Optochemical sensing of hydrogen chloride gas using meso-tetramesitylporphyrin deposited glass plate

Meso-tetramesitylporphyrin (MTMP) deposited glass plate (solid state sensor) was used to sense hydrogen chloride (HCl) gas based on optochemical method. Exposure of the solid state sensor to HCl vapor results in the formation of protonated meso-tetramesitylporphyrin (PMTMP). UV-vis and fluorescence spectral techniques were used to study the protonation of MTMP in dichloromethane-methanol mixture. The optical spectra of MTMP show an intense Soret band at 418 nm with a 14 nm red shift upon protonation by HCl. Ab-initio calculations were carried out to visualize the effect of protonation on planarity and stability of the porphyrin ring. The solid state sensor was characterized by UV-vis spectral technique. The sensor exhibits characteristic Soret and Q bands for the deposited MTMP with slight red shift when compared to MTMP in dichloromethane. The concentration of gaseous HCl was monitored from the changes in the absorbance of Soret band of PMTMP at 452 nm. The detection limit of the solid state sensor towards gaseous HCl was found to be 0.03 ppm. The present solid state sensor was highly stable for several months.     

Density functional theory study and vibrational analysis of FT‐IR and FT‐Raman spectra of N‐hydroxyphthalimide

The Fourier transform infrared (FT‐IR) spectrum of N‐hydroxyphthalimide has been recorded in the range of 4000–400 cm⁻¹, and the Fourier transform Raman (FT‐Raman) spectrum of N‐hydroxyphthalimide has been recorded in the range of 4000–50 cm⁻¹. With the hope of providing more and effective information on the fundamental vibrations, the Density Functional Theory (DFT)‐Becke3‐Lee‐Yang‐Parr (B3LYP) level with 6‐31G* basis set has been employed in quantum chemical analysis, and normal coordinate analysis has been performed on N‐hydroxyphthalimide by assuming C_s symmetry. The computational wavenumbers are in good agreement with the observed results. The theoretical spectra obtained along with intensity data agree well with the observed spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrochemical determination of the lithium ion diffusion coefficient in TiS2

Long-time chronoamperometry of TiS₂ electrodes immersed in saturated LiClO₄/DMF solution was employed to investigate the charge transport processes which govern the rate of Li⁺ intercalation in TiS₂. The intercalation rate and hence, the current, appears to be controlled by the rate of Li⁺ diffusion within the TiS₂. A model has been developed which predicts the current-time behavior under the control of Li⁺ solid state diffusion. The close agreement of this model with the experimental data allows the solid state diffusion coefficient and other transport parameters (such as effective electrode area) to be evaluated from the measured average grain boundary distance. Typical TiS₂ grain boundary distances in the 3–10 μm range yield a geometric mean value of 1.3 × 10^?9 cm²/s for the solid state diffusion coefficient; this is in close agreement with previously reported diffusivities as measured by NMR spin-lattice relaxation techniques.     

Site-Directed Mutagenesis of Cytochrome P450 2D6 and 2C19 Enzymes: Expression and Spectral Characterization of Naturally Occurring Allelic Variants

Genetic polymorphism of the cytochrome P450 (CYP) genes particularly affects CYP2D6 and CYP2C19 to a functionally relevant extent, and it is therefore crucial to elucidate the enzyme kinetic and molecular basis for altered catalytic activity of these allelic variants. This study explored the expression and function of the reported alleles CYP2D6*2, CYP2D6*10, CYP2D6*17, CYP2C19*23, CYP2C19*24, and CYP2C19*25 with respect to gene polymorphisms. Site-directed mutagenesis (SDM) was carried out to generate these six alleles. After DNA sequencing, the CYP2D6 and CYP2C19 wild types alongside with their alleles were each independently co-expressed with NADPH-CYP oxidoreductase (OxR) in Escherichia coli. The expressed proteins were analyzed using Western blotting, reduced carbon monoxide (CO) difference spectral scanning, and cytochrome c reductase assay. Results from Western blot revealed the presence of all CYP wild-type and allelic proteins in E. coli membrane fractions. The reduced CO difference spectra scanning presented the distinct peak of absorbance at 450 nm, and the cytochrome c reductase assay has confirmed that spectrally active OxR was expressed in each protein preparation. As a conclusion, the results obtained from this study have proven the CYP variants to be immunoreactive and spectrally active and are suitable for use to examine biotransformation and interaction mechanism of the enzymes.     

