湿法消解-原子荧光法测定全血中硒

以全血样品为原料,探讨湿法消解-原子荧光法测定全血中的硒含量。血样经硝酸-高氯酸消解后,用硼氢化钠将硒还原成硒化氢,由氩气载入原子化器,产生的原子荧光强度与试液中硒元素含量在一定范围内呈正比,外标法定量。以消解效率为指标,优化样品的消解条件,测定血中硒在0-10μg/L范围内线性情况良好,相关系数为0.9992,最低检出限为0.143μg/L,相对标准偏差为1.51%-1.58%,平均加标回收率为90.86%-104.62%。血中硒的原子荧光测定法灵敏度高,精密度和稳定性好,可应用于血中硒的生物监测。     

Novel thionin-functionalised core shell magnetic nanoparticles for dispersive solid-phase extraction of Hg(II) in food and water samples

To develop an accurate and precise method for separation and pre-concentration of Hg(II), a novel thionin functionalised core shell structure magnetic material has been prepared and characterised. The extraction ability of the material was evaluated by magnetic solid-phase extraction coupled with inductively coupled plasma mass spectrometry determination of Hg(II) in food and water samples. Combining the advantages of magnetic separation with selective extraction of thionin towards Hg(II), the material exhibits enhanced enrich selectivity and efficiency for Hg(II). The experimental parameters influencing Hg(II) extraction efficiency, including pH of the aqueous solution, the dosage of the adsorbent, extraction time and sample volume, were systematically investigated. Under the optimised conditions, concentration of Hg(II) at 1.0 μg L^?1 can be successfully enriched by the material without the interference of the common co-existing ions. The enrichment factor and adsorption capacity were 250 and 75.2 mg g^?1, and precise of the method was confirmed by analysing the spiked food, water samples and standard water reference samples with the recoveries of 92.5–101.8%.     

具有高安全性和有效性的Ⅱ期两阶段临床试验

Ⅱ期临床试验的主要目的是对药物治疗的安全性和有效性进行评估.针对具有高安全性的Ⅱ期两阶段临床试验,给出小样本量下关于安全性和有效性的精确检验方法,并证明最大Ⅰ类错误概率与Ⅱ类错误概率分别在原假设和备择假设的边界处达到.在期望样本量最小原则下,给出最优两阶段设计的构造方法和常用设计表,供实际应用选用.     

Improving signal-to-noise ratio for the forensic analysis of glass using micro X-ray fluorescence spectrometry

Micro X-ray fluorescence spectrometry (μXRF) is a standard technique used for the elemental analysis of glass fragments in forensic casework. The glass specimens encountered in casework are usually small (<1 mm), thin fragments that are partially transparent to the exciting X-ray beam. In addition to providing fluorescence from the small glass fragments, the primary beam X-rays can scatter within the chamber and provide noise in the measurements. To reduce scatter from the sample stage, the fragments are typically mounted on a thin plastic film and raised on an XRF sample cup (≤3 cm in height). However, at these heights, there may still be significant scatter from the sample stage, which adversely affects the signal-to-noise ratio (SNR) and the limit of detection (LOD). A plastic mount was designed and 3D-printed in-house to allow fragments to be raised as high as possible from the sample stage, thereby minimizing stage scatter. Most elements detected in glass showed an improvement in the SNR when using the 3D-printed mount for analyses. The greatest improvement (>30%) was observed for lower atomic number elements (Na and Mg) and higher atomic number elements (Sr and Zr). Another simple method to improve SNR is the use of primary beam filters; when using primary beam filters during analyses, elements with characteristic lines in the high-energy range (Rb, Sr, and Zr) showed the greatest improvement (>70%) in SNR. The impact of both strategies for the improvement of SNR is presented here.     

Nonlinear Measures to Evaluate Upright Postural Stability: A Systematic Review

Conventional biomechanical analyses of human movement have been generally derived from linear mathematics. While these methods can be useful in many situations, they fail to describe the behavior of the human body systems that are predominately nonlinear. For this reason, nonlinear analyses have become more prevalent in recent literature. These analytical techniques are typically investigated using concepts related to variability, stability, complexity, and adaptability. This review aims to investigate the application of nonlinear metrics to assess postural stability. A systematic review was conducted of papers published from 2009 to 2019. Databases searched were PubMed, Google Scholar, Science-Direct and EBSCO. The main inclusion consisted of: Sample entropy, fractal dimension, Lyapunov exponent used as nonlinear measures, and assessment of the variability of the center of pressure during standing using force plate. Following screening, 43 articles out of the initial 1100 were reviewed including 33 articles on sample entropy, 10 articles on fractal dimension, and 4 papers on the Lyapunov exponent. This systematic study shows the reductions in postural regularity related to aging and the disease or injures in the adaptive capabilities of the movement system and how the predictability changes with different task constraints.     

