A new pH and thermo-responsive chiral hydrogel for stimulated release

Chirality of the amphiphile to promote gelation in the given solvent medium is narrated in a new catanionic surfactant mixture from a twin-chiral, twin-tailed surfactant derived from tartaric acid and cetyltrimethylammonium bromide (CTAB). The surfactant bis(decyloxy) succinic acid (BDSA), a chiral Gemini-type surfactant with a rigid spacer, in association with CTAB formed pH and temperature responsive vesicles and hydrogels. Molecular chirality gave rise to supertwisted fibrillar hydrogels at a BDSA:CTAB molar ratio of 1:2 and in 31% water content. The hydrogels from enantiomeric BDSA were reversibly pH and irreversibly temperature responsive at pH<6.2 and at 55 degrees C, respectively, whereas the corresponding sodium succinates formed transparent clear gels reversible to both pH and temperature. The hydrogels were able to entrap and release model dye molecules, Rhodamine B, and Congo red, responding to thermal and pH stimuli. Circular dichroism unraveled the chiro-optical behavior of the assembled fibers, allowing monitoring of aggregation and packing. The presence and the relative configuration of the stereogenic centers in the structure of this low molecular weight gelator have been observed to be critical to form gels. The high curvature Gaussian gel network was modeled based on the chiral elastic membrane approach and the pitch angle of the Gaussian twist was estimated to be 45 degrees.     

Geometry and stability of BenCm (n=1-10; m=1, 2, ..., to 11-n) clusters

Density functional theory B3PW91/6-31+G* calculations on BenCm (n=1-10; m=1, 2, ..., to 11-n) clusters have been carried out to examine the effect of cluster size, relative composition, binding energy per atom, HOMO-LUMO gap, vertical ionization potential, and electron affinity on their relative stabilities. The most stable planar cyclic conformations of these clusters always show at least a set of two carbon atoms between two beryllium atoms, while structures where beryllium atoms cluster together, or allow the intercalation of one carbon atom between two of them, generally seem to be the least stable ones. Clusters containing 1, 2, and 3 beryllium atoms (Be2C8, Be3C6, Be2C6, BeC6, Be2C4, BeC4, Be2C2, and BeC2) are identified as clusters of "magic numbers" in terms of their high binding energy per atom, high HOMO-LUMO gap, vertical ionization potential, and second difference in energy per beryllium atom.     

Value of zeolites in asymmetric induction during photocyclization of pyridones, cyclohexadienones and naphthalenones

Two strategies, namely chiral inductor and chiral auxiliary approaches, have been examined within zeolites with the aim of achieving asymmetric induction during the photocyclization of cyclohexadienone, naphthalenone and pyridone derivatives. Within zeolites, enantioselectivity as high as 55% and diastereoselectivity as high as 88% have been obtained. The observed stereoselectivities are significant given the fact that these reactions gave very little stereoselectivities in isotropic solution media. The results obtained on the photocyclization of dienones, naphthalenones and N-alkyl pyridones within zeolites compliment our earlier investigations on the photocyclization of tropolone derivatives, the geometric isomerization of 1,2-diphenylcyclopropanes and 2,3-diphenyl-1-benzoyl cyclopropanes, and the Norrish type II reaction of alpha-oxoamides, phenyl adamantyl ketones, phenyl norbornyl ketones and phenyl cyclohexyl ketones. With the help of these examples, we have established the importance of zeolite and its charge compensating cations in effecting asymmetric induction in photochemical reactions.     

Green synthesis and anticancer activity of tetrahydrodipyrazolo[3,4-b:4′,3′-e]pyridines catalyzed by phospho sulfonic acid

Biologically portent/significant tetrahydrodipyrazolo[3,4-b:4′,3′-e]pyridines are synthesized by an efficient green synthesis of various aldehydes with 3-methyl-1H-pyrazol-5(4H)-one in ammonium acetate using phospho sulfonic acid as a solid catalyst under microwave-assisted interaction under solvent-free conditions at 70°C. This methodology is easy to handle and get good to excellent yields. Later the potential in vitro antiproliferation of the titled compounds is evaluated. Among all the titled compounds, 4s and 4t showed the most potent anticancer potentiality on the used cancer cell lines of SK-BR-3 and HeLa (IC₅₀ = 10.70 ± 0.27 and 12.58 ± 0.38, and 19.38 ± 0.32 and 21.55 ± 0.41 μg/mL for SK-BR-3 cells lines and HeLa cells lines, respectively), which were comparable to the positive control.     

