基于荧光非共线光参量放大光谱技术的溶剂化动力学研究中的光谱矫正

利用荧光非共线光参量放大光谱技术测量了DCM染料乙醇溶液的溶剂化动力学过程. 实验结果表明,瞬态荧光光谱经过光谱矫正后,可以产生准确的溶剂化相关函数以及溶剂化过程中瞬态光谱峰值频率移动. 本文的工作表明荧光非共线光参量放大光谱技术有益同时关注荧光强度动力学以及光谱谱型演化的研究领域.     

紫细菌捕光天线LH2中的超快光物理研究

采用飞秒泵浦探测技术研究了紫细菌外周捕光天线LH2中的超快光动力学过程.从B800蓝侧的激发态动力学中观察到B800到B850的能量传递时间,实验结果与理论计算结果的差别说明激发B800时可能引起B850上激子带的直接激发,或存在由B800到B850上激子态的能量传递通道.在B800红侧激发的动力学过程中,漂白信号前端存在的一个快速光吸收信号主要来源于B850上激子带的直接激发.在天然RS601和突变体GM309的LH2中,800 nm激发时的动力学过程都表现为一个类似的光漂白过程,动力学曲线的衰减时间常量在天然LH2中明显快于突变体中,说明在GM309中B800到B850的激发能传递速率有所降低.而在845 nm激发下两个样品中的快过程类似,但慢过程在GM309中有所增快,激发态中的能量重新分布包括逆向的能量传递也受到类胡萝卜素微结构的影响.     

捕光天线LHCⅡ的荧光光谱特性研究

采用稳态荧光光谱技术在低温83 K下用波长为436 nm和507 nm的连续光激发对LHCⅡ进行研究,得到两种波长光激发下LHCⅡ的荧光光谱,并采用高斯组分光谱解析的方法,分别解析出四个谱带,结合吸收光谱和发射光谱分析,认为各自其中两个反映了两种光谱特性：Chl a683.6680/681、Chl a694.0690.0和Chl a/b671.4670.0和Chl a683.8680/681,其余两个长波长组分可能是Chl a分子主发射峰的振动副带.另外还将两种波长光激发下得到的荧光光谱特性做了比较,436 nm光激发下LHCⅡ发出的荧光强度要高于507 nm光的激发,这是由于接收436 nm光的Chl a分子数目多于接收507 nm光的类胡萝卜素分子,且436 nm下Chl a的吸收率也大于507 nm下类胡萝卜素的.从峰值上看,436 nm较507 nm光激励下的荧光光谱峰值产生红移,表明在不同波长光激励下,色素分子之间的能量传递途径是不同的.     

捕光天线和反应中心的超快光物理研究

文章主要介绍了紫细菌Rhodobacter sphaeroide光合作用原初过程中的两种重要的功能体——捕光天线和反应中心的超快光物理研究，利用飞秒抽运一探测和飞秒瞬态吸收探测技术已经对捕光天线内两种色素（B80 HD和B850）内部或之间的能量传递过程作了广泛的研究和测试，其能量传递过程发生在几百飞秒至几个皮秒时域；而在反应中心中，在几种色素间的电荷分离以及电子传递过程也仅为皮秒量级。     

基于单晶体的可调谐参量超荧光的产生

研究了一种基于单晶体的可调谐超荧光产生机理，在一个偏硼酸钡(BBO)晶体中实现了飞秒脉冲倍频过程和光参量产生过程.实验中采用kHz高功率钛宝石激光系统输出的飞秒脉冲光倍频后的蓝光作为抽运光，获得了可调谐范围为480—530 nm参量超荧光光谱输出.理论上分析了这种超荧光产生机理，并利用放大传递函数模拟出参量超荧光环的产生过程.结果表明，在一个BBO晶体中，当抽运光源输出光入射晶体角度同时满足倍频相位匹配角和非共线光参量产生相位匹配角时可产生参量超荧光环，通过微调相位匹配角可控制参量超荧光光谱调谐输出.该理论和实验研究为控制参量超荧光和量子纠缠态的产生提供了理论依据，对于量子成像和量子通讯等领域的发展具有重要意义.     

