重要性采样方法与自由能计算

分子动力学模拟与自由能计算已经在化学、生物学与材料学等领域得到广泛的应用。然而,由于在传统分子动力学模拟的时间尺度内,体系很难跨越较高的自由能能垒,在相空间内的采样大大受限,采样困难使自由能计算难以收敛。增强采样是解决这一问题的有效途径,重要性采样方法就是其中一类。本文综述了四种广泛应用的重要性采样方法--伞状采样方法、metadynamics方法、自适应偏置力方法和温度加速分子动力学方法的原理和进展,其中重点概述了自适应偏置力方法的最新发展--扩展自适应偏置力方法和扩展广义自适应偏置力方法,并对这四种重要性采样方法的优缺点进行了比较。最后,讨论和展望了重要性采样与自由能计算方法面临的挑战和前景,并提出了对自适应偏置力方法可能的改进,如与加速分子动力学（aMD）或弦方法结合以提高在高维度空间中的采样效率。     

对科学方法和科学方法教育的再认识——祝贺《化学教育》30周年刊庆

科学方法是科学活动经验升华、程序化、规范化、强化的结果,是科学活动的过程规定性工具。方法的思维是科学方法的精髓。对具体的科学方法进行概括,形成科学方法的适用范围不同的层次。科学方法大体上可以分为经验方法、理性方法和具有补充、完善意义的"第三类方法"以及综合性方法。科学方法有局限性,需要关注方法的改进,注意创新。要搞好科学方法教育,必须以科学方法形成和发展的规律为基础,既要考虑科学方法的特点,也要考虑教育对象的特点。     

数据离群值的检验及处理方法讨论

由目前普遍使用的分析化学教材中与离群值相关的内容出发,对其进行对比和分析,说明数据离群值检验的意义和重要性。对几种常见的离群值判定方法进行了列举和比较,并对已确认为异常值的数据的处理方法也进行了对比和讨论。各种检验和处理方法各有其优势和劣势,根据实际情况选择不同方法或多种方法配合使用,能够更好地实现对离群值的检验和处理。     

色谱峰纯度的定性方法

较系统地介绍了近年来国内外文献中有关色谱峰纯度的定性方法──仪器方法和化学计量学方法。仪器方法重点介绍了归一化比较光谱、吸收比法、光谱抑制法及导数技术。化学计量方法介绍了主成分分析法和渐近因子分析法。通过对文献方法和应用的简单介绍,比较了各种方法的特点及优缺点,总结了规律。     

对微孔吸附常用经典分析模型的比较

文章采用列表对比的方式,简要介绍了微孔吸附常用经典模型的出处、应用范围、发展历史和各自的特点。为了方便系统了解和掌握物理吸附中的微孔经典分析方法,文章将其分成三类：(1)由标准等温线发展出的方法,包括t-图法、αs-图法、n-图法和MP法;(2)基于微孔填充理论的方法,包括D-R方法、D-A方法和D-R-S方法;(3)目前普遍使用的方法,包括原始HK方法(狭缝型孔)、HK-SF方法(圆柱型孔)和HK-CY方法(球型孔)以及三种改进后的HK方法。     

烟草制品及烟气中重金属检测方法的研究进展

从烟草制品及其烟气的前处理方法和检测方法两方面对烟草中重金属含量测定的研究进展进行了综述。重点介绍了湿法消解、微波消解、萃取和悬浮进样技术等样品前处理方法,以及原子光谱法、质谱法和液相色谱法等测定方法。列举了不同方法的灵敏度、准确性和适用范围,对各方法的优缺点进行了比较,并对烟草中重金属检测方法的发展进行了展望。     

中学化学中的科学方法教育与课程教材改革

本文论述了什么是科学方法;科学方法的特点、性质、类型和结构;为什么要重视科学方法教育;中学化学中应该着重进行哪些科学方法教育;怎样才能有效地进行科学方法教育等问题。指出:科学方法是科学素质的重要构成因素。加强科学方法教育是全面提高学生素质、保证学生可持续发展的需要,也是搞好当前的课程教材改革的需要。文中提出了确定中学化学中科学方法教学内容的原则、各年级教学内容和教学要求的设想,还就科学方法教育的途径和原则提出了自己的看法。作者认为,科学方法教育要力戒教条式灌输,要注意让学生在积累经验基础上进行归纳;重视组织学生参加有关的实践活动;科学方法教育要跟科学精神、科学思想和科学知识的教育相互结合,跟人文精神教育结合。在进行科学方法教育时,还应该重视技术方法教育。     

微流控芯片设计方法研究进展

本文综述了微流控芯片设计方法的研究进展,归纳和总结了目前主要的设计方法,包括数值模拟法和基于宏模型的设计方法。最后介绍了宏-微模型设计方法,通过建立宏-微接口,实现了数值模拟和宏模型的灵巧桥接,有助于改善微流控芯片设计方法的兼容性和自适应性。     

