Synthesis of mesoporous TiO2/SiO2 hybrid films as an efficient photocatalyst by polymeric micelle assembly

Thermally stable mesoporous TiO2/SiO2 hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle-assembly method. A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles. The effective interaction of titanium tetraisopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) with the polymeric micelles enabled us to fabricate stable mesoporous films. By changing the molar ratio of TEOS and TTIP, several mesoporous TiO2/SiO2 hybrid films with different compositions can be synthesized. The presence of amorphous SiO2 phase effectively retards the growth of anatase TiO2 crystal in the pore walls and retains the original mesoporous structure, even at higher temperature (650 °C). These TiO2/SiO2 hybrid films are of very high quality, without any cracks or voids. The addition of SiO2 phase to mesoporous TiO2 films not only adsorbs more organic dyes, but also significantly enhances the photocatalytic activity compared to mesoporous pure TiO2 film without SiO2 phase.

PVA-PSSA Membrane with Interpenetrating Networks and its Methanol Crossover Mitigating Effect in DMFCs

A membrane with interpenetrating networks between poly(vinyl alcohol) (PVA) and poly(styrene sulfonic acid) (PSSA) coupled with a high proton conductivity is realized and evaluated as a proton exchange membrane electrolyte for a direct methanol fuel cell (DMFC). Its reduced methanol permeability and improved performance in DMFCs suggest the new blend as an alternative membrane to Nafion membranes. The membrane has been characterized by powder X-ray diffraction, scanning electron microscopy, time-modulated differential scanning calorimetry, and thermogravimetric analysis in conjunction with its mechanical strength. The maximum proton conductivity of 3.3×10−2 S/cm for the PVA–PSSA blend membrane is observed at 373 K. From nuclear magnetic resonance imaging and volume localized spectroscopy experiments, the PVA–PSSA membrane has been found to exhibit a promising methanol impermeability, in DMFCs. On evaluating its utility in a DMFC, it has been found that a peak power density of 90 mW/cm2 at a load current density of 320 mA/cm2 is achieved with the PVA–PSSA membrane compared to a peak power density of 75 mW/cm2 at a load current density of 250 mA/cm2 achievable for a DMFC employing Nafion membrane electrolyte while operating under identical conditions; this is attributed primarily to the methanol crossover mitigating property of the PVA–PSSA membrane.

Structure of Ferroverdin

FERROVERDIN, a green iron-containing pigment, was isolated in 1955 by Chain, Tonolo and Carilli1 from an unidentified species of Streptomyces. It was at first assigned the formula C30H24O8N2Fe and the iron was shown by measurements of magnetic susceptibility to be in the ferrous state2. Later the ligand present was proved to be the p-vinyl phenyl ester of 3-nitroso-4-hydroxy-benzoic acid3,4. X-ray crystallographic measurements were undertaken to find the atomic arrangement in this unusual complex; they show, in two different crystal structures, that each iron atom is attached to three nitrosophenyl ligands and that the charge is balanced by sodium ions.

Bufadienolides. 8. 12(13→14)abeo skeletal rearrangements

Several methods were developed for converting isodigitoxigenin (2a) into methyl acetals 4b and 4c. Of these, methanolysis (followed by acetylation) of isodigitoxigenin in the presence of p-toluenesulfonic acid proved most useful. Each isomer reached an equilibrium corresponding to ca. 3:1 acetal 4c to 4b within 15 min in benzene containing p-toluenesulfonic acid. Addition of dihydropyran to the equilibrium mixture resulted in excellent conversion into vinyl ether 5a. Heating either acetal 4b or 4c in benzene containing p-toluenesulfonic acid led to a skeletal rearrangement culminating in formation of C-norcardenolide 6. In addition to results of physical measurements, the structure of spiran 6 was confirmed by degradation to methyl ketone 8. Similar rearrangement of isodigitoxigenin gave spiran 9 accompanied by C-norcardenolide 6. Treating lactone 9 with p-toluenesulfonic acid in methanol-water provided acetals 10a and 10b, which on further contact with p-toluenesulfonic acid in refluxing benzene gave lactone 9 and cardenolide 6. Evidence underlying the stereochemical assignments noted for structures 4, 9, and 10 was also discussed.

Microbially Induced Mineral Beneficiation

The divergent role of microbes in the field of mineral processing starting from mining and beneficiation to efficient waste disposal has been well recognized now. The roles of various microorganisms and bioreagents in the beneficiation of minerals are illustrated in this paper. Various types of microorganisms useful in bringing about selective flotation and flocculation of various oxide and sulfide minerals are illustrated. Interfacial phenomena governing microbe-mineral interactions are discussed with reference to bacterial cell wall architecture, cell surface hydrophobicity, electrokinetic data, and adsorption behavior on various minerals. Applications of microbially induced mineral beneficiation are demonstrated with respect to beneficiation of iron ores, bauxite, limestone, and complex multimetal sulfides.

