Pressure-induced polymorphism in enstatite (MgSiO3) at room temperature: clinoenstatite and orthoenstatite

The phase transition of a synthetic clinoenstatite in a diamond-anvil cell has been studied by using Raman spectroscopy at various pressures and room temperature. The phenomena observed in clinoenstatite have been compared with that observed in orthoenstatite. It is found that the pressure-induced phase transitions in the two enstatites are reversible, but with different transition pressures and transition behavior. An analysis of Raman spectra has revealed that the two enstatites have different high-pressure polymorphs. This result suggests that the space group of the high-pressure polymorph of orthoenstatite is not of C2/c, and that orthoenstatite and orthoferrosilite have different transition routes at room temperature and high pressure. The compressional behavior of the high-PC2/c enstatite is also discussed according to the pressure dependences of Raman frequencies.     

Optical characterization of CdTe/ZnSe fractional monolayer structures grown by atomic layer epitaxy

Luminescence properties of CdTe/ZnSe fractional monolayer grown by atomic layer epitaxy have been investigated. To investigate the origin of the highly efficient luminescence, various optical spectroscopic methods such as, photoluminescence (PL), temporal/spatial resolved PL, temperature dependence PL, and excitation power dependence PL have been used. It is found that structural inhomogeneities affect dominant influence on the line width and line shape of luminescence. The luminescence intensity greatly enhanced by the localization of exciton at the disorder induced localized states.     

Microwave Assisted Conversion of Oximes and Semicarbazones to Carbonyl Compounds Using Benzyltriphenylphosphonium Peroxymonosulfate

Summary.  Benzyltriphenylphosphonium peroxymonosulfate in the presence of catalytic amounts of bismuth chloride was found to be an efficient and mild reagent for the oxidative cleavage of oximes and semicarbazones to the corresponding carbonyl compounds under microwave irradiation. Corresponding author. E-mail: haji@cc.iut.ac.ir Received March 4, 2002; accepted (revised) April 8, 2002     

Insertion of benzothiazolium compounds into montmorillonite interlayers

Benzothiazolium compounds exhibit pronounced antimicrobial activities and stimulation effects on plant growth. When applied to fields they can pollute soil colloids. In contact with the soil they can potentially interact with a clay fraction giving rise to clay organocomplexes. Model intercalation complexes were prepared using monoionic montmorillonite and a variety of water-soluble benzothia zolium salts. It was found that the adsorption into the silicate interlayer space proceeds via a cation exchange process. Substantial differences were observed in the extent of the reaction between non-substituted andN-substituted species. The sulphur atoms present in the benzothiazolium molecules repel the surface oxygen atom: this is considered to be the factor responsible for prevention of insertion of the guest cations perpendicular to the layers.     

Thermal Behavior of Urea-(D) Tartaric Acid and Urea-(DL) Tartaric Acid Crystals

The thermal behavior of two new non-linear optical (NLO) materials, urea-(D) tartaric acid (UDT) and urea-(DL) tartaric acid (UDLT) were studied by using DSC, TG and TMA. The results show that: 1) The two crystals have different melting points but similar decomposition temperatures due to the influences of intermolecular forces, which is attributed to the stereo effects of (D)-tartaric and (DL)-tartaric acid molecules; 2) There was only thermal expansion and no thermal contraction when the UDT and UDLT crystals were heated; 3) There was no phase transition within the measured temperature range; 4) The thermal expansion of the UDT and UDLT crystals shows a small anisotropy; 5) The specific heats of UDT and UDLT change linearly with temperature in the measured temperature range and the value for UDT is 1.321 J g-1 K-1 at 320 K while the specific heat of UDLT is 1.357 J g-1 K-1 at the same temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of humic substances on sorption and methylation processes of inorganic- and organo-tin species

The influence of humic substances on sorption and methylation processes for inorganic- and organotin species is presented. Four sediment samples from different locations of the Rivers Elbe, Mulde and Spittelwasser, Germany, with different organotin and humic contents were selected to extract the humic and fulvic acids. The various fractions—the original sediment, the humic acid, the fulvic acid and the residual sediment—were analysed for their organotin content. The individual buyltin species show quite different distribution patterns. Monobutyltin is found mostly associated with humic acids. Dibutyltin shows a nonunique behaviour. At low total organotin content, dibutyltin is found bonded to humic and fulvic acids, whereas at high organotin content dibutyltin is distributed more with the residual sediment. Most of the tributyltin remains in the sediment unextracted; only small quantities of it are in the fulvic acid fraction. Tetrabutyltin is only in the humic acid fraction when it binds to humic matter; it mostly remains in the sediment. General observations indicate that ionic butyltin species bind to fulvic acids whereas the non-polar tetrabutyltin is not found in the fulvic acid fractions in any of the samples. The appearance of monomethyl- and dimethyl-tin species in the humic and fulvic acid fractions after the alkaline extraction was surprising. There is a correlation between the humic content of the sample and the formation of methyltin species. Evidence is provided by experiments that humic substances act as methylation agents.     

Facile syntheses of surface-functionalized micelles and shell cross-linked nanoparticles

Block copolymer micelles and shell cross-linked nanoparticles (SCKs) presenting Click-reactive functional groups on their surfaces were prepared using two separate synthetic strategies, each employing functionalized initiators for the controlled radical polymerization of acrylate and styrenic monomers to afford amphiphilic block copolymers bearing an alkynyl or azido group at the α-terminus. The first route for the synthesis of the azide-functionalized nanostructures was achieved via sequential nitroxide-mediated radical polymerization (NMP) of tert-butyl acrylate and styrene, originating from a benzylic chloride-functionalized initiator, followed by deprotection of the acrylic acids, supramolecular assembly of the block copolymer in water and conversion of the benzylic chloride to a benzylic azide. In contrast, the second strategy utilized an alkynyl-functionalized reversible addition fragmentation transfer (RAFT) agent directly for the RAFT-based sequential polymerization of tetrahydropyran acrylate and styrene, followed by selective cleavage of the tetrahydropyran esters to give the α-alkynyl-functionalized block copolymers. These Click-functionalized polymers, with the functionality located at the hydrophilic polymer termini, were then self-assembled using a mixed-micelle methodology to afford surface-functionalized “Clickable” micelles in aqueous solutions. The optimum degree of incorporation of the Click-functionalized polymers was investigated and determined to be ca. 25%, which allowed for the synthesis of well-defined surface-functionalized nanoparticles after cross-linking selectively throughout the shell layer using established amidation chemistry. Functionalization of the chain ends was shown to be an efficient process under standard Click conditions and the resulting functional groups revealed a more “solution-like” environment when compared to the functional group randomly inserted into the hydrophilic shell layer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5203–5217, 2006