一种时间分辨激光诱导击穿光谱的测量方法

激光诱导击穿光谱(LIBS)是一种动态光谱。时间分辨LIBS光谱测量是研究激光诱导等离子体演化和谱线自吸收的重要技术。结合激光诱导击穿光谱测量的时序特性,提出一种利用常规性能光谱探测设备获得微秒级时间分辨LIBS光谱的测量方法。通过控制毫秒级光谱探测设备的积分延迟时间,获得不同延时下的LIBS光谱信号,对所得光谱进行处理得到相应特征谱线拟合强度,将所测的特征谱线强度按照一定的时间间隔进行差分,得到差值即为差分间隔时间内特征谱线的积分强度。采用差分时间间隔应大于系统最差时序精度,同时优选无重叠干扰和背底连续的谱线信号进行分析。以等离子体产生后持续时间为横坐标,计算所得谱线差值强度为纵坐标,即可获得特征谱线的强度演化曲线。通过实验验证,使用积分时间为毫秒量级光谱仪和时序精度为0.021微秒控制系统,该方法可以实现微秒量级时间分辨LIBS光谱测量,可用于表征LIBS光谱特征谱线演化过程,降低了LIBS光谱时间分辨测量系统成本。     

离子迁移谱在环境污染物检测中的应用

目前对环境污染物的检测手段有多种,但都存在一定的局限性,作者介绍了一种环境污染气体检测的新方法—离子迁移谱(IMS)法.结合本实验室的研究工作简述了设计制作IMS的基本结构,介绍了IMS的基本原理,阐述了近期国际上IMS在环境污染物(如苯系物、卤代烯烃、全氟化碳、醇类及多环芳香烃等)检测中的研究进展,最后通过对研究结果进行分析,得出IMS在环境污染物检测这一领域中正逐步吸引越来越多的科学家的兴趣,是一种非常有效的环境检测方法,具有重要的应用价值和发展前景.     

自模型曲线分辨法校正ICP-AES中谱线重叠干扰——测量误差对结果的影响

本文将自模型曲线分辨方法(SMCR)应用于ICP-AES谱线重叠光谱干扰的校正,并就测量误差对重叠光谱解析结果的影响作了详细的研究和讨论。两谱线的重叠程度越大,随机误差对光谱干扰校正的影响越大。对测量数据作平滑处理。可以减小数据随机误差对结果的影响,但平滑次数增加,将导致光谱图变形,使干扰校正结果产生较大的误差。数据的平滑不能减小光谱偏离加和性的误差。本工作对两条光谱重叠的情况作了讨论,并取得了较好的结果,表明SMCR法是校正ICP-AES中重叠谱线干扰的一种简便、快速的方法。     

多元曲线分辨法在聚合物红外成像研究中的应用

多元曲线分辨(MCR)是一种强有力的多维数据分析及建模工具,它能够从混合体系中提取独立组分的纯光谱及其浓度分布,而不需要提前知道体系中的纯组分数或组分的性质。红外图像包含大量多维信息,将多元曲线分辨应用于红外成像可以提取图像数据集中隐藏的化学信息。该工作将MCR与红外成像结合应用于聚合物研究,取得很好的结果。这种方法在其他领域同样也有很好的应用前景。     

舰船螺旋桨轴频估计中线谱要素提取算法

舰船辐射噪声DEMON谱(调制解调谱)线谱要素提取是舰船螺旋桨轴频估计中的关键步骤。现有的线谱提取技术主要用于功率谱线谱检测,侧重于线谱频率的确定,不能满足舰船螺旋桨轴频估计需求。本文根据DEMON谱线谱的特点及人工提取线谱的过程,设计了一种新的线谱要素提取算法,改进了谱峰筛选技术,将多时刻的DEMON线谱基于最大似然估计和谱峰序列相似度加以融合决策,最终确定了线谱频率和幅值(峰值)及边界。通过实际数据验证,此线谱要素提取算法更适用于螺旋桨轴频估计,可提高轴频估计的准确率。     

形状平滑约束在多元曲线分辨交替最小二乘(MCR-ALS)解析高光谱成像中的应用

高光谱成像在多学科研究中提供了丰富的数据信息,由于数据量庞大,研究人员使用化学计量学方法对这些数据的信息进行提取。多元曲线分辨交替最小二乘(MCR-ALS)方法能够分辨混合体系的高光谱数据中的纯组分对应的光谱和浓度信息,得到了广泛的使用。为了进一步提高MCR-ALS对高光谱的解析能力,本文使用了形状平滑约束(SSC)分别分析了模拟数据和实验数据,结果表明,通过形状平滑约束,能够进一步提高MCR-ALS对高光谱数据解析的准确度,而且使MCR减少了扭曲模糊,在二线性分辨中获得了唯一解。     

