可见光诱导8-氨基喹啉衍生物二氟烷基化反应

室温条件下,研究了铜催化可见光诱导8-氨基喹啉衍生物C5位二氟烷基化反应。以蓝色LED为光源,面式-三(2-苯基吡啶)合铱配合物〔fac-Ir(ppy)3〕为光敏剂,8-氨基喹啉衍生物与二氟溴乙酸乙酯产生的二氟乙酸乙酯自由基发生C—C偶联反应。在CuI催化下合成15个C5位二氟烷基化的8-氨基喹啉衍生物（Ⅲa~Ⅲo）。通过1HNMR、13CNMR、FTIR和HR-MS对产物的结构进行确证。8-氨基喹啉衍生物的转化率为50%~90%,反应收率范围为21%~58%。该反应条件温和,含有卤素、硫醚和氰基官能团的底物都能发生反应。自由基捕获剂2,2,6,6-四甲基哌啶-1-氧（TEMPO）能捕获到二氟乙酸乙酯自由基,验证该反应过程可能经过自由基单电子转移。     

Macromolecular Conjugates of Methotrexate, Ferrocene and Platinum in Cancer Chemotherapy

Most of the polyaspartamide carrier polymers synthesized in this program, were conjugated with methotrexate (MTX) and with organoiron compound (ferrocene), whereas other polyamides were conjugated with 1,2-diaminocyclohexanediaquaplatinum(II)dinitrate (DACH-Pt aq). The ferrocenylation agent throughout this project was 4-ferrocenylbutanoic acid. MTX and 4-ferrocenylbutanoic acid as well as folic acid were conjugated to pendant amino groups of various polyaspartamide carriers, through amidation reactions, via the HBTU-method. A very satisfactory degree of MTX and Fe were achieved. MTX content found was in range of 10–19% by mass, and Fe content found was in range of 6–13% by mass. The anchoring of platination agent (DACH-Pt aq) proceeded via well established methods involving dihydroxylato ligands. Pt content found was in the range of 6–8% by mass. Platinum incorporation was satisfactory.     

Water-Soluble Macromolecular Platinum Conjugates Derived from 1,2-Dihydroxyl-Functionalized Carrier Polymers

The class of platinum-containing bioactive agents, including cisplatin as the prototype, and structurally related second- and third-generation compounds, has developed during the past two decades as one of the most important family of antitumor drugs. However, despite a highly valued general antineoplastic performance profile, their unrestricted oncological administration continues to be hampered by pharmacological shortcomings, notably excessive toxicity and induction of drug resistance. This has prompted ongoing intensive development activities in pharmaceutic laboratories worldwide, and one of the most promising approaches emanating from these activities involves the drug conjugation to biomedically functional, water-soluble carrier polymers. Such macromolecular conjugates, judiciously designed and synthesized, provide significant pharmacological advantages over non-polymeric drug systems, notably increased cell specificity and facilitated cell entry, paired with reduced toxicity and resistance problems. In the present project, this technology has been applied specifically to the synthesis of Pt-containing polymers in which the metal is carrier-bound via dihydroxylatoplatinum chelation. In the cancerous target cell, such conjugates will deliver the free bioactive Pt complex hydrolytically for its cytotoxic action. The water-soluble polymeric products, fractionated by dialysis in membrane tubing with molecular-mass cut-off of 25,000, will be submitted to an outside institution for in vitro evaluation of cytotoxic properties.     

4-(芳氨基甲酰甲基)-1,4-苯并噁嗪类化合物的合成

利用3,4-二氢-1,4-苯并噁嗪(2)和氯乙酰芳胺经N-烷基化反应合成了4-(芳氨基甲酰甲基)-1,4-苯并噁嗪类衍生物1a～1h.研究了溶剂、温度及反应时间对反应的影响,优化条件下,收率达50％～70％.用IR、1H NMR、13C NMR等对产物的结构进行了表征.     

8-氨基喹啉两亲配体的光谱性质、Langmuir-Blodgett膜及其对铜离子的传感作用

研究了两亲配体2-十二烷基丙二酸二(8-氨基喹啉)酰胺(H2A)的UV-Vis光谱和荧光光谱。铜离子对配体的荧光有明显的猝灭作用。研究了H2A及其与铜的两类配合物的单分子成膜性能和LB膜的俄歇电子能谱。CuA的成膜性能明显比H2A好,俄歇电子能谱表明H2A单分子膜在膜/水界面与亚相Cu2+生成了1∶1的配合物。H2A的LB膜可以用作为Cu2+离子的传感材料,线性范围为0.1～1.0μmol/L。     

The Cytotoxic Activity of Macromolecular Ferrocene Conjugates Against the Colo 320 DM Human Colon Cancer Line