Synthetic investigations in the sesamin group - Part I. Synthesis of samin, a degradation product of sesamolin

Ethylα-bromovinylacetate (VII) was condensed with the sodio derivative of ethyl piperonoylacetate (VIII) to give diethylα-vinyl-α′-piperonoylsuccinate (IX). The latter on reduction with lithium aluminium hydride furnished the triol (X), which underwent smooth cyclisation with 1% ethanolic hydrogen chloride to 2-(3′, -methylenedioxyphenyl)-hydroxymethyl-4-vinyltetrahydrofuran (XIa). The structure of XIa was established by Oppenauer oxidation to an aldehyde. Ozonolysis of XIa afforded samin (I).

Synthesis of cyclohexylideneacetaldehyde 2-, 3- and 4-methylcyclohexylideneacetaldehyde

Cyclohexanone and 2-, 3- and 4-methylcyclohexanones have been condensed with acetylene to give the respective 1-ethinylcyclohexanola. The 1-ethinylcyclohexanols were hydrogenated to the respective 1-vinyl- and 1-ethylcyclohexanols. The 1-vinylcyclohexanols have been treated with phosphorus tribromide to give the corresponding rearranged β-cyclohexylidenethyl bromides which have been converted to the pyridinium salts. The latter were treated with p-nitrosodimethylaniline and alkali (Krohnke's method) to give the corresponding nitrones which were hydrolyzed to the corresponding aldehydes. The 1-ethinyl-, 1-vinyl- and 1-ethylcyclohexanols prepared were subjected to pharmacological tests.

Mechanical and Thermal Properties of Eva Blended with Biodegradable Ethyl Cellulose

In this study, biodegradable blend of Poly (Ethylene-co-Vinyl Acetate) (EVA) and Ethyl Cellulose (EC) were prepared. Ethylene vinyl alcohol (EVOH) copolymer was used as an interfacial compatibilizer to enhance adhesion between EVA and EC. The melt blended compatibilized biocomposites were examined for mechanical and thermal properties as per the ASTM standards. It has been found that the EC has a reinforcing effect on EVA leading to enhanced tensile strength and also impart biodegradability. Thus, a high loading of 50% EC could be added without compromising Much on the mechanical properties. Analysis of the tensile data using predictive theories showed an enhanced interaction of the dispersed phase (EC) and the matrix (EVA). The compatibilizing effects of EVOH on these blends were confirmed by the significant improvement in the mechanical properties comparable with neat EVA as also observed by SEM microscopy. The TGA thermograms exhibits two-stage degradation and as EC content increases, the onset temperature for thermal degradation reduces. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 1044-1056, 2010

Direct observation of low frequency confined acoustic phonons in silver nanoparticles: Terahertz time domain spectroscopy

Terahertz time domain spectroscopy has been used to study low frequency confined acoustic phonons of silver nanoparticles embedded in poly (vinyl alcohol) matrix in the spectral range of 0.1-2.5 THz. The real and imaginary parts of the dielectric function show two bands at 0.60 and 2.12 THz attributed to the spheroidal and toroidal modes of silver nanoparticles, thus demonstrating the usefulness of terahertz time domain spectroscopy as a complementary technique to Raman spectroscopy in characterizing the nanoparticles. (C) 2010 American Institute of Physics. [doi:10.1063/1.3456372]

Terahertz Spectroscopy of Single-Walled Carbon Nanotubes in a Polymer Film: Observation of Low-Frequency Phonons

We investigate the dielectric response of single-walled carbon nanotubes dispersed in poly(vinyl alcohol) matrix by using terahertz time domain spectroscopy. Frequency-dependent real and imaginary parts of the complex dielectric function are measured experimentally in the terahertz regime. The low-frequency phonons of carbon nanotubes, though predicted theoretically, are directly observed for the first time at frequencies 0.26, 0.60, and 0.85 THz. Further, a broad resonance is observed at 1.15 THz associated with the longitudinal acoustic mode of vibration of straight-chain segments of the long polymeric molecules in the film. The latter is observed at 1.24 THz for a pristine polymer film and has been used to derive the size of crystalline lamellae in the film.

