尿嘧啶-BH3复合物构型与性质的MP2理论研究

用MP2方法在6—31G基组水平对尿嘧啶-BH3复合物进行了理论计算，以预测该复合物的构型及稳定化能，得到了5种构型，对各构型进行了振动频率分析和自然键轨道分析．结果表明，B与O直接结合的构型比较稳定，其稳定化能分别为95．5和93．4kJ／mol．各种构型都存在不同程度的电荷转移，转移方式和转移量与结合方式有关．复合物的形成使红外光谱中的N-H键，B-H键和C-O键的伸缩振动频率均有所降低．     

Effect of Particle Size and Capping on Photoluminescence Quantum Efficiency of 1,3,5-Triphenyl-2-pyrazoline Nanocrystals

Organic nanocrystals of 1,3,5-triphenyl-2-pyrazoline(TPP) with a series of sizes were synthesized by reprecipitation method.The luminescence quantum efficiency of TPP nanocrystals increases from 24.2% for the nanocrystals with an average size of 300nm to 34.6% for those with an average size of 20nm.Surface capping by polyvinyl pyrrolidone(PVP) will improve the quantum efficiency of TPP nanocrystals.The size-dependence and capping-induced variation of the luminescence quantum efficiency was elucidated in viewpoint of aggregation quenching and the equilibrium between the TPP monomers and the aggregates in TPP nanocrystals.     

Cu-Ce/γ-Al2O3对硬脂酸催化水热脱氧产生烷烃的效果

利用等体积浸渍法制备Cu-Ce/γ-Al₂O₃催化剂，并在无H₂存在的条件下对硬脂酸进行催化水热液化。对催化剂进行BET比表面积分析和X射线衍射（XRD）分析可知，Cu-Ce/γ-Al₂O₃催化剂中存在CuO和CeO₂两种晶型，在300℃条件下水热反应12 h后具有更好的热稳定性。通过对硬脂酸进行水热液化实验和对生物油进行气相色谱-质谱（GC-MS）分析发现，加入Cu-Ce/γ-Al₂O₃催化剂能够获得最高的硬脂酸转化率（94.71%）和总烃产率（81.41%），水热液化脱氧效果最好。分析正烷烃的产率，结果发现硬脂酸在高温水热条件下主要发生脱羧反应。Cu-Ce/γ-Al₂O₃催化剂的加入能够同时促进反应过程中脱羧反应、加氢脱氧反应和裂化反应。此外，Cu-Ce/γ-Al₂O₃还能够促进羰基基团的脱除，有效减少产物中的醛和酮类物质。     

中国内陆大气颗粒物的搬运、沉积及反映的气候变化——Ⅰ.现代大气气溶胶

分析了中国内陆3个地点尘暴和非尘暴期间大气颗粒物中17种微量元素的浓度-粒度分布。表明这些地点的大气颗粒物主要由矿物气溶胶(即粉尘)组成。对黄土高原上空非尘暴大气微量元素的统计分析,导出粗粒子主要有两种来源——土壤粉尘和被污染的粉尘,细粒子的两种来源是土壤粉尘和人为污染物。在年尺度上,粉尘对黄土高原的大气干输入主要取决于非尘暴过程。利用清除系数估算的粉尘湿沉积通量只占总沉积的4％—11％。     

新型β-环糊精固载化高分子对内、外源性毒物的包络吸附研究

高分子吸附剂作为医用生物材料进行血液灌流已广泛应用,它具有特定的化学结构和物理结构,可选择性吸附不同种类的内、外源性毒物;它的机械强度高,可避免在血液净化中因微小颗粒脱落而引起血栓.本文将β-环糊精环状低聚糖以磺酸醣键固载到交联聚苯乙烯载体上,制备新型的β-环糊精高分子进行吸附内、外源性毒物分子研究,取得了良好的结果.     

Synthesis of 2-Aminochromene Derivatives Catalyzed by KF／Al2O3

A series of 2-aminochromene derivatives including 2-amino-ben-zo[ h ] chromene, 2-amino-benzo [ f ] chromene and 2-amino-pyrano [3,2-h ]quinolin derivatives was synthesized from aryl-aldehyde, malononitrile or ethyl cyanoacetate and 1-naphthol or 2-naphthoi or 8-hydroxyquinoline in refluxing ethyl alcohol cat-alyzed by KF-Al2O3. The structures were confirmed by X-ray analysis.     

