Comparative study of the water oxidizing reactions and the millisecond delayed chlorophyll fluorescence in photosystem II at different pH

Water splitting activity, the multiline EPR signal associated with S(2)-state of the CaMn(4)-cluster and the fast and slow phases of the induction curve of the millisecond delayed chlorophyll fluorescence from photosystem II (PSII) in the pH range of 4.5-8.5 were studied in the thylakoid membranes and purified PSII particles. It has been found that O(2) evolution and the multiline EPR signal were inhibited at acidic (pK approximately 5.3) and alkaline (pK approximately 8.1) pH values, and were maximal at pH 6.0-7.0. Our results indicate that the loss of O(2) evolution and the S(2)-state multiline EPR signal associated with the decrease of the millisecond delayed chlorophyll fluorescence only in alkaline region (pH 7.0-8.5). Possible correlations of the millisecond delayed chlorophyll fluorescence components with the donor side reactions in PSII are discussed.     

Self-organization of polymer particles on hydrophobic solid substrates in aqueous media. II. Self-organization of cationic polymer particles on polymer films and wettability control with particle monolayers

Self-organization of cationic polymer particles through hydrophobic interaction on polymer films in aqueous system and characteristic properties of the resulting particle monolayers were investigated. Cationic polymer particles bearing quaternary ammonium groups on their surfaces effectively self-organized on polymer films. With an increase of the particle surface charge density, the surface coverage and average aggregate size (N _a) decreased. The surface coverage control was accomplished by tuning the ionic strength of the media. The wettability of polymer films for water was imparted by the formation of particle monolayers on them. Annealing of the particle monolayers resulted in the increase of the adhesive strength, while the wettability for water was lost. Further improvements of both wettability and adhesive strength of particle monolayers were achieved by the immobilization of silica colloids on the particle monolayers. This method would be effective for the hydrophilization of polymer films.     

Multi‐input–Multi‐output Molecular Response System Based on Dynamic Redox Behavior of Hexaphenylethane‐type Electron Donors with the Tetrahydrophenanthrazepine Skeleton: Strong Chiroptical Signals through the Transmission of Point Chirality to Helicity

The title heterocyclic donors undergo reversible C? C bond formation/cleavage upon electron transfer (dynamic redox behavior). The helical sense in both neutral and cationic states is interconvertible by facile ring flipping. The π‐type asymmetric center on the azepine nitrogen atom induces a significant degree of diasteromeric preference, thus endowing strong CD activity based on exciton coupling. Chiroptical properties could be modified not only by redox reactions but also by heat and protonation. The present redox pairs can serve as unprecedented three‐way‐input (e, H⁺, Δ) and two‐way‐output (UV/Vis, CD) response systems.     

Sequence-dependent conformational energy of DNA derived from molecular dynamics simulations: toward understanding the indirect readout mechanism in protein-DNA recognition

Sequence dependence of DNA conformation plays a crucial role in its recognition by proteins and ligands. To clarify the relationship between sequence and conformation, it is necessary to quantify the conformational energy and specificity of DNA. Here, we make a systematic analysis of dodecamer DNA structures including all the 136 unique tetranucleotide sequences at the center by molecular dynamics simulations. Using a simplified conformational model with six parameters to describe the geometry of adjacent base pairs and harmonic potentials along these coordinates, we estimated the equilibrium conformational parameters and the harmonic potentials of mean force for the central base-pair steps from many trajectories of the simulations. This enabled us to estimate the conformational energy and the specificity for any given DNA sequence and structure. We tested our method by using sequence-structure threading to estimate the conformational energy and the Z-score as a measure of specificity for many B-DNA and A-DNA crystal structures. The average Z-scores were negative for both kinds of structures, indicating that the potential of mean force from the simulation is capable of predicting sequence specificity for the crystal structures and that it may be used to study the sequence specificity of both types of DNA. We also estimated the positional distribution of conformational energy and Z-score within DNA and showed that they are strongly position dependent. This analysis enabled us to identify particular conformations responsible for the specificity. The presented results will provide an insight into the mechanisms of DNA sequence recognition by proteins and ligands.     

Stereoselective synthesis of cis- and trans-2,3-disubstituted eight-membered medium-ring ethers based on Ireland-Claisen rearrangement of 3-alkoxy-2-propenyl glycolate esters and ring-closing olefin metathesis

A simple stereoselective synthesis of cis- and trans-2,3-disubstituted medium-sized cyclic ethers has been developed based on geometry-selective synthesis of 3-alkoxy-2-propenyl glycolate esters, Ireland-Claisen rearrangement of the glycolate esters, and ring-closing olefin metathesis.     

