酮类有机物放电离子淌度谱研究

离子淌度谱是一种快速检测痕量挥发性有机物的高灵敏方法。在放电离子源离子淌度谱装置上,研究了八种酮类有机物的离子淌度谱。实验测量了各种离子的约化迁移率,其中丙酮、正丁酮、1-甲基-2-吡咯烷酮、环己酮、苯乙酮的实验结果与前人63Ni放射源离子淌度谱相一致,而甲基异丙基酮、4-甲基-2-戊酮、环戊酮单体和二聚体离子的约化迁移率则是首次报道。实验测量的约化迁移率与离子质量线性相关,获得的对酮类有机物检测灵敏度在ng·L-1量级。     

TG-FTIR法研究低变质煤共热解过程气体的析出规律

采用热重-红外联用技术（TG-FTIR）对比研究了陕北低变质粉煤（SJC）与重油（HS）、焦煤（JM）、液化残渣（DCLR）共热解过程中气相产物的析出特性。研究表明,随热解温度升高,SJC与HS,JM,DCLR的共热解过程均可分为三个阶段。第一阶段表现为原料表面吸附物的释放,第二阶段发生解聚和分解反应,随温度继续升高,第三阶段形成更为稳定的半焦。在热解第二阶段中均存在煤与添加剂之间的协同效应,SJC作为主要的供氢体,热解产生的氢自由基与HS,JM,DCLR热解产生的小分子自由基碎片之间发生相互作用生成焦油和煤气。SJC和SJC+DCLR在450 ℃附近的温度区间内热解反应进行的更加充分,大部分N元素转移到了焦油组分中。热解过程气相产物中H₂O和酚类物质、含N杂环物质及CO的析出伴随着热解的整个温度区间,SJC+JM和SJC+HS热解过程含N物质的转移主要集中在400~650 ℃区间,CH₄和脂肪烃类物质的析出最高峰出现在450 ℃附近,而SJC+DCLR和SJC则出现在550 ℃。JM,HS及DCLR的添加可促使焦油中芳香族化合物的析出,SJC+JM与SJC+HS热解过程芳香族物质大量析出的温度区间在400~550 ℃。该研究结果为低变质粉煤的清洁转化与提质分级新技术的研究开发提供理论依据,对低变质煤的增值利用具有重要的意义。     

基于TG-FTIR的落叶松木材热失重与热解气相演变规律研究

采用热重红外光谱联用分析法考察了落叶松木材在不同升温速率下的热失重特性及气相演变规律,并与其组分模混物的热解特性进行了对比分析。结果表明,落叶松的主要失重区域相对于模混物较宽,落叶松残炭率(18.97%)相对于模混物(29.83%)较低;在低温段,模混物的活化能高于落叶松木材,而在高温段二者差别不大;落叶松木材热解过程经历了水分析出、主成分热分解、后期炭化等阶段,气体析出主要集中在375℃左右;落叶松在热解反应过程中,主要气体产物生成量顺序为CO2>H2O>CH4>CO,随着升温速率的增加,上述气体产物的生成量明显增多;模混物与落叶松木材热解生成气体规律基本相似,但模混物中各气体析出强度均相对较高。     

Spatiotemporal measurement using L-band ESR-CT system for water sonolysis in the presence of 1-Hydroxy-2,2,5,5-tetramethyl-3-imidazoline-3-oxide

When using ESR to measure the radicals generated by ultrasound, it is necessary to extract a solution and place it in the ESR system. To avoid this process, we incorporated an ultrasonic reaction cell in an L-band ESR-CT system, producing a system that allows the detection of the concentration of radicals during ultrasonic irradiation. This system was used to measure the time and space dependences of OH radicals generated by ultrasonic irradiation. When a 10 ml aqueous solution of 1-hydroxy-2,2,5,5-tetramethyl-3-imidazoline-3-oxide (HTIO) was irradiated with ultrasound, it was found that the generation of radicals was clearly shown in a CT image after a period of 10 min. It was also found that continued irradiation resulted in an increased concentration of radicals. In addition to this system, an X-band ESR system was also used to measure the concentration of OH radicals generated, and the results of both systems were then compared. Both results are very similar, showing that the proposed system, which was realized by incorporating an ultrasonic irradiation cell in the L-band ESR-CT system, operated properly. Because this system allows the measurement of sonochemical reactions in an opaque cell or an opaque solution such as blood and industrial wastewater, it is a very useful measurement system for achieving the applying of sonochemistry to the medical engineering field.     

