Complexes of Cobalt(II), Nickel(II) and Copper(II) Chloroacetates with Quinoline N-Oxide

Some 1:1 and 1:2 adducts of cobalt(II), nickel(II) and copper(II) chloroacetates with quinoline N -oxide have been isolated by the interaction of the appropriate metal chloroacetate with quinoline N -oxide (QuinNo). The complexes isolated are of 1:1 stoichiometry of formula (M(CH_3-xCl_xCOO)₂QuinNO) (when M=Co(II), Ni(Il); X=l, 2 and 3 and when M=Cu(II), X=1 and 2) except copper(II) trichloroacetate which yields an adduct of 1:2 stoichiometry of formula[Cu(CCl₃COO)₂ (QuinNO)₃]. The adducts isolated are soluble in common organic solvents.     

Pre-equilibrium effects in (n, 2n) reactions at 14.2 MeV+

With a view to study the pre-equilibrium effects in neutron-induced reactions, the activation cross-sections for (n, 2n) reactions at 14.2±0.2 MeV in the heavy mass region have been measured using the versatile mixed powder technique and high resolution Ge(Li) detection. The experimental cross-sections are found to be consistently smaller than the predictions based on the statistical theory and this is attributed to the effect of pre-equilibrium decay in these reactions. The cross-sections due to pre-equilibrium decay were estimated using exciton, hybrid and unified models. When this cross-section was included in comparing the experimental cross-sections with theory, we obtained better agreement, within the limitations of the present-day preequilibrium theories. Preliminary results of this work were reported at the Nuclear Physics and Solid State Physics Symposium, Pune (1978).     

Synthesis of New Reagent 2‐Acetylthiophenethiocynate and its Use in Extraction of Pt(IV) Spectrophotometrically

2‐Acetyl thiophenethiocynate (ATT) was synthesized and its characterization study was carried out using elemental analysis, IR and NMR techniques. The new reagent was proposed as an extractant for the development of the extractive spectrophotometric method for determination of Pt(IV) metal. The reagent complexes with the metal to produce a yellow colored complex which was then extracted into ethyl acetate at pH 11.2–11.6 having an absorption maxima at 400 nm. The thermal study showed that the extraction reactions are exothermic in nature with the reagent, and the stoichiometric ratio of Pt(IV) to 2‐acetyl thiophenethiocynate in the organic phase was 1:2. The method permits separation and determination of platinum from real and binary mixtures. The separation of Pt(IV) from bivalent metal ions has been also studied.     

Studies of Nucleophilic Substitution Reactions of p‐Nitrophenyl Acetate with Some Dihydroxamate Ions in Cationic Micellar Media

Pseudo‐first‐order rate constants have been determined for the nucleophilic substitution reactions of p‐nitrophenyl acetate with oxalo, malono, and succinodihydroxamate ions (^?ONHC(O)(CH₂)_nC(O)NHO^?) in phosphate buffer (pH=7.9) at 27°C. The rate data of the reaction revealed that the nucleophilic reactivity sequence of these hydroxamate ions is generally ODHA>MDHA>SDHA. The k_obs value increases upon addition of cationic surfactants to the reaction medium which is typical behavior of micelle‐assisted bimolecular reactions. The pseudo‐phase ion exchange model has been successfully applied to determine binding constant.     

Development of Petri Net-Based Dynamic Model for Improved Production of Farnesyl Pyrophosphate by Integrating Mevalonate and Methylerythritol Phosphate Pathways in Yeast

