北京同步辐射装置3W1B软X射线光束线偏振特性测量

应用自行研制的Mo/Si周期多层膜作为起偏器和检偏器的光学元件, 测量了北京同步辐射装置3W1B束线的偏振状态. 通过数据分析, 得到了3W1B软X射线的有关偏振参数, 在86—89eV能区经过起偏器后的偏振度超过98%, 圆偏振分量介于1%—3%之间.     

Total electron yield mode for XANES measurements in the energy region of 2.1——6.0 keV

The total electron yield (TEY) mode has been developed successfully for XANES measurements at Beamline 4B7A of BSRF (Beijing Synchrotron Radiation Facility). Its performance was studied by measuring sulphur K-edge XANES of three CdS samples (mixed with graphite powder as an electric conductor) with different concentration: 75%, 50% and 25%. The data are collected in TEY mode and fluorescence yield (FY) mode respectively for comparison. The results demonstrate that the TEY spectra of three samples agree well with each other after the background is subtracted and normalized. The measured XANES spectra by TEY mode without bias and with 100V bias are almost identical to one another, but the signal-to-noise ratio of spectra measured without bias is better than that with 100V bias. The consistency of the self-absorption corrected FY spectra and TEY spectra are within 10% for the three samples.     

北京同步辐射装置软X光束线通量谱的绝对测量与计算

在北京同步辐射装置(BSRF)上用全吸收平行板充氙电离室作一级标准探测器,对硅光电二极管(AXUV—100)的效率在光子能量5—6.5keV进行了标定,建立了二级标准探测器;AXUV—100硅光电二极管在50eV-6keV有很好的线性响应,将其在硬X射线波段已标定的效率曲线外推到软X射线波段,并对BSRF3B1A和4B9B光束线在软X射线波段光子通量谱进行了初步地测量,测量结果与理论计算结果较为符合.在3B1A软X光学实验站,利用二级标准探测器对用于惯性约束聚变(ICF)的软X光探测器的灵敏度进行了标定,并取得了满意的结果.     

Total electron yield mode for XANES measurements in the energy region of 2.1-6.0 keV

The total electron yield (TEY)mode has been developed successfully for XANES measurements at Beamline 4B7A of BSRF (Beijing Synchrotron Radiation Facility).Its performance was studied by measuring sulphur K-edge XANES of three CdS samples (mixed with graphite powder as an electric conductor)with different concentration:75%,50% and 25%.The data are collected in TEY mode and fluorescence yield (FY)mode respectively for comparison.The results demonstrate that the TEY spectra of three samples agree well with each other after the background is subtracted and normalized.The measured XANES spectra by TEY mode without bias and with 100V bias are almost identical to one another,but the signal-to-noise ratio of spectra measured without bias is better than that with 100V bias.The consistency of the self-absorption corrected FY spectra and TEY spectra are within 10% for the three samples.     

Performance on absolute scattering intensity calibration and protein molecular weight determination at BL16B1, a dedicated SAXS beamline at SSRF

The optical system and end‐station of bending‐magnet beamline BL16B1, dedicated to small‐angle X‐ray scattering (SAXS) at the Shanghai Synchrotron Radiation Facility, is described. Constructed in 2009 and upgraded in 2013, this beamline has been open to users since May 2009 and supports methodologies including SAXS, wide‐angle X‐ray scattering (WAXS), simultaneous SAXS/WAXS, grazing‐incidence small‐angle X‐ray scattering (GISAXS) and anomalous small‐angle X‐ray scattering (ASAXS). Considering that an increasing necessity for absolute calibration of SAXS intensity has been recognized in in‐depth investigations, SAXS intensity is re‐stated according to the extent of data processing, and the absolute intensity is suggested to be a unified presentation of SAXS data in this article. Theory with a practical procedure for absolute intensity calibration is established based on BL16B1, using glass carbon and water as primary and secondary standards, respectively. The calibration procedure can be completed in minutes and shows good reliability under different conditions. An empirical line of scale factor estimation is also established for any specific SAXS setup at the beamline. Beamline performance on molecular weight (MW) determination is provided as a straightforward application and verification of the absolute intensity calibration. Results show good accuracy with a deviation of less than 10% compared with the known value, which is also the best attainable accuracy in recent studies using SAXS to measure protein MW. Fast MW measurement following the demonstrated method also enables an instant check or pre‐diagnosis of the SAXS performance to improve the data acquisition.     

