激光剥蚀电感耦合等离子体质谱小激光斑束线扫描定量分析技术

采用激光剥蚀-扇形磁场电感耦合等离子体质谱(LA-SF-ICP-MS)技术建立了小激光斑束(15μm)线扫描定量分析方法。对比了硅酸盐矿物LA-ICP-MS分析中不同激光进样模式(点剥蚀和线扫描)对于元素信号强度和分馏效应的影响。小激光斑束点剥蚀分析元素信号强度随时间下降明显,并且剥蚀过程中元素深度分馏效应影响明显。深度分馏效应主要是由于各元素倾向于富集在不同粒径颗粒中,而不同大小颗粒在剥蚀坑附近发生冷凝沉淀的几率差异造成。实验结果表明,相对于内标元素Ca,Na、K、Cr、Co、Cd和U等元素富集在更小颗粒中;Cu、Zn、V、Mn、Fe、Ni、Tl、W、Rb、Cs等元素与Ca富集行为相似;Al、Y、Sc、Zr、Nb、Hf、Ta、Th和REE等元素易进入大颗粒中。线扫描分析具有高且稳定的元素信号强度,分析过程中剥蚀行为一致,不受深度剥蚀效应的影响。采用双剥蚀池结构进样系统研究单脉冲激光剥蚀信号结构,不同元素信号强度降低至50%需0.8~1.2 s;降低至20%需1.2~1.6 s;降低至背景值需2~3 s。本研究通过优化仪器参数降低信号叠加作用的影响,在均质和非均质样品(榍石)线扫描分析中,获得了准确的元素含量和元素比值。线扫描定量分析技术可有效降低激光斑束(≤15μm),相对于采用线扫描元素强度分布研究,数据更加直观,可表现元素比值的变化特征。通过调整激光斑束大小和扫描速度可在不同分辨率尺度下全面了解矿物中元素的分布特征。     

火花源质谱法定量分析高纯氧化钬和氧化镥中痕量元素

本文采用相对灵敏度因子，研究了９９．９９９％－９９．９９９９％的Ｈｏ２Ｏ３和Ｌｕ２Ｏ３中４０余种杂质元素的火花源定量分析方法，讨论了谱线干扰。做了加入回收及生理性实验，大多数元素的相对标准偏差在３０％以内，检测下限为０．００ｘμｇ／ｇ。     

激光双光路定量分析方法探讨

目前,国内外关于激光显微光谱定量分析方面的文章报导甚少,一般处于定性、半定量分析阶段。其原因是多方面的,最主要的是激光仪器的综合稳定性不够;还有自然界被分析样品是多种多样的,用人工的方法很难制备出一套与天然样品在化学成分及物理性能上很相似的标准样品,特别是样品中的夹杂物及各种材料的腐饨产物等无主量元素的定量分析问题     

看谱法分析镍基高温合金中的铪

交流电弧火花发生器与样品之间产生交流电弧,使用光栅看谱镜对弧光的可见光光谱进行观测。采用531.16 nm处铪元素谱线为分析线,531.02 nm处钴元素谱线为比较线,对镍基高温合金样品中的铪元素含量进行定性和半定量分析。当观测到Hf 531.16 nm稳定出现并且强度小于Co 531.02 nm时,可判定样品中铪元素质量分数约为1%～2%;若观测不到Hf 531.16 nm时,可判定样品中铪元素质量分数小于1%。采用电感耦合等离子体原子发射光谱法对样品中铪元素含量进行测量,测定结果与看谱分析结果一致。看谱分析法可用于镍基高温合金中铪元素的定性、半定量分析和牌号鉴别。     

二甲苯的联合散射光谱分析

近年来,国内外利用联合散射光谱进行碳氢化合物的定量分析方面作了不少工作。以联合散射光谱进行定量分析,是根据谱线强度与化合物的含量成正比这一原理进行的。Ландсберг等发表了大量的碳氢化合物联合散射光谱的强度数据。按照这些数据进行定量分析,无需配制标准混合物系列,从而避免了制备纯化合物的困难。因此,该数据很有实用意     

