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Reaction Center (reaction + center)
Kinds of Reaction Center Selected AbstractsReconstitution of Photosystem II Reaction Center with Cu-Chlorophyll aJOURNAL OF INTEGRATIVE PLANT BIOLOGY, Issue 11 2006Shuang Liu Abstract An isolated photosystem (PS) II reaction center (RC) with altered pigment content was obtained by chemical exchange of native chlorophyll a (Chl) with externally added Cu-Chl a (Cu-Chl). Pigment composition and spectroscopic properties of the RC exchanged with Cu-Chl were compared with native RC and RC treated with Chl in the same way. High-performance liquid chromatography analysis showed approximately 0.5 Cu-Chl per two pheophytin in the Cu-Chl-reconstituted RC preparation. Insertion of Cu-Chl resulted in a decrease in absorption at 670 nm and an increase at 660 nm, suggesting that the peripheral Chl may have been displaced. Fluorescence emission spectra of the Cu-Chl-reconstituted RC displayed a marked decrease in fluorescence yield and a blue shift of the band maximum, accompanied by the appearance of a broad peak at a shorter wavelength, indicating that energy transfer in the modified RC was disturbed by Cu-Chl, a quencher of the excited state. However, there were few differences in the circular dichroism (CD) spectra, suggesting that the arrangement of pigments and proteins responsible for the CD signal was not significantly affected. In addition, no obvious change in peptide components was found after the exchange procedure. (Managing editor: Ping He) [source] Control of Hydrogen Bond Strengths through Push,Pull Effects Triggered by a Remote Reaction Center: A Theoretical StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 7 2004Tsong-Song Hwang Dr. Abstract In an effort to manipulate the bond strengths of hydrogen bonds, we have studied a three-component chemical system consisting of a reaction center, a conjugated bridge, and a hydrogen-bonding site. Protonation of the reaction center triggers intramolecular charge transfer from the hydrogen-bonding site, altering its affinity to bind to an acceptor. Previously, we had found that this communication (signal transduction) between the reaction center and the hydrogen-bonding site does not necessarily die out with increasing length of the conjugated bridge. In certain cases, this signal transduction is maintained,and even amplified,over long distances (I. Chao, T.-S. Hwang, Angew. Chem.2001, 113, 2775,2777; Angew. Chem. Int. Ed.2001, 40, 2703,2705). In this study we report the results of an extensive theoretical investigation of this problem to provide insights into this intriguing phenomenon. In the systems we investigated it was found that the push,pull process between the hydrogen-bonding site and the protonatable reaction center was mediated with the greatest facility by conjugated bridges with low-lying , and ,* orbitals. [source] Potential Energy Landscape for Conformationally Gated Secondary Ubiquinone Binding in the Photosynthetic Reaction Center of Rhodobacter SphaeroidesCHEMPHYSCHEM, Issue 2 2004Asif Rahaman Migration of the secondary ubiquinone, UQB, to a site proximal to His-L190 was proposed to be rate-determining for electron transfer in bacterial photosynthetic reaction centers (shown). This study shows that 1) the proximal binding site is the global minimum on the potential energy landscape, 2) multiple minima exist, in qualitative agreement with various binding sites observed in X-ray diffraction studies, and 3) the energy barrier for direct migration of UQB and migration gated by a protein conformational change both agree with the activation energy measured for electron transfer. [source] Fluorescent Quantum Dots as Artificial Antennas for Enhanced Light Harvesting and Energy Transfer to Photosynthetic Reaction Centers,ANGEWANDTE CHEMIE, Issue 40 2010Prof. Igor Nabiev Bio-Nano: Quantenpunkte (QDs) können mit photosynthetischen Reaktionszentren (RCs) so markiert werden (siehe Bild), dass der FRET vom QD zum RC eine annähernde Verdreifachung der Geschwindigkeit, in der Excitonen im RC erzeugt werden, zur Folge hat. Es werden sogar noch größere Verstärkungen vorhergesagt, was dafür spricht, dass solche Komplexe die Effizienz der Photosynthese erheblich steigern könnten. [source] Cytochrome b559 content in isolated photosystem II reaction center preparationsFEBS JOURNAL, Issue 10 2003Inmaculada Yruela The cytochrome b559 content was examined in five types of isolated photosystem II D1-D2-cytochrome b559 reaction center preparations containing either five or six chlorophylls per reaction center. The reaction center complexes were obtained following isolation procedures that differed in chromatographic column material, washing buffer composition and detergent concentration. Two different types of cytochrome b559 assays were performed. The absolute heme content in each preparation was obtained using the oxidized-minus-reduced difference extinction coefficient of cytochrome b559 at 559 nm. The relative amount of D1 and cytochrome b559,-subunit polypeptide was also calculated for each preparation from immunoblots obtained using antibodies raised against the two polypeptides. The results indicate that the cytochrome b559 heme content in photosystem II reaction center complexes can vary with the isolation procedure, but the variation of the cytochrome b559,-subunit/D1 polypeptide ratio was even greater. This variation was not found in the PSII-enriched membrane fragments used as the RC-isolation starting material, as different batches of membranes obtained from spinach harvested at different seasons of the year or those from sugar beets grown in a chamber under controlled environmental