锂同位素分离

锂的同位素在核能源中具有重要应用,锂同位素分离近年受到世界各国政府和学术界的高度重视,开展了大量的理论与应用研究工作,并在许多领域,尤其是非汞萃取体系取得了很大的进展。本文对目前主要的锂同位素分离方法如锂汞齐法、萃取法、离子交换色谱法等进行了较为系统的总结、归类及评述。     

锂化学试剂中锂同位素丰度及原子量的异常

锂化学试剂中锂同位素丰度及原子量的异常刘卫国，肖应凯，周引民（中国科学院青海盐湖研究所，西宁８１０００８）在１９９３年第３７届国际纯粹与应用化学联会（ＩＵＰＡＣ）上，原子量与同位素丰度委员会（ＣＡＷＩＡ）根据世界上对锂化学试剂中锂同位素丰度异常的报道...     

多齿络合法分离锂同位素的冠醚化学

锂的两种天然同位素锂-6和锂-7在核能工业中具有重要的作用.在众多锂同位素的分离方法和体系中,多齿络合法普遍具有较高的同位素分离系数.冠醚由于其对金属阳离子具有较强的选择性络合能力,被认为是多齿络合法分离锂同位素最有效的萃取剂.综述了冠醚及冠醚树脂在多齿络合法分离锂同位素中的应用,并简述新型金属冠醚与金属离子络合的进展,展望其在锂同位素分离中的潜在应用前景.     

冠醚B15C5萃取分离锂同位素的阴离子效应

本文研究了B15C5冠醚萃取锂盐时,不同阴离子对体系的同位素分离效应的影响。结果表明,阴离子在冠醚萃取过程中不仅对萃取络合物的稳定性有显著影响,而且阴离子半径及软度越大时,萃取体系的锂同位素分离系数(α_(LI))也越大。     

我国锂矿物中锂同位素丰度研究

锂同位素~6Li和~7Li由于相对质量差相当大,在自然界矿物形成时发生同位素分馏效应很明显。国际原子量委员会“元素的同位素丰     

大气气溶胶中锂的化学分离与同位素比的质谱检测

通过大量条件实验,确定离子交换法分离Li+、Na+的最佳淋洗条件柱填料为Dowex-50w×8阳离子树脂,柱高为12 cm,淋洗液为0.8 mol/mL HCl-50%CH3OH,淋洗速度约为0.48 mL/min.采用离子交换法分离大气气溶胶中Li与其它元素,采用Li3PO3为样品涂样形式的热电离质谱法测量了大气气溶胶中Li的同位素比值.化学分离过程中Li的回收率大于95%,大气气溶胶中稳定Li同位素6Li/7Li比值为0.08206.     

人牙齿中锶的特效树脂分离及其同位素测定

采用锶特效树脂(Sr-Spec)建立了快速分离富集人牙齿中微量元素锶,并测定87Sr/86Sr的有效方法。采用HNO3-HClO4体系消解牙齿样品,以8mol/L HNO3为介质上柱,8mol/L HNO3淋洗,0.05mol/LHNO3洗脱,收集淋洗液,蒸干;采用正热电离质谱法进行87Sr/86Sr的测定。结果表明,利用Sr-Spec树脂,不仅能将锶与基质中大量钙分离,并能有效分离同位素测定中干扰元素铷。本方法可以缩短分离时间,提高分离效率,减少试剂用量,降低实验空白。采用本方法对陕南地区人牙齿牙釉质中锶进行分离,测得的87Sr/86Sr值在0.710948～0.711037之间。     

阳离子交换树脂在线富集／火焰原子发射光谱法直接测定健康人尿中锂的研究

采用732磺酸型阳离子交换树脂在线富集、4mol／L HCl洗脱，直接进样火焰原子发射光谱法测定健康人尿中的痕量锂。方法可消除尿中大量有机物的干扰，富集5．0mL标准试液比直接测定信号增大3．5倍，绝对检出限达7．5ng。标准加入法5次测定尿样的RSD为4．7％。     

