水溶液中硫酸根离子的拉曼光谱定量分析

拉曼光谱因其具有无损、非接触以及原位的技术优势被广泛应用于科学研究领域。但是,当前拉曼光谱主要应用于定性研究,即根据拉曼波数偏移进行物质分子的鉴别,相比之下,拉曼光谱定量分析则明显不足。因此,有必要进一步开展拉曼光谱定量方面的研究。根据拉曼光谱原理分析可知,拉曼光谱定量研究应当根据相对强度比进行,也就是在定量化过程中需要选择一个参考系,可以分为内标法和外标法。拉曼光谱定量可以根据被测分子与该参考系的拉曼强度比值进行,通过这个方法可以消除测试条件的影响。对水溶液而言,可将液态水的OH伸缩振动作为内标,进行拉曼光谱定量分析。本文研究了Na₂SO₄-H₂O,K₂SO₄-H₂O以及NaCl-Na₂SO₄-H₂O体系的拉曼光谱特征。通过将水分子的OH伸缩振动（2 750~3 900 cm-1附近）拟合为两个高斯谱峰,并以I_SO2-4/I_W为参数来确定溶液中的硫酸根离子浓度,其中I_SO2-4为硫酸根离子的特征峰强度,I_W为水的两个高斯谱峰强度之和。实验结果表明,水溶液中SO2-₄浓度与拉曼强度比I_SO2-4/I_W之间有较好的线性关系,其中,R2=0.997 73,符合定量要求。据此,本文应用拉曼光谱定量分析,建立了一种相对快速、准确测量水溶液中SO2-₄浓度的方法。     

高温高压下草酸脱羧反应中的拉曼光谱研究

应用水热金刚石压腔结合拉曼光谱技术研究了高温高压下草酸溶液的热稳定,使用拉曼光谱对其脱羧反应及产物进行监测。结果表明低温升温过程中,草酸的拉曼谱图中各个特征振动峰没有发生变化,随着温度的继续升高,其特征振动峰逐渐变弱。达到一定温度后,羧基的拉曼特征峰消失,草酸发生脱羧反应:C2H2O4—2CO2+H2生成CO2和H2。高温高压下草酸发生热分解的温度压力之间呈线性关系,其线性回归方程为P(MPa)=12.839 T(K)-5 953.7,R2=0.99。草酸脱羧反应的摩尔体积变化与温度压力的关系为ΔV(cm-3.mol-1)=16.69-0.002P(MPa)+0.005 2T(K),R2=0.99。     

硫酸铵溶液的拉曼光谱特征及其产生机理研究

实验研究了硫酸铵溶液的拉曼光谱特征,得到了硫酸铵溶液中SO2-4的几种典型拉曼特征峰,发现SO2-4浓度和对应的拉曼峰强度间存在线性关系,根据实验结果建立了拉曼光谱参数与离子浓度间的关系数据库。理论上通过Gaussian 03和Hartree-Fock方法(从头计算)对SO2-4的几何结构进行优化并计算出该离子的振动基频,将得到的理论振动基频与实验结果进行比较,发现实验与理论计算结果吻合较好。研究结果证实了利用拉曼光谱技术对硫酸铵进行定量分析的可行性,对工业上鉴别铵盐类别、精确测量不同铵盐含量、生产铵盐等均具有一定的参考价值。     

四氯化碳萃取辅助的水中甲烷拉曼探测技术研究

在常温常压下,由于甲烷(CH4)在水中的溶解度很低,使用常规拉曼光谱技术很难获得水中溶解的低浓度甲烷的拉曼信号。为解决上述问题,提出了一种四氯化碳(CCl4)萃取辅助的探测新方法。利用萃取作用,把溶解在水中的微量甲烷富集到四氯化碳溶液中,通过对其中溶解的CH4拉曼信号的探测以检验水中微量CH4的存在,以此提高实验室条件下水中溶解甲烷的探测灵敏度。在实验室条件(25℃,1atm)下,分别对CH4的饱和水溶液(浓度约为1.14mmol·L-1)、CCl4萃取液以及CH4的饱和CCl4溶液进行了光谱探测分析。结果表明,对CH4的饱和水溶液直接探测,未能获得CH4的拉曼信号;通过萃取辅助,成功地在CCl4萃取液中检测到CH4的拉曼信号,其强度与CH4的饱和CCl4溶液的信号强度相近,实现了在实验室条件下对水中溶存甲烷气体的探测。     