飞秒BBO光参量放大中闲频光二次谐波的产生

由于相位匹配条件和非线性晶体透光范围的限制，400nm蓝光抽运的飞秒β-BaB₂O₄（BBO）光参量放大（OPA）输出的参量光调谐范围有限，很难得到波长小于460nm的蓝光和近紫外光.实验采用1kHz钛宝石九通啁啾脉冲放大器的倍频蓝光作抽运光，超连续白光 作种子光，在Ⅰ类非共线相位匹配条件下，利用宽带的飞秒BBO OPA，在一定的实验参数下 获得了530—810nm放大的信号光，以及810nm—17μm波段范围的闲频光.与此同时 ，还获得了410—700nm连续可调的闲频光的二次谐波，其与闲频光层叠分布，单脉冲能量 为26μJ，转换效率大于5%.仅利用单块晶体的飞秒BBO OPA就可以获得410—810nm连 续可调的飞秒脉冲输出，从而为更多研究和应用的需要提供了重要的光源.对飞秒光参量放 大中闲频光二次谐波产生的条件也进行了理论分析. 关键词： 二次谐波 闲频光 非共线相位匹配 飞秒光参量放大     

微腔中单分子对荧光共振能量转移光谱学的理论研究

生物大分子动态的结构变化能够使用单分子对荧光共振能量转移谱技术来研究.主要研究了微腔在单分子对共振能量转移实验中有效提高相应单分子对的荧光发射信号的作用,从而提高该技术的时间分辨率.研究发现.由于受体一微腔的强耦合相互作用,光学微腔使得受体分子变成了一个类似于单原子激光的激光体.此外,随着距离的增加.受体的光子数会很快下降.微腔使受体的发射光对单分子对间的距离有更大的依赖性,在腔体中进行单分子对共振能量转移实验町以得到更高的时间分辨率.研究结果为单分子对荧光共振能量转移技术提供了实验方法和理论指导.     

BBOⅠ类相位匹配光参量放大中群速失配的补偿

描述了在BBOⅠ类相位匹配的飞秒光参量放大（OPA）中，利用非共线结构和倾斜抽运光的脉 冲波面来完全补偿三波群速失配的方法.理论计算了三波群速匹配时，非共线角、相位匹配 角、抽运光的脉冲波面倾斜角随信号光波长的变化，并分析了对抽运光光斑尺寸的要求和对 空间走离长度的影响.结果表明，利用该方法不仅能够实现最大的参量带宽，而且能够完全 补偿飞秒OPA中三波的群速失配.此外，选取合适的抽运光光斑尺寸和非线性晶体的长度对提 高参量增益也至关重要. 关键词： 群速匹配 非共线相位匹配 脉冲波面倾斜 飞秒光参量放大     

紫细菌Rb. Sphaeroides 601外周捕光天线(LH2) B800吸收带的超快动力学研究

利用从紫细菌Rb.sphaeroides 601 所提取出的外周捕光天线LH2以及其不同pH值酸化样品(部分和全部去除B800分子LH2)并采用不同波长下的飞秒单色抽运探测技术详细研究了LH2中B800吸收带内的激发态动力学过程.通过对野生型与部分/完全去B800分子LH2的比较研究,分析了B800吸收带激发后所表现出的丰富变化的动力学过程,研究结果表明激发B800带的动力学过程中包含着B850上激子带的直接激发而产生的对激发态动力学的贡献.     

紫细菌Rb.Sphaeroides 601外周捕光天线(LH2) B800吸收带的超快动力学研究

利用从紫细菌Rb.sphaeroides 601 所提取出的外周捕光天线LH2以及其不同pH值酸化样品(部分和全部去除B800分子LH2)并采用不同波长下的飞秒单色抽运探测技术详细研究了LH2中B800吸收带内的激发态动力学过程.通过对野生型与部分/完全去B800分子LH2的比较研究，分析了B800吸收带激发后所表现出的丰富变化的动力学过程，研究结果表明激发B800带的动力学过程中包含着B850上激子带的直接激发而产生的对激发态动力学的贡献. 关键词： 紫细菌外周捕光天线LH2 部分和全部去除B800分子LH2 激发态动力学的演变 飞秒抽运探测     