高盐样品中锂的电感耦合等离子体发射光谱法(ICP-OES)测定研究

锂是重要的战略金属和新能源材料,其开发利用受到全球的高度关注。在高盐卤水特别是盐湖卤水和地下卤水中富含巨量的锂资源,在对这些资源进行锂的开发利用过程中,需对锂的含量进行准确测定,然而卤水中共存的高浓度Na+, K+, Ca2+和Mg2+会对微量锂的准确测定产生严重的干扰。电感耦合等离子体发射光谱法(ICP-OES)具有线性范围宽和多元素同步分析能力,针对卤水中锂的快速准确测定,详细开展了高盐样品中锂的ICP-OES分析方法研究。结果表明,锂在610.364 nm处具有较高的信噪比,且Na+, K+, Ca2+, Mg2+和Ar不会对锂的测定产生显著的谱线干扰。然而,样品中大量共存的Na+, K+和Mg2+会对锂的测定产生严重的基体正干扰,而Ca2+产生负干扰。尽管内标法在消除基体干扰方面具有广泛的应用,但传统的以钇和钪为内标元素的内标法不能有效解决该问题。此外,针对标准加入法操作繁琐、不适合批量样品分析问题,以及基体匹配法需多离子匹配,且不适合样品基体组成变化的批量样品分析等问题,考察了采用单一组分进行复杂基体匹配的可行性。由于NaCl广泛存在于卤水中,且对锂的测定具有显著的增敏效应,通过系列研究发现,通过同时向样品和标准溶液中加入10 g·L-1的NaCl,成功解决了总量不超过40 g·L-1的NaCl, KCl和MgCl2所产生的干扰。尽管采用该法或沉淀预分离方式均不能消除Ca2+产生的负干扰,但当样品中Ca2+含量不高于1.8 g·L-1时,对测定不产生显著的影响。通过采用该方法对三种不同基体组成的卤水样品进行加标回收测定,其回收率在96.60%~104.20%范围内。此外,通过与电感耦合等离子体质谱法(ICP-MS)测定结果进行对比,充分论证了该法的准确性和可靠性(相对误差±3.66%)。该法仅以单一的NaCl进行复杂基体匹配,不仅简化了操作,还实现了基体组成变化的批量样品分析,因而在卤水中锂的快速准确测定及锂资源开发利用方面具有重要意义。     

Determination of sulfa antibiotic residues in river and particulate matter by field-amplified sample injection-capillary zone electrophoresis

In the present research, field-amplified sample injection–CZE (FASI–CZE) coupled with a diode array detector was established to determine trace level sulfa antibiotic. Sulfathiazole, sulfadiazine, sulfamethazine, sulfadimethoxine, sulfamethoxazole, and sulfisoxazole were selected as analytes for the experiments. The background electrolyte solution consisted of 70.0 mmol/L borax and 60.0 mmol/L boric acid (including 10% methanol, pH 9.1). The plug was 2.5 mmol/L borax, which was injected into the capillary at a pressure of 0.5 psi for 5 s. Then the sample was injected into the capillary at an injection voltage of –10 kV for 20 s. The electrophoretic separation was carried out under a voltage of +19 kV. The capillary temperature was maintained at 20˚C throughout the analysis, and six sulfonamides were completely separated within 35 min. Compared with pressure injection-CZE, the sensitivity of FASI-CZE was increased by 6.25–10.0 times, and the LODs were reduced from 0.2–0.5 to 0.02–0.05 μg/mL. The method was applied to the determination of sulfonamides in river water and particulate matter samples. The recoveries were 78.59–106.59%. The intraday and interday precisions were 2.89–7.35% and 2.77–7.09%, respectively. This provides a simpler and faster method for the analysis of sulfa antibiotic residues in environmental samples.     

催化光度法时间程序测定土壤中痕量碘

碘是评价环境的重要元素之一,是地球化学勘察样品常测元素。本实验建立了艾斯卡试剂分解-热水提取样品,催化分光光度法时间程序测定碘的方法。详细讨论了艾斯卡试剂手工制作与行星球磨机制作的利弊;;参比液的选择;17℃-25℃不同环境温度条件对实验结果的影响;全程序空白溶液,与36g/L的碳酸钠溶液两种方法制作标准曲线及标准曲线线性范围;样品烧结时间及温度;乙酸用量对样品测试吸光度的影响。结果表明：利用行星球磨机制作艾斯卡试剂,选择试剂空白为参比液,在19℃的恒温环境下,采用36g/L的碳酸钠溶液制作0-8ug/mL标准曲线,样品采用0-300℃、300-500℃、500-750℃三阶段升温,750℃保持30min的烧结程序,乙酸用量为5mL时可以得到可靠的结果。该方法克服了艾斯卡试剂制作困难、样品烧结结块及实验反应速率过快等困难。通过方法学考察表明：基于所建方法碘元素校准曲线系数＞0.999;方法检出限为0.2 mg/kg;测定GSS36、GSS37、GSS38、GSS40、GSS47、GSS48、GSS49等9种国家一级标准物质,结果均在参考值范围内,相对标准偏差RSD＜5%。该方法测定的结果准确度及精密度高、 检出限低、减少碘记忆效应的存在,适用于地球化学勘察土壤样品中碘的测定。     

Magnetic solid-phase extraction of warfarin and gemfibrozil in biological samples using polydopamine-coated magnetic nanoparticles via core-shell nanostructure

Herein, polydopamine-coated Fe₃O₄ spheres were synthesized using a very simple, easy, cost-effective, efficient, and fast method. First, magnetic nanoparticles (Fe₃O₄) were synthesized and were followed by accommodating polydopamine on the surface of the prepared Fe₃O₄. The prepared polydopamine-coated Fe₃O₄ spheres were utilized as a sorbent in magnetic solid phase extraction of gemfibrozil and warfarin (as the model analytes). The extracted model analytes were desorbed by a suitable organic solvent and were analyzed by high-performance liquid chromatography. Under optimized condition, the linearity of the method was in the range of 0.1–200.0 μg/L for the selected analytes in water. The limits of detection were calculated to be in the range of 0.026–0.055 μg/L for warfarin and gemfibrozil, respectively. The limits of quantification were calculated to be in the range of 0.089–0.185 μg/L. The inter-day and intra-day relative standard deviations were determined to be in the range of 1.4%–3.3% in three concentrations in order to calculate the method precision. Furthermore, the enrichment factors were found to be 78 and 81 for warfarin and gemfibrozil, respectively. Moreover, the calculated absolute recoveries were between 78% and 81%. The obtained recoveries indicated that the method was useful and applicable in complicated real samples.