conditions lack variation in their ,-subunit/D1 polypeptide ratio. A precise determination of the ratio using an RC1-control sample calibration curve gave a ratio of 1.25 cytochrome b559,-subunit per 1.0 D1 polypeptide in photosystem II membranes. We conclude that the variations found in the reaction center preparations were due to the different procedures used to isolate and purify the different reaction center complexes. [source] Role of the N- and C-terminal regions of the PufX protein in the structural organization of the photosynthetic core complex of Rhodobacter sphaeroidesFEBS JOURNAL, Issue 7 2002Francesco Francia The core complex of Rhodobacter sphaeroides is formed by the association of the light-harvesting antenna 1 (LH1) and the reaction center (RC). The PufX protein is essential for photosynthetic growth; it is located within the core in a 1 : 1 stoichiometry with the RC. PufX is required for a fast ubiquinol exchange between the QB site of the RC and the Qo site of the cytochrome bc1 complex. In vivo the LH1,PufX,RC complex is assembled in a dimeric form, where PufX is involved as a structural organizer. We have modified the PufX protein at the N and the C-terminus with progressive deletions. The nine mutants obtained have been characterized for their ability for photosynthetic growth, the insertion of PufX in the core LH1,RC complex, the stability of the dimers and the kinetics of flash-induced reduction of cytochrome b561 of the cytochrome bc1 complex. Deletion of 18 residues at the N-terminus destabilizes the dimer in vitro without preventing photosynthetic growth. The dimer (or a stable dimer) does not seem to be a necessary requisite for the photosynthetic phenotype. Partial C-terminal deletions impede the insertion of PufX, while the complete absence of the C-terminus leads to the insertion of a PufX protein composed of only its first 53 residues and does not affect the photosynthetic growth of the bacterium. Overall, the results point to a complex role of the N and C domains in the structural organization of the core complex; the N-terminus is suggested to be responsible mainly for dimerization, while the C-terminus is thought to be involved mainly in PufX assembly. [source] Exploring the primary electron acceptor (QA)-site of the bacterial reaction center from Rhodobacter sphaeroidesFEBS JOURNAL, Issue 4 2002Binding mode of vitamin K derivatives The functional replacement of the primary ubiquinone (QA) in the photosynthetic reaction center (RC) from Rhodobacter sphaeroides with synthetic vitamin K derivatives has provided a powerful tool to investigate the electron transfer mechanism. To investigate the binding mode of these quinones to the QA binding site we have determined the binding free energy and charge recombination rate from QA, to D+ (kAD) of 29 different 1,4-naphthoquinone derivatives with systematically altered structures. The most striking result was that none of the eight tested compounds carrying methyl groups in both positions 5 and 8 of the aromatic ring exhibited functional binding. To understand the binding properties of these quinones on a molecular level, the structures of the reaction center-naphthoquinone complexes were predicted with ligand docking calculations. All protein,ligand structures show hydrogen bonds between the carbonyl oxygens of the quinone and AlaM260 and HisM219 as found for the native ubiquinone-10 in the X-ray structure. The center-to-center distance between the naphthoquinones at QA and the native ubiquinone-10 at QB (the secondary electron acceptor) is essentially the same, compared to the native structure. A detailed analysis of the docking calculations reveals that 5,8-disubstitution prohibits binding due to steric clashes of the 5-methyl group with the backbone atoms of AlaM260 and AlaM249. The experimentally determined binding free energies were reproduced with an rmsd of ,,4 kJ·mol,1 in most cases providing a valuable tool for the design of new artificial electron acceptors and inhibitors. [source] A Photosynthetic Reaction Center Covalently Bound to Carbon Nanotubes,ADVANCED MATERIALS, Issue 22 2007I. Carmeli The photosystem reaction center I is covalently bound to carbon nanotubes using carbodiimide chemistry. The hybrid systems are characterized by atomic force microscopy, and UV-VIS spectroscopy, indicating a high degree of conjugation between the photosystem reaction center and the carbon nanotubes. Three different architectures for optoelectronic circuits are presented, which have the potential to serve as basis for molecular optoelectronic devices. [source] Kinetic investigation on the reactions of p -toluenesulfonyl chloride with p -substituted benzoic acid(s) in the presence of triethylamine in aprotic solventsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2009Subbiah Ananthalakshmi Second-order rate constants of the reactions of p -toluenesulfonyl chloride with p -substituted benzoic acids in the presence of triethylamine in acetonitrile/acetone under equimolar and pseudo-first-order conditions have been determined by the conductometric method using the Guggenheim principle at 25, 30, 35, and 40°C. The reactions follow second order with respect to the whole and first order with respect to each of the reactants. The order of reactivity of the substituents in benzoic acid is rationalized. Activation parameters are obtained by applying the usual methods. The Hammett plot has been found nonlinear, whereas the Bronsted plot shows good correlation. This may be explained on the basis of electronic effects of substituents on the reaction center. Kinetic data and the product analyses indicate that the reaction proceeds through direct nucleophilic attack on the sulfur center. