Enzymatic hydrolysis of ammonia-treated rice straw

Rice straw pretreated with liquid anhydrous ammonia was hydrolyzed with cellulase, cellobiase, and hemicellulase. Ammonia-processing conditions were 1.5 g of NH₃/g of dry matter, 85°C, and several sample moisture contents. There were four ammonia addition time (min)-processing time (min) combinations. Sugars produced were analyzed as reducing sugars (dinitrosalicylic acid method) and by high-performance liquid chromatography. Monomeric sugars increased from 11% in the nontreated rice straw to 61% of theoretical in treated rice straw (79.2% conversion as reducing sugars). Production of monosaccharides was greater at higher moisture content and was processing time dependent. Glucose was the monosaccharide produced in greater amounts, 56.0%, followed by xylose, arabinose, and fructose, with 35.8, 6.6, and 1.4%, respectively.     

An experimental and computational investigation of the Diels-Alder cycloadditions of halogen-substituted 2(H)-pyran-2-ones

[reaction: see text] Diels-Alder reactions of 3- and 5-halo-subsituted 2(H)-pyran-2-ones with both electron-rich and electron-deficient dienophiles afford stable and readily isolable bridged bicyclic lactone cycloadducts. These cycloadditions proceed with excellent regioselectivity and very good stereoselectivity. In contrast, Diels-Alder reactions of 4-halo-subsituted 2(H)-pyran-2-ones afford cycloadducts which are very prone to loss of bridging CO(2) and the subsequent formation of barrelenes ([2.2.2]cyclooctenes). Furthermore, these cycloadditions proceed with only moderate regio- and stereoselectivity. For both series of the 3- and 5-halo-subsituted 2(H)-pyran-2-ones and 4-halo-subsituted 2(H)-pyran-2-ones, the reactivity patterns do not significantly change between the halogens. The regio- and stereochemical preferences of the cycloadditions of halo-substituted 2(H)-pyran-2-ones are investigated computationally. Calculations were carried out on the transition states leading to the four possible regio- and stereoisomeric cycloadducts by using density functional theory (B3LYP/6-31G). These studies allow prediction of the regio- and stereoselectivity in these reactions which are broadly in line with experimental observations.     

A general, two-directional approach to aza-C-(1 --> 1)-linked disaccharide mimetics

The Upjohn and Donohoe dihydroxylations were exploited in divergent syntheses of aza-C-(1 --> 1)-linked disaccharides.     

Meta-conjugation and excited-state coupling in phenylacetylene dendrimers

Traditional pictures of optical properties in phenylacetylene dendrimers view the molecule as a collection of independent chromophores, linked by meta-substitution at the central phenyl ring. While this picture is reasonable for explaining the observed absorption trends, it breaks down in describing the emission behavior. We utilize a combination of ab initio theory and experiment to demonstrate that differences in the absorbing and emitting states can be described using an exciton model with very weak chromophore coupling for the absorption geometry and strong coupling for the emission geometry. This result may have significant implications for the design of energy-funneling dendrimeric molecules.     

A Letter from the Editorial Board

It has been 15 years that the Journal of Natural Gas Chemistry, an international, academic Journal focusing on the publication of worldwide research in the field of natural gas chemistry, has been published. Five years ago, the Editorial Board of the Journal was reorganized and moved to the Dalian Institute of Chemistry Physics, Chinese Academy of Sciences. The Journal has concentrated on the reporting of fundamental research and development information in the field of natural gas     

Selective domino ring-closing metathesis-cross-metathesis reactions between enynes and electron-deficient alkenes

[reaction: see text] A selective domino ring-closing metathesis (RCM)-cross-metathesis (CM) process between enynes and electron-deficient alkenes is reported. The conditions have been optimized for enynes 3 and methyl acrylate with catalyst IV. The scope and limitations of this reaction are described, and a possible mechanism is discussed.     

Application of a validated stability-indicating chromatographic method to evaluate the reproducibility between batches of small peptides in solution

A stability-indicating reversed-phase high-performance liquid chromatographic method was developed and validated as per the International Conference on Harmonization (ICH) guidelines to evaluate the reproducibility of batches of synthetic peptides included in a stability program, in particular cholecystokinin (CCK-4) peptide.Both isothermal and nonisothermal approaches were used to determine stability under experimental conditions and the resulting degradation products were identified by liquid chromatography-mass spectrometry (LC-MS). The principal degradation product was the cyclic dimer, although another two products derived from it were also detected, due to the loss of one or two Phe-NH₂ residues. The dimerization follows first-order kinetics, whereas the hydrolytic cleavage implies both consecutive and in-parallel processes. The linear Arrhenius plot indicates that the degradation mechanism and kinetics do not change with temperature or the batch, but the degradation rate does depend on the batch, for example, the shelf-life at 25 °C was 2.54 days for batch 3, which is 13-times lower than batch 2. This variability is caused by a change in the synthesis process introduced by the manufacturer.The combination of these two elements: the analytical and stability-evaluating methods provide enough data to establish a stability-indicating profile, as required by the guideline ICH-Q6B for biotechnological/biological products.