超快多维红外光谱学:分子结构的时空分辨

利用时间分辨的超快二维红外(2DIR)光谱、稳态一维红外光谱等手段,本文探讨了从溶液中的小分子体系到生物大分子体系的超快振动特性及所反映的分子结构动力学过程。研究了五羰基溴化锰在四氯化碳中的时间分辨2DIR光谱,发现了分子对称性增强的13 CO配体的红外吸收信号,并利用2DIR对角峰和非对角峰表征了其与12 CO配体振动态的相互作用和分子内能量传递过程;实现了钌羰基配合物在光敏黄色蛋白突变体M100A上的定点标记,并研究了该外源标记物的羰基配体的结构动力学,发现了探针分子的振动光谱指纹对其所处的空间位置的敏感性,还发现该探针分子的振动扩散过程对水相中的蛋白质结构涨落具有灵敏性。     

Raman紫外双共振研究C_2H_2分子的碰撞转动弛豫

本文利用受激Raman抽运,选择性地制备了C_2H_2分子电子基态的红外非激活振动能级的单一转动态(X~1∑~+,v″=1,J″=9,11,13),并从紫外激光诱导的A~1Au(v′=1)←X~1∑~+(v″=1)荧光谱,直接测定上述三个转动态的C_2H_2—C_2H_2碰撞的消激活速率常数,它们分别为(7.96±1.04)×10~(-10),(8.79±0.97)×10~(-10),(8.76±0.88)×10~(-10)cm~3~(-1),以及由这些初始转动态向其它不同转动态(v′=1,J′=1,3,5,7,9,11,13,15)多量子跃迁转移的激活速率常数。     

光系统Ⅱ捕光复合物中能量传递动力学研究

采用时间分辩荧光光谱技术研究捕光色素复合体(LHCⅡ)荧光的时间光谱特性.以脉宽为120fs、重复率为82MHz、波长为360nm～420nm激光激发LHCⅡ样品荧光.原始信号经过数据处理,多指数拟合,解得了能量在LHCⅡ中传递的时间常量分别为320±10fs、4.0±0.1ps、20.0±0.1ps.相对应的各组分荧光占总荧光的百分比分别为3.4%、50%、46.6%.经过全局分析,解得荧光强度随波长变化曲线,其三个峰值波长分别为652nm、673nm、692nm(以去离子水为悬浮液)和658nm、687nm、700nm(以酒精为悬浮液).根据LHCⅡ结构以及荧光的时间、光谱特性分析,认为320±10fs的时间组分属于一个单体内同一膜平面中Chlb→Chla的能量传递时间;4.0±0.1ps的时间组分属于同一单体中不同膜平面间Chlb→Chla和Chla→Chla的能量传递时间;20.0±0.1ps的时间组分属于不同单体之间、不同三聚体之间Chla→Chla的能量传递时间.     

从核心天线到反应中心分子传能研究

利用飞秒时间分辨光谱技术研究了PSⅡ核心复合物内β-Car分子和Chla分子传递光能到反应中心的时间特性.实验测得,在CP47中的β-Car分子用了150 ps,Chla分子用了15 ps;在CP43中β-Car分子用了160 ps,Chla分子用了20 ps.利用超快光谱动力学实验曲线,理论计算出在核心天线中β-Car分子到Chla 662之间的能量传递速率为1.18×10¹²s^-1,β-Car分子到相邻β-Car分子之间按速率 1.14×10¹²s^-1传递能量.理论研究得出,在核心天线中β-Car分子接收到光能,以Dexter电子交换机制和Frster共振传能机制进行激发能传递,最后由Chla分子把能量传递到反应中心,在CP47中用了139 ps,在CP43中用了152 ps.理论研究表明,在核心天线中,Chla分子接收到光能之后,以随机转移方式将能量迅速传递到反应中心P680,在CP47中用了16.8 ps,在CP43中用了18 ps.理论研究与实验研究基本符合.     

北京正负电子对撞机同步辐射光脉冲形状的高分辨率测量

用国产BWS-5kII型皮秒扫描相机测量了北京正负电子对撞机(BEPC)上极端相对论性运动正负电子束团产生的同步辐射光脉冲的时间结构、光脉冲长度与电子束流强度以及射频源电压的关系.当负电子束流强度由2mA增加到30mA时,光脉冲长度由220ps增加到670ps;在20mA电子束流强度条件下,射频源电压由250kV增加到500kV时,光脉冲长度在500ps到700ps范围内变化.测量系统的时间分辨率为30ps;时间刻度误差±15%,触发晃动小于±200ps.     

