P.M.R. relaxation time studies in some binary liquid systems

Proton magnetic resonance relaxation time measurements have been carried out in mixtures of water with formic acid, acetic acid, propionic acid and n-butyric acid. On account of molecular association, the results reveal strong deviation of these mixtures from the ideal behaviour. The molecular association effect is discussed in some detail. The molecular association ratios determined from the present studies are in excellent agreement with those obtained by the ultrasonic absorption technique. It is further shown that N.M.R. relaxation time studies reveal more information about molecular interactions in liquids than the ultrasonic absorption studies.     

Hydrogen‐bonded thermotropic liquid‐crystalline polyester–amides from bis(hydroxy alkamido)aranes: Synthesis and properties

Hydrogen‐bonded aromatic–aliphatic polyester–amides (PEAs) were prepared by solution/melt polycondensation of aromatic–aliphatic amidodiols 1,4‐bis(4‐hydroxybutyramide)benzene (BHBB), 1,4‐bis(5‐hydroxy pentamide)benzene, 1,4‐bis(6‐hydroxyhexamide)benzene, 1,4‐bis(4‐hydroxybutyramidexylene), 1,4‐bis(5‐hydroxypentamidexylene, 1,4‐bis(4‐hydroxybutyramide)benzene, and 1,4‐bis(6‐hydroxyhexamidexylene) with terephthaloyl chloride/dimethyl terephthalate. Aromatic–aliphatic amido diols were prepared by the aminolysis of γ‐butyrolactone, δ‐valerolactone, and ?‐caprolactone with aromatic diamines such as paraphenylene diamine and paraxylene diamine. The monomers and polymers were characterized by chemical analysis (hydroxyl value and elemental analysis), Fourier transform infrared spectroscopy, ¹H NMR, and ¹³C NMR. The thermal‐ and phase‐transition behaviors of the polymers were investigated by differential scanning calorimetry in combination with hot‐stage optical microscopy. Crystallinity of polymers was examined with wide‐angle X‐ray diffraction. The polymers exhibited liquid crystallinity with layered structures formed by self‐organization of the hetero intermolecular hydrogen‐bonded networks indicating smectic phases except for PEAs prepared from BHBB. The hydrogen atom of the phenyl‐substituent group forces the neighboring carbonyl groups out of plane of the rings preventing formation of layered structures in the case of BHBB. The PEAs retained intermolecular hydrogen bonding even in the mesomorphic state, and variations in the hydrogen‐bonded lamellae/micelles might be responsible for the variations from one smectic to another texture. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 335–346, 2003     

Monitoring of cephalosporin C during bioconversion

A simple method based on Schiff’s base formation betweenp-dimethylaminobenzaldehyde and cephalosporin C is developed for estimation of cephalosporin C. The calibration curve was linear up to 500 μg of cephalosporin C. The application of the method in monitoring bioconversion of cephalosporin C to glutaryl-7-amino cephalosporanic acid is described.     

Ortho-tellurated derivatives of some arylamines and imines

A range of novel bi-, tri- and multidentate organotellurium ligands containing Te and N donor atoms and their derivatives have been synthesised. The synthetic strategy involves telluration of orthochelating, monoanionic substrates derived from the following arylamines: N,N-dimethylbenzylamine, (S)-(-)-N,Ndimethyl-1-phenethylamine, N,N-dimethylnaphthylamine, (N,N-di-methylaminomethy l) ferrocene, tricarbony1(N, N-dimethylbenzenemethanamine) chromium and 2-(3-thienyl)-pyridine. In addition novel chiral hybrid Schiff base ligands have been prepared by the condensation reaction of bis(o-formylphenyl) telluride ando-butyltellurobenzaldehyde with (R)-(+)-l-phenethylamine and (1R, 2S)-(-)-norephedrine.     

Biosynthesis of (+)-,(-)- and (±)-tetrahydropalmatines

Specific incorporation of didehydroreticuline and reticuline into (±)- (+)-, and (-)-tetrahydropalmatines in Cocculus laurifolius and of (R)- and (S)-reticulines into (R)- and (S)-tetrahydropalmatines respectively has been demonstrated. Feeding of[l-³H, 4'-methoxy-¹⁴C]reticuline suggested that reticuline was not converted in the plants into didehydroreticuline and racemisation of optically active forms of tetrahydropalmatine did not take place via dehydrotetrahydropalmatine     

Biosynthesis of tetrahydropalmatine and palmatine

The incorporation of (±)-norlaudanosoline, norprotosinomenine, nororientaline, norlaudanidine, reticuline and laudanosine into tetrahydropalmatine and palmatine has been studied, and specific utilization of reticuline demonstrated. Feeding of (±)-[N-methyl-¹⁴C] reticuline showed that C atom 8 of tetrahydropalmatine and palmatine are formed by oxidative cyclisation of the N-Me group of reticuline. Parallel experiments with (R)-; and (S)-, reticulines demonstrated specific incorporation of (R)- isomer into these bases. Feeding experiments also revealed that the plants can convert tetrahydropalmatine into palmatine with high efficiency.     

Arc plasma synthesized LaB<Subscript>6</Subscript> nanocrystallite film on various substrates as a field emitter

Lanthanum hexaboride (LaB₆) nanocrystallites/nanowires have been successfully synthesized using gas phase condensation in arc plasma. Our results show that the LaB₆ nanowires have ~20 nm diameter and length of several micrometers. The as-synthesized LaB₆ nanocrystallites and nanowires are crystalline in nature. Field emission studies were carried out on as synthesized LaB₆ nano-powder deposited on W and Re tips and foils, and also on Si foil substrates under ultra high vacuum. The Fowler–Nordheim plots obtained from the current–voltage characteristics are found to be linear in accordance with the quantum mechanical tunneling phenomenon. High value of field enhancement factor (8177) is observed for LaB₆ on Re substrate, indicating that the electron emission is from the nanometric features of the LaB₆. Our results show that the arc plasma synthesized LaB₆ nanocrystalline film exhibits good emission stability as emitter without severe deviations from the initial set value and also a strong ability to withstand the ion bombardment, which is useful for low operation voltage vacuum micro/nano electronic devices.     

Solubility of water in a benzene-cyclohexane mixture

The solubility of a water molecule in a binary mixture of nonpolar cyclohexane and quadrupolar benzene is studied with the ab initio method. A novel self-consistent reaction field theory that properly accounts for benzene quadrupole moments in the continuum solvent framework is used to describe the solvation effects of the solvent mixture. The free energy of transfer from pure cyclohexane to the mixture solvent is obtained with the neglect of nonelectrostatic contributions. A reasonable agreement with experiments indicates that the theoretical method presented here provides a promising approach to electronic structure calculations in quadrupolar solvents and their mixtures with nonpolar solvents.