固载化催化剂在烯烃氧化合成醛酮中的应用

总结了固载化催化剂在烯烃氧化合成醛酮中的应用。着重介绍了钯配合物固载在无机载本上,钯盐和杂多化合物固载在无机载体上,钯盐固载在化催化剂在烯烃氧化合成醛酮中的应用。对负载型液相催化剂,负载型水相催化剂,负载型熔融盐Wacker催化剂,活性C固载的Pd膜及Pt膜催化剂催化烯烃氧化合成醛酮也作了简单介绍。     

抗坏血酸在聚甲苯胺蓝膜修饰的玻碳电极上的电催化氧化及流动注射分析

在玻碳电极上用循环伏安法电聚合一层聚甲苯胺蓝膜,该膜修饰电极对抗坏血酸(VC)的氧化具有良好的电催化作用,能够降低其过电位约100mV。将该修饰电极应用于流动注射能大大提高VC的检测灵敏度,其线性范围为2.0×10-7～1.2×10-3mol·L-1,检出限为4.8×10-8mol·L-1,连续注射检测,其电流信号能够保持稳定24h。     

离子色谱-抑制电导法分别测定海水中阴离子和阳离子

采用离子交换-抑制电导法测定海水中阴、阳离子。采用抑制电导可以降低淋洗液的背景电导,又可以增加被测离子的电导值,改善信噪比。采用的电化学自身再生抑制器,由连续电解水产生抑制淋洗液所需要的H^＋或者OH^-,加上电场引力,能用于高客量分离柱所用的淋洗液浓度和梯度淋洗。在试验条件下,利用阴离子和阳离子分离柱,配合抑制电导检测,可以同时分离和测定海水中7种阴离子和6种阳离子。且都可以得到很好的线性和较低的检出限。     

THE EFFECTS OF THROMBOXANE INHIBITORS ON THE MICROVASCULAR AND TUMOR RESPONSE TO PHOTODYNAMIC THERAPY

Abstract— Vascular stasis and tissue ischemia are known to cause tumor cell death in several experimental models after photodynamic therapy (PDT); however, the mechanisms leading to this damage remain unclear. Because previous studies indicated that thromboxane release is implicated in vessel damage, we further examined the role of throm-boxane in PDT. Rats bearing chondrosarcoma were injected with 25 mg/kg Photofrin® (intravenously) 24 h before treatment. Light (135 J/cm ² , 630 nm) was delivered to thc tumor area after injection of one of the following inhibitors: (1) R68070: a thromboxane synthetase inhibitor; (2) SQ-29548: a thromboxane receptor antagonist; and (3) Flunarizine: an inhibitor of platelet shape change. Systemic thromboxane levels were determined. Vessel constriction and leakage were evaluated by intravital microscopy. Tumor response was assessed after treatment. Thromboxane levels were decreased more than 50% with SQ-29548 as compared to controls. Thromboxane levels in animals given R68070 and Flunarizine remained at baseline levels. SQ-29548 and R68070 reduced vessel constriction compared to controls, while Flunarizine totally prevented vessel constriction. R68070 and SQ-29548 inhibited vessel permeability compared to PDT controls; Flunarizine did not. Animals given these inhibitors showed markedly reduced tumor cure. These results indicate that the release of thromboxane is linked to the vascular response in PDT.     

OXIDATION OF THE ALKYL-, ARYL-, AND AMINO-SULFONIUM IONS TO THE SULFOXONIUM IONS AND ITS REACTION MECHANISM

Abstract

Hitherto, the preparative method of the sulfoxonium ions has been practically limited to thealkylation of the sulfoxides with methyliodide. The yields of the desired sulfoxonium salts by this method are usually poor except that of trimethylsulfoxonium iodide, Diarylalkyl- or triaryl-sulfoxonium ions can not be prepared by this alkylation.     