磁控溅射沉积薄膜实验参数优化光谱诊断

采用磁控溅射仪、Omni-λ300系列光栅光谱仪、CCD数据采集系统和光纤导光系统等构成的等离子体光谱分析系统,采集了以Cu和Al为靶材、氩气为工作气体,射频磁控溅射法沉积硅基薄膜时的等离子体发射光谱。以CuⅠ324.754 nm,CuⅠ327.396 nm,CuⅠ333.784 nm,CuⅠ353.039 nm,AlⅠ394.403 nm和AlⅠ396.153 nm为分析线,研究了Cu和Al等离子体发射光谱强度随溅射时间、溅射功率、靶基距和气体压强等实验参数的变化。并与射频磁控溅射沉积薄膜实验参数的选择进行对比,表明发射光谱法对射频磁控溅射薄膜生长条件的优化有着很好的指导作用。     

基于TG-FTIR的杨木热解过程中脲醛树脂影响机理的模型物研究

热解是废弃人造板高效回收利用的方式,人造板中所含胶黏剂是其不同于生物质的主要特征。为了有效环保地利用热解技术处理废弃人造板,解明人造板热解过程中其所含脲醛树脂胶黏剂(UF)对木材热解特性的影响,深入探索UF对人造板中木材各组分的作用机制,以杨木及木材的三种主要组分(纤维素、半纤维素、木素)为研究对象,创新性地依据杨木的化学组成,以纤维素、木聚糖和木素配制成模型物,并加入UF模拟人造板的构成。利用热重红外光谱联用(TG-FTIR)分析法,对比分析了加入UF前后模型物以及杨木各主要组分的热失重特性及气相演变规律。热重及红外结果表明,UF促进了纤维素热解过程中水和羧酸类物质的生成。UF与木素结合生成热不稳定的含氮结构,释放大量氨气,并且在200～300 ℃区间内参与了木素的热解并直接影响木素热解产物的生成。由此推测,在人造板热解过程中,木材三种主要组分中与UF作用的主要成分是木素。     

A Simple X-ray Spectrometer and PC-based Data Acquisition System for Newly Developed X-ray Source Based on Laser Compton Scattering

A simple X-ray spectrometer and a PC-Based Data Acquisition System(DAS) have been developed newly in Shanghai Institute of Applied Physics(SINAP),Chinese Academy of Sciences (CAS) for the measurement of the X-ray source generated using laser Compton scattering.The system consists of liquid nitrogen cooled high resolution Si(Li) detector,electronics and a DAQ.The Si(Li) detector was designed and made by Center of Advanced Instruments in SINAP,CAS,it allows us to measure X-rays with the energy up to 60 keV and the energy resolution(FWHM) of 184 eV at 5.9 keV.We measured the system uncertainty was 0.2 eV and time drifting of detector was 0.05% both at 5.9 keV.The DAQ was based on Object-Oriented software LabVIEW 7.1,it has data on-line analysis and original data saved functions.     

285 nm激光光解对苯醌-乙二醇体系的CIDEP波谱解析

在285 nm紫外激光辐照下,用时间分辨电子自旋共振(TRESR)波谱仪研究了对苯醌/乙二醇(PBQ/EG)体系,得到了发射的苯半醌中性自由基PBQH.和乙二醇碳自由基R.(OH)2的CIDEP谱.在化学诱导动态电子极化(CIDEP)基本原理的基础上,建立合理的计算模型,编写相应的程序,对PBQH.和R.(OH)2的CIDEP形成机理进行了定量的解析.通过对不同延时下该体系各种自由基及不同机理成分的对比,明显看出由RPM形成的PBQH.比由TM形成的PBQH.衰减快.这种分析方法可以推广应用于其它体系的CIDEP实验谱的解析.     

