Manzar Sohail

Potentially bioactive organotin(IV) compounds: synthesis, characterization, in vitro bioactivities and interaction with SS-DNA.

Fourteen new organotin(IV) complexes with general formula R2SnL2 or R3SnL where R = CH3, C2H5, C4H9, C6H5, C6H11, CH2-C6H5, C(CH3)3, C8H17 and L = N-[(2-methoxyphenyl)]-4-oxo-4-[oxy]butanamide were synthesized and characterized by elemental analyses, FT-IR, NMR ((1)H, (13)C and (119)Sn), mass spectrometry and single crystal X-ray structural analysis. Crystallographic data for four triorganotin(IV) complexes (R3SnL, R = CH3, C2H5, C4H9, CH2-C6H5) showed the tin has approximate trigonal bipyramidal geometry with the R groups in the trigonal plane. The carboxylate groups of ligands L bridge adjacent tin atoms, resulting in polymeric chains. In case of the diorganotin(IV) derivatives a six-coordinate geometry at the tin atom is proposed from spectroscopic evidence. The Me-Sn-Me bond angle in complex 7 was determined from the (2)J[(119)Sn-(1)H] value as 166.3° that falls in the range of six-coordinate geometry. The ligand and its complexes (1-14) were screened for their antimicrobial, antitumor, cytotoxic and antileishmanial activities and found to be biologically active. The ligand and its complexes bind to DNA via intercalative interactions resulting in hypochromism and minor bathochromic shifts as confirmed by UV-visible spectroscopy. Based on in vitro studies such as the potato disc method, the synthesized compounds were found to possess significant antitumor activity. Also, from cytotoxicity and DNA interaction studies, these compounds can also be used for the prevention and treatment of cancer. Gel electrophoresis assay was used to investigate the damage to double stranded super coiled plasmid pBR322 DNA by the synthesized compounds and compounds 1 and 7 were found to cause the maximum damage. All the synthesized compounds exhibit strong antileishmanial activity that was even higher than that of Amphotericin B, with significant cytotoxicity. This study, therefore, demonstrated the potential use of these compounds as source of novel agents for the treatment of leishmaniasis.

Neuropeptides encoded by the genomes of the Akoya pearl oyster Pinctata fucata and Pacific oyster Crassostrea gigas: a bioinformatic and peptidomic survey

BackgroundOysters impart significant socio-ecological benefits from primary production of food supply, to estuarine ecosystems via reduction of water column nutrients, plankton and seston biomass. Little though is known at the molecular level of what genes are responsible for how oysters reproduce, filter nutrients, survive stressful physiological events and form reef communities. Neuropeptides represent a diverse class of chemical messengers, instrumental in orchestrating these complex physiological events in other species.ResultsBy a combination of in silico data mining and peptide analysis of ganglia, 74 putative neuropeptide genes were identified from genome and transcriptome databases of the Akoya pearl oyster, Pinctata fucata and the Pacific oyster, Crassostrea gigas, encoding precursors for over 300 predicted bioactive peptide products, including three newly identified neuropeptide precursors PFGx8amide, RxIamide and Wx3Yamide. Our findings also include a gene for the gonadotropin-releasing hormone (GnRH) and two egg-laying hormones (ELH) which were identified from both oysters. Multiple sequence alignments and phylogenetic analysis supports similar global organization of these mature peptides. Computer-based peptide modeling of the molecular tertiary structures of ELH highlights the structural homologies within ELH family, which may facilitate ELH activity leading to the release of gametes.ConclusionOur analysis demonstrates that oysters possess conserved molluscan neuropeptide domains and overall precursor organization whilst highlighting many previously unrecognized bivalve idiosyncrasies. This genomic analysis provides a solid foundation from which further studies aimed at the functional characterization of these molluscan neuropeptides can be conducted to further stimulate advances in understanding the ecology and cultivation of oysters.

Thin layer coulometric determination of nitrate in fresh waters

A nitrate ion-selective electrode (ISE) employing a permeable tubular membrane impregnated with a conventional ISE cocktail has been used successfully in the coulometric analysis of nitrate in fresh waters. The liquid ISE membrane comprising a nitrate ionophore [tridodecylmethylammonium nitrate (TDMAN)], lipophilic electrolyte [tetradodecyl-ammoniumtetrakis(4-chlorophenyl)borate (ETH 500)] and plasticizer [bis(3-ethyl-hexyl)sebacate (DOS)] was supported on a porous polypropylene tube. Coulometric analysis with the tubular membrane ISE showed that nitrate could be detected in the range 10-100 μM with a precision of 2.3% relative standard deviation (RSD), limit of detection of 1.1 μM and relative accuracy of 4.4% compared to a certified reference material (CRM) Lake sample.

