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     

共轭高分子中激子演化过程的非绝热动力学研究

有机共轭高分子受光激发或被电荷掺杂后可能会产生各种激发状态的激子,激子的演化过程对有机发光光谱有着至关重要的影响.通过非绝热动力学演化的方法模拟了受光激发后有机高分子中激子驰豫的动力学过程,结果表明高激发态激子不稳定,由于电声耦合作用,高激发态激子会持续向低激发态激子演化,同时,低激发态激子的复合发光会发生红移.稳定的激子复合发光光谱中,基态激子发光强度最大,可高达70-80%;第一激发态激子及其它激发态激子发光强度的总和不超过20%.     

Effect of the mutation of carotenoids on the dynamics of energy transfer in light-harvesting complexes （LH2） from Rhodobacter sphaeroides 601 at room temperature

Energy transfers in two kinds of peripheral light-harvesting complexes (LH2) of {Rhodobacter sphaeroides} (RS) 601 are studied by using femtosecond pump--probe spectroscopy with tunable laser wavelength at room temperature. These two complexes are native LH2 (RS601) and green carotenoid mutated LH2 (GM309). The obtained results demonstrate that, compared with spheroidenes with ten conjugated double bonds in native RS601, carotenoid in GM309 containing neurosporenes with nine conjugated double bonds can lead to a reduction in energy transfer rate in the B800-to-B850 band and the disturbance in the energy relaxation processes within the excitonic B850 band.     

通过飞秒泵浦探测技术研究PbS纳米颗粒的激发态瞬态动力学过程

利用飞秒泵浦探测技术研究了PbS半导体纳米颗粒复合的SiO₂溶胶凝胶薄膜的瞬态动力学过程。通过改变激发探测波长和激发光强度,研究引起PbS半导体纳米颗粒的非线性吸收的两种机制。当激发探测波长选在激子吸收峰附近(620nm)时,由于激子的饱和吸收引起的光致漂白,当激发波长选在激子能态的低能侧(753,800nm),同时观察到激子的饱和吸收和双激子效应引起的光致吸收。研究了激子的饱和吸收和双激子效应引起的激发态吸收随激发态电子-空穴对浓度的变化关系,表明双激子效应与载流子浓度有很大关系。在高激发强度下,双激子效应引起的诱导吸收远远大于激子跃迁引起的光致漂白,双激子效应在非线性吸收中起着决定性作用。     

紫细菌B800缺失LH2能量传递模型的构建及性质

构建B800缺失LH2对于阐明光合作用中光能传递的分子机制与捕光复合体组装机制具有重要意义。采用吸收光谱、荧光光谱、分子筛层析、超滤和SDS-PAGE等方法研究了紫细菌两个典型种外周捕光复合体 (LH2) 约800 nm特征光谱 (B800) 细菌叶绿素 (BChl) 缺失能量传递模型的构建方法及性质。结果表明：在pH 8.0 Tris-HCl(10 mmol·L-1) 缓冲液中,0.08% SDS能够使来自Rhodobacter azotoformans的LH2 B800 BChl特异性解离,解离体系中加入10%(φ) 甲醇,通过超滤脱除游离BChl,构建了B800缺失LH2,但该缺失模型不够稳定。在pH 1.9缓冲液中,来自Rhodopseudomonas palustris的LH2 B800 BChl能够特异性解离,通过层析得到两个组分。一个组分的B800 BChl不能通过层析脱除,能够重新自组装成LH2。另一个组分为B800缺失LH2,该缺失模型稳定。两种LH2均存在2类以上B800 BChl结合位点,并得到了两类Rhodopseudomonas palustris B800 BChl解离的LH2,但未发现类似紫色硫细菌中的B800吸收光谱劈裂现象。B800缺失LH2均未呈现约800 nm特征荧光光谱。采用两种方法构建了两个物种B800缺失LH2能量传递模型。利用BChl与缺失B800 LH2结合能力不同的特性,将Rhodopseudomonas palustris中的LH2分成两个类型,实现了异质性亚基LH2的分离。     

共轭聚合物中受激吸收与受激辐射的量子动力学研究

基于扩展的一维SSH紧束缚模型结合非绝热的分子动力学方法,理论研究了共轭聚合物分子(PPV)在光脉冲作用下受激吸收和受激辐射的量子动力学过程.首先,设定分子初始处于基态,讨论了受激吸收过程中不同的电子受激跃迁模式与光激发脉冲的关系.通过对终态的分析,发现分子受激后只能产生电子-空穴的束缚态,包括:激子、双激子和高能激子.计算了各种激发态的产率,特别是,给出了各种激发态产率与光激发能量的定量关系.此外,基于实验,分别讨论了光激发强度对高能激子和双激子产率的影响,并与实验结果进行了比较.最后,设定分子初始分别处于激子和双激子态,研究了分子内定域能级之间的受激辐射过程,并简单讨论了激子和双激子受激辐射与光激发能量及强度的关系.     

