长链脂肪酸影响胆红素-人血清蛋白复合物的激发态分化（英文）

胆红素与人血清白蛋白结合后会发生光异构和光诱导环化反应,其中后一反应将最终形成一种名为光红素的产物,这些光诱导化学反应是临床上治疗新生儿黄疸的基本原理.据前人研究报道,长链脂肪酸的加入有利于光红素的生成,但其背后的机理,特别是其激发态动力学尚不明确.本文利用飞秒瞬态吸收和飞秒荧光转换技术,探究了棕榈酸对胆红素在血清蛋白中的光化学反应的影响.研究表明,随着棕榈酸的加入,光激发后的胆红素更倾向于通过4 ps的衰减通道返回热基态,而不是通过固有的超快激发态衰减途径(小于1 ps).这一效应促进了热基态的胆红素发生由Z-Z到E-Z构型的异构化,从而提高了光红素的产率.这是首次利用飞秒时间分辨光谱技术对长链脂肪酸在光疗过程中的作用进行表征,其结果可为相关临床研究提供有利的信息.     

ZrO-双原子阴离子的光电子成像谱

利用激光溅射制备了ZrO^-双原子阴离子,测量了其光电子成像谱．实验观测到的光电子能谱可以在光学光谱和高精度从头计算的基础上得到很好的归属．ZrO^-的基态确定为²△态,其自旋-轨道分裂能为578±12 cm^-1,ZrO的电子亲和能测定为1.249±0.005 eV．第一次在实验上观测到ZrO的c³∑^-激发态,其相对于X¹∑⁺基态的能量为13316±24 cm^-1,同时还对ZrO与其等电子体NbN的电子结构进行了比较．     

交叉分子束实验研究F+D2(v=1, j=0)反应

本文使用交叉分子束方法研究了氟原子和振动激发态氘分子D₂(v=1, j=0)的反应. 使用受激拉曼抽运的方法制备了振动激发的D₂分子. 实验中未观测到来自于旋轨耦合激发态氟原子F^*(²P_1/2)与振动激发态D₂分子的贡献. 观测到来自于旋轨耦合基态氟原子F(²P_3/2)和振动激发态D₂的反应信号,相应的产物DF分子布居于v''=2,3,4,5振动态上. 与振动基态反应F+D₂(v=1,j=0)相比,振动激发态反应F+D₂(v=1,j=0)生成的DF产物转动分布更“热”. 获得了振动激发反应的四个碰撞能在0.32至2.62 kcal/mol范围内的微分反应截面. 在最低的碰撞能0.32 kcal/mol下,所有振动态的DF产物都以后向散射为主. 随着碰撞能的增加,DF产物的角分布逐渐从后向转移到侧向. 测量了DF(v''=5)产物的前向微分散射截面随碰撞能变化的曲线. 前向散射的DF(v''=5)信号出现于1.0 kcal/mol. 在2.62 kcal/mol碰撞能下DF(v''=5)主要为前向散射.     

超短脉冲激光场中间二氯苯的激发态动力学

利用飞秒时间分辨的飞行时间质谱技术研究了间二氯苯的激发态动力学.间二氯苯分子吸收一个200 nm或者267 nm的光子被抽运到激发态,随后再吸收多个800 nm的光子被电离.实验获得了电离产生的离子质谱信号及其随抽运探测激光延迟时间的变化曲线.在200 nm时,分子被抽运到激发态(π,π*),可观察到三个相互竞争的解离通道的寿命:内转换到排斥态(n,σ*)或者(π,σ*)并发生快速解离,其寿命约(0.15±0.01)ps;内转换到基态的高振动态,能量在基态"热"振动态间弛豫的寿命约为(4.94±0.08)ps;系间窜越到相邻的三重态从而发生预解离过程,其寿命约为(110.09±4.33)ps.在267 nm时,分子被抽运到第一激发态的低振动态,可观察到一个长寿命(约(1.06±0.05)ns)的系间窜越过程.除此之外,在碎片离子信号中还观察到了激发态与基态的高振动态之间的内转换过程.     

