ESEEM study of the location of spin-polarized chlorophyll-quinone radical pair in membrane-oriented spinach photosystems I and II complexes

Light-induced spin-polarized radical pairs, P700⁺A₁ ^? in spinach photosystem (PS) I particles and P680⁺Q_A ^? in Zn-substituted PS II core complexes, in oriented membranes were studied by pulsed electron paramagnetic resonance (EPR). Based on the determined distance of 25.2 ± 0.2 Å between P700 and A₁, the angular dependence of the spin-polarized electron spin echo envelope modulation (ESEEM) spectra on the magnetic field suggests that the angle between $R_{P700 - {\rm A}_1 } $ , the radius-vector connecting P700 and A₁, and the membrane normaln was 24 ± 4° in PS I particles. Obtained angle and distance of P700-A₁ axis suggested Q_K side in the molecular geometry of cofactors presented in a recent X-ray crystallography of cyanobacterial PS I reaction center to be an active branch of electron transfer. The distance between P680 and Q_A was determined to be 27.4 ± 0.3 Å for a nonoriented PS II. The angle between $R_{P680 - Q_{\rm A} } $ , the radius-vector connecting P680 and Q_A, andn was determined to be 21 ± 5°. The angle of P680-Q_A axis was close to that of 20° of P870-Q_A axis reported in X-ray analysis of the purple bacterial reaction center crystal.     

Ferroelectric liquid crystalline phase transition of (S)-hexakis(4-(4'-(6-methyl)octyloxy)biphenoxy) cyclotriphosphazene

(S)-Hexakis(4-(4'-(6-methyl)octyloxy)biphenoxy)cyclotriphosphazene (SMOCP) was synthesized in a search for new ferroelectric liquid crystalline compounds. We found an enantiotropic ferroelectric smectic C* phase between 419 and 441 K in SMOCP by using polarizing microscopy and DSC measurements. The spontaneous polarization was estimated to be -130.5 μCm^-2 at 437.6 K, several times larger than that of DOBAMBC ((S)-2-methylbutyl 4-(4'-decyloxybenzylidene)aminocinnamate.     

Remarks on the relation between the Lee-Yang circle theorem and the correlation inequalities

We investigate the relation between the Lee-Yang circle theorem and the correlation inequalities. These results are general and independent of models. General properties of the partition functions which belong to the Lee-Yang class are given.     

Spectroscopic study of J aggregates of amphiphilic merocyanine dyes formed in their pure Langmuir films

It is known that an amphiphilic merocyanine dye, 3-carboxymethyl-5-[2-(3-octadecyl-2(3H)- benzothiazolylidene)ethylidene]-2-thioxo-4-thiazolidinone (DS) and its derivatives DSe and 6MeDS form J aggregates under the presence of metallic cations, although the dyes' static dipole moments must be favorable for H aggregates. A metal-free J aggregate of 6MeDS has been generated in its pure Langmuir films and transferred onto CaF2 substrates to investigate the molecular environment around the carboxylic group born by the dye. Combining visible and infrared spectroscopy, geometrical consideration based on ab initio calculations, and simulation of the excitation energy, a structural model of this J aggregate has been proposed. With this model, formation of intermolecular carboxyl-keto hydrogen bonds, which can compensate the electrostatic disadvantage of the J aggregate under the presence of water, has been suggested. As for another derivative of DS, DO, similar discussion has been made for its Mg2+ -containing J aggregate, which is found in this work. In addition, the proposed structural model can tell the cause of the difference in the tendency to J aggregate among 6MeDS, DSe, DS, and DO.     

Role of Arg123 in Light‐driven Anion Pump Mechanisms of pharaonis Halorhodopsin†

Halorhodopsin (HR) acts as a light‐driven chloride pump which transports a chloride ion from the extracellular (EC) to the cytoplasmic space during a photocycle reaction that includes some photointermediates initiated by illumination. To understand the chloride uptake mechanisms, we focused on a basic residue Arg123 of HR from Natronomonas pharaonis (NpHR), which is the only basic residue located in the EC half ion channel. By the measurements of the visible absorption spectra in the dark and the light‐induced inward current through the membrane, it was shown that the chloride binding and transport ability of NpHR completely disappeared by the change of arginine to glutamine. From flashphotolysis analysis, the photocycle of R123Q differed from that of wildtype NpHR completely. The response of the R123H mutant depended on pH. These facts imply that the positive charge at position 123 is essential for chloride binding in the ground state and for the chloride uptake under illumination. On the basis of the molecular structures of HR and the anion‐transportable mutants of bacteriorhodopsin, the effects of the positive charge and the conformational change of the Arg123 side chain as well as the chloride‐pumping mechanism are discussed.     

Development of sulfide glass-ceramic electrolytes for all-solid-state lithium rechargeable batteries

Development of Li₂S–P₂S₅-based glass-ceramic electrolytes is reviewed. Superionic crystals of Li₇P₃S₁₁ and Li_3.25P_0.95S₄ were precipitated from the Li₂S–P₂S₅ glasses at the selected compositions. These high temperature or metastable phases enhanced conductivity of glass ceramics up to over 10⁻³ S cm⁻¹ at room temperature. The original (or mother) glass electrolytes itself showed somewhat lower conductivity of 10⁻⁴ S cm⁻¹ and have important role as a precursor for obtaining the superionic crystals, which were not synthesized by a conventional solid-state reaction. The substitution of P₂O₅ for P₂S₅ at the composition 70Li₂S·30P₂S₅ (mol%) improved both conductivity and electrochemical stability of glass-ceramic electrolytes. The all-solid-state In/LiCoO₂ cell using the 70Li₂S·27P₂S₅·3P₂O₅ (mol%) glass-ceramic electrolyte showed initial capacity of 105 mAh g⁻¹ (gram of LiCoO₂) at the current density of 0.13 mA cm⁻² and exhibited higher electrochemical performance than that using the 70Li₂S·30P₂S₅ glass-ceramic electrolyte.