Digital EPR with an arbitrary waveform generator and direct detection at the carrier frequency

A digital EPR spectrometer was constructed by replacing the traditional bridge with an arbitrary waveform generator (AWG) to produce excitation patterns and a high-speed digitizer for direct detection of the spin system response at the carrier frequency. Digital down-conversion produced baseband signals in quadrature with very precise orthogonality. Real-time resonator tuning was performed by monitoring the Fourier transforms of signals reflected from the resonator during frequency sweeps generated by the AWG. The capabilities of the system were demonstrated by rapid magnetic field scans at 256 MHz carrier frequency, and FID and spin echo experiments at 1 and 10 GHz carrier frequencies. For the rapid scan experiments the leakage through a cross-loop resonator was compensated by adjusting the amplitude and phase of a sinusoid at the carrier frequency that was generated with another AWG channel.     

Critical evaluation of screening techniques for emerging environmental contaminants based on accurate mass measurements with time-of-flight mass spectrometry

Emerging contaminants from wastewater effluent samples were analysed, using posttarget and nontarget analysis techniques. The samples were analysed with an ultra performance liquid chromatograph-time-of-flight mass spectrometer (UPLC-TOF-MS), and the resulting data were processed with commercial deconvolution software. The method works well for posttarget analysis with prior information about the retention times of the compounds of interest. With positive polarity, 63 of 66 compounds and with negative polarity, 18 of 20 compounds were correctly identified in a spiked sample, while two compounds of a total of 88 fell out of the mass range. Furthermore, a four-stage process for identification was developed for the posttarget analysis lacking the retention time data. In the process, the number of candidate compounds was reduced by using the accurate mass of selected compounds in two steps (stages 1 and 2), structure-property relationships (stage 3) and isotope patterns of the analytes (stage 4). The process developed was validated by analysing wastewater samples spiked with 88 compounds. This procedure can be used to gain a preliminary indication of the presence of certain analytes in the samples. Nontarget analysis was tested by applying a theoretical mass spectra library for a wastewater sample spiked with six pharmaceuticals. The results showed a high number of false identifications. In addition, manual processing of the data was considered laborious and ineffective. Finally, the posttarget analysis was applied to a real wastewater sample. The analysis revealed the presence of six compounds that were afterwards confirmed with standard compounds as being correct. Three psycholeptics (nordiazepam, oxazepam and temazepam) could be tentatively identified, using the identification process developed. Posttarget analysis with UPLC-TOF-MS proved to be a promising method for analysing wastewater samples, while we concluded that the software for nontarget analysis will need improvement before it can be used in environmental analytical work with LC-TOF-MS systems.     

Generation of multiply charged atomic ions of halogens using second harmonic of nanosecond Nd:YAG laser

Using the second harmonic output (532 nm) of a commercially available pulsed Nd:YAG laser interacting with pure and mixed clusters of iodo compounds, multiply charged ions of halogen group (F, Cl, Br and I) atoms have been generated based on the phenomenon of low intensity Coulomb explosion. This method provides a useful rugged tool for generation of multiply charged ions which can then be used for various applications. The effect of boiling point (vapour pressure) of the compound forming clusters has been correlated with the highest charged state of ion observed in time of flight mass spectrometer.     

Confined direct analysis in real time ion source and its applications in analysis of volatile organic compounds of Citrus limon (lemon) and Allium cepa (onion)

The DART (direct analysis in real time) ion source is a novel atmospheric pressure ionization technique that enables efficient ionization of gases, liquids and solids with high throughput. A major limit to its wider application in the analysis of gases is its poor detection sensitivity caused by open-air sampling. In this study, a confined interface between the DART ion source outlet and mass spectrometer sampling orifice was developed, where the plasma generated by the atmospheric pressure glow discharge collides and ionizes gas-phase molecules in a Tee-shaped flow tube instead of in open air. It leads to significant increase of collision reaction probability between high energy metastable molecules and analytes. The experimental results show that the ionization efficiency was increased at least by two orders of magnitude. This technique was then applied in the real time analysis of volatile organic compounds (VOCs) of Citrus Limon (lemon) and wounded Allium Cepa (onion). The confined DART ion source was proved to be a powerful tool for the studies of plant metabolomics.     

