Femtosecond Dynamics of Energy Transfer in Native B800-B850 and B800-Released LH2 Complexes of Rhodobacter Sphaeroides

Two kinds of antenna complexes LH2 of Rhodobacter sphaeroides, wild type RS601 and the removal of B800pigments (B800-released), were used in our experiment. These two LH2 complexes show quite different behaviour in absorption and femtosecond dynamics. By using the femtosecond pump-probe technique, the energy transfer processes occurring in two complexes were studied. Because of removing the B800 pigment from the LH2 in B800-released LH2 complex, the energy transfer between the B800 to B850 pigment was completely eliminated, while the pure internal energy transfer within the exciton states of B850 pigment could be carefully investigated. The results show that, at B800 absorption band, B800-released LH2 obviously shows a dominated transient absorption different from the photobleaching observed in RS601; while at the B850 band, these two complexes show similar photobleaching behaviour.     

Effect of Photo-Oxidation on Energy Transfer in Light Harvesting Complex （LH2） from Rhodobacter Sphaeroides 601

We study the photo-oxidation of bacteriochlorophylls （BChls） in peripheral light harvesting complexes （LH2） from rhodobacter sphaeroides by using the steady absorption and the femtosecond pump-probe measurement, to realize the detailed dynamics of LH2 in the presence of photo-oxidation. The experimental results reveal that BChl-B850 radical cations may act as an additional channel to compete with the unoxidized BChl-B850 molecules for rapidly releasing the excitation energy, while the B800→B850 energy transfer rate is almost unaffected in the oxidation process.     

First-principles calculation of the electronic structure,chemical bonding,and thermodynamic properties of β-US_2

The electronic structure, magnetic states, chemical bonding, and thermodynamic properties of β-US2 are investigated by using first-principles calculation through the density functional theory(DFT) +U approach. The obtained band structure exhibits a direct band gap semiconductor at Γ point with a band gap of 0.9 e V for β-US2, which is in good agreement with the recent experimental data. The charge-density differences, the Bader charge analysis, and the Born effective charges suggest that the U–S bonds of the β-US2 have a mixture of covalent and ionic characters, but the ionic character is stronger than covalent character. The Raman-active, infrared-active, and silent modes at the Γ point are further assigned and discussed. The obtained optical-mode frequencies indicate that the three apparent LO–TO(longitudinal optical–transverse optical) splittings occur in B1 u, B2 u, and B3 umodes, respectively. Furthermore, the Helmholtz free energy ?F, the specific heat ?E, vibrational entropy S, and constant volume CVare studied over a range from 0 K~100 K. We expect that our work can provide some valuable information for further experimental investigation of the dielectric properties and the infrared reflectivity spectrum of uranium chalcogenide.     

Analysis of X-Ray Photoelectron Spectroscopy of Polymethyl Methacrylate Etched by a KrF Excimer Laser

The C ls and 0 ls electrons in polymethyl methacrylate etched by different incident laser intensities are analysed by x-ray photoelectron spectroscopy. The results show that when the incident laser fluence increases gradually,the percentage of carbon atoms in C-C bonds decreases while the one in carbonyl group (C=O) and alkoxy group (C-O) increases, and the percentage of oxygen atoms in C=O bonds increases while the one in C-O bonds decreases. Based on the analysis of the chemical structure, the energy level transition, energy diversion, and dissociation of bonds are theoretically examined, which is consistent with the experimental results.     

Excitonic level structures of LH1 and LH2 of purple photosynthetic bacteria using an analytical approach

The excitonic level structure of a ring-like chain of dimers is discussed analytically in order to aid the understanding of the possible spectral properties of LH1 and LH2 of purple photosynthetic bacteria. Under the approximation of dipole－dipole interaction between Bchls, the excitonic levels, bandwidths and energy gap between two Davydov subbands are expressed analytically in terms of interaction energies and configurational parameters of dipoles. Our model includes all the interactions between pigment molecules in the system. The oscillator strengths and circular dichroism (CD) for the excitonic states are also presented analytically. The simulated absorption and CD spectra of LH1 and LH2 complexes reproduce the main features of the measured results.     

