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Ester Linkage (ester + linkage)
Selected AbstractsDrug design: hiding in full viewDRUG DEVELOPMENT RESEARCH, Issue 1 2008Norman S. Radin Abstract Compounds that can produce potent biological effects in cells encompass a variety of structural motifs. Many of these compounds share a structural feature that has rarely been noted. It is an allylic cluster of atoms, a 3-carbon chain with a double bond between two of the atoms and an oxygen atom at the other end. The oxygen can be in a hydroxyl group, or in an ether or ketal or ester linkage, or simply a carbonyl form. In the latter case, the linkage is an allylic ketone (ene-one) structure. Nitrogen is often seen in equivalent forms. Inclusion of at least one allylic moiety appears to be able to turn a modestly active or inert compound into an effective drug or toxin. Some compounds lack the allylic moiety but develop one by enzymatic action, usually via cytochrome P-450 enzymes. These metabolites probably represent the active drug forms. The above concepts seem to be radically simplistic and improbable, but the evidence supporting them and the explanations for the biological activities are hidden "in plain view." Comparisons with the pleiotropic activities of the allylic sphingolipid, ceramide, indicate that many allylic drugs operate by controlling the state of protein phosphorylation, by activating proteases, by generating reactive oxygen species, by slowing mitochondrial electron transport, or by lowering cellular glutathione concentrations. Drug Dev Res 69:15,25, 2008 © 2008 Wiley-Liss, Inc. [source] Synthesis and Structure,Property Relations of a Series of Photochromic Molecular Glasses for Controlled and Efficient Formation of Surface Relief NanostructuresADVANCED FUNCTIONAL MATERIALS, Issue 16 2009Roland Walker Abstract This paper reports on the synthesis and properties of a new series of photochromic molecular glasses and their structure,property relations with respect to a controlled and efficient formation of surface relief nanostructures. The aim of the paper is to establish a correlation between molecular structure, optical susceptibility, and the achievable surface relief heights. The molecular glasses consist of a triphenylamine core and three azobenzene side groups attached via an ester linkage. Structural variations are performed with respect to the substitution at the azobenzene moiety in order to promote a formation of a stable amorphous phase and to tune absorption properties and molecular dynamics. Surface relief gratings (SRGs) and complex surface patterns can easily be inscribed via holographic techniques. The modulation heights are determined with an equation adapted from the theory for thin gratings, and the values are confirmed with AFM measurements. Temperature-dependent holographic measurements allow for monitoring of SRG build-up and decay and the stability at elevated temperatures, as well as determination of the glass transition temperature. SRG modulation heights of above 600,nm are achieved. These are the highest values reported for molecular glasses to date. The surface patterns of the molecular glasses are stable enough to be copied in a replica molding process. It is demonstrated that the replica can be used to transfer the surface pattern onto a common thermoplastic polymer. [source] Synthesis and in vitro degradation of poly(N -vinyl-2-pyrrolidone)-based graft copolymers for biomedical applicationsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2002Carl F. Brunius Abstract This work is devoted to the design of a novel family of hydrosoluble biomaterials: poly(N -vinyl-2-pyrrolidone) (PVP)-based graft copolymers. A synthesis route has been elaborated in which ,-functionalized PVP is prepared via chain-transfer radical polymerization, end-group modified, and subsequently grafted onto a polyhydroxylated backbone, typically dextran or poly(vinyl alcohol). The resulting graft copolymer biomaterials are designed for use in various biomedical applications, particularly as materials with a stronger potential for plasma expansion than already existing products have. The graft copolymers are potentially degradable because the PVP grafts are connected to the polyol backbone via a hydrolytically labile carbonate or ester linkage. The degradation of the graft copolymers was performed in vitro over a period of 6 weeks. