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991.
992.
Giovanni Ricci Anna Sommazzi Francesco Masi Marco Ricci Aldo Boglia Giuseppe Leone 《Coordination chemistry reviews》2010,254(5-6):661-676
This article provides an overview on recent progress in the polymerization of 1,3-dienes catalyzed by transition metal complexes with phosphorus and nitrogen ligands. Polymers having different microstructures (cis-1,4; 1,2; mixed cis-1,4/1,2) and tacticity (iso- or syndiotactic) were obtained from various 1,3-dienes (1,3-butadiene, isoprene, 1,3-pentadienes, 1,3-hexadienes) depending on the catalyst used, clearly suggesting that the catalyst structure (i.e. metal nature, type of ligand) strongly affects the polymerization chemo- and stereoselectivity. However, as indicated by the results obtained in the polymerization of substituted butadienes, a fundamental role in determining the selectivity is also played by the type of monomer: polymers with different structure, some of them completely new, were obtained from different monomers with the same catalyst. All these observations permitted to confirm, and in some cases to improve, the knowledge on the diene polymerization mechanism. 相似文献
993.
Carrozzo MM Cannazza G Battisti U Braghiroli D Troisi L Parenti C 《Journal of chromatography. A》2010,1217(52):8136-8145
In this study, configurational and chemical stability of (R,R),(S,S),(R,S),(S,R)-3,6-dimethyl-2,3,5,6-tetrahydro[1,2,4]thiadiazino[6,5,4-hi]indole 1,1-dioxide (1) were investigated by dynamic and stopped-flow HPLC methods. Single epimeric mixtures (R,R),(R,S)-1 and (S,S),(S,R)-1 were obtained combining synthetic and chromatographic strategies. Separation of (R,R)-1 and (R,S)-1 was achieved by chiral chromatography and absolute configuration of eluted epimers has been assigned basing on molecular modelling calculations. Epimerization and hydrolysis of (R,R),(R,S)-1 have been studied by classical off-column, dynamic HPLC and stopped-flow HPLC methods. The influence of different parameters, such as temperature, pH and dielectric constant was evaluated. The data obtained indicate that (R,R),(R,S)-1 undergoes to a rapid epimerization in aqueous solvent and hydrolysis in acidic conditions. Moreover, epimerization and hydrolysis were investigated in presence of an artificial membrane and in physiological buffers (pH 2.2 and 7.0 at 37.5°C) to simulate in vivo conditions. 相似文献
994.
Ortensia Ilaria Parisi Francesco Puoci Francesca Iemma Giuseppina De Luca Manuela Curcio Giuseppe Cirillo Umile Gianfranco Spizzirri Nevio Picci 《先进技术聚合物》2010,21(11):774-779
A novel, simple synthetic strategy for the preparation of crosslinked polymers with significant antioxidant properties is proposed. Ferulic acid (FA), a well‐known antioxidant compound, due to its reactivity toward free radical process, was inserted into a polymeric network with methacrylic acid (MAA) and ethylene glycole dimethacrylate acting as comonomer and crosslinker, respectively. All the reactants were simultaneously mixed in the polymerization feed and one‐pot radical reaction was carried out. Irregular microparticles were prepared by bulk polymerization and microspheres by precipitation polymerization. The materials were characterized by nuclear magnetic resonance–magic angle spinning (NMR‐MAS) studies, to verify effective FA insertion into polymeric networks, and by morphological, dimensional analyses, and water absorption measurement to study their superficial and swelling properties, respectively. Antioxidant properties of materials were evaluated by linoleic acid emulsion system–thiocyanate assay, determination of scavenging activity on DPPH radicals, determination of available phenolic groups in polymeric matrices, and determination of total antioxidant capacity. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
995.
Graziano G 《Physical chemistry chemical physics : PCCP》2010,12(42):14245-14252
A polypeptide chain can adopt very different conformations, a fundamental distinguishing feature of which is the water accessible surface area, WASA, that is a measure of the layer around the polypeptide chain where the center of water molecules cannot physically enter, generating a solvent-excluded volume effect. The large WASA decrease associated with the folding of a globular protein leads to a large decrease in the solvent-excluded volume, and so to a large increase in the configurational/translational freedom of water molecules. The latter is a quantity that depends upon temperature. Simple calculations over the -30 to 150 °C temperature range, where liquid water can exist at 1 atm, show that such a gain decreases significantly on lowering the temperature below 0 °C, paralleling the decrease in liquid water density. There will be a temperature where the destabilizing contribution of the polypeptide chain conformational entropy exactly matches the stabilizing contribution of the water configurational/translational entropy, leading to cold denaturation. 相似文献
996.