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 303,308, 2009 [source] Reaction of 4-benzylidene-2-methyl-5-oxazolone with amines, Part 2: Influence of substituents in para-position in the phenyl ring and a substituent on amine nitrogen atom on the reaction kineticsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2002B. Bet, akowska An influence of a structure of the amine (benzylamine, N -methyl-benzylamine, N -isopropyl-benzylamine, N -methyl-butylamine, N -ethyl-butylamine, sec -butylamine, and tert -butylamine) on a rate constant of the ring-opening reaction of 4-benzylidene-2-methyl-5-oxazolone (Ox) was studied. The good correlation between logarithm of the rate constants and Charton's steric substituent constant , as well as good correlation with a form of the simple branching equation indicate that there is a steric effect because of substitution at C1 carbon atom of nucleophile which decreases the reaction rate. Additionally, an influence of a structure of the benzylidene moiety of Ox on a rate of the oxazolone ring-opening reaction was studied. The substituents (OH, OCH3, N(CH3)2, Cl, NO2) in para-position of the phenyl ring of Ox substantially modified the rate of the reaction with benzylamine in acetonitrile. The rate of the Ox ring-opening reaction decreased with increase of the electron-donating properties of the substituent. A good correlation between the rate constants of the reaction of 4-(4,-substituted-benzylidene)-2-methyl-5-oxazolones with benzylamine and the electron density at the reaction center (carbon C5 of the oxazolone ring), calculated using ab initio method, and the Hammett substituent constants, and CR equation were established. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 148,155, 2002; DOI 10.1002/kin.10039 [source] Semilocalized approach to investigation of chemical reactivityINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 6 2003V. GineityteArticle first published online: 21 JUL 200 Abstract Application of the power series for the one-electron density matrix Gineityte, V., J Mol Struct Theochem 1995, 343, 183 to the case of two interacting molecules is shown to yield a semilocalized approach to investigate chemical reactivity, which is characterized by the following distinctive features: (1) Electron density (ED) redistributions embracing orbitals of the reaction centers of both molecules and of their neighboring fragments are studied instead of the total intermolecular interaction energy; (2) the ED redistributions are expressed directly in the basis of fragmental orbitals (FOs) without passing to the basis of delocalized molecular orbitals (MOs) of initial molecules; (3) terms describing the ED redistributions due to an intermolecular contact arise as additive corrections to the purely monomolecular terms and thereby may be analyzed independently; (4) local ED redistributions only between orbitals of the reaction centers of both molecules are described by lower-order ter s of the power series, whereas those embracing both the reaction centers and their neighborhoods are represented by higher-order terms. As opposed to the standard perturbative methods based on invoking the delocalized (canonical) MOs of isolated molecules, the results of the approach suggested are in-line with the well-known intuition-based concepts of the classic chemistry concerning reactivity, namely, with the assumption about different roles of the reaction center and of its neighborhood in a chemical process, with the expectation about extinction of the indirect influence of a certain fragment (substituent) when its distance from the reaction center grows, etc. Such a parallelism yields quantum chemical analogs for the classic concepts and thereby gives an additional insight into their nature. The scope of validity of these concepts also is discussed. Applicability of the approach suggested to specific chemical problems is illustrated by a brief consideration of the SN2 and AdE2 reactions. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 302,316, 2003 [source] Xanthophyll Cycle and Inactivation of Photosystem II Reaction Centers Alleviating Reducing Pressure to Photosystem I in Morning Glory Leaves under Short-term High IrradianceJOURNAL OF INTEGRATIVE PLANT BIOLOGY, Issue 7 2007Xin-Guo Li Abstract Under 30-min high irradiance (1500 ,mol m,2 s,1), the roles of the xanthophyll cycle and D1 protein turnover were investigated through chlorophyll fluorescence parameters in morning glory (Ipomoea setosa) leaves, which were dipped into water, dithiothreitol (DTT) and lincomycin (LM), respectively. During the stress, both the xanthophyll cycle and D1 protein turnover could protect PSI from photoinhibition. In DTT leaves, non-photochemical quenching (NPQ) was inhibited greatly and the oxidation level of P700 (P700+) was the lowest one. However, the maximal photochemical efficiency of PSII (Fv/Fm) in DTT leaves was higher than that of LM leaves and was lower than that of control leaves. These results suggested that PSI was more sensitive to the loss of the xanthophyll cycle than PSII under high irradiance. In LM leaves, NPQ was partly inhibited, Fv/Fm was the lowest one among three treatments under high irradiance and P700+ was at a similar level as that of control leaves. These results implied that inactivation of PSII reaction centers could protect PSI from further photoinhibition. Additionally, the lowest of the number of active reaction centers to one inactive reaction center for a PSII cross-section (RC/CSo), maximal trapping rate in a PSII cross-section (TRo/CSo), electron transport in a PSII cross-section (ETo/CSo) and the highest of 