Development of anabolic-androgenic steroids purity certified reference materials for anti-doping

Background

The need for certified reference materials (CRM) of anabolic-androgenic steroids reference materials was emphasized by the Beijing 2008 Olympic game as a tool to improve comparability, ensuring accuracy and traceability of analytical results for competing athletes. The China National Institute of Metrology (NIM) responded to the state request by providing seven anabolic-androgenic steroids (AAS) reference materials for Beijing Olympic anti-doping, GBW (E) 100086-GBW (E) 100092.

Experimental

This work describes the production of the series of AAS CRMs, according to ISO Guides 34 and 35 [1] and [2], which comprises the material processing, homogeneity and stability assessment, CRMs’ characterization including moisture content, trace metal content. The AASs’ purity values were assigned with collaborative study involved eight laboratories applying high resolution liquid chromatography-diode array detector (HPLC-DAD). Homogeneity of the AAS CRMs were determined by an in-house validated liquid chromatographic methodology. Potential degradation during storage was also investigated and a shelf-life based on this value was established.

Results

The certified values of CRMs were 99.76 ± 0.079%, 99.76 ± 0.25%, 99.63 ± 0.09%, 99.67 ± 0.11%, 98.82 ± 0.56%, 96.30 ± 0.39% and 99.71 ± 0.49% (purity ± expanded uncertainty with confidence level of 95%) for methyltestosterone, testosterone propionate, nandrolone, nandrolone 17-propionate, boldenone, trenbolone acetate and testosterone respectively.

Conclusions

The certified values for all the studied AAS reference materials are traceable to the international system of units (SI). The CRMs developed were applied by 32 laboratory including sports organizations and analytical laboratories during the 2008 Olympic game for anti-doping control.     

陕北黄土高原气象要素对植被覆盖的空间分异影响及风险探测

陕北黄土高原地处我国西北生态环境脆弱区,近年来受退耕还林（草）影响,区域植被覆盖变化显著,与气象要素的响应关系也呈现出了复杂的空间分异性和不确定性,亟待厘清。以不同地貌分区为响应单元,探究了陕北黄土高原变绿前后（1982-1992年与2005-2015年）NDVI指数的时空演化特征,分析了植被覆盖变化与气象要素之间的分异性响应关系,并透过最优参数的地理探测器模型（OPGD）探测了气象要素变化对植被覆盖演变的交互影响及风险。研究结果表明：（1）陕北黄土高原及各地貌分区在研究期内NDVI指数均呈显著上升趋势,且阶段化分异明显;各地貌区气温和实际蒸散发量在高原变绿前后趋势变化差异明显,1982-1992年主要呈不显著增加趋势,而2005-2015年则表现为不显著减少趋势;两个时期降水量的空间异质性较为显著,其中北部地区为持续增加趋势,而南部地区则由减少逆转为增加趋势。（2）不同地貌区NDVI指数与气温和蒸散发均呈正相关,且蒸散发与NDVI的相关性强于气温;相对高原变绿前,2005-2015年NDVI指数对各气象要素的响应强度均有所增大。（3）OPGD因子检测结果显示5km空间网格是评价气候变化对陕北黄土高原植被覆盖变化影响的最佳空间尺度,各地貌分区对NDVI指数变化影响最大的气象因子依次为：气温（黄土塬）、降水（盖沙黄土丘陵）、蒸散发（黄土峁状丘陵）、降水（黄土梁状丘陵）、降水（黄土宽谷丘陵）、蒸散发（风沙丘陵）、降水（土石丘陵）;交互探测表明气象因子间的交互作用对NDVI指数的空间分异具有协同增强性,但不同时期各地貌区的主导交互因子略有差异。（4）风险探测发现不同实际蒸散发量对NDVI指数的影响有显著空间差异。（5）陕北黄土高原的植被覆盖变化并不能简单归因于退耕还林（草）等生态修复措施,而应是多要素耦合驱动的结果,气象要素在其中扮演了不可忽视的作用。     

Reliable HPLC separation,vibrational circular dichroism spectra,and absolute configurations of isoborneol enantiomers