Synthesis and Spectroscopic Characterizations on the Complexation of Three Different Metal Ions Ba(Ⅱ), Ni(Ⅱ), and Ce(Ⅲ) with Atenolol Drug Chelate

Three types of metal ions barium(Ⅱ), nickel(Ⅱ) and cerium(Ⅲ) complexity of ATN drug have been prepared and characterized using molar conductance method, FT-IR, electronic, and ~1H-NMR analysis measurements. The chemical and physical results for all atenolol complexes are agreement with the speculated structures. For the divalent(Ba Ni) and trivalent(Ce) metal atenolol a molar ratio 1∶2 was established. Qualitative chemical analysis showed that for the divalent metal complexes, the chloride ions are not involved in the complexes, suggesting that all of these complexes, [Ba(ATN)_2]·2 H_2O and [Ni(ATN)_2(H_2O)_2]·4 H_2O are neutral. However, for the cerium(Ⅲ) complex, [Ce(ATN)_2(NO_3)]·3 H_2O, the nitrate group is existed inside the coordination sphere. ATN make astable metal complexity with barium(Ⅱ), nickel(Ⅱ) and cerium(Ⅲ) ions. Electronic absorption analysis of Atenolol give two fundamental peaks at 225 nm and 274 nm refers to variation in transition electrons of ligand, UV spectral analysis of the three complexity obtained give asymmetric broad band in the range 200～400 nm, the reults are convenient with the suggestion of metal-nitrogen and metal-oxygen bonds. The infrared analysis data proved that ATN act as bidentate ligand through the N atom of the —NH group and O atom of the deprotonated alcoholic OH group. Nickel(Ⅱ) and cerium(Ⅲ) complexity make six-coordinate geometry, whereas the barium(Ⅱ) complex exhibit four-coordinate geometry. Ni(Ⅱ)-ATN complex has an effective magnetic moment equal 3.12 B.M, that is assigned to octahedral structure. The ~1H-NMR spectral results of Ba(Ⅱ)-ATN complexity give strong signal at ～4.00 ppm due to protons of —CH_2 that influenced by low degree due to complexity. These results confirm the position of chelation through the N atom of the —NH group and O atom of the deprotonated alcoholic OH group.     

Production of γγ+2 jets from double parton scattering in proton-proton collisions at the LHC

Cross sections for the production of pairs of photons plus two additional jets produced from double parton scattering in high-energy proton-proton collisions at the LHC are calculated for the first time.The estimates are based on the theoretical perturbative QCD predictions for the productions of γγ at next-to-next-to-leading-order,jet+jet and γ+jet at next-to-leading-order,for their corresponding single-scattering cross sections.The cross sections and expected event rates for γγ+2 jets from double parton scattering,after typical acceptance and selections,are given for proton-proton collisions with the collision energy s~(1/2)=13 TeV and integrated luminosity of 100 fb~(-1) planned for the following years,and also s~(1/2)=14 TeV with 3000 fb~(-1) of integrated luminosity as the LHC design.     

One-colour resonant two-photon ionization spectrum of the 1-fluoronaphthalene dimer and ab initio calculation

The one-colour resonant two-photon ionization(R2PI) spectrum of the 1-fluoronaphthalene(1FN) dimer has been studied in the wavelength range of 304 to 322 nm by using a supersonic molecular beam and time-of-flight mass spectrometry.Compared with the original band 00(at 313.8 nm) of the S1 ← S0 transition of the 1FN monomer,a red-shifted band was observed in the 1FN dimer spectrum at about 315 nm with a relatively large linewidth,nearly 2 nm.Based on the consideration of inductive effect and ab initio calculations,this red-shifted band is assigned to the first electronic excited transition of the 1FN dimer.A possible geometric structure of the 1FN dimer is also obtained with calculations that the two 1FN molecules are combined through two hydrogen bonds which are formed between the hydrogen atom of a molecule and the fluorine atom of a neighbouring molecule.A time-dependent calculation was also carried out and the results are consistent with the experimental data.     

Effects of CeO_2 and nano-ZrO_2 agents on the crystallization behavior and mechanism of CaO–Al_2O_3–MgO–SiO_2-based glass ceramics

The crystallization behavior and mechanism of CaO–Al_2O_3–MgO–SiO_2(CAMS)-based diopside glass ceramics with nano-ZrO_2 nucleators and CeO_2 agents have been investigated.The use of nanoscale ZrO_2 as nucleators is favorable to the crystallization of glass ceramic at a relatively lower temperature due to the reduction of the activation energy, while the activation energy is increased after adding the CeO_2 agent.The microstructure and orientation have been analyzed by scanning electron microscopy and electron backscatter diffraction.Two discernible layers are observed, featured in glass and crystalline phases, respectively.Remarkably textured polycrystalline diopsides are verified for the samples(A and B)free of CeO_2 agents, with c-axes perpendicular to the interface of the two layers.Comparatively, the c-axes of diopside grains of the sample(C) with CeO_2 agents are proved to be parallel to the interface.Nanocrystals are detected in the vicinity of the interface for sample C.     