Alena Průšová Pellegrino Conte Jiří Kučerík Giuseppe Alonzo 《Analytical and bioanalytical chemistry》2010,397(7):3023-3028
Fast field cycling (FFC) NMR relaxometry has been used to study the conformational properties of aqueous solutions of hyaluronan
(HYA) at three concentrations in the range 10 to 25 mg mL–1. Results revealed that, irrespective of the solution concentration, three different hydration layers surround hyaluronan.
The inner layer consists of water molecules strongly retained in the proximity of the HYA surface. Because of their strong
interactions with HYA, water molecules in this inner hydration layer are subject to very slow dynamics and have the largest
correlation times. The other two hydration layers are made of water molecules which are located progressively further from
the HYA surface. As a result, decreasing correlation times caused by faster molecular motion were measured. The NMRD profiles
obtained by FFC-NMR relaxometry also showed peaks attributable to 1H–14N quadrupole interactions. Changes in intensity and position of the quadrupolar peaks in the NMRD profiles suggested that
with increasing concentration the amido group is progressively involved in the formation of weak and transient intramolecular
water bridging adjacent hyaluronan chains. In this work, FFC-NMR was used for the first time to obtain deeper insight into
HYA–water interactions and proved itself a powerful and promising tool in hyaluronan chemistry. 相似文献
997.
Equilibrium states of elastic-brittle solids that may suffer nucleation of cracks in finite deformation setting are analyzed. Crack patterns are described in terms of appropriate Radon measures, namely curvature varifolds with boundary. A new form of the energy is presented: it includes terms associated with the curvature of margins and tips of possible cracks. Existence of minima of the energy is established in classes of pairs of deformation and families of varifolds. Configurational balances in weak form are determined with reference to generic curvature varifolds with boundary. They include non-standard terms associated with the curvatures involved in the energy. Pointwise balances of configurational actions are also evaluated in a special case: new pointwise balances at the tips and along the margins of the crack pattern emerge. 相似文献
998.
Francesco Crea Concetta De Stefano Giuseppe Manfredi Silvio Sammartano 《Journal of Molecular Liquids》2010,151(2-3):138-144
The interactions of two high molecular weight polycarboxylic ligands [polyacrylic-co-maleic, MW = 70 kDa, and poly(methyl vinyl ether-co-maleic acid), MW = 15 kDa] with some polyamines [1,4-diaminobutane (or putrescine), histamine and poly(allyl)amine, MW = 15 kDa] were studied, at t = 25 °C and at low ionic strength (I = 0.015 mol L? 1) by potentiometric measurements. For all investigated systems, the formation of (am)(L)Hi species was found (am = amine, L = polycarboxylic ligand, i = 1…4); the stability of polyammonium–polycarboxylate complexes is fairly high and the formation percentage of most species reaches ~ 90% in the experimental conditions (mmolar concentration of reactants). The dependence on temperature and ionic strength of the stability of polyamine–polycarboxylate species was studied using some semiempirical equations and enthalpy data for the protonation of both components. The sequestering ability of polyelectrolytes towards amines was modeled by a sigmoid Boltzman type equation and was defined by calculating the parameter pL50 (the total ligand concentration, as ? log CL, able to bind 50% of cation); this parameter gives an objective representation of this ability. The dependence of pL50 on pH, ionic strength and temperature was studied too. 相似文献
999.
In order to improve textile fabric abrasion resistance, in this work a SiOxCyHz thin film was realized by low pressure plasma chemical vapour deposition (PCVD) at room temperature, using hexamethyldisiloxane (HMDSO) as precursor compound. To test changes in the performance properties of the surface finished samples as a function of the type of the substrate, the deposition was carried out on different textile fabrics. The polymerization processes were followed by weight measurements of textile fabrics. It was found that, after PCVD, a significantly lower fabric weight loss was observed on treated samples after rubbing than on the untreated samples. The morphology, elemental composition and type of chemical bonding present in the film applied on textile fabrics were also investigated using electron scanning microscopy (SEM), energy dispersive X-ray (EDX) and infrared spectroscopy techniques (FT-IR (ATR)). The results showed a substantial enhancement of wear resistance for the surfaces modified with the presented process, while tensile and tearing strength were adversely affected. 相似文献
1000.
Danilo Cuccato Marco Dossi Davide Moscatelli Giuseppe Storti 《Macromolecular Symposia》2011,302(1):100-109
Summary: Quantum chemistry was applied to the free radical polymerization of Vinyl Chloride with the aim of elucidating the reaction kinetics and especially the formation of structural defects and low molecular weight polymer. The radical reactions were studied using the Density Functional Theory. All calculations were performed with B3LYP functionals and in particular the 6-31G(d,p) basis set was selected to evaluate the exchange and correlation energies. The computational method was first validated by predicting the rate constant of the propagation step and comparing the calculated values to experimental ones. Then intramolecular chain transfer, β-scission and branching reactions were also investigated, due to their direct connection with the production of defects in the growing chains. A comparison of the evaluated kinetic constants of such secondary reactions with other computational evaluations and experimental data was finally made. 相似文献