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1.
陈琳  汪蕾  郑敏  王琳 《化学物理学报》2021,34(2):188-196
本文利用纳秒瞬态吸收光谱技术,在不同溶剂中,研究了噻吨酮的光物理和光化学行为. TX的激发三重态(3TX*)涉及2种电子态,3*3ππ*态. 随着溶剂极性的增强,3ππ*态的贡献加大. 在CH3CN,CH3CN/CH3OH(1:1)和CH3CN/H2O(1:1)溶剂中,3TX*的自猝灭速率常数ksq逐渐减小. 这可能由于通过氢键形成的激基复合物阻碍了3TX*的碰撞猝灭. 二苯胺通过电子转移还原3TX*,生成TX·-阴离子和DPA·+阳离子自由基. 溶剂对该转移过程的影响不明显,表明TX的3*3ππ*态夺取电子的能力相近. 然而,溶剂的依赖性在TX·-的猝灭过程中表现明显. 在强酸性条件下(pH=3.0),质子化的TX和非质子化的TX之间存在着动态平衡. 在激发光作用下,生成3TXH+*,光谱上呈现出520 nm处的吸收峰.  相似文献   

2.
采用纳秒时间分辨的激光闪光光解技术研究了乙腈/水混合溶液中二羟基蒽醌和腺嘌呤或胞嘧啶之间的电子转移反应. 在355 nm紫外光作用下,经由系间窜跃产生的三重态二羟基蒽醌与两碱基分别发生电子转移反应,其中碱基作为典型的电子给体. 基于测量到的反应瞬态中间体的动力学淬灭速率,两个反应过程被认为分步进行,先电子转移之后发生质子转移反应. 通过研究表观淬灭速率与两个碱基浓度的依赖关系,分别得到了两个双分子间电子转移反应的速率常数,分别是9.0×108 L/(mol·s) (胞嘧啶)、3.3×108 L/(mol·s) (腺嘌呤).  相似文献   

3.
本文用激光闪光光解技术研究了光诱导生物醌杜醌激发三重态(3DQ*)和色氨酸(Trp)与酪氨酸(Tyr)在乙腈-水(MeCN-H2O)及乙二醇-水(EG-H2O)均相溶液中的光化学反应,分析了反应的机理,并基于Stern-Volmer方法测量了反应速率常数. 光解DQ体系可以生成3DQ*3DQ*与Trp、Tyr发生的氢原子转移反应占主导地位. 对于DQ/Trp/MeCN-H2O和DQ/Trp/EG-H2O溶液,3DQ*与Trp反应生成杜醌中性自由基DQH·、以碳为中心的色氨酸中性自由基Trp·/NH和以氮为中心的色氨酸中性自由基Trp/N·. 对于DQ/Tyr/MeCN-H2O和DQ/Tyr/EG-H2O溶液,3DQ*与Tyr反应生成DQH·和酪氨酸中性自由基Tyr/O·. 3DQ*与Trp、Tyr的氢原子转移反应速率常数都在109 L·mol-1·s-1量级,反应近似受扩散控制. MeCN/H2O均相溶液中3DQ*与Trp、Tyr的反应速率常数要明显高于EG/H2O均相溶液中的反应速率常数,这与Stokes-Einstein方程定性一致.  相似文献   

4.
电子通量对ZnO/K2SiO3热控涂层光学性能的影响   总被引:4,自引:2,他引:2       下载免费PDF全文
 研究了电子通量对ZnO/K2SiO3热控涂层光学性能的影响。分别采用通量为5×1011/cm2·s,8×1011/cm2·s,1×1012/cm2·s 和5×1012/cm2·s的电子对试样进行辐照。电子辐照下涂层的光学性能发生了退化,并且发现了退化涂层在空气中的“漂白”现象。分析了ZnO/K2SiO3热控涂层光学性能的退化机制,同时讨论了电子通量对太阳光谱吸收系数的影响。实验结果发现,在5×1011~1×1012/cm2·s的电子通量范围内,电子通量对ZnO/K2SiO3热控涂层光学性能的影响相同。因此在这个电子通量范围内,采用加速地面试验来模拟空间的电子辐照效应是有效的。  相似文献   

