负载咖啡因-活性炭新吸附材料对钼(VI)的吸附行为的研究

以生物碱（咖啡因）为衍生化试剂，用浸渍法使其负载于活性炭（ＡＣ）上，制成一种新的金属阴离子吸附材料———负载咖啡因－活性炭（ＣＡＣ）。用ＩＣＰ－ＡＥＳ研究了该吸附材料对金属阴离子［Ｍｏ７Ｏ２４］６－的吸附性能；考察了其化学稳定性；还研究了不同浓度硫酸和氨水对待测物吸附率和解脱率的影响及共存离子的干扰影响。     

烯烃氢甲酰化催化剂活性物种的原位~1H NMR研究

有机磷配位铐或钴联基配合物是生产难或醇的工业催化剂，一般公认金属氢化物是反应的催化活性物种．通常反应活性物种仅存在干反应状态下，其结构表征非常困难，在许多研究中只能关联催化剂母体与其活性的关系［‘1；而未能揭示出催化的本质，给催化剂设计造成很大困难，因而对催化剂活性物种的直接表征受到普遍关注．B。wn问、Morrista］及本文作者研究组＊均采用加压原位红外光谱方法，在烯烃氢甲酸化反应条件下捕捉到HCO（CO）3L存在的信息·但用相同方法在反应条件下，在RhH键特征吸收谱带195O－2200Cm‘内未观测到错氢化物的Rh－…     

Modification of the GV-MSA model in obtaining the activity and osmotic coefficients of aqueous electrolyte solutions

In this work a modified form of the Ghotbi–Vera Mean Spherical Approximation model (MGV-MSA) has been used to correlate the mean ionic activity coefficients (MIAC) for a number of symmetric and asymmetric aqueous electrolyte solutions at 25 °C. In the proposed model the hard sphere as well as the electrostatic contributions to the MIAC and the osmotic coefficient of the previously GV-MSA model has been modified. The results of the proposed model for the MIAC of the electrolyte solutions studied in this work are used to directly calculate the values of the osmotic coefficients without introducing any new adjustable parameter. In the MGV-MSA model the cation diameter as well as the relative permittivity of water depends on the electrolyte concentration. Having considered such dependency for both cation and relative permittivity for water in an electrolyte solution the modification of the GV-MSA has been made. It should be stated that in the MGV-MSA model the anion diameter in the solution similar to that in the GV-MSA model remains constant and independent of the electrolyte concentration. The results obtained from the proposed model have been favorably compared with those of the GV-MSA model. The results showed that the MGV-MSA model can more accurately correlate the MIAC of the single electrolyte solutions than those of the GV-MSA model. The same comparison has been observed in case of the osmotic coefficients for the electrolyte solutions studied in this work. It should be noted that in order to do an unequivocal comparison between the results obtained from the models used in this work the same minimization procedure and the same experimental data for the MIAC and the osmotic coefficients have been used. Also it should be mentioned that in the MGV-MSA model the conversion from the McMillan–Mayer (MM) framework to that of the Lewis–Randall (LR) has been performed. It has been concluded that such transformation can affect the results in particular at higher electrolyte concentrations.     

Chromatographic performance of deuterated solvents in reversed phase micro high performance liquid chromatography

The chromatographic performance of the deuterated solvents, CD₃OD and D₂O, has been investigated in reversed-phase micro high performance liquid chromatography. The chromatographic performance of CD₃OD is only slightly superior to that of CH₃OH. However, the performance of D₂ is significantly superior to that of H₂O, separation of aromatics being improved by about 30%. D₂ is a particularly powerful solvent for the separation iof deuterated and non-deuterated compounds.     

Controlled synthesis of poly(acetone oxime acrylate) as a new reactive polymer: Stimuli-responsive reactive copolymers

Acetone oxime acrylate has been synthesized as a new active ester monomer. Free radical polymerization yielded a reactive polymer soluble in various organic solvents, such as chloroform, dioxane, DMSO, acetone, methanol, dichloromethane, DMF, and ethanol. Controlled radical polymerization of acetone oxime acrylate was successfully conducted using the RAFT, NMP and Iniferter method. Partly polymer analogous reaction with N-isopropylamine resulted in the reactive copolymer poly(N-isopropylacrylamide-co-acetone oxime acrylate), which featured a lower critical solution temperature (LCST) of 61 °C in water. Further, the reactivity of the copolymer was exemplary proven by complete reaction with ammonia yielding poly(N-isopropylacrylamide-co-acrylamide), which does not possess a LCST.     

