Chiral Discrimination Mechanisms by Silylated-Acetylated Cyclodextrins: Superficial Interactions vs. Inclusion

Cyclodextrin derivatives constitute a powerful class of auxiliary agents for the discrimination of apolar chiral substrates. Both host–guest inclusion phenomena and interactions with the derivatizing groups located on the surface of the macrocycle could drive the enantiodiscrimination; thus, it is important to understand the role that these processes play in the rational design of new chiral selectors. The purpose of this study is to compare via nuclear magnetic resonance (NMR) spectroscopy the efficiency of silylated-acetylated α-, β-, and γ-cyclodextrins in the chiral discrimination of 1,1,1,3,3-pentafluoro-2-(fluoromethoxy)-3-methoxypropane (compound B) and methyl 2-chloropropionate (MCP). NMR DOSY (Diffusion Ordered SpectroscopY) experiments were conducted for the determination of the bound molar fractions and the association constants, whereas ROESY (Rotating-frame Overhauser Enhancement SpectroscopY) measurements provided information on the hosts’ conformation and on the interaction phenomena with the guests. Compound B, endowed with fluorinated moieties, is not deeply included due to attractive Si-F interactions occurring at the external surface of the cyclodextrins. Therefore, a low selectivity toward the size of cyclodextrin cavity is found. By contrast, enantiodiscrimination of MCP relies on the optimal fitting between the size of the guest and that of the cyclodextrin cavity.     

The adsorption of methyl nitrite on the Au(111) surface

The interaction of the methyl nitrite molecule (CH₃ONO) with the gold(111) surface has been studied by means of density functional calculations. The perfect Au(111) surface has been represented by a rather large cluster model, Au₂₂, that was in turn used to extract information about the preferred adsorption geometry of the CH₃ONO species. Vibrational frequencies and adsorption energy are also reported. The calculated adsorption energies are 31.2 kJ/mol with respect to gas phase cis-conformer and 35.1 kJ/mol with respect to trans-methyl nitrite, very close to the experimental adsorption energy of 33.5 kJ/mol. From the analysis of vibrational frequencies of gas phase and adsorbed species it is concluded that only the cis-conformer is present at the Au(111) surface.     

丁苯胶乳_苯乙烯_甲基丙烯酸甲酯核壳乳液接枝共聚的研究

以过氧化苯甲酰(BPO)-Fe~(2+)为引发体系,硬脂酸钾和歧化松香酸皂为乳化剂,硫醇为调节剂,于600mL釜内、70℃下进行丁苯胶乳-苯乙烯-甲基丙烯酸甲酯(SBR-S-MMA)的核壳乳液接枝共聚。研究认为本体系的反应机理为:Fe~(2+)与乳化剂结合为部分油溶性化合物,再与溶解在乳胶粒中的BPO反应,生成自由基与Fe~(3+),Fe~(3+)被雕白块还原为Fe~(2+)后完成一个循环。在乳胶粒相产生的自由基与单体反应或进攻橡胶链,从而引起链引发和链增长反应。S和MMA接枝聚合的初始速率(R_(PO))与[BPO]~(0.5)成正比,R_(PO)随反应温度的升高而增大,随硫醇用量的增加而减小。该体系S和MMA两步接枝反应的表观分解活化能分别为16.56kJ/mol和17.50kJ/mol。     

Polymer-grafted cellulose fibers. I. Enhanced water absorbency and tensile strength

To enhance the water absorbency of wood fibers, various acrylic monomers were grafted to these fibers using cerium IV initiation followed by base hydrolysis. The absorbent capacity of hydrolyzed methyl acrylate- or acrylonitrile-grafted wood pulp fibers was an order of magnitude greater than ungrafted pulp fibers. A portion of this enhanced absorbency could be attributed to graft-induced osmotic forces. Enhanced absorbency was relatively independent of wood fiber type. Paper handsheets incorporating 20% grafted fibers had a fivefold increase in absorbent capacity, a twofold increase in dry tensile strength, a threefold or greater increase in wet tensile strength, and were more stretchable. In addition to enhanced absorbent capacity, the rate of absorbency was approximately 50% greater. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1463–1469, 1997     

Preparation of monoglycerides by guanidine-catalyzed processes

Glycerolysis of methyl stearate and tristearin has been carried out in the presence of alkylguanidines—strong nonionic bases—as catalysts. When applied at 10 mol%, 1,5,7-triazabicyclo [4.4.0]dec-5-ene, 1,2,3-tricyclohexylguanidine, and 1,3-dicyclohexyl-2-n-octylguanidine give monoglycerides in more than 90% selectivity, in a maximum of 6 h reaction time.     