重量法配气的称量数学模型及其不确定度评定

对重量法制备气体标准物质中充入气体质量的计算方法进行了研究,建立了基于单盘电子天平的钢瓶称量方法,并建立了系统的数学模型和不确定度评价方法。为重量法制备气体标准物质提供一种简单、实用和精确的钢瓶称量方法和气体加入质量的计算方法。     

纳米银粒子的制备方法进展

综述了纳米银粒子的制备方法,包括物理方法和化学方法。     

Fast determination of trace elements on aerosol-loaded filters by X-ray fluorescence analysis considering the inhomogeneous elemental distribution

X-ray fluorescence (XRF) analysis was successfully applied for the determination of Ca, Cu, Fe, Mn, Ni, Pb, V and Zn on aerosol filters with a diameter of 150 mm. Ambient aerosol was collected on quartz-fibre filters by Digitel high-volume samplers. For XRF analysis three small filter pieces with a diameter of 32 mm were cut out of each filter, considering the radial dependence of elemental distribution on the filter. Elemental concentration decreases by 8–10% from the centre to the outer circle for coarse mode elements. Distribution of fine mode elements display only small radial dependence (2–4%). Results of quantitative analysis by XRF were compared with atomic spectrometric methods (GF-AAS, ICP-OES). The good agreement between the methods confirmed the application of XRF spectrometry for routine analysis of filter samples loaded with ambient aerosol.     

Fast determination of trace elements on aerosol-loaded filters by X-ray fluorescence analysis considering the inhomogeneous elemental distribution

X-ray fluorescence (XRF) analysis was successfully applied for the determination of Ca, Cu, Fe, Mn, Ni, Pb, V and Zn on aerosol filters with a diameter of 150 mm. Ambient aerosol was collected on quartz-fibre filters by Digitel high-volume samplers. For XRF analysis three small filter pieces with a diameter of 32 mm were cut out of each filter, considering the radial dependence of elemental distribution on the filter. Elemental concentration decreases by 8-10% from the centre to the outer circle for coarse mode elements. Distribution of fine mode elements display only small radial dependence (2-4%). Results of quantitative analysis by XRF were compared with atomic spectrometric methods (GF-AAS, ICP-OES). The good agreement between the methods confirmed the application of XRF spectrometry for routine analysis of filter samples loaded with ambient aerosol.     

金属材料分析国内外标准中波长色散X射线荧光光谱法的应用

对国内外金属材料分析方法标准(包括ASTM、JIS、EN和GB)中应用波长色散X射线荧光光谱法(XRF)的现状,从方法所涵盖的测定元素及其测定的含量范围以及谱线重叠和基体效应的校正等几个方面,并以钢铁分析中的应用为例作了评述。美国材料与试验协会在2012-2016年间先后发布了3个XRF标准方法,分别应用于铸铁、不锈钢、合金钢和低合金钢的分析,测定元素达13项,根据相关钢材的技术规格确定了各元素含量的测定范围。日本工业标准调查会于1997年并于2010年和2013年经修订公布了钢铁XRF分析法JIS标准,可测定各类钢材中主量、次量以及痕量元素达31项,其中镍、铁、钴和测定下限分别延伸至99.5%,50%和60%,从而使此方法有可能扩展应用于镍基、铁镍基和钴基高温合金的分析。我国先后于2007年和2018年由国家标准经主管部门颁布了XRF分析钢铁和高合金钢的两个标准,可测定这2类钢材中的元素为13项和11项,其测定含量范围系根据材料的技术规格确定。关于谱线重叠和基体效应的校正,各标准中在相关部分作了说明,而ASTM有两则独立标准专门论述这两个问题。在此评述对其他金属材料的XRF分析标准也作了介绍(引用文献15篇)。     

Comparative analysis of ancient ceramics by neutron activation analysis,inductively coupled plasma-optical-emission spectrometry,inductively coupled plasma-mass spectrometry,and X-ray fluorescence

The accurate measurement of the maximum possible number of elements in ancient ceramic samples is the main requirement in provenance studies. For this reason neutron activation analysis (NAA) and X-ray fluorescence (XRF) have been successfully used for most of the studies. In this work the analytical performance of inductively coupled plasma-optical-emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS) has been compared with that of XRF and NAA for the chemical characterization of archaeological pottery. Correlation coefficients between ICP techniques and XRF or NAA data were generally better than 0.90. The reproducibility of data calculated on a sample prepared and analysed independently ten times was approximately 5% for most of the elements. Results from the ICP techniques were finally evaluated for their capacity to identify the same compositional pottery groups as results from XRF and NAA analysis, by use of multivariate statistics.     

