2,8-二氨基-10-甲氧基-5,10-二氢磷杂吖嗪-10-氧化物的合成、诱变性及应用性能研究

10-羟基-5,10-二氢磷杂吖嗪-10-氧化物(1)经酰氯化、甲基化得到10-甲氧基-5,10-二氢磷杂吖嗪-10-氧化物(2),2经硝化得到10-甲氧基-2,8-二硝基,5,10-二氢磷杂吖嗪-10-氧化物(3.62％)．3在Pd／C(u=0．05)存在下,用氢气还原为2,8-二氨基-10-甲氧基-5,10-二氢磷杂吖嗪-10-氧化物(4.71％),考察了Bd／C(w=0．05)用量对氢化还原反应的影响．经过Salmonella／mammalian microsome assay测试,4表现为非诱变性,用4与乙酰J-酸作用得到新型双偶氮酸性染料(5)．5对羊毛和丝绸分别在2％与3％色度下浸染郜得到黑色染样,考察了5的上染曲线,并对染样进行了测色研究,发现该染料属于酸性蓝黑染料,其黑度优于目前市场上流行的酸性黑10B．     

液相色谱-离子阱-飞行时间质谱法测定调味品中9种酸性工业染料

建立了辣椒酱、干辣椒、花椒等酱类和香辛料类调味品中9种酸性工业染料的液相色谱-离子阱-飞行时间质谱(LCMS-IT-TOF)检测方法。样品用甲醇-水(80∶20)溶液提取,经弱阴离子交换(WatersOasis WAX)固相萃取柱净化,以Shimadu Shim-pack XR-ODS(2.0 mm×100 mm,2.2μm)柱进行分离,采用10 mmol/L乙酸铵溶液-甲醇为流动相梯度洗脱,流速为0.2 mL/min。采用电喷雾离子化源,在负离子模式下进行检测,外标法定量。结果表明,9种酸性工业染料的基质校准曲线在一定范围内线性关系良好,相关系数均大于0.99。3个加标水平的平均回收率为64.8%～106.0%,相对标准偏差(n=5)不高于6.7%。该方法操作简单、灵敏度高、分析时间短,离子阱飞行时间多级质谱的定性功能增加了定性结果的可靠性,适用于酱类和香辛料类调味品中9种酸性工业染料的同时测定。     

用亚铁氰化钛钾从模拟高放废液中吸附Cs研究

本文研究了溶胶-凝胶法合成的无机离子交换剂亚铁氰化钛钾的耐酸性和辐照稳定性等性能，测定了从模拟酸性高放废液中主要常量组分离子相对于Cs的分离系数，研究了流速对Cs吸附曲线的影响。实验结果表明，该交换剂具有良好的辐照稳定性，交换剂经2×106Gy的辐照，亚铁氰化钛钾对Cs的表观交换容量下降6～7％，为0．873mmolCs／g干交换剂。在0．5～1．5mol／LHNO3中具有良好的化学稳定性。在模拟酸性高放废液中对几种离子的选择吸附顺序为：Cs＞＞M＞Fe＞Sr＞Na＞Cr＞Nd，Mn，该交换剂具有较高的吸附容量，对Cs具有良好的选择性，有希望用作从酸性高放废液中去除Cs的材料。     

类Fenton试剂-罗丹明B-HCI体系动力学荧光法测定环境水样中2，4-二氯酚

在酸性介质中,痕量2,4-二氯酚对类Fenton试剂与罗丹明B的反应具有明显阻抑作用,且其阻抑作用大小与2,4-二氯酚的浓度有关。据此建立了一种动力学荧光法测定痕量2,4-二氯酚的新方法。考察了各种因素对测定方法灵敏度的影响。在最佳条件下,方法的线性范围为0．04～0．8 μg/mL,检出限为0．012 μg／mL。将该方法用于7种环境水样和6种合成样品中2,4-二氯酚的测定,加标回收率为93．5％～108．0％。相对误差为-5．45％～4．60％。     

含笑花挥发油的超临界二氧化碳萃取及气相色谱-质谱分析

采用超临界二氧化碳萃取含笑花的挥发油性成分，经毛细管气相色谱-质谱联用仪（GC-MS）分析，鉴定了其中的31个挥发性化合物，用气相色谱峰面积归一法测定各组分的相对百分含量。其挥发性组分主要是倍半萜氧化物、倍半萜类物质，其相对含量分别是49．87％和32．08％。该法获得的相对含量最高的是丁香烯环氧物（30．25％），其次是匙叶桉油醇（6．78％）、β-榄香烯（5．83％）。其它含量较高的成分依次是：长蠕孢吉码烯（5．62％）、棕榈酸（4．02％）、α依兰烯醇（3．26%）、β-香桦烯（3．25％）．     