一种离子迁移谱谱图重构及特征峰提取算法

离子迁移谱(IMS)是一种常压下快速、高灵敏度的痕量化学物质检测方法,广泛应用于化学战剂、爆炸物和毒品等检测领域。在离子迁移谱定性和定量分析中,采集到的原始谱图除了包含样品自身信息外,还包含了电噪声、背景干扰等噪声,特别是当分析物浓度低时,噪声会严重影响定性和定量分析的准确性。为提高离子迁移谱技术化学物质识别准确率,需要对离子迁移谱谱图信号进行重构。本文提出一种可同时实现离子迁移谱谱图重构和特征峰提取的新方法。通过建立优化目标函数,采用l_1范数作为线性惩罚项,λ为正则化参数用来调节惩罚项在优化过程中的比例。为了求解优化目标函数,首先构造一个由Gaussian分布函数构成的超完备字典来表示离子迁移谱离子特征峰峰形,采用替代函数方法对优化目标函数进行迭代求解,当达到重构谱图与原始谱图均方根误差小于设定的阈值时停止迭代。为了验证提出的方法性能,分别采用仿真数据和甲基磷酸二甲酯(DMMP)样本数据进行验证,其中仿真数据由高斯分布函数字典原子及高斯白噪声组成。与此同时,我们对仿真数据和真实样本数据分别采用小波软阈值、小波硬阈值及S-G平滑滤波算法进行去噪重构。采用均方根误差(RMSE)和信噪比(SNR)作为评价指标,实验结果表明该方法成功实现离子迁移谱谱图重构和特征峰提取,预处理结果比其他三种方法有显著的性能提升,为开展离子迁移谱定性和定量分析研究提供了基础。     

荧光分子层析中的全时间分辨图像重建法

在荧光分子层析(Fluorescence molecular tomography,FMT)中.全时间分辨(Time Resolved.TR)测量包含了最多的光子传输信息.基于有限元一有限差分扩散方程的正向模型和Newtown-Raphson的逆向模型,将全时间分辨方法用于时域荧光分子层析中.用模拟数据对算法在空间分辨率、定量性、重建尺寸和灰度的保真度以及噪声稳健性等方面进行了验证.结果表明,此方法能够实时重建荧光产率和荧光寿命图像.与以前发展的基于广义脉冲谱技术(Generalized pulse spectrum technique,GPST)的特征数据法进行图像重建相比较.整体上优于广义脉冲谱技术.     

头相关传输函数幅度谱的听觉空间分辨阈值的分析

提出一种分析头相关传输函数(head-related transfer function,HRTF)幅度谱的听觉空间分辨阈值模型。采用数值计算得到的高空间分辨率HRTF数据,计算了声源空间位置变化引起的HRTF幅度谱的变化,进一步利用Moore响度模型分析双耳响度级差、双耳响度级谱和总响度级等三个听觉感知量的变化。根据现有的3个听觉感知量最小可察觉差异,模型利用双耳响度级差和双耳响度级谱的变化得到的估计结果与心理声学实验一致,因此是一种有效预测听觉空间分辨阈值的方法,可用于为简化虚拟听觉信号处理和数据储存。      

头相关传输函数幅度谱的听觉空间分辨阈值的分析

提出一种分析头相关传输函数(head-related transfer function,HRTF)幅度谱的听觉空间分辨阈值模型。采用数值计算得到的高空间分辨率HRTF数据,计算了声源空间位置变化引起的HRTF幅度谱的变化,进一步利用Moore响度模型分析双耳响度级差、双耳响度级谱和总响度级等三个听觉感知量的变化。根据现有的3个听觉感知量最小可察觉差异,模型利用双耳响度级差和双耳响度级谱的变化得到的估计结果与心理声学实验一致,因此是一种有效预测听觉空间分辨阈值的方法,可用于为简化虚拟听觉信号处理和数据储存。     

