A light-harvesting siphonax-anthin-chlorophyll a／b-protein complex of marine green alga, Bryopsis corticulans

A light-harvesting chlorophyll a/b-protein complex (LHCP) was isolated directly from thylakoid membranes of marine green alga, Bryopsis corticulans, by two consecutive runs of liquid chromatography. The trimeric form of the light-harvesting complex has been obtained by sucrose gradient ultracentrifugation. The result of SDSPAGE shows that the light-harvesting complex is composed of at least five apoproteins in which a protein with apparent molecular weight of about 31 kD was never found in the major light-harvesting complex (LHC II ) from higher plants. The isolated Bryopsis corticulans light-harvesting complex contains a specific carotenoid, siphonaxanthin, as well as chlorophyll (Chl) a, Chl b, neoxanthin and violaxanthin. Siphonaxanthin which is present in the light-harvesting siphonaxanthin-chlorophyll a/b-protein complex of Bryopsis corticulans is responsible for enhanced absorption in the blue-green region (530 nm). Efficient energy transfer from both siphonaxanthin and Chl b to Chl a in Bryopsis corticulans LHCP, which has similar absorption and fluorescence emission spectra to those of the lutein-chlorophyll a/b-protein of higher plants, proved that molecular arrangement of the light-harvesting pigments was highly ordered in the Bryopsis corticulans LHCP. The siphonaxanthin-chlorophyll a/b-proteins allow enhanced absorption of blue-green light, the predominant light available in deep ocean waters or shaded subtidal marine habitats.     

Self-aggregation of vapor-liquid phase transition

The concept of the molecular free path is introduced to derive a criterion distinguishing active molecules from inactive molecules in liquid phase. Based on molecular self-aggregation theory a concept of the critical aggregation concentration (CAC) of active molecules is proposed to describe the physical configuration before the formation of the nuclei in the process of vapor-liquid phase transition. All active molecules exist in the form of the monomer when the concentration of active molecules is lower than CAC, while the active molecules will generate aggregation once the concentration of the active molecules reaches CAC. However, these aggregates with the aggregation number N smaller than 5 can steadily exist in bulk phase. The other excess active molecules can only produce infinite aggregation and form a critical nucleus of vapor-liquid phase transition. Without outer perturbation the state point of CAC corresponds to the critical superheated or supercooled state in the process of vapor-liquid phase transition. With the aggregate property, the interfacial tension between the bulk phase and the tiny new phase is predicted and a correction is made for the classical nucleation rate in a quite good agreement with experimental results.     

Mg~(2+)-induced LHC Ⅱ aggregation in thylakoid membrane

Mg2+-induced changes in 77K fluorescence spectra of wheat thylakoid membranes were analyzed by a Gaussian deconvolution program. All spectra were fitted well with 7 Gaussian sub-bands. The sub-band areas for the LHC Ⅱ macroaggregate (F699) and PS Ⅱ (F685 and F695) were increased and those for the LHC Ⅱ trimer (F681) and PS Ⅰ (F729 and F740) were decreased by Mg2+ . Moreover, it was found that the sub-band area ratio for F699 over F681 was dramatically enhanced by Mg2+ by 1.72 times. It was concluded that the LHC Ⅱ trimer in thylakoid membranes could be aggregated and transformed into its macroaggregate by Mg2+ on a large scale. The possible implication of the Mg2+-induced LHC Ⅱ aggregation was also discussed .     

New mechanism revealed for light-state transition in cyanobacterium Arthrospira platensis according to 77-K fluorescence kinetics

The mechanisms of oxygen evolution and carbon fixation in oxygenic organisms depend on the equal distribution of excitation energy to photosystems Ⅰ and Ⅱ, which is regulated by a mechanism referred to as light-state transition. In this work, a novel mechanism, energy spillover from PS Ⅰ to PS Ⅱ referred to as "inverse spillover", was revealed besides "mobile phycobilisome (PBS)" and the "spillover" of energy from PS Ⅱ to PS Ⅰ in cyanobacteria. Under continuous illumination with blue light, time-dependent 77-K fluorescence spectra demonstrated heterogeneous kinetics for the PBS and photosystem components, indicating that inverse spillover and mobile PBS work successively to regulate the excitation to a balanced distribution in cyanobacterial cells under blue light. Inverse spillover and mobile PBS occur under both 100 and 300 μmol m-2 s-1 blue-light conditions but they are accelerated under the latter.     

