NO2分子内能传递和弛豫过程的光声和荧光光谱探测

将荧光光谱和光声光谱两种互补的探测技术结合起来,从辐射和无辐射跃迁两个方面,分析了 532nm激光作用下,NO2分子的激发和弛豫过程.发现NO2分子在激光作用下,将跃迁至第一激发电子态.当样品气压较低时,受激NO2分子除辐射荧光外,可通过快速的内能转移过程实现在几个振转能级的再布居;随样品气压的升高,分子间碰撞加剧,受激NO2分子通过分子间的碰撞,实现在多个振转能级的再布居.激光布居能级的荧光辐射效率随样品气压的升高逐渐降低,而长波区域的荧光辐射及光声信号强度逐渐增强,说明在高样品气压条件下,受激NO2分子的弛豫过程除辐射荧光外,还存在很强的碰撞弛豫过程,在碰撞弛豫过程中受激NO2分子将振动能转化为热运动的平动能,引起温度升高而产生很强的声信号.     

基于可调谐多模二极管激光吸收光谱的二氧化碳浓度测量

可调谐二极管激光吸收光谱技术(TDLAS)具有高分辨率、高灵敏度和快速测量等特点,是气体探测中的主流技术。使用多模二极管激光器作为光源,将多模二极管激光吸收光谱技术与关联光谱技术相结合有助于提高测试可靠性和稳定性,同时还可有效解决单模二极管激光器长时间工作时中心波长随外界温度或机械特性的变化而发生偏移的问题。以1 570 nm多模二极管激光器为光源,利用多模二极管激光关联光谱和波长调制的气体测量技术(TMDL-COSPEC-WMS),通过计算待测气体和参考池气体之间二次谐波信号峰值高度之间的关系,实现了对二氧化碳浓度的测量。实验中二氧化碳浓度测量范围在0.6%～30%之间,计算结果表明,二氧化碳浓度与真实浓度值之间具有良好的线性关系,其线性度为0.998 7,线性拟合的斜率为1.061±0.016 8。对二氧化碳与氮气混合气体的连续测量结果表明,系统的探测极限达到335 ppm·m,对同一样品在20 min内的20次连续测量的标准偏差为0.036 7%,表明了系统良好的稳定性,所有测量结果都显示了系统用于二氧化碳气体监测的有效性。     

基于石英增强光声光谱的HCl痕量气体高灵敏度探测研究

HCl是一种有毒有害气体,对其高灵敏度探测具有非常重要的意义,然而到目前为止,采用激光光谱的手段对其探测的研究报道很少。石英增强光声光谱(QEPAS)是近年来发展起来的一种痕量气体探测技术,具有系统体积小、价格低廉、探测灵敏度高等优点。以5 000 ppm HCl∶N₂混合气作为待测目标,采用输出波长为1 742.38 nm的分布反馈连续波单纵模半导体激光器,开展对基于QEPAS技术的HCl高灵敏度探测研究。为了提高信噪比和简化数据处理过程,QEPAS传感器系统采用波长调制和2次谐波探测技术。研究中,首先对声波探测系统中微共振腔强声波增强特性进行了讨论,选择了“共轴”形式的声波微共振腔,并对其尺寸进行了优化,选择的微共振管长度为4 mm、内径为0.5 mm。实验中研究了激光波长调制深度对QEPAS系统产生的信号幅度的影响,当QEPAS系统积分时间为1 s、激光波长调制深度为0.23 cm-1时,获得了815 ppb的优异检测极限,归一化噪声等效吸收系数为7.41×10-9 cm-1·W·Hz-1/2。在后续的实验中,可在待测HCl气体中加入水汽分子,提高HCl分子的热弛豫速率,进一步提高HCl-QEPAS传感器系统的信号强度。     

基于光克尔门空间扫描单次激光信噪比测量

提出一种基于光克尔门空间扫描的单次激光信噪比测量方法.在该方法中,门光和探测光在光克尔介质中正交传输,通过光克尔门对探测光的空间扫描实现激光信噪比测量.采用该测量方法进行了单次激光信噪比测量的实验研究,测得时间窗口和分辨率分别为88.2ps、2.7ps.由于取样门是由光克尔效应来控制,因此该激光信噪比测量方法对于待测激光的波长没有限制.     

