Np(V)在人体体液的形态模拟研究

建立了含多种金属离子和小分子配体组成的多相Np(V)体液平衡模型.模拟研究了Np(V)在胃液、汗液、组织液、细胞液和尿液中的形态分布.结果表明:胃液中,当[Np]为1×10-15mol 形态存在.汗液中,当[Np]=1×10-6mol·L-1时,Np(V)以NpO2 形态存在,当[Np]=1×10-3mol·L-1,pH4.2～5.0时,主要以NpO2 形态存在;随着pH升高,Np(V)逐渐以固相Np2O5为主,到pH7.0时,Np2O5含量达99%.组织液中,当[Np]<4×10-6mol·L-1时,Np(V)以NpO2CO3-、NpO2 和NpO2HPO4-形态存在,随[Np]增高,固相NaNpO2CO3逐渐占据主导地位,当[Np]=1×10-4mol·L-1时,固相含量达100%.当[Np]=1×10-3mol·L-1时,随组织液中添加的EDTA的浓度增加,固相含量逐渐降低,当[EDTA]=0.0085 mol·L-1时,已无固相Np(V)形态.细胞液中,当[Np]=1×10-6mol·L-1时,Np(V)以NpO2CO3-、NpO2 和NpO2HPO4-形态存在;当[Np]=1×10-3mol·L-1时,主要以固相Np2O5存在,但在巨噬细胞极低pH值的细胞液中以NpO2 形态存在.尿液中,当[Np]=1×10-6 mol·L-1时,Np(V)以NpO2 和NpO2HPO4-两种形态存在;当[Np]=1×10-3mol·L-1,pH>5.0时,随pH升高,固相Np2O5含量增加并逐渐占主导地位,但当pH<5.0时,Np(V)主要以NpO2 形态存在,提示可降低尿液pH值促进肾脏Np(V)排出.     

Np(Ⅴ)在人体体液的形态模拟研究

建立了含多种金属离子和小分子配体组成的多相Np(Ⅴ)体液平衡模型。模拟研究了Np(Ⅴ)在胃液、汗液、组织液、细胞液和尿液中的形态分布。结果表明:胃液中,当[Np]为1×10-15mol.L-1~1×10-3mol.L-1时,Np(Ⅴ)以NpO2 形态存在。汗液中,当[Np]=1×10-6mol.L-1时,Np(Ⅴ)以NpO2 形态存在,当[Np]=1×10-3mol.L-1,pH4.2~5.0时,主要以NpO2 形态存在;随着pH升高,Np(Ⅴ)逐渐以固相Np2O5为主,到pH7.0时,Np2O5含量达99%。组织液中,当[Np]<4×10-6mol.L-1时,Np(Ⅴ)以NpO2CO3-、NpO2 和NpO2HPO4-形态存在,随[Np]增高,固相NaNpO2CO3逐渐占据主导地位,当[Np]=1×10-4mol.L-1时,固相含量达100%。当[Np]=1×10-3mol.L-1时,随组织液中添加的EDTA的浓度增加,固相含量逐渐降低,当[EDTA]=0.0085 mol.L-1时,已无固相Np(Ⅴ)形态。细胞液中,当[Np]=1×10-6mol.L-1时,Np(Ⅴ)以NpO2CO3-、NpO2 和NpO2HPO4-形态存在;当[Np]=1×10-3mol.L-1时,主要以固相Np2O5存在,但在巨噬细胞极低pH值的细胞液中以NpO2 形态存在。尿液中,当[Np]=1×10-6mol.L-1时,Np(Ⅴ)以NpO2 和NpO2HPO4-两种形态存在;当[Np]=1×10-3mol.L-1,pH>5.0时,随pH升高,固相Np2O5含量增加并逐渐占主导地位,但当pH<5.0时,Np(Ⅴ)主要以NpO2 形态存在,提示可降低尿液pH值促进肾脏Np(Ⅴ)排出。     

曲克芦丁对发光碳量子点的荧光猝灭作用

以D-麦芽糖为碳源,L-赖氨酸为钝化剂,采用微波法合成了发光碳量子点(CQDs)。采用荧光光谱法、紫外光谱法研究了曲克芦丁(TRT)对CQDs的荧光猝灭作用,构建了以CQDs为荧光探针测定TRT含量的新方法。实验表明,TRT浓度在1. 0×10-7～3. 0×10-5mol·L-1范围内与CQDs荧光强度的猝灭呈现良好的线性关系,相关系数为r=0. 9980,检出限为7. 0×10-8mol·L-1。对片剂中TRT含量的测定,回收率为97. 30%～102. 9%。同时,探讨了TRT与CQDs相互作用机理。     

3,5-diCl-PADAP光度法测定微量重铬酸根的研究

铬的测定对生命科学及工农业等领域具有重要意义[1]。铬的测定有吸光光度法、原子吸收光谱法、ICP-AES法等[2-5]。本文依据3,5-d iC l-PADAP在酸性介质中质子化后与Cr2O72-形成二元离子缔合物的性质,建立了吸光光度法测定微量Cr2O72-的方法,用于环境水样和茶叶中铬的测定,结果满意。1试验部分1·1仪器和试剂722型分光光度计;TU-1901双光束紫外可见分光光度计;K2Cr2O7标准溶液:1·00×10-3mol·L-1;3,5-d iC l-PADAP乙醇溶液:1·00×10-3mol·L-1。试剂均为分析纯,水为二次蒸馏水。1·2实验方法移取1·00×10-3mol·L-1 3,5-d i…     

