β-Cyclodextrin Mediated Synthesis of Syndiotactic-rich Polystyrene

Stereoregular polystyrene (PS) was prepared using various molarequivalents of -cyclodextrin (-CD) by polymerisingstyrene in the presence of -CD. Stereoregular (isotactic,atactic and syndiotactic) distributions of the preparedpolystyrene polymers were determined from terminal modelBernoullian statistics using ¹³C NMR data. Inclusioncomplexation of styrene by -cyclodextrin was detected byUV-Visible spectroscopy, which gave a binding constant value of31606 ± 3350 M^-1 for the 1 : 1 complex. With anincrease in the styrene : -CD ratios, the proportionof syndiotactic polymers increased. The glass transitiontemperature (T_g) of the polymer also increased along withmelting temperature (T_m) at higher styrene : -CDratios. In addition, the molecular weight of the polymers prepareddecreased with increase in the -CD concentration.     

Computation of scattering from N spheres using multipole reexpansion

A computational technique for the solution of problems of wave scattering from multiple spheres is developed. This technique, based on the T-matrix method, uses the theory for the translation and reexpansion of multipole solutions of the Helmholtz equation for fast and exact recursive computation of the matrix elements. The spheres can have prescribed radii, impedances, and locations. Results are validated by comparison with boundary element calculations, and by convergence analyses. The method is much faster than numerical methods based on discretization of space, or of the sphere surfaces. An even faster method is presented for the case when the spheres are aligned coaxially.     

Isolation,Purification and Characterisation of an Organic Solvent-Tolerant Ca2+-Dependent Protease from Bacillus megaterium AU02

A new organic solvent-tolerant strain Bacillus megaterium AU02 which secretes an organic solvent-tolerant protease was isolated from milk industry waste. Statistical methods were employed to achieve optimum protease production of 43.6 U/ml in shake flask cultures. The productivity of the protease was increased to 53 U/ml when cultivated under controlled conditions in a 7-L fermentor. The protease was purified to homogeneity by a three-step process with 24 % yield and specific activity of 5,375 U/mg. The molecular mass of the protease was found to be 59 kDa. The enzyme was active over a wide range of pH (6.0–9.0), with an optimum activity at pH 7.0 and temperature from 40 to 70 °C having an optimum activity at 50 °C. The thermal stability of the enzyme increased significantly in the presence of CaCl₂, and it retained 90 % activity at 50 °C for 3 h. The K _m and V _max values were determined as 0.722 mg/ml and 0.018 U/mg respectively. The metalloprotease exhibited significant stability in the presence of organic solvents with log P values more than 2.5, nonionic detergents and oxidising agent. An attempt was made to test the synthesis of aspartame precursor (Cbz-Asp-Phe-NH₂) which was catalysed by AU02 protease in the presence of 50 % DMSO. These properties of AU02 protease make it an ideal choice for enzymatic peptide synthesis in organic media.     

How Many Timesteps for a Cycle? Analysis of the Wisdom-Holman Algorithm

The Wisdom-Holman algorithm is an effective method for numerically solving nearly integrable systems. It takes into account the exact solution of the integrable part. If the nearly integrable system is the solar system, for example, the Wisdom-Holman algorithm uses the solution consisting of Keplerian orbits obtained when the interplanetary interactions are ignored. The effectiveness of the algorithm lies in its ability to take long timesteps. We use the Duffing oscillator and Kepler's problem with forcing to deduce how long those timesteps can be. For nearly Keplerian orbits, the timesteps must be at least six per orbital period even when the orbital eccentricity is zero. High eccentricity of the Keplerian orbits constrains the algorithm and forces it to take shorter timesteps. The analysis is applied to the solar system and other problems.     

