Synthesis of cyclic carbonates from CO2 and epoxides catalyzed by hexaalkylguanidinium halides

Hexaalkylguanidinium halides exhibit an efficient catalytic activity in the synthesis of cyclic carbonates from, epoxides and carbon dioxide. By this method cyclic carbonates can be obtained in a high yield and a high selectivity at a low temperature and atmospheric pressure. This procedure is easy for the product isolation and recycling of the catalyst.

Carbon dioxide/propylene oxide coupling reaction catalyzed by chromium salen complexes

A series of chromium/Schiff base complexes N,N'-bis(salicylidene)-1,2-phenylenediamino chromium(III) X were prepared and employed for the alternating copolymerization of carbon dioxide with racemic propylene oxide in the presence of (4-dimethylamino)pyridine. The effect of the complex structure and reaction conditions on the catalytic activity, the poly(propylene carbonate)/cyclic carbonate (PPC/PC) selectivity, and the polymer head-to-tail linkages was examined. The experiments indicated that N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamino chromium(III) (NO3) exhibited the highest PPC/PC selectivity as well as polymer head-to-tail linkages and N,N'-bis(3,5-dichlorosalicylidene)-1,2-phenylenediimino chromiu(III) (NO3) possessed the highest catalytic activity among these chromium/Schiff base complexes. The structure of the produced copolymer was characterized by the IR, H-1 NMR, and C-13 NMR measurements.

Polymerization of 2,2 '-Dimethyltrimethylene Carbonate by Lutetium Complexes Bearing Amino-Phosphine Ligands

A series of lutetium alkyl, amino, and guanidinato complexes based upon an amino-phosphine ligand framework had been prepared. These complexes were applied to initiate ring-opening polymerization of 2,2'-dimethyltrimethylene carbonate (DTC). The type of the initiator significantly influenced the catalytic activity of these complexes in a trend as follows: alkyl approximate to guanidinate > amide, whereas the complexes with flexible backbone between P and N atoms within the ligand exhibited higher activity than those with rigid backbone. The isolated PDTC had bimodal-mode molecular weight distribution. The molecular weights of each fraction increased linearly with the conversion, indicating that there might be two active species. This had been confirmed by analyses of oligomeric DTC living species and oligomer with NMR technique as the metal-alkoxide and the four-membered metallocyclic lactate. Kinetic investigation displayed that the polymerization rate was the first order with the monomer concentration.

Biodegradable amphiphilic polymer-drug conjugate micelles

The coupling of drugs to macromolecular carriers received an important impetus from Ringsdorf's notion of polymer-drug conjugates. Several water-soluble polymers, poly(ethylene glycol), poly[N-(2-hydroxypropyl) methacrylamidel, poly(L-glutamic acid) and dextran, are studied intensively and have been utilized successfully in clinical research. The promising results arising from clinical trials with polymer-drug conjugates (e.g., paclitaxel, doxorubicin, camptothecins) have provided a firm foundation for other synthetic polymers, especially biodegradable polymers, used as drug delivery vehicles. This review discusses biodegradable polymeric micelles as an alternative drug-conjugate system. Particular focus is on A-B or B-A-B type biodegradable amphiphilic block copolymer such as polylactide, morpholine-2,5-dione derivatives and cyclic carbonates, which can form a core-shell micellar structure, with the hydrophobic drug-binding segment forming the hydrophobic core and the hydrophilic segment as a hydrated outer shell. Polymeric micelles can be designed to avoid uptake by cells of reticuloendothelial system and thus enhance their blood lifetime via the enhanced permeability and retention effect.

Synthesis and characterization of novel poly(ester carbonate)s based on pentaerythritol

Novel poly(ester carbonate)s were synthesized by the ring-opening polymerization Of L-lactide and functionalized carbonate monomer 9-phenyl-2,4,8,10-tetraoxaspiro[5,5]undecan-3-one derived from pentaerythritol with diethyl zinc as an initiator. H-1 NMR analysis revealed that the carbonate content in the copolymer was almost equal to that in the feed. DSC results indicated that T-g of the copolymer increased with increasing carbonate content in the copolymer. Moreover, the protecting benzylidene groups in the copolymer poly(L-lactide-co-9-phenyl-2,4,8,10-tetraoxaspiro[5,5]undecan-3-one) were removed by hydrogenation with palladium hydroxide on activated charcoal as a catalyst to give a functional copolymer, poly(L-lactide-co-2,2-dihydroxylmethyl-propylene carbonate), containing pendant primary hydroxyl groups. Complete deprotection was confirmed by H-1 NMR and FTIR spectroscopy. The in vitro degradation rate of the deprotected copolymers was faster than that of the protected copolymers in the presence of proteinase K. The cell morphology and viability on a copolymer film evaluated with ECV-304 cells showed that poly(ester carbonate)s derived from pentaerythritol are good biocompatible materials suitable for biomedical applications.

