum mechanical calculations, the broad band observed in the visible region was assigned to the pi*(a2) <-- pi(b1) transition and a band observed between 300 and 400 nm was assigned to the pi*(a2) <-- pi(a2) transition. The solid CT complexes of aromatic thiols and DDQ were prepared and characterized by FT-IR spectroscopy. The stoichiometry of the CT complexes was determined by Job's continuous variation method. The association constant (KCT), molar extinction coefficient (epsilon), oscillator strength (f), and transition dipole moment (micro) values were calculated from the electronic spectra. The vertical ionization potentials (ID) of the donors were calculated from their corresponding lambdaCT. Quantum mechanical (QM) calculations were performed to determine the ionization potential and the energies of the highest occupied molecular orbital (HOMO) of donors and lowest unoccupied molecular orbital (LUMO) of an acceptor.     

Biofilm inhibition and antimicrobial action of lipopeptide biosurfactant produced by heavy metal tolerant strain Bacillus cereus NK1

Biosurfactants are worthful microbial amphiphilic molecules with efficient surface-active and biological properties applicable to several industries and processes. Among them lipopeptides represent a class of microbial surfactants with increasing scientific, therapeutic and biotechnological interests. A heavy metal tolerant Bacillus strain has been isolated and the biofilm inhibition and antimicrobial activity of biosurfactant produced by the strain have been studied. Biosurfactant production was confirmed by the conventional screening methods including hemolytic activity, drop collapsing test, oil displacement test, emulsification and lipase production assays. The biosurfactant produced by this strain was a lipopeptide and exhibited strong surface activity. The biosurfactant has been characterized using FTIR, TLC and HPLC. The minimum active dose of this biosurfactant when compared with the other chemical surfactants was found as 0.150±0.06 μg. The critical micelle concentration was found to be 45 mg/l. The biosurfactant was found to be stable and active over a wide range of pH, temperature and NaCl concentration. It was also able to emulsify a wide range of hydrocarbons and oils thereby extending its application for the bioremediation of oil contaminated sites. The biosurfactant exhibited significant reduction in biofilm formation by pathogens and showed potent antimicrobial activity against various gram positive, gram negative bacteria and fungi. Agar diffusion assay for heavy metal resistance showed that the isolate was resistant to ferrous, lead and zinc. Considering the biofilm inhibition and antimicrobial property of biosurfactant, it can be utilized as a potential therapeutic molecule for numerous microbial infections. The heavy metal resistance of the strain can also be harnessed as an invaluable biological tool for in situ bioremediation.     

Biosynthesis, purification and characterization of silver nanoparticles using Escherichia coli

The application of nanoscale materials and structures, usually ranging from 1 to 100 nanometers (nm), is an emerging area of nanoscience and nanotechnology. Nanomaterials may provide solutions to technological and environmental challenges in the areas of solar energy conversion, catalysis, medicine, and water-treatment. The development of techniques for the controlled synthesis of nanoparticles of well-defined size, shape and composition, to be used in the biomedical field and areas such as optics and electronics, has become a big challenge. Development of reliable and eco-friendly processes for synthesis of metallic nanoparticles is an important step in the field of application of nanotechnology. One of the options to achieve this objective is to use ‘natural factories’ such as biological systems. This study reports the optimal conditions for maximum synthesis of silver nanoparticles (AgNPs) through reduction of Ag⁺ ions by the culture supernatant of Escherichia coli. The synthesized silver nanoparticles were purified by using sucrose density gradient centrifugation. The purified sample was further characterized by UV–vis spectra, fluorescence spectroscopy and TEM. The purified solution yielded the maximum absorbance peak at 420 nm and the TEM characterization showed a uniform distribution of nanoparticles, with an average size of 50 nm. X-ray diffraction (XRD) spectrum of the silver nanoparticles exhibited 2θ values corresponding to the silver nanocrystal. The size-distribution of nanoparticles was determined using a particle-size analyzer and the average particle size was found to be 50 nm. This study also demonstrates that particle size could be controlled by varying the parameters such as temperature, pH and concentration of AgNO₃.