β-Cyclodextrin Mediated Synthesis of Sterically Controlled Styrene-acrylonitrile Copolymer

Sterically controlled styrene-acrylonitrile (SAN)copolymers were prepared by inclusion polymerizationusing molar equivalents of -cyclodextrin(-CD) and its derivative. Comonomercompositions, reactivity ratios, monomer sequence andaverage styrene and acrylonitrile sequence lengthswere determined using ¹³C NMR spectroscopy. Themolecular weight of the polymers prepared increasedwith decreasing -CD concentration, but wasfound to be less than the control. With increase inthe styrene: -CD ratios the averageacrylonitrile sequence length and run number of thepolymers increased. The glass transition temperature(_g) also increased along with the meltingtemperature (_m) of the polymers at higherstyrene:-CD ratios.     

Inclusion of Ring A of Cholesterol Inside the β-Cyclodextrin Cavity: Evidence from Oxidation Reactions and Structural Studies

The disposition of cholesterol inside the -cyclodextrin cavity(-CD) was deduced from oxidation of cholesterol secondary alcoholgroups by Ca(OCl)₂ and H₂O₂ in thepyridine–acetic acid system. The amount of cholest-4-ene-3-one formedwas found to be proportional to the concentration of -cyclodextrin,resulting in 56.1% of ketone. The oxidation rate was enhanced by-cyclodextrin and its methyl, polymer and 1 : 1copper(II)–-cyclodextrin derivatives. Detailed investigationsinvolving UV-visible, ¹³C- and ¹H-NMR(T₁, 1D NOE and ROESY) spectroscopic studies were carried out.A binding constant value of 15,385 ± 1500 M^-2 wasobtained for the 2 : 1heptakis-2,6-di-O-methyl--cyclodextrin(DM-CD) : cholesterolcomplex in chloroform from UV studies. Proton and solid state¹³C-CP MAS spectra of the -CD–cholesterol mixtureshowed large magnitude shifts for the protons from the wider end of the-CD cavity as well as those of ring A and ring B of cholesterol. Both1D NOE and ROESY measurements indicated the proximity between ring A andring B protons of cholesterol and the wider end protons of -CD andDM-CD. Besides, analysis of _c,_i and tau;_m from T₁measurements showed not only a lowering of rotational motions but a value of 0.016–0.048 for some of the cholesterol protons, typical of aweak complex. Based on these studies, a probable structure for the 2 : 1complex involving two molecules of -CD/DM-CD was proposed withportions of ring A and ring B being present inside the wider end of the-CD/DM-CD cavity and ring D and the side chain attached atposition 17, projecting into the wider end of the secondCD/DM-CD molecule.     

Structural Studies on Inclusion Compounds of β-Cyclodextrin with Some Substituted Phenols

A detailed structural study of the inclusion compounds of some substituted phenols such as catechol, guaiacol, protocatechuic aldehyde, vanillin, caffeic acid, ferulic acid and eugenol with -cyclodextrin (CD) was carried out by using UV-visible, fluorescence, 1H and solid-state 13C NMR spectroscopic and potentiometric investigations. Based on these studies guaiacol, catechol and eugenol were found to exhibit identical orientations - with the phenyl ring within the cavity and the hydroxyl and methoxyl groups projecting outside; protocatechuic aldehyde, caffeic acid, ferulic acid and vanillin display a different orientation - with the phenol part within the cavity and the aldehyde or carboxyl part projecting outside.     

Indirect spectrophotometric methods for the determination of antibiotics with iodine or periodate, and metol and sulphanilamide

Two spectrophotometric methods are described for the determination of antibiotics. In the first method, penicillins, cephalosporins, streptomycin and griseofulvin are estimated by oxidizing them under neutral or slightly acidic conditions, after alkaline hydrolysis, by means of a known and excessive quantity of iodine solution. The excess of iodine is determined at pH 3.0 with metol and sulphanilamide. In the second method, dihydrostreptomycin, framycetin and the acid hydrolysis product of chloramphenicol are determined by a method involving oxidation with sodium metaperiodate, masking the excess of periodate with sodium molybdate, and using metol and sulphanilamide at pH 3.0 to determine the iodate formed. In both methods the absorbance of the resulting p-N-methylbenzoquinonemonoimine sulphanilamide charge-transfer complex is measured at 520 nm.