树状聚酰胺-胺桥联受阻酚类抗氧化剂的合成及清除DPPH·活性研究

以系列1.0、2.0代树状聚酰胺-胺(PAMAM)为桥联基,3-(3,5-二叔丁基-4-羟基苯基)丙酰氯为抗氧化基团,通过酰胺化缩合反应合成了系列树状桥联受阻酚类抗氧化剂。红外光谱和核磁共振氢谱证实了系列树状聚酰胺-胺桥联受阻酚类抗氧化剂的化学结构。采用EPR技术研究系列树状聚酰胺-胺桥联受阻酚类抗氧化剂清除DPPH·的能力,结果表明,系列树状聚酰胺-胺桥联受阻酚类抗氧化剂具有良好清除DPPH·活性,且随着清除时间的延长、桥联基长度和代数的增加,其清除活性增强。     

超支化分子桥联受阻酚抗氧化剂的合成与表征

以正十八胺为核的1.0代超支化大分子和β-(3,5-二叔丁基-4-羟基苯基)丙酰氯为原料,通过酰胺化缩合反应,合成了一种具有长链烷基和2个受阻酚基团的新型超支化分子桥联受阻酚类抗氧化剂.通过正交实验确定了超支化分子桥联受阻酚类抗氧化剂的最佳合成体系为:3,5-丙酰氯为酰化剂、K_2CO_3为缚酸剂、苯和水为反应溶剂.通过条件优化实验确定了超支化分子桥联受阻酚类抗氧化剂的最佳合成条件为:3,5-丙酰氯与1.0代超支化大分子的物质的量比为6∶1、反应温度为25 ℃、反应时间为12 h、体系苯与水体积比为6∶1、3,5-丙酰氯与缚酸剂K_2CO_3的物质的量比为1∶1,在此条件下,超支化分子桥联受阻酚类抗氧化剂的收率高达75.5%.FT-IR和1H NMR证实了合成抗氧化剂的化学结构与其理论结构相符.超支化分子桥联受阻酚类抗氧化剂在聚乙烯树脂中的抗氧化性能优于抗氧化剂1076,且随着烷基链长度的增加,抗氧化性能增强.     

仪器分析实验教学内容改革与实践

针对现行的仪器分析实验教学内容中存在的验证性实验偏多、缺少条件实验、忽视样品的预处理等问题,提出了改革方案。以提高学生的实践能力为出发点,从筛选与生产、生活联系密切的实验,重视样品的预处理和实验条件的选择,加强综合性、设计性实验,开设开放性和创新性实验,吸引学生参与教师的科研工作等方面对仪器分析实验教学内容改革进行了探讨。     

基于微流控芯片的磁性没食子酸丙酯分子印迹聚合物的制备及应用

以3-(甲基丙烯酸酰氧)丙基三甲氧基硅烷修饰的Fe3O4为载体,没食子酸丙酯为模板分子,采用表面印迹技术制备了核壳结构的磁性没食子酸丙酯分子印迹聚合物(Fe3O4@SiO2-MIPS),并将该磁性分子印迹聚合物作为吸附剂引入到微流控芯片中,与HPLC联用,实现对痕量酚类抗氧化剂的分离富集.采用扫描电镜、磁滞回线、热重分析、红外光谱及X射线衍射对该磁性分子印迹聚合物表征.在最佳萃取条件下(样品体积3 mL,样品溶液pH=5.0,样品流速为0.5 mL./min,洗脱液流速为0.3 mL/min),该聚合物对酚类抗氧化剂具有较强的富集作用.3种酚类抗氧化剂在10～5000 ng/mL范围内呈现良好的线性关系,线性相关系数均大于0.9901,日内和日间相对标准偏差(n=5)分别低于2.8％和3.5％.将本方法用于化妆水中酚类抗氧化剂的分析检测,加标回收率在87.9％ ～ 104.0％之间,相对标准偏差(n=3)小于3.7％.     

Al-MCM-41介孔分子筛催化对甲酚叔丁基化反应的研究

2-叔丁基对甲酚是一种有机中间体,在有机合成领域中占有重要地位,被广泛应用于表面活性剂、高档酚类抗氧化剂2246和2246-S、紫外线吸收剂UV-326等的生产[1]。特别是近十年来,以抗热老化为特征的功能性高档酚类抗氧化剂在国内外相继问世,它们对于提高聚合物材料的成型加工性能、     

品红甲亚胺染料影像光稳定性的研究——抗氧化剂和单重态氧的反应能力及其对染料影像光褪色的影响

本文研究了苯酚类(A),双酚类(B),对苯二酚类(C),色满类(D)和双螺色满类(E)抗氧化剂的性能。通过循环伏安法测定了它们的氧化电位;用类似Stern-Volmer关系图求得各抗氧化剂和单重态氧的反应速率常数。抗氧化剂的氧化电位越小,和单重态氧的反应速率常数越大,对品红甲亚胺染料影像的防褪色效果越好,进一步证实了染料褪色的光氧化反应机理。在这些抗氧化剂中,它们的防褪色效果依次为D>E>C>B>A。     

使用本征值方法研究抗氧化剂的构效关系

利用本征值(EVA)方法对一组分子多样性较大的酚类或苯胺类抗氧化剂进行了理论研究,在未采用任何实验数据的情况下,研究结果接近于文献报道的QSAR模型,表明EVA方法是研究抗氧化剂抗氧化活性构效关系的良好工具.     

手性药物对映体分离检测的研究式开放性实验

以市售手性药物氧氟沙星药片为实际样品,采用毛细管电泳/非接触式电导法分离检测药片中的氧氟沙星对映体含量.实验内容包括：石英毛细管的处理,样品的前处理技术,实验条件和仪器参数调试,样品分析及实验报告.该实验可推荐作为高年级本科生的仪器分析研究式开放性教学实验.     

仪器分析设计性实验的探索与实践——从“酱油中防腐剂山梨酸和苯甲酸含量的测定”谈起

通过分析"酱油中防腐剂山梨酸和苯甲酸含量的测定"的实验过程,阐述了开设仪器分析设计性实验对于拓宽学生视野、提高学生的文献检索能力和多渠道获取信息能力、加深学生对仪器分析原理的理解、培养学生综合分析和解决问题的能力、强化学生实验技能训练及发挥学生的主动性和创造性等各方面的积极意义,同时也分析了设计性实验中存在的不足,并指出开设验证性实验的必要性。     

浅谈仪器分析实验教学的实践和体会

为帮助学生深刻领会仪器分析理论基础知识,高效掌握有关实验内容,培养学生动手能力、观察能力和团队协作精神,增强实验教学效果,我们以紫外-可见分光光度法及荧光分光光度法实验教学为例,进行了一段时间的摸索。通过调整教学内容、强化理论知识与实验联系、归纳仪器操作步骤、注重细节培养等措施,提高了仪器分析实验教学质量,取得了较好的效果。学生完成基础实验后,能自由运用所学知识,独立设计实验方案,获得所需实验结果。     

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.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。