水热金刚石压腔结合拉曼光谱技术进行Na2SO4-水体系溶解结晶动力学研究

成矿作用过程中,温压条件改变导致矿物溶解重结晶,溶液中溶质浓度发生变化。从溶液中析出晶体的粒度同时存在着时间和空间的分布,是复杂的动力学过程。当前对矿物在流体中溶解重结晶动力学研究主要使用高压釜或活塞圆筒等封闭设备测定溶液溶质浓度的变化或固相矿物的形态变化,降温淬火反应会影响样品的真实组成。使用可进行原位观测的金刚石压腔结合拉曼光谱分析技术,研究无水芒硝-饱和Na₂SO₄溶液随体系温度压力变化所出现的晶体溶解重结晶过程。通过原位观测无水芒硝溶解、结晶变化来探究硫酸钠晶体在不同温压条件下的溶解结晶动力学反应机制。结果表明常温条件下无水芒硝拉曼位移分别位于449.9,620.5,632.9,647.4,993.3,1 101.8,1 132.2和1 153.1 cm-1。随着体系温度的缓慢升高,固相Na₂SO₄的晶形不断发生变化,温度至193 ℃时无水芒硝（Na₂SO₄）完全溶解,降温重结晶出现了新的1 196.5 cm-1拉曼特征峰,重结晶晶体为芒硝（Na₂SO₄·10H₂O）;金刚石原位观测结果显示迅速升温过程中无水芒硝发生部分溶解重结晶,重结晶区域拉曼特征峰显示依然为无水芒硝。拉曼光谱定量分析结果显示,溶液中SO2-₄,H₂O的拉曼谱峰面积比值参数更能反映SO2-₄浓度的变化, 体系达到溶解重结晶平衡状态时,SO2-₄/H₂O峰面积比值AR为(0.016 6±0.000 4),误差为2.4%。应用Johnson-Mehl-Avrami-Kolmogorov（JMAK）模型结合溶液中SO2-₄/H₂O峰面积比值变化对体系中固相无水Na₂SO₄的溶解重结晶过程进行动力学拟合,计算得出无水硫酸钠在109 ℃条件下的溶解结晶反应的反应级数为1.266 7,反应平衡常数为0.001 26。综上所述,水热金刚石压腔装置实验步骤少,过程简便,可避免由于淬火过程中退化交换作用等造成的误差,应用水热金刚石压腔原位观测的装置优势结合拉曼光谱定量分析技术可实现高温高压条件下矿物在水溶液中溶解结晶动力学过程的原位观察和测定,是一种高效的动力学研究手段。     

几种盐水溶液拉曼工作曲线的绘制

用激光拉曼光谱对几种常见盐水溶液进行测定 ,并采用了两种不同的方法对数据进行分析 ,结果表明强度比值法对Na2 CO3、NaHCO3、Na2 SO4 等具有强拉曼特征峰的盐水溶液适用 ,而频移参数法对NaCl溶液效果较好。同时观察到 ,当水溶液中盐度越大时 ,水拉曼峰的不对称性越明显。     