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3652,3661, 2002 [source] Optimization of enzymatic extraction of ferulic acid from wheat bran, using response surface methodology, and characterization of the resulting fractionsJOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 10 2009Hélène Barberousse Abstract BACKGROUND: The agro-industries generate thousands of tons of by-products, such as bran or pulps, each year. They are, at best, used for cattle feeding. Through biocracking, this biomass may constitute a renewable source for various molecules of interest for the industry. For instance, ferulic acid, a compound showing antioxidant ability, is found in abundance in cereal bran. Its release depends mainly on the breaking of its ester linkage to other constitutive elements of the cell wall, such as arabinoxylans. Response surface methodology was used to evaluate the effects of ferulic acid esterase (FAE) and xylanase activities, as well as incubation time and temperature, on ferulic acid extraction yield from wheat bran. Under optimized conditions, the composition of the hydrolysate and of residual bran were compared to native bran. RESULTS: Experiments carried out under the predicted optimal conditions (FAE amount, 27 U g,1; xylanase amount, 304 U g,1; incubation time, 2 h; and temperature, 65 °C) led to an extraction yield of 52.8%, agreeing with the expected value (51.0%). The crude ferulic acid fraction was purified with Amberlite XAD16, leading to a final concentration of 125 µg mL,1 of ferulic acid in ethanol. The antioxidant capacity of this purified fraction was evaluated by the DPPH· scavenging method: it exhibited better efficiency (EC50 = 10.6 µmol L,1 in ferulic acid) than the ferulic acid standard (EC50 = 13.7 µmol L,1). CONCLUSION: These results confirm the potential of wheat bran valorization in the field of natural antioxidant extraction, possibly viable in an industrial scheme. Copyright © 2009 Society of Chemical Industry [source] 20-Hydroxyimino-5,-pregna-9(11),16-dien-3,-yl acetate and 17-oxo-5,-androst-9(11)-en-3,-yl acetateACTA CRYSTALLOGRAPHICA SECTION C, Issue 12 2000Héctor Novoa de Armas In the title compounds, C23H33NO3 and C21H30O3, respectively, the ester linkage in ring A is equatorial. In these steroids, the six-membered rings A and B have chair conformations, but ring C can be better described as a half-chair. The five-membered ring D adopts a 14,-envelop conformation. The A/B, B/C and C/D ring junctions are trans. [source] Hydrolytic Reactions of Thymidine 5,- O -Phenyl- N -Alkylphosphoramidates, Models of Nucleoside 5,-Monophosphate ProdrugsCHEMISTRY - A EUROPEAN JOURNAL, Issue 30 2007Mikko Ora Dr. Abstract To obtain detailed data on the kinetics of hydrolytic reactions of triester-like nucleoside 5,- O -aryl- N -alkylphosphoramidates, potential prodrugs of antiviral nucleoside monophosphates, the hydrolysis of diastereomeric (RP/SP) thymidine 5,-{O -phenyl- N -[(1S)-2-oxo-2-methoxy-1-methylethyl]phosphoramidate} (3), a phosphoramidate derived from the methyl ester of L -alanine, has been followed by reversed-phase HPLC over the range from H0=0 to pH,8 at 90,°C. According to the time-dependent product distributions, the hydrolysis of 3 proceeds at pH<4 by two parallel routes, namely by nucleophilic displacement of the alaninyl ester moiety by a water molecule and by hydrolysis of the carboxylic ester linkage that allows intramolecular attack of the carboxy group on the phosphorus atom, thereby resulting in the departure of either thymidine or phenol without marked accumulation of any intermediates. Both routes represent about half of the overall disappearance of 3. The departure of phenol eventually leads to the formation of thymidine 5,-phosphate. At pH>5, the predominant reaction is hydrolysis of the carboxylic ester linkage followed by intramolecular displacement of a phenoxide ion by the carboxylate ion and hydrolysis of the resulting cyclic mixed anhydride into an acyclic diester-like thymidine 5,-phosphoramidate. The latter product accumulated quantitatively without any indication of further decomposition. Hydroxide-ion-catalyzed POPh bond cleavage of the starting material 3 occurred as a side reaction. Comparative measurements with thymidine 5,-{N -[(1S)-2-oxo-2-methoxy-1-methylethyl]phosphoramidate} (4) revealed that, under acidic conditions, this diester-like compound is hydrolyzed by PN bond cleavage three orders of magnitude more rapidly than the triester-like 3. At pH>5, the stability order is reversed, with 3 being hydrolyzed six times as rapidly as 4. Mechanisms of the partial reactions are discussed. [source] New thermosets obtained by the cationic copolymerization of diglycidyl ether of bisphenol A with ,-caprolactone with an