一种新型三角架罗丹明B荧光探针对Cu~(2+)识别性能研究

设计、合成了一种新颖的三角架结构罗丹明B衍生物(2).在乙醇-水(8/1,V/V)介质中,用Tris-HCl控制体系pH为6.8,观察到Cu2+对化合物2的荧光及紫外-可见吸收增强性能,同时化合物2对Cu2+具有较高的选择性响应.选择最大激发和发射波长为557/577nm,测定了探针2(1.00×10-5mol·L-1)对Cu2+响应的校准曲线,线性范围为0.10~10.00×10-5mol·L-1,相关系数R2=0.9964(n=15),检出限为1.129×10-7mol·L-1,平行测定5次的相对标准偏差(R.S.D.)为2.2%;以557nm为最大吸收波长测定紫外吸收,Cu2+响应的浓度线性范围为0.50~25.00×10-5mol·L-1,相关系数R2=0.9948(n=13),检出限为3.338×10-7mol·L-1.     

巯基乙酸修饰的CdTe量子点荧光光度法测定赤泥中痕量镍

用巯基乙酸(TGA)作稳定剂,采用水相合成法制备了巯基乙酸修饰的Cd Te量子点(TGA-Cd Te QDs)。基于镍离子在p H 10.0的Na2B4O7缓冲溶液中对Cd Te量子点的荧光具有较强的猝灭作用,建立了一种测定镍离子的荧光光度方法。结果表明,在最佳试验条件下,镍离子浓度在2.0×10-7mol·L-1~7.8×10-5mol·L-1范围内与Cd Te量子点的相对荧光强度呈良好的线性关系,其线性回归方程为△F=1.0089+0.0308c(μmol·L-1),相关系数r=0.9987,检出限1.5×10-7mol·L-1。样品中的镍经2-羟基-4-仲辛氧基二苯甲酮肟(N530)磺化煤油萃取分离后,大多数常见离子不干扰测定。方法应用于赤泥中痕量镍的测定,测定结果与催化光度法相符,加标回收率在98.3%~104.2%之间。     

螺吡喃衍生物在固相基质中的应用--锌离子PVC膜荧光传感器

合成了一种新的螺吡喃衍生物,将其应用到PVC膜固相基质中,用于Zn2+的荧光检测.优化条件下,该敏感膜对Zn2+的响应范围为4.94(10-7～4.15(10-4mol·L-1,检测限为1.51(10-7mol·L-1.实验发现,该敏感膜具有很好的光学稳定性、重现性和可逆性,而且与其他过渡金属离子如Hg2+,Cd2+,Pb2+,Cu2+,Fe3+或碱金属和碱土金属离子相比,该敏感膜对Zn2+的荧光增强具有高选择性.     

杯[4]芳烃化学修饰玻碳电极对多巴胺的测定

研究了多巴胺在杯[4]芳烃化学修饰玻碳电极上的电化学行为,建立了一种直接测定多巴胺的电化学方法.在0.1 mol·L-1KH2PO4-Na2HPO4(pH 7.4)底液中,开路搅拌富集300 s后,多巴胺在+0.158 V(vs SCE)处产生1个灵敏的准可逆氧化峰,电极反应主要受扩散控制,氧化峰电流Ip与多巴胺浓度在1.0×10-6 ～5.0×10-4 mol·L-1范围内呈现良好的线性关系,检出限达7.0×10-7 mol·L-1.同一支电极连续10次测定1.0×10-4 mol·L-1的多巴胺溶液,相对标准偏差为2.6%.该法用于盐酸多巴胺针剂中多巴胺含量的测定,结果令人满意.     

丹皮酚在APTS与离子液体复合修饰碳糊电极上的电化学性质及电分析方法

研究了丹皮酚(PN)在3-氨基丙基三氧基硅烷(APTS)与离子液体([BnMIM]PF6)复合修饰碳糊电极(APTS-[BnMIM]PF6/CPE)上的电化学行为和电化学动力学性质,并用循环伏安法(CV)及计时电流法(CA)测得PN在APTS-[BnMIM]PF6/CPE上的电极反应动力学参数。实验结果表明,PN在APTS-[BnMIM]PF6/CPE上发生了受扩散控制的不可逆电化学氧化过程。用方波伏安法(SWV)测得PN氧化峰电流与其浓度在9.0×10-7~2.0×10-4mol·L-1和3.0×10-4~1.5×10-3mol·L-1范围内呈良好线性关系,检出限(LOD,S/N=3)和定量下限(LOQ,S/N=10)分别为3.5×10-8mol·L-1和1.2×10-7mol·L-1。同时运用该方法对丹皮酚注射液中PN含量进行了电化学定量测定,其RSD为0.58%~2.4%,加标回收率为96.0%~102.0%。     

N-(9-蒽甲基)-L-酪氨酸盐酸盐的合成及其对阴离子的分子识别

利用荧光基团9-蒽醛与L-酪氨酸反应,合成了荧光主体N-(9-蒽甲基)-L-酪氨酸盐酸盐;采用荧光光谱方法检测了荧光主体与不同阴离子之间的识别作用;通过加入不同摩尔比的配体确定了主体与配体之间识别的最佳摩尔配比.结果表明,配置浓度为5×10-5mol·L-1的Cr2O2-7溶液后,用微量进样器加入100μL浓度为1×1...     

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。