同分异构体挥发性有机物的放电离子淌度谱研究

离子淌度谱利用大气压下不同离子在电场中的运动速度不同来达到分离离子的目的。离子在电场中的运动速度不仅与离子的质量有关,也与离子的结构有关,因此离子淌度谱可以有效地用来区分同分异构体。文章报道了用自行研制的放电离子源离子淌度谱仪对碳骨架异构、官能团类别异构和官能团位置异构的三类同分异构体进行了实验研究,得到了九种挥发性有机物的离子淌度谱,测量了各离子的约化迁移率,与前人使用神经网络理论得到的计算值相一致。实验表明这些同分异构体有机物能够在高分辨的离子淌度谱中实现分离,而且对本实验所研究的九种同分异构体有机物而言,迁移率大小符合规律：醇类<酮类<芳香类,直链<分支<环状,对位<间位<邻位。实验中使用指数稀释法对样品进行了定量分析,利用该方法得到的检测限达到ng·L-1量级。其中对官能团类别异构的同分异构体以及丁醇同分异构体的放电离子淌度谱研究均为首次报道。     

痕量挥发性有机物的高场不对称波形离子迁移谱研究

高场不对称波形离子迁移谱(high-field asymmetric waveform ion mobility spectrometry,FAIMS)技术是一种快速、高灵敏的痕量物质检测技术.利用自制的高场不对称波形离子迁移谱仪分别对丙酮、苯和甲苯样品进行了检测,结果表明三种挥发性物质在谱图中的分离效果优于传统离子迁...     

强度调制偏振光谱仪解调系数参考光测量方法

针对由理论计算得到的解调系数无法实现强度调制偏振光谱仪实验系统(以下简称"实验系统")测量数据解调处理的问题,提出了测量参考光获取实验系统解调系数的解决方法。该方法通过测量已知偏振态参考光经过实验系统调制器后输出的强度谱,结合傅里叶变换、滤波和逆傅里叶变换等数字信号处理过程,可从测量结果中分离出实验系统的真实解调系数。分析了该方法的理论依据,给出了实验系统解调系数的实测结果,并利用得到的解调系数,对实验系统测量典型待测光源(近似自然光和完全线偏振光)的测量数据进行了解调处理。解调处理结果显示:在有效测量波段范围内(550～650nm),以卤钨灯为光源的平行光管直接输出光的偏振度值约为10%;经过线偏振器起偏后,其偏振度值接近100%,与实际分析结果完全相符。验证了强度调制系统解调系数参考光测量方法的可行性。     

The Interchangeable Module Stellarator

The Interchangeable Module Stellarator (IMS) is a new toroidal stellarator-type device under design and construction at the University of Wisconsin Torsatron/Stellarator Laboratory. A new design strategy for constructing stellarator magnetic fields from discrete modular coils has been developed, utilizing orthogonal toroidal coordinates. Application of this method has resulted in a modular coil system (IMS), whose magnetic structure closely approximates that of the Proto-Cleo Q = 3 7-field period device (i. e., rotational transform, shear, flux volume, etc.).     

Rapid detection of a foreign protein in milk using IMS–SERS

A method for rapid detection of foreign protein contamination in complex food matrices is critically needed. Here we present a novel method that combines immunomagnetic separation (IMS) and surface‐enhanced Raman scattering (SERS) to detect ovalbumin (OVA), an egg white protein, added into whole milk. IMS was used to specifically capture the OVA out of the milk. Then SERS was applied to analyze the IMS eluate using silver dendrites as the substrate. Two SERS sample preparation methods, namely solution based and substrate based, were used to prepare the IMS eluate for SERS analysis. Results show both methods were able to detect 1 µg OVA in 1 ml milk (1 part per million). Based on the results of principal component analysis and partial least‐squares analysis, solution SERS was more capable of quantitative analysis, while substrate SERS was more sensitive for qualitative analysis. The total analytical time for IMS–SERS was less than 20 min, which satisfied the requirement of rapid detection in a milk processing facility. Copyright © 2011 John Wiley & Sons, Ltd.     