improvement in the shrinkage.JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2007Abstract Diglycidyl ether of bisphenol A was cured with different proportions of ,-caprolactone with ytterbium triflate as an initiator. The curing was studied by means of differential scanning calorimetry and Fourier transform infrared in the attenuated total reflection mode. The latter was used to monitor the competitive reactive processes and to quantify the conversions of the epoxide, lactone, and intermediate spiroorthoester groups. A partial depolymerization process from the cured material to free ,-caprolactone was also identified. The formation of a stable carbocation and the coordinative capability of ytterbium triflate were the reasons for this unexpected process. The thermal and dynamic mechanical properties of the cured materials were determined with differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis. An increase in the proportion of ,-caprolactone resulted in an increased curing rate, a decrease in the shrinkage after gelation, and a significant decrease in the glass transition temperature. The introduction of ester linkages into the three-dimensional structure led to more thermally degradable thermosets. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1968,1979, 2007 [source] Syntheses and characterizations of thermally degradable epoxy resins.JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2002Abstract In flip-chip technology, the development of reworkable underfill materials has been one of the keys to the recovery of highly integrated and expensive board assembly designs through the replacement of defective chips. This article reports the syntheses, formulations, and characterizations of two new diepoxides, one containing secondary ester linkages and the other containing tertiary ester linkages, that are thermally degradable below 300 °C. The secondary and tertiary ester diepoxides were synthesized in three and two steps, respectively. Both compounds were characterized with NMR and Fourier transform infrared spectroscopy and formulated into underfill materials with an anhydride as the hardener and an imidazole as the catalyst. A dual-epoxy system was also formulated containing the tertiary ester diepoxide and a conventional aliphatic diepoxide, 3,4-epoxy cyclohexyl methyl-3,4-epoxycyclohexyl carboxylate (ERL-4221E), with the same hardener and catalyst. The curing kinetics of the formulas were studied with differential scanning calorimetry (DSC). Thermal properties of cured samples were characterized with DSC, thermogravimetric analysis, and thermomechanical analysis. The dual-epoxy system showed a viscosity of 18.7 and 0.87 P at 25 and 100 °C, respectively. The cured secondary, tertiary, and dual-epoxy formulas showed decomposition temperatures around 265, 190, and 220 °C, glass-transition temperatures around 120,140, 110,157, and 140,157 °C, and coefficients of thermal expansion of 70, 72, and 64 ppm/°C below their glass-transition temperatures, respectively. The shear strength of the cured dual-epoxy system decreased quickly with aging at 230 °C. The reworkability test showed that the removal of a chip underfilled with this material from the board was quite easy, and the residue on the board could be thoroughly removed with a mechanical brush without obvious damage to the solder mask. In summary, the synthesized tertiary epoxide can be used as a reworkable underfill for flip-chip applications. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1796,1807, 2002 [source] Alkali-based AFEX pretreatment for the conversion of sugarcane bagasse and cane leaf residues to ethanolBIOTECHNOLOGY & BIOENGINEERING, Issue 3 2010Chandraraj Krishnan Abstract Sugarcane is one of the major agricultural crops cultivated in tropical climate regions of the world. Each tonne of raw cane production is associated with the generation of 130,kg dry weight of bagasse after juice extraction and 250,kg dry weight of cane leaf residue postharvest. The annual world production of sugarcane is ,1.6 billion tones, generating 279 MMT tones of biomass residues (bagasse and cane leaf matter) that would be available for cellulosic ethanol production. Here, we investigated the production of cellulosic ethanol from sugar cane bagasse and sugar cane leaf residue using an alkaline pretreatment: ammonia fiber expansion (AFEX). The AFEX pretreatment improved the accessibility of cellulose and hemicelluloses to enzymes during hydrolysis by breaking down the ester linkages and other lignin carbohydrate complex (LCC) bonds and the sugar