高效液相色谱-荧光检测法测定辣椒制品中5种罗丹明染料北大核心CSCD

建立了辣椒制品中罗丹明110、磺酰基罗丹明B、罗丹明B、罗丹明6G和丁基罗丹明B 5种罗丹明染料的高效液相色谱-荧光检测法。方法采用Zorbax SB-C18柱(250×4.6mm,5.0μm),以乙腈和水(均含0.1%的甲酸)为流动相进行梯度洗脱,5种组分可基线分离。结果表明,5种罗丹明染料在相应浓度范围内线性关系良好,线性相关系数均大于0.999,平均加标回收率在84.0%~105.8%之间,相对标准偏差为1.2%~4.8%。该方法简单、准确、灵敏度高,适用于辣椒制品中罗丹明染料含量的同时测定。     

酸性媒介红稀土染料的制备、表征及其羊毛染色性能

制备并提纯了酸性媒介红稀土(La, Nd, Y, Er)染料, 稀土及元素分析测得其稀土与配体酸性媒介红染料物质的量的比为1∶1; 红外光谱、紫外-可见光谱分析表明, 在酸性媒介红稀土染料的结构中, 稀土离子(La3+, Nd3+, Y3+)与配体染料分子中的羧基、羟基产生配位作用, 其中Y3+同时还与偶氮基(-N=N-)作用,在3个稀土染料中稀土离子与染料分子中的磺酸基(-SO3-)也产生作用; 所有样品的羊毛布料染色实验及其各项牢度测试结果表明 酸性媒介红稀土染料羊毛染色比相应配体酸性媒介红染料色光纯正, La, Nd染料染色增深, Y, Er染料染色增艳, 但均比铬金属络合染料颜色鲜艳, 钇染料的各项羊毛染色牢度比配体染料好, 与Cr金属络合染料相当, 具有实用价值.     

酸性媒介深黄GG稀土染料的制备、表征及染色性能

制备并提纯了酸性媒介深黄GG稀土(La, Nd, Y)染料, 稀土及元素分析测得其稀土与酸性媒介深黄GG染料物质的量的比为1∶2, 红外光谱、紫外-可见光谱分析表明, 在酸性媒介深黄GG稀土染料的结构中, 稀土离子(La3+, Nd3+, Y3+)与配体染料分子中的羧基、羟基产生配位作用, 并与磺酸基作用;所有样品的羊毛布料染色实验及其各项牢度测试结果表明 酸性媒介深黄GG稀土染料羊毛染色比相应配体酸性媒介深黄GG染料和相应的铬络合染料染色颜色鲜艳, 酸性媒介深黄GG稀土染料的多项羊毛染色牢度比相应的配体酸性媒介深黄GG染料好, 但比相应的铬络合染料差.     

碳酸二甲酯和苯胺胺解反应产物的液相色谱分析

采用气-质联用仪对碳酸二甲酯和苯胺胺解反应合成苯氨基甲酸甲酯的反应体系的副产物N,N-二甲基苯胺进行定性分析,并提出了该反应体系主、副产物的液相色谱的分析方法,以硝基苯为内标物,实现了苯胺、苯氨基甲酸甲酯、N-甲基苯胺、二苯脲及N,N-二甲基苯胺的定量分析,实验结果表明,在一定浓度下,这5种组分与峰高线性良好,回收率在97．8％～102．7％,相对标准偏差小于2．01％。     

电镀废水中三价铬和六价铬含量的测定

建立了一种可分别同时测定电镀废水中三价铬和六价铬含量的紫外-可见分光光度法。在同一样品溶液中分别于540nm和350nm处同时测定Cr（Ⅲ）和Cr（Ⅵ）的吸光度,在控制酸度的条件下,由于两组分不相互干扰,通过线性方程分别可求出组分中的含量。Cr（Ⅲ）在8．85×10^-7～1．54×10^-5mol／L范围内服从比耳定律,回收率为99．6％,100．2％;Cr（Ⅵ）在9．23×10^-57-1．15×10^-5mol／L范围内服从比耳定律,回收率为97．0％-101．1％。该法与传统国标法相比,操作简便、快速、准确。     

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.     

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.     

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。     

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.     

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.

     

Investigation of Kinetics of Solid-Phase Synthesis of Lithium Orthosilicate

The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m²g^-1 instead of aerosil with one of 175 m²g^-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended. This revised version was published online in July 2006 with corrections to the Cover Date.     

小环化合物中饱和碳质子化学位移的计算

小环化合物由于其张力、构型、构象和各向异性效应等原因,环碳上质子化学位移缺乏规律性,难以预测,对此作者曾提出一种近似算法。本文根据303种小环化合物中饱和碳质子的化学位移实验数据,将适于计算这类质子化学位移的公式表述为:     

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。     

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.