Investigations of enantioreversal in both direct and directed enantioselective aldol reactions catalyzed by CuCl2[(−)-sparteine] and NiCl2[(−)-sparteine] complexes

The use of structurally well-defined chiral [CuCl₂(sparteine)] 1 and [NiCl₂(sparteine)] 2 complexes as catalysts under fluoride anion-promoted double catalytic activation (DCA) conditions cause enantioreversal in the asymmetric Mukaiyama aldol reaction of 1-phenyl-1-trimethylsiloxyethylene with various aromatic aldehydes. A similar enantioreversal also occurs in the direct aldol reaction between methyl vinyl ketone and various aromatic aldehydes under Et₃N promoted DCA conditions. We have quantitatively analyzed using group theoretical analysis via symmetry deformation coordinates, the molecular structures of 1 and 2 from the X-ray structural data; the results from the study show that the innate stereochemical differences that are present in their molecular structures, form the basis for the enantioreversal phenomenon in the asymmetric C–C bond-forming aldol reactions.     

Novel route to spiropiperidines using N-methyl-4-piperidone,malononitrile and electrophiles

A new pathway to spiropiperidine rings via sequential one pot reaction of N-methyl-4-piperidone, malononitrile, and electrophiles or Michael acceptor in the presence of triethyl amine in ethanol under reflux condition is reported.     

Structural,electronic and magnetic properties of quaternary half‐metallic Heusler alloy CoFeCrAl

We have investigated the structural, electronic and magnetic properties in quaternary CoFeCrAl Heusler alloy. Rietveld refinement and Mössbauer spectroscopy of samples quenched from 973 K show absence of the A2 phase and presence of a highly ordered B2‐type structure. Full‐potential linearized augmented plane wave calculations using the experimental lattice constant show that there is an energy gap of 0.41 eV around the Fermi level in the bands for minority spin electrons. Partial substitution of Co by Fe in Co₂CrAl thus brings excellent structural ordering while retaining the high Curie temperature, spontaneous magnetization and half‐metallicity necessary for application as spin valves. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Change of phase by annealing on TiO2 nanoparticles

The decomposition of silver selenide and sulfide to metallic silver and chalcogen containing oxygen compounds by sintering with an equimolar mixture of sodium nitrate and nitrite was examined. It was found that 100% recovery of silver in a metal phase is reached at 5% excess of sodium nitrate and nitrite and a time of the isothermal exposure at 375 °C for 1 hour or 0.5 hours at 400°C.     

Potential of Thermo and Alkali Stable Xylanases from Thielaviopsis basicola (MTCC-1467) in Biobleaching of Wood Kraft Pulp

Thermo- and alkali-stable xylanases produced from Thielaviopsis basicola (MTCC-1467) on low-cost carbon source like rice straw were evaluated for their potential application in biobleaching of wood kraft pulp. Enzyme treatment at retention time of 240?min with 20?IU/gm of dried pulp resulted in ~85.2?% of reduction in kappa number. When compared to control, 110.8, 93, and 72.2?% of enhancement in brightness (percent International Organization of Standardization), whiteness, and fluorescence, respectively, were observed for enzyme-treated pulp. Spectroscopic analysis showed significant release of chromophoric compounds from enzyme-treated pulp. Furthermore, scanning electron microscope studies of unbleached and enzyme bleached pulp revealed the effectiveness of enzymatic treatment. The enzyme-treated pulp subjected to later stages of chemical bleaching resulted in 16?% decrease in chlorine consumption along with considerable reduction in chemical oxygen demand percentage (14.5?%) level of effluent. Various pulp properties like fiber length, fiber width, burst strength, burst index, tear strength, tear index, tensile strength, and breaking length were also significantly improved after enzyme treatment when compared to control.     

SYNTHESIS,SPECTRAL STUDIES,AND ANTIMICROBIAL ACTIVITIES OF [N-(UN)ALKYLATED-2-ARYLINDOL-3-YL]THIOCARBOXAMIDES

A series of [N-(un)alkylated-2-arylindol-3-yl]thiocarboxamides(6) have been synthesized by the condensation of alkyl [N-(un)alkylated-2-arylindol-3-yl]dithiocarboxylates (5) with appropriate secondary amines in absolute alcohol. Compound 5 was prepared by the reaction of N-(un)alkylated-2-arylindoles with carbon disulphide in the presence of potassium-t-butoxide followed by alkyl iodide under nitrogen atmosphere. All of the compounds have been characterized on the basis of their elemental and spectral data and have been screened for their antibacterial and antifungal activities. Some of the synthesized compounds have shown promising activity.