Two Step Purification of <Emphasis Type="Italic">Acinetobacter</Emphasis> sp. Lipase and Its Evaluation as a Detergent Additive at Low Temperatures

Acinetobacter sp. lipase was purified to homogeneity by a two-step process. The crude enzyme (along with biomass) was subjected to partial purification by aqueous two phase system (ATPS), avoiding centrifugation and filtration steps. Conditions for lipase partitioning by ATPS were optimized by response surface methodology (RSM) and a combination of 29.45% polyethylene glycol 8000, 15.5% phosphate, and a pH of 7.0 resulted in an optimal partition coefficient. Partially pure lipase was further purified by a modified batch process using Octyl Sepharose CL-4B in a vacuum filtration apparatus. This two-step process resulted in a purified lipase with a yield of 74.6% having a specific activity of 88.8 U/mg of protein and a purification fold of 14.92. The homogeneity of the lipase preparation obtained by the purification process was confirmed by reversed phase high performance liquid chromatography profile. The molecular weight of the purified lipase was found to be around 32 kDa as determined by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The purified lipase exhibited pH and temperature optima of 8.5 and 37 degrees C, respectively. The lipase was active at low temperatures and it retained 86.8% activity at 10 degrees C. It also displayed other features such as stability over a broad range of pH (3.0-9.0) as well as stability in the presence of hydrogen peroxide and commercial detergents. Based on these characteristics, the potential of this lipase as an additive in laundry detergent formulation was evaluated under low temperature wash conditions. The results indicated that Acinetobacter sp. lipase increased the washing efficiency of the detergent Nirma by 21-24% at 15 degrees C-20 degrees C, respectively.     

Selective and sensitive determination of dopamine by composites of polypyrrole and graphene modified electrodes

A novel method is developed to fabricate the polypyrrole (PPy) and graphene thin films on electrodes by electrochemical polymerization of pyrrole with graphene oxide (GO) as a dopant, followed by electrochemical reduction of GO in the composite film. The composite of PPy and electrochemically reduced graphene oxide (eRGO)-modified electrode is highly sensitive and selective toward the detection of dopamine (DA) in the presence of high concentrations of ascorbic acid (AA) and uric acid (UA). The sensing performance of the PPy/eRGO-modified electrode is investigated by differential pulse voltammetry (DPV), revealing a linear range of 0.1-150 μM with a detection limit of 23 nM (S/N = 3). The practical application of the PPy/eRGO-modified electrode is successfully demonstrated for DA determination in human blood serum.     

Size-selective template-assisted electrophoretic assembly of nanoparticles for biosensing applications

The precise, size-selective assembly of nanoparticles gives rise to many applications where the assembly of nano building blocks with different biological or chemical functionalizations is necessary. We introduce a simple, fast, reproducible-directed assembly technique that enables a complete sorting of nanoparticles with single-particle resolution. Nanoparticles are size-selectively assembled into prefabricated via arrays using a sequential template-directed electrophoretic assembly method. Polystyrene latex (PSL) nanoparticles with diameters ranging from 200 to 50 nm are selectively assembled into vias comparable to nanoparticle diameter. We investigate the effects of particle size and via size on the sorting efficiency. We show that complete sorting can be achieved when the size of the vias is close to the diameter of the nanoparticles and the size distribution of the chosen nanoparticles does not overlap. The results also show that it is necessary to keep the electric field on during the insertion and removal of the template. To elucidate the versatility and nil effects that the electrophoresis assembly technique has on the assembled nanoparticle characteristics, we have assembled cancer-specific monoclonal antibody-2C5-coated nanoparticles and have also shown that they can successfully measure low concentrations of the nucleosome (NS) antigen.     

Value of zeolites in asymmetric induction during photocyclization of pyridones, cyclohexadienones and naphthalenones

Two strategies, namely chiral inductor and chiral auxiliary approaches, have been examined within zeolites with the aim of achieving asymmetric induction during the photocyclization of cyclohexadienone, naphthalenone and pyridone derivatives. Within zeolites, enantioselectivity as high as 55% and diastereoselectivity as high as 88% have been obtained. The observed stereoselectivities are significant given the fact that these reactions gave very little stereoselectivities in isotropic solution media. The results obtained on the photocyclization of dienones, naphthalenones and N-alkyl pyridones within zeolites compliment our earlier investigations on the photocyclization of tropolone derivatives, the geometric isomerization of 1,2-diphenylcyclopropanes and 2,3-diphenyl-1-benzoyl cyclopropanes, and the Norrish type II reaction of alpha-oxoamides, phenyl adamantyl ketones, phenyl norbornyl ketones and phenyl cyclohexyl ketones. With the help of these examples, we have established the importance of zeolite and its charge compensating cations in effecting asymmetric induction in photochemical reactions.     

Inclusion Complexes of Conjugated Nitroolefins in β-Cyclodextrin

Physical studies such as Powder X-ray,FT-IR, UV, ¹H and ¹³C NMR clearly identifya 1 : 1 inclusion complex formed between-cyclodextrin and nitroolefins such as-nitrostyrene, 1-nitrocyclohexene in thesolid state as well as in solution. The olefins lieshallow inside the cavity leaving the nitro groupoutside the torus. It has been found that the complexis capable of reacting with a-phenyl-N-p-methylphenyl nitrone ina 1,3-dipolar cycloaddition with excellent rateacceleration and regioselection. The NaBH₄reduction of the complex in the solid state leads tothe corresponding nitroalkane.