Facile chemoselective synthesis of dehydroalanine-containing peptides

Useful methodology is described for the synthesis of dehydroalanine residues (II) within peptides. The unnatural amino acid (Se)-phenylselenocysteine (I) can be incorporated into growing peptide chains via standard peptide synthesis procedures. Subsequent oxidative elimination affords a dehydroalanine at the desired position. The oxidation conditions are mild and tolerate functionalities commonly found in peptides, including variously protected cysteine residues. To illustrate its utility, cyclic lanthionines have been synthesized by this method.     

Thermal degradation of wood treated with guanidine compounds in air: Flammability study

Wood has been treated with guanidine phosphate, guanidine nitrate, guanidine carbonate and guanidine chloride to impart flame retardancy. The samples were subjected to differential thermal analysis (DTA) and thermogravimetry (TG) from ambient temperature to 800°C in air to study their thermal behaviors. From the resulting data, kinetic parameters for different stages of thermal degradation were obtained following the method of Broido. For the decomposition of wood and flame retardant wood, the activation energy was found to decrease from 116 to 54 kJ mol^–1; the char yield was found to increase from 5.6 to 34.9%, LOI from 18 to 41.5, which indicated that the flame retardancy of treated wood was improved. Effects of the different compounds on the degradation and flammability of wood have also been proposed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Low-energy paths for the unimolecular decomposition of CH3OH: a G2M/statistical theory study

The potential energy surface (PES) of the CH3OH system has been characterized by ab initio molecular orbital theory calculations at the G2M level of theory. The mechanisms for the decomposition of CH3OH and the related bimolecular reactions, CH3 + OH and 1CH2 + H2O, have been elucidated. The rate constants for these processes have been calculated using variational RRKM theory and compared with available experimental data. The total decomposition rate constants of CH3OH at the high- and low-pressure limits can be represented by k infinity = 1.56 x 10(16) exp(-44,310/T) s-1 and kAr0 = 1.60 x 10(36) T-12.2 exp(-48,140/T) cm3 molecule-1 s-1, respectively, covering the temperature range 1000-3000 K, in reasonable agreement with the experimental values. Our results indicate that the product branching ratios are strongly pressure dependent, with the production of CH3 + OH and 1CH2 + H2O dominant under high (P > 10(3) Torr) and low (P < 1 atm) pressures, respectively. For the bimolecular reaction of CH3 and OH, the total rate constant and the yields of 1CH2 + H2O and H2 + HCOH at lower pressures (P < 5 Torr) could be reasonably accounted for by the theory. For the reaction of 1CH2 with H2O, both the yield of CH3 + OH and the total rate constant could also be satisfactorily predicted theoretically. The production of 3CH2 + H2O by the singlet to triplet surface crossing, predicted to occur at 4.3 kcal mol-1 above the H2C...OH2 van der Waals complex (which lies 82.7 kcal mol-1 above CH3OH), was neglected in our calculations.     

聚N—异丙基丙烯酰胺溶液的温度依赖关系

用自由基聚合法合成了聚Ｎ－异丙基丙烯酰胺（ＰＮＩＰＡＡＭ）样品，用乌氏粘度计考查了该聚合物的四氢呋喃（ＴＨＦ）溶液和水溶液的粘度与温度的依赖关系。发现ＰＮＩＰＡＡＭ－ＴＨＦ体系的特性粘数随温度升高而增大，ＰＮＩＰＡＡＭ－Ｈ２Ｏ体系的特性粘数－温度曲线表现出较为复杂的变化规律。并用实验确定的特性粘数对合成样品的分子量进行了表征Ｍｎ＝８．４４×１０＾５ｇ·ｍｏｌ＾－１。     

Synthesis and Insulin—sensitizing Activity of a Series of 2—Benzyl—1,3—dicarbonyl Derivatives

A series of 2-benzyl-1,3-dicabonyl derivatives was synthesized.Their insulin-sensitizing activity was evaluated in 3T3-L1 preadipocyte cells.Compounds3,26 and 27 were found to possess strong insulin-sensitizing activity in vitro and were selected for further hypoglycemic evaluation in vivo.     