头发元素分析的科学意义及医学应用价值

对近100年来头发元素分析发展历史作了简要回顾，并从头发元素水平代表身体元素总体水平、头发元素含量可以准确测定，以及头发元素分析可用于医学诊断等三个方面论述了头发元素分析的生物学基础及临床意义，重点介绍了中国科学工作者在实验研究和临床实践中的探索和发现。科学实践证明，头发元素分析不仅为揭开古代头发神话提供了解释基础，也为头发的现代应用提供了可靠工具和科学依据。     

分枝定界算法用于有机混合物的同时定性定量分析

分枝定界法用于多组分同时定性定量分析，只需解析一份试样测得的数据，即可同时得到待测样品中所含组分的种类、数目及含量，具有简单、快速、准确等优点。此文对分枝定界法在判据应用方面进行了改进，应用四个判据，解决了最佳子集难判断的问题。建立了精蒽中不经分离同时测定蒽、菲和咔唑的方法。     

X-射线荧光光谱法(XRF)测定钼精矿中多种元素

详细论述了压片法及熔融片法测定钼精矿的分析条件。其中压片法通过大量采用同一矿区的生产样品经化学定值后作为校准样品建立校准曲线,因此粒度效应和矿物效应基本上可忽略。详细地讨论了元素之间谱线干扰、背景和脉冲高度选择。使用经验系数法校正基体效应,可准确测定钼精矿中的钼、硫、铁、铜、铅、锌等11种元素。在熔融片法中主要讨论了元素谱线的选择及其相互之间的干扰,经理论α系数校正后,可准确测定不同钼矿中的多种元素,其适用范围更广。     

目标特征谱线选取对猪肉中Cr元素LIBS检测精度比较

结合激光诱导击穿光谱和线性回归对猪肉中Cr元素进行定量分析,比较了Cr特征谱线单变量分析与多变量分析对猪肉中Cr元素检测精度的影响。先采用特征谱线Cr I425.43nm进行单变量分析,得到Cr浓度与LIBS强度的线性相关系数为0.9434;再利用Cr的三特征谱线Cr I425.43nm,Cr I427.48nm,Cr I428.97nm进行多变量分析,研究了Cr元素预测质量分数与实际质量分数之间的线性相关性。结果显示,单变量分析与多变量分析的线性相关性分别为0.9749和0.9769,定标集平均预测相对误差分别为4.8%和4.2%,验证集AREP分别为5.3%和3.3%。结果表明,选取目标元素Cr的单特征谱线与多特征谱线均能对样品Cr含量进行有效预测,多变量分析能在一定程度上提高Cr元素含量预测的准确性但与单变量比较差异性不大,且采用单一最灵敏线定量分析更简便可行。     

电感耦合等离子体原子发射光谱法同时测定植物样品中多种元素

本文为环境样品分析建立了准确、灵敏、快速的分析方法,探讨了酸类及酸度对谱线强度的影响,同时对基体元素的谱线干扰进行了校正和背景扣除,测定了环境背景值样品树干和树叶中15种元素,经标样测定结果满意。     

A wavelength table for emission lines of non-metallic elements with transition assignments and relative intensities observed in an atmospheric pressure helium microwave-induced plasma

The emission lines of 10 non-metallic elements (H, C, N, O, F, Cl, P, S, Br and I) excited by an atmospheric pressure helium microwave-induced plasma have been tabulated with their relative intensities and transitions. These non-metallic elements were introduced into the plasma mostly as the vapor of organic compounds, although the emissions of H, N and O were observed due to the impurities in the helium gas. The spectral lines observed in the wavelength region from 190 to 850 nm were assigned with reference to established wavelength tables and tables of atomic energy levels. All emission line intensities of an element were normalized with respect to the most intense emission line of the element taken as 100.     

