Reduction of Chemical Reactions in Nitrogen and Nitrogen–Hydrogen Plasma Jets Flowing into Atmospheric Air

The large number of possible chemical reactions represents a severe burdenfor modeling of even relatively simple plasma systems. Reduced sets ofchemical reactions have been obtained for numerical simulations of nitrogenand nitrogen-hydrogen plasma jets flowing into an atmospheric airenvironment. The important or active reactions are determined based on asimplified reduction method. A reaction is considered active if it leadsto higher sensitivities than a specified cutoff sensitivity of 1%. Theactive reactions exert a significant influence on main plasma parameters,such as velocity, temperature, and species concentrations. The sensitivityanalysis for the specified systems shows that two NO reactions, known asZel'dovich reactions (N₂+ONO+N andNO+OO₂+N),⁽¹⁾ are both active in a nitrogenplasma jet. On the other hand, the latter is not active and may be omittedin a nitrogen–hydrogen plasma jet. A nitrogen–hydrogen plasmajet requires contribution of two active charge exchange reactions:N₂+N⁺N⁺ ₂+N andN+H+N+ +H, while only the former is needed in a nitrogen plasmajet. The dissociation reactions are all active in both plasma jets, exceptthe dissociation of OH.     

Chemical conversion of various celluloses to glucose and its derivatives in supercritical water

The supercritical water biomass conversion system was designed and developed in our laboratory. The reaction vessel with cellulose sample was treated with this system at supercritical state of water for a designated period (3–105s) under the conditions of a tin bath temperature of 500°C and pressure of 35MPa. The recovered products of hydrolysates were then analyzed by high performance liquid chromatography. The obtained results indicated that a high amount of glucose and levoglucosan can be achieved from both celluloses I and II for 5–10s supercritical treatment, while that from starch for 3–5s treatment. Although this difference could be due to a difference in the molecular structure between cellulose and starch, a difference between celluloses I and II was not significant. Instead, an accessibility of the water towards cellulose molecules seemed to be significant for their chemical conversion. With the longer treatment, amounts of these compounds observed were decreased due to decomposition. Therefore, it may be concluded that, compared with acid hydrolysis or enzymatic saccharification, cellulose may be hydrolyzed to glucose and its derivatives more or less to the same degree as in corn starch under supercritical state. This finding suggests that the supercritical treatment can overcome the difficulties in hydrolyzing cellulose to glucose, found in the acid hydrolysis or enzymatic saccharification techniques.     

Koexistenzbeziehungen,Darstellung und Eigenschaften ternärer Phasen im System Cu/Mo/O

Coexistence Relations, Preparation and Properties of Ternary Compounds in the System Cu/Mo/O The phase diagram of the ternary system Cu/Mo/O is presented at 773 K. The compounds CuMoO₄, Cu₃Mo₂O₉, Cu₄Mo₅O₁₇, Cu₆Mo₅O₁₈, Cu_4–xMo₃O₁₂, and Cu_xMoO₃ are found to be thermodynamical stable. The homogeneity range of Cu_4–xMo₃O₁₂ runs to x = 0.1–0.2. Single crystals of CuMoO₄ and Cu₃Mo₂O₉ were grown by chemical transport reactions with TeCl₄, Cl₂, HCl, and Br₂ as transport agent. The results were compared with thermochemical calculations. The decomposition of CuMoO₄ and Cu₃Mo₂O₉ was investigated with thermal analysis and decompositon pressure measurements.     

Chemical modification of polymer surfaces: a review

The main approaches that have been taken to chemically modify polymer surfaces are introduced and reviewed. These are wet chemical oxidation, plasma treatment, classical organic chemistry, and attachment of polymer chains. The extent to which each of these approaches can produce the specific modifications desired is discussed, and any unwanted effects that commonly occur are cited. Finally, the need for using several methods of surface analysis in concert to obtain adequate surface characterization is described.     