卟啉和钌二元体的超快能量转移

采用超快时间分辨的荧光光谱技术测量了一种由柔性链连接的卟啉-钌二元体分子内的能量转移动力学过程.通过在钌的吸收峰(～453nm)对二元体进行光激发,实验上观测到了从钌基团到卟啉基团的超快能量转移过程(～400ps).而在卟啉的吸收峰(～400nm)对二元体进行光激发,实验上没有观测到从卟啉基团到钌基团的能量转移.采用Frster理论对二元体系能量转移过程的产生机理进行了分析,结果表明,钌和卟啉之间的能量转移来源于基于光谱重叠的偶极-偶极相互作用. 关键词： 卟啉-钌二元体 能量转移 超快激光光谱技术     

飞秒时间分辨拉曼光谱用于研究β-胡萝卜素单重激发态内转换和振动弛豫过程

搭建了飞秒时间分辨受激拉曼光谱(FSRS)装置，并用于研究全反式β-胡萝卜素单重电子激发态超快内转换和振动弛豫过程.基于三脉冲“抽运-探测”方案搭建的时间分辨受激拉曼光谱装置同时实现了150fs的时间分辨率和23.7cm^-1的光谱分辨率，光谱检测范围为300—4000cm^-1.对全反式β-胡萝卜素电子激发态的飞秒时间分辨拉曼光谱研究表明，β-胡萝卜素被激发到S₂态后，经由寿命约为0.3ps的中间态S_X态实     

皮秒级时间分辨超快高能脉冲激光光谱

介绍了一种利用光电摄谱法和条纹管相结合测量ps级时间分辨超快高能脉冲激光光谱的方法。论述了条纹相机工作原理和平面衍射光栅的分光原理,分析指出利用介绍的装置,可以实现波长300 nm ～1 600 nm、脉宽＞2 ps超快高能脉冲激光的光谱测量。采用1 054 nm超快高能脉冲激光器,实验得到了条纹像,对条纹像进行数据处理后得到测量光谱曲线,通过能量标定后,得到了超快高能脉冲激光器实际光谱曲线,验证了ps级时间分辨超快高能脉冲激光光谱方法。讨论了系统中耦合透镜组对光谱测量和光纤色散角对条纹图像的影响,论述了ps级时间分辨超快高能脉冲激光光谱的作用。随着条纹管制造技术的飞速发展,该方法可用于fs级激光光谱的测量。     

Al激光等离子体电子温度的时间分辨诊断

 将门控分幅相机与平面晶体谱仪耦合，构成时间分辨光谱测量系统，对Al激光等离子体的K壳层发射谱进行测量，获得了相对入射激光延迟约1ns，积累时间约200ps的光谱信号。利用稳态碰撞-辐射平衡（CRE）近似条件下的等离子体光谱辐射动力学模型，给出了Al激光等离子体Ly-β线与He-β线强度比以及Ly-γ线与He-γ线强度比与电子温度的函数关系。在此基础上，根据实验谱线强度比，得到激光强度为2.319×10¹⁴，1.937×10¹⁴和3.946×10¹⁴ W/cm²时，等离子体冕区电子温度分别为1.190(1±27%)，1.165(1±27%)和1.525(1±27%)keV。     

阿秒光谱技术的探讨(综述)

<正> 1965年美国贝尔实验室首先用红宝石激光器获得ps超短光脉冲。从此高速光谱技术进入超高速领域,即ps光谱技术。不久又出现了ps扫描摄影机,使ps技术逐步应用到物理学、化学、生物学以及光电子学等各个方面,研究各种超快速过程。在1965年以前的100多年间,高速光谱技术只提高了两个数量级,即从10~(-7)s发展到10~(-9)s。然而,从六十年代初出现激光器算起,到现在才20多年,高速光谱技术却从10~(-9)s发展到了10~(-14)s,提高了五个数量级,接近了10~(-15)s,即fs的范畴。贝尔实验室在这个领域一直占领先地位。它在1981年得到90fs的     

N-乙基吡咯S1态超快动力学：飞秒时间分辨光电子成像研究

N-乙基吡咯是吡咯分子的一个乙基取代衍生物,它的激发态衰变动力学目前为止很少被研究. 本文利用飞秒时间分辨光电子成像的实验方法研究N-乙基吡咯分子S₁态的衰变动力学. 实验采用241.9和237.7 nm的泵浦激发波长. 在241.9 nm激发下,得到5.0±0.7 ps,66.4±15.6 ps和1.3±0.1 ns三个寿命常数. 在237.7 nm激发下,得到2.1±0.1 ps和13.1±1.2 ps两个寿命常数. 所有寿命常数都归属为S₁态的振动态. 本文并对不同S₁振动态的弛豫机理进行了讨论.     

