An electrolytic device for preparation of hydrogen and oxygen from water for isotopic analysis

An electrolytic device for decomposition of water has been developed which readily gives hydrogen and oxygen for isotopic measurement with a mass spectrometer. A 20-mul sample can be decomposed quantitatively in 10 min with good reproducibility. The results produced are comparable with those obtained by reduction with uranium.     

Synthesis of a novel cis-proline-derived cyclic type VI beta-turn mimic via ring-closing metathesis

A cis-proline derived cyclic mimic of a type VI beta-turn is synthesized via a ring-closing metathesis reaction. The solution NMR conformational study indicates that the major conformer of the cyclic peptide adopts a type VIa beta-turn in CDCl(3) and a type VIb beta-turn in DMSO-d(6).     

Palladium(0)-catalyzed regioselective synthesis of alpha-dehydro-beta-amino esters from amines and allyl acetates: synthesis of a alpha-dehydro-beta-amino acid derived cyclic peptide as a constrained beta-turn mimic

Acetates derived from the adducts of the Baylis-Hillman reaction can be reacted in a regioselective manner with amines in the presence of palladium(0) catalyst to afford alpha-dehydro-beta-amino esters (2 and 3) in good yields. The regioselectivity of the reaction can be controlled by temperature and reaction medium leading to the synthesis of regioisomers 2 or 3. The alpha-dehydro-beta-amino acid 3 is a turn inducer, and the dipeptides 6 derived from it show the presence of an eight-membered intramolecular hydrogen bond. Also, cobalt(II) chloride catalyzes the cleavage of epoxy peptides with alpha-dehydro-beta-amino acid derivative 3b to afford the corresponding dipeptide derivatives 8, which exhibit an intramolecular hydrogen bond and thus mimic a beta-turn. This intramolecular hydrogen bonding preorganizes the corresponding diallylated peptide 8c for cyclization via ring-closing metathesis to afford the cyclic peptide 9 as a constrained mimic of a beta-turn.     

Reverse turn induced pi-facial selectivity during polyaniline-supported cobalt(II) salen catalyzed aerobic epoxidation of N-cinnamoyl L-proline derived peptides

A novel chemo- and diastereoselective aerobic epoxidation of the N-cinnamoyl peptides catalyzed by polyaniline-supported cobalt(II) salen (PASCOS) is described. The N-cinnamoyl proline derived peptides 1 show a high pi-facial selectivity during these epoxidations. The origin of this diastereoselectivity in 1 has been attributed to (i) the propensity of the N-cinnamoyl proline amide to exist predominantly as trans rotamer in CDCl3, DMSO-d6, and CH3CN medium and (ii) existence of these peptides as organized structures (gamma- and beta-turns) due to the presence of intramolecular hydrogen bonds. An extensive solution NMR and MD simulation study on 1d and 1f indicates that the origin of the high pi-facial selectivity is due to the well-defined gamma- and beta-turns which result in the hindrance of one face of the cinnamoyl double bond in the transition state of the epoxidation reaction.     

Solvent effects on charge transport through solid deposits of [Os(4,4'-diphenyl-2,2'-dipyridyl)2Cl2

Mechanically attached, solid-state films of [Os(4,4'-diphenyl-2,2'-dipyridyl)2Cl2] have been formed on gold macro- and microelectrodes and their voltammetric properties investigated. The voltammetric response of these films associated with the Os(2+/3+) redox reaction is reminiscent of that observed for an ideal reversible, solution phase redox couple only when the contacting electrolyte contains of the order of 40% v/v of acetonitrile (ACN). The origin of this effect appears to involve preferential solvation of the redox centres by acetonitrile which facilitates the incorporation of charge compensating counterions. Scanning electron microscopy reveals that voltammetric cycling in 40:60 ACN-H2O containing 1.0 M LiClO4 as the electrolyte induces the formation of microcrystals. Voltammetry conducted under semi-infinite linear diffusion conditions has been used to determine the apparent diffusion coefficient, Dapp, for homogeneous charge transport through the deposit. The dynamics of charge transport decrease with increasing film thickness but appear to increase with increasing electrolyte concentration. These observations suggest that ion transport rather than the rate of electron self-exchange limit the overall rate of charge transport through these solids. When in contact with 40:60 ACN-H2O containing 1.0 M LiClO4 as electrolyte, Dapp values for oxidation and reduction are identical at 1.7 +/- 0.4 x 10(-12) cm2 s(-1). In the same electrolyte, the standard heterogeneous electron transfer rate constant, k(o), determined by fitting the full voltammogram using the Butler-Volmer formalism, is 8.3 +/- 0.5 x 10(-7) cm s(-1). The importance of these results for the rational design of solid state redox active materials for battery, display and sensor applications is considered.     

Enzymatic method for assaying calcium in serum with Ca++ -ATPase

A kinetic assay for total calcium in serum was developed which is based on the activation of Ca(++)-ATPase by free Ca(++) [Ca(++)](f) maintained by EGTA in the reaction mixture. The concentration of Ca(++)(f) was dependent on total reference calcium added or serum calcium. Ca(++)-ATPase activity was coupled to the reduction of NADH by pyruvate kinase (PK) and lactate dehydrogenase (LDH) and monitored by change in absorbance at 340 nm. The calcium in normal serum was 10.08 +/- 0.24 mg/dl (n = 35) by our method while with o-cresolphthalein complexone (CPC) method, the total calcium in the same 35 serum samples was 10.14 +/- 0.54 mg/dl. The range of within-run coefficient of variations (CVs) by this method was 0.9-2.87% at 8-12 mg/dl and day-to-day CVs were 0.72-3.17%. The presence of other ions and standard clinical interfering agents did not affect this assay system. The correlation between values obtained with our method (y) and CPC method (x) for normal serum was: y = 1.064x-0.580 mg/dl (r = 0.912, n = 59).     

