瓜环与喹啉衍生物包结配合行为研究

利用¹H NMR以及荧光技术研究了六、七、八元瓜环与2-苯基喹啉、N-正丙基溴化异喹啉、3-氨基喹啉及7,8-苯并喹啉的相互作用.两种方法的考察结果均表明,2-苯基喹啉能与这3种瓜环发生相互作用,其中六、七元瓜环与2-苯基喹啉形成1∶1的稳定包结配合物,包结常数分别为1.6×10⁴和3.2×10³L/mol.八元瓜环能与2-苯基喹啉形成1∶2包结物.¹H NMR结果还表明,3种瓜环均能与N-正丙基溴化异喹啉相互作用,其化学计量比均为1∶2;七元瓜环与7,8-苯并喹啉相互作用,化学计量比约为1∶1.荧光法也表明八元瓜环能与N-正丙基溴化异喹啉、3-氨基喹啉及7,8-苯并喹啉发生相互作用,并且荧光强度随瓜环浓度增加而下降,其化学计量比为1∶2.同时,讨论了上述主客体包结配合物的作用模式.     

荧光素钠与牛血清蛋白相互作用的荧光光谱研究及其分析应用

采用荧光光谱研究了荧光素钠与牛血清蛋白(BSA)间的相互作用, 根据荧光淬灭相关方程分别计算了淬灭速率常数、结合常数、结合位点数及热力学参数, 确定了BSA对荧光素钠的淬灭机理及作用方式, 根据能量转移理论求得荧光素钠与BSA的结合距离及能量转移率, 结合三维、同步荧光光谱研究了荧光素钠对BSA构象的影响|在一定范围内荧光素钠的淬灭程度与BSA浓度成正比, 据此建立一种荧光素钠测定蛋白的方法, 线性范围为0.15×10^－7～15× 10^－7 mol•L^–1, 方法具有高灵敏度, 检测极限为0.146×10^－8 mol•L^–1, 文中还考察了不同pH值和干扰物质对于测定结果的影响, 用于人血清中总蛋白含量测定结果与考马斯亮蓝法基本一致.     

Co-W合金镀层表面氧化膜在碱性体系中的电化学研究

采用电化学手段以及Mott-Schottky理论, 并结合氧化膜点缺陷模型(PDM)分析研究了Co-W合金镀层在1 mol• L^－1 NaOH溶液中表面氧化膜的半导体性质, 并分别计算出了不同W含量的Co-W合金镀层在－0.15, －0.25和－0.35 V三个不同电位下阳极氧化后氧化膜的供体密度、平带电位及氧空穴扩散系数. 结果表明, Co-W合金镀层在1 mol•L^－1 NaOH溶液中表面氧化膜的Mott-Schottky曲线线性区斜率为正, 表现出N型半导体性质|随着阳极氧化电位的升高或合金镀层W含量的降低, 氧化膜供体密度N_D逐渐增大, 导致氧化膜被破坏或发生点蚀的几率升高|随着阳极氧化电位的降低或合金镀层W含量的降低, 氧化膜平带电位呈降低趋势, 说明其耐蚀性升高|不同W含量的Co-W合金镀层在三个不同电位下阳极氧化后的氧化膜的氧空穴扩散系数为(1.543～8.533)×10^－14 cm²•s^－1.     

八元瓜环对氯化矢车菊素溶解性、稳定性及抗氧化性的影响

采用核磁共振氢谱(¹H NMR)、 红外光谱及紫外吸收光谱等方法考察了八元瓜环(Q[8])对氯化矢车菊素(Cy)的包结作用. 结果表明, 在pH=0.8的盐酸介质中, Q[8]可与Cy形成摩尔比为1:1的主客体配合物, 紫外吸收光谱法测得的主-客体结合常数为1.51×10⁶ . 相溶解度研究结果表明, Q[8]能使饱和Cy溶液的溶解度增大, 当Q[8]浓度为100 μmol/L时, 可使Cy的溶解度增大12.21倍. 紫外吸收光谱随时间变化结果表明, 在较为稳定存在形态及相同实验条件下, Q[8]/Cy溶液比Cy溶液的稳定性提高了2.58倍. 抗氧化性实验结果表明, Q[8]/Cy包合物和Cy均表现出较好的抗氧化活性.     