1-qP in LM leaves further indicated that severe photoinhibition of PSII in LM leaves was mainly induced by inactivation of PSII reaction centers, which limited electrons transporting to PSI. However, relative to the LM leaves the higher level of RC/CSo, TRo/CSo, Fv/Fm and the lower level of 1-qP in DTT leaves indicated that PSI photoinhibition was mainly induced by the electron accumulation at the PSI acceptor side, which induced the decrease of P700+ under high irradiance. [source] Reconstitution of Photosystem II Reaction Center with Cu-Chlorophyll aJOURNAL OF INTEGRATIVE PLANT BIOLOGY, Issue 11 2006Shuang Liu Abstract An isolated photosystem (PS) II reaction center (RC) with altered pigment content was obtained by chemical exchange of native chlorophyll a (Chl) with externally added Cu-Chl a (Cu-Chl). Pigment composition and spectroscopic properties of the RC exchanged with Cu-Chl were compared with native RC and RC treated with Chl in the same way. High-performance liquid chromatography analysis showed approximately 0.5 Cu-Chl per two pheophytin in the Cu-Chl-reconstituted RC preparation. Insertion of Cu-Chl resulted in a decrease in absorption at 670 nm and an increase at 660 nm, suggesting that the peripheral Chl may have been displaced. Fluorescence emission spectra of the Cu-Chl-reconstituted RC displayed a marked decrease in fluorescence yield and a blue shift of the band maximum, accompanied by the appearance of a broad peak at a shorter wavelength, indicating that energy transfer in the modified RC was disturbed by Cu-Chl, a quencher of the excited state. However, there were few differences in the circular dichroism (CD) spectra, suggesting that the arrangement of pigments and proteins responsible for the CD signal was not significantly affected. In addition, no obvious change in peptide components was found after the exchange procedure. (Managing editor: Ping He) [source] Synthesis and photochemistry of a carotene,porphyrin,fullerene model photosynthetic reaction centerJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 9 2004Gerdenis Kodis Abstract A new photosynthetic reaction center mimic consisting of a porphyrin (P) linked to both a fullerene electron acceptor (C60) and a carotenoid secondary electron donor (C) was synthesized and studied in 2-methyltetrahydrofuran using transient spectroscopic methods. Excitation of the porphyrin is followed by photoinduced electron transfer to the fullerene (,,=,32,ps) to yield C,P·+,C60·,. Electron transfer from the carotene to the porphyrin radical cation (,,=,125,ps) gives a final C·+,P,C60·, state with an overall yield of 0.95. This state decays to give the carotenoid triplet state with a time constant of 57,ns. The molecular triad is highly soluble in organic solvents and readily synthesized. These qualities make the molecule a useful artificial photosynthetic reaction center for a variety of spectroscopic and photochemical investigations. Copyright © 2004 John Wiley & Sons, Ltd. [source] Estimation of Carboxylic Acid Ester Hydrolysis Rate ConstantsMOLECULAR INFORMATICS, Issue 9-10 2003H. Hilal Abstract SPARC chemical reactivity models were extended to calculate hydrolysis rate constants for carboxylic acid esters from molecular structure. The energy differences between the initial state and the transition state for a molecule of interest are factored into internal and external mechanistic perturbation components. The internal perturbations quantify the interactions of the appended perturber (P) with the reaction center (C). These internal perturbations are factored into SPARC's mechanistic components of electrostatic and resonance effects. External perturbations quantify the solute-solvent interactions and are factored into H-bonding, field stabilization and steric effects. These models have been tested using 1471 measured hydrolysis rate constants in water and mixed-solvent systems at different temperatures. The aggregate RMS deviation of the calculated versus observed values was 0.374,M,1s,1; close to the intralaboratory experimental error. [source] ,Senescence-associated vacuoles' are involved in the degradation of chloroplast proteins in tobacco leavesTHE PLANT JOURNAL, Issue 2 2008Dana E. Martínez Summary Massive degradation of photosynthetic proteins is the hallmark of leaf senescence; however the mechanism involved in chloroplast protein breakdown is not completely understood. As small ,senescence-associated vacuoles' (SAVs) with intense proteolytic activity accumulate in senescing leaves of soybean and Arabidopsis, the main goal of this work was to determine whether SAVs are involved in the degradation of chloroplastic components. SAVs with protease activity were readily detected through confocal microscopy of naturally senescing leaves of tobacco (Nicotiana tabacum L.). In detached leaves incubated in darkness, acceleration of the chloroplast degradation rate by ethylene treatment correlated with a twofold increase in the number of SAVs per cell, compared to untreated leaves. In a tobacco line expressing GFP targeted to plastids, GFP was re-located to SAVs in senescing leaves. SAVs were isolated by sucrose density gradient centrifugation. Isolated SAVs contained chloroplast-targeted GFP and the chloroplast stromal proteins Rubisco (ribulose-1,5-bisphosphate carboxylase/oxygenase) and glutamine synthetase, but lacked the thylakoid proteins D1 and light-harvesting complex II of the photosystem II reaction center and photosystem II antenna, respectively. In SAVs incubated at 30°C, there was a steady decrease in Rubisco levels, which was completely abolished by addition of protease inhibitors. These results indicate that SAVs are involved in degradation