Uniaxial stress influence on lattice, band gap and optical properties of n-type ZnO： first-principles calculations

The lattice,the band gap and the optical properties of n-type ZnO under uniaxial stress are investigated by firstprinciples calculations.The results show that the lattice constants change linearly with stress.Band gaps are broadened linearly as the uniaxial compressive stress increases.The change of band gap for n-type ZnO comes mainly from the contribution of stress in the c-axis direction,and the reason for band gap of n-type ZnO changing with stress is also explained.The calculated results of optical properties reveal that the imaginary part of the dielectric function decreases with the increase of uniaxial compressive stress at low energy.However,when the energy is higher than 4.0 eV,the imaginary part of the dielectric function increases with the increase of stress and a blueshift appears.There are two peaks in the absorption spectrum in an energy range of 4.0-13.0 eV.The stress coefficient of the band gap of n-type ZnO is larger than that of pure ZnO,which supplies the theoretical reference value for the modulation of the band gap of doped ZnO.     

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.     

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     

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.     

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.     

紫色光合细菌中类胡萝卜素的选择性分布及功能

紫色光合细菌Rhodopseudomonas (Rps.) palustris光合膜中的外周捕光天线(LH2)及核心复合物(LH1-RC)中都含有多种类胡萝卜素分子(Crt)。研究不同种类的Crt在上述色素蛋白复合物中的分布及其生理学功能具有重要意义。采用了高效液相色谱(HPLC)手段分析了中等光强(～4 000 lux)培养条件下所获得的Rps. palustris的LH2及LH1-RC中的Crt组成,发现共轭双键数目(n)为11或12的类胡萝卜素分子(包括lycopene(n=11),Anhydrorhodivibrin(n=12)及Rhodopin(n=12)等,主要集中在LH2复合物中,而n=13的类胡萝卜素分子Spirilloxanthin则优先结合到LH1-RC中。通过将稳态吸收光谱及近红外荧光激发光谱在细菌叶绿素的Qx带处归一化,并比较两者的数值,发现在LH2中Crt从单重态向BChl的传能效率［30.9%(v=0),25.4%(v=1),30.4%(v=2)］明显高于在LH1-RC中的传能效率［10.7%(v=0),7.8%(v=1),11.4%(v=2)］。此外,本文还运用亚微秒时间分辨吸收光谱检测了类胡萝卜素三重态T_n←T₁吸收,发现伴随着532 nm激光脉冲激发,LH1-RC和LH2中Crt三重态的吸收主峰位于571及560 nm左右,它们分别归属于n=13和n=12的类胡萝卜素分子。通过对动力学衰减曲线进行单指数拟合,发现前者的衰减时间常数(1.6 μs)明显短于后者(2.2 μs)。上述研究结果表明,短链Crt易于结合到LH2中承担捕光的功能,而长链Crt优先结合到LH1-RC中发挥光保护功能。     

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。     

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.     

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.     

Search for singlet-triplet bistability or biradicaloid properties in polycyclic conjugated hydrocarbons: a valence-bond analysis

Two classes of molecules displaying singlet-triplet biradical bistability (i.e. species having significant biradicaloid properties) can be designed as follows. Alternant conjugated polycyclic hydrocarbons with numerous fixed double bonds (double bonds that remain unchanged in all its Kekulé resonance structures), a large number of Dewar resonance structures which measures the corresponding diradical resonance, and a small HOMO-LUMO band gap which measures the ease of thermal spin inversion are candidates for singlet triplet biradical bistability. Chichibabin's hydrocarbon ( 1 ) is an example. In addition, in the search for candidate molecules having singlet triplet bistability, one should also examine polycyclic conjugated systems having nonalternant induced spin frustration. Spin frustrated nonalternant polycyclic conjugated hydrocarbons will display singlet-triplet bistability (biradicaloid properties) and are generated from alternant valence-bond diradicals or Hückel molecular orbital diradicals having classical Kekulé structures by appropriate intramolecular joining of two starred or nonstarred positions with bonds, respectively.     

淡水养殖珍珠中有机物的激光共振拉曼光谱分析

采用3个不同的激发波长λ=514,633和785 nm对淡水养殖珍珠进行了较为系统的原位拉曼光谱研究,且与相同条件下测定的苹果蜗牛卵壳拉曼光谱进行对比,结果表明:(1)珍珠中所探测到的有机物拉曼峰频率色散明显,推测为聚乙炔类物质,而非前人所认为的类胡萝卜素;(2)苹果蜗牛卵壳中有机物为典型的类胡萝卜素,当λ变化时其拉曼峰基本无频率色散现象;(3)根据拉曼峰位置推测珍珠中聚乙炔类物质共轭C=C双键的数目约为10和16,蜗牛卵壳中类胡萝卜素的共轭C=C双键的数目约为13.