离子色谱技术在污水监测中的应用和发展趋势

从前处理技术、色谱柱、淋洗系统、抑制器和检测项目等方面,分析总结了自20世纪80年代以来离子色谱技术在污水监测中的应用情况,并结合离子色谱技术的最新发展,分析了离子色谱技术在污水监测中的发展趋势。     

四氰基醌二甲烷修饰碳糊电极电催化氧化测定多巴胺

以四氰基醌二甲烷(TCNQ)作介体,制成TCNQ修饰碳糊电极.研究该电极的性能.该电极对多巴胺(DA)有良好的电催化氧化作用,在DA浓度6.75×10~5～6.75×10~(-3)mol·L~(-1)内,催化电流与DA浓度呈线性关系.响应时间小于10s.该电极用于针剂中多巴胺测量,结果较好.     

SENSITIVITY OF THE ELECTRON TRANSPORT CHAIN OF PIGMENTED AND NON-PIGMENTED SARCINA MEMBRANES TO PHOTODYNAMIC ACTION

Abstract— With malate as substrate, the respiratory system of Sarcina lutea is subject to photodynamic action when toluidine blue is added as a photosensitiser. Both whole cells and isolated cell membranes show similar photoinactivation. Cell and membrane suspensions of a carotenoid-containing strain are significantly less sensitive than those from a non-pigmented mutant prepared from the pigmented strain. Addition of histidine also provides photoprotection. Attempts to locate the site of photoinactivation within the respiratory system lead to the conclusion that several sites are affected. Short periods of illumination do not result in permanent damage since activity is recovered in these suspensions when incubated in the dark subsequent to illumination. The significance of these results and the possible mechanisms involved are discussed.     

4-氯-2,6-二(羟甲基)苯酚(试铁酚)的合成及其在测定铁中的应用

对氯苯酚与多聚甲醛在氢氧化钠存在下70℃反应3小时,即得粗产率98%的4-氯-2,6-二(羟甲基)苯酚(试铁酚).实验表明铁(Ⅲ)-试铁酚在pH6.4时,可生成稳定的橙红色络合物,吸收峰在480nm处,摩尔吸收系数为6.4×10³可用于铁(Ⅲ)的定量测定.本法的优点是选择性较高,测定范围广,方法简便、迅速,可用于土壤、岩石等样品中铁的直接测定.本法与其它方法测得的结果一致.     

水溶苯胺蓝与蛋白质结合反应的研究及应用

在pH 2.36的Britton-Robinson(B-R)缓冲介质中,水溶苯胺蓝与蛋白质形成显色化合物,其最大吸收波长为688nm,比试剂本身红移88nm,表观摩尔吸光系数达4.25×105L·mol-1·cm-1(牛血清白蛋白)。制定了四种蛋白质的标准工作曲线,用于人血清样品中总蛋白的测定,结果与溴甲酚绿法一致。     

三乙胺与咪唑在酯交换反应中的应用(英文)

采用三乙胺（TEA）和咪唑（IMZ）作催化剂,研究了甲醇与乙酸乙酯及苯甲酸乙酯的酯交换反应。实验结果表明,在没有环氧丙烷（PO）助剂时,三乙胺和眯唑的酯交换催化活性较低;当加入环氧丙烷助催化剂时,它们都有较高的酯交换催化活性。环氧丙烷助催化的三乙胺和咪唑催化剂的酯交换催化活性分别是无环氧丙烷助催化的三乙胺和咪唑催化剂的29倍和38倍考察了溶剂、温度催化剂及助剂浓度对催化剂的活性的影响。     

微波消解测定水样中总磷

研究了以H2O2-HNO3为氧化剂,用微波消解测定水样中总磷的分析方法。通过正交试验选择合适的消解条件与氧化剂投入量,选择合适的显色酸度及测定波长,方法对自然水样测定平均相对标准偏差为3．3％,平均回收率为100．3%。     

浊点萃取技术在金属离子分离和富集以及形态分析中应用的进展

介绍了新兴的环保型液液萃取方法——浊点萃取的原理及操作方法，讨论了影响浊点萃取效率的因素，重点回顾了近年来该技术在金属离子分离和富集以及形态分析中应用的进展，探讨了该技术的发展前景。     

