Physicochemical studies on hydrophobic PEO‐PPO‐PEO triblock copolymer micelles in SDS micellar environment

The shape, size, aggregation, hydration, and correlation times of water insoluble PEO‐PPO‐PEO triblock copolymer micelles with sodium dodecylsulfate (SDS) micelles were investigated using transport studies and dynamic light scattering technique. From the conductance of micellar solutions of the polymer in 25 mM SDS and 5 mM NaCl, the hydration of polymer micelles were determined using the principle of obstruction of electrolyte migration by the polymer. The asymmetry of the micellar particles of polymer and polymer‐SDS mixed micellar systems in 5 mM NaCl and their average axial ratios were calculated using intrinsic viscosity and hydration data obeying Simha–Einstein equation. Hydration number and micellar sizes were variable with temperature. The shape of the polymer micelles has been ellipsoidal rather than spherical. The micellar volume, hydrodynamic radius, radius of gyration, diffusional coefficients as well as translational, rotational and effective correlation times have been calculated from the absolute values of the axes. The partial molal volume of polymer micelles has also been determined and its comparison with the molar volume of pure polymer suggested a volume contraction due to immobilization of the water phase by the hydrophilic head groups of the polymer. The thermodynamic activation parameters for viscous flow favor a more ordered water structure around polymer micelles at higher temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2410–2420, 2007     

Macromolecular crystallography research at Trombay

Neutron diffraction studies of hydrogen positions in small molecules of biological interest at Trombay have provided valuable information that has been used in protein and enzyme structure model-building and in developing hydrogen bond potential functions. The new R-5 reactor is expected to provide higher neutron fluxes and also make possible smallangle neutron scattering studies of large biomolecules and bio-aggregates. In the last few years infrastructure facilities have also been established for macromolecular x-ray crystallography research. Meanwhile, the refinement of carbonic hydrases’ and lysozyme structures have been carried out and interesting results obtained on protein dynamics and structure-function relationships. Some interesting presynaptic toxin phospholipases have also been taken up for study.     

On the Rayleigh-Plateau instability

In this paper,we study the surface instability of a cylindrical pore in the absence of stress. This instability is called the Rayleigh-Plateau instabilty. We consider the model developed by Spencer et ...     

Synthesis,Antibacterial, and Antioxidant Evaluation of Novel Series of Condensed Thiazoloquinazoline with Pyrido,Pyrano, and Benzol Moieties as Five- and Six-Membered Heterocycle Derivatives

A novel synthesis of thiazolo[2,3-b]quinazolines 4(a–e), pyrido[2′,3′:4,5]thiazolo[2,3-b]quinazolines {5(a–e), 6(a–e), and 7(a–e)}, pyrano[2′,3′:4,5]thiazolo[2,3-b]quinazolines 8(a–e), and benzo[4,5]thiazolo[2,3-b]quinazoloine9(a–e) derivatives starting from 2-(Bis-methylsulfanyl-methylene)-5,5-dimethyl-cyclohexane-1,3-dione 2 as efficient α,α dioxoketen dithioacetal is reported and the synthetic approaches of these types of compounds will provide an innovative molecular framework to the designing of new active heterocyclic compounds. In our study, we also present optimization of the synthetic method along with a biological evaluation of these newly synthesized compounds as antioxidants and antibacterial agents against the bacterial strains, like S. aureus, E. coli, and P. aeruginosa. Among all the evaluated compounds, it was found that some showed significant antioxidant activity at 10 μg/mL while the others exhibited better antibacterial activity at 100 μg/mL. The results of this study showed that compound 6(c) possessed remarkable antibacterial activity, whereas compound 9(c) exhibited the highest efficacy as an antioxidant. The structures of the new synthetic compounds were elucidated by elemental analysis, IR, ¹H-NMR, and ¹³C-NMR.     

KOtBu‐Catalyzed Michael Addition Reactions Under Mild and Solvent‐Free Conditions

Designed transition metal complexes predominantly catalyze Michael addition reactions. Inorganic and organic base‐catalyzed Michael addition reactions have been reported. However, known base‐catalyzed reactions suffer from the requirement of solvents, additives, high pressure and also side‐reactions. Herein, we demonstrate a mild and environmentally friendly strategy of readily available KO^tBu‐catalyzed Michael addition reactions. This simple inorganic base efficiently catalyzes the Michael addition of underexplored acrylonitriles, esters and amides with (oxa‐, aza‐, and thia‐) heteroatom nucleophiles. This catalytic process proceeds under solvent‐free conditions and at room temperature. Notably, this protocol offers an easy operational procedure, broad substrate scope with excellent selectivity, reaction scalability and excellent TON (>9900). Preliminary mechanistic studies revealed that the reaction follows an ionic mechanism. Formal synthesis of promazine is demonstrated using this catalytic protocol.     

Structure determination of Ls-threonine by neutron diffraction

The structure of the aminoacid, L_s-threonine [NH ₃ ⁺ CH(CHOHCH₃)COO^?], space groupP2₁2₁2₁,a=13.630(5),b=7.753(1),c=5.162(2) Å,z=4, has been determined from neutron diffraction data using direct methods. The intensities of 1148 neutron Bragg reflections were measured from a single crystal. The structural parameters were refined by the method of least squares using anisotropic temperature factors. The finalR(F ²) is 0.068. The structure was also refined from the x-ray data of Shoemakeret al (1950J. Am. Chem. Soc. 72 2328); there is good agreement between the two sets of heavy atom parameters. The parameters of hydrogen atoms are of course more precisely determined in our neutron study. The molecular conformation and the hydrogen bonding scheme are discussed. Weighted average values of bond distances and angles from 14 aminoacid structures with ionized carboxylic groups studied by neutron diffraction at Brookheven and Trombay are also presented.     

Novel microscopic mechanism of intermixing during growth on soft metallic substrates

Generic computer simulations using empiric interatomic potentials suggest a new, collective mechanism that could be responsible for mixing at heteroepitaxial interfaces. Even if single adsorbate atoms diffuse by hopping on the substrate surface and do not mix at the terraces, two-dimensional islands formed by nucleation may become unstable above a certain critical size and explode upwards forming clusters of several atomic layers. This process is accompanied by strong distortions of the underlying atomic layers, and on soft materials it can result in surface etching and incorporation of substrate atoms into the islands.     

High pressure phase transitions in organic solids II: X-ray diffraction study ofp-dichlorobenzene at high pressures

X-ray diffraction experiments onp-dichlorobenzene at high pressures show a transition at ～ 0.3 GPa, to a new phase, the diffraction pattern of which cannot be indexed on the anticipated low temperature monoclinic crystal structure. We have instead found an orthorhombic cell, very closely related to the low temperature monoclinic cell, for this new phase. This structure, which also occurs inp-diiodobenzene at ambient conditions, has cell constantsa =14.02,b = 6.06,c = 7.41Å andZ = 4. The space group is Pbca. This new phase has a non-β herring-bone structure, in contrast with the initialα phase which has aβ-structure with ribbon-like arrangement of molecules, with Cl-Cl contacts of ～ 4A between adjacent molecules. This implies that with pressure the halogen-halogen interaction in this compound plays a less dominant role in crystal engineering.