高碘酸钠催化微晶纤维素的氧化

主要讨论了使用高碘酸钠(NaIO4)溶液氧化微晶纤维素的过程及性能,用红外光谱(IR)验证了氧化纤维素的生成;通过扫描电镜(SEM)、热重分析(TG-DSC)以及X射线衍射(XRD)对比了反应前后纤维素的变化;考察了氧化时间、氧化温度、氧化剂的浓度以及溶液的pH值对氧化纤维素的产率及醛基含量的影响;结果表明,反应前后纤维素的晶型和形貌基本没有变化,随着氧化程度的加深,氧化纤维素的热稳定性越来越差;并且随着氧化温度的提高和氧化剂浓度的增大,醛基含量相应提高,而氧化时间和pH值对醛基含量存在相对最高值。     

固定化血红蛋白氧载体的研究（Ⅱ）：氧化纤维素共价键联 …

以纤维素为载体，经高碘酸钠氧化后共价键联血红蛋白，制备氧载体。研究了氧化条件对血红蛋白固定量的影响。纤维素只有经过预氧化，碱处理和再氧化三步活化反应，才能使血红蛋白大量化，每克纤维素固定血红蛋白量达１．０ｇ。氧载体稳定性好，血红蛋白不脱落。经铁氰化钾氧化，氧载体放氧效率为３３．１％。     

新型两性球形离子交换纤维素的制备

本文在自制的球形纤维素基础上,以Ｆｅ＾２＋Ｈ２Ｏ２－二氧化硫脲为氧化还原引发系统,通过甲基丙为稀酸与丙烯酰胺的二元混合物与珠体纤维素接枝共聚,制得了含－ＮＨ２和－ＣＯＯＨ两种官能团的两性离子交换纤维素,其中阳离子交换容量在０．１５～０．６７ｍｍｏｌ／ｇ,阴离子交换容量在０．０５～０．５０ｍｍｏｌ／ｇ。该离子交换剂可用于生物大分子如蛋白质、肽的分离。     

固定化血红蛋白氧载体的研究(Ⅱ)——氧化纤维素共价键联血红蛋白

以纤维素为载体,经高碘酸钠氧化后共价键联血红蛋白,制备氧载体.研究了氧化条件对血红蛋白固定量的影响.纤维素只有经过预氧化、碱处理和再氧化三步活化反应,才能使血红蛋白大量固定化,每克纤维素固定血红蛋白量达1.0g.氧载体稳定性好,血红蛋白不脱落.经铁氰化钾氧化,氧载体放氧效率为33.1%.     

三维结构和氧化度对C6位氧化再生纤维素止血材料性能影响

C6位氧化再生纤维素作为可吸收止血材料,其止血性能受材料理化性质的影响。通过比较氧化再生纤维素的吸水率、凝胶化速率、溶解速率、降解速率、抗老化性能和止血效果,研究三维结构和氧化度对氧化再生纤维素性能影响。结果发现,氧化度增高,氧化再生纤维素吸水率增强,凝胶化速率加快,溶解速率和降解速率变快,抗老化性能变差,产品有效期变短。纤丝松散网状多孔结构比纱布致密结构更有利于提高吸水率,加快凝胶化速率和溶解速率;同时降低氧化剂用量,提高抗老化性能。同一氧化度条件下,纤丝止血速率优于纱布,止血效果更好。     

pH值对邻苯二亚胺纤维素的制备及荧光性能的影响

制备了席夫碱（Ｓｃｈｉｆｆ’ｓ ｂａｓｅ）邻苯二亚胺纤维素（ＰＤＩＭＣ），考查ｐＨ值对制备反应和产物荧光性能的影响。结果表明：氧化度为１００％的二醛纤维素在ｐＨ＝７￣１３、室温下、反应３０ｈ生成的邻苯二亚胺纤维素，具有强较的荧光性能，熔点４１０ｋ，分解温度为５７８Ｋ；ＰＤＩＭＣ水溶液在ＰＨ＝７．６，浓度为７．６×１０＾－４ｇ／ｍＬ，２０℃时，Ｅｘ＝４７０ｎｍ，Ｅｍ＝５５５ｎｍ处荧光最强。     

纤维素基磁性聚偕胺肟树脂的研究——溴在树脂上的氧化还原反应

用羟胺作模拟物与溴反应，测定了吸溴前后的酸式纤维素基磁性聚偕胺肟树脂的红外光谱，结合Ｆｒｅｕｎｄｌｉｃｈ及Ｌａｎｇｍｕｉｒ等温吸附方程的分析和吸溴前后树脂重量变化的测定，证明纤维素基磁性聚偕胺肟树脂吸溴后随即发生氧化还原反应，偕胺肟基被氧化为羧基，溴则被还原为溴离子，在溴浓度较高时，纤维素葡萄糖单元上的羟基被溴代或被氧化成羰酸，若葡萄糖苷键氧化断裂，将导致大分子降解。     

纤维素/甲壳素共混膜的结构表征与抗凝血性能

以 6wt %NaOH 4wt%尿素为纤维素的新溶剂 ,采用溶液共混法制备出纤维素 甲壳素共混膜 ,为甲壳素在碱性溶液中制膜提供了新的方法 .红外光谱、X 射线衍射、扫描电镜和力学性能、抗凝血性能测试结果表明 ,共混膜中甲壳素含量低于 4 0wt%时 ,纤维素与甲壳素分子间具有良好的相容性 ;在纤维素中引入适量甲壳素可提高共混膜的抗张强度 ,共混膜的干、湿态抗张强度在甲壳素含量 10wt%时最大 ,其值分别为 89 1MPa和 4 3 7MPa ,比纯态纤维素膜的干、湿态抗张强度分别提高了 6 7%和 11 5 % ;甲壳素的引入可明显降低血小板在共混膜表面的粘附、凝聚与变性 ,增大共混膜的抗凝血参数 ,甲壳素含量达到 5 0wt%时 ,该共混膜具有良好的抗凝血性能     

LiCl／DMAc溶剂体系中长链脂肪酸纤维素酯的制备及其药物释放性能

在ＬｉＣｌ／ＤＭＡｃ溶剂体系中由纤维素与长链脂肪酸氯反应制备长链脂肪酸纤维素酯，并研究了反应条件对酯化反应取代度的影响。结果表明在适当的反应条件下，酯化聚代度可达到２．８５（９５％）。还研究了纤维酯作为药物控制释放载体对ＬＮＧ、Ａｓｐｉｒｉｎ、ＢＡＳ的释放性能。     

β-环糊精接枝纤维素纤维的研究

以环氧基为交联桥,制备了β-环糊精接枝纤维素纤维,获得了接枝最佳工艺条件,同时运用DSC和IR进行了表征。实验结果表明,环氧化反应乃接枝中关键步骤,其适宜工艺条件为:1g纤维素纤维所需环氧氯丙烷7mL,40%的NaOH溶液6mL,温度为40℃,时间为2.5h。侧链局部运动使纤维素纤维接枝β-环糊精后发生了次级转变。该研究有利于开发β-环糊精在纤维纺织工业的应用。     

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。