DMSO溶剂中All-trans-astaxanthin激发态的飞秒时间分辨光谱

基于飞秒时间分辨瞬态吸收和多元瞬态光栅光谱技术对全反式Astaxanthin(AXT)在DMSO溶剂中的超快激发态弛豫动力学进行了观测.结果表明,光激发后AXT/DMSO体系直接发生S_0→S_2跃迁,基态漂白对应光谱范围为420~550nm.由S_2→S_1的内转换过程发生的时间常数为120~160fs.S_1态激发态吸收对应的光谱范围为550~740nm,基态漂白恢复过程对应的是S_1→S_0的内转换过程,其时间尺度为4.50~5.50ps.     

飞秒瞬态吸收光谱技术研究反式对氨基偶氮苯的超快激发态动力学 (cited: 1)

利用飞秒瞬态吸收光谱技术研究了反式对氨基偶氮苯(AAB)溶解在乙醇中的超快激发态动力学．当利用400 nm光激发分子到S₂态后,由S_{211102412相似文献}   

μ-介子在Be7原子核上的俘获

利用考虑到重正化效果的普适V-A理论,本文计算了μ^-被Be⁷俘获后跃迁到Li⁷的基态与第一激发态的俘获几率,Li⁷核第一激发态的极化,以及由此跃迁到其基态时放出γ光的偏振度,其中对于不同的超精细结构态分别进行了计算,计算过程中,采用了壳层模型的原子核波函数。并假定忽略二次效应下,S态的四个核子没有参加作用。     

Au(111)上过氧化氢在碱性介质中氧化反应的pH效应

本文经过系统地研究Au(111)上过氧化氢在pH值从10到13的不同碱性溶液体系中氧化反应(HPOOR),发现随着溶液pH的增大,HPOOR的活性增大,电流电势i-iE极化曲线的斜率减小. HO₂^-是碱性溶液中HPOOR的主要反应物种,在高pH溶液下有很快的动力学反应主要是由于电极表面的正电荷与体系中的阴离子HO₂^-和OH^-等有静电相互作用的原因. 因此在溶液反应物随pH增大的时候,热力学的驱动力也加快了HO₂^-的氧化过程.     

飞秒差异吸收微弱信号测量技术

本文报道一种用飞秒差异吸收光谱装置探测光合作用光系统Ⅱ(PS Ⅱ)颗粒复合物电子传递、电荷分离、能量传递技术,装置的时间分辨率小于120fs,光谱调谐范围为720～860nm,采用低温双探头Boxcar平均处理器进行信息采集处理,测得了PS Ⅱ颗粒复合物3.2±0.3Ps的P680^* Pheo到P680⁺Pheo^-的电荷分离时间,还获得了由外周天线到内周天线CP43和CP47,再到PSⅡ反应中心的能量传递时间25ps,以及电荷分离后的能量衰变时间37.2ps.     

使用超快拉曼光谱技术研究四极矩给体-受体-给体分子的激发态动力学

具有对称结构和四极矩性质的给体-受体-给体分子在激发态通常展现出从离域的电荷转移态向局域的电荷转移态转化的电荷重分布过程，该现象已被多种超快时间分辨光谱技术进行了大量研究. 飞秒受激拉曼光谱是一种常用的超快时间分辨光谱，该光谱可以通过检测分子内特定的振动模来研究分子激发态动力学. 本研究采用的4，4''-(1，3-丁二炔-1，4-二基)双(N，N-二(4-甲氧苯基)苯胺)含有位于中间位置的两个相邻炔基(电子受体)和对称分布在分子两侧的N，N-二(4-甲氧苯基)苯胺(电子给体). 研究发现，飞秒受激拉曼光谱能够实时观测该分子在溶剂中发生的激发态电荷重分布过程. 该结果将有助于深入研究具有相邻特征官能团的对称四极矩分子光致电荷局域/离域动力学.     

