Metal chelates in vinyl polymerization: Bulk polymerization of acrylonitrile initiated by Cu(II)–imine complexes

This article deals with the kinetics and mechanism of acrylonitrile (AN) polymerization initiated by Cu(II)–4-anilino 3-pentene 2-one[Cu(II)ANIPO], Cu(II)–4-p-toluedeno 3-pentene 2-one [Cu(II)TPO], and Cu(II)–4-p-nitroanilino 3-pentene 2-one [Cu(II)NAPO] in bulk at 60°C. The polymerization is free radical in nature. The exponent of initiator(I) is ? 0.5. The initiation step is a complex formation between the chelate and monomer and subsequent decomposition of the intermediate complex giving rise to free radical and Cu(I). This is substantiated by ultraviolet (UV) and electron spin resonance (ESR) studies. The activation energies and kinetic and chain transfer constants have also been evaluated.     

Polymerization of methyl methacrylate with cupric laurate–benzoin system as initiator

The polymerization of methyl methacrylate initiated by cupric laurate in combination with benzoin has been investigated in carbon tetrachloride medium at 60°C. The rate of polymerization was found to be proportional to the square root of both cupric ion and benzoin concentrations, and to the 1.5th power of the monomer concentration. Spectral studies indicated that there is a complex formation between cupric ion and the monomer methyl methacrylate. A reaction scheme, based on initial formation of the complex and its subsequent reaction with benzoin to produce the free radicals responsible for initiation has been postulated to explain the observed results.     

Molecular pair potential of chiral amino acid amphiphile in Langmuir monolayers on the basis of an atomistic model

In the present work, the pair potential of enantiomeric N-palmitoyl aspartic acid amphiphile monolayer at the air/water interface is calculated based on an atomistic model. The molecular structure and partial charges are calculated using two semi empirical (PM3, AM1) and one empirical (Gasteiger and Marcili) methods. A distance-dependent dielectric function is used to represent the interfacial dielectric constant at the aqueous subphase. The present study indicates that a pair of molecules have favorable interaction at specific ranges of mutual orientations. Other orientations are favorable but at larger separations. Favorable electrostatic interaction at a specific combination of orientation and short separations of the head groups significantly contribute to the total energy. The curvature of the domain boundary is suggested to be driven by the favorable arrangement which is dependent on the pair potential of molecules. The use of charges obtained by the PM3 and GM do not lead to a significant variation of the orientation-dependent features, while the AM1 predicts higher partial charges and interactions are stronger than the former two methods. However, orientation-dependent features remain the same. The variations in the LJ parameters and charges indicate that the conclusions made are insensitive to the choice of parameters. The mutual favorable interaction predicted by calculation agree with the handedness of curvature of domains.     

Interaction of adenine and thymine with aqueous sugar solutions

The solubility of the nucleic acid bases, adenine and thymine, in aqueous erythritol, xylose, glucose, and sucrose solutions has been studied. The solubility of adenine increases linearly with glucose and sucrose concentration, whereas with the other reagents a nonlinear increase is observed. Below 1.5M reagent concentration, the solubility of adenine increases in the order erythritol < robose, xylose < glucose < sucrose. The solubility of thymine in these solutions, on the other hand, decreases, increases, or does not change depending upon the reagent. The effect of temperature on the solubility of adenine and thymine in sugar solution indicates that the transfer of these molecules from water to sugar solution is exothermic.Presented in part at the VIIth All-India Symposium in Biophysics held at Visva Bharati University during October 1976.     

Effects of concentration, relative permittivity, and temperature on the solution behavior of sodium carboxymethylcellulose as probed by electrical conductivity

Precise measurements on the electrical conductivity of solutions of sodium salt of carboxymethylcellulose in acetonitrile/water mixed-solvent media containing 10, 20, and 40 vol % of acetonitrile are reported as a function of temperature. The degree of substitution of carboxymethylcellulose used was 0.70, and the concentrations were varied from approximately 1 x 10(-4) to approximately 1 x 10(-2) equiv L(-1). The results showed a decrease in the equivalent conductivity with increasing polyelectrolyte concentration. The applicability of Manning's theory for salt-free polyelectrolyte solutions was examined, and a major discrepancy against the theory was observed. The calculated values of the equivalent conductivity deduced on the basis of this theory were found to be higher than the experimental ones. Possible reasons for this discrepancy have been discussed. The fractions of uncondensed counterions were evaluated, and these were found to depend on the polyelectrolyte concentration. The effects of the temperature and relative permittivity of the medium on the equivalent conductivity as well as on the fraction of uncondensed counterions were also investigated.     