Three-dimensional fluorescence spectral characteristics of dissolved organic carbon in cave drip waters and their responses to environment changes: Four cave systems as an example in Guizhou Province,China

Understanding the responses of fluorescence spectral characteristics of cave drip waters to modern environment and climate changes is key to the reconstructions of environmental and climatic changes using fluorescence spectral characteristics of speleothems. The fluorescence spectral characteristics of dissolved organic carbon （DOC） in four active cave systems were analyzed with a three-dimensional （3D） fluorescence spectral analysis method. We found that the fluorescence types of DOC were mainly of fulvic-like and protein-like fluorescences, both in soil waters and cave drip waters. The intensity of fulvic-like fluorescence was positively correlated with the concentrations of DOC, suggesting that the DOC of cave drip waters was derived from the overlying soil layer of a cave system. Compared with the other cave systems, the variation range of the excitation and emission wavelengths for fulvic-like fluorescence of cave drip waters in Liangfeng cave system that had forest vegetation was smaller and the excitation wavelength was longer, while its fluorescence intensity varied significantly. By contrast, the excitation and emission wavelengths and fluorescence intensity for that in Jiangjun cave system that had a scrub and tussock vegetation showed the most significant variation, while its excitation wavelength was shorter. This implies that the variation of vegetation overlying a cave appears to be a factor affecting the fluorescence spectral characteristics of cave drip waters.     

Effect of Coordinate Bond in Molecular Recognition of Enrofloxacin with Imprinted Polymers

1 Results Molecular imprinting is a technique for the preparation of functional materials with molecular recognition properties.Molecular imprinted polymers (MIPs) have become an increasingly active field of study for the construction of new material capable of molecular recognition.In general,MIPs are synthesized by polymerization of cross-linking complexes of template molecules and functional monomers.After removing the template molecules from de polymers,binding sites are formed by functional monomer derived residues complementary for the template molecules[1]. According to the principle,the stability of monomer-template complexes present in the solution prior to polymerization as well as the polymerization reaction itself undoubtedly play a dominant role in determining the recognition performance of the polymer.     

Hypoosmotic shock induces a stateⅠtransition of photosynthetic apparatus in Dunaliella salina

The effects of hypoosmotic shock on state transition in darkness in Dunaliella salina were studied. When the concentration of NaCI in culture medium was dropped from 1.5 to 0.5 mol/L abruptly, the photosynthetic rate of D.salina declined, but the respiratory rate and intracellular ATP content increased in the dark. The FpsⅡ/FpsⅠ ratio at 77 K of D. salina cells exposed to hypoosmotic shock was higher than that of control cells, indicating that more excitation energy was distributed to PS Ⅱ in stressed D.salina cells upon illumination. A decrease in LHC Ⅱ phosphorylation level was also observed when D.salina was exposed to hypoosmotic shock. Thus a state Ⅰ transition of photosynthetic apparatus occurs when D.salina suffers hypoosmotic shock in darkness, which is supposed to be related to an enhancement of respiration and an increase in ATP content in stressed D.salina cells.     

Effect of solvents on the barrierless reaction in the excited state of cyanine dye

UV－Vis,fluorescence spectroscopy and time resolved spectroscopic technique on picosecond and femto-second scales have been utilized to investigate the effect of steric hindrance and multiple hydroxyl groups of solvents on the barreierless isomerization in excited state of 3,3 ′-di(3-sulfopropyl)thiacyanine triethylamminium salt,The results show that the factors mentioned above may be responsible for a different “short-time behavior “of the bleaching signal on the ground state and nonlinear viscosity dependence of the excited-state lifetime in ispropanol and glycol,These phenomena are distinguished from the situation repored in the long-chained monhydroxyl alcoloh solvents.However,the dye molecule still exhibits the analyzing-wavelength dependence of the observed fluorescence lifetime,that is ,the fluorescence lifetime increases with the increasing of analyzing-wavelength ,The conclusions are in agreement with those drawn from femtosecond upconversion fluorescence experiments and further exemplify the barrierless isomerization model in the excited state.     

Simultaneous Fluorescence Detection of Mercury(Ⅱ) and Silver Ions Based on Rhodamine B Isothiocyanate and 5-Carboxyfluorescein-ss DNA Modified Probe

A new fluorescence sensor is developed for simultaneous detection of Hg~(2+) and Ag~+. During the detection process,Hg~(2+) forms complexes with the fluorescent dye rhodamine B isothiocyanate(RBITC) modified onto the surface of gold nanoparticles(Au NPs),resulting in RBITC's displacement from the surface of Au NPs and the recovery of fluorescence. Meanwhile,Ag~+ forms “C-Ag~+-C” complex with C-rich 5-carboxyfluorescein(FAM)-ss DNA modified onto the surface of Au NPs,which keeps the fluorescent dye FAM close to the Au NPs and results in quench of fluorescence. The experimental results show a wide linear range and a good sensitivity. The limit of detection is 1.06 nmol/L for Ag~+ and 0.48 nmol/L for Hg~(2+). This detection method is not only easy to operate but also efficient.     

