Crystal engineering of a versatile building block toward the design of novel inorganic-organic coordination architectures

Six novel inorganic-organic coordination supramolecular networks based on a versatile linking unit 4-pyridylthioacetate (pyta) and inorganic Co(II), Cu(II), Ag(I), Zn(II), Mn(II) and Pb(II) salts have been prepared in water medium and structurally characterized by single-crystal X-ray diffraction analysis. Reaction of CoCl(2).6H(2)O with Hpyta afforded a neutral mononuclear complex [Co(pyta)(2)(H(2)O)(4)](1), which exhibits a two-dimensional (2-D) layered architecture through intermolecular O-HO interactions. Reaction of CuCl(2.2H(2)O with Hpyta yielded a neutral one-dimensional (1-D) coordination polymer [[Cu(pyta)(2)(H(2)O].0.5H(2)O](n)(2) consisting of rectangle molecular square units, which show a three-dimensional (3-D) supramolecular network through S...S and O-H...O weak interactions. However, when AgNO(3), Zn(OAc)(2).2H(2)O or MnCl(2).4H(2)O salts were used in the above self-assembled processes, the neutral 2-D coordination polymers [Ag(pyta)](n)(3), [[Zn(pyta)(2)].4H(2)O](n)(4) or [[Mn(pyta)(2)(H(2)O)]](n)(5) with different topologies were obtained, respectively. While substituting the transition metal ions used in 1-5 with Pb(OAc)(2).3H(2)O, a one-dimensional coordination polymer [Pb(pyta)(2)](n)(6), which shows a novel 2-fold interpenetrating 2-D supramolecular architecture through weak SS interactions, was isolated. It is interesting to note that the building block pyta anion exhibits different configurations and coordination modes in the solid structures of complexes 1-6. These results indicate that the versatile nature of this flexible ligand, together with the coordination preferences of the metal centers, play a critical role in construction of these novel coordination polymers or supramolecules. The spectral and thermal properties of these new materials have also been investigated.     

A new isocoumarin from bark of Pellodendron chinense

A new isocoumarin, 3-acetyl-3,4-dihydro-5,6-dimethoxy-1H-2-benzopyran-1-one, was isolated from the cortex of Phellodendron chinense schneid. The structure was determined on the basis of spectroscopic evidences.     

Fibre optic fluorometric enzyme sensors for hydrogen peroxide and lactate,based on horseradish peroxidase and lactate oxidase

An optical biosensor for the determination of hydrogen peroxide based on immobilized horseradish peroxidase is described. The fluorescence of the dimeric product of the enzyme catalysed oxidation of homovanillic acid is utilized to determine the concentration of H₂O₂. The membrane-bound enzyme is attached to a bifurcated fibre bundle permitting excitation and detection of the fluorescence by a fluorometer. The response of the sensor is linear from 1 to 130 M hydrogen peroxide; the coefficient of variation is 3%. The sensor is stable for more than 10 weeks. The operating pH for maximal sensor response is 8.15. This allows the sensor to be used in combination with oxidase reactions producing hydrogen peroxide, as is demonstrated with a co-immobilized lactate oxidase-horseradish peroxidase optode for the determination of L-lactate. The fluorescence intensity of this sensor depends linearly on the concentration of lactate between 3 and 200 M and a throughput of 10 samples per hour is possible. The precision is in the same range as that of the monoenzyme optode. The lifetime of the bienzyme sensor for lactate is considerably shorter than that of the peroxidase sensor; it is limited by the stability of the immobilized lactate oxidase enzyme. The sensor has been applied to the determination of lactate in control serum.     

Remarkable nanosize effect of zirconia in Au/ZrO2 catalyst for CO oxidation

Nanosize effect of ZrO2 in Au/ZrO2 catalyst was studied by deposition-precipitation of Au nanoparticles in similar sizes (4-5 nm) on ZrO2 nanoparticles of varying sizes. The catalysts were characterized with XRD, TEM, XPS, and nitrogen adsorption to understand the effect of ZrO2 particle size on the catalytic nanostructures. Nanocomposite Au/ZrO2 catalysts consisting of comparably sized Au-metal (4-5 nm) and ZrO2 (5-15 nm) nanoparticles are found advantageous over those containing similarly sized Au-metal but larger ZrO2 (40-200 nm) particles for CO oxidation. This finding may have important implications on the designed preparation of advanced nanostructured catalysts and other chemical materials.     

Debye type dielectric relaxation and the glass transition of alcohols

Many hydrogen-bonded liquids, especially glass-forming cases, display a dielectric relaxation behavior that differs qualitatively from that of other simple liquids. The majority of models aimed at explaining this unusual dielectric behavior associate the prominent Debye process with structural relaxation, viscous flow, and the glass transition. We perform dielectric and calorimetric studies of glass-forming mixtures of 2-ethylhexylamine and 2-ethyl-1-hexanol across the entire composition range. The kinetic glass transition temperature derived from the large dielectric Debye peak decreases, whereas that of the much smaller and asymmetrically broadened peak increases upon addition of amine. Only the latter feature coincides with the calorimetric glass transition results, implying that molecular structure and dielectric polarization fluctuate on time scales that can differ by orders of magnitude in many hydrogen-bonding liquids.     