Amino-Modified Silicate Xerogels Complexed with Cu(II) as Catalyst Precursors. Coordination State and Thermal Decomposition

The sol-gel process is a useful method for preparing two series of organically and co-ordinately modified xerogels of the types [CuN _n ]·N _5–n ·5xSiO_4/2 (n < 4) and [Cu(N–N)_n]·(N–N)_2–n ·2x SiO_4/2(n 2), where N = NH₂(CH₂)₃ SiO_3/2, N–N = NH₂(CH₂)₂NH·(CH₂)₃SiO_3/2 and x = [SiO_4/2]/[N] or [SiO_4/2]/[N–N]. The amino groups in the materials are coordinately active and participate partly in the coordination sphere of Cu(II) ions. The composition of the coordination sphere can be varied with the SiO_4/2 content and also as a result of the thermal decomposition of the organic residues at higher temperatures.Because the xerogel materials are considered to be catalyst precursors, this study is focused on their coordination and thermal properties. The prepared xerogels, such as silica, aminated silicates with N and N–N, as well as those entities complexed with Cu(II), were characterised by FT-IR spectroscopy. During gelation and thermal decomposition the materials were analysed by electron paramagnetic resonance (EPR) spectroscopy. The xerogels were additionally studied by UV-Vis absorption spectroscopy. The gaseous products of the thermal decomposition of these materials in an Ar atmosphere were investigated by the use of FT-IR spectroscopy coupled with TG and DTG thermal analysis. These data were complemented by temperature-programmed decomposition (TPDec) in a 2% O₂ + 98% Ar stream coupled with quadrupole mass spectroscopy.     

Neue acetonylsubstituierte Azole I. 5-Acetonyl-1,2,4-oxadiazole

Aliphatic amidoximesR—C (NH₂)=NOH react with diketene to yield 5-acetonyl-3-alkyl-1,2,4-oxadiazoles, which are susceptible to a wide variety of reactions at the keto-group as well as at the methylene-group. Their transformations into 1-methyl-2-oxadiazolyl-vinylN,N-dimethylcarbamates, 2-chloro-1-oxadiazolylpropenes, 1-oxadiazolyl-2-(1,2,4-triazol-1-yl)propenes, 1,1-dichloro-1-oxadiazolylacetones and 3-hydroxy-2-oxadiazolyl-crotonic amides are described as well as their reactions with diazonium salts, with sodium nitrite and with carbon disulfide. Further products obtained are carbamates of of 1-oxadiazolyl-2-oxo-propane-1-oximes, 2-chloro-2-oxadiazolylvinyl phosphates and an oxadiazolyl pyrimidine.

Herrn Prof. Dr.Klaus Weissermel zu seinem 60. Geburtstag.     

Yb~(3+):Cs_2NaYbCl_6和Yb~(3+):Cs_2NaYbBr_6的能级

本文应用双层点电荷配位场(DSPF)模型计算了Yb~(3+):Cs_2NaYbCl_6和Yb~(3+):Cs_2NaYbBr_6的能级,分析了二体系中Yb~(3+)与Cl~-、Br~-的成键。     

Approximate expressions of determining the double layer energy and force of interaction between two charged colloidal spheres

The approximate expressions have been obtained to calculate the electrical double layer energy and force between two spherical colloidal particles based on the improved Derjaguin approximation. Results for identical spheres interacting under constant surface potential, constant surface charge are given. Comparison of present results with numerical results calculated by Carnie and Chan is made. The expressions are found to work quite well for the constant surface potential case, and for the constant charge case, we make correction for the expressions. The results given are satisfactory providedkh0.4.     

Histidine in enzyme active centers.

The presence of histidine in the active center of an enzyme can be demonstrated by kinetic measurements, chemical modification, NMR spectroscopy or X-ray structure analysis. Histidine is the only naturally occurring amino acid to contain an imidazole residue as a side chain. The role of histidine in enzyme catalysis depends, inter alia, upon the special features of the imidazole residue: it thus tends to form hydrogen bonds, combines donor and acceptor properties and can take part in either nucleophilic or base catalysis. In some of these enzymes the position of each atom is known; however, the theories as to how the catalysis proceeds at a molecular level are controversial.