基于二向色及透射准直的小型近红外拉曼光谱仪

搭建了可用于生物医学检测的小型近红外拉曼光谱仪。通过理论计算,几何光路设计,完成了系统组装。有别于传统反射式准直结构：(1)本光谱仪色散系统采用透射式准直的方法,将散射光投射到光栅上进行色散;(2)经二向色镜分光,采用物镜对入射光会聚和散射光收集,设计了与色散系统入射狭缝相匹配(共焦面)的外光路系统,进而有效收集拉曼信号和去除杂散光;(3)实现了高分辨率(3 cm-1)、高重复性和高灵敏度光谱检测,检测范围500~2 200 cm-1(785 nm激发);(4)小型化设计,整个系统尺寸约240 mm×200 mm×130 mm,自由度高。将此自开发小型拉曼光谱仪应用于葡萄糖和膝关节软骨的拉曼光谱测试,获得了与大型商业拉曼光谱仪相媲美的结果,验证了该光谱仪具有高分辨率,高重复性和高灵敏度的优越性能,可灵活地应用于生物医学等多领域的研究。     

基于自适应共振神经网络的单粒子激光电离质谱数据分析

气溶胶激光飞行时间质谱仪(ALUOFMS)可以在线地对气溶胶单粒子进行物理和化学特性分析,利用双束连续激光对单个粒子的空气动力学粒径进行测量,并通过飞行时间完成单粒子化学成分的检测。该仪器在运行过程中将产生海量的实验数据,对这些数据快速、自动处理并提取有价值的信息是整机系统的关键之一。文章介绍了基于神经网络的自适应共振算法(ART-2a)在随机混和的氯化钠、氯化钙、邻苯二甲酸二正辛酯(DOP)和2,5二羟基苯甲酸(DHB)气溶胶单粒子聚类分析中的成功运用。同以往的质谱分析方法相比,ART-2a可以实现对任意多和任意复杂的输入模式进行自组织,自适应和自稳定的快速识别,更有利于质谱数据的分析。实验结果表明,当警戒值为0.40,学习速率为0.05以及迭代次数为6时,ART-2a可以成功地对这四种物质进行分类,同时得到4类物质的聚类中心,每类的聚类中心都能很好的代表该类物质的特征。     

基于棱镜气室的光纤甲烷传感系统的研究

综合运用棱镜气室与谐波检测技术,构建了适用于宽广浓度范围内的光纤甲烷检测系统。以大气环境为背景,基于比尔-朗伯(Beer-Lambert)定律在气体弱吸收时的近似表述,利用背景扣除和比值处理技术,实现了常压下甲烷不同浓度水平(0～20%)的检测。利用渐变折射率透镜(GRIN)气室测量了甲烷在不同浓度时的直接吸收谱,结合现有DFB-LD光源选择甲烷2ν₃带的R5支(1 648.212 nm)作为被测吸收峰。在不同浓度气体配置过程中,进行了系统的在线实验,结果表明系统示值与浓度变化间线性良好,而且系统的稳定性和动态响应特性比较理想。该系统可根据不同现场环境的甲烷浓度水平,选择适当强度的吸收线,通过步进电机调节棱镜中线间的距离,进而改变气室内有效吸收光程,拓展了仪器的应用领域,可作为煤矿巷道或天然气管道沿线的瓦斯监测仪器。     

基于可调谐光纤激光器的C_2H_2气体光声光谱检测

研制了基于可调谐掺Er光纤激光器的共振式光声光谱乙炔气体检测系统,结合波长调制和锁相放大器的二次谐波信号检测技术,有效地消除了光声池窗片和池壁吸收入射光而引起的背景噪声,通过对该系统的光学、声学和电子检测系统的优化,实现了低浓度乙炔气体的流动式检测.实验结果证明,当气体浓度较低时,二次谐波振幅与气体浓度成正比,其线性响应相关度达到0.999 53.在常温常压和3.5 mW平均光功率以及100 ms锁相积分时间条件下,乙炔气体的极限检测灵敏度达到了0.3 ppm(1 ppm=1μg·mL-1)(SNR=1时),系统用可调谐掺Er光纤激光器代替半导体激光器作光源,降低了成本,为发展低成本、实用、便携式微量气体光谱榆测仪器奠定了基础.若采用多光程光声池,或者采用EDFA提高激光功率,可大幅度提高信噪比,将极限检测灵敏度提高至ppb(1 ppb=1 ng·mL-1)量级.     