TODGA树脂小柱分离-多接收电感耦合等离子体质谱（MC-ICP-MS）法测定岩石样品中Nd同位素比值

通过改进岩石样品分析物Nd的化学分离,实现Nd同位素比值的准确分析,为研究青藏高原岩石成因,揭示物质来源提供技术支持。采用TODGA萃淋树脂分离基体及其与Nd相邻的稀土元素,多接收电感耦合等离子体质谱（MC-ICP-MS）法测定Nd同位素比值,建立了简捷实用的地质样品Nd同位素分析方法。样品HF-HNO3分解, HNO3(3 mol/L )- H3BO3(0.12 mol/L)提取,上柱后,先用6 mL HCl(2.8 mol/L)淋洗干扰轻稀土,再用6 mL HCl(2.2 mol/L)淋洗分析物Nd,Nd淋洗液由MC-ICP-MS测定其同位素比值。分析国际岩石标准物质BCR-2、BHVO-2和AGV-2,所得143Nd/144Nd同位素比值（平均值 ± 2σ）分别为0.512638 ± 0.0000007、0.512990 ± 0.0000012和0.512792 ± 0.000016,这些同位素数据在误差范围内,与推荐值和文献值完全一致。方法适合各种类型地质样品,为西藏不同地区不同岩石提供了可靠的Nd同位素分析数据。     

Determination of Background Concentrations of Ag,Pd, Pt and Au in Highly Mineralized Ground Waters at Sub-ng L–1 Concentrations by Online Matrix Separation/Pre-Concentration Coupled to ICP-SFMS

Though not regulated in directives such as the Water Framework Directive of the European Union, the investigation of geogenic background concentrations of certain elements such as precious metals is of increasing interest, in particular for the early detection of a potential environmental pollution due to the increased use in various industrial and technological applications and in medicine. However, the precise and accurate quantification of precious metals in natural waters is challenging due to the complex matrices and the ultra-low concentrations in the (sub-) ng L⁻¹ range. A methodological approach, based on matrix separation and pre-concentration on the strong anion exchange resin TEVA^® Resin in an online mode directly coupled to ICP-SFMS, has been developed for the determination of Ag, Pt, Pd and Au in ground water. Membrane desolvation sample introduction was used to reduce oxide-based spectral interferences, which complicate the quantification of these metals with high accuracy. To overcome errors arising from matrix effects—in particular, the highly varying major ion composition of the investigated ground water samples—an isotope dilution analysis and quantification based on standard additions, respectively, were performed. The method allowed to process four samples per hour in a fully automated mode. With a sample volume of only 8 mL, enrichment factors of 6–9 could be achieved, yielding detection limits <1 ng L⁻¹. Validation of the trueness was performed based on the reference samples. This method has been used for the analysis of the total concentrations of Ag, Pt, Pd and Au in highly mineralized ground waters collected from springs located in important geological fault zones of Austria’s territory. Concentrations ranges of 0.21–64.2 ng L⁻¹ for Ag, 0.65–6.26 ng L⁻¹ for Pd, 0.07–1.55 ng L⁻¹ for Pt and 0.26–1.95 ng L⁻¹ for Au were found.     

Determination of Boron with Isotope Dilution Method

100 ng or less amount of boron in the form of Na₂B₄O₇ was loaded on tantalum filament of thermal ionization mass spectrometer. A serial isotope ratios of metaborate, Me=88 (Na₂ ¹¹BO₂) and Me=89 (Na₂ ¹¹BO₂) prepared with spike (¹⁰B enriched) and nature boron were determined successfully and compared with reference values.     

丙烯腈和二甲基亚砜中铁离子的高效低成本纯化

D315, D311, D301和D335四种大孔弱碱型丙烯酸系阴离子交换树脂被用来吸附丙烯腈和二甲基亚砜中的Fe^3＋, 以纯化丙烯腈和二甲基亚砜. 通过改变温度、用量比和时间等实验条件以寻找最优的纯化条件, 实验结果证明D315大孔弱碱型丙烯酸系阴离子交换树脂的吸附效果是最佳的, 能够在室温下达到高效率低成本地纯化丙烯腈和二甲基亚砜中的Fe^3＋.     

