光声位相理论及其在化学中的应用研究进展

光声位相作为光声光谱重要的一部分, 包含着很多有价值的信息, 对它的研究可以获得其它光谱甚至光声振幅谱都不能得到的信息。光声位相在测定样品的光学和热学性质、样品无辐射弛豫过程的研究以及深度剖面分析等方面显示了特有的能力。本文结合本实验室近几年的工作, 在光声光谱理论的基础上,对光声位相理论及其在化学中的应用作一综述。     

时间分辨脉冲光声量热法及其应用

光声量热法是一种研究快速光化学反应的新方法，已广泛应用于有机和有机金属化学中涉及自由基中间体以及生物体系中光诱导化学反应生成亚稳态物质的动力学和热力学性质的研究。本文介绍了光声量热的基本原理、实验装置和它在化学、生物体系中的应用。     

脉冲时间分辨光声量热法用于光厚溶液

近年来,用光声量热法(photoacoustic calorimetry,缩写PAC)测量液相体系中的光物理或光化学过程有了较快发展.这对于观测无辐射的瞬态粒子有重要意义。Peters及其同事曾分析过这种光声技术的原理.简言之,脉冲激光被体系吸收后将     

固态Nd化合物f-f跃迁的光声光谱研究

通过光声光谱对固态 Nd化合物的 f -f跃迁进行了研究。根据 Nd F3、Nd(sal) 3· H2 O和 Nd(sal) 3(phen) 2 的谱峰位置 ,计算了它们的电子云重排参数β、键合参数 b1/2 和 Sinha共价参数δ,表明三元配合物中钕离子形成键的共价程度最高 ,而 Nd F3中键的共价性最弱。通过光声支量表征了不同化合物中 Nd3+ 的 f -f跃迁光声强度的变化 ,证实了随着键的共价程度增加和配位数的增大 ,超灵敏跃迁强度显著增大     

毛细管流动池在光声检测中的应用

设计了适于激光诱导光声流动检测的毛细管流动池,讨论了池的特点及其在分析化学中的应用,用该池检测Co~(2+),检测限相当于2×10~(-6)cm~(-1)光吸收。     

Photoacoustic spectrometry for trace gas analysis and leak detection using different cell geometries

A photoacoustic (PA) spectrometer with high selectivity and sensitivity has been developed for trace gas analysis and for the detection of gas leak at part per trillion by volume (pptV) level. This PA system comprises of a resonant photoacoustic cell, a pulsed line tunable CO₂ laser as an excitation source and a sensitive electret microphone as a photoacoustic detector with an option to trigger the safety alarm system for early warning of gas leaks. In this work, three resonant PA cells with various geometries have been developed at our laboratory for the detection of photoacoustic signal using pulsed laser system and their comparative performance have been studied. As a special application of this PA system, the detection of sulfur hexa fluoride (SF₆) gas using these three cells has been carried out for optimizing the sensitivity. Besides this, our PA system can very well be applied for pollution monitoring and detection of hazardous gases in a noisy environment.     

Novel Helmholtz-based photoacoustic sensor for trace gas detection at ppm level using GaInAsSb/GaAlAsSb DFB lasers

A new and compact photoacoustic sensor for trace gas detection in the 2-2.5 microm atmospheric window is reported. Both the development of antimonide-based DFB lasers with singlemode emission in this spectral range and a novel design of photoacoustic cell adapted to the characteristics of these lasers are discussed. The laser fabrication was made in two steps. The structure was firstly grown by molecular beam epitaxy then a metallic DFB grating was processed. The photoacoustic cell is based on a Helmholtz resonator that was designed in order to fully benefit from the highly divergent emission of the antimonide laser. An optimized modulation scheme based on wavelength modulation of the laser source combined with second harmonic detection has been implemented for efficient suppression of wall noise. Using a 2211 nm laser, sub-ppm detection limit has been demonstrated for ammonia.     

Ion-exchanger phase photoacoustic spectrometry for trace analysis of metal ions

Laser-induced photoacoustic spectroscopy has been applied to the determination of chromate, uranyl, and Cr(VI) and Fe(II) ions as coloured complexes that were sorbed on ion-exchanger beads. A simple photoacoustic cell has been constructed; it consisted of a fused silica glass tube and an attached cylindrical piezoelectric transducer. A pulsed laser fight at 532 or 355 nm irradiated the ion-exchanger beads that had been collected in the glass tube of the cell. Since a sample material was effectively concentrated on the ion exchanger, the sensitivity was much higher than that in the corresponding photoacoustic spectrometry in a solution state. The lowest detection limit was 0.21 ng/ml Fe for Fe(II)-DPPS (4,7-diphenyl-1,10-phenanthrolinedisulphonate) complex sorbed on QAE-Sephadex gel. Analytical characteristics of the present method are described.     

Near-infrared diode laser wavelength modulation-based photoacoustic spectrometer

An inexpensive resonant photoacoustic spectrometer based on a low-power distributed feedback diode laser and wavelength modulation spectroscopy is developed. This sensor has been applied to the detection of acetylene (C2H2) using a properly designed photoacoustic cell operating on its second longitudinal mode. The minimum detectable limit of about 10 parts-per-million volume (signal to noise ratio=1) is achieved at atmospheric pressure, and the pressure and laser power linear dependence of the photoacoustic signal is also investigated. Moreover, in this paper we also describe some basic theory of gas photoacoustic spectroscopy.     

