Transfer reactions in the investigation of light-nuclei nucleosynthesis

Cross sections for the (6)Li(p,gamma)(7)Be, (7)Li(n,gamma)(8)Li (8)Li(n,gamma)(9)Li and (8)Li(p,gamma)(9)Be capture reactions have been investigated in the framework of the potential model. The main ingredients of the potential model are the potentials used to generate the continuum and bound-state wave functions and spectroscopic factors of the corresponding bound systems. The spectroscopic factors for the (7)Li circle times n=(8)Li(gs), (8)Li circle times n=(9)Li(gs) bound systems were obtained from a FR-DWBA analysis of neutron transfer reactions induced by (8)Li radioactive beam on a (9)Be target, while spetroscopic factor for the (8)Li circle times n=(9)Be(gs) bound system were obained from a proton transfer reaction. From the obtained capture reaction cross section, reaction rate for the (8)Li(n,gamma)(9)Li and (8)Li(p,gamma)(9)Be direct neutron and proton capture were determined and compared with other experimental and calculated values.

Molecular interactions and signal transfer between sensory rhodopsin-I and its cognate transducer

SRI is unique among known photoreceptors in that it produces opposite signals depending on the color of light stimuli. Absorption of orange light (587 nm) triggers an attractant response by the cell, whereas absorption of orange light followed by near-UV light (373 run) triggers a repellent response. Using behavioral mutants that exhibit aberrant color-sensing ability, we tested a two-conformation equilibrium model, using FRET and EPR spectroscopy. The essence of the model applied to SRI-HtrI is that the complex exists in a metastable two-conformer equilibrium which is shifted in one direction by orange light absorption (producing an attractant signal) and in the opposite direction by a second UV-violet photon (producing a repellent signal). First, by FRET we found that the E-F cytoplasmic loop of SRI moves toward the RAMP domain of the HtrI transducer during the formation of the orange-light activated signaling state of the complex. This is the first localization of a change in the physical relationship between the receptor and transducer subunits of the complex and provides a structural property of the two proposed conformers that we can monitor. Second, EPR spectra of a spin label probe at this cytoplasmic position showed shifts in the dark in the mutants toward shorter or longer EF loop-RAMP distances, explaining their behavior in terms of their mutations causing pre-stimulus shifts into one or the other conformer. ^ Next, we applied a novel electrophysiological method for monitoring the directionality of proton movement during photoactivation of SRI, to investigate the process of proton transfer in the photoactive site from the chromophore to proton acceptors on both the wildtype and aberrant color-response mutants. We observed an unexpected and critical difference in the two signaling conformations of the SRI-HtrI complex. The finding is that the vectoriality (i.e. movement away or toward the cytoplasm) of the light-induced proton transfer from the chromophore to the protein is opposite in formation of the two conformations. Retinylidene proton transfer is a common critical process in rhodopsins and these results are the first to show differences in vectoriality in a rhodopsin receptor, and to demonstrate functional importance of the direction of proton transfer. ^

Chemical complementation identifies a proton acceptor for redox-active tyrosine D in photosystem II

Through the use of site-directed mutagenesis and chemical rescue, we have identified the proton acceptor for redox-active tyrosine D in photosystem II (PSII). Effects of chemical rescue on the tyrosyl radical were monitored by EPR spectroscopy. We also have acquired the Fourier–transform infrared (FT-IR) spectrum associated with the oxidation of tyrosine D and concomitant protonation of the acceptor. Mutant and isotopically labeled PSII samples are used to assign vibrational lines in the 3,600–3,100 cm−1 region to N-H modes of His-189 in the D2 polypeptide. When His-189 in D2 is changed to a leucine (HL189D2) in PSII, dramatic alterations of both EPR and FT-IR spectra are observed. When imidazole is introduced into HL189D2 samples, results from both EPR and FT-IR spectroscopy argue that imidazole is functionally reconstituted into an accessible pocket and that imidazole acts as a chemical mimic for His-189. Small perturbations of EPR and FT-IR spectra are consistent with access to this pocket in wild-type PSII, as well. Structures of the analogous site in bacterial reaction centers suggest that an accessible pocket, large enough to contain imidazole, is bordered by tyrosine D and His-189 in the D2 polypeptide. These data provide evidence that His-189 in the D2 polypeptide of PSII acts as a proton acceptor for redox-active tyrosine D and that proton transfer to the imidazole ring facilitates the efficient oxidation/reduction of tyrosine D.