KCl—O_2体系高温高压拉曼光谱研究

利用金刚石压腔装置和激光加热技术,在高温高压下对KCl—O_2体系进行化学反应研究。实验中先将样品体系预压到37 GPa,然后对样品进行激光加热处理,加热温度(1 800±200) K,淬火至常温后进行激光拉曼测试。拉曼测试结果显示KCl—O_2体系在高温高压下发生了新奇的化学反应,生成三方(P-3c1)结构的非传统化合物KCl_3、少量KClO_4、固体Cl_2(Cmca)以及可能存在的另外一种非传统化合物KO_4。实验中P-3c1-KCl_3高压下测到了11个拉曼振动峰,基于P-3c1-KCl_3第一性原理拉曼光谱的理论计算,将这11个拉曼振动峰进行振动模式归属。P-3c1-KCl_3在卸压过程中拉曼峰强度逐渐变弱,于压力小于10 GPa时逐渐分解变成KCl和Cl_2,反映其不能在常压下保存。KO_4在高压下受到金刚石拉曼峰的干扰难以检测到拉曼峰,而在常压下打开金刚石压腔后测到了KO_4的3个拉曼振动峰。实验显示易吸潮的KO_4黑色粉末能够保存到常压。KCl_3和KO_4中分别具有带分数负电荷的非线性对称Cl—Cl—Cl聚阴离子链和O—O原子对,反映高压有利于形成非常规聚阴离子(Cl~-_3)和阴离子(O~-_4),表现出与常压或者低压不一样的化学特性。实验显示在高压下存在数个不同寻常的化学反应,通过对反应物和生成物的氧化还原价态分析显示, O得到电子由0价变成负价态,而Cl失去电子由负价态变成0价或者正价态,反映高压下O得电子能力强于Cl。这些新奇的化学反应以及非常规聚氯阴离子化合物P-3c1-KCl_3的实验观察为合成具有奇特性质的聚阴离子化合物提供了新的思路。     

基于SERS技术快速检测水溶液、尿液和血清中咪达唑仑的研究

为了快速检测水溶液、尿液和血清中的咪达唑仑,建立了一种基于表面增强拉曼光谱(SERS)技术的检测方案。使用BWS415-785H型便携式拉曼光谱仪采集了拉曼光谱,其激发光波长为785 nm,光谱测量范围为68～2 700 cm~(-1),光谱分辨率小于3 cm~(-1),激光功率为80 mW,积分时间为5 s。首先通过密度泛函理论对咪达唑仑的拉曼光谱进行了计算,并与实验值进行对比,对拉曼峰进行了归属。然后以银溶胶作为表面增强基底,以硫酸镁(MgSO_4)水溶液作为促凝剂,选取689和827 cm~(-1)处的拉曼峰作为特征峰,对咪达唑仑进行了SERS检测。在水溶液中咪达唑仑的检测限为6μg·mL~(-1),在5～40μg·mL~(-1)浓度范围内,拉曼特征峰的强度随咪达唑仑水溶液浓度的线性曲线方程为y=188.18x-743.05,相关系数为r=0.972,回收率范围为98.2%～107.2%, RSD范围为2.08%～3.25%。在尿液中咪达唑仑的检测限为20μg·mL~(-1),在20～125μg·mL~(-1)浓度范围内,拉曼特征峰的强度随咪达唑仑尿液浓度的线性曲线方程为y=59.78x-640.71,相关系数为r=0.958,回收率范围为96.9%～107.9%, RSD范围为4.45%～5.75%。在血清中咪达唑仑的检测限为20μg·mL~(-1),在15～125μg·mL~(-1)浓度范围内,拉曼特征峰的强度随咪达唑仑血清浓度的线性曲线方程为y=30.81x+176.66,相关系数为r=0.963,回收率范围为94.2%～105.7%, RSD范围为3.60%～4.41%。该方法具有快速、准确、无损、操作简便等优点,为咪达唑仑的现场快速检测打下了良好的基础。     