Synthesis of cationic water-soluble esters of chlorin e6

Two esters of chlorin e₆ have been synthesized by esterification with aminoalcohols via the formation of acid chloride using oxalyl chloride and converted to the corresponding cationic water-soluble esters of chlorin e₆. The visible absorption and circular dichroism spectra have revealed that these two cationic chlorin e₆ esters synthesized are readily soluble in water as a monomer.     

Synthesis of the common left-half part of pectenotoxins

The common left-half [C31-C33(OC1-C7)-C40] part of pectenotoxins has been synthesized convergently from the C31-C35, C36-C40, and C1-C7 parts. The C31-C35 part, prepared via a new route shorter than our previous route, was coupled with the C36-C40 part through reductive lithiation and addition reactions to give an adduct stereoselectively, which was converted to a cyclic acetal corresponding to the C31-C40 part. The left-half was synthesized by a three-step process including esterification of the C31-C40 part with the C1-C7 part.     

Enhanced electrical properties of highly oriented poly(vinylidene fluoride) films prepared by solid‐state coextrusion

Oriented poly(vinylidene fluoride) (PVDF) films with β‐form crystals have been commonly prepared by cold drawing of a melt‐quenched film consisting of α‐form crystals. In this study, we have successfully produced highly oriented PVDF thin films (20 µm thick) with β‐crystals and a high crystallinity (55–76%), by solid‐state coextrusion of a gel film to eight times the original length at an established optimum extrusion temperature of 160°C, some 10°C below the melting temperature. The resultant drawn films had a highly oriented (orientation function f_c = 0.993) fibrous structure, showing high mechanical properties of an extensional elastic modulus of 8.3 GPa and tensile strength of 0.84 GPa, along the draw direction. Such highly oriented and crystalline films exhibited excellent ferroelectric and piezoelectric properties. The square hysteresis loop was significantly sharper than that of a conventional sample. The sharp switching transient yielded the remnant polarization P_r of 90 mC/m², and the electromechanical coupling factor k_t was 0.24 at room temperature. These values are about 1.5 times greater than those of a conventional β‐PVDF film. Thus, solid‐state coextrusion near the melting point was found to be a useful technique for the preparation of highly oriented and highly crystalline β‐PVDF films with superior mechanical and electrical properties. The morphology of the extrudate relevant to such properties is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2549–2556, 1999     

De novo design of a redox-active minimal rubredoxin mimic

Metal-binding sites in metalloproteins frequently occur at the interfaces of elements of secondary structure, which has enabled the retrostructural analysis of natural proteins and the de novo design of helical bundles that bind metal ion cofactors. However, the design of metalloproteins containing beta-structure is less well developed, despite the frequent occurrence of beta-conformations in natural metalloproteins. Here, we describe the design and construction of a beta-protein, RM1, that forms a stable, redox-active 4-Cys thiolate Fe(II/III) site analogous to the active site of rubredoxin. The protein folds into a beta-structure in the presence and absence of metal ions and binds Fe(II/III) to form a redox-active site that is stable to repeated cycles of oxidation and reduction, even in an aerobic environment.     

Kinetic study of the quenching reaction of singlet oxygen by flavonoids in ethanol solution

The quenching rate of singlet oxygen (1O2) by seven kinds of flavonoids (flavone, flavonol, chrysin, apigenin, rutin, quercetin, and myricetin) with 2,3-double bonds has been measured spectrophotometrically in ethanol at 35 degrees C. The overall rate constants kQ (= kq + kr, physical quenching + chemical reaction) increased as the number of OH groups substituted to the flavone skeleton (that is, the total electron-donating capacity of flavonoids) increases. The existence of catechol or pyrogallol structure in the B-ring is essential for the 1O2 quenching of flavonoids. Log kQ was found to correlate with their peak oxidation potentials, E(P); the flavonoids that have smaller E(P) values show higher reactivities. Similarly, log kQ values of flavonoids correlate with the energy level of the highest occupied molecular orbital (E(HOMO)), calculated by the PM3 MO method, and the longest wavelength pi pi* excitation energy (E(ex)). The contribution of the chemical reaction (kr) was found to be negligible in these flavonoids. The kQ values of rutin, quercetin, and myricetin [(1.21 approximately 5.12) x 10(8) M(-1) s(-1)] were found to be larger than those of lipids [(0.9 approximately 6.4) x 10(4) M(-1) s(-1)], amino acids (<3.7 x 10(7) M(-1) s(-1)), and DNA (5.1 x 10(5) M(-1) s(-1)). The result suggests that these flavonoids may contribute to the protection of oxidative damage in foods and plants, by quenching 1O2.