离子色谱法测定瓶(桶)装纯净水中痕量溴酸盐和亚硝酸盐的含量

采用离子色谱法同时测定瓶(桶)装纯净水中溴酸盐和亚硝酸盐的含量。水样经AG19-4mm保护柱及DIONEX AS19色谱柱分离,以不同浓度的氢氧化钾溶液为淋洗液,溴酸盐和亚硝酸盐得到很好的分离。BrO3-和NO2-分别在5.00～100.00μg.L-1和1.00～50.00μg.L-1范围内呈线性,检出限(3s/k)分别为0.08,0.14μg.L-1。方法用于瓶(桶)装水中溴酸盐和亚硝酸盐的测定,加标回收率在92.7%～98.4%之间,相对标准偏差(n=5)均小于5.0%。     

沉积物中氯化石蜡与多氯联苯的分离及气相色谱-质谱检测

建立了沉积物中氯化石蜡(CPs)和多氯联苯(PCBs)的提取、分离和检测方法。沉积物样品用二氯甲烷索氏抽提,采用弗罗里硅土/硅胶复合柱纯化和分离。先用80 mL正己烷淋洗得到PCBs组分,再用60 mL二氯甲烷淋洗得到CPs组分,从而实现两者的有效分离。以气相色谱-低分辨质谱(负离子化学源)-选择离子监测技术测定CPs组分,气相色谱-质谱(电子轰击源)-选择离子监测技术测定PCBs,内标法定量,并对样品前处理条件和色谱质谱条件进行优化。在优化条件下,目标化合物(工业品CP52和22种PCB单体)的回收率为86%～99%,RSD<10%。24种短链氯化石蜡(SCCPs)和24种中链氯化石蜡(MCCPs)的方法检出限分别为0.144～3.47 ng/g和0.530～2.24 ng/g。PCBs(一氯～七氯)的方法检出限为0.220～1.08 ng/g。应用该方法检测了东江6个沉积物中CPs和PCBs的含量,沉积物样品中SCCPs的含量为0.245～1.58μg/g(干重),MCCPs的含量为0.538～1.83μg/g,PCBs的含量为1～100 ng/g。     

气相色谱-电子捕获检测法和气相色谱-质谱法同时测定鱼体内19种有机氯农药

建立了气相色谱-电子捕获检测(GC-ECD)法同时测定,及气相色谱-离子阱-多级质谱(GC-IT-MS/MS)法定量确证鱼体中19种有机氯农药(OCPs)残留的检测方法。目标物采用浸渍-振荡法提取,固相萃取(SPE)(脂肪含量≤1.0%)和凝胶色谱(GPC)净化,浓缩,定容后上机测定。草鱼肌肉空白组织中目标化合物的添加浓度为2.0、5.0μg/kg时,GC-ECD法与GC-IT-MS/MS法的回收率分别为72.8%～96%和78.8%～106%,相对标准偏差分别为2.1%～14.9%和4.8%～11%。定量限(S/N=10)分别为0.07～1.44μg/kg和0.10～4.27μg/kg。本方法已成功应用于长江圆口铜鱼体中多种OCPs残留的同时测定。     

IO3--I--丁基罗丹明B体系测定面粉中痕量溴酸根

在磷酸介质中,BrO3-氧化I-形成I3-络阴离子,I3-络阴离子可进一步与丁基罗丹明B阳离子形成离子缔合物,在聚乙烯醇存在下,缔合物呈清亮的紫色溶液,以试剂空白为参比,最大吸收波长位于587nm,吸光度A与BrO3-浓度呈线性关系。线性范围0.20～3.50μg/10mL,表观摩尔吸光系数为9.79×104L·mol-1.cm-1,检出限为0.012μg·mL-1,样品回收率94.0%～100.3%,RSD为2.81%。该方法用于面粉中痕量溴酸根测定,结果令人满意。     

固相萃取净化/超高效液相色谱-串联质谱法测定养殖环境中地西泮及其代谢物

建立了固相萃取净化/超高效液相色谱-串联质谱(SPE/UPLC-MS/MS)同时测定养殖水和沉积物样品中地西泮及其3种代谢物的分析方法。水样经0.45μm玻璃纤维膜过滤,沉积物采用1%氨水-乙酸乙酯提取后,均通过混合型阳离子交换固相萃取(MCX SPE)柱富集净化。目标物用5%氨水-乙腈溶液洗脱后吹干,1 mL 40%乙腈水溶液溶解残渣,UPLC-MS/MS测定。经Phenomenex Kinetex C₁₈(100 mm×2.1 mm,1.7μm)色谱柱分离,乙腈和0.1%甲酸水溶液为流动相进行梯度洗脱。采用电喷雾正离子电离,多反应监测(MRM)模式下测定,内标法定量。4种目标物在0.1～100μg/L范围内的线性关系良好,相关系数(r²)大于0.999。水体和沉积物中的方法检出限分别为1.0～2.0 ng/L和0.02～0.05μg/kg,定量下限分别为2.0～5.0 ng/L和0.05～0.1μg/kg;平均加标回收率为90.2%～115%,相对标准偏差(RSD,n=6)为2.1%～9.6%。该方法灵敏度高,实用性强,可满足养殖环境中地...     