Identification of the proton pathway in bacterial reaction centers: Both protons associated with reduction of QB to QBH2 share a common entry point

The reaction center from Rhodobacter sphaeroides uses light energy for the reduction and protonation of a quinone molecule, QB. This process involves the transfer of two protons from the aqueous solution to the protein-bound QB molecule. The second proton, H+(2), is supplied to QB by Glu-L212, an internal residue protonated in response to formation of QA− and QB−. In this work, the pathway for H+(2) to Glu-L212 was studied by measuring the effects of divalent metal ion binding on the protonation of Glu-L212, which was assayed by two types of processes. One was proton uptake from solution after the one-electron reduction of QA (DQA→D+QA−) and QB (DQB→D+QB−), studied by using pH-sensitive dyes. The other was the electron transfer kAB(1) (QA−QB→QAQB−). At pH 8.5, binding of Zn2+, Cd2+, or Ni2+ reduced the rates of proton uptake upon QA− and QB− formation as well as kAB(1) by ≈an order of magnitude, resulting in similar final values, indicating that there is a common rate-limiting step. Because D+QA− is formed 105-fold faster than the induced proton uptake, the observed rate decrease must be caused by an inhibition of the proton transfer. The Glu-L212→Gln mutant reaction centers displayed greatly reduced amplitudes of proton uptake and exhibited no changes in rates of proton uptake or electron transfer upon Zn2+ binding. Therefore, metal binding specifically decreased the rate of proton transfer to Glu-L212, because the observed rates were decreased only when proton uptake by Glu-L212 was required. The entry point for the second proton H+(2) was thus identified to be the same as for the first proton H+(1), close to the metal binding region Asp-H124, His-H126, and His-H128.

Covalent intermediate trapped in 2-keto-3-deoxy-6- phosphogluconate (KDPG) aldolase structure at 1.95-Å resolution

2-Keto-3-deoxy-6-phosphogluconate (KDPG) aldolase catalyzes the reversible cleavage of KDPG to pyruvate and glyceraldehyde-3-phosphate. The enzyme is a class I aldolase whose reaction mechanism involves formation of Schiff base intermediates between Lys-133 and a keto substrate. A covalent adduct was trapped by flash freezing KDPG aldolase crystals soaked with 10 mM pyruvate in acidic conditions at pH 4.6. Structure determination to 1.95-Å resolution showed that pyruvate had undergone nucleophilic attack with Lys-133, forming a protonated carbinolamine intermediate, a functional Schiff base precursor, which was stabilized by hydrogen bonding with active site residues. Carbinolamine interaction with Glu-45 indicates general base catalysis of several rate steps. Stereospecific addition is ensured by aromatic interaction of Phe-135 with the pyruvate methyl group. In the native structure, Lys-133 donates all of its hydrogen bonds, indicating the presence of an ɛ-ammonium salt group. Nucleophilic activation is postulated to occur by proton transfer in the monoprotonated zwitterionic pair (Glu-45/Lys-133). Formation of the zwitterionic pair requires prior side chain rearrangement by protonated Lys-133 to displace a water molecule, hydrogen bonded to the zwitterionic residues.

Mécanismes de transfert de proton d’une réaction acido-basique en phase aqueuse : une étude ab-initio

Les réactions de transfert de proton se retrouvent abondamment dans la nature et sont des processus cruciaux dans plusieurs réactions chimiques et biologiques, qui se produisent souvent en milieu aqueux. Les mécanismes régissant ces échanges de protons sont complexes et encore mal compris, suscitant un intérêt des chercheurs en vue d’une meilleure compréhension fondamentale du processus de transfert. Le présent manuscrit présente une étude mécanistique portant sur une réaction de transfert de proton entre un acide (phénol fonctionnalisé) et une base (ion carboxylate) en phase aqueuse. Les résultats obtenus sont basés sur un grand nombre de simulations de dynamique moléculaire ab-initio réalisées pour des systèmes de type « donneur-pont-accepteur », où le pont se trouve à être une unique molécule d’eau, permettant ainsi l’élaboration d’un modèle cinétique détaillé pour le système étudié. La voie de transfert principalement observée est un processus ultra-rapide (moins d’une picoseconde) passant par la formation d’une structure de type « Eigen » (H9O4+) pour la molécule d’eau pontante, menant directement à la formation des produits. Une seconde structure de la molécule d’eau pontante est également observée, soit une configuration de type « Zündel » (H5O2+) impliquant l’accepteur de proton (l’ion carboxylate) qui semble agir comme un cul-de-sac pour la réaction de transfert de proton.