硫酸根拉曼频移用于深海热液温度探测的方法探讨

作为一种典型的深海极端环境,热液区域不仅分布着各种硫化物矿产,而且孕育着特殊的生态群落,对热液流体理化性质的研究有助于深入了解热液的运动机制。激光拉曼光谱技术除了定性分析方面的优势外,已经被逐步用于定量分析,并且在原位探测中发挥了重要作用。该研究模拟了深海热液喷口流体的高温高压环境,探讨了水分子和硫酸根离子的拉曼光谱在热液流体温度探测中的应用价值。通过对水峰ν₁（H₂O）、硫酸根ν₁(SO2-₄)的拉曼频移与温度、离子浓度的关系进行研究,结果表明水峰ν₁（H₂O）和硫酸根ν₁(SO2-₄)的拉曼频移随温度表现出明显的变化,水峰ν₁（H₂O）的拉曼频移受流体硫酸根浓度的影响明显,因此不适用于硫酸根离子浓度变化明显的热液流体温度的测量。相比之下,ν₁(SO2-₄)的拉曼频移对流体硫酸根浓度和流体压力不敏感,为温度的反演提供了很好的依据。建立了ν₁(SO2-₄)的拉曼频移与温度的线性方程：Rν₁(SO2-₄)=-0.03T+980.69,其中,R2=0.998 6,可用于对深海热液喷口流体温度的原位探测等实际应用。     

溶液浓度对CCl4费米共振的影响

测量了四氯化碳在苯中不同浓度的拉曼光谱,分析了不同浓度下四氯化碳v₁+v₄~v₃费米共振的变化。结果表明:随着浓度的降低,两费米双光谱强度比R增加,而频差Δ减小、费米共振耦合系数W减小、非谐力常数K增加。这种费米共振随浓度的变化是由溶剂效应引起的,即随着四氯化碳在苯中的浓度降低,其拉曼散射系数(光谱强度)增加,使两费米双线光谱强度增加而减弱了费米共振。     

Guided-Wave Two-Dimensional Acousto-Optic Scanner Using Proton-Exchanged Lithium Niobate Waveguide

Two-dimensional scanning of a 0.6328 mum guided-light beam has been realized using noncolinear acousto-optic (AO) coplanar Bragg diffraction together with colinear AO guided-mode to substrate radiation-mode conversion in a Z-cut Xpropagation LiNbO3 proton-exchanged (PE) waveguide. The two surface acoustic (SAW) waves utilized are at the center frequencies of 500 and 200 MHz, propagating in the Y and X axes, respectively. Two-dimensional scanning of approximately 720 resolvable light beam spots, namely, 18 40 (horizontal vertical) scanning, has been demonstrated using a light beam of 1.0 mm aperture. The total number of resolvable beam spots can be greatly increased from 720 by simply utilizing SAW transducers of larger bandwidth and a light beam of greater aperture. It should also be possible to significantly increase the diffraction efficiency from 3 % by optimizing the parameters of the PE waveguide and the SAWs.     

Femtosecond Transform-Limited Pulse Generation by Compensating for the Linear Chirp of SPM Spectra in Dispersion Shifted Fibers

A simple technique of pulse compression, based on the linear chirp compensation of self-phase modulation (SPM) spectra in dispersion shifted fibers, is demonstrated. The optimization procedure is carried out, for a short span of a single-mode fiber, using a parabolic law, which describes the behavior of the squared output pulse width versus the pump peak power in the case of Gaussian pulses. The experimental results give a minimum pulse duration of 233 fs, which is in good agreement with the model. Shorter and coherent pulses, down to 90 fs, have been obtained by inserting an interference filter at the optical output.     

Effect ofγ-radiation on the spectral luminescence characteristics of impure cadmium tungstate crystals

Results of a study of the effect of γ-radiation on the spectral luminescence properties of cadmium tungstate crystals doped with silver, bismuth, and molybdenum cations are presented. Spectral characteristics of the nondnnnoped crystals are briefly described. Absorption and photo and X-ray luminescence spectra of the crystals taken before and after exposure to γ-radiation (5.5·10⁴ Gy) are compared. It is found that the spectral characteristics of the crystals doped with silver, bismuth, and molybdenum cations do not change markedly after the exposure. The relation between the type of impurity-induced defects, individual characteristics of the impurity cations, and the character of the effect of γ-radiation on the spectral luminescence properties of impure crystals is analyzed (preliminarily). Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 55–60, January–February, 1997.     