Unexpected formation of the novel fluorinated diazenes

Fluoroalkanesulfonyl azides reacted with morpholine giving unexpectedly N-fluoroalkanesulfonyl-N-morpholino diazenes, which were fully characterized by using spectral methods and X-ray diffraction analysis.     

Lattice Thermal Transport in the Homogeneous Cage-Like Compounds Cu3VSe4 and Cu3NbSe4: Interplay between Phonon-Phase Space,Anharmonicity, and Atomic Mass

Understanding the correlation between crystal structure and thermal conductivity in semiconductors is very important for designing heat-transport-related devices, such as high-performance thermoelectric materials and heat dissipation in micro-nano-scale devices. In this work, the lattice thermal conductivity ( ) of the cage-like compounds Cu₃VSe₄ and Cu₃NbSe₄ was investigated by experimental measurements and first-principles calculations. The experimental of Cu₃NbSe₄ is approximately 25 % lower than that of Cu₃VSe₄ at 300 K. The relevant important physical parameters, including the sound velocity, heat capacity, weighted phonon phase space (W), and third-order force constants along with atomic mass were theoretically analyzed. It is found that W is the dominant parameter in determining the , and the other factors only play a minor role. The physical origin is the relatively “soft” lattice of Cu₃NbSe₄ with heavier atomic mass. This research provides deep insight into the correlation between the thermal conductivity and crystal structure and paves the way for discovering high-performance thermal management device and thermoelectric materials with intrinsically low .     

利用高炉水淬渣制备(Ca/Y)-α-Sialon陶瓷的组织与性能

以高炉水淬渣合成的Ca-α-Sialon粉体为原料采用无压烧结技术制备了（Ca/Y）-α-Sialon陶瓷。通过用排水法、三点弯曲实验法、金相显微镜法、XRD法等手段研究了（Ca/Y）-α-Sialon陶瓷的烧结致密化过程、材料的力学性能、显微组织、相组成和材料的断裂特征。结果表明,适量的Y2O3促进材料的烧结致密化和提高材料的力学性能,但Y2O3过量（大于10%）时对材料的烧结和力学性能不利。掺杂Y^3＋的（Ca/Y）-α-Sialon呈柱状晶,随着Y2O3含量的增加和烧结温度的提高,（Ca/Y）-α-Sialon呈柱状晶出现粗化和等轴化。含10%Y2O3的材料在1700℃烧结时可获得较高的力学性能。     

Solvent extraction of uranium(VI) with benzyloctadecyldimethylammonium chloride (BODMAC) from highly concentrated chloride solution

The ²²²Rn emanation fraction (EF) released from the technically enhanced naturally occurring radioactive material (TE-NORM) wastes at certain sites of petroleum and gas production was determined. The samples were analyzed by γ-ray spectrometry to determine the activity concentration of the ²²⁶Ra content, of which the ²²²Rn emanation fraction was calculated. The results showed that the ²²²Rn emanation fraction differs in the oil and gas production sites and it is independent of the activity concentration of ²²⁶Ra. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hydrothermal synthesis and novel two-dimensional architecture with fluorescent properties constructed using 2-bromo-1,4-benzenedicarboxylate

A novel two-dimensional complex, [Cu(bbdc)(phen)]·(H₂O)(bbdc = 2-bromo-1,4-benzenedicarboxylate dianion; phen = 1,10-phenanthroline), has been synthesized and structurally characterized by single crystal X-ray analysis. The crystal structure consists of infinite chains of [Cu₂( ₄-bbdc)]²⁺ units connected by bis-monodentate bbdc ligands, the coordination mode of which [ ₄-bbdc] is very rare in the phenyldicarboxylate complexes. The substituent group of bbdc is believed to be the growth key of this coordination network.