共轭高分子中激子形成的非绝热动力学研究

有机共轭高分子被光激发后,其电子结构会发生明显的变化,通过非绝热数值计算的方法模拟了受光激发后有机高分子中激子生成的动力学过程.结果表明,激子的生成一般需要数十飞秒时间,激子的生成周期随分子链长度的增大而增大.高激发态激子可以根据生成周期分为两类,第一类激子的生成周期在数十到上百飞秒之间,第二类激子的生成周期可达上千飞秒.对于超过200个碳原子的高分子,第二类激子的生成周期可达5000飞秒以上.这个计算结果说明,相比于有机高分子,有机小分子中更容易观测到激子.     

LDAO对Rhodobacter azotoformans外周捕光复合体LH2构象及其细菌叶绿素解离行为的影响

为探求LDAO与LH2的相互作用关系和规律,深入认识LDAO对LH2结构和功能的影响。采用光谱法系统地研究了LDAO对Rhodobacter azotoformans134K20菌株LH2构象及其在极端环境中细菌叶绿素(BChl)解离行为的影响。结果表明:(1)在室温pH 8.0缓冲溶液中,LDAO导致LH2构象变化,α-螺旋含量提高,Tyr和B850细菌叶绿素特征峰蓝移,能量传递效率提高。(2)在60℃pH 8.0缓冲溶液中,LH2B800和B850细菌叶绿素可解离为游离BChl。LDAO能增加LH2的高温稳定性,延缓并改变B800和B850解离过程和行为。(3)在室温强酸和强碱溶液中,LDAO加剧了B800和B850的解离并分别转化为游离细菌脱镁叶绿素(BPhe)和游离BChl,表现出不同的解离行为。在不含LDAO的强酸溶液中,B850呈现先解离再自组装的过程。LDAO作用于LH2,可使其B800和B850在不同极端环境中的解离行为发生变化。     

双分子链中非线性多激子态的动力学研究

在超快激光激发下分子聚集体内有多个激子产生.针对具有链间耦合的双分子链系统,应用密度矩阵理论,在偶极-偶极近似和算符算术平均值近似下通过求解量子主方程计算了不同双链构型下的多激子动力学过程.研究发现在光激发作用下的多激子离域在双链分子系统中,在能量表象下形成激子态能带.激子态能带的宽度和激子占据能级随双分子链构型的不同而不同.对于链间和链内均为H型排列的分子链,激子态能带变宽,激子态优先占据在高阶能级上.在不同能级下的激子具有不同的动力学演变特点.若链间耦合较强,激子态通过链间耦合传递,与分子是否直接受到激发没有直接关系,激发态在两个链内的转移周期与最近邻的链间耦合有直接关系.     

Nonlinear optical studies in semiconductor-doped glasses under femtosecond pulse excitation

Nonlinear optical studies in semiconductor-doped glasses (SDGs) are performed under femtosecond laser pulse excitation. Z-scan experiments with 800 nm wavelength pulses are used to excite SDG samples in the resonance and non-resonance regimes. Schott colour glass filter OG 515 shows stronger two-photon absorption than GG 420 and both the samples exhibit positive nonlinearity. However, in resonantly excited RG 850 the intensity-dependent Z-scan shows transition from saturable to reverse saturable absorption behaviour with the increase in intensity.     

The study of photo-induced ultrafast dynamics in light-harvesting complex LH2 of purple bacteria

In this paper, we introduce the photo-induced ultrafast dynamics taking place in the peripheral light harvesting antenna LH2 from purple bacteria Rhodobacter sphaeroides by using absorption, fluorescence emission and ultrafast spectroscopic techniques. Three kinds of LH2 samples, pH treated LH2 (complete removal of B800 pigments), carotenoid mutated LH2 (GM 309) and electrochemical oxidation treated LH2 were used in comparison with native LH2 to investigate the mechanism of photo-induced ultrafast energy transfer within the LH2 complex.     

双光子吸收材料二苯乙烯衍生物的合成及光谱性质

设计、合成并用红外光谱、1H NMR、元素分析表征了三种用于双光子吸收材料的二苯乙烯衍生物,4,4′-双(二苯氨基-反式-苯乙烯基)联苯(BPSBP),4,4′-双(二乙氨基-反式-苯乙烯基)联苯(BESBP)和4,4′-双(9-咔唑基-反式-苯乙烯基)联苯(BCSBP)。实验结果表明三者最强的单光子吸收出现在350～400 nm之间,且单光子吸收和荧光光谱中表现出明显的溶剂化显色效应,揭示了分子内对称电荷转移的本质,双光子荧光光谱则揭示了单光子和双光子吸收具有相同的发射机理。利用双光子上转换荧光法测试发现,三种双光子吸收材料在800 nm飞秒激光的激发下具有较大的吸收截面,分别为892,617和483 GM,这表明在双光子领域有潜在的应用价值。     

The Paths of Excitation Energy Deactivation in LH1 Reduced Mutant and Wild-Type Strains of Rhodobacter sphaeroides

