QUANTUM EFFICIENCY FOR THE PHOTOCONVERSION OF BACTERIORHODOPSIN AT VERY LOW TEMPERATURES

Abstract— Quantum efficiencies for photoconversion of bacteriorhodopsin (trans-bR) to a bathochromic product (batho-bR^t) and its photoreversion in purple membrane at 77 and 9 K were investigated with low temperature spectrophotometry. The kinetics of the photoconversion and its photoreversion cannot be expressed by a single exponential curve. The photoconversions at 77 and 9 K showed the same slope in the early stage. The kinetics of the photoreversions were identical at the two temperatures. These results indicate that the quantum efficiencies for the conversion of trans-bR to batho-bR^t or for its photoreversion are identical at the two temperatures.
The fact that the photoreversion cannot be expressed by a single exponential curve suggests the existence of several conformational states of batho-bR^t due to the trimer structure of the purple membrane.     

Optical modulator using metal-oxide-semiconductor type Si ring resonator

Electric-field drive optical modulators using a Si ring resonator were fabricated on silicon-on-insulator (SOI) wafers. The fabricated resonators consisted of Si waveguides with width and thickness of 1.0 and 0.3 μm, respectively. In order to induce the linear electro-optic (EO) effect in the Si core layer, the strain was applied by covering the layer with Si₃N₄ film (0.26 μm thick) deposited by low pressure chemical vapor deposition (LPCVD) at 750 °C. The vertical electric-field was applied to the Si waveguide through the top and bottom cladding layers, and the optical output from the drop port at the resonance wavelength was measured. At a wavelength of 1501.6 nm, the optical modulation of 33% was obtained at 200V (electric-field at the silicon surface ∼3 × 10⁵ V/cm, nearly the breakdown field). The resonance wavelength was shifted toward the short wavelength side by applying both positive and negative voltages, this shift was explained by carrier concentration modulation. The linear EO effect in the Si core layer was not observed, presumably because the strain in the Si core layer was too small.     

Internal modes and the local symmetry of PO4 tetrahedra in K(H1−xDx)2PO4 by Raman scattering

The v₃ and v₄ internal modes of PO^3?₄ tetrahedra are observable in KH₂PO₄ even above the transition temperature in the scattering geometry x(zz)y contrary to the selection rule of the site symmetry S₄ in the D_2d space group. Tominaga et al. discussed that the origin of this broken selection rule is due to the momentary site symmetry C₂ of these tetrahedra, and that the mechanism of the phase transition is of the order-disorder type of these distorted tetrahedra. Parallel studies compatible with their results have been carried out on mixed crystals K(H_1?xD_x)₂PO₄ and the same conclusion has been obtained as to the momentary site symmetry. These internal modes increase in intensity with deuteration, and the origin of this increase is discussed.     

Dendrimer N-heterocyclic carbene complexes with rhodium(I) at the core

Novel dendrimer N-heterocyclic carbene complexes with rhodium(I) located at the core were synthesized, and a positive dendrimer effect was found in the hydrosilylation of ketones catalyzed by them.     

Homogeneous palladium catalyst suppressing Pd black formation in air oxidation of alcohols

In homogeneous catalyst systems, there is the persistent problem that metal aggregation and precipitation cause catalyst decomposition and considerable loss of catalytic activity. Pd black formation is a typical example. Pd catalysts are known to easily aggregate and form Pd black, although they realize a wide variety of useful reactions in organic synthesis. In order to overcome this intrinsic problem of homogeneous Pd catalysis, we explored a new class of Pd catalyst by adopting aerobic oxidation of alcohols as a probe reaction. Herein we report a new catalyst system that suppresses the Pd black formation even under air and with a high substrate to catalyst molar ratio (S/C: more than 1000) in oxidation of alcohols. The novel pyridine derivatives having a 2,3,4,5-tetraphenylphenyl substituent and its higher dendritic unit at the 3-position of the pyridine ring were found to be excellent ligands with Pd(OAc)2 in the palladium-catalyzed air (balloon) oxidation of alcohols in toluene at 80 degrees C. Comparison with structurally related pyridine ligands revealed that introduction of the 2,3,4,5-tetraphenylphenyl substituent at the 3-position of pyridine ring effectively suppresses the Pd black formation, maintaining the catalytic activity for a long time to give aldehydes or ketones as products in high yields.     

The counterion releasing effect and the partition coefficient of branched alkanols in ionic micellar solution

In the micellar solution of SDS, the partition coefficient (K_x) of following branched alkanols at infinite dilution was determined by applying a differential conductivity method: the alkanols used were i-C_mH_2m+1OH (m=4-9, i=1-5) in which the position of OH group (i) shifts from an end to the center of a hydrocarbon chain. The method provides two significant quantities, d!/dX_am and dC_sf/dC_af in addition to K_x. The following results have been obtained. (1) The dependence of K_x on i indicates that the hydrophobicity of alkanol is weakened with increasing i, whereas the increase in m strengthens the hydrophobicity. (2) The degree of counterion disossiation of micelles (!) is accelerated by the solubilized alkanols in micelles (mole fraction: X_am) and the acceleration rate, d!/dX_am (=0.17), depends on neither m nor i. (3) In the bulk water, the monomerically dissolved alkanols (concentration: C_af) depresses the concentration of free monomer surfactant (C_sf), and the depressing rate, dC_sf/dC_af, in micellar solution is identical with the corresponding quantity, ((CMC/(C_a)_o at CMC.     

New reactions of 1-alkynes catalyzed by transition metal complexes

Recently discovered catalytic reactions with ruthenium and lanthanide metal complexes have extended the scope of 1-alkynes as useful reagents. The specific formation of aryl-substituted (Z)-1,3-enzymes via the dimerization of HC(triple bond) CR(1) (R(1) = aryl) has been attained using dimeric lanthanide complexes, the catalytic activity of which appears to be unaffected by time. The dimerization of HC(triple bond) CR(2) (R(2) = t-Bu, SiMe(3)) catalyzed by Ru(cod)(cot)/PR(3) or RuH(2)(PPh(3))(3) produces a good yield of butatrienes (Z)R(2)CH=C=C=CHR(2) with a high degree of selectivity. Under certain conditions, HC(triple bond) C=SiMe(3) dimerizes to yield exclusively (Z)-M(3)Si-C(triple bond) C-CH=CH-SiMe(3). The hydration of HC(triple bond)CR(3) (R(3) = alkyl, aryl) catalyzed by RuCl(2)/PR'(3) or CpRuCl(PR"(3))(2) has realized the first example of anti-Markovnikov regioselectivity in an addition reaction of water that produces aldehydes R(3)CH(2)bond;CHO. The application of this reaction to propargylic alcohols has lead to their formal isomerization to alpha,beta-unsaturated aldehydes. In contrast, the addition of amines R(4)bond;NH(2) (R(4) = aryl) to HCtbond;CR(5) (R(5) = alkyl, aryl) conforms to Markovnikov's rule to produce ketimines R(5)bond;(C=NR(4))bond;CH(3) when catalyzed by a Ru(3)(CO)(12)/additive. Since the reaction can be performed in air without the need for any solvents, it enables the practical synthesis of aromatic ketimines, which are difficult to prepare by conventional methods. The synthesis of indoles using deactivated anilines is one practical application of this reaction. The mechanisms of some of these reactions have been analyzed in detail with the aid of theoretical calculations.