FOURIER TRANSFORM INFRARED SPECTRAL STUDIES ON THE SCHIFF BASE MODE OF ALL-trans BACTERIORHODOPSIN and ITS PHOTOINTERMEDIATES,K and L*

Abstract– Difference Fourier transform infrared spectra were recorded for bacteriorhodopsin upon irradiation at 230, 170 or 77 K, which gave, respectively, the spectrum of the M, L or K intermediate minus unphotolyzed all-trans bacteriorhodopsin (denoted as BR). By replacement of the Schiff base nitrogen with ¹⁵N, or of either its hydrogen at N or C₁₅ with deuterium, the vibrational bands related to the Schiff base were identified and the isotope-shifts evaluated for BR, K and L. The 1348 cm^?l band of BR and K and the 1400 cm^?1 band of L were sensitive to each of these isotope substitutions. The 1254 cm^?1 band of BR, the 1245 cm^?1 band of K and the 1301 cm^?1 band of L were sensitive to either N- or C₁₅-deuteration but not to ¹⁵N-substitution. The N—D in-plane bending vibration of K and L appeared at 969 and 997 cm^?1, respectively, upon substitution with D₂O. All the results show that L is larger in frequencies related to the N—H in-plane bending vibration than K or BR and suggest that L has the strongest interaction with the protein. Among the bands containing an N—H bending vibration, the 1348 cm^?1 band of K was more intense than the corresponding band of L at 1400 cm^?1. The C₁₅-deuteration-induced upshift of the 1245 cm^?1 band of K was unobservable for the 1301 cm^?1 band of L. Such differences between L and K might be brought about by a distortion in the retinal moiety close to the protonated Schiff base of the 13-cis chromophore.     

Studies on orally active cephalosporin esters. IV. Effect of the C-3 substituent of cephalosporin on the gastrointestinal absorption in mice

The effect of the C-3 substituent on the oral absorbability of pivaloyloxymethyl (POM) ester of cephalosporin in mice is described. The C-3 substituent affects the physicochemical and biochemical properties of POM ester, such as lipophilicity, water solubility, chemical stability and enzymatic stability. Quantitative analyses of the relationships between these properties and the oral bioavailability have been attempted. Lipophilicity made a parabolic contribution to the absorption. The optimum log P octanol/water value was estimated to be around 2.22. The chemical isomerization of the cephem double bond from delta 3 to delta 2 in the intestinal lumen prior to absorption contributed linearly to decrease of absorption. In the case of POM ester having a larger isomerization rate, more delta 2 isomer was detected in feces and urine. Enzymatic hydrolysis of POM ester to the parent acid in intestinal tissue was faster for a more lipophilic ester. Hydrolytic activity, which was detected in the content of the intestinal lumen, would lower the absorption. The effect of the C-3 substituent on water solubility was not important for the absorption of cephalosporin employed in the present study. Isomerization of the double bond, which was found to be characteristic for cephalosporin ester, presented a problem in the prodrug approach for oral use.     

Anomalous momentum dependence of the superconducting coherence peak and its relation to the pseudogap of La1.85Sr0.15CuO4

We performed high-resolution angle-resolved photoemission spectroscopy on La1.85Sr0.15CuO4 to study the nature of the single-particle excitation gap. We found that there is a well-defined superconducting coherence peak in the off-nodal region while it is strongly suppressed around the antinode. The momentum dependence of the single-particle excitation gap shows a striking deviation from the dx-y2--wave symmetry with anomalous enhancement around the antinode in both the superconducting and the pseudogap state. The observed close correlation between the superconducting coherence peak and the pseudogap suggests a substantial contribution of the pseudogap to the anomalous behavior of the gap in the superconducting state.     