塑化剂邻苯二甲酸二辛酯的拉曼光谱计算及分析

近几年,国内有关塑化剂的食品安全事件频发,迫切需求加强对于食品中塑化剂的检测研究工作。邻苯二甲酸二辛酯是塑化剂的一种。理论计算和实验测量了邻苯二甲酸二辛酯的拉曼光谱。利用密度泛函理论DFT(B3LYP)的三参数混合方法对其进行了空间结构优化;然后分别用(Hartree-Fock)HF/3-21G和DFT/3-21G两种算法计算了它的拉曼光谱和红外光谱,给出了光谱强度图。实验测量了分析纯级邻苯二甲酸二辛酯的拉曼光谱,并和理论计算结果进行了对比,显示了很好的一致性,与此同时由于计算方法的不同,从图中可以看出Gaussian计算的HF和DFT算法无论是峰的位置还是相对强度等都均存在差别。还给出了常用塑化剂邻苯二甲酸二辛酯的各个键长、键角等空间结构参数,并对邻苯二甲酸二辛酯分子在400～3 500 cm-1区间的振动谱做了指认。报道了常用塑化剂邻苯二甲酸二辛酯的拉曼光谱研究工作。这些工作将有助于拉曼光谱技术在食品检测领域的研究和应用。     

氯化钾对银胶中碱性品红表面增强拉曼散射的影响

测量了银胶中碱性品红的表面增强拉曼散射（ＳＥＲＳ）光谱。系统考察了不同波长光激发下ＫＣｌ对碱性品红ＳＥＲＳ光谱的影响，给出了不同波长光激发下碱怀品红的１３６６ｃｍ＾－１和２４２ｃｍ＾－１峰相对强度随ＫＣｌ量（或浓度对数值）的变化曲线，５１４．５ｎｍ和６３２．８ｎｍ光激发的碱性品红的ＳＥＲＳ谱有明显差异，２４２ｃｍ＾－１峰与其他峰的相对强度发生变化。     

Direct-detected rapid-scan EPR at 250 MHz

EPR spectra at 250 MHz for a single crystal of lithium phthalocyanine (LiPc) in the absence of oxygen and for a deoxygenated aqueous solution of a Nycomed triarylmethyl (trityl-CD3) radical were obtained at scan rates between 1.3 x 10(3) and 3.4 x 10(5)G/s. These scan rates are rapid relative to the reciprocals of the electron spin relaxation times (LiPc: T1 = 3.5 micros and T2 = 2.5 micros; trityl: T1 = 12 micros and T2 = 11.5 micros) and cause characteristic oscillations in the direct-detected absorption spectra. For a given scan rate, shorter values of T2 and increased inhomogeneous broadening cause less deep oscillations that damp out more quickly than for longer T2. There is excellent agreement between experimental and calculated lineshapes and signal amplitudes as a function of radiofrequency magnetic field (B1) and scan rate. When B1 is adjusted for maximum signal amplitude as a function of scan rate, signal intensity for constant number of scans is enhanced by up to a factor of three relative to slow scans. The number of scans that can be averaged in a defined period of time is proportional to the scan rate, which further enhances signal amplitude per unit time. Longer relaxation times cause the maximum signal intensity to occur at slower scan rates. These experiments provide the first systematic characterization of direct-detected rapid-scan EPR signals.     

基于多层膜偏振元件的同步辐射光束线偏振特性测量研究

利用自行研制的同步辐射软X射线多层膜综合偏振测量装置, 对北京同步辐射装置(BSRF)的3W1B软X射线光束线的偏振特性进行了系统的研究. 给出了多层膜偏振元件起偏前后的测量结果, 测量能量为206eV时, 经反射镜、光栅等光束线光学元件后输出的线偏振度(起偏前)为0.585, 经多层膜偏振元件起偏后输出光的 线偏振度达到0.995.     

