Synthesis of benzimidazole derivatives as potential H1-antihistaminic agents

Several types of benzimidazole derivatives were prepared and were screened for H ₁-antihistaminic activity. Most of the compounds showed potent antihistaminic activity in vitro. Among them 2-[(1-piperazinyl)methyl]-benzimidazoles 14 and 2-[(1-homopiperazinyi)methyl]benzimidazoles 15 exhibited potent activity also in vivo.     

Quantum stochastic theory of exchange dephasing model for a vibrating molecule in dense medium

The exchange dephasing model is investigated theoretically. An equation of motion satisfied by a reduced density matrix for the observed high-frequency mode is derived by a cumulant perturbation expansion method up to fourth order. The calculation shows a temperature dependence of the width and shift of the spectral line.     

Canonical linear transformation on fock space with an indefinite metric

We first construct a Fock space with an indefinite metric ,=( , ), where is a unitary and Hermitian operator. We define a -selfadjoint (Segal's) field (f) which obeys the canonical commutation relations (CCR) with an indefinite metric. We consider a transformation 349-2 (T = real linear) which leaves the CCR invariant. We investigate the implementability of T by an operator on the Fock space.     

Preparation of enol ethers by carbonyl olefination utilizing an alkoxymethyl chloride-titanocene(II) system

Aldehydes, ketones, esters and lactones are transformed into enol ethers or 1,2-dialkoxy-1-alkenes by treatment with organotitanium species prepared from alkoxymethyl chlorides and a titanocene(II) complex.     

New resveratrol oligomers in the stem bark of Vatica pauciflora

Five new resveratrol oligomers; pauciflorols A-C (1-3), isovaticanols B (6) and C (8), and three new oligostilbene glucosides; pauciflorosides A (11), B (13), C (14), were isolated from the stem bark of Vatica pauciflora (Dipterocarpaceae) together with known 17 resveratrol oligomers (4, 5, 7, 9, 10, 12 and 15-25) and bergenin (26). The structures of isolates were established on the basis of detailed spectroscopic analysis. The typical and characteristic spectral properties of some resveratrol oligomers were also discussed.     

Effects of pressure and solvent on the diffusion of aromatic compounds through polymers

The diffusion of six azo and five anthraquinone derivatives through nylon 6, poly(ethylene terephthalate) and secondary cellulose acetate films were studied under high hydrostatic pressures of up to 3000 bar and at temperatures 80–130 °C, by analyzing the diffusion profiles yielded in a stacked multiple film, placed in the solution of the diffusant. It was found that the diffusion coefficient,D, of the diffusant decreased with increasing pressure, giving a linear relationship between InD and the pressure, the slope of which gave the activation volume for the diffusion,V . It was revealedV increased linearly with increasing intrinsic molecular volume of the diffusant,V _w , the slopes being different between the azo and the anthraquinone derivatives. The ratio ofV toV _w (V /V _w ) ranged from 0.13 to 0.93, depending in a sensitive manner on the degree of swelling of the polymer matrix which in turn was varied by the solvent. The overall results could be explained in accordance with the formulation,V _{f, local} +V =V _w , whereV _{f, local} represents the free volume contribution. It was proposed thatV _w is increased by solvation when the solvent is good for the diffusant.     

Experimental observations of the hydrodynamic behavior of solvent systems in high-speed counter-current chromatography. I. Hydrodynamic distribution of two solvent phases in a helical column subjected to two types of synchronous planetary motion

Hydrodynamic distribution of two-phase solvent systems in a rotating helical column subjected to centrifugal fields produced by two different types of synchronous planetary motion has been studied by the use of the combined horizontal flow-through coil planet centrifuge. With continuous elution of the mobile phase, the simpler type of motion resulted in low retention of the stationary phase in the column whereas a more complex motion, which produces a quasi-radial centrifugal field varying in both intensity and direction, yielded high stationary phase retention for commonly used solvent systems having a wide range of hydrophobicity. These solvent systems display highly complex modes of hydrodynamic interaction in the coil according to their particular physical properties.     