Highly active, hexabutylguanidinium salt/zinc bromide binary catalyst for the coupling reaction of carbon dioxide and epoxides

An experimentally simple and inexpensive catalyst system based on hexabutylguanidinium/ZnBr, has been developed for the coupling of carbon dioxide and epoxides to form cyclic carbonates with significant catalytic activity under mild reaction conditions without using additional organic solvents (e.g. the turnover frequencies (TOF, h(-1)) values as high as 6.6 x 10(3) h(-1) for styrene oxide and 1.01 x 10(4) h(-1) for epichlorohydrin). This catalyst system also offers the advantages of recyclability and reusability. Therefore, it is a very effective, environmentally benign, and simple catalytic process. The special steric and electrophilic characteristics of hexabutylguanidinium bromide ionic liquid result in the prominent performance of this novel catalyst system.

X-ray crystallographic structure of cyclic tetramer ester based on bisphenol-A and o-phthaloyldichloride

The polycrystalline powder of the cyclic tetramer ester based on bisphenol-A and o-phthaloyldichloride has been prepared by recrystallization from nitrobenzene and its crystal structure determined by wide-angle X-ray diffraction. The unit cell is orthorhombic and has dimensions a=0.967 nm, b=0.8699 nm, c = 2.0859 nm. With two tetramers per unit cell, the crystal density is 1.36 g cm(-3). Indices of crystal diffraction peaks are also detailed in the present work. Copyright (C) 1996 Elsevier Science Ltd.

On The Cyclic Bending Behaviour Of A Hard Coating On A Ductile Substrate With Periodic Surface Hardened Regions

A cyclic bending experiment is designed to investigate the interface fracture behaviour of a hard chromium coating on a ductile substrate with periodic surface hardened regions. The unique deflection pattern of the vertical cracks after they run through the coating and impinge at the interface is revealed experimentally. A simple double-layer elastic beam model is adopted to investigate the interfacial shear stresses analytically. A FE model is employed to compute the stresses of the tri-phase structure under a single round of bending, and to investigate the effect of the loading conditions on the deflection pattern of the vertical cracks at the interface. (C) 2008 Elsevier Ltd. All rights reserved.

Stability Of Adhesion Clusters And Cell Reorientation Under Lateral Cyclic Tension

This work is motivated by experimental observations that cells on stretched substrate exhibit different responses to static and dynamic loads. A model of focal adhesion that can consider the mechanics of stress fiber, adhesion bonds, and substrate was developed at the molecular level by treating the focal adhesion as an adhesion cluster. The stability of the cluster under dynamic load was studied by applying cyclic external strain on the substrate. We show that a threshold value of external strain amplitude exists beyond which the adhesion cluster disrupts quickly. In addition, our results show that the adhesion cluster is prone to losing stability under high-frequency loading, because the receptors and ligands cannot get enough contact time to form bonds due to the high-speed deformation of the substrate. At the same time, the viscoelastic stress fiber becomes rigid at high frequency, which leads to significant deformation of the bonds. Furthermore, we find that the stiffness and relaxation time of stress fibers play important roles in the stability of the adhesion cluster. The essence of this work is to connect the dynamics of the adhesion bonds (molecular level) with the cell's behavior during reorientation (cell level) through the mechanics of stress fiber. The predictions of the cluster model are consistent with experimental observations.

Centrifuge modeling of suction bucket foundations for platforms under ice-sheet-induced cyclic lateral loadings

This paper presents the results of a series of centrifuge model tests performed to study the behavior of suction bucket foundations for a tension leg platform in the Bohai Bay, China. The target lateral loadings were from ice-sheet-induced structural vibrations at a frequency of 0.8-1.0 Hz. The results indicate that excess pore water pressures reach the highest values within a depth of 1.0-1.5 in below the mud line. The pore pressures and the induced settlement and lateral displacement increase with the amplitude of the cyclic loading. Two failure modes were observed: liquefaction in early excitations and settlement-induced problems after long-term excitations. (c) 2006 Elsevier Ltd. All rights reserved.

Fracture behavior of axisymmetrical bars under high triaxial stress and large strain cyclic loading

Axisymmetric notched bars with notch roots of large and small radii were tested under large strain cyclic loading. The main attention is focused on the fracture behaviour of steels having cycles to failure within the range 1-100. Our study shows that a gradual transition from a static ductile nature to one of fatigue cleavage can be observed and characterized by the Coffin-Manson formula in a generalized form. Both the triaxial tensile stress within the central region of specimens and static damage caused by the first increasing load have effects on the final failure event. A generalized cyclic strain range parameter DELTAepsilon is proposed as a measure of the numerous factors affecting behaviour. Fractographs are presented to illustrate the behaviour reported in the paper.