Comparison of instrumental neutron activation analysis of geological materials with other multielement techniques

Results obtained for 12 elements in approximately 1600 rocks by instrumental neutron activation analysis (INAA) are compared with those obtained by ICP emission spectrometry (ICP-ES), XRF, and atomic-absorption spectrometry (AAS). Sample duplicates and two controls are used to evaluate the precison of the methods investigated. Application of a method (Maximum Likelihood Functional Relationship) to determine and quantify rotational and translational bias is demonstrated. The elements Na, Fe, Ba, Co, Cr, La, Ni and Rb can be determined in rocks by INAA with sufficient sensitivity and precision, whereas the determination of Ag, Yb, Zn and Zr suffers from inadequate sensitivity. Good agreement is seen in the results for Na (by INAA, ICP-ES and XRF) and AG (INAA and AAS). A significant positive bias (13% or less) is evident in the comparison of results by INAA and ICP-ES or XRF for Cr, Ba, Ni and Fe over a wide range of concentration. A similar trend, though less significant, is observed for the elements Yb, Rb, La and Co; the upper limit of concentration for satisfactory determination is within a decade of the highest detection limit for these elements. Rotational and translational bias is evident for Zn in the comparison of data obtained by INAA and ICP-ES, the results by INAA being appreciably lower above about 400 ppm Zn.     

Preliminary homogeneity study of in-house reference material using neutron activation analysis and X-ray fluorescence

Summary Although many biological reference materials for quality control of trace element analysis are commercially available, there is still a need for additional local materials for special matrices. In the Latin American region a preliminary study has been commenced involving analytical strategies for the characterization of in-house reference material. A biological sample, prepared in Brazil, constitutes the first regional attempt to prepare reference material. It was analyzed by neutron activation analysis (NAA) and X-ray fluorescence (XRF) to verify its homogeneity. The determination of the trace elements and certain major elements was carried out by instrumental NAA. Trace elements such as Cd, Mn, Mo and Cu were determined using NAA with radiochemical separations to improve the sensitivity and precision. XRF was applied only to major constituents and some trace elements with concentration of more than 10 g/g. From a total of 18 elements analyzed, only Fe, Cr and Sc were not homogeneously distributed.     

X射线荧光光谱熔融法测定锶永磁铁氧体中各组分含量

本文使用自制标准样品,采用混合熔剂熔融样品,用X射线荧光光谱法(XRF)测定锶永磁铁氧体半成品中Fe,Sr,Si等元素的含量.熔融制样有效地消除了矿物效应,并降低了基体效应的影响.实验结果表明,本法准确度高,重现性好,平行测定11次相对标准偏差(RSD)可达到0.1%.该方法用于实际样品分析,其结果与传统化学分析方法结...     

Identification of glass and ceramics by X-ray fluorescence analysis with a pyroelectric X-ray generator.

Applications of X-ray fluorescence (XRF) analysis with a pyroelectric X-ray generator are presented. Glass and ceramics were analyzed with this novel X-ray generator to examine its capability for analyzing nonmetallic inorganic material. Although the power of X-ray output was a few orders of magnitude lower than conventional X-ray tubes, many elements such as Si, K, Ca, Ti, Cr, Fe, Zn, Sr, Ba, and Pb were detected in glass and ceramic samples. Light elements such as Na, Mg, and Al were not detected because of the low fluorescence yield and the absorption of fluorescent X-rays in air. The elements detected or the relative peak intensities of the elements were different from each other, and the samples analyzed were identified by the XRF spectrum, notwithstanding the low power of the X-ray output. This novel device showed the sufficient capability for preliminary screening before strict identification of analytes. The pyroelectric X-ray generator can also be used to analyze large samples that cannot be put into ordinary XRF spectrometers because the device has no dimensional limitation of analytes.     

Determination of trace elements in Syrian medicinal plants and their infusions by energy dispersive X-ray fluorescence and total reflection X-ray fluorescence spectrometry

X-ray fluorescence (XRF) and total-reflection X-ray fluorescence (TXRF) techniques suited well for a multi-element determination of K, Ca, Mn, Fe, Cu, Zn, Rb, and Sr in some Syrian medicinal plant species. The accuracy and the precision of both techniques were verified by analyzing the Standard Reference Materials (SRM) peach-1547 and apple leaves-1515. A good agreement between the measured concentrations of the previously mentioned elements and the certified values were obtained with errors less than 10.7% for TXRF and 15.8% for XRF. The determination of Br was acceptable only by XRF with an error less than 24%. Furthermore, the XRF method showed a very good applicability for the determination of K, Ca, Mn, Fe, Cu, Zn, Rb, Sr, and Br in infusions of different Syrian medicinal plant species, namely anise (Anisum vulgare), licorice root (Glycyrrhiza glabra), and white wormwood (Artemisia herba-alba).     

X-射线荧光光谱法测定钛铁中的硅、锰、磷、铝

介绍用X-射线荧光光谱仪测定钛铁中Si、Mn、P、Al含量的方法,通过试验确定了合适的研磨时间、压力和保压时间,用压片法制样,建立了各元素的工作曲线,各元素的测定范围分别为Si3.00%～6.00%,Mn1.00%～3.00%,P0.030%～0.070%,Al5.00%～9.00%。通过强度测量得到测定Si、Mn、P、Al的相对标准偏差分别为0.074%、0.308%、0.383%、0.040%,精密度满足测试要求。将该方法测定结果与化学法比对,准确度满足国家标准方法分析误差的要求。