复合层析柱净化-气相色谱-负化学源质谱法测定海洋沉积物中多溴联苯醚

采用去活硅胶-酸化硅胶-去活硅胶-弗罗里硅土-无水硫酸钠填装的复合层析柱，结合气相色谱-负化学源质谱法(GC-NCI/MS)对海洋沉积物样品中的13种多溴联苯醚(PBDEs)进行分析检测。样品用正己烷-二氯甲烷(3∶1, v/v)混合溶剂进行超声提取，提取液经复合层析柱净化及正己烷-二氯甲烷(3∶1, v/v)混合溶剂洗脱后，利用GC-NCI/MS的选择离子监测(SIM)模式分析测定13种PBDEs。对比分析了复合层析柱中不同填料、不同洗脱剂以及不同洗脱体积对PBDEs净化效果的影响，并对GC-NCI/MS分析条件进行优化处理。最终13种PBDEs在0.1～20μg/L内线性关系良好，相关系数(r²)>0.995(BED-209,r²>0.99),定量限(S/N=10)为0.002～0.126μg/kg。以海洋沉积物样品为基质，13种PBDEs在0.2、1.0、4.0μg/kg 3个加标水平下的平均回收率分别为85.3%～101.3%、84.8%～113.6%、86.3%～94.7%,相对标准偏差分别为4.4%～14.0%、0.4...     

铱催化高碘酸钾氧化钍试剂动力学光度法测定痕量铱

在磷酸和热水浴中,铱(Ⅳ)对高碘酸钾氧化钍试剂的反应具有催化作用,依此建立了测定铱的新催化光度法。铱的浓度在0.20μg/10mL～2.0μg/10mL范围内与催化反应速率有良好的线性关系,检出限为6.24×10-3μg/mL。对0.50μg/10mLIr(Ⅳ)测定的相对标准偏差为2.0%(n=10)。该催化反应对铱(Ⅳ)和钍试剂分别为一级反应,其表观活化能为81.66kJ/mol。实验了40多种共存离子的影响,大多数的常见离子不干扰。用该方法测定岩矿和冶金产品中铱的含量,相对标准偏差为1.0%～1.1%,加标回收率为95%～100%。     

单柱离子色谱法测定硒酸根和亚硒酸根的研究

本实验采用单柱离子色谱系统,在SeO_4~(2-)、SeO_3~(2-)与F~-、Cl~-、NO_3~-、SO_4~(2-)离子共存时,以1.0mmol/L邻苯二甲酸氢钾为淋洗液测定了SeO_4~(2-),以1.0mmol/LKNO_3为淋洗液测定了SeO_3~(2-)。SeO_4~(1-)和SeO_3~(2-)的最低检出浓度分别为0.3μg/mL和0.7μg/mL,线性范围分别为0.8～80μg/mL和1.4～150μg/mL,相对标准偏差分别为2.01%和1.85%。并应用本方法测定了加SeO_4~(2-)和SeO_3~(2-)的自来水样,SeO_4~(2-)和SeO_3~(2-)的回收率分别为96%和98%。     

吹扫捕集-气相色谱-质谱法测定土壤中乙酸乙酯和丙烯酸乙酯

建立吹扫捕集-气相色谱-质谱法测定土壤中乙酸乙酯和丙烯酸乙酯的方法。称量5 g土壤样品于40 mL吹扫瓶中,加入5 mL超纯水进行吹扫捕集提取,用DB-624毛细管色谱柱（60 m×250μm,1.4μm）分离,全扫描后进行谱库检索定性,内标法定量。乙酸乙酯和丙烯酸乙酯的质量浓度在5.0～200μg/L范围内与定量离子与内标定量离子色谱峰面积的比值线性关系良好,相关系数分别为0.999 6和0.999 2,检出限分别为1.2、1.4μg/kg。样品加标平均回收率分别为95.8%～108%,79.9%～98.0%,测定结果的相对标准偏差分别为1.92%～13.7%、2.05%～13.8%(n=6)。该方法可用于土壤中乙酸乙酯和丙烯酸乙酯的测定。     

高效液相色谱-电感耦合等离子体质谱测定地下水中碘形态稳定性

研究了高效液相色谱-电感耦合等离子体质谱(HPLC-ICPMS)联用技术测定天然水中IO3-和I-的方法。采用ICS-A23色谱柱分离IO3-和I-,以(NH4)2CO3为流动相,浓度0.03mol/L,流速1mL/min。在Shield Torch高灵敏度条件下,进样量为1mL时IO3-及I-的方法检出限可达到0.035μg/L和0.025μg/L。可满足地下水中碘形态的定量分析。对实验中发现的IO3-及I-标准溶液的ICP-MS响应值存在显著性差异的现象进行了研究,结果表明I-形态的稳定性与溶液介质的关系很大。本实验通过改变标准溶液的储存介质解决了IO3-与I-形态不稳定的问题。在0.01%KOH介质下储存5d,两者的响应值仍能达到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。