土壤样品中放射性核素活度γ谱分析比对

2014年中国计量科学研究院组织γ谱仪放射性核素活度测量全国比对,按照要求使用低本底高纯锗γ谱仪测量土壤样品中的~(241)Am,~(137)Cs,~(60)Co,~(226)Ra,~(232)Th(~(208)Tl,~(228)Ac),~(238)U和~(40)K等常见的天然及人工放射性核素的活度。测量中利用与比对样品几何规格一致的效率源进行效率刻度,采用Gamma Vision谱分析软件进行数据分析。结果显示,土壤样品中的~(241)Am,~(137)Cs,~(60)Co,~(232)Th(~(208)Tl,~(228)Ac)和~(238)U放射性核素活度浓度的测量值与参考值在扩展不确定度(k=2)范围内一致,峰面积、本底、效率刻度、样品自吸收和符合相加效应是影响测量结果的主要因素。     

55Fe液闪计数分析样品源制备方法

利用CIEMAT/NIST方法在液体闪烁计数装置上测量放射性核素55Fe,高质量样品是得到好的测量结果的关键。影响样品源质量的因素有闪烁液的选择,混合物的兼容性、均匀性、稳定性、放射性活度以及液闪计数瓶。在Ultima–GoldAB闪烁液中进行混合物配方试验,优化液体闪烁计数性能,完善满足测量需要的样品源制备方法和影响因素的解决办法,得到55Fe探测效率为0.48的理想结果。     

总α放射性标准源的制备

采用掺标法将放射性核素241Am标准溶液加入到碳酸钙中,经过物理混合得到总α放射性粉末标准源。利用液体闪烁计数法测量掺标物质241Am在碳酸钙基材中的放射性活度,并使用同一测量方法考查了均匀性和稳定性。统计结果显示均匀性FFα,表明组内与组间无明显差异;12个月长期试验稳定性t检验结果符合要求。标准源使用液体闪烁计数法进行绝对测量定值,获得标准源的标准值为9.45 Bq/g,相对扩展不确定度为5.6%(k=2),借助锗γ谱仪能谱分析法验证,偏差为3.0%。该α放射性标准源可用于水中总α放射性测定方法的验证。     

高分辨电感耦合等离子体质谱法测定地质样品中的微量锗

应用高分辨电感耦合等离子体质谱法测定地质样品中的微量锗。研究了地质样品中不同酸消解方法、提取方法对测定锗的影响,以及在高分辨电感耦合等离子体质谱仪高、中、低分辨率模式下测定地质样品中锗的质谱行为。用氢氟酸-硝酸体系分解样品,硝酸提取,在中分辨率模式下进行测定。方法的检出限(3s)为10ng·g-1。方法用于10个国家标准物质中锗含量的测定,测定值与认定值相符,测定值的相对标准偏差(n=10)小于4.5%。     

单扫描极谱法测定食品中苏丹红Ⅰ的不确定度评定

依据标准曲线法建立了单扫描极谱法测定食品中苏丹红Ⅰ的不确定度评定的数学模型,对影响测量结果的不确定度分量进行了分析,较全面地评定了测定结果的不确定度.单扫描极谱法测定食品中苏丹红Ⅰ的不确定度主要来源于峰电流的重复性、标准曲线的影响、样品称量、标准物质的纯度和称量、实验中量器的校准等因素,其中最主要的分量是通过标准曲线拟合求样品溶液浓度时引入的测量不确定度.     

火花源质谱水质定量的分析方法

一、前言火花源质谱分析具有高灵敏度,同时测定多元素和测定较快的特点。目前,广泛用于高纯金属材料、高纯半导体材料、激光材料、矿物、土壤、生物、水质、月球样品诸方面分析测定中,是一种较好的分析方法。火花源质谱法在国内大多数工作为半定量分析,用在水质定量分析尚未见报导。国外应用火花源质谱于水质分析的报导亦不甚多。资料采用静电滴样法,测定水中的Be、Cr、Cu、As、Si、Pb和S,灵     

反应堆退役石墨中36Cl的分析

在反应堆退役中,为有效开展放射性石墨的处理,需对石墨中放射性核素进行测量。~(36)Cl是石墨中一种重要的放射性核素,其半衰期长、环境中易迁移,无法直接测量其活度。为建立满足反应堆退役石墨中~(36)Cl分析的方法,本文将堆退役石墨样品完全溶解后,再通过共沉淀和离子交换去除干扰核素,获得~(36)Cl待测液,然后用液闪测量~(36)Cl的活度。当石墨样品量为0.2g时,该方法的化学回收率为88.7%,最低可探测活度为67mBq·g~(-1),对主要干扰核素有较高的去除能力。该方法可用于反应堆退役石墨中~(36)Cl的分析。     

锗-连苯三酚-过氧化氢体系的催化极谱性质的研究

过氧化氢能被一系列物质在电极上的还原产物所催化分解。我们发现锗(Ⅳ)与邻苯二酚或连苯三酚的络合物对过氧化氢也有催化分解作用。当溶液中有过氧化氢存在时,能使上述络合物的极谱波增高(图1),并在一定浓度范围内,随过氧化氢浓度的增大而线性地增高。可应用此催化波于测定样品中的锗、微量氧或过氧化氢。本文研究锗-连苯三酚-过氧化氢体系的催化极谱性质。在883型极谱仪上应用此催化波测定锗的灵敏度为0.2微克/毫升。     

微型ICP激发源对液体样品中砷与汞的定性分析

将自制微型ICP激发源与氢化物发生器组成实验平台,对溶液中的砷、汞进行了定性分析探索,解决了自制的微型ICP激发源无法测试液体样品的问题。采用硼氢化钠-盐酸体系在氢化物发生器中运用气动型断续流动发生法制取含砷、汞的氢化物气体样品。利用高纯氩作为载气将收集到的样品气体送入微型ICP激发源放电室,在RF功率为12 W,气压为70 Pa的工作条件下起燃后检测到光谱信号,利用Sepcline软件辨识出2条砷(211.30,234.98nm)元素谱线、2条汞(296.73,313.15 nm)元素谱线。实验分析得出了砷、汞检测所用盐酸和硼氢化钠的最佳配比。采用自制微型ICP激发源检测到砷、汞谱线,该激发源可用于液体砷汞样品的定性检测。     

激光功率和积分时间对表面增强拉曼光谱的影响EI北大核心CSCD

表面增强拉曼光谱(SERS)技术能够有效增强低浓度样品的拉曼光谱强度,然而由于SERS的结构、材质等工艺原因,SERS实际应用中往往由于未能正确选择激光功率与积分时间而导致测量效果显著下降。本文以浓度为2,0.08μg/mL的三聚氰胺溶液样品、Au@Ag NPs纳米柱结构固态SERS基底为例,使用自主搭建的便携式拉曼光谱仪,采集不同激光功率和积分时间下的SERS光谱,使用算法平滑光谱、计算光谱基线,得到样品SERS光谱强度和SERS光谱基线强度变化趋势。实验表明,激发光源功率和积分时间改变时,SERS光谱基线强度在不同光谱区域变化幅度不同,部分光谱区域基线强度的变化幅度远大于样品光谱强度,导致使用拉曼光谱仪进行光谱测量时极易造成光谱强度饱和,影响低浓度样品的测量。临时更换样品试剂或SERS基底又会增加成本,且操作繁琐。研究发现,通过控制激光功率和积分时间这2个简单可控的变量,可以在一定程度上抑制SERS光谱基线、提高样品光谱强度,从而避免因光谱强度易饱和而无法测得低浓度样品光谱信号的问题。     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

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.     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

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.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

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。