Synthesis and characterization of organophosphoryl polyoxotungstates [RP(O)]2X n+W11O39 (8−n)− (X n+ = P5+, Si4+, Ge4+, Ga3+)

In the presence of n-Bu₄NBr acting as phase-transfer reagent, n-Bu₄N⁺ salts of organophosphoryl polyoxotungstate derivatives [RP(O)]₂X ⁿ⁺W₁₁O₃₉ ^(8–n)– [R = PhCH₂CH₂P(O), X = P, Si; R = C₆H₁₁P(O); X = Ge, Ga] have been prepared and characterized by elemental analysis, i.r., ³¹P- and ¹⁸³W-n.m.r. spectroscopy. According to the elemental analysis and spectroscopic data, the hybrid anions consist of an -[XW₁₁O₃₉] framework on which are grafted two equivalent organophosphoryl groups through P—O—W bridges; these new species still retain the Keggin structure. The six-line ¹⁸³W spectrum indicates that hybrid anions possess C _s symmetry in MeCN.     

Cycloaddition reactions of β-trifluoroacetylvinyl ethers

β-Trifluoroacetyl vinyl ethers ROCHCHCOCF₃ react smoothly as dienophiles with α,β-unsaturated carbonyl compounds to give the unexpected 2-alkoxyl-5-trifluoroacetyl-3,4-dihydro-2H pyrans. These products are formed by elimination and addition of the alcohol to the products of the normal hetero Diels-Alder reaction (2-alkoxyl-3-trifluoroacetyl-2,3-dihydro-2H pyrans). In contrast, 1,3-dipolar cycloaddition of ROCHCHCOCF₃ with ArCHN(O)Me proceeds via a Z-endo transition state to give regio- and stereospecific 4-trifluoroacetyl substituted isoxazolidines and their derivatives.     

Highly efficient visible-light photocatalytic ethane oxidation into ethyl hydroperoxide as a radical reservoir

Photocatalytic ethane conversion into value-added chemicals is a great challenge especially under visible light irradiation. The production of ethyl hydroperoxide (CH₃CH₂OOH), which is a promising radical reservoir for regulating the oxidative stress in cells, is even more challenging due to its facile decomposition. Here, we demonstrated a design of a highly efficient visible-light-responsive photocatalyst, Au/WO₃, for ethane oxidation into CH₃CH₂OOH, achieving an impressive yield of 1887 μmol g_cat⁻¹ in two hours under visible light irradiation at room temperature for the first time. Furthermore, thermal energy was introduced into the photocatalytic system to increase the driving force for ethane oxidation, enhancing CH₃CH₂OOH production by six times to 11 233 μmol g_cat⁻¹ at 100 °C and achieving a significant apparent quantum efficiency of 17.9% at 450 nm. In addition, trapping active species and isotope-labeling reactants revealed the reaction pathway. These findings pave the way for scalable ethane conversion into CH₃CH₂OOH as a potential anticancer drug.

Highly efficient visible-light driven photocatalytic oxidation of ethane into ethyl hydroperoxide was realized for the first time over Au/WO₃.     

Selenium Nanoparticles Prepared from Reverse Microemulsion Process

Selenium nanoparticles were prepared by a reverse microemulsion system. Sodium selenosulfate was used as selenium source. The results showed that hydrochloric acid concentration and reaction temperature had great influence on the morphology of products. The crystalline selenium nanowires and amorphous selenium nanorods were obtained in given condition.     

一种利用质谱信息进行结构特征鉴定的模式识别方法

本文提出了分段式离子系列谱编码方法,实验证明具有很好的结构表征能力。本程序主要是以模式识别技术为基础,实现了对未知物谱图的KNN分类,进而得到未知物的主要结构特征。这个程序应用于有机化合物的分类,取得了满意的结果。     

高富勒烯的提取,分离和分析

采用二硫化碳重结晶富勒烯混合物或二硫化碳二次抽提烟灰以提取高富勒烯（ｈｉｇｈｅｒｆｕｌｅｒｅｎｅｓ，Ｃｎ，ｎ＞７０）。产物经高效液相色谱分析，高富勒烯的含量从１％分别提高到４％和６％；经激光飞行时间质谱证明，产物中除含主要成分Ｃ６０和Ｃ７０以外，还含有Ｃ７６、Ｃ７８、Ｃ８２、Ｃ８４以及更高碳原子的富勒烯。     

碳氟链与碳氢链表面活性剂在固液界面上的吸附

全氟辛酸及其钠盐和十二烷基硫酸钠在R972上的吸附等温线均为S型或LS型，指示固液界面吸附过程中有表面疏水缔合物生成．碳氟表面活性剂的饱和吸附量显著高于碳氢表面活性剂的饱和吸附量．加电解质于液相使各体系吸附量上升．对于碳氟表面活性剂，甚至引起吸附等温线类型变化．例如，不加电解质时全氟辛酸在R972上的吸附等温线为S型，而加入HCl（c＝0．05mol·dm－3）使吸附等混线变成LS型．全氟辛酸比全氟辛酸钠在R972上的吸附更强．几种表面活性剂在R972上的吸附均随温度升高而减少。应用两阶段吸附模型及通用吸附等温线公式可以很好地解释所得实验结果．     

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.