Photoacoustic spectroscopic studies on the solid phase cell with a differential type microphone using a diode laser as radiation source

The design and applications of the solid phase photoacoustic cell with a differential type microphone are described. This cell has higher sensitivity and reproducibility relative to a cell without a differential microphone. The method has been applied to the determination of phosphate ion in water samples. The detection limit for phosphate ion concentrated from 22.5 ml of sample solution on a membrane filter as molybdophosphate-n-dodecyltrimethylammonium bromide was 3.0 ng PO(3-)(4)/ml and the coefficient of variation for five measurements at 20 ng PO(3-)(4)/ml of phosphate ion was 3% using a diode laser (30 mW, 826 nm) as radiation source. The calibration graph for phosphate ion was linear over the range 5-50 ng PO(3-)(4)/ml.     

Laser diode photoacoustic detection in the infrared and near infrared spectral ranges

A new technique for high resolution photoacoustic detection based on application of laser diodes has been developed. This method was tested and compared using identical photoacoustic instrumentation (cell and microphone) to study gas absorption in three different spectral regions, namely: the infrared range near 2100 cm(-1), CO and OCS fundamental band absorption; the ranges near 4200 and 4350 cm(-1), CH4, NH3 and N2O overtone and combination band absorption; the near infrared range near 6500 cm(-1), CO, CO2 and NH3 overtone absorption. Several types of diode laser operating at room temperature or at liquid nitrogen temperature were compared. The optimum gas pressures for the maximum sensitivity of the photoacoustic signals were found and the detection limits were estimated for all of the gases studied. The best sensitivity was achieved for NH3 at 100 ppbv. The sensitivity of the developed system was tested on detection of traces of NH3 and CO2 gases from car exhaust.     

Application of ion-exchanger phase photoacoustic spectroscopy to flow analysis of trace amounts of iron in water

Ion-exchanger phase photoacoustic spectroscopy has been applied to the flow analysis of trace amounts of iron in water. The reaction product of iron(II) with 4,7-diphenyl-1,10-phenanthroline-disulphonate, introduced into a carrier solution stream in the flow system, was concentrated on a small amount of QAE-Sephadex gel settled in a fused silica glass tube (1.5 mm i.d.) of a photoacoustic cell. The photoacoustic signal produced by pulsed laser irradiation of the gel beads at 532 nm was detected by a cylindrical piezoelectric transducer which was attached outside the glass tube. When 3.7 ml of a sample solution was introduced into the flow system, the sensitivity of this method was 590 times higher than that of the corresponding solution photoacoustic spectrometry and the detection limit of iron was 0.33 ng/ml. Because the coloured complex was desorbed from the cell with a desorbing agent solution, the present method could afford repeated analyses of natural water samples containing iron at ng/ml levels without any preconcentration procedures.     

傅里叶变换红外光声光谱法在聚合物研究中应用——Ⅱ.定量测定组合浆料中变性聚乙烯醇

本文叙述了用傅里叶交换红外光声光谱法测定组合浆料中变性聚乙烯醇和淀粉醋酸酯混合比的快速定量分析方法。变性聚乙烯醇和淀粉醋酸酯的红外光声光谱和红外吸收光谱具有相同图谱。观察了干涉仪动镜扫描速度,扫描次数及试样用量对红外光声光谱信号强度的影响。以变性聚乙烯醇的C=O伸缩振动1570cm~(-1)作为定量分析依据。变性聚乙烯醇含量与1600～1516cm~(-1)范围内的积分强度值成线性关系。用红外光声光谱法测定混合试样中变性聚乙烯醇含量与真实值相吻合。     

乙型肝炎表面抗原的激光光声酶联免疫测定

乙型肝炎表面抗原的激光光声酶联免疫测定刘风华,邓延倬,曾云鹗（武汉大学化学系,武汉大学分析测试科学系,武汉,４３００７２）关键词激光光声谱,酶联免疫吸附分析,聚偏二氟乙烯,乙型肝炎表面抗原激光光声谱是微量和痕量分析的一种新技术,可检测１０－６～１０－...     

LOW-TEMPERATURE PHOTOACOUSTIC SPECTROSCOPY OF PORPHYROPSIN IN THE INTACT RETINA OF THE CREEK CHUB, Semotilus atromaculatus

Abstract— The photoacoustic spectra of porphyropsin in the creek chub (Semotilus atromaculatus) have been successfully measured on single retinae of small size (< 0.5 cm in diameter) at low temperatures. The relative intensities of the spectra, corresponding to the thermal release, are strong enough to be comparable to those for the big cattle retina. The photoacoustic spectrum of porphyropsin at – 167^°C exhibits a principal maximum at 540 nm with a small shoulder near 580 nm. A sequence of porphyropsin bleaching resulted from thermal reaction has been clearly observed above -90^°C.