基于光克尔门空间扫描单次激光信噪比测量（英文）

提出一种基于光克尔门空间扫描的单次激光信噪比测量方法.在该方法中,门光和探测光在光克尔介质中正交传输,通过光克尔门对探测光的空间扫描实现激光信噪比测量.采用该测量方法进行了单次激光信噪比测量的实验研究,测得时间窗口和分辨率分别为88.2ps、2.7ps.由于取样门是由光克尔效应来控制,因此该激光信噪比测量方法对于待测激光的波长没有限制.     

纳米光学和生物单分子探测

纳米光学技术展示了纳米级探测本领,同时生物单分子探测所需要分辨尺度也是纳米数量级的,因此在生物单分子探测过程中,纳米光学发挥了巨大的作用.文章介绍了与生物单分子探测技术相关的纳米光学技术,包括量子近场光学探针技术、近场光学成像技术（包括扫描近场光学显微术及全内反射荧光显微术）和激光光钳测控技术及它们在生物单分子探测上的进展,从而在染色、成像、测控三个方面展示了纳米光学技术在生物方面的应用,并对其未来的发展方向进行了展望.     

基于TDLAS技术的天然气中痕量硫化氢分析的PLS算法应用

基于可调谐二极管激光吸收光谱技术的光谱分析仪测量天然气中硫化氢浓度的过程中,各种轻烃和二氧化碳等背景成分对光谱产生干扰,导致多个吸收峰叠加,对提取吸收光谱真实特征造成影响.应用偏最小二乘法消除背景成分的干扰,设计了检测天然气中硫化氢气体的可调谐二极管激光吸收光谱实验系统,采用偏最小二乘法和最小二乘法模型,分别检测了天然气中0~50ppm硫化氢成分的直测光谱和差分光谱.偏最小二乘法算法的测量结果均优于最小二乘法算法,且偏最小二乘法算法对于直测谱的测量误差保持在±1ppm范围内,满足分析仪器2%的准确度要求.利用偏最小二乘法算法避免了最小二乘法所必须的大量参考光谱数据的存储,分析仪可省掉复杂的差分光谱系统,从而达到降低成本、提高系统鲁棒性和实时性的效果.     

调谐半导体激光吸收光谱自平衡检测方法研究

可调谐半导体激光吸收光谱技术(TDLAS)是利用半导体激光器的波长调谐特性,扫描待测气体特征吸收线,从而获得待测气体的浓度信息。基于可调谐半导体激光吸收光谱的自平衡检测方法能够有效地消除激光器光强波动等共模噪声和其他同性干扰的影响。实验表明自平衡检测方法可以获得较理想的结果,检测限低于体积比1.2×10-6,与直接吸收光谱法相比降低了一个数量级。自平衡检测电路简单,自带的电子增益补偿机制能够自动进行平衡探测,该方法不用加信号调制和锁相放大器,直接探测待测气体的吸收光谱,从而降低成本,减小系统装置体积,易于集成为便携式痕量气体检测仪。     

21世纪的光学和光电子学讲座 第一讲 激光化学：化学物理学中的一个新研究

基于激光同分子的相互作用,激光既可用于分子结构、性质及化学反应过程的探测。也可用于化学反应的引发和控制,从而形成了一个研究领域－－激光化学。文章对该领域的发展作了介绍。     

激光斯塔克光谱的光声探测与光电探测的比较

本文报导了~(12)CH_3CT和~(12)CH_3F分子的激光斯塔克光谱的光声探测实验结果.实验表明,当为了达到高的电场而降低气压时,从斯塔克电极之间产生和传播的光声信号急骤下降.与光电控测法的实验比较表明,在类似的实验条件下,光电探测比光声探测具有更高的灵敏度和信噪比.     