Technical Improvements in the Experiment of Isochronous Mass Measurement of 58Ni Projectile Fragments

 The combination of in-flight fragment separator and the isochronous mass spectrometry(IMS) in storage rings have been proven to be a powerful tool for the precision mass measurements of shortlived exotic nuclei. In IMS, the mass-over-charge ratio is only related to the revolution period of stored ions, and the relative mass resolution can reach up to the order of 10−6. However, the instability of the magnetic field of storage ring deteriorates the resolution of revolution period, making it very difficult to distinguish the ions with very close mass-over-charge ratio via their revolution periods. To improve the resolution of revolution periods, a new method of weighted shift correction (WSC) has been developed to accurately correct the influence of the magnetic field instabilities in the isochronous mass measurements of 58Ni projectile fragments. By using the new method, the influence of unstable magnetic fields can be greatly reduced, and the mass resolution can be improved by a factor up to 1.7. Moreover, for the ions that still cannot be distinguished after correcting the magnetic field instabilities, we developed a new method of pulse height analysis for particle identification. By analyzing the mean pulse amplitude of each ion from the timing detector, the stored ions with close mass-over-charge ratios but different charge states such as 34Ar and 51Co can be identified, and thus the mass of 51Co can be determined. The charge-resolved IMS may be helpful in the future experiments of isochronous mass measurement even for N =Z nuclei.     

2D EXSY实验和几何平均法研究水与天然化合物的羟基之间的化学交换速率常数

利用二维核磁共振交换谱(2DEXSY)研究了三种天然产物的羟基质子与水的交换,三种天然产物分别含有四到八个羟基质子.较为简单的几何平均法(GA)被用来进行数据处理.GA法在假定体系和实际体系中,与全矩阵分析和初级速率近似比较,结果尚好。     

Latent variable analysis of Raman spectra for structural characterization of proteins

Latent variable analysis of deep UV resonance Raman spectra was demonstrated to be a powerful tool for characterizing protein secondary structural composition. Non-negative independent component analysis (ICA) and pure variable methods, such as stepwise maximum angle calculation (SMAC) and simple-to-use interactive self-modeling mixture analysis (SIMPLISMA), were employed for examination of 10 deep UV Raman (DUVRR) spectra of lysozyme obtained at various stages of its partial denaturation, the first stage of amyloid fibril formation. The non-negative ICA allowed for extracting the spectrum of the β-sheet from deep UV resonance Raman spectra of lysozyme while principle component analysis (PCA) and multivariate curve resolution (MCR) could not separate the β-sheet constituent as an individual component. No initial guess about the features of the β-sheet spectrum was used. Pure variable methods SMAC and SIMPLISMA were found to resolve three independent spectral components assigned to β-sheet, random coil, and native lysozyme.     

Random Initialisation of the Spectral Variables: an Alternate Approach for Initiating Multivariate Curve Resolution Alternating Least Square (MCR-ALS) Analysis

Multivariate curve resolution alternating least square (MCR-ALS) analysis is the most commonly used curve resolution technique. The MCR-ALS model is fitted using the alternate least square (ALS) algorithm that needs initialisation of either contribution profiles or spectral profiles of each of the factor. The contribution profiles can be initialised using the evolve factor analysis; however, in principle, this approach requires that data must belong to the sequential process. The initialisation of the spectral profiles are usually carried out using the pure variable approach such as SIMPLISMA algorithm, this approach demands that each factor must have the pure variables in the data sets. Despite these limitations, the existing approaches have been quite a successful for initiating the MCR-ALS analysis. However, the present work proposes an alternate approach for the initialisation of the spectral variables by generating the random variables in the limits spanned by the maxima and minima of each spectral variable of the data set. The proposed approach does not require that there must be pure variables for each component of the multicomponent system or the concentration direction must follow the sequential process. The proposed approach is successfully validated using the excitation-emission matrix fluorescence data sets acquired for certain fluorophores with significant spectral overlap. The calculated contribution and spectral profiles of these fluorophores are found to correlate well with the experimental results. In summary, the present work proposes an alternate way to initiate the MCR-ALS analysis.     

A brief review on mass/optical spectrometry for imaging analysis of biological samples

Imaging analysis, especially bioimaging analysis, has been a hot research topic in recent years. There are numerous imaging analysis techniques for diverse applications of a wide spectrum of samples, with their unique advantages and disadvantages, and there are several related reviews published yearly. Among them, imaging mass spectrometry (IMS) is a relatively novel analytical technique for studying the distribution of molecular or ionic species at the level of tissue, cell, or subcellular, with its main feature of combining mass spectra for molecular identification and image visualization for quick and convenient analysis. The IMS does not require chemical labeling or complex sample preparation. This review, therefore, mainly focuses on the popular emerging IMS technique, including related ionization techniques in connection with their IMS applications, and some unique optical imaging techniques such as chemiluminescence imaging and dual-modal bioimaging for biological sample analysis, with 105 related recent references.