Cross-linking chemistry and biology: development of multifunctional photoaffinity probes

An efficient method of photoaffinity labeling has been developed based on rationally designed multifunctional photoprobes. Photoaffinity techniques have been used to elucidate the protein structure at the interface of biomolecules by the photochemical labeling of interacting sites. However, the identification of labeled sites within target proteins is often difficult. Novel biotinyl bioprobes bearing a diazirine photophore have contributed significantly to the rapid elucidation of ligand binding sites within proteins, thereby extending conventional photoaffinity methods. This article discusses the synthesis and applications of various photoprobes bearing a biotin, including strategies using cleavable linkages between photophores. The combination of photoaffinity methods with chip technology is also described as a novel entry to rapid affinity-based screening of inhibitors. This review focuses on a rapid and reliable photoaffinity method utilizing diazirine-based multifunctional photoprobes with numerous potential applications in functional proteomics of biomolecular interactions.     

纳米SiO_2颗粒表面修饰的有机分子在介质中的光物理行为研究

利用Sol-Gel方法投篮了单分散性很好的球型二氧化硅纳米颗粒，通过表面化 学修饰法引入了带有荧光发色团的有机分子，通过稳态光物理方法研究了纳米颗粒 表面的有机分子在水、乙醇以及阴、阳离子表面活性剂悬浮液中的光物理行为。实 验表明，纳米颗粒表面有机分子的分散状态是决定其光物理行为的主要因素。这一 结果为设计和开发新型“壳-核”型纳米二氧化硅荧光传感器提供了有用的参考。     

磷酸三乙酯改性HZSM-5沸石的活性及理论研究

采用XRD表征了水蒸气和磷联合改性的HZSM-5沸石分子筛的结构．通过NH3-TPD和N2吸附脱附研究了样品的酸性和比表面．采用正庚烷的裂化反应研究了样品的裂化活性，研究结果表明，磷改性样品与母体样品相比，经过水蒸气处理后显示出较高的酸量和正庚烷裂化活性．上述结果首次用模型簇和计算量子化学方法进行了解释．采用Gaussian94软件包和PM3半经验量子化学方法对模型簇进行了全优化和频率分析．计算结果显示磷改性后样品的脱铝补硅反应热大于母体样品脱铝补硅反应热，从而显示出磷对骨架的稳定化作用．     

源内裂解液相色谱-质谱鉴别人参皂甙砒和拟人参皂甙F11

研究了利用源内碰撞诱导解离（in-source collision—induced dissociation）的高效液相色谱-大气压化学电离质谱（HPLC—APCI／MS）获取人参和西洋参的化学标志物——人参皂甙Rf和拟人参皂甙F11的特征结构信息及鉴别人参和西洋参的方法。在乙腈-水梯度洗脱反相液相色谱及源内碰撞诱导解离条件下，能获得人参皂甙Rf和拟人参皂甙F11的母核离子及去糖基离子的源内碰撞诱导解离谱，从其差别能清楚区分这对同分异构体。本方法对人参皂甙Rf和拟人参皂甙F11的检出限能达到10^-7g柱上样量，简单、快速，单次质谱实验就能鉴别人参和西洋参。     

铌酸锂晶体性能的组成依赖性(英文)

总结了铌酸锂晶体的各项性能指标,显示了其对晶体实际组成的强烈依赖性.利用化学键模型定量地解释了这种依赖性产生的根源,从而说明了制约该晶体性能提高的关键因素是晶体结构中的缺陷控制.     

Synthese und Kristallstruktur einer Neuen hexagonalen Modifikation von Al2S3 mit fünffach koordiniertem Aluminium

Synthesis and Crystal Structure of a Novel Hexagonal Modification of Al₂S₃ with Five-coordinated Aluminum A new hexagonal high temperature modification of Al₂S₃ could be prepared by chemical vapour transport with iodine (860 → 750°C) or by annealing of α -Al₂S₃ at 550°C. According to the single crystal X-ray structure determination the novel form of Al₂S₃ crystallizes in space group P 6₁ (No. 169) with a = 6.491(1), c = 17.169(4) Å, V = 626.5 ų, Z = 6; R = 0.0253. In this modification one half of the aluminum atoms are tetrahedrally coordinated [d(Al? S): 2.226–2.267 Å], whereas the other half are in trigonal bipyramidal coordination of five S atoms with bond lengths of 2.272–2.315 Å (equatorial) and 2.495–2.521 Å (axial). Aluminum in AlS₅ coordination is observed for the first time in this compound. The crystal structure is isotypic to In₂Se₃ and AlInS₃. In addition, results of a refinement of the α -Al₂S₃ crystal structure are reported which were obtained on crystals prepared also by chemical vapour transport with iodine.