PVA-SSA-HPA Mixed-Matrix-Membrane Electrolytes for DMFCs

Stabilized forms of heteropolyacids (HPAs), namely phosphomolybdic acid (PMA), phosphotungstic acid (PTA), and silicotungstic acid (STA), are incorporated into poly (vinyl alcohol) (PVA) cross-linked with sulfosuccinic acid (SSA) to form mixed-matrix membranes for application in direct methanol fuel cells (DMFCs). Bridging SSA between PVA molecules not only strengthens the network but also facilitates proton conduction in HPAs. The mixed-matrix membranes are characterized for their mechanical stability, sorption capability, ion-exchange capacity, and wetting in conjunction with their proton conductivity, methanol permeability, and DMFC performance. Methanol-release kinetics is studied ex situ by volume-localized NMR spectroscopy (employing point-resolved spectroscopy'') with the results clearly demonstrating that the incorporation of certain inorganic fillers in PVA-SSA viz., STA and PTA, retards the methanol-release kinetics under osmotic drag compared to Nafion, although PVA-SSA itself exhibits a still lower methanol permeability. The methanol crossover rate for PVA-SSA-HPA-bridged-mixed-matrix membranes decreases dramatically with increasing current density rendering higher DMFC performance in relation to a DMFC using a pristine PVA-SSA membrane. A peak power density of 150 mW/cm(2) at a load current density of 500 mA/cm(2) is achieved for the DMFC using a PVA-SSA-STA-bridged-mixed-matrix-membrane electrolyte. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3465653] All rights reserved.

Synthesis of Diversified Thioethers,1-Aroylalkylisoquinolin-1-yl Thioethers, by Electrophilic S-Alkylation of 3-Phenyl Isoquinoline-1(2H)-thione

A mild and efficient method for the synthesis of thioethers has been developed. The 3-phenylisoquinoline-1(2H)-thione underwent S-alkylation to afford structurally diverse sulfides in high yield.

Study of the growth of capped ZnO nanocrystals: A route to rational synthesis

We report the study of complex and unexpected dependencies of nanocrystal size as well as nanocrystalsize distribution on various reaction parameters in the synthesis of ZnO nanocrystals using poly(vinyl pyrollidone) (PVP) as a capping agent. This method establishes a qualitatively different growth mechanism to the anticipated Ostwald ripening behavior. The study of size-distribution kinetics and an understanding of the observed non-monotonic behaviors provides a route to rational synthesis. We used a simple, but accurate, approach to estimate the size-distribution function of nanocrystals from the UV-absorption spectrum. Our results demonstrate the accuracy and generality of this approach, and we also illustrate its application to various semiconducting nanocrystals, such as ZnO, ZnS, and CdSe, over a wide size range (1.8-5.3 nm).

Facile hydrothermal synthesis and observation of bubbled growth mechanism in nano-ribbons aggregated microspherical Covellite blue-phosphor

Well uniform microspheres of phase pure Covellite were synthesized through a simple hydrothermal approach using poly vinyl pyrrolidone (PVP) as surfactant. The micro-spheres were constituted of numerous self-organized knitted nano-ribbons of similar to 30 nm thickness. The effect of conc. PVP in the hydrothermal precursor solution on the product morphology was investigated. Based on the out-coming product micro-architecture a growth mechanism was proposed which emphasized bubbled nucleation inside the hydrothermal reactor. In a comparative study on linear optical properties, enhancement of luminescent intensity was observed for nano-ribbon clung microspheres rather than that of agglomerates of distorted particles, which may be attributed to better crystallinity as well as reduced surface defects and ionic vacancies for ribbon-like nano-structures.

Chemoenzymatic Synthesis of Chiral Organosulfur Compounds

This thesis is primarily concerned with the enzyme- catalysed synthesis of sulfoxides using reductase and dioxygenase enzymes. Chapter 1 provides an introduction to the topic of redox chemistry with particular emphasis on the application of reductase and dioxygenase enzymes in organosulfur chemistry. Earlier literature methods for the production of enantiopure sulfoxides are reviewed. A brief discussion of the methods used for the determination of enantiomeric excess and absolute configuration is provided. Chapter 2 contains results obtained using a range of whole-cell bacteria each using a dimethyl sulfoxide reductase enzyme. The synthesis of a series of racemic sulfoxides and the development of appropriate CSPHPLC analytical methods is discussed. Kinetic resolutions of a series of sulfoxides have been achieved. Chapter 3 contains a presentation of results using dioxygenase enzymes as biocatalysts for the asymmetric sulfoxidation of dialkyl sulfoxides including thioacetal sulfoxides. A new range of monosulfoxides, cis-dihydrodiols and cis- dihydrodiol sulfoxides have been isolated in enantiopure form. Chapter 4 is focussed on the application of chiral sulfoxides in synthesis. A new chemoenzymatic route to diol sulfoxide enantiomers and the derived enantiopure phenols and catechols is discussed. The application of chemically synthesised sulfoxide enantiomers in the production of hydroxy sulfoxides is reported. Chapter 5 provides a full experimental section where the synthesis of sulfides and racemic sulfoxides is included. The methods used in the isolation and characterisation of bioproducts from the biotransformation are discussed and full experimental details given.