Influence of organic modifiers on morphology and crystallization of poly(ϵ‐caprolactone)/synthetic clay intercalated nanocomposites

ε‐caprolactone was polymerized in the presence of neat montmorillonite or organomontmorillonites to obtain a variety of poly(ε‐caprolactone) (PCL)‐based systems loaded with 10 wt % of the silicates. The materials were thoroughly investigated by different X‐ray scattering techniques to determine factors affecting structure of the systems. For one of the nanocomposites it was found that varying the temperature in the range corresponding to crystallization of PCL causes reversible changes in the interlayer distance of the organoclay. Extensive experimental and literature studies on this phenomenon provided clues indicating that this effect might be a result of two‐dimensional ordering of PCL chains inside the galleries of the silicate. Small angle X‐ray scattering and wide angle X‐ray scattering investigation of filaments oriented above melting point of PCL revealed that polymer lamellae were oriented perpendicularly to particles of unmodified silicate, while in PCL/organoclay systems they were found parallel to clay tactoids. Calorimetric and microscopic studies shown that clay particles are effective nucleating agents. In the nanocomposites, PCL crystallized 20‐fold faster than in the neat polymer. The crystallization rate in nanocomposites was also significantly higher than in microcomposite. Further research provided an insight how the presence of the filler affects crystalline fraction and spherulitic structure of the polymer matrix in the investigated systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2350–2367, 2007     

Synthesis and capsule formation of upper rim substituted tetra-acrylamido calix[4]arenes

Upper rim substituted tetraiodo calix[4]arenes are coupled to a variety of acrylamides using the palladium catalysed Heck reaction. Tetra-acrylamido upper rim substituted calix[4]arenes are obtained in good yields with exceptionally high stereoselectivity, to produce the all-trans isomers. Tetra-acrylamido calix[4]arenes derived from secondary acrylamides are shown to dimerise via eight hydrogen bonds to form dimeric capsules, which are able to include small organic molecules.     

Determination of uranium after its selective extraction as phenylacetate

The method described is based on the extraction of uranium with a chloroform solution of phenylacetic acid from slightly acidic solution containing nitrilotriacetic acid, which masks all interfering metals. After stripping into very dilute hydrochloric acid, uranium is reduced with ascorbic acid and determined complexometrically. The method permits reliable determination of uranium in the presence of all quadri-, ter- and bivalent metals investigated, molybdenum(VI), tungsten(VI), and vanadium(V).     

The Synthesis of Unusual Organic Molecules Using Cyclic Peroxides. New synthetic methods (3)

The photodecarboxylation of malonyl peroxides into α-lactones^[1] and the thermal conversion of the 1,4-endo-peroxide 4,5-epoxy-3,6-epidioxy-1-cyclohexene into the novel benzene trioxide^[2] are two recent examples of the potential of cyclic peroxides in the synthesis of unusual organic molecules. The former transformation entails a fragmentation, the latter a rearrangement process. Most reported examples fall into one of these two gross reaction types. Of the numerous examples that have been reported in the literature during the last two decades, only those shall be focused on that lead to unusual compounds or constitute efficient syntheses of known compounds, in order to stress the convenience of cyclic peroxides in the synthesis of organic compounds.     

Synthetically attractive indolization processes and newer methods for the preparation of selectively substituted indoles

The synthetically interesting processes available for indolization reactions are discussed and illustrated in tabular form and particular emphasis is placed on the more recent methods.     

Internal molecular disorder in the nematic and smectic phases of thermotropic liquid crystals studied by NMR SPDE experiments

The recently developed NMR SPDE experiment is shown to provide a new and particularly convenient technique for probing the conformational dynamics of mesogens in thermotropic liquid crystals. Measurements have been made in the nematic and smectic phases of the 4,4′-di-n-alkoxyazoxybenzenes. It is shown for the first time that the internal disorder of the alkyl end chains is intimately related to the molecular organization of these mesophases.     

Preparative uv-laser photochemistry of the azoalkane spiro(2,3-diazabicyclo [2.2.1]hept-2-ene-7′,1-cyclopropane): Trapping of the 1,4-Diradical 2-(3-Cyclopentenyl) ethyl by Molecular Oxygen

Photo-extrusion of nitrogen from the azoalkane 1 in the presence of molecular oxygen gave besides the hydrocarbons 3 and 5, the endoperoxide 10 and hydroperoxide 11, the former via trapping of the 1,4-diradical 4 by triplet oxygen, the latter by ene-reaction-6f hydrocarbon 5 with singlet oxygen.     

Electron impact mass spectrometry of some 6-substituted tetrazolo[1,5-c]pyrimidin-5(6H)-ones

The electron impact mass spectra of 6-methyltetrazolo[1,5-c]pyrimidin-5(6H)-one, its 7- and 8-methyl derivatives, three 8-halo derivatives and two related nucleosides are reported. On the basis of the high-resolution data and detected metastable ions, the fragmentation routes of their molecular ions are proposed. Coexistence of the tautomeric forms of the title compounds of cyclic (tetrazole) or linear (azide) structure can be suggested owing to the fragmentation pathways identified for the bases. Decomposition of the related nucleosides lies in the breaking of nucleoside bonds to produce the appropriate base and sugar fragments.     

Solvent-modulated chemoselective deprotections of trialkylsilyl esters and chemoselective esterifications

A series of trialkylsilyl esters were deprotected or transesterificated into their corresponding carboxylic acids or methyl esters under a catalytic amount of CBr₄ in alcohol reaction system. This method enables to desilylate secondary sp³-carbon, sp²-carbon, sp-carbon and aryl tethered trialkylsilyl esters to carboxylic acids, whereas primary sp³-carbon tethered trialkylsilyl esters were further converted into their methyl esters under CBr₄/MeOH reaction conditions. The highly chemoselective deprotections can be modulated and achieved by the introduced protecting trialkylsilyl groups and the used alcohols such as MeOH and EtOH under this photochemically-induced reaction conditions.