produced by this process is found to be highly fermentable. The maximum glucan conversion of AFEX pretreated bagasse and cane leaf residue by cellulases was ,85%. Supplementation with hemicellulases during enzymatic hydrolysis improved the xylan conversion up to 95,98%. Xylanase supplementation also contributed to a marginal improvement in the glucan conversion. AFEX-treated cane leaf residue was found to have a greater enzymatic digestibility compared to AFEX-treated bagasse. Co-fermentation of glucose and xylose, produced from high solid loading (6% glucan) hydrolysis of AFEX-treated bagasse and cane leaf residue, using the recombinant Saccharomyces cerevisiae (424A LNH-ST) produced 34,36,g/L of ethanol with 92% theoretical yield. These results demonstrate that AFEX pretreatment is a viable process for conversion of bagasse and cane leaf residue into cellulosic ethanol. Biotechnol. Bioeng. 2010;107: 441,450. © 2010 Wiley Periodicals, Inc. [source] Detection of human neutrophil elastase with peptide-bound cross-linked ethoxylate acrylate resin analogsCHEMICAL BIOLOGY & DRUG DESIGN, Issue 4 2005J.V. Edwards Abstract:, An assessment of elastase-substrate kinetics and adsorption at the solid,liquid interface of peptide-bound resin was made in an approach to the solid-phase detection of human neutrophil elastase (HNE), which is found in high concentration in chronic wound fluid. N-succinyl-alanine-alanine-proline-valine- p -nitroanilide (suc-Ala-Ala-Pro-Val- pNA), a chromogenic HNE substrate, was attached to glycine-cross-linked ethoxylate acrylate resins (Gly-CLEAR) by a carbodiimide reaction. To assess the enzyme-substrate reaction in a two-phase system, the kinetic profile of resin-bound peptide substrate hydrolysis by HNE was obtained. A glycine and di-glycine spacer was placed between the resin polymer and substrate to assess the steric and spatial requirements of resin to substrate with enzyme hydrolysis. The enzymatic activities of suc-Ala-Ala-Pro-Val- pNA and suc-Ala-Ala-Pro-Ala- pNA on the solid-phase resin were compared with similar analogs in solution. An increase in visible wavelength absorbance was observed with increasing amounts of substrate-resin and enzyme concentration. Enzyme hydrolysis of the resin-bound substrate was also demonstrated on a polypropylene surface, which was employed for visible absorbance of released chromophore. A soluble active substrate analog was released from the resin through saponification of the ethoxylate ester linkages in the resin polymer. The resin-released conjugate of the HNE substrate demonstrated an increased dose response with increasing enzyme concentration. The synthesis and assay of elastase substrates bound to CLEAR resin gives an understanding of substrate-elastase adsorption and activity at the resin's solid,liquid interface for HNE detection with a solid-phase peptide. [source] Relationship between temporary inhibition and structure of disulfide-linkage analogs of marinostatin, a natural ester-linked protein protease inhibitorCHEMICAL BIOLOGY & DRUG DESIGN, Issue 2 2005M. Taniguchi Abstract:, A 12-residue marinostatin [MST(1,12): 1FATMRYPSDSDE12] which contains two ester linkages of Thr3,Asp9 and Ser8,Asp11 strongly inhibits subtilisin. In order to study the relationship between the inhibitory activity, structure, and stability of MST, MST analogs were prepared by changing ester linkages to a disulfide linkages. The analogs without the disulfide linkage between 3 and 9 positions lost their inhibitory activity. The Ki value of 1SS(C3,C9) (1FACMRYPSCSDE12), which has a single disulfide linkage of Cys3,Cys9 was comparable with those of MST(1,12) and MST-2SS (1FACMRYPCCSCE12), a doubly linked analog of Cys3,Cys9 and Cys8,Cys11. However, 1SS(C3,C9) and MST-2SS showed temporary inhibition, but not MST(1,12): These analogs were inactivated after incubation with subtilisin for 30 min, and were specifically hydrolyzed at the reactive site. 1H NMR study showed that 1SS(C3,C9) has two conformations, which contain a cis - (70%) or trans - (30%) Pro residue, while MST-2SS as well as MST(1,12) takes a single conformation containing only a cis -Pro residue. Hydrogen,deuterium exchange rate of the Arg5 (P1,) NH proton of the MST analogs was about 100 times faster than that of MST(1,12). These results indicate that the linkage between the positions 8 and 11 plays a role for fixing the cis -conformation of the Pro7 residue, and that the linkage between 3 and 9 is indispensable for the inhibition, but not enough for stable protease-inhibitor complex. [source] | ||||||||||||||||