Resolution of chiral compounds has played an important role in the pharmaceutical field, involving detailed studies of pharmacokinetics, physiological, toxicological, and metabolic activities of enantiomers. Herein, a reliable method by high‐performance liquid chromatography (HPLC) coupled with an optical rotation detector was developed to separate isoborneol enantiomers. A cellulose tris(3, 5‐dimethylphenylcarbamate)‐coated chiral stationary phase showed the best separation performance for isoborneol enantiomers in the normal phase among four polysaccharide chiral packings. The effects of alcoholic modifiers and column temperature were studied in detail. Resolution of the isoborneol racemate displayed a downward trend along with an increase in the content of ethanol and column temperature, indicating that less ethanol in the mobile phase and lower temperature were favorable to this process. Moreover, two isoborneol enantiomers were obtained via a semipreparative chiral HPLC technique under optimum conditions, and further characterized by analytical HPLC, and experimental and calculated vibrational circular dichroism (VCD) spectroscopy, respectively. The solution VCD spectrum of the first‐eluted component was consistent with the Density Functional Theory (DFT) calculated pattern based on the SSS configuration, indicating that this enantiomer should be (1S , 2S , 4S )‐(+)‐isoborneol. Briefly, these results have provided reliable information to establish a method for analysis, preparative separation, and absolute configuration of chiral compounds without typical chromophoric groups.     

CADEIA and REJECT

CADEIA and REJECT are computer codes for generating γ-γ and γ-X true-coincidence lines for calculation of correction factors for absolute counting of gamma rays in a low energy photon detector. They are written in FORTRAN 77. True-coincidence lines are generated by CADEIA; they are submitted to selection by REJECT according to the rejection criteria defined by L. Moens et al. and F. De Corte. Final relevant lines for true-coincidence correction factors are given as output of REJECT.     

A Simple, Sensitive, and Economic Assay for Choline and Acetylcholine Using HPLC, an Enzyme Reactor, and an Electrochemical Detector

A simple, efficient, economic, and sensitive method is presented for the detection of choline and acetylcholine in neuronal tissue using HPLC, a postcolumn enzyme reactor with immobilized enzyme, and electrochemical detection. The method is based on a separation of choline and acetylcholine by cation exchange HPLC followed by passage of the effluent through a postcolumn reactor containing a mixture of acetylcholinesterase and choline oxidase; the latter enzyme converts choline to betaine and hydrogen peroxide, the former enzyme hydrolyzes acetylcholine to acetate and choline. The hydrogen peroxide produced is electrochemically detected. A simple and efficient preparation of neuronal tissue is described using an optional prepurification step on Sephadex G-10 columns, offering the possibility to detect choline and acetylcholine as well as catecholamines and their related metabolites in the same tissue sample. The sensitivity of the assay system is 250 fmol for choline and 500 fmol for acetylcholine.     

加压毛细管电色谱-微流蒸发光散射联用仪检测5种糖醇

目的:本论文使用加压毛细管电色谱-微流蒸发光散射(p CEC-μELSD)联用仪,建立了一种赤藓糖醇、木糖醇、山梨糖醇、麦芽糖醇和乳糖醇的分离检测方法。方法:实验采用亲水作用色谱柱,80%乙腈-水(含40 mmol/L三乙胺)为流动相,施加+5KV电压进行分离;蒸发光散射检测器蒸发温度120℃,氮气载气流量0.8 L/min进行检测。结果:实验结果表明,5种糖醇在线性范围内线性关系良好,线性相关系数(r)均大于0.998;3个添加水平下的样品平均回收率在82.4%-107.2%之间,相对标准偏差RSD(n=3)小于4.0%;方法最低检出限(LOD,S/N=3)在4-11 ng之间。结论:该方法对比常规HPLC-ELSD法,分离速度快、重现性好、经济环保,具有较高的实用性,为无糖食品中糖醇的定量检测提供了一种快速且行之有效的方法。     

Controls on isoprene emission from trees in a subtropical dry forest

Isoprene emission from vegetation is the single most important source of photochemically active reduced compounds to the atmosphere. We present the first controlled-environment measurements of isoprene emission from leaves of tropical forest trees. Our studies were conducted in the Guanica State Forest in Puerto Rico. We report the effects of temperature and light variations on biogenic isoprene emissions during 1995. Maximum emission rates varied among species from 0 to 268 nmol m^?2 s^?1. Values at the upper end of this range of maximum emission rates are 2–3 times higher than values reported from any temperate taxa. Isoprene emission showed strong sensitivity to light and temperature variations. In contrast to temperate plants, whose emissions tend to saturate at a light intensity of ～1000 μmol m^?2 s^?1, emissions from the tropical species increased with light intensity up to 2500 μmol m^?2 s^?1. The temperature optima for emissions from these plants were similar to those previously reported for temperate plants: ～40 °C. The high maximum emission rates and lack of light saturation indicate that estimates of isoprene emission from tropical forests need to be revised upwards.     

同步辐射小角散射实验站探测系统的改进

同步辐射小角X射线散射（SAXS）实验站所用的探测器由原来的NaI闪烁计数器改为位置灵敏探测器,其位置分辨好于100 μm,有效探测面积为50 mm×10 mm,得到了较以往更高质量的SAXS谱,并成功地对液体样品的SAXS谱进行了测试.