稀土盐水溶液单泡声致发光中的特征光谱

在溶有稀有气体的稀土盐氯化铽水溶液中进行了单泡声致发光光谱的研究. 在固定驱动超声频率、不同驱动声压下, 观察到了一系列OH自由基从第一激发态A²∑⁺到基态X²Π 各振动能级跃迁所产生的谱线, 包括波长307 nm处的(0, 0)跃迁谱线, 335 nm处的(0, 1)跃迁谱线以及276 nm处的(1, 0) 跃迁谱线等. 实验结果表明较高的驱动声压有利于 276 nm处谱线的产生, 而较低的驱动声压则有利于 307 与 335 nm 处谱线的产生. 通过定义线状光谱与连续谱的光强比, 定量地表征了线状光谱在总光谱中的相对强度, 并给出了驱动声压对各跃迁谱线光强比的影响. 关键词： 单泡声致发光 驱动声压 线状光谱 光强比     

08B1‐1: an automated beamline for macromolecular crystallography experiments at the Canadian Light Source

Beamline 08B1‐1 is a recently commissioned bending‐magnet beamline at the Canadian Light Source. The beamline is designed for automation and remote access. Together with the undulator‐based beamline 08ID‐1, they constitute the Canadian Macromolecular Crystallography Facility. This paper describes the design, specifications, hardware and software of beamline 08B1‐1. A few scientific results using data obtained at the beamline will be highlighted.     

基于2D-COS红外光谱的附子炮制过程时序段解析研究

采用傅里叶变换红外光谱技术,获得蒸制过程中附子红外光谱及二维相关谱(Tow-dimensional correlation, 2D-COS),研究附子炮制过程特征。分别比较原始红外光谱、二阶导数谱及二维相关谱,结果表明红外原始光谱图十分相似,结合二阶导数光谱分析1 634.87 cm-1为羰基峰;1 603.18,1 571.58,1 485.09和1 413.08 cm-1为苯环的骨架振动峰,851.41和759.24 cm-1 为苯环C-H键的振动峰;1 153.73,1 081.84和1 021.35 cm-1为生物碱中酯键和醇羟基的特征峰。二维相关谱结果揭示附子在炮制过程中发生的2个过程时序段,分别为2～3和8～9 h。研究数据有助于临床根据适应证选择适宜的煎煮时间,避免煎煮不足导致中毒或煎煮太过影响疗效。     

EPR study of gamma-irradiated 2-Bromo-4′-methoxyacetophenone single crystals

The gamma-irradiated single crystals of 2-Bromo-4′-methoxyaceto-phenone (2B4MA) were investigated using electron paramagnetic resonance (EPR) technique. Density-functional theory calculations were employed to investigate and identify the radicals that have been assumed to be formed upon irradiation of 2B4MA single crystals. The EPR spectra of 2B4MA were recorded at different orientations in the magnetic field at room temperature. Taking into account the chemical structure and experimental spectra of irradiated single crystal of 2B4MA, it was assumed that at least two different radicals were produced in the sample. Following this assumption, six possible radicals were modeled and EPR parameters were calculated by using the DFT, B3LYP/6-311+G(d), for the modeled radicals individually. The calculated hyperfine coupling constants and g-tensors were used as initial values for simulation studies. The three crystallographic axes on the simulated spectra were well matched with experimental spectra for the two modeled radicals. Thus, we identified the R1 type radical and R4 type radical as paramagnetic species produced in gamma-irradiated 2B4MA.     

K_3Ba_3C_(60)在不同温度下的Raman光谱研究

研究了K3Ba3C60 在不同温度下的Raman光谱 .发现Raman光谱随温度的变化发生有规律的变化 .随着温度的降低 ,所有模的线宽和强度的变化情况与纯的C60 的情况明显不同 .径向Ag(2 )模的频率在 2 0K到室温之间有一个反常大的向高频漂移 (9cm-1) ,这表明在C60 分子和掺杂离子之间存在着轨道杂化 .另外Raman光谱中Ag(1)模两个分量的相对强度随着温度的降低发生有规律的变化 .     

氮化铝铬的制备及其光学性质

利用直接氮化法得到了氮化铝和氮化铬,并用两种途径得到Cr³⁺掺杂的氮化铝样品。用X射线衍射仪分析了样品晶相并测试了两种样品的激发和发射光谱,计算了晶体场劈裂参数D_q和Racah参数B及D_q/B分别为1 800,693.69和2.59。光谱数据表明,Cr³⁺在氮化铝中属于强场环境,光发射来自于最低激发态²E能级,与在氧化铝中的环境相似。根据光谱数据给出了Cr³⁺在氮化铝晶体场中的能级。     