Theoretical analysis and simulation of conjugate heights for dual-conjugate AO system in lidar

A multi-conjugate adaptive optics （MCAO） can offer a possibility of widening field of view （FOV） characterized by the isoplanatic angle, and the choose of conjugate height becomes a basic problem for MCAO, which influences the size of iosplanatic angle. Considering the application of lidar, the isoplanatic angle＇s expressions of two deformable mirrors （DMs） MCAO for uplink and downlink are deduced. The effects of conjugate heights for dual-conjugate AO are thoughtfully discussed, and the isoplanatic angles are further analyzed. The results show that the isopanatic angle varies with the conjugate height and reaches the maximum as the conjugate height is at the optimal altitude. Moreover, the optimal conjugate height changes with the propagation distance.     

Quick single-photon detector with many avalanche photo diodes working on the time division

Due to the limit of response speed of the present single-photon detector, the code rate is still too low to come into practical use for the present quantum key distribution (QKD) system.A new idea is put up to design a quick single-photon detector.This quick single-photon detector is composed of a multi-port optic-fiber splitter and many avalanche photo diodes (APDs).Au of the ports with APDs work on the time division and cooperate with a logic discriminating and deciding unit driven by the clock signal.The operation frequency lies on the number N of ports, and can reach N times of the conventional single-photon detector.The single-photon prompt detection can come true for high repetition-rate pulses.The applying of this detector will largely raise the code rate of the QKD, and boost the commercial use.     

Sorting of bending magnets for the SSRF booster

The Shanghai Synchrotron Radiation Facility(SSRF)booster ring,a full energy injector for the storage ring,is deigned to accelerate the electron beam energy from 150MeV to 3.5GeV that demands high extraction efficiency at the extraction energy with low beam loss rate when electrons are ramping.Closed orbit distortion(COD)caused by bending magnet field uniformity errors which affects the machine performance harmfully could be effectively reduced by bending magnet location sorting.Considering the affections of random errors in measurement,both ideal sorting and realistic sorting are studied based on measured bending magnet field uniformity errors and one reasonable combination of bending magnets which can reduce the horizontal COD by a factor of 5is given as the final installation sequence of the booster bending magnets in this paper.     

Improvement of four-wave mixing-based wavelength conversion efficiency in dispersion shifted fiber by 40-GHz clock pumping

40-GHz clock modulated signal as a pump to improve the efficiency of four-wave mixing (FWM)-based wavelength conversion in a 26.5-km dispersion shifted fiber (DSF) is investigated. The experimental results demonstrate that the conjugated FWM component has higher intensity with the clock pumping than that with the continuous-wave (CW) light pumping. The improvement of FWM-based wavelength conversion efficiency is negligible when the pump power is less than Brillouin threshold. But when the pump power is greater than Brillouin threshold, the improvement becomes significant and increases with the increment of pump power. The improvement can increase up to 9 dB if pump power reaches 17 dBm.     

Characterization of PolyA and PolyC mismatches by Raman spectroscopy

A.C mismatches are studied by Raman spectral characterization of PolyA, PolyC, and their equimolar complex in solution of 0.14 mol/L Na ,pH7.0.Experimental results show that A·C mismatches occur to be A/B (mainly A) conformers, and unlike Watson-Crick base pairing, this kind of mismatches is stabilized by only one hydrogen bond involving cytosine N4H2 and adenine N7.The formation of A·C complex makes the base stacking interactions much stronger, and conformation of the backbone more ordered, which leads to obvious Raman hypochromic effect with some shifts in corresponding bands.