Selective adsorption of thorium on activated charcoal from electrolytic aqueous solution

The adsorption of thorium on activated charcoal has been studied as a function of shaking time, amount of adsorbent, pH, concentration of adsorbate and temperature. Adsorption of thorium obeys the Langmuir isotherm. H⁰ and S⁰ were calculated from the slope and intercept of ln K_D vs. 1/T plots. The influence of different anions and cations on thorium adsorption has been examined. The adsorption of other metal ions on activated charcoal has been studied under specified conditions to check its selectivity. Consequently, thorium was removed from Cs, Co, Ba, Cr, Sr, Cd, Cu, Mn and Zn. More than 98% adsorbed thorium on activated charcoal can be recovered with 55 ml 3M HNO₃ solution. Wavelength dispersive X-rays fluorescence spectrometer was used for measuring thorium concentration.     

Green synthesis and characterizations of Nickel oxide nanoparticles using leaf extract of Rhamnus virgata and their potential biological applications

In the present report, Nickel oxide nanoparticles (NiONPs) were synthesized using Rhamnus virgata (Roxb.) (Family: Rhamnaceae) as a potential stabilizing, reducing and chelating agent. The formation, morphology, structure and other physicochemical properties of resulting NiONPs were characterized by Ultra violet spectroscopy, X‐ray diffraction (XRD), Fourier Transform Infrared analysis (FTIR), Scanning electron microscopy (SEM), Energy‐dispersive‐spectroscopy (EDS), Transmission electron microscopy (TEM), Raman spectroscopy and dynamic light scattering (DLS). Detailed in vitro biological activities revealed significant therapeutic potential for NiONPs. The antimicrobial efficacy of biogenic NiONPs was demonstrated against five different gram positive and gram negative bacterial strains. Klebsiella pneumoniae and Pseudomonas aeruginosa (MIC: 125 μg/mL) were found to be the least susceptible and Bacillus subtilis (MIC: 31.25 μg/mL) was found to be the most susceptible strain to NiONPs. Biogenic NiONPs were reported to be highly potent against HepG2 cells (IC₅₀: 29.68 μg/ml). Moderate antileishmanial activity against Leishmania tropica (KMH₂₃) promastigotes (IC₅₀: 10.62 μg/ml) and amastigotes (IC₅₀: 27.58 μg/ml) cultures are reported. The cytotoxic activity was studied using brine shrimps and their IC₅₀ value was recorded as 43.73 μg/ml. For toxicological assessment, NiONPs were found compatible towards human RBCs (IC₅₀: > 200 μg/ml) and macrophages (IC₅₀: > 200 μg/ml), deeming particles safe for various applications in nanomedicines. Moderate antioxidant activities: total antioxidant capacity (TAC) (51.43%), 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) activity (70.36%) and total reducing power (TRP) (45%) are reported for NiONPs. In addition, protein kinase and alpha amylase inhibition assays were also performed. Our results concluded that Rhamnus virgata synthesized NiONPs could find important biomedical applications with low cytotoxicity to normal cells.     

QbD approached comparison of reaction mechanism in microwave synthesized gold nanoparticles and their superior catalytic role against hazardous nirto‐dye

Microwave irradiation (MI) process characteristically enables extremely rapid “in‐core” heating of dipoles and ions, in comparison to conventional thermal (conductance) process of heat transfer. During the process of nanoparticles synthesis, MI both modulates functionality behaviors as well as dynamic of reaction in favorable direction. So, MI providing a facile, favorable and alternative approach during nanoparticles synthesis nanoparticles with enhanced catalytic performances. Although, conventionally used reducing and capping reagents of synthetic origin, are usually environmentally hazardous and toxic for living organism. But, in absence of suitable capping agent; stability, shelf life and catalytic activity of metallic nanoparticles adversely affected. However, polymeric templates which emerged as suitable choice of agent for both reducing and capping purposes; bearing additional advantages in terms of catalyst free one step green synthesis process with high degree of biosafety and efficiency. Another aspect of current works was to understand role of process variables in growth mechanism and catalytic performances of microwave processed metallic nanoparticles, as well as comparison of these parameters with conventional heating method. However, due to poor prediction ability with previously published architect OFAT (One factor at a time) design with these nanoparticles as well as random selection of process variables with their different levels, such comparison couldn't be possible. Hence, using gum Ghatti (Anogeissus latifolia) as a model bio‐template and under simulated reaction conditions; architect of QbD design systems were integrated in microwave processed nanoparticles to establish mechanistic role these variables. Furthermore, in comparison to conventional heating; we reported well validated mathematical modeling of process variables on characteristic of nanoparticles as well as synthesized gold nanoparticles of desired and identical dimensions, in both thermal and microwave‐based processes. Interestingly, despite of identical dimension, MI processed gold nanoparticles bearing higher efficiency (kinetic rate) against remediation of hazardous nitro dye (4‐nitrophenol), into safer amino (4‐aminophenol) analogues.