Water-soluble and biocompatible polymers containing bioreversibly attached ferrocene units as side chain terminals have in recent years attracted interest in drug research. In preliminary screens, polymers of this type have shown high antiproliferative activity against selected human carcinoma cell lines, paired with low in vivo toxicity. They may thus lend themselves as efficacious prodrugs in cancer chemotherapy. Cancers of the intestinal system are known to resist chemotherapeutic treatment. This general lack of sensitivity of the colorectal malignancies prompted us to investigate the in vitro behavior of selected carrier-bound ferrocene prodrugs against the Colo 320 DM cell line, a representative human adenocarcinoma of the colon. The findings of this investigation are reported in the present communication. The carriers 1 to 10 used for conjugation with the metallocene are water-soluble aliphatic polyamides featuring primary or secondary amine functionality as side chain terminals or main chain constituents. By previously developed methodology these amino groups are coupled with the ferrocenylation agent, 4-ferrocenylbutanoic acid, generating the target conjugates 1-Fc to 10-Fc, in which the metallocene is bound through amide or hydrazone links. Cell culture tests are performed by established protocol against the Colo line and, for comparison, also against the HeLa cells. Significantly, while outstanding performance is observed for most of the conjugates against both cell lines, the results indicate activities in the Colo screens to be higher on average than determined in the sensitive HeLa tests.     

水溶性大分子紫外线吸收剂PVAm-g-BP-4的合成

合成了一类以2-羟基二苯甲酮为紫外线吸收功能基,以聚乙烯胺(PVAm)为接枝骨架的新型水溶性大分子紫外线吸收剂PVAm-g-BP-4。PVAm-g-BP-4的合成分两步,首先,将2-羟基-4-甲氧基-5-磺酸基二苯甲酮(BP-4)结构中的磺酸基转变为磺酰氯,合成了反应中间体2-羟基-4-甲氧基-5-氯磺酰基二苯甲酮(CBP-4),采用二氯亚砜为反应溶剂和氯代试剂,N,N-二甲基甲酰胺(DMF)为催化剂,产率达94.5%;然后,将CBP-4接枝到聚乙烯胺(PVAm)骨架上,合成了PVAm-g-BP-4。目标产物经过TLC、IR、UV分析证明,CBP-4已接枝到PVAm上。通过实验优化了催化剂用量、反应温度、反应时间、溶剂体积比等反应条件。在棉织物上的初步应用结果表明,PVAm-BP-4可赋予棉织物良好的紫外线防护功能,而且耐洗牢度优异。     

新型荧光试剂5-(4-溴苯偶氮)-8-(8-喹啉重氮氨基)喹啉的合成及其分析应用

将具有荧光特性的8-氨基喹啉结构与具有良好特性的三氮烯结构相结合,首次合成了标题化合物。其结构经过元素分析、红外光谱、核磁共振谱证实。研究表明,在碱性介质中,该试剂在λex/λem=416 nm/512 nm处产生强荧光,并且能被Cu2+荧光增强。基于此,建立了BPAQAQ测定Cu2+的新型荧光分析法。该方法的线性范围为1.4×10-8~1.0×10-5mol/L,检测限为1.1×10-8mol/L。将其应用于大米粉和小麦粉中Cu2+的测定,结果满意。     

新荧光试剂5-（4-氯苯偶氮）-8-（8-喹啉重氮氨基）喹啉的合成及其荧光分析

合成了标题化合物(p-ClPAQAQ),其结构经IR、1HNMR、元素分析证实.在碱性介质中,该试剂于λex/λem=427 nm/498 nm产生荧光,且能与Al(Ⅲ)络合并发生荧光增强,基于此,建立了p-CIPAQAQ对Al(Ⅲ)的新荧光分析法.     

7-(Dialkylamino)coumarin-4-yl]methyl-Caged Compounds as Ultrafast and Effective Long-Wavelength Phototriggers of 8-Bromo-Substituted Cyclic Nucleotides

[7-(Dimethylamino)coumarin-4-yl]methyl (DMACM) and [7-(diethylamino)coumarin-4-yl]methyl (DEACM) esters of 8-bromoadenosine 3',5'-cyclic monophosphate (8-Br-cAMP) and 8-bromoguanosine 3',5'-cyclic monophosphate (8-Br-cGMP) are described as novel caged compounds for 8-bromo-substituted cyclic nucleotides. Synthesis is accomplished by treatment of the free acids of the cyclic nucleotides with the corresponding 7(dialkylamino)-substituted 4(diazomethyl)coumarins. Irradiation of the DMACM- and DEACM-caged cyclic nucleotides with UV light stimulates the release of the cyclic nucleotides within roughly a nanosecond. The new caged compounds are resistant to hydrolysis in aqueous buffers and exhibit long-wavelength absorption properties with maxima at 400 nm, high extinction coefficients, and high quantum yields (0.15-0.31). Their favorable properties render these compounds the most efficient and rapid phototriggers of 8-bromo-substituted cyclic nucleotides known. The usefulness of the compounds for physiological studies under nondamaging light conditions was examined in HEK293 cells expressing the alpha subunit of the cyclic-nucleotide-gated (CNG) channel of cone photoreceptors (CNGA3) and of olfactory neurons (CNGA2) by using confocal laser scanning microscopy and the patch clamp technique.     