The P3 mutant of Rhodobacter sphaeroides had an altered ratio of reaction center to core (LH1) and peripheral (LH2) antenna complexes compared to the wild-type strain. Intracytoplasmic membranes from these two strains were purified and then resuspended in buffer or immobilized in isotropic and stretched polymer film. The absorption, photoacoustic, and delayed luminescence spectra were measured. The ratios of infrared absorption and photoacoustic bands (located at about 880 nm for LH1 and at 850 and about 800 nm for LH2) as well as the half-width of these bands are different for the LH2 and LH1 mutants and wild-type strain. The whole yields of thermal deactivation of the two strains were comparable, but in the absorption region of LH2 it was slightly lower in the case of the mutant than for the wild-type strain. The delayed luminescence main maxima were observed at about 860 and 700 nm. The first one could be due to emission of bacteriochlorophyll a of LH2 complexes. The emission at about 700 nm is probably due to dihydromesochlorophyll, which is usually, to some extent, produced from bacteriochlorophyll a in bacterial complexes. The delayed luminescence emission is competing with excitation energy transfer to the reaction center. The intensity of the delayed luminescence of the mutant strain was higher than that of the wild-type strain when both samples were excited in a region of carotenoid absorption. The mutant contains less carotenoids than the wild-type strain. Carotenoids work as efficient antenna. When they at a lower concentration the excitation can be trapped more easily by some chlorophyll-like pigment isolated from the excitation energy chain. The dependences of delayed luminescence spectra on the light polarization and excitation wavelengths for the wild-type strain and for the mutant were different. The anisotropy of delayed luminescence showed that bacteriochlorophyll a molecules of different orientations were contributing to the mutant and the wild-type strain emission. All the results suggest that the excitation energy transfer from the antenna to the reaction center in the mutant and the wild-type strain is similar.     

Eu3+激活的硼钒酸钇的光致发光

找出了合成Eu3+激活的硼钒酸钇铕发光粉的适宜条件和发光最佳化学组分,它是(Y0.94Eu0.06)(V0.69B0.31)O3.7.对其发光光谱的温度依赖关系的研究指出,发光最佳温度在350℃左右.发光的这种温度依赖关系与基质和Eu3+对能量的吸收,以及基质向Eu3+能量传递效率的提高有关.此外,试验结果还表明,在365nm激发下,少显Gd2O3、Zn2GeO4·GeO2:Mn2+等添加剂的加入提高了样品的发光亮度.     

Single-shot ultrabroadband two-dimensional electronic spectroscopy of the light-harvesting complex LH2

Here we present two-dimensional (2D) electronic spectra of the light-harvesting complex LH2 from purple bacteria using coherent pulses with bandwidth of over 100 nm FWHM. This broadband excitation and detection has allowed the simultaneous capture of both the B800 and B850 bands using a single light source. We demonstrate that one laser pulse is sufficient to capture the entire 2D electronic spectrum with a high signal-to-noise ratio. At a waiting time of 800 fs, we observe population transfer from the B800 to B850 band as manifested by a prominent cross peak. These results will enable observation of the dynamics of biological systems across both ultrafast (<1 ps) and slower (>1 ms) timescales simultaneously.     

Influence of LDAO on the conformation and release of bacteriochlorophyll of peripheral light-harvesting complex (LH2) from Rhodobacter azotoformans

The aim of this study is to reveal the interaction relationships between lauryl dimethylamine N-oxide (LDAO) and peripheral light-harvesting complex (LH2) as well as the influence of LDAO on structure and function of LH2. In the present work, the effects of LDAO on the conformation and release processes of bacteriochlorophyll (BChl) of LH2 when incubated under different temperature and pH in the presence and absence of LDAO were investigated by spectroscopy. The results indicated that (1) the presence of LDAO resulted in alterations in the conformation, alpha-helix content, and spectra of Tyr and B850 band of LH2 at room temperature and pH 8.0. Moreover, energy transfer efficiency of LH2 was enhanced markedly in the presence of LDAO. (2) At 60 degrees C, both the B800 and B850 band of LH2 were released and transited into free BChl at pH 8.0. However, the release rates of bacteriochlorophylls of B800 and B850 band from LH2 were slowed down and the release processes were changed when incubated in the presence of LDAO. Hence, the stability of LH2 was improved in the presence of LDAO. (3) The accelerated release processes of bacteriochlorophylls of B800 and B850 band of LH2 were induced to transform into bacteriopheophytin (BPhe) and free BChl by LDAO in strong acid and strong alkalic solution at room temperature. However, the kinetic patterns of the B800 and B850 band were remarkably different. The release and self-assemble processes of B850 in LH2 were observed in strong acid solution without LDAO. Therefore, the different release behaviors of B800 and B850 of LH2 are induced by LDAO under different extreme environmental conditions.     

Dielectric function dynamics during femtosecond laser excitation of bulk ZnO

Using a broad band dual-angle pump-probe reflectometry technique, we obtained the ultrafast dielectric function dynamics of bulk ZnO under femtosecond laser excitation. We determined that multiphoton absorption of the 800-nm femtosecond laser excitation creates a large population of excited carriers with excess energy. Screening of the Coulomb interaction by the excited free carriers causes damping of the exciton resonance and renormalization of the band gap causing broadband (2.3–3.5 eV) changes in the dielectric function of ZnO. From the dielectric function, many transient material properties, such as the index of refraction of ZnO under excitation, can be determined to optimize ZnO-based devices.