Preparation and Characterization of N-4-Nitrophenyl-L-prolinol Nanocrystals in Sol-Gel Matrices

Organic nanocrystals of N-4-nitrophenyl-l-prolinol (NPP) have been grown in sol-gel matrices prepared from silicon alkoxide precursors. Our process is based on the control of the nucleation and growth kinetics of the dye in the pores of dense gels. Nanocomposites gel-glasses are obtained with a high optical quality due to the small size of the nanocrystals (10-20 nm). Differential scanning calorimetry experiments evidenced clearly the melting point of NPP nanocrystals, which is registered 51°C above that of NPP powder. Micro-Raman and solid state NMR spectroscopies allowed us to demonstrate that our nanocrystallization process does not chemically modify NPP molecules. We specified also the nature of interactions existing between the NPP nanocrystals and the xerogels. These strong interactions, which explain the important increase of the melting point of the nanocrystals in comparison to the NPP powder, are hydrogen bonds between nitro groups of NPP and uncondensed silanol functions of the silicate network.     

影响混合酸中各组分含量测定的因素及条件

作者曾提出，两种一元弱酸混合酸以及强酸与一元弱酸混合酸中，第一终点ｐＨ〉３．７的情况下，测定各组分酸含量的方法。在此基础上，本文在理论上推导出第一终点ｐＨ值测量误差ΔｐＨ与分析结果的误差ΔＶｅ２／Ｖｅ＾Ｔ之间的关系式，从而明确了影响误差的因素，并提出误差ΔＶｅ２／Ｖｅ＾Ｔ≤１．０％时的测定条件以及第一终点ｐＨ〈３．７时的测定方法。实验结果表明，如果能满足本文提出的条件，可以获得满意的结果。     

Al2O3／WO3／ZrO2固体强酸催化剂对正丁烷异构化的催化性能

 通过沉淀、回流、浸渍和焙烧等步骤制备了Al2O3／WO3／ZrO2固体强酸催化剂．采用XRD，N2吸附，UV－Vis光谱，NH3－TPD和H2－TPR等技术测定了Al2O3对WO3／ZrO2催化剂的结构、表面酸性、氧化还原性及正丁烷异构化反应性能的影响．结果表明，在WO3／ZrO2中引入适量的Al2O3对其表面酸强度及酸量无显著影响，但可使催化剂中的ZrO2组分以稳定的四方相形式存在，并能有效地抑制催化剂中WO3的聚集长大，从而提高催化剂的稳定性和正丁烷异构化的转化率和选择性．添加铂于Al2O3／WO3／ZrO2中可进一步提高其催化性能．还考察了催化剂的焙烧温度、Al含量、反应温度和反应气氛对正丁烷异构化反应的影响．     

担体对Fe—MnO催化剂CO＋H2反应性能的影响

考察氧化物担体对Fe-MnO催化剂反应性能影响的结果表明,担体的类型对Fe-MnO催化剂CO加氢反应性能影响很大,其低碳烯烃选择性相差悬殊,Al_2O_3、SiO_2和MgO担载的Fe-MnO催化剂都不利于低碳烯烃的生成,而TiO_2担载的Fe-MnO催化剂则具有较高的烯烃选择性和催化活性。从担体-金属相互作用本质的差异,研究了担体对金属活性组分化学状态的影响及催化活性相与F-T合成烯烃的关系,发现担体-金属间的电子效应有利于催化剂活性和选择性的提高,其它物理化学效应引起的相互作用则不利于改善催化剂性能;还表明Fe_(?)C是催化活性相,Fe~(2+)物种的存在不利于提高烯烃的选择性。     

Theory of the Lamellar Superstructure of an ABC 3‐Miktoarm Star‐Terpolymer

Summary: The theory of lamellar superstructures of an ABC 3‐miktoarm star terpolymer in the conditions corresponding to the strong segregation limit for linear ABC triblock terpolymer has been developed. According to the particular molecular topology (namely, the common junction point for all three blocks), the system cannot avoid volume interactions between monomers of different blocks even in this limit. Hence, in the lamellar superstructure, there exists the so‐called “mixed” domain containing monomers of all three blocks but formed mainly of the block with the lowest degree of incompatibility. It is shown that unfavorable volume interactions in this domain are minimized by the increase of the interfacial area per ABC molecule which makes the mixed domain narrow. This leads to an unusual behavior of the period of the superstructure which decreases with an increase in the length of the block with the lowest incompatibility. However, in the case of a “synchronous” increase in the size of the branches of the ABC 3‐miktoarm star terpolymer, the period of the superstructure increases similarly to that for a linear ABC triblock terpolymer.

ABC 3‐miktoarm star terpolymer.     