Photosensitized splitting of cis-syn 1,3-dimethyluracil dimer by tryptophan and its peptides

Photosensitized splitting of cis-syn 1,3-dimethyluracil dimer by tryptophan (Trp) and its peptides (Trp-Tyr and Trp-Phe) is studied by fluorescence quenching experiments and irradiation experiments.It reveals that 1,3-dimethyluracil dimer is mainly split by e?-?aq resulting from two-photon ionization of Trp and its peptides under irradiation with light (λ>290 nm).Moreover,the excited singlet state of Trp and its peptides can transfer an electron to the dimer,which splits and gives two pyrimidines.In addition,because of its lower oxidative potential,the excited triplet state of Trp-Tyr can also split the dimer via transfering an electron to the dimer.     

Mg2+-induced LHC II aggregation in thylakoid membrane

Mg²⁺-induced changes in 77K fluorescence spectra of wheat thylakoid membranes were analyzed by a Gaussian deconvolution program. All spectra were fitted well with 7 Gaussian sub-bands. The sub-band areas for the LHC H macroaggregate (F₆₉₉) and PS II (F₆₈₅ and F₆₉₅) were increased and those for the LHC II trimer (F₆₈₁) and PS I (F₇₂₉ and F₇₄₀) were decreased by Mg²⁺. Moreover, it was found that the sub-band area ratio for F₆₉₉ over F₆₈₁ was dramatically enhanced by Mg²⁺ by 1.72 times. It was concluded that the LHC II trimer in thylakoid membranes could be aggregated and transformed into its macroaggregate by Mg²⁺ on a large scale. The possible implication of the Mg²⁺-induced LHC II aggregation was also discussed.     

Interaction between tetrasulfophthalocyanines and colloidal titanium dioxide and photoelectric behavior on sensitized microporous TiO2 electrodes

Conclusion Strong interaction between sulfophthalocyanines and TiO₂ occur when the former is adsorbed on the colloidal TiO₂ surface. Upon excitation, electron transfer from excited singlet state of sulfophthalocyanine to the conduction band of TiO₂ occurs, leading to the quenching of sulfophthalocyanine fluorescence. Sensitization of the TiO₂ microporous electrode with sulfophthalocyanine extends the photoresponse of the electrode to visible and near IR region as shown by the photocurrent spectra. It is indicated that only monomeric sulfophthalocyanine plays a dominant role in the photoresponse of the electrode, while the sulfophthalocyanine aggregates give less or even no contribution to the conversion of visible light into electricity.     

PSII核心复合物超快动力学研究

应用时间分辨荧光光谱技术，研究了高等植物光系统Ⅱ（PSⅡ）核心复合物中能量传递超快动力学。对实验测得的荧光衰减曲线，进行数据处理，解得荧光衰减的3个时间常数分别为3.9,20.4,930.5ps，各组分荧光占总荧光的百分比分别为1.0%,12.7%,86.3%。对由全局分析得以的荧光强度随波长变化曲线运用高斯多峰解叠运算，解得3个峰值波长分别为671.03,684.74,696.16nm。通过分析，给出了激发能在PSⅡ核心复合物中超快传递的动力学信息及相应的能级关系图。     

Kinetics of charge separation and energy transfer in photosystem II reaction center

Conclusion In the present study we investigated the kinetics of the initial charge separation and energy transfer in the PS II reaction center using pico-second and femto-second time-resolved techniques. We conclude that there are energy transfer processes between ?-Car or Pheo and P680 in the PSII reaction center. The time constant of energy transfer from Pheo to P680 is less than 100 ps, while that from (?-Car to P680 is about 350 ps. For the initial charge separation in the PS II reaction center, the preliminary finding supported the about 3-ps time constant of charge separation. The possible kinetic scheme in PS II reaction center was proposed. Further experiments are in progress.     

Expression, purification and characterization of the soluble CuA domain of cytochrome c oxidase ofParacoccus versutus

The key subunit Ⅱ of cytochrome c oxidase (CcO) contains a soluble binuclear copper center (Cu_A) domain. The Cu_A domain of Paracoccus versutus was cloned, expressed, purified and characterized. The gene encoding the Cu_A domain in pET11d vector was expressed in E. coli BL21 (DE3). The results showed that the Cu_A domain was expressed mostly in inclusion bodies and the Cu_A domain protein synthesized in E. coli cells represents approximately 10 percent of the total cellular proteins. Dissolved in urea, dialyzed and recombined with Cu⁺/Cu²⁺ and purified by the Q-sepharose fast flow anion-exchange column and Sephadex G-75 gel filtration column, the soluble purple-colored protein, which shows a single band in electrophoresis, was obtained. The UV-visible absorption spectrum of Cu_A domain showed that there are intense band at 478 nm and a shoulder peak at 530 nm, and two weak bands at 360 and 806 nm respectively, which can be assigned to the charge transfer and the interactions of obitals of Cu—S and Cu——Cu in the mixed-valence binuclear metal center (Cu₂S₂R₂). The far-UV CD spectrum indicated that this domain is predominantly in β-sheet structure. The fluorescence spectra showed that its maximal excitation wavelength and maximal emission wavelength are at 280 and 345 nm, respectively.     