6-氨基喹啉合成研究

以4-硝基苯胺和甘油为起始原料,经Skraup反应、80%水合肼和10%Pd/C还原,合成了AQC的重要中间体6-氨基喹啉。产品含量达99%(HPLC),总收率为53%。其结构经ESI-MS、1H NMR确证。     

Effect of Ozonation on the Chlorine Demand of a Treated Surface Water and Some Macromolecular Compounds

The study described in this paper was conducted to examine the effects of ozonation and ozone-GAC filtration treatment steps on chlorine consumption of the Seine river water treated in the Choisy-le-Roi drinking water works. Ozone-GAC combined treatment was found to significantly reduce both the initial chlorine demand and the long-term chlorine demand of waters, excepting for waters sampled during cold months of the year. The removal of the chlorine demand potential by ozonation alone was found to be limited for the studied waters and for solutions of macromolecular compounds even in the presence of carbonate species. Ozonation carried out in the absence of bicarbonate ion was found to increase reactive sites with chlorine treatment of an aquatic fulvic extracted from the Seine river water.     

3-氨基喹啉衍生物的合成研究

氨基苯甲醛类化合物和硝基乙醛缩二甲醇Friedlnder环合得到硝基喹啉化合物,然后用二氯化锡还原得到3-氨基基喹啉衍生物。该反应条件温和,收率较高,路线简洁步骤简洁。     

4-(6-甲氧基-8-喹啉偶氮)-间苯三酚的合成及分析应用

首次合成了4－（6－甲氧基－8－喹啉偶氮）－间苯三酚（MQAPG）。产品通过了元素分析、红外光谱、薄层色谱、核磁共振鉴定。MQAPG在碱性溶液中,与钴（Ⅱ）形成配合物,λmax＝518nm,△λ＝79nm。在0．02－1．5μg/mL范围内服从比尔定律。测定了指甲及河水中的微量钴（Ⅱ）,结果稳定可靠。     

液相色谱-柱后衍生-原子荧光联用测定8种砷化合物

应用高效液相色谱-柱后衍生-原子荧光光谱联用法,建立了食品和饲料中三价砷、五价砷、一甲基胂酸、二甲基胂酸、洛克沙胂、4-氨基-苯胂酸、4-硝基-苯胂酸、4-羟基-苯胂酸8种食品和饲料中比较常见的砷化合物的检测方法。样品通过稀硝酸热浸提后,用正己烷脱脂净化,通过汉密尔顿PRP-X100阴离子交换柱或CNW Athena C18色谱柱分离,在无机砷化合物10~40μg/L,有机砷化合物20~600μg/L浓度内线性良好,相关系数大于0.99,在无机砷添加10μg/L、20μg/L,有机砷化合物添加20~300μg/L的添加水平下,平均回收率80.3%~101.3%,相对标准偏差小于5%,检测限0.001~0.07 mg/kg。该方法简单、快速、准确,并兼顾了GB 5009.11-2014中对于无机砷检测的需求。     

高分子水溶性胶粉的研制及应用

本文概述了由龙胶、无机凝胶及改性植物纤维粉、PVA－9粉等材料复合而成的一种天然环保高分子水溶性胶粉的生产工艺、条件、性能，并着重介绍其在建材领域中的应用，提示了该技术项目正在成为当今人们投资的热点。     

Etherification of C5- and C8-Alkenes with C1- to C4-Alcohols

Etherification of two alkenes, 2-methyl-1-butene and 2,4,4-trimethyl-1-pentene, was studied with seven different C₁- to C₄-alcohols. Although etherification was of primary interest, the isomerisation of the alkenes was the main reaction to occur. For the primary alcohols the etherification and isomerisation rates correlated well with the properties of the alcohols. Both rates increased with decreasing polarity and with increasing carbon number, acidity and Mulliken charge of the oxygen atom of the alcohol. It is difficult to distinguish the effect of each property separately, and probably the differences in the reactivities are not due to any one property alone but rather the synergy of the properties affects the reactivities. The secondary alcohols behaved in a different way than the primary ones: the etherification was almost negligible. The effect of alcohol on the isomerisation of alkenes was notable even though alcohol does not directly react in the reaction, which was concluded to be due to the stronger adsorption of the more polar alcohols which hinders the reactions of other components.