Interelement correlations detectable in plant samples based on data from reference materials and highly accurate research samples

Summary A correlation analysis of 45 elements from various plant standard reference materials provided a number of highly correlated element pairs (r0.9) leading to the expectation of an interelement interaction. For the elements Fe³⁺, Al³⁺, Sc³⁺ and the lanthanides, these high correlations may be attributed to the similar ionic radius of the hydrated ions or the same charge. The highly correlated occurrence of some macroelements such as P and N reflects the close association of the two elements, particularly during protein biosynthesis. Of the alkali metals, K, and the alkaline earth metals Ca, Mg and, to some extent, also Sr display high correlations amongst themselves and with the macronutrients N and P. In correlating the transition elements with each other and with the micro- and macroelements, it was only possible to find a few high correlation coefficients; only the two element pairs Co/Mo and Cr/Co display high correlation coefficients. One of the reasons for this is probably the inaccuracy of the data material. It was not possible to confirm the highly negatively correlated element pairs reported in earlier work. It was not even possible to determine a clear negative trend for typical pairs of antagonists such as Al/Ca or Mn/Ca. The highest negative correlation was found for the B/Sb element pair at r=–0.75.     

Synthesis and application of quinazoline-oxazoline-containing (quinazox) ligands

A practical synthesis of potentially tridentate P,N,N-ligands containing two stereogenic elements incorporated into the axially chiral Quinazolinap and centrally chiral 2-oxazoline subunits is reported. The application of these novel hybrid ligands in Pd(0)-catalyzed asymmetric allylic alkylation revealed the matched and mismatched diastereomer, dominant stereogenic element, as well as the effect of the oxazoline R substituent on the level of enantioselectivity (ee's up to 81%). [structure: see text]     

四川某金矿中非金属单矿物的元素分析及意义

利用中子活化分析法对四川某地区的非金属单矿物(热液脉矿物)的元素进行了测试,并利用元素地球化学研究方法对元素间的相关关系进行了分析。结果表明,在该地区可以利用元素间的伴生关系指导找矿。     

Use of low-background instrumental neutron activation analysis to measure contaminants in silicon and biological samples

Instrumental Neutron Activation Analysis (INAA) is a common method of trace element analysis whose sensitivity is limited either by interference from other trace elements in the sample or by interference from ambient background radiation in the detection system. In at least two cases, a true low-background facility, such as that at Lawrence Berkeley National Laboratory, substantially enhances senitivity: (1) Ultra-pure silicon, such as that used in semiconductor fabrication. Even after prolonged exposure within a nuclear reactor, minimal observable gamma-ray emitting activities are produced in the silicon. Extrapolated from our 7 gram sample size experiments, parts-per-quadrillion (1.E-15) sensitivity to 23 elements should be obtainable for 400 gram sample sizes. (2) Similarly, the life elements H, C, N, O are effectively inert within the reactor, and this enhances sensitivity to trace elements in, for example, bacteria. Data will be presented for these two cases.     

Prediction of the adsorption behavior of elements 112 and 114 on inert surfaces from ab initio Dirac-Coulomb atomic calculations

The interaction of elements 112 and 114 with inert surfaces has been studied on the basis of fully relativistic ab initio Dirac-Coulomb CCSD(T) calculations of their atomic properties. The calculated polarizabilities of elements 112 and 114 are significantly lower than corresponding Hg and Pb values due to the relativistic contraction of the valence ns and np(12) orbitals, respectively, in the heavier elements. Due to the same reason, the estimated van der Waals radius of element 114 is smaller than that of Pb. The enthalpies of adsorption of Hg, Pb, and elements 112 and 114 on inert surfaces such as quartz, ice, and Teflon were predicted on the basis of these atomic calculations using a physisorption model. At the present level of accuracy, -DeltaH(ads) of element 112 on these surfaces is slightly (about 2 kJ/mol) larger than -DeltaH(ads)(Hg). The calculated -DeltaH(ads) of element 114 on quartz is about 7 kJ/mol and on Teflon is about 3 kJ/mol smaller than the respective values of -DeltaH(ads)(Pb). The trend of increasing -DeltaH(ads) in group 14 from C to Sn is thus reversed, giving decreasing values from Sn to Pb to element 114 due to the relativistic stabilization and contraction of the np(12) atomic orbitals. This is similar to trends shown by other atomic properties of these elements. The small difference in DeltaH(ads) of Pb and element 114 on inert surfaces obtained within a picture of physisorption contrasts with the large difference (more than 100 kJ/mol) in the chemical reactivity between these elements.     

