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991.
The ω-iodo-α,β-alkynoates and their ketone, sulfone or phosphonate analogues react with δ-chloropropylamines in MeCN assisted with K2CO3 to undergo a sequential SN2/Michael addition/SN2/SN2 reaction process, giving polysubstituted indolizidines or quinolizidines in good to excellent yields. This sequential reaction process is also compatible with three other substituted α,β-alkynoates, affording quinolizidine analogues in moderate to good yields. 相似文献
992.
The hydrogen peroxide-oxidation of o-phenylenediamine (OPD) catalyzed by horseradish peroxidase (HRP) at 37 °C in 50 mM phosphate buffer (pH 7.0) was studied by calorimetry. The apparent molar reaction enthalpy with respect to OPD and hydrogen peroxide were −447 ± 8 kJ mol−1 and −298 ± 9 kJ mol−1, respectively. Oxidation of OPD by H2O2 catalyzed by HRP (1.25 nM) at pH 7.0 and 37 °C follows a ping-pong mechanism. The maximum rate Vmax (0.91 ± 0.05 μM s−1), Michaelis constant for OPD Km,S (51 ± 3 μM), Michaelis constant for hydrogen peroxide Km,H2O2 (136 ± 8 μM), the catalytic constant kcat (364 ± 18 s−1) and the second-order rate constants k+1 = (2.7 ± 0.3) × 106 M−1 s−1 and k+5 = (7.1 ± 0.8) × 106 M−1 s−1 were obtained by the initial rate method. 相似文献
993.
Charles Allgood Yi Lin Yee-Chung Ma Burnaby Munson 《Journal of mass spectrometry : JMS》1990,25(10):497-502
Dilute mixtures of C6H6 or C6D6 in He provide abundant [C6H6]+· or [C6D6]+· ions and small amounts of [C6H7]+ or [C6D7]+ ions as chemical ionization (CI) reagent ions. The C6H6 or C6D6 CI spectra of alkylbenzenes and alkylanilines contain predominantly M+· ions from reactions of [C6H6]+· or [C6D6]+· and small amounts of MH+ or MD+ ions from reactions of [C6H7]+ or [C6D7]+. Benzene CI spectra of aliphatic amines contain M+·, fragment ions and sample-size-dependent MH+ ions from sample ion-sample molecules reactions. The C6D6 CI spectra of substituted pyridines contain M+· and MD+ ions in different ratios depending on the substituent (which alters the ionization energy of the substituted pyridine), as well as sample-size-dependent MH+ ions from sample ion-sample molecule reactions. Two mechanisms are observed for the formation of MD+ ions: proton transfer from [C6D6]+· or charge transfer from [C6D6]+· to give M+·, followed by deuteron transfer from C6D6 to M+·. The mechanisms of reactions were established by ion cyclotron resonance (ICR) experiments. Proton transfer from [C6H6]+· or [C6D6]+· is rapid only for compounds for which proton transfer is exothermic and charge transfer is endothermic. For compounds for which both charge transfer and proton transfer are exothermic, charge transfer is the almost exclusive reaction. 相似文献
994.
响应性凝胶及其在药物控释上的应用 总被引:19,自引:1,他引:19
综述近年来在响应性凝胶材料研究方面的进展,介绍了能感应pH、温度、光、电场以及生化物质等外界因素变化的响应性凝胶的结构特点与响应机理,同时介绍了此类凝胶应用于药物控制释放方面的研究近况。 相似文献
995.
Trimetric ion (TCNQ)2?3 has been discovered in mixed solutions of TCNQ and LiTCNQ in acetonitrile. The estimated association constant isKT = 5.6 × 1010 øl2 mol?2. 相似文献
996.