Mécanismes de transfert de proton d’une réaction acido-basique en phase aqueuse : une étude ab-initio

Les réactions de transfert de proton se retrouvent abondamment dans la nature et sont des processus cruciaux dans plusieurs réactions chimiques et biologiques, qui se produisent souvent en milieu aqueux. Les mécanismes régissant ces échanges de protons sont complexes et encore mal compris, suscitant un intérêt des chercheurs en vue d’une meilleure compréhension fondamentale du processus de transfert. Le présent manuscrit présente une étude mécanistique portant sur une réaction de transfert de proton entre un acide (phénol fonctionnalisé) et une base (ion carboxylate) en phase aqueuse. Les résultats obtenus sont basés sur un grand nombre de simulations de dynamique moléculaire ab-initio réalisées pour des systèmes de type « donneur-pont-accepteur », où le pont se trouve à être une unique molécule d’eau, permettant ainsi l’élaboration d’un modèle cinétique détaillé pour le système étudié. La voie de transfert principalement observée est un processus ultra-rapide (moins d’une picoseconde) passant par la formation d’une structure de type « Eigen » (H9O4+) pour la molécule d’eau pontante, menant directement à la formation des produits. Une seconde structure de la molécule d’eau pontante est également observée, soit une configuration de type « Zündel » (H5O2+) impliquant l’accepteur de proton (l’ion carboxylate) qui semble agir comme un cul-de-sac pour la réaction de transfert de proton.

Air-sea transfer of gas phase controlled compounds

Gases in the atmosphere/ocean have solubility that spans several orders of magnitude. Resistance in the molecular sublayer on the waterside limits the air-sea exchange of sparingly soluble gases such as SF6 and CO2. In contrast, both aerodynamic and molecular diffusive resistances on the airside limit the exchange of highly soluble gases (as well as heat). Here we present direct measurements of air-sea methanol and acetone transfer from two open cruises: the Atlantic Meridional Transect in 2012 and the High Wind Gas Exchange Study in 2013. The transfer of the highly soluble methanol is essentially completely airside controlled, while the less soluble acetone is subject to both airside and waterside resistances. Both compounds were measured concurrently using a proton-transfer-reaction mass spectrometer, with their fluxes quantified by the eddy covariance method. Up to a wind speed of 15 m s-1, observed air-sea transfer velocities of these two gases are largely consistent with the expected near linear wind speed dependence. Measured acetone transfer velocity is ~30% lower than that of methanol, which is primarily due to the lower solubility of acetone. From this difference we estimate the "zero bubble" waterside transfer velocity, which agrees fairly well with interfacial gas transfer velocities predicted by the COARE model. At wind speeds above 15 m s-1, the transfer velocities of both compounds are lower than expected in the mean. Air-sea transfer of sensible heat (also airside controlled) also appears to be reduced at wind speeds over 20 m s-1. During these conditions, large waves and abundant whitecaps generate large amounts of sea spray, which is predicted to alter heat transfer and could also affect the air-sea exchange of soluble trace gases. We make an order of magnitude estimate for the impacts of sea spray on air-sea methanol transfer.

Air-sea transfer of gas phase controlled compounds

Gases in the atmosphere/ocean have solubility that spans several orders of magnitude. Resistance in the molecular sublayer on the waterside limits the air-sea exchange of sparingly soluble gases such as SF6 and CO2. In contrast, both aerodynamic and molecular diffusive resistances on the airside limit the exchange of highly soluble gases (as well as heat). Here we present direct measurements of air-sea methanol and acetone transfer from two open cruises: the Atlantic Meridional Transect in 2012 and the High Wind Gas Exchange Study in 2013. The transfer of the highly soluble methanol is essentially completely airside controlled, while the less soluble acetone is subject to both airside and waterside resistances. Both compounds were measured concurrently using a proton-transfer-reaction mass spectrometer, with their fluxes quantified by the eddy covariance method. Up to a wind speed of 15 m s-1, observed air-sea transfer velocities of these two gases are largely consistent with the expected near linear wind speed dependence. Measured acetone transfer velocity is ~30% lower than that of methanol, which is primarily due to the lower solubility of acetone. From this difference we estimate the "zero bubble" waterside transfer velocity, which agrees fairly well with interfacial gas transfer velocities predicted by the COARE model. At wind speeds above 15 m s-1, the transfer velocities of both compounds are lower than expected in the mean. Air-sea transfer of sensible heat (also airside controlled) also appears to be reduced at wind speeds over 20 m s-1. During these conditions, large waves and abundant whitecaps generate large amounts of sea spray, which is predicted to alter heat transfer and could also affect the air-sea exchange of soluble trace gases. We make an order of magnitude estimate for the impacts of sea spray on air-sea methanol transfer.

