Search results for "RISA"
showing 10 items of 788 documents
A “click” approach to ROMP block copolymers
2008
Amphiphilic block copolymers can be conveniently prepared via convergent syntheses, allowing each individual polymer block to be prepared via the polymerization technique that gives the best architectural control. The convergent “click-chemistry” route presented here, gives access to amphiphilic diblock copolymers prepared from a ring opening metathesis polymer and polyethylene glycol. Because of the high functional group tolerance of ruthenium carbene initiators, highly functional ring opening metathesis polymerization (ROMP) polymer blocks can be prepared. The described synthetic route allows the conjugation of these polymer blocks with other end-functional polymers to give well-defined a…
Carbon fibre composite materials produced by gamma radiation induced curing of epoxy resins
2008
It is well known that ionizing radiation can initiate polymerization of suitable monomers for many applications. In this work an epoxy dlfunctional monomer has been used as matrix of a carbon fibre composite in order to produce materials through gamma radiation, for aerospace and advanced automotive applications. Radiation curing has been performed at different absorbed doses and, as comparison, also thermal curing of the same monomer formulations has been done. Furthermore some Irradiated samples have been also subjected to a post Irradiation thermal curing in order to complete the polymerization reactions. The properties of the cured materials have been studied by moisture absorption isot…
Normal-phase (temperature gradient) interaction chromatography – A powerful tool for the characterisation of high molecular weight chain-end function…
2015
Abstract We report here, for the first time, quantitative analysis of end-group functionalisation and the extent of end-group modification of polymers with molar mass up to 200,000 g mol −1 , using a combination of isothermal and temperature gradient interaction chromatography. At such high molecular weights, other common analytical techniques such as MALDI-ToF-MS and NMR spectroscopy are simply unable to offer any quantitative insight into the end-group functionality of polymers. Thus, normal phase isothermal interaction chromatography (NP-IIC) has been used to characterise a series of polystyrene samples, with identical molar mass (c. 90,000 g mol −1 ), each carrying a single chain-end fu…
Functional end groups for polymers prepared using ring-opening metathesis polymerization.
2011
The precise placement of functional groups on the chain-ends of macromolecules is a major focus of polymer research. Most common living polymerization techniques offer specific methods of end-functionalization governed by the active propagating species and the kinetics of the polymerization reaction. Ring-opening metathesis polymerization has established itself as one of the most functional-group-tolerant living polymerization techniques known, but this tolerance has limited the number of available functionalization reactions. Metathesis chemists have therefore been required to develop a variety of end-functionalizations, adapting each of them to the reactivity scheme of the particular cata…
N-Methyldehydroamino acids promote a configuration cis of N-methylamide bond
2008
Abstract Dehydroamino acids with a methylated N-terminal tertiary amide bond occur in natural small cyclic peptide toxins. To investigate their conformational preferences a systematic theoretical analysis was performed on N ′-methylamides of N -acetyl- N -methyldehydroamino acids (Ac-Δ(Me)Xaa-NHMe, where Xaa = ( Z )-Abu, ( E )-Abu, Val, ( Z )-Phe, and ( E )-Phe) considering the configuration trans and cis of the tertiary amide bond. The ϕ , ψ potential energy surfaces were calculated at the B3LYP/6-31+G ∗∗ //HF/3-21G level with inclusion of the solvent (water) effect (SCRF method). The conformers localised were fully optimised at the B3LYP/6-31+G ∗∗ in vacuo. The accessible areas of the pot…
Properties and morphology of PMMA/ABN blends obtained via MMA in situ polymerisation through γ-rays
2001
Abstract Methylmethacrylate polymerisation in the presence of 4 wt% butadiene-acrylonitrile rubber was carried out at fixed dose-rate and temperature. The effect of irradiation was investigated with respect to the mechanical and dynamic-mechanical properties in the solid state. A general increase of the “compatibilisation” on irradiation is obtained. In fact both rubber and polymethylmethacrylate glass transition temperatures, determined through dynamic-mechanical analysis, reveal the presence of strong interactions between the components. Furthermore an improvement of the mechanical tensile properties of the blends is observed when irradiation is continued after polymerisation, at least un…
Racemic and Optically Pure Heptahelicene-2-carboxylic Acid: Its Synthesis and Self-Assembly into Nanowire-Like Aggregates
2010
Heptahelicene-2-carboxylic acid was effectively synthesised from suitably functionalised naphthalene building blocks. Methoxy-substituted 1,1'-ethyne-1,2-diylbis(2-but-3-yn-1-ylnaphthalene) was cyclised in the presence of CpCo(CO)(2)/PPh(3) to 2-methoxy-7,8,11,12-tetrahydroheptahelicene, which was converted into heptahelicen-2-yl trifluoromethanesulfonate. This reactive intermediate underwent Pd(OAc)(2)/dppp-catalysed methoxycarbonylation reaction to provide, after hydrolysis, heptahelicene-2-carboxylic acid. The racemate was resolved into enantiomers by semipreparative HPLC on a chiral column. The helicity of (+)-(P)-heptahelicene-2-carboxylic acid was assigned by correlating its CD spectr…
On the Importance of Carbohydrate-Aromatic Interactions for the Molecular Recognition of Oligosaccharides by Proteins: NMR Studies of the Structure a…
2005
The specific interaction of a variety of modified hevein domains to chitooligosaccharides has been studied by NMR spectroscopy in order to assess the importance of aromatic-carbohydrate interactions for the molecular recognition of neutral sugars. These mutant AcAMP2-like peptides, which have 4-fluoro-phenylalanine, tryptophan, or 2-naphthylalanine at the key interacting positions, have been prepared by solid-phase synthesis. Their three-dimensional structures, when bound to the chitin-derived trisaccharide, have been deduced by NMR spectroscopy. By using DYANA and restrained molecular dynamics simulations with the AMBER 5.0 force field, the three-dimensional structures of the protein-sugar…
Capillary column gas chromatographic identification of sugars in honey as trimethylsilyl derivatives.
1987
A method for identifying carbohydrates (mono-, di- and trisaccharides) in honey is presented. It is based on the separate preparation of both trimethylsilyl ethers and oxime trimethylsilyl ethers of the sugars followed by their gas chromatographic separation on a fused-silica capillary column coated with OV-101 using temperature programming. From the two chromatograms, the number of peaks given by each derivatized sugar, their relative retention times and peak-area ratios are used for identification. The identities of two unidentified trisaccharide peaks are considered. Quantitative applications to honey sugar analysis are discussed.
ChemInform Abstract: Oligosaccharide Synthesis via Electrophile-Induced Activation of Glycosyl-N-allylcarbamates.
2010
Abstract Glycosyl-N-allyl carbamates, obtained by reaction of anomerically unprotected saccharides with allyl isocyanate, can be activated by an electrophile-induced cyclisation and reacted with glycosyl acceptors to form the corresponding oligosaccharides By this method the mucin core 2 trisaccharide2 has successfully been synthesized. Due to the mild glycosylation conditions even 1-O-acetyl protected glycosyl acceptors can be used. This was demonstrated in the synthesis of a 1,6-linked glucosyl trisaccharide whereby a reptitious glycosylation strategy could be applied. 1. Dedicated to the memory of Professor Akira Hasegawa.