An online UV photolysis and UV/TiO2 photocatalysis reduction device (UV–UV/TiO2 PCRD) and an electrochemical vapor generation (ECVG) cell have been used for the first time as an interface between high-performance liquid chromatography (HPLC) and atomic fluorescence spectrometry (AFS) for selenium speciation. The newly designed ECVG cell of approximately 115 L dead volume consists of a carbon fiber cathode and a platinum loop anode; the atomic hydrogen generated on the cathode was used to reduce selenium to vapor species for AFS determination. The noise was greatly reduced compared with that obtained by use of the UV–UV/TiO2 PCRD–KBH4–acid interface. The detection limits obtained for seleno-DL-cystine (SeCys), selenite (SeIV), seleno-DL-methionine (SeMet), and selenate (SeVI) were 2.1, 2.9, 4.3, and 3.5 ng mL–1, respectively. The proposed method was successfully applied to the speciation of selenium in water-soluble extracts of garlic shoots cultured with different selenium species. The results obtained suggested that UV–UV/TiO2 PCRD–ECVG should be an effective interface between HPLC and AFS for the speciation of elements amenable to vapor generation, and is superior to methods involving KBH4. 相似文献
997.
The reaction of Cu(I)(CH(3)CN)(4)BF(4) with 4-pyridylacrylic acid (4-HPYA) affords an unprecedented 8-fold interpenetrating diamondoid-like coordination polymer network [Cu(I)(3)(4-PYA)(2)(H(2)O)(BF(4)) ] (1) with a Cu(+)(4)(CO(2))(4) cluster as connecting node. The interpenetration in metal coordination polymers is the highest degree ever found within diamondoid nets containing a cluster as connecting note. Its fluorescent property was also reported. 相似文献
998.
999.
The Lycopodium alkaloids 总被引:5,自引:0,他引:5
Lycopodium alkaloids are quinolizine, or pyridine and alpha-pyridone type alkaloids. Some Lycopodium alkaloids are potent inhibitors of acetylcholinesterase (AChE). Huperzine A (HupA) is reported to increase efficiency for learning and memory in animals, and it shows promise in the treatment of Alzheimer's disease (AD). 201 Lycopodium alkaloids from 54 species of Lycopodium (sensu lato) have been reported so far. This review is intended to to cover the chemical, pharmacological and clinical research on Lycopodium alkaloids reported in the literature from the spring of 1993 to August 2004. Structures of 81 new Lycopodium alkaloids are presented, classified and analyzed. The structural characters and biogenetic relationships of the four major Lycopodium alkaloid groups (lycopodine, lycodine, fawcettimine and miscellaneous) are discussed. Bioactivities of Lycopodium alkaloids, especially HupA, are summarized. In particular, the effect of HupA and other cholinesterase inhibitors (anti-AD drugs) on acetylcholine esterase (AChE) activity in the rat cortex and butylcholine esterase activity are compared. Structure-activity relationships and structure modifications of HupA and its analogs are described. Information on clinical trials with HupA and its derivative ZT-1 is presented. The state of HupA availability and recent advances in in vitro propagation of HupA producing plants are outlined. Finally, hypotheses about Lycopodium alkaloid biosynthetic pathways are discussed. 相似文献
1000.
Huifang Xu Wei Wei Chengliang Zhang Shujiang Ding Xiaozhong Qu Dr. Jiguang Liu Dr. Yunfeng Lu Prof. Zhenzhong Yang Prof. 《化学:亚洲杂志》2007,2(7):828-836
This report presents a facile approach for the low‐temperature synthesis of crystalline inorganic‐oxide composite hollow spheres by employing the bulk controlled synthesis of inorganic‐oxide nanocrystals with polymer spheres as templates. The sulfonated polystyrene gel layer can adsorb the target precursor and induce inorganic nanocrystals to grow on the template in situ. The crystalline phase and morphology of the composite shell is tunable. By simply adjusting the acidity of the titania sol, crystalline titania composite hollow spheres with tunable crystalline phases of anatase, rutile, or a mixture of both were achieved. The approach is general and has been extended to synthesize the representative perovskite oxide (barium and strontium titanate) composite hollow spheres. The traditional thermal treatment for crystallite transformation is not required, thus intact shells can be guaranteed. The combination of oxide properties such as high refractive index, high dielectric constant, and catalytic ability with the cavity of the hollow spheres is promising for applications such as opacifiers, photonic crystals, high‐κ‐gate dielectrics, and photocatalysis. 相似文献