5.
用时间分辨电子自旋共振技术研究了乙二醇(EG)均相溶液和反胶束溶液中抗氧化剂维生素C(VC)对菲醌(PAQ)分子激发三重态3PAQ*的淬灭反应.利用反胶束模拟生物细胞和组织的生理环境.光解PAQ/EG-H2O均相溶液,3PAQ*与溶剂分子EG之间发生氢转移反应.当体系中加入VC后,3PAQ*不仅从EG上夺氢,还从VC上夺氢,VC对3PAQ*的淬灭速率常数为1.409×108 L/(mol·s), 反应受扩散控制. 在CTAB/EG-H2O和AOT/EG-H2O反胶束溶液中,3PAQ*和VC之间的夺氢反应发生在反胶束的水/油界面附近,3PAQ*扩散到油/水界面的过程降低了反应的速率.对于TX-100/EG-H2O反胶束溶液, 由于PAQ增溶于亲水的聚氧乙烯链中,VC对3PAQ*的淬灭速率常数比CTAB/EG-H2O和AOT/EG-H2O反胶束中的都大,甚至比EG-H2O均相溶液中的也略大.很强的VC负离子自由基As-的CIDEP信号来源于3PAQ*与VC之间发生抽氢反应过程中的三重态机理自旋极化转移  相似文献   

6.
药物活性化合物阿替洛尔是一种β受体阻滞剂,若将其排放到地表水资源中会对人类健康和生态系统产生不利的影响. 受光驱动的直接光降解以及间接光降解法可以有效去除环境中的阿替洛尔. 在间接光降解方法中,1O2是降解阿替洛尔这类污染物的重要活性物种. 然而,关于阿替洛尔与1O2反应动力学的信息还比较缺乏,二者间的反应速率常数仍存在争议. 本文通过直接观察1O2在1270 nm处衰减动力学来研究阿替洛尔与1O2在不同溶剂中的反应速率常数:在重水中为7.0×105 (mol/L)-1·s-1,在乙腈中为8.0×106 (mol/L)-1·s-1,在乙醇中为8.4×105 (mol/L)-1·s-1. 在极性强、给氢能力弱的溶剂中阿替洛尔与1O2的反应速率常数更大. 这些结果对光降解阿替洛尔等β受体阻滞剂提供相关动力学信息.  相似文献   

7.
近年利用超快光谱技术对于4-硝基联苯酚(HO-Bp-NO2)的研究发现,其在单重态和三重态时均会发生光致质子耦合电子转移(PCET)反应. 其瞬态吸收光谱450 nm处有一个独特的尖锐吸收带,但无羟基取代的对硝基联苯(Bp-NO2)未观察到此现象. 本文利用酸性溶液作为外加可控质子供体,通过在强酸(∽10-1 mol/L)和弱酸(∽10-4 mol/L)溶液中的光谱和动力学结果,指认这个新吸收带为开壳层单重态O-Bp-NO2H. 它是HO-Bp-NO2的互变异构体,由三重态HO-Bp-NO2中硝基氧得质子后羟基快速去质子产生. 动力学分析表明,非质子极性溶剂中三重态HO-Bp-NO2与基态母体间还会发生PCET或先质子后电子转移生成自由基·O-Bp-NO2. 这一反应与O-Bp-NO2H竞争,导致其产率较低. 这些结果阐明了三重态HO-Bp-NO2在非质子极性溶剂中的失活机制.  相似文献   

8.
青蒿素是一种优异的抗疟药,广泛用于临床医学. 但由于青蒿素天然来源的限制,青蒿素的化学合成一直受到高度关注. 二氢青蒿酸是合成青蒿素的关键前体. 二氢青蒿酸与单线态氧反应形成过氧化物是青蒿素光化学制备中的关键步骤,制约着青蒿素化学合成的产率. 然而关于二氢青蒿酸与单线态氧反应的重要动力学信息并未有报道. 本文通过光敏化法产生单线态氧,研究二氢青蒿酸与单线态氧之间的反应速率常数. 通过直接检测单线态氧在1270 nm处的发光衰减动力学,得出单线态氧与二氢青蒿酸在不同溶剂中的反应速率常数分别为:在CCl4中为1.81×105 (mol/L)-1·s-1,在CH3CN中为5.69×105 (mol/L)-1·s-1,DMSO中为3.27×106 (mol/L)-1·s-1. 发现在三种溶剂中二氢青蒿酸与单线态氧的反应速率常数随着溶剂极性的增加而增加. 这些结果为优化青蒿素光化学合成的实验条件提供了基础知识,有助于提高青蒿素的合成效率.  相似文献   