Vibrational dynamics of the CN stretching mode of [Ru(CN)_6]~(4-) in D_2O studied by nonlinear infrared spectroscopy

We have studied vibrational dynamics of the T1u mode of the CN stretching mode of [Ru(CN)6 ]4- in D2O by infrared(IR) nonlinear spectroscopy such as an IR three-pulse photon echo experiment and polarization-sensitive IR pump-probe spectroscopy. The isotropic component of the pump-probe signal shows a bi-exponential decay with time constants of 0.8 ps and 20.8 ps. The fast and slow components correspond to the rapid equilibration between the T1u mode and the Raman active modes of the CN stretching mode and the vibrational population relaxation from the v=1 state of the T1u mode,respectively. Anisotropy of the pump-probe signal decays with a time constant of 3.1 ps,which is due to the time evolution of the superposition states of the triply degenerate T1u modes. Three pulse photon echo measurements showed that the time correlation function of the frequency fluctuation decays bi-exponentially with time constants of 80 fs and 1.4 ps. These time constants depend only on the solute and are independent of the solvent,whereas the amplitudes depend on both the solute and solvent.     

Swelling and Drying Mechanisms of Freeze-Thawed Polyvinyl Alcohol/Egg White/Montmorillonite Bionanocomposite Hydrogels

Abstract

Polyvinyl alcohol and egg white bionanocomposite hydrogels loaded with montmorillonite clay were fabricated by a freezing-thawing technique. The bionanocomposite hydrogels showed an exfoliated morphology and they had a more interconnected and dense network as compared with the clay-free sample. The montmorillonite layers acted as multifunctional crosslinkers and the bionanocomposite hydrogels had nanoscale, slit-shaped pores. The swelling ratios of the bionanocomposite hydrogels were increased either by decreasing the content of incorporated montmorillonite or by increasing the pH of the swelling medium. It was found that the bionanocomposite hydrogels having a higher content of montmorillonite exhibited a slightly slower drying process with a longer drying duration. Using the Ritger-Peppas model, it was shown that the swelling and drying mechanisms for all bionanocomposite hydrogels were non-Fickian diffusion. According to the Peppas-Sahlin model, it was found that the absorption of the swelling agent molecules during the swelling process and also the removal of water molecules during the drying process in the early stages of the processes occurred mostly due to their diffusion. At higher swelling or drying times, the contribution of the relaxation (for swelling) and shrinkage (for drying) of the polyvinyl alcohol polymeric chains and egg white protein chains was increased.     

Ultrafast reaction dynamics of the complete photo cycle of an indolylfulgimide studied by absorption, fluorescence and vibrational spectroscopy

The reaction dynamics of the complete photo cycle, ring-opening (C → E) and ring-closure (E → C), of N-methyl-(6-bromo-1,2-dimethyl-3-indolyl)fulgimide dissolved in acetonitrile are analysed via steady-state and ultrafast spectroscopy using transient absorption in the UV/VIS and mid-IR complemented by ultrafast fluorescence broad-band spectroscopy with a Kerr-gate setup. For the C → E ring-opening reaction induced by light at ~ 550 nm, a time constant of ~ 3 ps was found for the S₁ decay and the S₀ repopulation. Non-exponential signatures, which occur in the 10 ps time domain, were observed and are assigned to the cooling of hot molecules in the electronic ground state. The E → C reaction dynamics induced by UV-light pulses at 360 nm and 387 nm occur within less than 1 ps and are followed by vibrational cooling on the 10 ps time domain. Thus, both ring-opening and ring-closure reactions are completed within a few picoseconds. From transient IR studies and fluorescence measurements it is concluded that these pericyclic reactions occur from different geometries on the excited state potential energy surface.     

Swelling/deswelling of polyacrylamide gels in aqueous NaCl solution: Light scattering and macroscopic swelling study

Swelling kinetics of water-swollen polyacrylamide (PAAm) hydrogels (WSG) was investigated in various concentrations of aqueous NaCl by macroscopic swelling measurements. For lower concentration of NaCl, WSG showed exponential swelling whereas at higher concentration of NaCl it underwent deswelling at short times and exponential swelling at long times. From these studies, collective diffusion coefficient, D, of the polymer network and polymer?Csolvent interaction parameter, ??, were calculated and found to decrease with increase in [NaCl]. Collective diffusion coefficients measured from dynamic light scattering (DLS) and that obtained from macroscopic swelling measurements are found to agree well. Measured ensemble-averaged dynamic structure factor f(q,t) for WSG and salt-swollen gels (SSG) showed an initial decay followed by a plateau at long times and it can be described by harmonically bound Brownian particle (HBBP) model. Enhanced scattering intensity at low scattering angles using static light scattering (SLS) measurements revealed the presence of inhomogeneities in PAAm gels. The reasons for increased scattering intensity of SSG over WSG gel and the linear decrease of D with increase in NaCl concentration are explained.     

