Ultrasonic Degradation of Hydroxypropyl Cellulose Solutions in Water,Ethanol, and Tetrahydrofuran

Ultrasonic degradations of hydroxypropyl cellulose (HPC) have been carried out in water, ethanol, and tetrahydrofuran (THF) solutions. In the HPC-water system, cavitation intensity did not increase linearly with ultrasound intensity because of a lower threshold of ultrasonic intensity below which cavitation does not occur. At 27°C the rate of degradation in the three solvents followed the order water > ethanol > THF which is not in line with their characteristic impedance values. The rate of degradation for 20 kHz, 70 W ultrasound intensity was found to increase with a decrease in solution volumes, concentration of HPC, and temperature. Increased rate of degradation at lower temperatures supports the concept based on sonoluminescence experiments that it is the cavitation in a polymer solution that is responsible for ultrasonic degradations and the dissolved polymer molecules do not act as cavitation nuclei. Increased surface tension and density of the solvent are thought to be responsible for improved cavitation at low temperatures. Infrared spectroscopy and x-ray analysis of HPC subjected to ultrasonic treatments remained unchanged, suggesting that there were no chemical or structural (e.g., degree of order) changes on irradiation. The decreases in molecular weights on irradiation arise due to random chain scission whereas similar decreases in Huggins coefficients can be attributed to physical changes (decrease in molecular weight or branching) in the degraded HPC samples.     

Thermal Decomposition and Glass Transition Temperature Study of Poly-p-isopropylstyrene

Thermal decomposition and glass transition temperature studies have been carried out on poly-p-isopropylstyrene (PpiPrS) with a differential scanning calorimeter. The un-decomposed polymer as well as its decomposition products were analyzed by gel permeation chromatography (GPC), infrared spectroscopy (IR) and nuclear magnetic resonance (NMR). During isothermal treatments in the 25–150°C temperature range (α < 3%), the observed increase in M arose primarily from interchain linking between the longer radical-bearing chains. Beyond 315°C (α > 6%), the molecular weight increases result from crosslinking reactions between decomposed polymer and longer undecomposed chains. During interchain linking, the number of isomethyl groups (iso-CH³) increase. In the crosslinking reactions that take place at temperatures beyond 315°C, the number of iso-CH³ and terminal or α-methyl groups (α-CH³) both increase while the number of methylene groups (CH²) decreases. Activation energies of decomposition for various homologs of polystyrene (PS) obey the following order: E_PS > E_PpiPrS > E_PpiPrαMeS ≥ E_PαMeS. A comparison of the Tg_e values of PS with those of PpiPrS, poly-α-methylstyrene (PαMeS) and poly-p-isopropyl-α- methylstyrene (PpiPrαMeS) shows that the presence of the p-isopropyl groups lowers the T_g of PS as well as that of PaMeS by about 30–35° K.     

Kinetics of Alkali-Catalyzed 2,5-Dimethylphenol-Forrnaldehyde Reaction

A kinetic study of the reaction between 2,5-dimethylphenol (2,5-DMP) and formaldehyde has been carried out at 65, 70, 75, and 80 ± 0.05° C by using sodium hydroxide as the catalyst. The solvent mixture used in the kinetic experiments was 50% (v/v) methanol-water. The various alkali concentrations used were 0.003, 0.006, 0.010, 0.018 and 0.025 N. The reaction was found to obey second-order rate law. The rate of reaction was observed to increase with an increase in the alkali concentration. The effect of changing the reactant concentrations and the nature of the solvent was also studied. The overall rate constant has been resolved into stepwise rate constants. The entropy of activation and Arrhenius parameters for the overall reaction have also been calculated.     

Synthesis and Characterization of Photoactive Amphiphilic Polymers

We have synthesized light sensitive nano micelles for their applications as drug delivery agents. Various azo compounds having different dipole moment values have been covalently attached to an amphiphilic pegylated co‐polymer and their light sensitive behavior has been studied in both aqueous and organic media with ultra violet light to understand the light dependent supramolecular organization.     

Ultrasonic Solution Degradations of Polystyrene and Substituted Polystyrenes in Tetrahydrofuran as Solvent

Abstract

Ultrasonic (70 W, 20 kHz) solution (2% THF) degradations of polystyrene (PS), poly(α-methylstyrene) (PαMeS), poly(p-isopropyl α-methylstyrene) (PpiPrαMeS), poly(p-chlorostyrene) (PpCIS), poly(p-bromostyrene) (PpBrS), and poly(p-methoxystyrene) (PpOMeS) have been carried out in tetrahydrofuran at 27° C. The average number of chain scissions S (where S = [(M _n)₀/(M _n)_t] - 1), computed from the overall values of [(M _n)₀ and (M _n)_t, were found to be different from those of S' (where S' = α([(M _n)₀/(M _n)_t] - 1)) based on the component (only that part of the polymer which is involved in degradation) data of the weight fraction (α), (M _n)₀, and (M _n)_t), S' for polystyrene and substituted polystyrene follows the order PS gt; PpCIS gt; PpiPrαMeS gt; PpBrS gt; PpOMeS gt; PαMeS. In the case of PS where degradations were also carried out at -20°C, lowering of the temperature increased the weight fraction of polymer degraded as well as S. Based on the viscosity and GPC data, it is concluded that the ultrasonic solution degradation of PS does not lead to branched polymers.     

Asymmetric Stereodivergent Strategy Towards Aminocyclitols

A concise asymmetric synthesis of aminocyclitols, such as diastereomeric 2‐deoxystreptamine analogues and conduramine A, is described. The Pd‐catalyzed asymmetric desymmetrization of meso 1,4‐dibenzolate enables the synthesis of highly oxidized cyclohexane architectures. These scaffolds can potentially be used to access new aminoglycoside antibiotics and enantiomerically pure α‐glucosidase inhibitors.     

Chemical analysis of norrisolide-induced Golgi vesiculation

The chemical origin of the norrisolide-induced irreversible Golgi vesiculation was studied using a variety of norrisolide probes. This natural product was found to bind to a receptor on the Golgi membranes using the perhydroindane core fragment as the recognition element. The acetylated gamma-lactol-gamma-lactone side chain of norrisolide is essential for the irreversible Golgi vesiculation and can be replaced by other electrophilic motifs without loss of biological function. In particular, compound 10 reproduces the cellular phenotype of the natural product.