石墨烯/铁氰化钴复合膜修饰玻碳电极同时测定对苯二酚、邻苯二酚和间苯二酚

采用滴涂法和电沉积法制备了石墨烯/铁氰化钴复合膜修饰玻碳电极. 用扫描电镜对该纳米复合膜进行了表征.用循环伏安法研究了对苯二酚(HQ)、邻苯二酚(CT)和间苯二酚(RS)在修饰电极上的电化学行为. 实验结果表明, 相对于裸玻碳电极和石墨烯修饰电极, HQ, CT 和RS 在石墨烯/铁氰化钴修饰电极上的氧化峰电流显著提高. 利用差分脉冲伏安法测定, HQ, CT 和RS 分别在1.0×10^－6～1.5×10^－4 mol/L, 1.0×10^－6～2.0×10^－4 mol/L 和3.5×10^－6～2.5×10^－4 mol/L浓度范围内与氧化峰电流呈良好的线性关系, 相关系数分别为0.991, 0.993 和0.992. 信噪比为3 时, HQ, CT 和RS 检出限分别为2.0×10^－7, 2.1×10^－7 和3.5×10^－7 mol/L. 将该方法用于水样分析, 回收率为95.6%～106.1%.     

八元瓜环与1,7-二(2-苯并咪唑)-庚烷的超分子自组装

以氯化1,7-二（2-苯并咪唑）-庚烷（SBHt）为客体,八元瓜环（Q[8]）为主体,利用¹H NMR技术、动态光散射实验、荧光发射光谱、紫外吸收光谱详细探索了其在溶液中的相互作用、超分子自组装过程及作用模式. 首先考察了八元瓜环对客体pKa的影响,确定了研究主客体相互作用的条件,并详细探索了主客体的超分子自组装过程及作用模式. 主体Q[8]与客体SBHt相互作用的¹H NMR谱图表明,主客体相互作用自组装形成1：1超分子聚合物. 这一推断得到动态光散射实验、紫外吸收光谱、荧光发射光谱测定结果的证实,并通过紫外吸收光谱、荧光发射光谱确定其表观稳定常数分别为2.79×10⁵ L/mol及2.48×10⁵ L/mol. 而晶体结构测定表明主体Q[8]与客体SBHt自组装形成1：2的简单包结配合物. 导致Q[8]与SBHt在溶液中和固体状态下形成不同自组装结构可能源于瓜环的外壁作用与包结作用竞争所致.     

氮掺杂碳纳米管修饰电极的电化学行为

制备了氮掺杂改性的碳纳米管, 并用循环伏安法(CV)测定了多巴胺(DA)和抗坏血酸(AA)在不同氮含量的碳纳米管修饰电极上的电化学行为. 结果表明, 氮掺杂碳纳米管修饰电极对AA和DA有不同的电催化行为, 其中高氮含量修饰电极对AA的催化作用强, 而低氮含量修饰电极对DA的催化作用强. 微分脉冲伏安法(DPV)的结果显示, DA的氧化峰电流与其浓度在5.0×10^－6～2.0×10^－4 mol/L范围内呈良好的线性关系, 检出限达1.64×10^－6 mol/L (S/N＝3); AA氧化峰电流与其浓度在3.0×10^－5～1.0×10^－2 mol/L范围内呈良好的线性关系, 检出限达3.26×10^－6 mol/L (S/N＝3). 该修饰电极在AA大量存在(AA浓度为DA浓度两万倍)时可选择性地实现多巴胺的测定而不造成干扰.     