Effect of axial ligation or pi-pi-type interactions on photochemical charge stabilization in "two-point" bound supramolecular porphyrin-fullerene conjugates

Two types of structurally well-defined, self-assembled zinc porphyrin-fullerene conjugates were formed by "two-point" binding strategies to probe the effect of axial ligation or pi-pi-type interactions on the photochemical charge stabilization in the supramolecular dyads. To achieve this, meso-tetraphenylporphyrin was functionalized to possess one or four [18]crown-6 moieties at different locations on the porphyrin macrocycle while fullerene was functionalized to possess an alkyl ammonium cation, and a pyridine or phenyl entities. As a result of the crown ether-ammonium cation complexation, and zinc-pyridine coordination or pi-pi-type interactions, stable zinc porphyrin-fullerene conjugates with defined distance and orientation were formed. Evidence for the zinc-pyridine complexation or pi-pi-type interactions was obtained from the spectral and computational studies. Steady-state and time-resolved emission studies revealed efficient quenching of the zinc-porphyrin singlet excited state in these dyads, and the measured rates of charge separation, k(CS) were found to be slightly better in the case of the dyads held by axial coordination and crown ether-cation complexation. Nanosecond transient absorption studies provided evidence for the electron transfer reactions, and these studies also revealed charge stabilization in these dyads. The lifetimes of the radical ion pairs were found to depend upon the type of porphyrins utilized to form the dyads, that is, porphyrin possessing the crown ether moiety at the ortho position of one of the phenyl rings yielded prolonged charge stabilized states. Addition of pyridine to the supramolecular dyads eliminated the zinc-pyridine coordination or pi-pi-type interactions of the "two-point" bound systems due to the formation of a new zinc-pyridine axial bond thus giving a unique opportunity to probe the effect of axial coordination or pi-pi interactions on k(CS) and k(CR). Under these conditions, the measured electron transfer rates revealed faster k(CS) and slower k(CR) as compared to those obtained in the absence of added pyridine. The evaluated lifetimes of the radical ion-pairs were found to be hundreds of nanoseconds and were longer in the presence of pyridine.     

Multiple and irreversible binding of cis-diamminedichloroplatinum(II) to human serum albumin and its effect on warfarin binding.

Irreversible bindings of cis-diamminedichloroplatinum(II) (cis-DDP) to human serum albumin (HSA) were investigated in a pH 7.4 buffer containing 0.1 M NaCl at various molar ratios (cis-DDP/HSA) up to 60 over a 14 d period (37 degrees C). The metal binding seemed to reach a plateau when incubated at less than 10 times excess of cis-DDP. As the molar ratio increased, the reaction rate was relatively fast within the first day, followed by a moderate increase in the metal binding. When incubated at 60 times excess of cis-DDP, the metal bound as much as 20 mol per mol of HSA in 14 d. Fluorescence quenching of the metal-bound protein suggested that the tryptophan residue was gradually exposed to a hydrophilic environment as the metal binding increased. Furthermore, cis-DDP cleaved disulfide bonds at the ratio of 1 mol of disulfide bond per 5.3 mol of the metal binding. It was therefore suggested that the metal binding also occurred at several sites other than the disulfide bond. Warfarin binding to the metal-bound protein, examined by fluorescence changes, also decreased with increasing metal binding or cleavage of the disulfide bonds. Thus, cis-DDP bound to multiple sites in addition to the lone sulfhydryl group (Cys-34), suggesting that massive conformational changes of the protein took place.     

Interaction between peroxide ion and phenol group which are coordinated to the same iron(III) ion

We have prepared several new iron(III) complexes with ligands which contain a phenol group; these are tetradentate [(X-phpy)H, X and H(phpy) represent the substituents on the phenol ring and N,N-bis(2-pyridylmethyl)-N-(2-hydroxybenzyl)amine, respectively] and pentadentate ligands [(R-enph-X)H; R=ethyl(Et) or methyl(Me) derivative and H(Me-enph) denotes N,N-bis(2-pyridylmethyl)-N″-methyl-N″-(2″-hydroxyl-benzylamine)ethylenediamine] and have determined the crystal structures of Fe(phpy)Cl₂, Fe(5-NO₂-phpy)Cl₂, and Fe(Me-enph)ClPF₆, which are of a mononuclear six-coordinate iron(III) complex with coordination of one or two chloride ion(s). These compounds are highly colored (dark violet) due to the coordination of phenol group to an iron(III) atom. When hydrogen peroxide was added to the solution of the iron(III) complex, a color change occurs with bleaching of the violet color, indicating that oxidative degradation of the phenol moiety occurred in the ligand system. The bleaching of the violet color was also observed by the addition of t-butylhydroperoxide. The rate of the disappearance of the violet color is highly dependent on the substituent on the phenol ring; introduction of an electron-withdrawing group in the phenol ring decreases the rate of bleaching, suggesting that disappearance of the violet band should be due to a chemical reaction between the phenol group and a peroxide adduct of the iron(III) species with an η¹-coordination mode and that in this reaction the peroxide adduct acts as an electrophile towards phenol ring. The intramolecular interaction between the phenol moiety and an iron(III)-peroxide adduct may induce activation of the peroxide ion, and this was supported by several facts that the solution containing an iron(III) complex and hydrogen peroxide exhibits high activities for degradation of nucleosides and albumin.