P(NIPAM-co-AA)/Clay nanocomposite hydrogels exhibiting high swelling ratio accompanied by excellent mechanical strength

In this paper, a series of P(NIPAM-co-AA)/Clay composite hydrogels (abbreviated as NAC gels) with high swelling ratio and excellent mechanical strength were synthesized and characterized by DMA, SEM, and IR. In NAC gels composed of a unique organic P(NIPAM-co-AA)/inorganic (clay) network, the inorganic clay acts as a multifunctional cross-linker in place of an organic cross-linker as used in the conventional chemically cross-linked hydrogels (abbreviated as OR gels). The NAC gels exhibit excellent swelling ratio, and there was no detectable change in properties on altering the concentration of clay, while the swelling ratio tends to decrease slightly when C _clay increases up to 25 wt%, which was revealed in swelling measurements. IR spectra show that clay has been intercalated by copolymers. Furthermore, results of DMA reveal that the composite hydrogel has an excellent mechanical strength by using a wide range of clay concentration, while the moduli improve with increasing C _clay.     

反式-4-甲氧基偶氮苯超快激发态性质研究

本文利用飞秒瞬态吸收光谱结合量化计算研究了反式-4-甲氧基偶氮苯的超快激发态动力学和光异构过程. 瞬态光谱中在400∽480 nm波段出现永久的正吸收,表明反式分子被激发到第二激发态后最终产生了顺式结构. 在乙醇和乙二醇溶剂环境中分别获得了三个衰减组分,时间分别为0.11、1.4、2.9 ps和0.16、1.5、7.5 ps. 快速的时间组分是源自第二激发态弛豫到第一激发态的内转换过程. 另外两个组分和第一激发态的弛豫相关:一个是经第一激发态的内转化和光异构过程,另一个是顺式结构的振动冷却过程. 基于不同溶剂环境中的动力学差别,证实了光异构路径是反转机制而不是旋转机制.     

Ultrafast carrier dynamics in wide gap hydrogenated amorphous silicon

We report on picosecond and femtosecond pump and probe measurements of the dynamics of photoexcited carriers in wide gap a-Si : H prepared by microwave electron–cyclotron resonance plasma-enhanced chemical-vapour-deposition. We interpret the picosecond dynamics of transient absorption under strong picosecond excitation in terms of a bimolecular recombination process with the rate constant B≈5×10⁻¹⁰ cm³ s⁻¹, followed by a slower nanosecond decay. In the femtosecond measurements, we observed an initial decay with effective time constant ≈20 ps. We have not found any change in the picosecond dynamics when tuning the excitation wavelength through photoluminescence (PL) excitation spectrum profile. The ultrafast dynamics do not differ in the samples with PL efficiency differing in more than one order of magnitude, and they agree well with those in standard a-Si : H.     

1 and 2-Photon Fluorescence Anisotropy Decay to Probe the Kinetic and Structural Evolution of Sol-Gel Glasses: A Summary

We review recent 1- and 2-photon fluorescence studies of the formation dynamics and structure of sol-gel glasses, from nanometre-sized particles to clusters, prepared from both aqueous silicates and tetramethylorthosilicate (TMOS), over a broad pH range. Through the careful choice of a fluorescent probe, anisotropy decay has been shown to provide both silica particle size and viscosity information and offers advantages over traditional techniques for silica particle sizing based on small-angle neutron, Xray, or light scattering. Subsequently, we are now able to observe the self-assembly mechanisms (or recently termed kinetic life history) of silica, produced under both acidic and alkaline conditions from sodium silicate solution (water glass) in the case of hydrogels and from alkoxides in the case of alcogels. The controlled preparation of hydrogels, often deemed a blackart, is also discussed in some detail, as are the potential applications and benefits of fluorescence anisotropy decay to industrial sol-gel systems. The insight into the sol-gel process provided by these new interpretations of fluorescence decay data, promises to have implications for both our fundamental understanding and the production of sol-gel systems in general.     

Solvation and rotational relaxation of coumarin 153 in a new hydrophobic ionic liquid: An excitation wavelength dependence study

The solvent relaxation and rotational dynamics of coumarin 153 have been investigated in a new room temperature ionic liquid, 1-(2-methoxyethyl)-1-methylpyrrolidiniumtris(pentafluorethyl)trifluorophosphate [[MOEMPL][FAP]], at three different excitation wavelengths with a variation in temperature. Wavelength -dependent fluorescence decay behavior of the probe molecule in the present medium has been investigated by studying the time dependent fluorescence Stokes shift in the ps–ns time scale. The dynamic fluorescence Stokes shift measurements suggest that the time-resolvable part of the solvation dynamics is biphasic in nature and the average solvation time depends on the excitation wavelengths. Rotational coupling constants, obtained from the time- resolved anisotropy data, indicate no specific interaction between the probe molecule and the ionic liquids. The excitation wavelength dependent solvation dynamics is attributed to the heterogeneous nature of the present ionic liquid.