In this case study, we designed a farnesyl pyrophosphate (FPP) biosynthetic network using hybrid functional Petri net with extension (HFPNe) which is derived from traditional Petri net theory and allows easy modeling with graphical approach of various types of entities in the networks together. Our main objective is to improve the production of FPP in yeast, which is further converted to amorphadiene (AD), a precursor of artemisinin (antimalarial drug). Natively, mevalonate (MEV) pathway is present in yeast. Methyl erythritol phosphate pathways (MEP) are present only in higher plant plastids and eubacteria, but not present in yeast. IPP and DAMP are common isomeric intermediate in these two pathways, which immediately yields FPP. By integrating these two pathways in yeast, we augmented the FPP synthesis approximately two folds higher (431.16 U/pt) than in MEV pathway alone (259.91 U/pt) by using HFPNe technique. Further enhanced FPP levels converted to AD by amorphadiene synthase gene yielding 436.5 U/pt of AD which approximately two folds higher compared to the AD (258.5 U/pt) synthesized by MEV pathway exclusively. Simulation and validation processes performed using these models are reliable with identified biological information and data.     

Complete pi-facial diastereoselectivity in Diels-Alder reactions of dissymmetric 2,4-cyclohexadienones

[reaction: see text] The studies in the Diels-Alder reactions of 5-methoxy-masked o-benzoquinone (1a, R = OMe) and simple dissymmetric 2,4-cyclohexadienones 1b-e with methyl vinyl ketone, styrene, and benzyl vinyl ether are described. The dienones 1b-e reacted with dienophiles to form syn adducts (dienophile approach is syn to allylic methoxy group) exclusively.     

Structure and dynamics of solutions of a polystyrene–polybutadiene pentablock copolymer in a styrene‐selective solvent

We have examined solutions of a polystyrene–polybutadiene pentablock copolymer in 1,4‐dioxane, a slightly selective solvent for polystyrene and a θ solvent for polybutadiene, with static light scattering (SLS), dynamic light scattering (DLS), and small‐angle neutron scattering (SANS). The SANS data have been analyzed with the Percus–Yevick model to represent the scattering from interacting cores, approximated as hard spheres, and with a Lorentzian function to represent the scattering from unassociated and associated polymer chains. The SANS data at 25 °C clearly reveal interacting domains, approximately 6 nm in radius, formed by the association of the insoluble polybutadiene block in the 20% sample. The 4% sample does not show such domains, whereas the 7% sample represents an intermediate situation, with both unassociated polymer and associated polymer. At higher temperatures, the domains dissolve. The DLS data for samples with concentrations of 2–22% show two diffusive modes: a fast mode corresponding to the cooperative dynamics of concentration fluctuations and a slow mode corresponding to the diffusion of clusters. The large length‐scale heterogeneities, indicated by the strong angular dependence of SLS, implies that the small microdomains of about 10–15 polybutadiene blocks are bridged by the polystyrene chains, forming large aggregates with randomly distributed crosslinks on length scales much larger than the domain size. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2807–2816, 2002     

β-Cyclodextrin-polyurethane polymer as solid phase extraction material for the analysis of carcinogenic aromatic amines

β-Cyclodextrin-polyurethane (β-CDPU) polymer was synthesized by the reaction of β-cyclodextrin with hexamethylene diisocyanate in dry dimethylformamide and used as a sorbent for the solid phase extraction (SPE) of carcinogenic aromatic amines from water. The polymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and particle size analysis. The separation and quantification was performed by Liquid chromatography with RP-C₁₈ column and diode array detection using standard arylamines for quantification. When compared with commercially available sorbents, β-CDPU gave better recovery for the aromatic amines. From the variation of pH of the extractant from 4.0 to 8.5 recovery was highest at pH 8.5. The breakthrough volume has been ascertained to be 100 ml for 200 mg of the resin. The new SPE material offers better recovery and estimation of banned arylamines.     

Numerical simulation of rapid pressurization and depressurization of a zeolite column using nitrogen

The required durations of pressurization and depressurization steps of a rapid pressure swing adsorption process are primarily governed by adsorbent particle size, adsorption kinetics, column pressure drop, column length to diameter ratio, and the valve constant of the gas inlet and outlet control valve attached to the adsorbent column. A numerical model study of the influence of these variables for an adiabatic LiX zeolite column is presented using pure N₂ as an adsorbate gas. An adsorbent particle size range of 200–350 μm was found to minimize (<1 s) the times required for the pressurization and depressurization steps.