Elemento-Organic Amines and Imines

Amines with mixed substituents containing two or three El? N bonds

1 El = a higher IVa, Va, or VIa element; by IVa, Va, and VIa elements are meant elements of the IV, V, and VI main groups of the periodic system

. are relatively stable if one or two of these bonds are (CH₃)₃ Si? N bonds. IR and ¹H? NMR studies indicate that the (p → d)π bond components of the element-nitrogen bonds steadily decrease from silicon, phosphorus, and sulfur toward their higher homologs. Because of the differences in the polarities of the element-nitrogen bonds, these substances can be used for selective insertion and cleavage reactions. The reaction of metalated N-silylaminoarsines with methyl chloride as well as the reaction of metalated N-trimethyl(IVa)-element-substituted amino-tert-butylphosphines with halogenotrimethyl(IVa) element compounds open new, simple routes for the conversion of elemento-organic amine systems into imine systems. The problem of reversible and irreversible (CH₃)₃ El ligand migration (1,3 shift) is discussed for trimethyl(IVa)element-substitued benzamidines, diaminophosphines, aminoiminophosphoranes, sulfinamides, and aminosulfimines.     

Non-metal element detection by radio-frequency glow-discharge optical-emission spectrometry (rf-GD-OES) for determination of sol–gel-immobilized nucleotides

A new method is presented for qualitative and quantitative determination of non-metal elements present in organic analyte species immobilized in a sol–gel matrix. Nucleic acids were chosen as well-defined relevant biomolecules for which element ratios could be used for detection and identification. Solid, lyophilized powders of ribose-form nucleotides (AMP, ADP, and ATP) were immobilized/entrapped in a methlytrimethoxysilane (mTMOS) sol–gel matrix and monitored for P (I) 214.9 nm, C (I) 193.0 nm, O (I) 130.2, and N (I) 149.3 nm emission by radio-frequency glow-discharge optical-emission spectroscopy (rf-GD-OES). Using the sol–gel method, analytical blanks were obtained by use of un-doped sol–gels. Empirical formula calculations by use of P (I) and C (I), P (I) and N (I), and P (I) and O (I) emission response ratios demonstrate the versatility of the technique as an element and species-specific detector. Results show there is high correlation between phosphorus and oxygen emission responses and the extent of phosphorylation, demonstrating the capacity of the method to produce vital qualitative and quantitative information for the specific nucleotide. Absolute sub-nanogram detection limits were achieved for all the elements studied.     

Determination of trace elements in total particulate matter of cigarette smoke by instrumental neutron activation analysis

Trace elements play an important role in the metabolism of the human body. Some of the trace elements are essential, whereas others are toxic and even carcinogenic. Cigarette smoke contains many of these hazardous trace elements. Tobacco samples have been analyzed by the authors for their trace element contents and the results have been reported earlier. This paper presents results on the trace element content analyzed in cigarette smoke using an automatic smoking machine developed in this laboratory to simulate actual smoking pattern. The trace element levels in the total particulate matter samples of the cigarette smoke collected on filter papers were measured and compared with those of cigarette smoke condensate reported in the literature. Both methods of collection give comparable results.     

南昌大学（北区）饮用水中As,Se,Hg,Zn,Fe等无机元素的研究

从南昌大学和水的Ａｓ、Ｈｇ、Ｐｂ、Ｃｄ、Ｓｅ、Ｚｎ等１０种无机元素的测定研究入手，论述了这些无机元素与人体的关系。并将南昌大学的饮用水和南昌市市区饮用水与生活用水水质标准进行对比，证明南昌大学的饮用水并未污染。