9.
采用共振拉曼光谱和完全活化空间自洽场方法研究了N,N-二甲基硫代乙酰胺在被激发至S3(ππ*)态后的衰减动力学. 指认了紫外吸收光谱和振动光谱. 获得了乙腈、甲醇和水溶剂中不同激发波长下的A带共振拉曼光谱,以探测Franck-Condon区域的结构动力学. 开展了CASSCF计算以确定低能单重激发态和锥形交叉点的电子激发能和优化几何结构. 通过共振拉曼强度分析和CASSCF计算获得了结构参数、A带结构动力学和S3(ππ*)态衰减机制. 提出了主要衰减通道为3,FC(ππ*)→S3(ππ*)/S1(nπ*)→1(nπ*).  相似文献   

10.
采用纳秒时间分辨的激光闪光光解实验技术,研究了四氯苯醌(TCBQ)分子与两种嘧啶核酸碱基(胸腺嘧啶和尿嘧啶)分子在355nm激发下的光化学反应动力学. 355 nm将TCBQ分子布居到激发三重态3TCBQ*,高反应活性的3TCBQ*与碱基分子发生两个平行的反应,氢抽取反应和电子转移反应,分别对应生成瞬态光谱上观测到的两个光反应产物TCBQH·和TCBQ·-. 这两个反应同时生成的碱基自由基和碱基阳  相似文献   

11.
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.  相似文献   

12.
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.  相似文献   

13.
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.  相似文献   

14.
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.  相似文献   

15.
A review of schemes for multiple access in fiber optic networks shows that a hybrid of wavelength and code division multiple access (WCDMA) combines the best features of both. In particular, the hybrid scheme retains the large information carrying capacity of wavelength division multiple access (WDMA) and flexibility of code division multiple access (CDMA). In this paper WDMA, optical CDMA (OCDMA), and WCDMA networks are discussed. In OCDMA networks, concept of incoherent and coherent coding including inverse decoding and matched filter is introduced. The delay performance of both WDMA and WCDMA networks, under the simple suboptimum access protocols based on cyclic search, is computed. It has been shown quantitatively that tuning delay significantly affects the delay performance of both WDMA and WCDMA networks. Futhermore, delay performance of WCDMA networks is always better than the WDMA networks for the same tuning delay, load, and number of users.  相似文献   

16.
17.
A transient suppression method for piezoelectric ceramic transducer is presented. By adding some special pedestal pulses to the original transmitted signal, the transient effects in the output of the transducer can be just precisely transmission by use of a narrowband transducer. canceled, thereby achieving the broadband The experimental results show that the transient responses of the sinusoid pulses and coded signals are suppressed successfully and the acoustic waveforms radiated into the surrounding water are improved significantly.  相似文献   

18.
We experimentally demonstrate amplitude squeezed soliton utilizing intensity-dependent self-phase modulation in an asymmetric Sagnac interferometer.The system.whose components are connected via ferrule connector/physical connection(FC/PC)fiber connectors,constitutes all-fiber configuration to generate squeezed soliton.Soliton amplitude reduction measured by homodyne detection is near 4.0 dB below the shot-noise level.Optimal squeezing fields in both simple and compact all-fiber configuration are obtained.  相似文献   

19.
The(2 1)-dimensional nonlinear Schr(o)dinger(NLS)equation with spatially inhomogeneous nonlinearities is investigated,which describes propagation of light in(2 1)-dimensional nonlinear optical media with inhomogeneous nonlinearities.New types of optical modes and nonlinear effects in optical media are presented numerically.The results reveal that the regular split of beam can be obtained in (2 1)-dimensional nonlinear optical media with inhomogeneous nonlinearities,by adjusting the guiding parameter.Furthermore,the stability of beam regular split is discussed numerically,and the results reveal that the beam regular split is stable to the finite initial perturbations.  相似文献   

20.
In the real-world application of face recognition system, owing to the difficulties of collecting samples or storage space of systems, only one sample image per person is stored in the system, which is so-called one sample per person problem. Moreover, pose and illumination have impact on recognition performance. We propose a novel pose and illumination robust algorithm for face recognition with a single training image per person to solve the above limitations. Experimental results show that the proposed algorithm is an efficient and practical approach for face recognition.  相似文献   

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