LHCⅡ三聚体中叶绿素分子间能量传递的瞬态差异吸收光谱分析

应用飞秒时间分辨差异吸收光谱技术对PSⅡ的LHCⅡ三聚体中的能量传递过程进行实验研究,分析得到三组能量传递的时间寿命组分：748 fs、3.28 ps、32.15 ps.其中748 fs的组分为单体内Chl b649分子经Chl b658将能量传递给Chl a665分子的过程；3.28 ps时间常量反映单体内能量从Chl a677向吸收更长波长的Chl a688分子的能量传递过程,以及Chl b643、Chl b658和Chl a668～670分子获得能量的过程；而32.15 ps的时间与三聚体内的单体间的能量传递过程有关.     

从捕光天线到反应中心分子能量传递研究

利用飞秒时间分辨光谱技术研究了PSⅡ中捕光天线LHCⅡ内Chla分子和β-Car分子传递光能到反应中心的时间特性,实验测得Chla分子用了25 ps,β-Car分子用了250 ps.理论研究得出:25 ps是相邻Chl分子之间随机转移传能的时间常数,250 ps是LHCⅡ内相邻β-Car分子,通过Chla分子单步FÖrster共振传递、Dexter电子交换机制、激子转移把能量转移到反应中心的总时间.理论计算与实验结果基本符合,激子随机转移传递激发能快而有效.     

瞬态荧光方法研究溶剂诱导的三苯胺衍生物的对称性破缺电荷转移动力学

在缺乏特征红外振动的情况下追踪具有四极或八极对称性分子的激发态对称性破缺电荷转移通常是很困难的.本文以一种具有八极对称性的三苯胺衍生物为研究对象,利用飞秒时间分辨瞬态荧光光谱方法获得发光跃迁偶极矩的演化动力学,进而实时表征了其溶剂诱导对称性破缺电荷转移的动力学过程.当该分子处于弱极性甲苯溶液中时,在激发态弛豫过程中其发射偶极矩变化较小;当处于较强极性的四氢呋喃溶液中时,其发射偶极矩在数皮秒内快速减小.在对比单体偶极分子的荧光动力学后,推断八极分子的发光态在强极性溶剂中经历溶剂诱导的结构变化,由激子耦合的八极对称性降低至激发定域的偶极对称性;而在较弱极性的溶剂中,其八极对称性在溶剂化稳定中得以较大程度的保持.     

Detection and Analysis of Protein Aggregation with Confocal Single Molecule Fluorescence Spectroscopy

The misfolding and aggregation of proteins is a common phenomenon both in the cell, in in vitro protein refolding, and the corresponding biotechnological applications. Most importantly, it is involved in a wide range of diseases, including some of the most prevalent neurodegenerative disorders. However, the range of methods available to analyze this highly heterogeneous process and the resulting aggregate structures has been very limited. Here we present an approach that uses confocal single molecule detection of FRET-labeled samples employing four detection channels to obtain information about diffusivity, anisotropy, fluorescence lifetimes and Förster transfer efficiencies from a single measurement. By combining these observables, this method allows the separation of subpopulations of folded and misfolded proteins in solution with high sensitivity and a differentiation of aggregates generated under different conditions. We demonstrate the versatility of the method with experiments on rhodanese, an aggregation-prone two-domain protein.     

稀土配合物分子内能量传递和弛豫过程的光声和荧光光谱研究

将光声光谱和荧光光谱两种互补的手段结合起来 ,从无辐射跃迁和辐射跃迁两个角度讨论了固态稀土配合物的激发 弛豫过程。测定了稀土配合物 (Tb(AA) 3·2H2 O、Tb(AA) 3bpy和Tb(AA) 3phen)固体粉末的光声光谱和荧光光谱。与荧光光谱相结合 ,光声光谱反映了不同配合物发光效率的变化 ,Tb(AA) 3phen、Tb(AA) 3·2H2 O和Tb(AA) 3bpy的发光效率依次增强。研究了配合物的分子内能量传递和弛豫过程 ,配体最低三重态能级与稀土离子共振能级之间的能级差是否匹配是配体敏化中心离子发光的关键因素     

