Pd(0)‐catalyzed polyaddition of bifunctional vinyloxiranes with 1,3‐dicarbonyl compounds: The synthesis of polymers containing hydroxy and carbonyl groups

The palladium(0)‐catalyzed polyaddition of bifunctional vinyloxiranes [1,4‐bis(2‐vinylepoxyethyl)benzene ( 1a ) and 1,4‐bis(1‐methyl‐2‐vinylepoxyethyl)benzene ( 1b )] with 1,3‐dicarbonyl compounds [methyl acetoacetate ( 4 ), dimethyl malonate ( 6 ), and Meldrum's acid ( 8 )] was investigated under various conditions. The polyaddition of 1 with 4 was carried out in tetrahydrofuran with phosphine ligands such as PPh₃ and 1,2‐bis(diphenylphosphino)ethane (dppe). Polymers having hydroxy, ketone, and ester groups in the side groups ( 5 ) were obtained in good yields despite the kinds of ligands employed. The number‐average molecular weight value of 5b was higher than that of 5a . The polyaddition of 1b and 6 was affected by the kinds of ligands employed. The corresponding polymer 7b was not obtained when PPh₃ and 1,2‐bis(diphenylphosphino)ferrocene were used. The polyaddition was carried out with dppe as the ligand and gave polymer 7b in a good yield. The molecular weight of the polymer obtained from 1b and 8 was much higher than those of polymers 5b and 7b . The polyaddition with Pd₂(dba)₃ · CHCl₃/dppe as a catalyst (where dba is dibenzylideneacetone) produced polymer 9b in a 92% yield (number‐average molecular weight = 45,600). The stereochemistries of all the obtained polymers were confirmed as an E configuration by the coupling constant of the vinyl proton. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2487–2494, 2002     

Rapid analysis of triterpenic acids by liquid chromatography using porous graphitic carbon and evaporative light scattering detection

An original system which uses Porous Graphitic Carbon as support and a mixture of organic solvents as mobile phase is proposed for the analysis of triterpenic acids by liquid chromatography. The separation of betulinic acid, ursolic acid, oleanolic acid, and 18alpha- and 18beta-glycyrrhetinic acids was carried out within a short time and monitored by evaporative light scattering detection as universal detection method. Molecular modelling studies show that the main contribution to the selectivity comes from the electrostatic interaction characterised by the dipole moment of the products.     

CuO／活性炭和Fe2O3／活性炭催化还原NO

ＣｕＯ／活性炭和Ｆｅ_２Ｏ_３／活性炭催化还原ＮＯ高志明，赵震，杨向光，吴越（中国科学院长春应用化学研究所长春１３００２２）关键词活性炭，还原，ＮＯ，氧化铜，氧化铁目前，对固定源的ＮＯ处理是采用Ｖ２Ｏ５／ＴｉＯ２作催化剂，ＮＨ３作还原剂的选择催化还原方...     

受限于纳米碳管中的乙醇分子的结构和扩散的分子模拟研究

利用分子模拟研究了常温常压下受限于(8,8) (管径1.081 nm)和(15,15) (管径 2.035 nm)单壁纳米碳管中的乙醇分子. 对受限分子的径向密度分布和氢键等静态性质以及扩散性质进行了分析. 结果显示在管内乙醇分子的平均氢键数目和主体相一致. 乙醇分子在(8,8)碳管内具有高度有序的结构, 而在(15,15)碳管内由于空间的增大导致结构有序度的降低, 其中分子取向已呈随机分布. 进一步对扩散系数的分析发现, 在管内乙醇分子的轴向扩散系数低于主体相, 特别在(8,8)碳管内乙醇分子几乎丧失了轴向扩散能力.     

Amperometric Glucose Biosensor Based on Platinum Nanoparticles Combined Aligned Carbon Nanotubes Electrode

A sensitive amperometric glucose biosensor based on platinum nanoparticles (PtNPs) combined aligned carbon nanotubes (ACNTs) electrode was investigated. PtNPs which can enhance the electrocatalytic activity of the electrode for electrooxidating hydrogen peroxide by enzymatic reaction were electrocrystallized on 4‐aminobenzene monolayer‐grafted ACNTs electrode by potential‐step method. These PtNPs combined ACNTs' (PtNPs/ACNTs) surfaces were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The highly dispersed PtNPs on ACNTs can be obtained. The enzyme electrode exhibits excellent response performance to glucose with linear range from 1×10^?5–7×10^?3 mol L^?1 and fast response time within 5 s. Furthermore, this glucose biosensor also has good reproducibility. It is demonstrated that the PtNPs/ACNTs electrode with high electrocatalytic activity is a suitable basic electrode for preparing enzyme electrodes.     