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.     

飞秒时间分辨离子成像研究NO2分子通道分辨超快解离动力学

本文利用飞秒激光泵浦-探测质谱和离子成像研究了NO_2分子的超快解离动力学.结果表明NO~+离子的动能释放包含两个部分,分别对应的能量是0.05和0.25 eV,并且指认了它们叫能的解离通道.NO~+离子通道分辨的瞬态测量提供了区分超快解离路径贡献的方法,不同动能释放的离子信号变化曲线可以通过双e指数函数进行拟合.其中衰减时间为0.25 ps的快速变化部分产生于里德堡态的演化.变化较慢的信号部分是山两个竞争的通道产生的,其中一个通道是吸收一个400 nm光子到A~2B_2激发态,它的衰减寿命是30 ps;另一个慢的通道是吸收三个400 nm光子到一个价电子类型的里德堡态,它的衰减寿命是短于7.2 ps.通道和时间分辨的实验测量对于区分分子复杂的超快解离动力学具有非常大的潜力.     

Two-dimensional random walk on the ground state energy surface: The N-Z distributions from nuclear heavy-ion collisions

The nucleon transfer process in deep inelastic collision is formulated as a two-dimensional random walk process on the N-Z plane. The probability of each step is assumed to be proportional to the available final state density which is determined by the ground state energy surface of the colliding dinuclear system. Here a model problem is considered, where the long and narrow valley in the energy surface is replaced by a slot with a flat bottom. Even in this crude model, good agreement is obtained between the calculated widths of the N-Z distribution and the experimental values, indicating that the ground state energy surface plays an important role in the mass and charge transfer phenomena in deep inelastic processes.     

O<Subscript>2</Subscript> photodesorption from a Ag<Subscript>8</Subscript>O<Stack><Subscript>2</Subscript><Superscript>-</Superscript></Stack> cluster

The decay path of an Ag₈(O₂)^- cluster photoexcited by a 3.1 eV photon is elucidated using time-resolved photoelectron spectroscopy. Photoabsorption results in the formation of an excited state giving rise to a peak in the photoelectron spectra with well-resolved vibrational finestructure. With a lifetime of about 100 fs this bound state decays into an anti-bonding state which dissociates into O₂ and Ag₈^- on a timescale of 10 ps. In the photoelectron spectra, this corresponds to a broad maximum shifting gradually towards higher binding energy while the O₂ and Ag₈^- separate. Finally, the spectrum of bare Ag₈^- appears. This process is unique to small clusters, because on metal surfaces excited state lifetimes are too short to allow for direct dissociation.     

Subnanosecond fluorescence spectroscopy of human serum albumin as a method to estimate the efficiency of the depression therapy

The efficiency of the therapy of psychiatric diseases is estimated using the fluorescence measurements of the conformational changes of human serum albumin in the course of medical treatment. The fluorescence decay curves of the CAPIDAN probe (N-carboxyphenylimide of the dimethylaminonaphthalic acid) in the blood serum are measured. The probe is specifically bound to the albumin drug binding sites and exhibits fluorescence as a reporter ligand. A variation in the conformation of the albumin molecule substantially affects the CAPIDAN fluorescence decay curve on the subnanosecond time scale. A subnanosecond pulsed laser or a Pico-Quant LED excitation source and a fast photon detector with a time resolution of about 50 ps are used for the kinetic measurements. The blood sera of ten patients suffering from depression and treated at the Institute of Psychiatry were preliminary clinically tested. Blood for analysis was taken from each patient prior to the treatment and on the third week of treatment. For ten patients, the analysis of the fluorescence decay curves of the probe in the blood serum using the three-exponential fitting shows that the difference between the amplitudes of the decay function corresponding to the long-lived (9 ns) fluorescence of the probe prior to and after the therapeutic procedure reliably differs from zero at a significance level of 1% (p < 0.01).     

