Substituent effects on the kinetics for the chemiluminescence reaction of 6-arylimidazo[1,2-a]pyrazin-3(7H)-ones (Cypridina luciferin analogues): support for the single electron transfer (SET)-oxygenation mechanism with triplet molecular oxygen

Kinetics of chemiluminescence reactions of 2-methyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one (1c, Cypridina luciferin analogue) and substituent effects of the 6-aryl group of derivatives 1 strongly suggest that the rate-determining step is a single electron transfer from an anion derived from 1 to a triplet molecular oxygen (O₂) in the oxygenation process.     

Importance of single electron-transfer in singlet oxygen reaction in aqueous solution : Oxidation of electron-rich thioanisoles

Oxidation of substituted thioanisoles by chemically generated singlet oxygen was investigated in polar aqueous media. The formation of the superoxide ion was observed during sulphoxidation of 4-hydroxythioanisole (4) in phosphate buffer at pH 7.5. Control experiments indicated that the superoxide ion was formed by a direct reaction between singlet oxygen and 4. The kinetics of the trapping reaction by diphenylsulphoxide indicated the involvement of a single intermediate. The overall rate constants of the reaction of thioanisoles with singlet oxygen in methanol-water (1:1) are one order of magnitude larger than those in benzene. On the basis of these results, a mechanism involving a charge-transfer complex has been proposed for the reaction of electron-rich thioanisoles with singlet oxygen, whereby the charge-transfer complex would produce persulphoxide directly or dissociate to the cation radical and superoxide ion in polar aqueous media.     

Studies on antiulcer drugs. VI. 4-Furyl-2-guanidinothiazoles and related compounds as potent histamine H2-receptor antagonists.

A series of 4-furyl-2-guanidinothiazole derivatives and related compounds were synthesized and evaluated for histamine H2-receptor antagonist and gastric acid antisecretory activities. Among them, compounds I-17, I-48 and I-49 showed high activities in these tests. In addition, compound I-17 possessed potent inhibitory activities on each of the gastric ulcers induced by stress, ethanol and HCl-aspirin. On the other hand, compound I-48 demonstrated antimicrobial activity against Helicobacter Pylori and the potency was far stronger than that of clinically used H2-antagonists. Some structure-activity relationships are discussed.     

Effects of Shosaikoto (kampo medicine) on lipid metabolism in macrophages.

We investigated effects of Shosaikoto treatment on cholesterol metabolism in macrophages. Although macrophages, harvested from mice treated with Shosaikoto, took up a small amount of control low density lipoprotein (LDL) (thiobarbituric acid-reactive substance (TBA-RS) value was 0.27 pmol/mg of protein) as control macrophages, they took up more LDL modified with CuSO4 (TBA-RS value was 6.12 pmol/mg of protein) than control macrophages. Degradation of both control LDL and oxidized LDL was enhanced in Shosaikoto treated macrophages. In the presence of control LDL or in the absence of LDL, incorporation of [3H]oleic acid into chlesteryl oleate was significantly reduced in Shosaikoto treated macrophages. This suggests that acyl-coenzyme A:cholesterol acyltransferase (ACAT) activity in macrophages was partly inhibited by Shosaikoto treatment. On the other hand, in the present of oxidized LDL, cholesteryl ester accumulated in Shosaikoto treated macrophages as much as in controls. However, cholesteryl oleate efflux from macrophages in the presence of high density lipoprotein (HDL) was enhanced in Shosaikoto treated macrophages. These result indicate that Shosaikoto facilitates oxidized LDL catabolism in macrophages, resulting in the augmentation of oxidized LDL uptake and the elimination of cholesterol from macrophages by HDL. These Shosaikoto effects may prevent foam cell formation and the progression of atherosclerotic lesions.     

Alternating copolymers consisting of arylalkyl methacrylates. I. Fluorescence properties of poly(arylalkyl methacrylate-alt-styrene) in organic solution

Alternating and random copolymers of 9-phenanthrylmethyl methacrylate or 2-(9-carbazolyl)ethyl methacrylate with styrene were synthesized and their fluorescence properties were examined. There was no noticeable difference in the spectral features of the alternating and random copolymers in tetrahydrofuran (THF), demonstrating that this type of polymers have no quenching sites in the polymer chains. The fluorescence quenching studies indicated that the alternating copolymers permitted singlet-state energy migration as efficiently as the corresponding random copolymers but less efficiently than the random copolymers with higher chromophore contents. These results strongly suggest that to be chromophores close to each other is most important for facilitation of an intramolecular energy migration. © 1995 John Wiley & Sons, Inc.     

Solubility of α-amino acids in water under high pressure: glycine, -alanine, -valine, -leucine, and -isoleucine

The solubility of glycine, -alanine, -valine, -leucine, and -isoleucine in water was measured at 298.15 K and pressures up to 400 MPa. The standard deviation of the logarithm of the solubility is 0.001–0.003, equal to or better than the accuracy of atmospheric pressure measurement in the literature (0.001–0.05). A variety of solubility phenomena were observed. The solubility of glycine decreased with increasing pressure, whereas that of -alanine increased. The -valine and -isoleucine have a solubility maximum at around 100 MPa, and -leucine seems to exhibit a solid-phase phase transition at around 200 MPa. Pressure coefficient of the solubilities at 0.10 MPa is compared with that thermodynamically estimated in reference to aqueous density measurements of glycine and -alanine at 298.15 K and 0.10 MPa, supporting a reliability of our high-pressure measurements.     

Synthesis and application of chiral bisphosphines through lithiation-conjugate addition tandem cyclization of chiral alpha,beta,psi,omega-unsaturated bisphosphine oxide

Upon treatment with lithium diisopropylamide achiral and chiral alpha,beta,psi,omega-unsaturated bisphosphine oxides underwent lithiation-conjugate addition tandem cyclization to afford the corresponding endo-alpha,beta-unsaturated cyclic bisphosphine oxides; sequential stereoselective reduction of the cyclized bisphosphine oxide gave the corresponding trans- and cis-bisphosphines that were successfully applicable in a catalytic asymmetric hydrogenation as chiral bisphosphine ligands.     

Synthesis of Molecular Wires of Linear and Branched Bis(terpyridine)‐Complex Oligomers and Electrochemical Observation of Through‐Bond Redox Conduction

Films of linear and branched oligomer wires of Fe(tpy)₂ (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C₆H₄N?NC₆H₄? S)₂ ( 1 ), two bridging ligands, 1,4‐(tpy)₂C₆H₄ ( 3 ) and 1,3,5‐(C?C? tpy)₃C₆H₃ ( 4 ), and metal ions were used. The quantitative complexation of the ligands and Fe^II ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k₁ (s^?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k₂ (cm² mol^?1 s^?1). The strong effect of the electrolyte concentration on both k₁ and k₂ indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k₁ and k₂ on the potential gave intrinsic kinetic parameters without overpotential effects: k₁⁰=110 s^?1, k₂⁰=2.6×10¹² cm² mol^?1 s^?1 for [n Fe 3 ], and k₁⁰=100 s^?1, k₂⁰=4.1×10¹¹ cm² mol^?1 s^?1 for [n Fe 4 ] (n=number of complexation cycles).