of the soluble photosynthetic proteins of the chloroplast stroma during senescence of leaves. [source] Effects of impurities on membrane-protein crystallization in different systemsACTA CRYSTALLOGRAPHICA SECTION D, Issue 10 2009Christopher A. Kors When starting a protein-crystallization project, scientists are faced with several unknowns. Amongst them are these questions: (i) is the purity of the starting material sufficient? and (ii) which type of crystallization experiment is the most promising to conduct? The difficulty in purifying active membrane-protein samples for crystallization trials and the high costs associated with producing such samples require an extremely pragmatic approach. Additionally, practical guidelines are needed to increase the efficiency of membrane-protein crystallization. In order to address these conundrums, the effects of commonly encountered impurities on various membrane-protein crystallization regimes have been investigated and it was found that the lipidic cubic phase (LCP) based crystallization methodology is more robust than crystallization in detergent environments using vapor diffusion or microbatch approaches in its ability to tolerate contamination in the forms of protein, lipid or other general membrane components. LCP-based crystallizations produced crystals of the photosynthetic reaction center (RC) of Rhodobacter sphaeroides from samples with substantial levels of residual impurities. Crystals were obtained with protein contamination levels of up to 50% and the addition of lipid material and membrane fragments to pure samples of RC had little effect on the number or on the quality of crystals obtained in LCP-based crystallization screens. If generally applicable, this tolerance for impurities may avoid the need for samples of ultrahigh purity when undertaking initial crystallization screening trials to determine preliminary crystallization conditions that can be optimized for a given target protein. [source] Cryogenic structure of the photosynthetic reaction center of Blastochloris viridis in the light and darkACTA CRYSTALLOGRAPHICA SECTION D, Issue 5 2005Richard H. G. Baxter The structure of the Blastochloris viridis photosynthetic reaction center has been determined at 100,K by flash-freezing crystals. A data set to 2.2,Å resolution provides a well determined model of the wild-type protein. Of particular interest are the position, occupancy and heterogeneity of the QB -binding site. Data were also collected from a crystal frozen immediately after illumination. The data support predominant binding of QB in the proximal position in both the neutral and charge-separated states. [source] Crystallization and preliminary X-ray analysis of a phosphopentomutase from Bacillus cereusACTA CRYSTALLOGRAPHICA SECTION F (ELECTRONIC), Issue 7 2010Timothy D. Panosian Phosphopentomutases (PPMs) interconvert d -ribose 5-phosphate and ,- d -ribose 1-phosphate to link glucose and nucleotide metabolism. PPM from Bacillus cereus was overexpressed in Escherichia coli, purified to homogeneity and crystallized. Bacterial PPMs are predicted to contain a di-metal reaction center, but the catalytically relevant metal has not previously been identified. Sparse-matrix crystallization screening was performed in the presence or absence of 50,mM MnCl2. This strategy resulted in the formation of two crystal forms from two chemically distinct conditions. The crystals that formed with 50,mM MnCl2 were more easily manipulated and diffracted to higher resolution. These results suggest that even if the catalytically relevant metal is not known, the crystallization of putative metalloproteins may still benefit from supplementation of the crystallization screens with potential catalytic metals. [source] Control of Hydrogen Bond Strengths through Push,Pull Effects Triggered by a Remote Reaction Center: A Theoretical StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 7 2004Tsong-Song Hwang Dr. Abstract In an effort to manipulate the bond strengths of hydrogen bonds, we have studied a three-component chemical system consisting of a reaction center, a conjugated bridge, and a hydrogen-bonding site. Protonation of the reaction center triggers intramolecular charge transfer from the hydrogen-bonding site, altering its affinity to bind to an acceptor. Previously, we had found that this communication (signal transduction) between the reaction center and the hydrogen-bonding site does not necessarily die out with increasing length of the conjugated bridge. In certain cases, this signal transduction is maintained,and even amplified,over long distances (I. Chao, T.-S. Hwang, Angew. Chem.2001, 113, 2775,2777; Angew. Chem. Int. Ed.2001, 40, 2703,2705). In this study we report the results of an extensive theoretical investigation of this problem to provide insights into this intriguing phenomenon. In the systems we investigated it was found that the push,pull process between the hydrogen-bonding site and the protonatable reaction center was mediated with the greatest facility by conjugated bridges with low-lying , and ,* orbitals. [source] Dendrimers: A Mimic Natural Light-Harvesting SystemCHEMISTRY - AN ASIAN JOURNAL, Issue 5 2010Yi Zeng Dr. Abstract In natural photosynthetic systems, a large array of chlorophyll molecules surrounds a single reaction center and channels the absorbed solar energy to the reaction center, ultimately resulting in ATP production. Dendrimers are well-defined tree-like macromolecules having numerous chain ends all emanating from a single core, which makes them an attractive candidate for light-harvesting applications. More importantly, their synthesis is controllable and the accurate