铂电极上溶液酸碱性的电位溶出法响应

提出了一个广谱测定强酸、强碱溶液浓度的方法。用铂电极作工作电极，电位溶出法对溶液酸碱性产生响应。通过调节沉积时间和沉积电位，利用电位溶出法可以检测溶液酸、大致 的浓度范围为2．5mol/L H^ -1.0mol/L OH^-。详细研究了不同测定范围的实验条件，以及溶出过程的响应机理。在不同酸碱性溶液中电沉积产生的氢吸附于电极表面，溶出过程中被溶液中的氧氧化成氢离子，从而产生电位平台。该平台的出现还与随后的电极表面金属／金属氧化物电对电位值有关。     

新型强阳离子交换聚合物整体柱的制备及其在奶制品中三聚氰胺测定中的应用

在内径为530 μm的石英毛细管中原位聚合得到一种新的强阳离子交换聚合物整体柱2-丙烯酰胺-2-甲基-1-丙磺酸-乙二醇二甲基丙烯酸酯聚合物(poly(AMPS-co-EDMA))整体柱,并将其作为聚合物整体柱微萃取(PMME)的萃取介质。优化N,N-二甲基甲酰胺(DMF)和聚乙二醇(PEG)致孔体系的比例,制备得到的poly(AMPS-co-EDMA)整体柱渗透性好、机械强度高且在水溶液中具有良好的稳定性。通过考察样品溶液的pH值、盐浓度和有机溶剂含量对萃取效率的影响,证明该整体柱主要通过强阳离子交换和疏水相互作用对三聚氰胺进行萃取富集。在PMME与高效液相色谱联用技术的基础上,建立了检测奶制品中三聚氰胺含量的分析方法。奶制品中三聚氰胺的检出限和定量限分别为0.09 mg/kg和0.3 mg/kg,在0.5~80 mg/kg的含量范围内具有良好的线性关系,日内、日间测定的相对标准偏差不高于7.5%。结果表明,该方法简便、快速、灵敏度高且成本低,适合于奶制品中微量三聚氰胺的检测。     

The perturbing effect of cholesterol on the interaction between labdanes and DPPC bilayers

Differential scanning calorimetry (DSC) was used to study the effect of cholesterol on the perturbation of DPPC bilayers induced by eight bioactive structurally related labdanes isolated from the resin ‘ladano’ of Cistus creticus subsp. creticus (Cistaceae) or semisynthesized from the mother compounds. Labdanes themselves induced profound modifications in DPPC bilayer organization and thermotropic properties that were altered when cholesterol was incorporated in equimolar amounts to the labdanes. The present work shows that, up to 10 mol% of the equimolar mixture of cholesterol and the labdanes, the modifications evoked on DPPC bilayer organization are in accordance to these induced by the labdanes themselves. When the concentration exceeded 20 mol%, cholesterol influence dominated while the effect of the labdanes was suppressed and their interaction with the bilayer was probably prevented. The degree by which cholesterol modulated the labdane interaction with the bilayer depended on their structural characteristics that determine their localization in the bilayer interior. Polar groups that force the labdanes to localize themselves at the interfacial region broadened the concentration range by which labdanes interacted with the DPPC bilayer even in the presence of high concentration of cholesterol where cholesterol-rich domains are preferentially formed. On the other hand, labdanes possessing functional groups that promote their deeper penetration in the bilayer interior compete with cholesterol in a high extent for the same localization sites resulting in their possible elimination from the bilayer when the concentration of cholesterol present exceeds the 20 mol%.     

溴胺酸Ullmann缩合反应工艺

采用强酸阳离子交换树脂-乙醇-铜粉催化体系代替传统工艺中硫酸-水-铜粉催化体系,对溴胺酸进行Ullmann缩合反应。考察了强酸离子交换树脂用量、有机溶剂种类及反应温度等因素对反应收率的影响。结果表明,在V(乙醇)∶V(水)=9∶1介质中,在溴胺酸、铜粉存在下,树脂用量为16g/L,在70℃下反应3h,溴胺酸缩合产物收率可达94.0%。反应中所使用的离子交换树脂、铜粉和乙醇均可回收再利用,强酸离子交换树脂重复使用5次后其催化活性仍未降低;乙醇回收率可达70%～80%,铜粉的回收率可达85%～90%。     

Synthesis, Crystal Structure and Bioactivities of 1-（4-Chlorophenyl）-3- [ 5-（pyrid-4-yl）- 1,3,4-thiadiazol-2-yl] urea

The title compound 1-(4-chlorophenyl)-3-[5-(pyrid-4-yl)-1,3,4-thiadiazol-2-yl]urea (C14H10ClN5OS, Mr = 331.79) has been synthesized by the reaction of 2-amino-5-(pyrid-4-yl)- 1,3,4-thiadiazole with 4-chlorobenzoyl azide, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic system, space group P with a = 5.8550(8), b = 7.5668(10), c = 16.416(2) , α = 78.364(2), β = 81.204(2), γ = 84.749(2)°, V = 702.58(16) 3, Z = 2, Dc = 1.568 g/cm3, μ = 0.429 mm-1, F(000) = 340, the final R = 0.0442 and wR = 0.1092 for 2001 observed reflections (I > 2σ(I)). X-ray diffraction analysis reveals that the title molecule is nearly planar. In the crystal structure, the molecules are linked by strong intermolecular N-H…N hydrogen bonds together with weak nonclassical intermolecular (C-H…Y, Y = N, O and Cl) hydrogen bonds and stacked through π-π interactions. The preliminary bioassay shows that the title compound exhibits good fungicidal activities against Rhizoctonia solani, Botrytis cinerea and Dothiorella gregaria.