SENSITIVITY OF ACTIVATED MURINE PERITONEAL MACROPHAGES TO PHOTODYNAMIC KILLING WITH BENZOPORPHYRIN DERIVATIVE

Abstract— This study compared the ability of highly purified resting and activated DBA/2 mouse peritoneal macrophages to survive treatment with the photosensitizer benzoporphyrin derivative (BPD, verteporfin) and light. Culture of macrophages with recombinant murine interferon-γ (rIFN-γ, 100 U/mL) for 72 h imparted a phenotypic and functional activation by dramatically increasing cell surface expression of major histocompatibility complex Class II (Ia) molecules and the formation of nitric oxide. The rIFN-γ-activated macrophages were significantly (P < 0.05) more sensitive (lethal dose to cause a 50% reduction in cell survival, LD₅₀= 14.4 ± 1.1 ng/mL) to photodynamic killing with BPD and light (10 J/cm²) than cells (LD₅₀= 18.2 ± 2.0 ng/mL) cultured in medium alone. In contrast, macrophages treated with different concentrations of bacterial lipopolysaccharide (LPS) were as resistant or more resistant to photodynamic killing than cells cultured in medium alone. No cytotoxic effect of BPD was detected in cultures containing the drug but protected from light. Comparable amounts of BPD were taken up in vitro by unactivated and rIFN-γ-activated macrophages, as detected by flow cytometric analysis. However, cells cultured with LPS (10 μg/mL) took up more BPD than macrophages cultured in medium alone or with rIFN-γ. The DBA/2 P815 mastocytoma cells took up greater amounts of the drug and were subsequently more vulnerable to treatment with BPD and light (LD₅₀= 6.9 ng/mL) than macrophages cultured under any condition. The explanation for the increased vulnerability of rIFN-γ-activated macrophages and the greater resistance of LPS-activated macrophages, relative to medium-cultured macrophages, to photodynamic killing with BPD is uncertain. However, the increased susceptibility of macrophages, activated with the immunomodulatory cytokine IFN-γ, to treatment with BPD and light might indicate how photodynamic therapy could interfere with the development of experimental autoimmune disease, conditions in which activated macrophages are known to be involved.     

二溴对甲偶氮磺光度法测定锌合金中微量铅

研究了新试剂二溴对甲偶氮磺与铅的显色反应,建立了直接测定锌合金中微量铅的光度分析方法。在硝酸介质中,二溴对甲偶氮磺与铅发生灵敏的显色反应,生成1∶2的蓝色配合物。铅配合物的最大吸收峰位于630nm,表观摩尔吸光系数和Sandell灵敏度分别为1.07×105L·mol-1·cm-1和1.94ng·cm-2;显色反应在常温下(<30℃)立即完成,而配合物及试剂空白的吸光度在24h内基本保持不变;铅在0～90μg/25ml范围内符合比耳定律;显色反应有良好的选择性,主要共存金属离子均有较大的允许量,可用于锌合金中微量铅的直接测定。     

PRODUCTS AND RELATIVE REACTION RATES OF THE OXIDATION OF TOCOPHEROLS WITH SINGLET MOLECULAR OXYGEN

Abstract— The relative reactivity of singlet molecular oxygen, 0₂(¹Δ_g), α-,β-,Γ-and δ with -tocopherol (vitamin E) was investigated using microwave discharge generation as a uniquely clean source of singlet oxygen and using a hydrocarbon solvent to approximate the membrane environment. The relative efficiencies of the tocopherols for O₂(¹Δg) were found to decrease in the order: D-α-tocopherol > D-β-tocopheroI > D–Γ-tocopherol > D-δ-tocopherol. The reaction products in all cases were found to be mixtures of quinone and quinone epoxides apparently resulting from decomposition of the primary product, the hydroperoxydienone.     