Proton conductivity and luminiscence properties of lanthanide aminotriphosphonates

Metal phosphonates are multifunctional solids with tunable properties, such as internal H-bond networks, and high chemical and thermal stability [1]. In the present work, we describe the synthesis, structural characterization, luminescent properties and proton conduction performance of a new family of isostructural cationic compounds with general formula [Ln(H4NMP)(H2O)2]Cl·2H2O [Ln = La3+, Pr3+, Sm3+, Gd3+, Tb3+, Dy3+, Ho3+, H6NMP = nitrilotris(methylphosphonic acid)]. These solids are formed by positively charge layers, which consist of isolated LnO8 polyhedra and bridge chelating NMP2- ligands, held apart by chloride ions and water molecules. This arrangement result in extended interlayer hydrogen networks with possible proton transfer pathways. The proton conductivity of Gd3+ sample, selected as prototype of the series, was measured. In the range between range 25º and 80 ºC, the conductivity increase with the temperature up to a maximum value of 3.10-4 S·cm-1, at relative humidity of 95 %. The activation energy obtained from the Arrhenius plot (Figure 1) is in the range corresponding to a Grotthuss transfer mechanism.

Elastic scattering and total reaction cross sections for the (8)Li+(12)C system

The elastic-scattering angular distribution for (8)Li on (12)C has been measured at E(LAB) = 23.9 MeV with (8)Li radioactive nuclear beam produced by the Radioactive Ion Beams in Brazil facility. This angular distribution was analyzed in terms of optical-model with Woods-Saxon and double-folding Sao Paulo potential. The roles of the breakup and inelastic channels were also investigated with cluster folding and deformed potentials, respectively, through coupled-channels calculations. The angular distribution for the proton-transfer (12)C((8)Li, (9)Be)(11)B reaction was also measured at the same energy. The spectroscopic factor for the <(9)Be|(8)Li + p > bound system was obtained and compared with shell-model calculations and with other experimental values. Total reaction cross sections for the present system were also extracted from the elastic-scattering analysis. A systematic of the reduced reaction cross sections obtained from the present and published data on (6,7,8)Li isotopes on (12)C was performed as a function of energy.

Making solar fuels by artificial photosynthesis

In order for solar energy to serve as a primary energy source, it must be paired with energy storage on a massive scale. At this scale, solar fuels and energy storage in chemical bonds is the only practical approach. Solar fuels are produced in massive amounts by photosynthesis with the reduction of CO(2) by water to give carbohydrates but efficiencies are low. In photosystem II (PSII), the oxygen-producing site for photosynthesis, light absorption and sensitization trigger a cascade of coupled electron-proton transfer events with time scales ranging from picoseconds to microseconds. Oxidative equivalents are built up at the oxygen evolving complex (OEC) for water oxidation by the Kok cycle. A systematic approach to artificial photo synthesis is available based on a ""modular approach"" in which the separate functions of a final device are studied separately, maximized for rates and stability, and used as modules in constructing integrated devices based on molecular assemblies, nanoscale arrays, self-assembled monolayers, etc. Considerable simplification is available by adopting a ""dyesensitized photoelectrosynthesis cell"" (DSPEC) approach inspired by dye-sensitized solar cells (DSSCs). Water oxidation catalysis is a key feature, and significant progress has been made in developing a single-site solution and surface catalysts based on polypyridyl complexes of Ru. In this series, ligand variations can be used to tune redox potentials and reactivity over a wide range. Water oxidation electrocatalysis has been extended to chromophore-catalyst assemblies for both water oxidation and DSPEC applications.

Photochemistry of anthocyanins and their biological role in plant tissues

Anthocyanins, the major red, purple, and blue pigments of plants, absorb visible as well as UV radiation and are effective antioxidants and scavengers of active oxygen species. In plant leaves, one of the functional roles proposed for anthocyanins is protection of the photosynthetic apparatus from the effects of excess incident visible or UV-B radiation and photooxidative stress. In essence, a photoprotective role requires that the excited singlet states of both complexed and uncomplexed anthocyanins deactivate back to the ground state so quickly that intersystem crossing, photoreaction, and diffusion-controlled quenching processes cannot compete. Studies of the photochemical properties of synthetic analogs of anthocyanins and of several naturally occurring anthocyanins show that this is indeed the case, uncomplexed anthocyanins decaying back to the ground state via fast (subnanosecond) excited-state proton transfer (ESPT) and anthocyanin-copigment complexes by fast (sub-picosecond) charge-transfer-mediated internal conversion.

2-(4-Methylphenyl)-1H-anthraceno-[1,2-d]imidazole-6,11-dione: a fluorescent chemosensor

In the title compound, C(22)H(14)N(2)O(2), the five rings of the molecule are not coplanar. There is a significant twist between the four fused rings, which have a slightly arched conformation, and the pendant aromatic ring, as seen in the dihedral angle of 13.16 (8)degrees between the anthraquinonic ring system and the pendant aromatic ring plane.