云南重楼中的新甾体皂苷

从云南重楼Paris polyphylla Sm. var. yunnanensis(France. )Hand.-Mazz.的干燥根茎中分离鉴定了4个甾体皂苷(1~4), 其中化合物1是新化合物, 采用波谱技术鉴定其结构为24-O-β-D-吡喃半乳糖基-(23S,24S)-螺甾-5, 25(27)-二烯-1β,3β,23,24-四醇-1-O-β-D-吡喃木糖基(1→6)-β-D-吡喃葡萄糖基(1→3)[α-L-吡喃鼠李糖基(1→2)]-β-D-吡喃葡萄糖苷.     

基于G-四链体-氯化血红素DNA酶比色法测定银离子和汞离子传感器的构筑

利用G-四链体DNA(5′-CTGGGAGGGAGGGAGGGA-3′)与氯化血红素结合形成G-四链体-Hemin DNA酶,其能高效催化H_2O_2氧化反应底物由无色变为绿色,当溶液中有Ag~+或Hg~(2+)存在时会阻碍该DNA酶的形成,导致绿色溶液变浅。基于此,建立了比色法测定Ag~+和Hg~(2+)的传感器。在最佳实验条件下,溶液的吸光度与Ag~+和Hg~(2+)浓度分别在100.0～1 000.0 nmol/L和80.0～800.0 nmol/L范围内具有良好的线性关系,检出限(3δ/Slope)分别为55.9 nmol/L和64.3 nmol/L。该方法具有较好的选择性,采用该方法对实际样品进行测试,结果满意。     

分光光度法测定脱氧核糖核酸——基于其与亚甲蓝的反应

试验发现在pH 6.5的B-R缓冲溶液中在加脱氧核糖核酸(DNA)后亚甲蓝溶液在其吸收峰666 nm波长处的吸收明显减弱(即色泽减褪),而且吸光度的减弱(ΔA)程度与DNA的质量浓度在10.0 mg.L-1以内保持线性关系,其相关系数为0.9998,此反应对DNA的检出限为0.10 mg.L-1,分别以蛋白酶、胰蛋白酶及溶菌酶作为基体定量加入DNA配制成3种合成样品,按所提出方法进行分析,测得回收率结果在98.4%~101.0%之间,分析结果的RSD(n=11)值在1.1%~3.1%之间。对反应条件(包括亚甲蓝的浓度、反应的温度、酸度及时间等因素)作了试验和选定,还对反应机理作了简要的讨论。     

西松烷型二萜内酯的全合成进展

按照内酯环的大小综述了西松烷二萜的合成方法。     

一种受阻胺封端的聚芴蓝光材料的合成及其稳定性研究

以五甲基哌啶醇、对溴苯酰氯为原料合成了一种受阻胺抗氧稳定剂,通过Suzuki反应将其封端到聚(9,9-二辛基)芴上.通过核磁共振谱、凝胶渗透色谱对合成材料的分子结构进行了表征;并利用荧光发射光谱和退火方法,对其光谱热稳定性进行了细致研究.实验结果表明,当在聚芴分子链上引入受阻胺五甲基哌啶醇后,其荧光发射光谱的稳定性显著提高,绿光区发射现象明显减弱.     

新型杀菌剂氟吗啉在黄瓜植株体内的吸收传导行为

利用生物测定技术和高效液相色谱法研究了氟吗啉在黄瓜植株体内的吸收、传导和分布行为及其机制. 结果表明, 氟吗啉能被黄瓜植株被动吸收, 并通过木质部在体内传导和分布.     

Reactions of CF3-enones with ethyl nitroacetate and nitromethane: synthesis of CF3-γ-nitroketones

Reactions of α,β-unsaturated CF₃-ketones with nitromethane and ethyl nitroacetate have been investigated. We found that α,β-unsaturated trifluoromethylketones react with ethyl nitroacetate in the presence of calcinated potassium fluoride to form two classes of 1,4-conjugated addition products: CF₃-γ-nitroketones and 6,6,6-trifluoro-2-nitro-5-oxohexanoates in nearly quantitative yields. The products obtained are precursors for CF₃-pyrrolidine synthesis.     

Intramolecular charge transfer with the planarized 4-aminobenzonitrile 1-tert-butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6)

Fast and efficient intramolecular charge transfer (ICT) and dual fluorescence is observed with the planarized aminobenzonitrile 1-tert-butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6) in a series of solvents from n-hexane to acetonitrile and methanol. Such a reaction does not take place for the related molecules with 1-isopropyl (NIC6) and 1-methyl (NMC6) groups, nor with the 1-alkyl-5-cyanoindolines with methyl (NMC5), isopropyl (NIC5), or tert-butyl (NTC5) substituents. For these molecules, a single fluorescence band from a locally excited (LE) state is found. The charge transfer reaction of NTC6 is favored by its relatively small energy gap DeltaE(S(1),S(2)), in accordance with the PICT model for ICT in aminobenzonitriles. For the ICT state of NTC6, a dipole moment of around 19 D is obtained from solvatochromic measurements, similar to micro(e)(ICT) = 17 D of 4-(dimethylamino)benzonitrile (DMABN). For NMC5, NIC5, NTC5, NMC6, and NIC6, a dipole moment of around 10 D is determined by solvatochromic analysis, the same as that of the LE state of DMABN. For NTC6 in diethyl ether at -70 degrees C, the forward ICT rate constant (1.3 x 10(11) s(-1)) is much smaller than that of the back reaction (5.9 x 10(9) s(-1)), showing that the equilibrium is on the ICT side. The results presented here make clear that ICT can very well take place with a planarized molecule such as NTC6, when DeltaE(S(1),S(2)) is sufficiently small, indicating that a perpendicular twist of the amino group relative to the rest of the molecule is not necessary for reaching an ICT state with a large dipole moment. The six-membered alicyclic ring in NMC6, for example, prevents ICT by increasing DeltaE(S(1),S(2)) relative to that of DMABN.     

过硫酸胺与N－［（3－二甲氨基）丙基］丙烯酰胺氧化还原引发体系的研究

过硫酸胺与Ｎ－［（３－二甲氨基）丙基］丙烯酰胺氧化还原引发体系的研究司堃，郭新秋，丘坤元（北京大学化学与分子工程学院北京１００８７１）关键词Ｎ－取代丙烯酰胺，氧化还原体系，反应动力学，端基分析，反应机理Ｎ－［（３一二甲氨基）两基］丙烯酸胺（ＤＭＡＰＡ...     

硝酸甘油:祸兮福所倚,福兮祸所伏——舞台剧剧本

自1846年硝酸甘油被合成以来,人们一直把其当作炸药来使用。但由于硝酸甘油过于敏感,导致事故不断。为解决这一问题,诺贝尔尝试改良硝酸甘油,将硅藻土与硝酸甘油混合,降低了敏感度,达到安全使用炸药的目的。后来人们发现硝酸甘油还有缓解心绞痛的功能,便对其进行了深入研究。本文以剧本的形式向大众科普硝酸甘油的上述功能。