以气质联用技术对白补药中挥发性成分的分析

为了寻找白补药的应用基础,确定白补药中挥发性物质的主要成分,用气相色谱-质谱联用技术对白补药石油醚浸膏的化学成分进行研究.用75%的乙醇提取白补药,将所得浸膏加水稀释后用石油醚萃取,再用气相色谱-质谱联用技术对石油醚浸膏进行分析,共分离出53个峰.通过中文数据系统检索和质谱资料核对,鉴定出其中46个化合物,其中主要成分为棕榈油酸甲基酯(质量分数28.94%)、硬脂酸甲酯(质量分数6.47%)、3,4,5,6-四甲基-2,5-辛二烯(质量分数5.42%)、6,10,14-三甲基-2-十五烷酮(质量分数5.07%)等.通过鉴定明确了白补药中石油醚部分的主要成分,为该植物的开发利用提供了科学依据.     

TiO_2-Pt同轴纳米管制备及光催化性能研究

该文利用毛细管作用和还原气氛处理相结合的方法,以TiO2纳米颗粒为原料制备了贵金属Pt纳米颗粒填充的TiO2-Pt同轴纳米管复合材料,并对其形貌和结构进行了表征。然后在紫外光源的照射下对甲基橙进行光催化降解实验,光催化实验结果表明该复合纳米材料具有比TiO2纳米颗粒更高的光催化降解甲基橙的催化活性。     

TiO2中空纤维光催化研究及设备设计

利用生物模板法-脱脂棉为模板,于不同温度烧结得二氧化钛（TiO2）中空纤维,利用X射线衍射、扫描电镜等进行表征,研究得出550℃高温下烧结的TiO2中空纤维光催化性能最佳,以浓度为10mg/L甲基橙为目标降解物,在pH值为2,TiO2中空纤维浓度为2.5g/L,紫外灯照射180min后降解率可达90%以上,二次降解率可达77%以上。在此最优实验条件的基础上,设计了一套新型光催化降解有机废水二级处理装置,第一级装置采用TiO2中空纤维作为催化剂,第二级装置采用活性炭和TiO2混合物作为催化剂,实验测试结果较好,极具实际应用与推广价值。     

Ti O2／Si O2复合光催化剂制备工艺参数优化及其表征

先以无机钛盐、硅酸盐为原料制取聚合硅酸硫酸钛,再通过液相水解法制得TiO2/SiO2复合光催化剂,并用SE M、X R D、BE T和甲基橙脱色率对复合光催化剂进行表征. 结果表明,TiO2/SiO2复合光催化剂制备优化工艺参数为：Ti（S O4）2作钛源、Ti/Si摩尔比为12 ： 1、水解反应p H值为6、煅烧温度为650oС,以此条件制备的复合光催化剂对甲基橙脱色率可达98 .6 %以上;TiO2/SiO2复合光催化剂为一种分散均匀的纳米级球形颗粒,其成分为以锐钛矿为主的TiO2,SiO2的复合有效抑制了TiO2晶粒的生长,同时提高了TiO2的热稳定性.     

尖晶石型Zn2SnO4光催化剂的制备与活性研究

运用化学共沉淀法,制备尖晶石型Zn2SnO4纳米粉体。通过X射线衍射分析(XRD)、光电子能谱分析(XPS)、扫描电镜(SEM)、光度法等手段研究粉体的结构。以波长λ=312 nm的光源对甲基橙和茜素红水溶液进行光催化降解实验,讨论光催化剂用量、染料浓度、催化剂烧结时间、试液的pH值、光照时间等与染料脱色率的关系。结果表明,该复合氧化物粉体平均粒径小于30 nm,属立方晶系,具有良好的光催化活性。