Evidence for a Surface Confined Ion-to-Electron Transduction Reaction in Solid-Contact Ion-Selective Electrodes Based on Poly(3-octylthiophene)

The ion-to-electron transduction reaction mechanism at the buried interface of the electrosynthesized poly(3-octylthiophene) (POT) solid-contact (SC) ion-selective electrode (ISE) polymeric membrane has been studied using synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS), near edge X-ray absorption fine structure (NEXAFS), and electrochemical impedance spectroscopy (EIS)/neutron reflectometry (NR). The tetrakis[3,5-bis(triflouromethyl)phenyl]borate (TFPB(-)) membrane dopant in the polymer ISE was transferred from the polymeric membrane to the outer surface layer of the SC on oxidation of POT but did not migrate further into the oxidized POT SC. The TFPB(-) and oxidized POT species could only be detected at the outer surface layer (≤14 Ǻ) of the SC material, even after oxidation of the electropolymerized POT SC for an hour at high anodic potential demonstrating that the ion-to-electron transduction reaction is a surface confined process. Accordingly, this study provides the first direct structural evidence of ion-to-electron transduction in the electropolymerized POT SC ISE by proving TFPB(-) transport from the polymeric ISE membrane to the oxidized POT SC at the buried interface of the SC ISE. It is inferred that the performance of the POT SC ISE is independent of the thickness of the POT SC but is instead contingent on the POT SC surface reactivity and/or electrical capacitance of the POT SC. In particular, the results suggest that the electropolymerized POT conducting polymer may spontaneously form a mixed surface/bulk oxidation state, which may explain the unusually high potential stability of the resulting ISE. It is anticipated that this new understanding of ion-to-electron transduction with electropolymerized POT SC ISEs will enable the development of new and improved devices with enhanced analytical performance attributes.

Synthesis, crystal structure description, electrochemical and DNA binding studies of ‘paddlewheel’ copper(II) carboxylate

Dimeric paddlewheel copper(II) complex, pyCu(phenylacetate)4Cupy, where py = pyridine, has been prepared and the crystal structure determined. Single crystal X-ray diffraction (XRD) revealed three crystallographically independent molecules in the unit cell. The geometry around each Cu(II) is square pyramidal with monodentate pyridine at the apical and bidentate carboxylates in the equatorial positions. The supramolecular structure of the complex arises primarily as a result of C–H⋯O along with some contribution of C–H⋯C interactions, resulting in the preferential alignment of the molecules along the c-axis. The purity of the crystalline complex has been confirmed through powder XRD study. Electrochemical solution study of the complex in aqueous DMSO (1 : 4) showed two redox couples corresponding to Cu(III)/Cu(II) and Cu(II)/Cu(I) irreversible electron transfer. The values of various voltammetric variables, such as diffusion coefficient (Do), heterogeneous rate constant (k°), formal potential (E°), and charge transfer coefficient (α), have been calculated before and after DNA addition. DNA binding of the complex has been explored through cyclic voltammetry, UV–visible spectrophotometry, and viscosity measurement which have exhibited a mixed electrostatic and intercalative mode of interaction. Cyclic voltammetry indicated self-induced redox activation and potential anticancer ability of the complex, supported by UV–visible spectrophotometry as well as viscometry. Graphical Abstract

Coulometric Sodium Chloride Removal System with Nafion Membrane for Seawater Sample Treatment

Seawater analysis is one of the most challenging in the field of environmental monitoring, mainly due to disparate concentration levels between the analyte and the salt matrix causing interferences in a variety of analytical techniques. We propose here a miniature electrochemical sample pretreatment system for a rapid removal of NaCl utilizing the coaxial arrangement of an electrode and a tubular Nafion membrane. Upon electrolysis, chloride is deposited at the Ag electrode as AgCl and the sodium counterions are transported across the membrane. This cell was found to work efficiently at potentials higher than 400 mV in both stationary and flow injection mode. Substantial residual currents observed during electrolysis were found to be a result of NaCl back diffusion from the outer side of the membrane due to insufficient permselectivity of the Nafion membrane. It was demonstrated that the residual current can be significantly reduced by adjusting the concentration of the outer solution. On the basis of ion chromatography results, it was found that the designed cell used in flow injection electrolysis mode reduced the NaCl concentration from 0.6 M to 3 mM. This attempt is very important in view of nutrient analysis in seawater where NaCl is a major interfering agent. We demonstrate that the pretreatment of artificial seawater samples does not reduce the content of nitrite or nitrate ions upon electrolysis. A simple diffusion/extraction steady state model is proposed for the optimization of the electrolysis cell characteristics.