2-(5-氟尿嘧啶-1-乙酰基)氨基-1,5-戊二酸二甲酯手性异构体与双链/G-四链体DNA相互作用的电化学研究

以自组装法制得的双链DNA(ds-DNA)和G-四链体DNA(G4-DNA)修饰的金电极为工作电极, 以 为电活性指示剂, 采用循环伏安法和微分脉冲伏安法研究了R和S型2-(5-氟尿嘧啶-1-乙酰基)氨基-1,5-戊二酸二甲酯(简称为(R)-5FUGlu和(S)-5FUGlu)与ds-DNA和G4-DNA相互作用. 实验结果表明: (1)与5-氟尿嘧啶(5-FU)相反, (R)-5FUGlu或(S)-5FUGlu导致 在Au/ds-DNA和Au/G4-DNA修饰电极上的峰电位呈现负移行为|(2)随着5-FU, (R)-或(S)-5FUGlu浓度的增加, 在上述修饰电极上的峰电流均呈现下降现象, 且峰电流的下降值△I_p的倒数与药物浓度的倒数呈现良好的线性关系|(3)运用Langmuir公式计算获得5-FU, (S)-5FUGlu和(R)-5FUGlu与ds-DNA的结合常数分别为6.16×10³, 0.42×10³和0.58×10³ L•mol^－1, 而与G4-DNA 的结合常数分别为0.78×10³, 2.60×10³和5.29×10³ L•mol^－1|(4) (R)-5FUGlu和(S)-5FUGlu在浓度为10^－4, 10^－6, 10^－8 mol•L^－1时对HL-60肿瘤细胞生长的抑制率分别为55.8和2.8, 12.8和1.5以及5.9和0.6, 这与(R)-5FUGlu比(S)-5FUGlu分子具有更强的靶向结合G4-DNA能力相吻合.     

利培酮的电化学行为及应用研究

采用循环伏安法、线性扫描伏安法、常规脉冲伏安法和恒电位电解法等电化学手段, 详细研究了利培酮在pH 7.07～10.32 B-R缓冲溶液和0.2 mol•L^－1 NaOH溶液中的电化学行为. 研究表明: 在pH 7.07～10.07 B-R缓冲溶液中, 利培酮产生的P₁波为催化氢波. 在pH＝10.32 B-R缓冲溶液中, 利培酮可以产生P₂和P₃两个波. 其中, P₂波为不可逆的单电子还原波, P₃波可以分裂成两个波P_3a和P_3b. P_3a波为P₂波的进一步单电子还原, 而P_3b波则属于催化氢波. 在0.2 mol•L^－1 NaOH溶液中, 利培酮产生的P₄波是一个两电子的不可逆还原波. 另外, 根据P₁波的一阶导数峰电流与利培酮浓度在1.6×10^－5～2.0×10^－6 mol•L^－1 (r＝0.9950)间的线性关系, 建立了利培酮片剂中利培酮含量的测定新方法. 新方法的检出限为1.0×10^－6 mol•L^－1, 回收率在105%～102%之间, 相对标准偏差为0.84%.     

土贝母皂苷II与人血清白蛋白相互作用机制的光谱研究

人血清白蛋白多种结合位点的存在使其成为许多药物可能的结合靶点. 土贝母皂苷具有广泛的生理和药理活性, 它与蛋白质相互作用机制的研究对于深入了解其药理药效具有重要的意义. 采用荧光光谱法研究了土贝母皂苷II (TBMSⅡ)与人血清白蛋白(HSA)之间的相互作用, 根据Stern-Volmer荧光淬灭方程计算得293, 298, 303, 308 K时TBMSⅡ与HSA相互作用的结合常数分别为1.002×10⁵, 0.701×10⁵, 0.514×10⁵, 0.411×10⁵ L•mol^－1. 由实验计算出热力学参数焓变ΔH为－44.829 kJ•mol^－1, 熵变ΔS为－57.497 J•mol^－1•K^－1, 表明分子间的氢键及疏水作用是TBMSⅡ-HSA复合物的主要作用力, 结合位点位于HSA的亚结构ⅡA, 这与分子模拟方法的结果相一致. 依据能量转移原理求得TBMSⅡ与HSA间的距离为4.95 nm|三维、同步荧光光谱及圆二色谱的结果表明TBMSⅡ的加入使HSA构象发生变化, α-螺旋结构有所下降.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。