Effects of Internal Rotations on the Time-Resolved Fluorescence in a Bichromophoric Protein System Under the Energy Transfer Interaction

Effects of internal rotations of chromophores under the energy transfer interaction in proteins on the time-resolved fluorescence were examined by numerical calculations. Expressions used for the calculations are based on the approximations that the energy transfer takes place according to Foöurster's mechanism and the rotational motions of the energy donor and acceptor along the surfaces of cones are described by a set of rotational diffusion equations. The intensity decay of the donor depended a little on the rotational diffusion coefficient of the donor in some cases, while that of the acceptor did very little. Anisotropy of the donor decayed faster as the diffusion coefficient of the donor increased. Anisotropy decay of the acceptor markedly depended not only on the mutual configuration of the pair in the protein, but also on the diffusion coefficient of the donor. The dependence of the time-resolved fluorescence on the diffusion coefficient of the acceptor was not as great as that of the donor.     

Deriving Intrinsic Parameters of Photoinduced Electron Transfer Reaction from the Transient Effect Probed by Picosecond Time-Resolved Fluorescence Quenching

Fluorescence quenching of a pyrylium salt (PDP²⁺) by toluene in acetonitrile gives rise to a nonexponential decay. This behavior is ascribed to the so-called transient effect occurring at high quencher concentrations for diffusion-controlled reactions. First, the Kalman filter was used to deconvolute the original signal from the experimental decay curve and the response function of the apparatus. This treatment led to a calculated deconvoluted decay curve which enabled the transient effect analysis to be conducted. This real decay curve was then analyzed using two models. The Smoluchowski—Collins—Kimball (SCK) model, applied to diffusion-controlled reactions, yielded the reaction radius r _AD and the intrinsic rate constant k _act of the bimolecular electron transfer reaction. The Marcus electron transfer/diffusion (ETD) model, which provides a powerful method to evaluate the electronic coupling H _el associate with the reaction, was also used but is more difficult to handle due to extensive computational needs. Finally, the adequacy of the two models (SCK and ETD) for analysis of the transient effect was addressed, as well as the appropriateness of the Kalman filter for fluorescence signal deconvolution.     

超快二维红外光谱用于研究单体水分子中的直接振动能量传递

Vibrational relaxation dynamics of monomeric water molecule dissolved in d-chloroform solution were revisited using the two dimensional Infrared (2D IR) spectroscopy. The vibrational lifetime of OH bending in monomeric water shows a bi-exponential decay. The fast component (T₁=(1.2±0.1) ps) is caused by the rapid population equilibration between the vibrational modes of the monomeric water molecule. The slow component (T₂=(26.4±0.2) ps) is mainly caused by the vibrational population decay of OH bending mode. The reorientation of the OH bending in monomeric water is determined with a time constant of τ=(1.2±0.1) ps which is much faster than the rotational dynamics of water molecules in the bulk solution. Furthermore, we are able to reveal the direct vibrational energy transfer from OH stretching to OH bending in monomeric water dissolved in d-chloroform for the first time. The vibrational coupling and relative orientation of transition dipole moment between OH bending and stretching that effect their intra-molecular vibrational energy transfer rates are discussed in detail.     

Competition Between Energy Transfer Quenching and Chelation Enhanced Fluorescence in a Cu (II) Coordinated Conjugated Polymer System

An investigation of the mechanism of the fluorescence quenching by Cu²⁺ for a conjugated polymer system initially designed as a fluorescence “turn-on” chemosensor based on chelation enhanced fluorescence (CHEF) is described in this paper. Unlike all other metal cations tested, the polymer/Cu²⁺ hybrid system with a 1:1 ratio between the receptor and Cu²⁺ has only weak fluorescence with λ_max = 490 nm and a quantum yield of 0.004 in THF at room temperature. In solvent glasses at 77 K the fluorescence remained quenched suggesting that the quenching mechanism was due to energy transfer between the Cu²⁺ and the conjugated polymer backbone. The energy transfer quenching competes effectively with the electron transfer involved in the CHEF resulting in a more selective chemosensory system. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.