树脂法分离纯化倒提壶生物碱的研究

采用阳离子交换树脂和大孔吸附树脂联用的方法,将倒提壶生物碱提取液依次经过阳离子交换树脂和两次大孔吸附树脂,对其中的天芥菜碱和毛果天芥菜碱进行分离纯化。结果表明,倒提壶生物碱溶液采用阳离子交换树脂经过水洗和NaCl洗脱与大孔吸附树脂两次经乙醚和50%乙醇洗脱后,毛果天芥菜碱与天芥菜碱的纯度分别从0.73%和2.2%提高至81.6%和79.2%,提取量分别由4.6 mg/g和10.7 mg/g提高至50.6mg/g和92.7 mg/g。该文所建立的分离纯化方法具有成本低、污染小、周期短、操作简便和分离纯化效率高等特点,适合工业化生产。     

簿层树脂相吸光光度法测定痕量钴的研究

提出了用薄层树脂相通过光度法测定痕量钴的新方法。本法具有灵敏度高，选择性好，快速等特点。钴离子（Ⅱ）与４－（５－氯－二吡啶）偶氮］－１，３－二氨基苯（简称５－Ｃｌ－ＰＡＤＡＢ）生成有色稳定配合物，将其富集在Ｈ＋型（７３２~＃）。阳离子交换树脂上，制作成薄层直接测定，λ_（ｍａｘ）＝５７１ｎｍ。本法既克服了需特制１ｍｍ比色皿的困难，又提高了测定精密度，使推广树脂相光度法成为可能。用本法实测了天然水中痕量钴，检测限２．８μｇ·Ｌ~（－１），回收率≥９８％。     

小肠蔗糖酶的化学修饰及对酶活力的影响

考察了苯甲基磺酰氟、N-溴化琥珀酰亚胺、琥珀酸酐、三硝基苯磺酸对猪小肠蔗糖酶活性的影响。将猪小肠匀浆后的粗提取物进行分段盐析、DEAB-Sepharose柱层析及Sephacryl S-200、Sephadex G-200凝胶过滤等纯化步骤，得到聚丙烯酰胺凝胶电泳为单一蛋白质区带，比活力为1．79units/mg，经12％SDS-聚丙烯酰胺凝胶电泳为一条区带，其亚基相对分子质量为51000。该酶的功能基团是半胱氨酸的巯基，蔗糖酶分子内没有二硫键存在。     

Facile synthesis of meso-substituted dipyrromethanes and porphyrins using cation exchange resins

The macroporosity and acidity of cation exchange resins play a crucial role in the synthesis of dipyrromethanes and porphyrins; for the first time, cation exchange resins have been used as heterogeneous solid acid catalysts to produce dipyrromethanes and porphyrins in good yields. The reaction, at room temperature, of substituted aromatic aldehydes with pyrrole catalysed by cation exchange resin afforded the corresponding meso-substituted dipyrromethane in yields ranging from 70 to 80%, indicating the broad scope of the reaction. Further, the condensation of meso-substituted dipyrromethane with similar or different substituted aromatic aldehydes, using cation exchange resins furnished meso-tetrakis-symmetrical and mixed porphyrins, respectively. One-pot synthesis of porphyrins can also be carried out directly from the aldehydes and pyrrole under the above conditions. Acidolysis of the dipyrromethane is negligible under the conditions of the porphyrin-forming reaction.     

Transition-Metal-Free Carbon Isotope Exchange of Phenyl Acetic Acids

A transition-metal-free carbon isotope exchange procedure on phenyl acetic acids is described. Utilizing the universal precursor CO₂, this protocol allows the carbon isotope to be inserted into the carboxylic acid position, with no need of precursor synthesis. This procedure enabled the labeling of 15 pharmaceuticals and was compatible with carbon isotopes [¹⁴C] and [¹³C]. A proof of concept with [¹¹C] was also obtained with low molar activity valuable for distribution studies.     

氧化镁烧结-电感耦合等离子质谱法测定冰铜中的铼

本文建立了一种利用电感耦合等离子体质谱法（ICP-MS）测定冰铜中铼的方法。样品经氧化镁烧结,热水浸取法处理,溶液经732强酸型阳离子交换树脂处理交换去除干扰离子,实现了ICP-MS直接测定冰铜中的铼。实验结果表明,在最佳试验条件下,方法的检出限可低至0.010mg/t,加标回收率为92.00%~104.00%,测定结果的相对标准偏差（RSD,n=7）小于5%,测定结果令人满意。由此可见,该方法精密度高,准确度高,可用于冰铜中铼的测定。