Sonochemical assisted synthesis of RGO/ZnO nanowire arrays for photoelectrochemical water splitting

This article presented the synthesis of a hybrid nanoarchitecture material composed of reduced graphene oxide (RGO) multiple sheets and ZnO nanowire arrays (NWAs) formed on an arbitrary ZnO coated fluorine doped tin oxide (FTO) substrates via pulse sonication and hydrothermal approach. The NWAs have high aspect-ratio, high density, apt positioning and well-ordered formation. FESEM images demonstrated that RGO layers have been effectively intercalated between and on the accessible surfaces of the ZnO NWAs. The diameter of ZnO nanowires is 80-150nm and length about 1-2μm. Raman spectrum of hybrid material exhibited characteristic D and suppressed G peaks for graphene and E2 mode at 437cm-1 for ZnO NWAs. UV-visible spectrum indicated slight red shift towards visible range after formation of RGO/ZnO NWAs heterostructure. The Photoelectrochemical results indicated higher current densities for RGO/ZnO NWAs heterostructure due to water oxidation reaction at the working electrode compared to pristine ZnO NWAs.

Nitrate biosensors and biological methods for nitrate determination

The inorganic nitrate (NO3‾) anion is present under a variety of both natural and artificial environmental conditions. Nitrate is ubiquitous within the environment, food, industrial and physiological systems and is mostly present as hydrated anion of a corresponding dissolved salt. Due to the significant environmental and toxicological effects of nitrate, its determination and monitoring in environmental and industrial waters are often necessary. A wide range of analytical techniques are available for nitrate determination in various sample matrices. This review discusses biosensors available for nitrate determination using the enzyme nitrate reductase (NaR). We conclude that nitrate determination using biosensors is an excellent non-toxic alternative to all other available analytical methods. Over the last fifteen years biosensing technology for nitrate analysis has progressed very well, however, there is a need to expedite the development of nitrate biosensors as a suitable alternative to non-enzymatic techniques through the use of different polymers, nanostructures, mediators and strategies to overcome oxygen interference.

Polypyrrole-based bilayer nitrate amperometric biosensor with an integrated permselective poly-ortho-phenylenediamine layer for exclusion of inorganic interferences

A bilayer amperometric nitrate biosensor with an integrated permselective layer has been developed for exclusion of inorganic anion and cation interferences. The inner PPy(polypyrrole)-NaR-NADH layer of the biosensor is formed by galvanostatic polymerization of pyrrole (Py) in presence of nitrate reductase (NaR) and nicotinamide adenine dinucleotide (NADH), followed by formation of the outer permselective poly-ortho-phenylenediamine (P-o-PDA) layer by potentiodynamic polymerization of ortho-phenylenediamine (o-PDA). The exclusion efficiency (E(eff)) of the outer layer in rejecting inorganic cation and anion interferences is evaluated by a new proposed relationship. 73-87% and 47-84% of anion and cation interferences, respectively, were efficiently rejected with the permselective layer. Further improvement in the exclusion efficiency for cations was accomplished by combining the use of the outer layer with the addition of 1mM EDTA into the measurement solution. The addition of EDTA improved the E(eff) achieved for cation rejection by 10-40% to give net E(eff) of 89-94%. The inclusion of the outer layer also aided the retention of NaR and NADH in the inner PPy-NaR-NADH layer and, hence, enabled improved amperometric detection of nitrate, achieving a detection limit of 0.20 μM and a linear concentration range of 10-500 μM with a 3.4%rsd (n=10).

Transport and accumulation of ferrocene tagged poly(vinyl chloride) at the buried interfaces of plasticized membrane electrodes

Cyclic voltammetry (CV), synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS) and near edge X-ray absorption fine structure (NEXAFS) show that oxidation of ferrocene tagged PVC induces an accumulation of high molecular weight polymer at the buried interface between the substrate electrode and the plasticized membrane.