Electric control of spin helicity in a magnetic ferroelectric

Magnetic ferroelectrics or multiferroics, which are currently extensively explored, may provide a good arena to realize a novel magnetoelectric function. Here we demonstrate the genuine electric control of the spiral magnetic structure in one such magnetic ferroelectric, TbMnO3. A spin-polarized neutron scattering experiment clearly shows that the spin helicity, clockwise or counterclockwise, is controlled by the direction of spontaneous polarization and hence by the polarity of the small electric field applied on cooling.     

Atmospheric pressure waves in the field of volcanology

Atmospheric pressure waves are a notable phenomenon associated with explosive volcanic eruptions. They can provide us with information about eruption processes that are useful both scientifically and practically. In this paper, we give a brief review of studies that have been carried out on this phenomenon in the field of volcanology. Then, we introduce a prototype tool called ‘MOVE’ (Mobile Observatory for Volcanic Explosions). It is a remote-controlled vehicle carrying various instruments to observe pressure waves and the eruption processes. PACS 91.40.Dr · 91.40.Ft · 93.65.+e · 93.85.+qThis paper was based on work presented at the 2nd International Symposium on Interdisciplinary Shock Wave Research, Sendai, Japan on March 1–3, 2005.     

Delayed nonlinear cournot and bertrand dynamics with product differentiation

Dynamic duopolies will be examined with product differentiation and isoelastic price functions. We will first prove that under realistic conditions the equilibrium is always locally asymptotically stable. The stability can however be lost if the firms use delayed information in forming their best responses. Stability conditions are derived in special cases, and simulation results illustrate the complexity of the dynamism of the systems. Both price and quantity adjusting models are discussed.     

Possible Involvement of a Tetrahydrobiopterin in Photoreception for UV‐B‐induced Anthocyanin Synthesis in Carrot

Our previous studies of action spectra for UV‐B‐induced anthocyanin accumulation in cultured carrot cells indicated that a reduced form of pterin, possibly tetrahydrobiopterin, contributes to UV‐B photoreception. In this report, we provide additional evidence for the involvement of pterin in UV‐B light sensing. UV‐B‐induced phenylalanine ammonia‐lyase (PAL) activity was considerably suppressed by N‐acetylserotonin (an inhibitor of tetrahydrobiopterin biosynthesis), and this suppression was partially recovered by adding biopterin or tetrahydrobiobiopterin. In addition, protein(s) specifically bound to biopterin were detected by radiolabeling experiments in N‐acetylserotonin‐treated cells. Furthermore, diphenyleneiodonium, a potent inhibitor of electron transfer, completely suppressed UV‐B‐induced PAL activity. These results suggest the occurrence of an unidentified UV‐B photoreceptor (other than UVR8, the tryptophan‐based UV‐B sensor originally identified in Arabidopsis) with reduced pterin in carrot cells. After reexamining published action spectra, we suggest that anthocyanin synthesis is coordinately regulated by these two UV‐B sensors.     

Pd-catalyzed cycloisomerization-allylation of 4-alkynones: synthesis of 5-homoallylfuran derivatives

In the presence of Pd₂(dba)₃-tBu₃P catalyst and Cs₂CO₃, cycloisomerization-allylation reactions of 4-alkynone derivatives with allyl carbonates in MeCN proceed in 5-exo mode to give highly-substituted furans having homoallyl groups at 5-position.     

PIFA-mediated oxidative cycloisomerization of 2-propargyl-1,3-dicarbonyl compounds: divergent synthesis of furfuryl alcohols and furfurals

PhI(OCOCF₃)₂ (PIFA) in the presence of trifluoroacetic acid (TFA) in CH₂Cl₂ efficiently promotes the oxidative cycloisomerization of 2-propargyl 1,3-dicarbonyl compounds to give 4,5-disubstituted furfuryl alcohols. PIFA in hexafluoroisopropanol (HFIP) or PIFA-BF₃·OEt₂ in CH₂Cl₂ bring about the direct formation of furfurals from 2-propargyl 1,3-dicarbonyl compounds. In a few cases, PhIO is suitable for the direct formation of furfurals.