Immunoassay of P-glycoprotein on single cell by capillary electrophoresis with laser induced fluorescence detection

The cellular mechanism based on P-glycoprotein (PGP) for its drug pump function has become very important in multidrug resistance (MDR) research. A method has been established to characterize PGP on single K562 cell by coupling capillary electrophoresis with laser induced fluorescence detection. A permeable intact cell after the immunoassay binding with fluorescence labeling antibody was injected into the capillary and directly separated without lysis. It was found that once 5-10 optional cells were detected in batch, the PGP amount on this cell line could be outlined and calculated clearly. The PGP amount on K562 MDR cell line is 3.88 times higher than that on K562 sensitive cell line. These two cell lines with immunoassay binding were also analyzed by injection of multi-cells in order to improve the throughput. A resistance factor so called multidrug resistance multiple (MRM) was introduced to evaluate the MDR difference between cell lines. The MRM values of the cell line K562 measured by single cell analysis are well correlated with those by flow cytometry, which also prove the validity of our method in single cell analysis for the possibility of cancer diagnosis, pharmacokinetics and drug screening in future.     

倾斜交叉差分式激光热透镜光谱法特性研究

本文描述了一个倾斜交叉、差分式激光热透镜光谱法。采用本方法可消除较高的溶剂空白的影响。文章讨论了调制频率和泵浦光功率对热透镜信号的影响,给出了检测Cu~(2+)的工作曲线,讨论了影响方法灵敏度的诸因素,提出了可能的改进方案。     

2,2′-对苯二甲硫基二乙酸配合物的合成及表征

本文报道了配体 2 ,2′-对苯二甲硫基二乙酸和过渡金属铜 ( )、钴 ( )、镍 ( )配合物的合成。经元素分析、X射线衍射分析、红外光谱、差热 -热重分析等推算了它们的组成并指认了谱带的归属。对铜 ( )配合物进行了电子顺磁共振谱研究。     

探究Cu/ZnO相互作用对CO2加氢制甲醇反应性能的影响

Using renewable green hydrogen and carbon dioxide (CO₂) to produce methanol is one of the fundamental ways to reduce CO₂ emissions in the future, and research and development related to catalysts for efficient and stable methanol synthesis is one of the key factors in determining the entire synthesis process. Metal nanoparticles stabilized on a support are frequently employed to catalyze the methanol synthesis reaction. Metal-support interactions (MSIs) in these supported catalysts can play a significant role in catalysis. Tuning the MSI is an effective strategy to modulate the activity, selectivity, and stability of heterogeneous catalysts. Numerous studies have been conducted on this topic; however, a systematic understanding of the role of various strengths of MSI is lacking. Herein, three Cu/ZnO-SiO₂ catalysts with different strengths of MSI, namely, normal precipitation Cu/ZnO-SiO₂ (Nor-CZS), co-precipitation Cu/ZnO-SiO₂ (Co-CZS), and reverse precipitation Cu/ZnO-SiO₂ (Re-CZS), were successfully prepared to determine the role of such interactions in the hydrogenation of CO₂ to methanol. The results of temperature-programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) characterization illustrated that the MSI of the catalysts was considerably affected by the precipitation sequence. Fourier transform infrared reflection spectroscopy (FT-IR) results indicated that the Cu species existed as CuO in all cases and that copper phyllosilicate was absent (except for strong Cu-SiO₂ interaction). Transmission electron microscopy (TEM), X-ray diffraction (XRD), and N₂O chemical titration results revealed that strong interactions between the Cu and Zn species would promote the dispersion of Cu species, thereby leading to a higher CO₂ conversion rate and improved catalytic stability. As expected, the Re-CZS catalyst exhibited the highest activity with 12.4% CO₂ conversion, followed by the Co-CZS catalyst (12.1%), and the Nor-CZS catalyst (9.8%). After the same reaction time, the normalized CO₂ conversion of the three catalysts decreased in the following order: Re-CZS (75%) > Co-CZS (70%) > Nor-CZS (65%). Notably, the methanol selectivity of the Re-CZS catalyst was found to level off after a prolonged period, in contrast to that of Co-CZS and Nor-CZS. Investigation of the structural evolution of the catalyst with time on stream revealed that the high methanol selectivity of the catalyst was caused by the reconstruction of the catalyst, which was induced by the strong MSI between the Cu and Zn species, and the migration of ZnO onto Cu species, which caused an enlargement of the Cu/ZnO interface. This work offers an alternative strategy for the rational and optimized design of efficient catalysts.     

在丙烯酰胺聚合反应中聚苯乙烯磺酸效应的研究

<正> 在聚合体系中添加具有一定结构的高分子化合物作模板,并利用此模板高分子与单体分子间存在的某种相互作用使单体分子按一定的排列进行聚合,这是所谓“模板聚合”的最初尝试,近年来,模板聚合已成为一类新的聚合方法,利用模板大分子对其周围单体分子反应过程和生成物结构、分子量的影响,有些研究者已由此成功地实现了对新生成物分子量和空间构型的控制,从而为实现高分子设计开创了新的途径。