positioning of chromophores can be achieved. Photoinduced electron transfer and energy transfer are main processes involved in photosynthesis. Studies on these processes in dendritic systems are important for the future application of dendrimers in optoelectronic devices. In this Focus Review we will discuss recent advances of light-harvesting dendrimers and emphasize the energy transfer and electron transfer characteristics in these systems. [source] Primary Photophysical Processes in Photosystem II: Bridging the Gap between Crystal Structure and Optical SpectraCHEMPHYSCHEM, Issue 6 2010Thomas Renger Prof. Dr. Abstract This Minireview summarizes our current knowledge of the optical properties of photosystem II (PS-II) and how these properties are related to the photosynthetic function, that is, excitation energy transfer from the antenna complexes to the reaction center (RC) and the subsequent transmembrane charge separation in the latter. Interpretation of the optical spectra of PS-II is much more difficult than for the RC of purple bacteria, due to the "spectral congestion" problem, namely, the strong spectral overlap of optical bands in PS-II. Recent developments in deciphering the optical properties of the pigments in PS-II, the identification of functional states, and the kinetic details of the primary excitation energy and charge-transfer reactions are summarized. The spectroscopic term P680 that is generally used in the literature no longer indicates the same entity in its cationic and singlet excited form but different subsets of the six innermost pigments of the RC. The accessory chlorophyll ChlD1 forms a sink for singlet excitation and triplet energy and most likely represents the primary electron donor in PS-II. In this respect, a special chlorophyll monomer in PS-II plays the role of the special pair in purple bacteria. Evidence that exciton transfer between the core antenna complexes CP43 and CP47 and the RC is the bottleneck for the overall photochemical trapping of excitation energy in PS-II is discussed. A short summary is provided of PS-II of Acaryochloris marina, which mainly contains chlorophyll d instead of the usual chlorophyll a. This system does not suffer from the spectral congestion problem and, therefore, represents an interesting model system. The final part of this Minireview provides a discussion of challenging problems to be solved in the future. [source] Selective Patterned Growth of Single-Crystal Ag,TCNQ Nanowires for Devices by Vapor,Solid Chemical Reaction,ADVANCED FUNCTIONAL MATERIALS, Issue 19 2008Kai Xiao Abstract We report the deterministic growth of individual single-crystal organic semiconductor nanowires of silver,tetracyanoquinodimethane (Ag,TCNQ) with high yield (>90%) by a vapor,solid chemical reaction process. Ag,metal films or patterned dots deposited onto substrates serve as chemical reaction centers and are completely consumed during the growth of the individual or multiple nanowires. Selective-area electron diffraction (SAED) revealed that the Ag,TCNQ nanowires grow preferentially along the strong ,,, stacking direction of Ag,TCNQ molecules. The vapor,solid chemical reaction process described here permits the growth of organic nanowires at lower temperatures than chemical vapor deposition (CVD) of inorganic nanowires. The single-crystal Ag,TCNQ nanowires are shown to act as memory switches with high on/off ratios, making them potentially useful in optical storage, ultrahigh-density nanoscale memory, and logic devices. [source] Semilocalized approach to investigation of chemical reactivityINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 6 2003V. GineityteArticle first published online: 21 JUL 200 Abstract Application of the power series for the one-electron density matrix Gineityte, V., J Mol Struct Theochem 1995, 343, 183 to the case of two interacting molecules is shown to yield a semilocalized approach to investigate chemical reactivity, which is characterized by the following distinctive features: (1) Electron density (ED) redistributions embracing orbitals of the reaction centers of both molecules and of their neighboring fragments are studied instead of the total intermolecular interaction energy; (2) the ED redistributions are expressed directly in the basis of fragmental orbitals (FOs) without passing to the basis of delocalized molecular orbitals (MOs) of initial molecules; (3) terms describing the ED redistributions due to an intermolecular contact arise as additive corrections to the purely monomolecular terms and thereby may be analyzed independently; (4) local ED redistributions only between orbitals of the reaction centers of both molecules are described by lower-order ter s of the power series, whereas those embracing both the reaction centers and their neighborhoods are represented by higher-order terms. As opposed to the standard perturbative methods based on invoking the delocalized (canonical) MOs of isolated molecules, the results of the approach suggested are in-line with the well-known intuition-based concepts of the classic chemistry concerning reactivity, namely, with the assumption about different roles of the reaction center and of its neighborhood in a chemical process, with the expectation about extinction of the indirect influence of a certain fragment (substituent) when its distance from the reaction center grows, etc. Such a parallelism yields quantum chemical analogs for the classic concepts and thereby gives an additional insight into their nature. The scope of validity of these concepts also is discussed. Applicability of the approach suggested to specific chemical problems is illustrated by a brief consideration of the SN2 and AdE2 reactions. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 302,316, 2003 [source] Xanthophyll Cycle and Inactivation of Photosystem II Reaction Centers Alleviating Reducing Pressure to Photosystem I in Morning Glory Leaves under Short-term High IrradianceJOURNAL OF INTEGRATIVE PLANT BIOLOGY, Issue 7 2007Xin-Guo Li Abstract Under 30-min high irradiance (1500 ,mol m,2 s,1), the roles of the xanthophyll cycle and D1 protein turnover were investigated through chlorophyll fluorescence parameters in morning glory (Ipomoea setosa) leaves, which were dipped into water, dithiothreitol (DTT) and lincomycin (LM), respectively. During the stress, both the xanthophyll cycle and D1 protein turnover could protect PSI from photoinhibition. In DTT leaves, non-photochemical quenching (NPQ) was inhibited greatly and the oxidation level of P700 (P700+) was the lowest one. However, the maximal photochemical efficiency of PSII (Fv/Fm) in DTT leaves was higher than that of LM leaves and was lower than that of control leaves. These results suggested that PSI was more sensitive to the loss of the xanthophyll cycle than PSII under high irradiance. In LM leaves, NPQ was partly inhibited, Fv/Fm was the lowest one among three treatments under high irradiance and P700+ was at a similar level as that of control leaves. These results implied that inactivation of PSII reaction centers could protect PSI from further photoinhibition. Additionally, the lowest of the number of active reaction centers to one inactive reaction center for a PSII cross-section (RC/CSo), maximal trapping rate in a PSII cross-section (TRo/CSo), electron transport in a PSII cross-section (ETo/CSo) and the highest of 1-qP in LM leaves further indicated that severe photoinhibition of PSII in LM leaves was mainly induced by inactivation of PSII reaction centers, which limited electrons transporting to PSI. However, relative to the LM leaves the higher level of RC/CSo, TRo/CSo, Fv/Fm and the lower level of 1-qP in DTT leaves indicated that PSI photoinhibition was mainly induced by the electron accumulation at the PSI acceptor side, which induced the decrease of P700+ under high irradiance. [source] Melting out of sea ice causes greater photosynthetic stress in algae than freezing in,JOURNAL OF PHYCOLOGY, Issue 5 2007Peter J. Ralph Sea ice is the dominant feature of polar oceans and contains significant quantities of microalgae. When sea ice forms and melts, the microalgal cells within the ice matrix are exposed to altered salinity and irradiance conditions, and subsequently, their photosynthetic apparatuses become stressed. To simulate the effect of ice formation and melting, samples of sea-ice algae from Cape Hallett (Antarctica) were exposed to altered salinity conditions and incubated under different levels of irradiance. The physiological condition of their photosynthetic apparatuses was monitored using fast and slow fluorescence-induction kinetics. Sea-ice algae exhibited the least photosynthetic stress when maintained in 35, and 51, salinity, whereas 16, 21, and 65, treatments resulted in significant photosynthetic stress. The greatest photosynthetic impact appeared on PSII, resulting in substantial closure of PSII reaction centers when exposed to extreme salinity treatments. Salinity stress to sea-ice algae was light dependent, such that incubated samples only suffered photosynthetic damage when irradiance was applied. Analysis of fast-induction curves showed reductions in J, I, and P transients (or steps) associated with combined salinity and irradiance stress. This stress manifests itself in the limited capacity for the reduction of the primary electron receptor, QA, and the plastoquinone pool, which ultimately inhibited effective quantum yield of PSII and electron transport rate. These results suggest that sea-ice algae undergo greater photosynthetic stress during the process of melting into the hyposaline meltwater lens at the ice edge during summer than do microalgae cells during their incorporation into the ice matrix during the process of freezing. [source] FLUORESCENCE-BASED MAXIMAL QUANTUM YIELD FOR PSII AS A DIAGNOSTIC OF NUTRIENT STRESSJOURNAL OF PHYCOLOGY, Issue 4 2001Jean-Paul Parkhill In biological oceanography, it has been widely accepted that the maximum quantum yield of photosynthesis is influenced by nutrient stress. A closely related parameter, the maximum quantum yield for stable charge separation of PSII, (,PSII)m, can be estimated by measuring the increase in fluorescence yield from dark-adapted minimal fluorescence (Fo) to maximal fluorescence (Fm) associated with the closing of photosynthetic reaction centers with saturating light or with a photosynthetic inhibitor such as 3,-(3,4-dichlorophenyl)-1,,1,-dimethyl urea (DCMU). The ratio Fv/Fm (= (Fm, Fo)/Fm) is thus used as a diagnostic of nutrient stress. Published results indicate that Fv/Fm is depressed for nutrient-stressed phytoplankton, both during nutrient starvation (unbalanced growth) and acclimated nutrient limitation (steady-state or balanced growth). In contrast to published results, fluorescence measurements from our laboratory indicate that Fv/Fm is high and insensitive to nutrient limitation for cultures in steady state under a wide range of relative growth rates and irradiance levels. This discrepancy between results could be attributed to differences in measurement systems or to differences in growth conditions. To resolve the uncertainty about Fv/Fm as a diagnostic of nutrient stress, we grew the neritic diatom Thalassiosira pseudonana (Hustedt) Hasle et Heimdal under nutrient-replete and nutrient-stressed conditions, using replicate semicontinuous, batch, and continuous