Analysis of Λb→pK- and pπ- decays in a flavor changing Z' mode

In this paper, we calculate the branching ratios of Λ_b→pK^- and pπ^- decays in the avor changing Z' model. We nd that the branching ratios for these two decay modes are sensitive to the contributions of the Z' boson. For Λ_b→pK^- decay, if the left-handed couplings are equal to the right-handed couplings, the branching ratio of this decay could match up to the currently experimental data for ξ_s=0.01 and -52°<φ_s^L<132°, or ξ_s=0.004 and 0°<φ_s^L<84°; if only the left-handed couplings are considered, it could match up to the experimental data for ξ_s=0.01 and -10°φ_s^L<138°. And for Λ_b→pK^- decay, if the left-handed and right-handed couplings are equal, the branching ratio of Λ_b→pK^- decay may be consistent with the currently experimental data with ξ_d=0.05 and -135°φ_d^L<43°, if only the left-handed couplings are considered, it may be consistent with ξ_d=0.05 and -114°φ_d^L<8°.     

Decays of intermediate vector bosons,radiative corrections and QCD jets

We investigate decay properties of the intermediate vector bosons W^± and Z⁰. QED and QCD radiative corrections to leptonic and hadronic decay modes are calculated. Implications of the results for decay widths, branching ratios, determination of the number of neutrino species, e-μ-τ universality and properties of hadronic jets produced in W^± and Z⁰ decays are examined.     

The study of B→K(*)l+l- decays in family non-universal Z' models

In a combined investigation of B→K^(*)l⁺l^- decays, constraints on the related couplings in family non-universal Z' models are derived. We find that within the allowed parameter space, the recently observed forward-backward asymmetry in the B→K^(*)l⁺l^- decay can be explained by flipping the signs of the Wilson coefficients C₉^eff and C₁₀. With the obtained constraints, we also calculate the branching ratio of the B_s→μ⁺μ^- decay. The upper bound of our prediction is nearly an order of magnitude smaller than the upper bound given by the CDF Collaboration recently.     

Sensitizing effect of <Emphasis Type="Italic">Z,Z</Emphasis>-bilirubin IXα and its photoproducts on enzymes in model solutions

In model systems, we have studied side effects which may be induced by light during phototherapy of hyperbilirubinemia (jaundice) in newborn infants, with the aim of reducing the Z,Z-bilirubin IXα (Z,Z-BR IXα) level. We have shown that the sensitizing effect of Z,Z-BR IXα, localized at strong binding sites of the human serum albumin (HSA) macromolecule, is primarily directed at the amino acid residues of the carrier protein and does not involve the molecules of the enzyme (lactate dehydrogenase (LDH)) present in the buffer solution. The detected photodynamic damage to LDH is due to sensitization by bilirubin photoisomers, characterized by lower HSA association constants and located (in contrast to native Z,Z-BR IXα) on the surface of the HSA protein globule. Based on study of the spectral characteristics of the photoproducts of Z,Z-BR IXα and comparison of their accumulation kinetics in solution and the enzyme photo-inactivation kinetics, we concluded that the determining role in sensitized damage to LDH is played by lumirubin. The photosensitization effect depends on the wavelength of the radiation used for photoconversion of bilirubin. When (at the beginning of exposure) we make sure that identical numbers of photons are absorbed by the pigment in the different spectral ranges, the side effect is minimal for radiation corresponding to the long-wavelength edge of the bilirubin absorption band. We have shown that for a bilirubin/HSA concentration ratio >2 (when some of the pigment molecules are sorbed on the surface of the protein globule), the bilirubin can act as a photosensitizing agent for the enzyme present in solution. We discuss methods for reducing unfavorable side effects of light on the body of newborn infants during phototherapy of hyperbilirubinemia. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 383–394, May–June, 2008.     

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.