钴(Ⅲ)络合物氧化对苯二胺类化合物的动力学与机理的研究

本文通过监测氧化中间体半醌(S~+)的吸光度变化跟踪反应进程。用初始速率法处理得到了HAc-NaAc介质中Fe(CN)_6~(3-)(Ox′)催化[CO~Ⅲ(NH_3)_5Cl]~(2+)(Ox)氧化CD-4遵循下列动力学方程: d[S~+]/dt=k_(obs).[Ox′]~(0.90)[Ox]~(0.85)认为Fe(CN)_6~(3-)的再生过程是整个反应的决速步骤。估算了决速步的速率常数k(298K)、活化焓△H~(0≠)和活化熵分别为1.92dm~3·mol~(-1)s~(-1)、23.1kcal/mol和20.5cal/mol.K。以TEPPD代替CD-4、以Fe(CN)_6~(4-)代替Fe(CN)_6~(3-)的实验结果支持了所提出的再生机理的合理性。 实验也得到了[Co~Ⅲen_2Cl_2]~+直接氧化CD-4或TEPPD的动力学方程。测定了反应的活化能。认为PPD氧化为半醌是反应的决速步骤。[Co~Ⅲ(NH_3)_6]~(3+)、[Co~Ⅲ(NH_3)_5Cl]~(2+),[CoⅢen_3]~(3+)、[CoⅢen_2Cl_2]~+氧化PPD的实验结果表明,钴(Ⅲ)络合物的取代活性增加,氧化活性亦增加。     

应用2-氯苯甲醛与苯肼的衍生化反应于2-氯苯甲醛的荧光光度测定

研究了2-氯苯甲醛(CBZD)与苯肼的衍生化反应,在pH 1.0的乙醇/水溶液中,2-氯苯甲醛与苯肼形成荧光希夫碱,研究了希夫碱的荧光性质,希夫碱的荧光激发波长eλx=552.0 nm,发射波长eλm=299.2 nm.其荧光强度与2-氯苯甲醛浓度在0~120μg.L-1范围内呈线性关系,检出限为0.2μg.L-1。方法应用于矿泉水、自来水、生理盐水、葡萄糖注射液中2-氯苯甲醛的测定。     

APPLICATION OF CLUSTER ANALYSIS TO THE TAXONOMY OF ORDER AND SUBORDER OF THE TRILOBITA

In the present paper, in accordance with the exoskeleton structure, the method of Q-mode cluster analysis is used for a taxonomic study of 17 orders (suborders) of the Tritobita that was established or adopted by H. J. Harrington (1959), J. Bergstrm (1973), and R. A. Fortey and R. M. Owens (1975). The author suggests that the Trilobita be subdivided into 9 orders and 14 suborders, i. e. order Agnostida Kobayashi, 1935 (suborder Agnostina Salter, 1864 and suborder Eodiscina Kobayashi, 1939), order Redlichiida Richter, 1933 (suborder Redlichiina Richter, 1933, suborder Bathynotina Lochman-Balk, 1959 and suborder Olenellina Resser, 1938), order Corynexochida Kobayashi, 1935, order Ptychopariida Swinnerton, 1915 (suborder Ptychopariina Richter, 1933, suborder Proetina Fortey & Owens, 1975, nom. transl, ex Proetida Fortey & Owens, 1975 and suborder Calymenina Swinnerton, 1915, emended herein), order Illaenida Jaanusson, 1959 (suborder Illaenina Jaanuson, 1959 and suborder Asaphina Salter, 1864, emended herei     

菁染料在荧光探针及光动力疗法中的应用

菁染料的研究及应用已有100多年的历史,近年来,它们在生物方面的应用研究已取得一定的成果.本文就近几年菁染料及其衍生物在生物医疗方面的研究及进展情况加以综述,特别阐述了这类染料用作荧光探针在生物大分子标识以及作为光敏剂在光动力疗法(PDT)中用于恶性肿瘤的诊断与治疗这两方面的研究进展.