Simulation for the primary electronic donor of photosystem IIin vitro

Histidine coordinated to Chi a is a distinct characteristic of Chl ain vivo. By using histidine analogue of 1-methylimidazole (C₄H₆N₂2) and measuring the UV/vis absorption, CD and MCD spectra of the interaction between C₄H₆N₂ and Chl a in CCI₄, we have obtained that: (i) In pure CCl₄ solvent, Chl a molecule is in five-coordinate state, and two Chl a molecules form an asymmetric compact-dimer with strong coupling interaction. We propose that the two Chl a molecules are connected by two unequally coordinated Mg-O bonds (the two oxygen atoms come from the C=O of C13¹ keto and C17 ester, respectively); (ii) when the molar ratio of C₄H₆N₂/Chl a is 0.5 or 1 (corresponding to 2Chl a · 1C₄H₆N₂ and 2Chl a · 2C₄H₆N₂, respectively), significant changes have been observed in the absorption, CD and MCD spectra, which indicate that the Chl a remains in dimer form, but the coupling interaction between them reduces greatly. We postulate that C₄H₆N₂ replaces the ligation of C=O of C17 ester and C13¹ keto to Mg atoms sequentially. The two Chl a molecules linked by two weakly interacted Mg…O bonds form a relaxed-dimer. The structure of the model is essentially similar to that of the primary electronic donor, P₆₈₀, of photosystem II in high plants and algae.     

Spectroscopic study on the photophysical properties of chlorine substituted tetraphenylporphyrin-histidine and its zinc(Ⅱ)complexes

The photophysical properties of ortho-CI,meta-CI and para-CI substituted tetraphenylporphy-rin-histidine and their zinc (II) complexes have been studied by means of steady-state absorption and fluo-rescence spectroscopies, as well as time-resolved fluo-rescence spectroscopy. For the cases of both free-base and zinc complexes, it was found that the ortho-chlorine substitution onto the phenyl rings significantly altered the fluorescence quantum yield, thefluorescence lifetime and the ratio between radiative and nonradiative deactivation rates of the porphyrin chromophore, i.e. the photophysical parameters were quite different from those of meta- and para-substituted compounds. On the other hand, however, the introduction of covalently-linked histidine did not exert much effects on the photophysical behavior of the porphyrin chromophore. The results are interpreted interms of the steric effect and the heavy-atom effect from the chlorine atoms substituted onto the phenyl rings.     

对-二苯氨基苯基硼酸的光谱及光物理行为研究

利用紫外可见吸收光谱和荧光光谱对新合成的化合物：对-二苯氨基苯基硼酸(DPBA，三苯胺衍生物)在不同极性介质中的光谱、光物理行为进行了研究，并利用Lippert-Mataga方程计算了该化合物基态和激发态偶极矩间的差值△μ=3．0D．实验结果表明，溶剂极性对DPBA的吸收光谱峰位和峰形产生相对较小的影响，而使DPBA荧光光谱发生较大的红移，荧光峰的半峰宽变宽且基态和激发态间的偶极矩差值△μ变大，表明了该化合物具有典型的分子内电荷转移(ICT)的特性．     

夏季东海陆架浮游植物类群结构对不同风场条件的响应分析

为探讨东海的主要物理过程对浮游植物生物量和类群结构的时空分布影响,采用高效液相色谱法分析2006年和2011年夏季东海陆架条件下的浮游植物光合色素的组成及含量,并通过CHEMTAX对浮游植物群落的结构进行分析。结果表明,不同风场条件下东海浮游植物生物量和类群结构均有显著差异。在2006年夏季航次,受弱西北风的控制,长江冲淡水向外延伸面积较大,东海陆架叶绿素a的平均浓度为1 228.6ng/L,主要特征光合色素多甲藻素(Peri)、19-己酰基氧化岩藻黄素(19-hex)、19-丁酰基氧化岩藻黄素(19-but)、玉米黄素(Zea)和二乙烯基叶绿素a(DV-Chl.a)相对较高,浮游植物以硅藻(41%)和甲藻(16%)为主要优势类群;2011年夏季航次,受强东南风影响,底层低温高盐水涌升现象明显,东海陆架叶绿素a(Chl.a)的平均浓度(2 677.9ng/L)比2006年高一倍,叶绿素b(Chlb.)、青绿藻素(Prasino)、新黄素(Neo)和别藻黄素(Allo)等光合色素浓度相对较高,硅藻(60%)在浮游植物群落中占主要优势。