快速、高精度可见光-近红外透射光谱测量技术研究

基于传统分光光度测量方法的构架,提出了一种快速、高精度测量可见光-近红外透射光谱的新方法,在该方法的测量过程中,光栅单色器的出射波长保持匀速的连续变化,同时参考光探测器和测试光探测器保持连续的光强采集。初步实验研究表明,新方法可把测量耗时降低到传统分光光度法所需时间的50%以下,测量得到的透射光谱与传统分光光度法的相对误差为0.070%,三次重复性测量的统计误差为0.042%。与现有常见可见光-近红外透射光谱的测量方法(分光光度法、CCD光谱仪法、傅里叶变换光谱仪法)相比,新方法同时具有以下优点：(1)有望显著提高可见光-近红外透射光谱的测量速度,从而应用于透射光谱的动态测量环境中;(2)具有较高的测量精度(0.1%～0.3%);(3)在测量过程中,系统的机械部件始终保持匀速的运动状态,测试系统因而具有较高的机械稳定性。     

A high‐resolution X‐ray fluorescence spectrometer and its application at SSRF

A high‐resolution X‐ray fluorescence spectrometer based on Rowland circle geometry was developed and installed at BL14W1 XAFS beamline of Shanghai Synchrotron Radiation Facility. The spectrometer mainly consists of three parts: a sample holder, a spherically curved Si crystal, and an avalanche photodiode detector. The simplicity of the spectrometer makes it easily assembled on the general purpose X‐ray absorption beamline. X‐ray emission spectroscopy and high‐resolution X‐ray absorption near edge spectroscopy can be carried out by using this spectrometer. X‐ray emission preliminary results with high‐resolution about 3 eV of Mn compounds were obtained, which confirmed the feasibility of the spectrometer. The application about Eu (III) retention on manganese dioxide was also studied using this spectrometer. Compared with conventional X‐ray absorption fine structure spectroscopy technique, the fluorescence peak of probed element [Eu (III) Lα] and matrix constituents (Mn Kα) were discriminated using this technique, indicating its superiority in fluorescence detection. Copyright © 2013 John Wiley & Sons, Ltd.     

PIPS-α谱仪探测效率蒙特卡罗模拟及其影响因素

在放射源能谱测量过程中,PIPS-谱仪探测效率的影响因素有几何因子、空气层吸收、死层吸收、本征探测效率等,为了更精确地计算放射源的活度,分析母体核素种类和浓度,探究各因素对探测效率的影响具有重要意义。使用蒙特卡罗软件模拟不同探源距、真空度下的放射源的能谱测量;使用SRIM模拟5 MeV 粒子在空气和死层中的射程及分布;使用PIPS-谱仪测量241Am,238Pu,239Pu三种标准源的实际能谱;根据实验与模拟的结果对各个因素对探测效率的影响进行分析,并计算得到谱仪对不同放射源的本征探测效率。结果表明:在PIPS-谱仪的能谱测量过程中,影响谱仪探测效率的主要因素是几何因子和本征探测效率,空气层和死层对粒子的吸收可以忽略不计;谱仪对241Am,238Pu,239Pu三种标准源的本征探测效率分别为64.84%,49.95%,51.55%。     

Improved LIBS limit of detection of Be, Mg, Si, Mn, Fe and Cu in aluminum alloy samples using a portable Echelle spectrometer with ICCD camera

Laser-induced breakdown spectroscopy (LIBS) is a laser-based technique that can provide non-intrusive, qualitative and quantitative measurement of metals in various environments. LIBS uses the plasma generated by a high-energy laser beam to prepare and excite the sample in one step. In the present work, LIBS has been applied to perform elemental analysis of six trace elements simultaneously in aluminum alloy targets. The plasma is generated by focusing a pulsed Nd:YAG laser on the target in air at atmospheric pressure. LIBS limit of detection (LOD) is affected by many experimental parameters such as interferences, self-absorption, spectral overlap and matrix effect. We aimed to improve the LIBS LOD by optimizing these experimental parameters as possible. In doing so, a portable Echelle spectrometer with intensified CCD camera was used to detect the LIBS plasma emission. This advanced Echelle spectrometer provides a constant spectral resolution (CSR) of 7500 corresponding to 4 pixels FWHM over a wavelength range 200–1000 nm displayable in a single spectrum. Then, the calibration curves for iron, beryllium, magnesium, silicon, manganese and copper as minor elements were achieved with linear regression coefficients between 98–99% on average in aluminum standard sample alloys. New LOD values were achieved in the ppm range with high precision (RSD 3–8%). From the application view point, improving LIBS LOD is very important in the on-line industrial process control to follow-up multi-elements for the correct alloying in metals.