基于光热效应的显微光谱技术在单粒子检测中应用和发展

高灵敏度的单粒子检测技术是纳米粒子在生物医学、化学、光电子等领域应用的前提条件。常见的单粒子检测技术主要包括基于粒子的荧光、拉曼、散射和吸收等信号而发展起来的光学显微成像及光谱技术。其中,拉曼光谱和荧光光谱技术主要适用于一些具有拉曼活性的分子/粒子或可发光的荧光分子或粒子,然而即使对于荧光效率高的有机染料分子和半导体纳米粒子,固有的光漂白和blinking现象也对单粒子探测形成了挑战。散射光谱测量是应用于单粒子检测的另外一种方法,从理论上讲,由于瑞利散射随着尺寸的减小而呈六次方减弱的趋势,在细胞或生物组织内,小尺寸粒子的散射信号很难从背景散射噪声中分离出来。众所周知,介质吸收激发光后会引起介质内的折射率变化,进而在光加热区附近出现折射率的梯度分布,称为光热效应(photothermal effect)。基于粒子光热效应的光学显微成像和光谱测量技术具有信号灵敏度高、无背景散射、原位和免标记等优点,在单粒子检测领域展现了良好的应用潜力。综述了近年来基于光热效应的显微光谱技术在单粒子检测中应用和研究发展,首先介绍了光热效应的测量原理;接着分别讨论了光热透镜测量技术、微分干涉相差测量技术和光热外差测量技术的实验装置,比较了各种测量技术的信噪比、灵敏度、分辨率等特点,并且介绍这些测量技术在单粒子检测中的应用研究进展;接着,论述了近年来研究人员在提高光热显微测量的信噪比、改善动态测量性能以及在红外波段拓展等方面的最新研究成果;最后,简单总结了光热测量技术在单粒子检测领域所面临的挑战。     

拉直的单个DNA分子的全内反射荧光实时成像研究

全内反射荧光(TIRF)成像技术利用穿透深度仅200 nm左右的隐失波来激发诱导荧光,探测灵敏度和图像信噪比大大提高,成为单分子研究的有力工具。分子梳技术利用DNA末端与固体表面的结合力和周围流体流动产生的侧向力将DNA分子拉伸并平铺在表面上。结合这两种技术,对分子梳拉直的单个DNA分子进行了清晰的实时荧光成像,发现TIRF成像条件下DNA分子与荧光探针YOYO-1组成的复合体可自然避免发生光敏断裂现象;实时监测了单个DNA-YOYO-1复合体的光漂白过程,通过对激发光照射时间与探测器曝光时间进行同步控制,可大幅降低光漂白程度,为拉直的单个DNA分子的长时间实时观察和成像研究优化了实验条件,为实时、可视化地研究其与蛋白质相互作用的动力学过程奠定了基础。     

The photo-association of 9-methyl anthracene molecules

Experimental investigations have been carried out on the photo-association of 9-methyl anthracene molecules by measuring the quantum yield of photodimerization for solutions of given concentrations at different temperatures. In addition, the fluorescence spectra of the solutions were measured as a function of temperature and the lifetime of molecular fluorescence was measured at room temperature as a function of concentration. The analysis of the results on the basis of a kinetic scheme proposed by Birks indicates that the photodimer results from the interaction between an excited molecule and an unexcited molecule with an activation energy for photodimer formation of about 0.23 eV.     

Temperature dependences of dual fluorescence as criterion for determining character of photoreactions

We performed comparative studies of the temperature quenching of dual fluorescence of acetonitrile solutions of several molecular probes with proton transfer reaction in an excited singlet state of 4′-(dieth-ylamino)-3-hydroxyflavone (FET), 1-methyl-2-(4-methoxy)phenyl-3-hydroxy-4(1H)-quinolone (QMOM), and 3-hydroxyflavone (3HF) parent molecule at different energies of excitation quanta. In accordance with expressions obtained from balance equations for photoreactions of the kinetic and thermodynamic character, the intensity ratios of fluorescence bands as functions of the degree of quenching behave differently. Namely, the quenching increases the relative intensity of bands normal form/tautomer for reactions of the kinetic type, retaining this ratio unchanged for reactions of the thermodynamic character. Our experimental studies showed that, for fluorescent probes with the kinetic reaction (3HF and QMOM), the intensity ratio fluorescence bands increases almost linearly with the degree of quenching, whereas, in the thermodynamic case (FET), this ratio is independent of this parameter. Conclusions about the character of reactions that we obtained in this work agree well with data of independent investigations of these molecules by laser spectroscopy with high time resolution, and the obtained relations allow us also to judge the mechanism of temperature quenching in the case of the reaction of the kinetic type. The method can be used for comparatively simple express selection of molecular probes, candidate for new applications.     