Heterodimerization of olefins. 1. Hydrovinylation reactions of olefins that are amenable to asymmetric catalysis

Through a systematic examination of ligand and counterion effects, new protocols for a nearly quantitative and highly selective codimerization of ethylene and various functionalized vinylarenes have been discovered. In a typical reaction, 4-bromostyrene and ethylene undergo codimerization in the presence of 0.0035 equiv each of [(allyl)NiBr]2, triphenylphosphine, and AgOTf in CH2Cl2 at -56 degrees C to give 3-(4-bromophenyl)-1-butene in >98% yield and selectivity. Corresponding reactions with [(allyl)PdX]2 are much less efficient and less selective and may require further optimization before a viable system can be identified. Another useful protocol that gives comparable yield and selectivity involves the use of a single-component catalyst prepared from allyl 2-diphenylphosphinobenzoate, Ni(COD)2, and (C6F5)3B. Recognition of a synergistic relationship between a chiral hemilabile ligand (for example, (R)-2-methoxy-2'-diphenylphosphino-1,1'-binaphthyl, MOP) and a highly dissociated counteranion (BARF or SbF6) in an enantioselective version of the Ni-catalyzed reaction raises the prospects of developing a practical route for the synthesis of 3-arylbutenes. Several pharmaceutically relevant compounds, including widely used 2-arylpropionic acids, can be synthesized from these key intermediates. This reaction appears to be quite general. Synthesis of several new 2-diphenylphosphino-1,1-binaphthyl derivatives, prepared to probe the effect of hemilabile coordination on the efficiency and selectivity of the reaction, are also described.     

Thermal hazards evaluation for sym-TCB nitration reaction using thermal screening unit (TSU)

A set of experiments was conducted in an HEL thermal screening unit with synthetic mixtures of raw materials in various proportions to evaluate the potential thermal hazards at normal and offset process conditions for nitration of symmetrical trichlorobenzene (TCB). The experiments were carried out in the adiabatic condition. The onset temperatures of the exotherms along with maximum temperature and pressure rise data for the desired and undesirable reactions were obtained. In the presence of excess nitric acid and oleum, the reaction shows a severe thermal runaway at the onset temperature of 138°C with a rapid rise in temperature and pressure leading to a potential explosion. This revised version was published online in July 2006 with corrections to the Cover Date.     

An Ultra-Microporous Metal–Organic Framework with Exceptional Xe Capacity

Molecular confinement plays a significant effect on trapped gas and solvent molecules. A fundamental understanding of gas adsorption within the porous confinement provides information necessary to design a material with improved selectivity. In this regard, metal–organic framework (MOF) adsorbents are ideal candidate materials to study confinement effects for weakly interacting gas molecules, such as noble gases. Among the noble gases, xenon (Xe) has practical applications in the medical, automotive and aerospace industries. In this Communication, we report an ultra-microporous nickel-isonicotinate MOF with exceptional Xe uptake and selectivity compared to all benchmark MOF and porous organic cage materials. The selectivity arises because of the near perfect fit of the atomic Xe inside the porous confinement. Notably, at low partial pressure, the Ni–MOF interacts very strongly with Xe compared to the closely related Krypton gas (Kr) and more polarizable CO₂. Further ¹²⁹Xe NMR suggests a broad isotropic chemical shift due to the reduced motion as a result of confinement.     

Irreversible Structural Changes of Copper Hexacyanoferrate Used as a Cathode in Zn-Ion Batteries

The structural changes of copper hexacyanoferrate (CuHCF), a Prussian blue analogue, which occur when used as a cathode in an aqueous Zn-ion battery, are investigated using electron microscopy techniques. The evolution of Zn_xCu_1−xHCF phases possessing wire and cubic morphologies from initial CuHCF nanoparticles are monitored after hundreds of cycles. Irreversible introduction of Zn ions to CuHCF is revealed locally using scanning transmission electron microscopy. A substitution mechanism is proposed to explain the increasing Zn content within the cathode material while simultaneously the Cu content is lowered during Zn-ion battery cycling. The present study demonstrates that the irreversible introduction of Zn ions is responsible for the decreasing Zn ion capacity of the CuHCF cathode in high electrolyte concentration.