对二甲胺基苯甲醛缩2,4-二硝基苯腙的合成和结构

利用对二甲氨基苯甲醛和2,4-二硝基苯肼的缩合反应合成了对二甲氨基苯甲醛缩2,4-二硝基苯腙,利用红外、紫外光谱和元素分析进行了结构表征.利用X射线衍射分析方法测定了晶体结构,结果表明化合物中分子为平面型结构,偏离平面的最大的N(2) 原子距平面0.00351(2) nm;分子内和分子间的氢键使晶胞内的分子沿c轴成锯齿型链,分子间有芳环堆积作用存在.     

Intrinsic Surface Reaction Constant in 1-pK Model of Mg-Fe Hydrotalcite-like Compounds

The relationship among intrinsic surface reaction constant (K) in 1-pK model, point of zero net charge (PZNC) and structural charge density (σst) for amphoteric solid with structural charges was established in order to investigate the effect of σst on pK. The theoretical analysis based on 1-pK model indicates that the independent PZNC of electrolyte concentration (c) exists for amphoteric solid with structural charges. A common intersection point (CIP) should appear on the acid-base titration curves at different c, and the pH at the CIP is pHPZNC. The pK can be expressed as pK=-pHPZNC log[(1 2αPZNC)/(1-2αPZNC)], where αPZNC≡σst/eNANs, in which e is the elementary charge, NA the Avogadro‘s constant and Ns the total density of surface sites. For solids without structural charges, pK=-pHPZNC. The pK values of hydrotalcite-like compounds (HTlc) with general formula of [Mg1-xFex(OH)2](Cl,OH)x were evaluated. With increasing x, the pK increases, which can be explained based on the affinity of metal cations for H^- or OH^- and the electrostatic interaction between charging surface and H^- or OH^-.     

Synthesis, Characterization and Crystal Structure of （Z）-1-[2-（Triarylstannyl）vinyl]-1-indanols and Their Arylhalostannyl Derivatives

(Z)-1-[2-(Tri-o-tolylstannyl)vinyl]-1-indanol (1) and (Z)-1-[2-(tri-p-tolylstannyl)vinyl]-l-indanol (2) were synthesized by the addition reaction of 1-ethynylindanol with tri-o-tolyltin and tri-p-tolyltin hydride. The aryl groups in compound 1 and 2 were substituted by Br2 or I2 to yield monohalide derivatives (3-6). The compounds 1-6 were characterized by elemental analysis, ^1H NMR and FT-IR spectroscopy. The crystal structures of 1, 2 and 4 have been determined by single crystal X-ray diffraction analysis. The Sn atom in 1 and 2 exhibits a tetrahedral geometry distorted towards trigonal bipyramid due to a weak intramolecular interaction between Sn and the hydroxyl O atoms [0.2839(4) nm and 0.2744(5) nm], while the Sn atom in 4 adopts a trigonal bipyramidal geometry with a significant O→Sn(1) interaction [0.2552(5) nm].     

Michael-Addition Reaction of Malononitrile with α,β-Unsaturated Cycloketones Catalyzed by KF／Al2O3

A series of KF/Al2O3 catalyzed Michael-addition reactions between malononitrile and α,β-unsaturated cycloketones in DMF solution were studied. At room temperature, 2-cyano-3-aryl-3-(1,2,3,4-tetrahydronaphthalen-1-one-2-yl) propionitrile derivatives were synthesized by the reaction between 2-arylmethylidene-1,2,3,4-tetra-hydronaphthalen-1-one and malononitrile. However, if the temperature was increased to 80℃, 2-amino-3-cyano-4-aryl-4H-benzo[h]chromene derivatives were obtained in high yields. When the α,β-unsaturated ketones were replaced by 2,6-biarylmethylidenecyclohexanone or 2,5-biarylmethylidenecyclopentanone, another series of 2-amino-3-cyano-4H-pyran derivatives was isolated successfully. The structures of the products were confirmed by X-ray diffraction analysis.