Molecular orbital calculations on the conformation of polypeptides and proteins

Quantum mechanical calculations using the PCILO method have been performed on the tripeptide model CH₃CO-X-Y-NHCH₃. Competition between C₅, C₇, C₁₀ rings and open structures has been investigated through mapping of the whole {φ, Ψ} conformational space and energy minimization. From these results, it appears that the C₁₀ ring simulating the folding named U-turn, involving a hydrogen bond between the i...i + 3 residues, is the most probable structure although not the most stable in energy. The results are used for predicting the frequency of U-turns in proteins, α-chymotrypsin is given as an example.     

A thermally stable polybenzimidazole polybenzoxazole segmented block copolymer

m-phenyl benzoate end-capped pre-polybenzoxazole oligomer and a 3,4-diaminobenzene endcapped pre-polybenzimidazole were synthesized. These functionalized oligomers were then condensed to give a polybenzoxazole-polybenzimidazole segmented block copolymer. The functionalized oligomers were characterized by proton NMR, diffuse reflectance FTIR, and thermal gravimetric analysis. The final block copolymer was characterized by diffuse reflectance FTIR and thermal gravimetric analysis.     

Engine Knock Detection from Vibration Signals Using Pattern Recognition

The paper deals with a diagnostic method that allows to detect engineknock. The developed algorithm differentiates three kinds of engine cycles:absence of knock, increasing knock and heavy knock. The decision is takenfrom a block vibration signal. The diagnostic method is based on patternrecognition. Three models of different data shapes provided from theaccelerometer are elaborated. This is done using a time-scale analysis toolcalled a wavelet network. It allows to extract relevant features from thesignal. The aim of the method is then to partition the feature space intoclasses representing the knock states. Experimental results are reported.     

Fluorénacènes et fluorénaphènes synthèses dans la série des indéno-fluorènes,XVII. Dérivés méthylés du cis-fluorénacène,du trans-fluorénacène et du trans-fluorénaphène

By condensation of the chlorides of the three 9-oxo-fluorene-2-, -3-, and -4-carboxylic acids with 4-bromo-1,2-xylene on one side, and of the chlorides of o-bromobenzoic acid, 2-bromo-4-methyl-benzoic acid and 2-bromo-4,5-dimethyl-benzoic acid with fluorene, 2-methylfluorene and 3-methylfluorene on the other side, followed by direct or indirect cyclisation and by final reduction, several new methyl derivatives of the indenofluorenes I, II and IV are synthesized.     

Étude thermochimique des sels alcalins de quelques amino-acides

Standard enthalpies of formation of alkaline earth salts M(NH₂RCOO) of several amino acids

are determined by calorimetry.The thermochemical radii, the standard enthalpies of formation and the protonic affinities of ions (NH₂RCOO^?) in the gaseous state are calculated.In the case of unbranched carbon chain amino acids, the thermochemical radii are an approximately linear function of protonic affinities of their conjugate bases.     

Combustion of methane over supported palladium-copper bimetallic catalysts

Monometallic and bimetallic catalysts based on palladium and copper deposited on a spinel carrier have been investigated in the catalytic combustion of methane. Great differences were found in catalytic activity, according to the sequence Pd/MgAl₂O₄>CuO–Pd/MgAl₂O₄>Pd–CuO/MgAl₂O₄>CuO/MgAl₂O₄. They were explained by changes in surface composition of the catalysts. In the case of bimetallic catalysts the metallic surface is preferentially enriched in copper, which acts as a diluting agent for the Pd atom ensembles. As a consequence, the adsorption of reactants is limited and the catalysts so obtained behave like copper slightly doped with palladium.     

A Visible‐Light‐Promoted O‐Glycosylation with a Thioglycoside Donor

Visible‐light irradiation of 4‐p‐methoxyphenyl‐3‐butenylthioglucoside donors in the presence of Umemoto's reagent and alcohol acceptors serves as a mild approach to O‐glycosylation. Visible‐light photocatalysts are not required for activation, and alkyl‐ and arylthioglycosides not bearing the p‐methoxystyrene are inert to these conditions. Experimental and computational evidence for an intervening electron donor–acceptor complex, which is necessary for reactivity, is provided. Yields with primary, secondary, and tertiary alcohol acceptors range from moderate to high. Complete β‐selectivity can be attained through neighboring‐group participation.     

Organic Stereochemistry. Part 6

Following the previous Part on the mechanisms of chiral recognition in pharmacology, the road was open to cover one aspect of stereoselectivity that had been evoked in Part 5 but not discussed explicitly, namely the pharmacological significance of the conformational behavior of active molecules. There, we saw how ligands and binding sites adapt to each other, but these results were not related explicitly to the conformational behavior of the ligand. The focus of the present Part is to use a few well‐known drugs, examine their conformational behavior, compare the 3D geometry of probable conformers with rigid analogs acting at the same receptor, and reflect on the concept of ‘active conformation’.     

Hydrolysis of Ammonia-pretreated Sugar Cane Bagasse with Cellulase, β-Glucosidase, and Hemicellulase Preparations

Sugar cane bagasse consists of hemicellulose (24%) and cellulose (38%), and bioconversion of both fractions to ethanol should be considered for a viable process. We have evaluated the hydrolysis of pretreated bagasse with combinations of cellulase, β-glucosidase, and hemicellulase. Ground bagasse was pretreated either by the AFEX process (2NH₃: 1 biomass, 100 °C, 30 min) or with NH₄OH (0.5 g NH₄OH of a 28% [v/v] per gram dry biomass; 160 °C, 60 min), and composition analysis showed that the glucan and xylan fractions remained largely intact. The enzyme activities of four commercial xylanase preparations and supernatants of four laboratory-grown fungi were determined and evaluated for their ability to boost xylan hydrolysis when added to cellulase and β-glucosidase (10 filter paper units [FPU]: 20 cellobiase units [CBU]/g glucan). At 1% glucan loading, the commercial enzyme preparations (added at 10% or 50% levels of total protein in the enzyme preparations) boosted xylan and glucan hydrolysis in both pretreated bagasse samples. Xylanase addition at 10% protein level also improved hydrolysis of xylan and glucan fractions up to 10% glucan loading (28% solids loading). Significant xylanase activity in enzyme cocktails appears to be required for improving hydrolysis of both glucan and xylan fractions of ammonia pretreated sugar cane bagasse.