基于溶剂化效应的BDE-15分子振动光谱增强特征振动研究

利用密度泛函与自洽反应场理论在B3LYP/6-31+G(d)水平下分别计算气态及24种不同极性溶剂中4,4’-二溴二苯醚(4,4’-dibrominated diphenyl ethers, BDE-15)的分子振动光谱(红外光谱、拉曼光谱),以气态分子振动光谱为基准,筛选出对溶剂极性敏感的特征振动作为指标构建溶剂对BDE-15振动光谱溶剂化效应指标体系,探究溶剂对BDE-15分子振动频率、红外/拉曼峰强溶剂化效应及综合效应,并寻求显著增强BDE-15分子特征振动频移/强度的溶剂。研究表明：从分子振动频率角度,溶剂极性敏感的(频移>1 cm-1)分子特征振动均为伸缩振和面外弯曲振,但24种溶剂对BDE-15分子振动频率溶剂化效应并不显著;从分子振动峰强角度,24种溶剂对BDE-15分子振动光谱峰强的增强效应主要发生在红外光谱的中低频区及拉曼光谱的高频区,其中起显著增强(红外/拉曼效应指标值分别大于6与5)的溶剂为醇类、乙腈、二甲亚砜、硝基苯;不同极性溶剂对BDE-15拉曼峰强溶剂化效应及综合效应指标值均表现出随溶剂介电常数增长由线性到对数的增长趋势,而红外峰强只保留低介电常数溶剂时的线性关系。利用上述BDE-15分子振动光谱峰强增强方法对BDE-153,BDE-154和BDE-209进行验证,醇类、乙腈、二甲亚砜、硝基苯对三者的振动光谱红外/拉曼峰强的效应指标值分别大于6与5,且最大峰强增倍数皆大于33,说明所建BDE-15分子振动光谱增强特征振动方法有助于进一步开展基于分子振动光谱的PBDEs同系物间辨识研究。     

异丙醇的O-H伸缩振动泛频光谱和分子构像

使用高灵敏的光腔衰范光谱（Ｃａｕｉｔｙ Ｒｉｎｇ Ｄｏｗｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ）技术测出了异丙醇的Ｏ－Ｈ伸缩ｖ＝４、５振动泛频光谱,每个技动能级都有三个吸收峰,被归属为分子构像的Ｏ－Ｈ伸缩泛叔汲收,给出了光腔衰范光谱的振动泛频吸收的振动谱强度公式,并求得分子不同构在不同振动能级的Ｏ－Ｈ伸缩局域模振子的机械频率（Ｘ１）、非谐性（Ｘ２）以及解离能（Ｄ）,用浓度泛函（ＤＦＴ）Ｂ３ＬＹＰ／６－３１＋     

The influence of cation additives on the NIR luminescence intensity of Er³⁺-doped borate glasses

Er3+-doped 25BaO-(25-x)SiO2-xAl2O3-25B2O3 transparent glasses are prepared with x = 0,12.5 and 25 by a solid-state reaction.The Er-related NIR luminescence intensity,which corresponds to the transition of 4I15/2-4I13/2,is obviously altered with different silicon/aluminum ratios.The Judd-Ofelt parameters of the Er3+ ions are adopted to explain the intensity change in the NIR fluorescence,and the Raman scattering intensity versus the amount of Al and/or Si components are discussed.The spectra of the three samples are quite similar in the peak positions,but different in intensity.The maximal phonon density of state for the samples is calculated from the Raman spectra and is correlated to the NIR luminescence efficiency.     

High-pressure facilities at the ESRF

Abstract

Several beamlines at the European Synchrotron Radiation Facility in Grenoble are being designed with high-pressure experiments in mind. Among the first seven beamlines the Microfocus Beamline, the Materials Science Beamline, the Laue White Beamline and the High Energy Beamline are of particular interest for high-pressure diffraction experiments. These experimental stations are outlined and their characteristics are compared.

Presented at the IUCr Workshop on ‘Synchrotron Radiation Instrumentation for High Pressure Crystallography’, Daresbury Laboratory 20-21 July 1991     

一种新型有机蓝光材料的合成及光物理性质研究

利用Witting反应合成了一种含吡啶和吡唑基团的π共轭结构刚性有机分子6-苯基-4'-(4-[4-(1H-吡唑)乙烯]苯基)-2,2'-联吡啶,采用元素分析、红外光谱、核磁共振氢谱、质谱等方法对其进行了表征。通过理论计算研究了化合物的吸收光谱特点,实验研究了化合物在几种不同溶剂中的紫外吸收光谱及荧光发射光谱。研究结果表明,所合成的化合物具有优良的蓝色荧光性能,作为发光材料具有潜在的应用价值。