Simultaneous propane dehydrogenation andco2hydrogenation overCrOx/SiO2catalyst

Summary Single reverse water-gas shift (RWGS) and dehydrogenation of propane with CO₂(DH-CO₂) reactions in the presence and absence of the CrO_x/SiO₂ catalyst have been studied between 673 and 873 K. It was found that the CrO_x/SiO₂ catalyst is active both in the dehydrogenation of propane and in the RWGS reactions. The obtained results suggest that the dehydrogenation of propane to propene in the presence of CO₂on CrO_x/SiO₂can be facilitated by the RWGS reaction.</o:p>     

二硫化碳对机体铜、锌水平的影响

为观察二硫化碳（CS2）对机体铜，锌水平的影响，对某化纤厂35名接触CS2工人和41名非接触工人的血铜，锌值进行调查，比较，并进行了动物染毒实验。SD大鼠吸入CS2浓度分别为5和50mg/m^3，每日5h，每周6d，连续6个月，于染毒2，4，6个月时测定血浆铜，锌值及染毒6个月时肝脏铜，锌含量。结果显示，CS2接触组工人血铜，锌水平较对照组显著降低（P＜0．05）。在CS2染毒6个月时，50mg/m^3 CS2染毒组血浆及肝脏铜水平均较对照组及5mg/m^3 CS2染毒组显著降低（P＜0．05）。可见接触CS2能干扰机体铜，锌代谢，导致体内铜，锌含量减少。     

Insoluble polystyrene-bound quaternary onium salt catalysts for the synthesis of cyclic carbonates by the reaction of oxiranes with carbon dioxide

The addition reaction of oxiranes ( 26a—e ) with carbon dioxide (CO₂) was performed using insoluble polystyrene beads containing pendant quaternary ammonium or phosphonium salts as catalysts under atmospheric pressure. The reaction of 26a—e with CO₂ proceeded smoothly catalyzed by 1–2 mol % of the polymer-supported quaternary onium salts to give the corresponding cyclic carbonates ( 27a—e ) in high yields at 80–90°C. In this reaction system, the catalytic activity of the polymer-supported quaternary onium salts was strongly affected by the following factors: degree of ring substitution (DRS) of the onium salt residues to the polymer, degree of crosslinking (DC) of the polystyrene beads, chain length of the alkylene spacer between the polymer back-bone and the onium salt, hydrophobicity of the alkyl group on the onium salts, and kind of onium salts. That is, the polymer-supported quaternary phosphonium salts with low DRS and DC and with long alkylene spacer chain were found to have higher catalytic activity than low molecualr weight quaternary onium salts. The above polymer-supported catalysts can easily be separated at the end of a reaction by filtration and can be reused for at least seven runs. It was also found that the rate of reaction was proportional to the products of catalyst concentration and oxirane concentration. © 1993 John Wiley & Sons, Inc.     

Classical Valence Similarity in Fullerene Derivatives

Summary.  The generalized Pauling bond order was enumerated in the C₆₀ fullerene cage molecule (truncated icosahedral symmetry). This index measures chemical similarity in fullerene derivatives such as dihydrofullerene (C₆₀H₂), anionized monohydrofullerene (C₆₀H⁻), N-substituted monohydrofullerene (C₅₉NH), the fullerene dimer ((C₆₀)₂), and the dianionic fullerene dimer ((C₆₀)₂ ²⁻). It is also useful in judging the chemical stability of isomers. Received October 9, 2001. Accepted November 9, 2001     

Spectroscopic and Electrochemical Characterization of Cytochrome P450st‐DDAB Films on a Plastic‐Formed Carbon Electrode

We have studied the characterization of thermophilic cytochrome P450 (P450st)‐didodecyldimethylammonium bromide (DDAB) films by using UV‐vis absorption, resonance Raman spectroscopy, and electrochemical methods. The observed Raman spectrum indicated near‐native conformation of the heme iron in DDAB film on the surface of a glass slide, while on the surface of a plastic‐formed carbon (PFC) electrode, the conformation of P450st‐DDAB was very similar to that of heme‐DDAB film, suggesting the release of heme from P450st in DDAB films on PFC electrodes. When NaBr was added as salt to the casting solution, the result of Raman spectrum indicated near‐native conformation of P450st in DDAB film even on the PFC electrode, but no redox potential of P450st which has near native structure was observed. This study suggests the essential experimental conditions when working with heme protein‐DDAB films as, in some cases, heme iron from proteins is released on the surface of the electrode.