cultures. Fv/Fm was determined using a conventional fluorometer and DCMU and with a pulse amplitude modulated (PAM) fluorometer. Reduction of excitation irradiance in the conventional fluorometer eliminated overestimation of Fo in the DCMU methodology for cultures grown at lower light levels, and for a large range of growth conditions there was a strong correlation between the measurements of Fv/Fm with DCMU and PAM (r2 = 0.77, n = 460). Consistent with the literature, nutrient-replete cultures showed consistently high Fv/Fm (,0.65), independent of growth irradiance. Under nutrient-starved (batch culture and perturbed steady state) conditions, Fv/Fm was significantly correlated to time without the limiting nutrient and to nutrient-limited growth rate before starvation. In contrast to published results, our continuous culture experiments showed that Fv/Fm was not a good measure of nutrient limitation under balanced growth conditions and remained constant (,0.65) and independent of nutrient-limited growth rate under different irradiance levels. Because variable fluorescence can only be used as a diagnostic for nutrient-starved unbalanced growth conditions, a robust measure of nutrient stressed oceanic waters is still required. [source] Chemistry and technology of 2-alkenyl azlactonesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2001Steven M. Heilmann Abstract The chronology of 2-alkenyl azlactone research at 3M is discussed in terms of its origination; consideration of economics, overall safety, and opportunities for patent protection; elaboration of the chemistry; and, finally, applying lessons learned toward the development of commercial technologies. The chemistry is dominated by the presence of three electrophilic reaction centers and a readily polymerizable 2-alkenyl group. Technological development has been focused in four general areas: acrylamide monomers, acrylamide materials, azlactone materials, and polymer modification. Application areas disinclude lithographic printing plates, contact lens materials, adhesives, dispersants for printing inks, and supports for immobilizing enzymes. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3655,3677, 2001 [source] Daily dynamics of photosynthesis of the freshwater red alga Sirodotia delicatula (Batrachospermales, Rhodophyta)PHYCOLOGICAL RESEARCH, Issue 4 2009Thiago Kusakariba SUMMARY The daily course of photosynthetic parameters of a population of the freshwater red alga Sirodotia delicatula from São Paulo State, Brazil (20°43,24,S, 49°18,21,W) was investigated under natural and laboratory conditions using dissolved oxygen and in vivo chlorophyll fluorescence techniques. Field specimens in laboratory conditions showed a defined daily pattern for net photosynthesis (NP) with two peaks observed in marine macroalgae and some freshwater red algae: the first (the highest) during the morning, and the second (the lowest and less evident) during the afternoon. Values of electron transport rate did not show a clear pattern of daily variation. NP results suggest the existence of an endogenous rhythm controlling photosynthesis. The study under natural conditions in two contrasting periods (autumn (June) and spring (October)) showed that the daily course of effective and potential quantum yield values was negatively correlated with irradiance and values were similar in the beginning and end of the day. These data evidenced, respectively, high excitement pressure on photosystem II and good recovery capacity (with lower values in spring) and a lack of irreversible photodamage to photosynthetic apparatus due to the prolonged exposure to high irradiances. Non-photochemical quenching values were also negatively correlated with the irradiance, suggesting a low dissipation capacity of excess energy absorbed by reaction centers. The results evidenced a typical pattern of daily variation with evident response to irradiance. [source] Drought stress effects on photosystem I content and photosystem II thermotolerance analyzed using Chl a fluorescence kinetics in barley varieties differing in their drought tolerancePHYSIOLOGIA PLANTARUM, Issue 2 2009Abdallah Oukarroum Drought stress has multiple effects on the photosynthetic system. Here, we show that a decrease of the relative contribution of the I-P phase, ,VIP = ,VI = (FM,FI)/(FM, Fo), to the fluorescence transient OJIP is observed in 10 drought-stressed barley and 9 chickpea varieties. The extent of the I-P loss in the barley varieties depended on their drought tolerance. The relative loss of the I-P phase seems to be related to a loss of photosystem (PS) I reaction centers as determined by 820-nm transmission measurements. In the second part of this study, the interaction of drought and heat stress in two barley varieties (the drought tolerant variety A¨t Baha and the drought sensitive variety Lannaceur) was studied using a new approach. Heat stress was induced by exposing the plant leaves to temperatures of 25,45°C and the inactivation of the O2 -evolving complex (OEC) was followed measuring chlorophyll a (Chl a) fluorescence using a protocol consisting of two 5-ms pulses spaced 2.3 ms apart. In active reaction centers, the dark interval is long enough to allow the OEC to recover from the first pulse; whereas in heat-inactivated reaction centers it is not. In the latter category of reaction centers, no further fluorescence rise is induced by the second pulse. Lannaceur, under well-watered conditions, was more heat tolerant than Aït Baha. However, this difference was lost following drought stress. Drought stress considerably increased the thermostability of PS II of both varieties. [source] | ||||||||||||||||||||||||||||