A Statistical Analysis of Fluorescence Correlation Data

Fluorescence correlation spectroscopy (FCS) is a relatively recent technique in which the diffusion coefficient of fluorescently labeled molecules can be determined. The change in diffusion behavior when these molecules interact with others can also be used to study interactions in solution. A new statistical method is proposed to analyze FCS measurements that cannot be evaluated with a classical autocorrelation function, which is normally used to analyze FCS data. It applies to binding studies where one of the interacting particles has a much brighter fluorescence intensity with respect to the other, which causes high fluorescence bursts whenever these molecules are detected. This biases the autocorrelation function, making it in most cases impossible to use this function as a fitting equation. Here, a statistical approach is used to quantify the amount of fluorescence found in bursts, thereby enabling to perform binding studies in cases where the fluorescence per molecule of both interacting species differs greatly. The method is demonstrated on a system of known composition, making it a promising tool for future FCS measurements.     

光缔合制备超冷铯分子的温度测量

利用光缔合超冷Cs原子形成超冷Cs2分子,采用多光子电离方法对超冷Cs2分子进行探测,对分子扩散过程中分子密度随时间的演化进行测量,获得了超冷Cs2分子的弛豫曲线.基于一个简单的模型即原子、分子样品的初始分布是位置和速度的高斯函数,通过理论模拟获得了超冷原子、分子样品的温度,测得的原子温度与释放-再俘获方法获得的结果相符合,这种方法避免了通过探测微弱分子荧光来获得分子温度的弊端,可广泛应用于超冷原子、分子样品的温度测量.     

Some Medical Applications of Radioisotopic Induced X-Ray Fluorescence Analysis

The X-ray fluorescence, induced by radioactive sources, provides a very sensitive technique for the analysis of trace elements in biological samples.

Liquid samples are deposited on filter paper disks, thus increasing the solids concentration, and are successively analyzed for single-element analysis by means of a very simple equipment which consists of a proportional gascounter,an amplification chain, a single channel analyzer and a timer-scaler. For multielement analysis a high resolution Si(Li) detector and a pulsehigh analyzer are employed. The sensitivity of the technique ranges from a tenth of part per million to some parts per million. The X-ray fluorescence analysis has been applied to trace elements determination in blood and hair samples. Further applications of the technique to the analysis of elements introduced into blood are discussed. Finally, applications of X-ray analysis to the study of kinetic processes are shown.     

某些稠环芳香碳氢化合物的荧光寿命测量

应用时间相关单光子计算仪器,测量了八个对荧光光谱学和生物化学重要的稠环芳烃.所有溶液在测量前均通高纯氮除氧,对所有化合物都使用337nm激发波长,对荧蒽还在351nm激发,以验证上述两组作者所给数值之间的分歧.我们的实验对于荧蒽在337nm激发给出荧光寿命39ns,在351nm激发给出36ns,表明两个激发波长不应导致寿命数值的实质性差异.我们对其余稠环芳烃所测得的寿命值或者与文献相符,或者看起来是合理的.     

Time-dependent delayed electron spectra: a direct measurement of total decay rate as a function of internal energy

We present a general method to measure internal energy dependant decay rate in the case of systems emitting thermal electrons. Our approach is based on the measurement of the time-dependent kinetic energy spectra of delayed electrons using time-resolved velocity map imaging spectrometry. We illustrate this method in the case of C₆₀ molecules. Indeed electron spectra for C₆₀ have been studied in great details in the past few years, allowing a complete analysis of the observed features. Moreover, C₆₀ offers the opportunity to study competing decay mechanisms demonstrating that the technique may have broader applicability to other molecules. Using a model that includes all contributing decay channels relevant in our time delay range (namely delayed ionization and dissociation by C₂ emission) we are able to derive quantitative information on the decay channels of the molecule. In the situation considered here, the time-dependent electron temperature extracted from the kinetic energy spectra is used to determine more precisely the rate constant for the dominant process, namely neutral C₂ dissociation channel. In other words, the measurement of the cooling of an ensemble of C₆₀ molecules as a function of time delay after heating provides a direct and quantitative access to its decay dynamics. This method may be used to map out the total rate for complex decay mechanisms.     

全内反射荧光显微术

全内反射荧光显微技术是当今世界上最具前途的新型生物光学显微技术之一，可以用来实现对单个荧光分子的直接探测。它利用全内反射产生的隐失波照明样品，使照明区域限定在样品表面的一薄层范围内，因此具有其它光学成像技术无法比拟的高的信噪比和对比度。近上来，已被生物物理学家们广泛应用于单分子的荧光成像中。本文系统的介绍了全内反射荧光显微技术的原理。国内外的发展和现状及其在生物学上的应用，并对其未来做了展望。