meso-Alkyl-substituted meso-meso linked diporphyrins and meso-alkyl-substituted meso-meso, beta-beta, beta-beta triply linked diporphyrins

[reaction: see text] AgPF6-promoted oxidation of 5,10,15-trialkyl zinc(II) porphyrins led to formation of meso-meso linked diporphyrins, which were further oxidized with Sc(OTf)3 and DDQ to give meso-meso, beta-beta, beta-beta triply linked diporphyrins that exhibited a stronger aggregation propensity than corresponding meso-aryl diporphyrins.     

Spectrophotometric study of the alkali metal-murexide complexes in some non-aqueous solutions

The complexes of murexide with alkali-metal cations have been studied spectrophotometrically in methanol, dimethylformamide and dimethylsulphoxide media at 25 degrees . The stoichiometry of the complexes was found to be 1:1. The formation constants of the complexes were determined, and found to decrease in the order Na(+) > K(+) > Rb(+) approximately Li(+) for all solvents studied. The complex formation constants varied inversely with the Gutmann donicity of the solvents.     

Molecular characteristics of the inhibition of human neutrophil elastase by nonsteroidal antiinflammatory drugs

Nonsteroidal antiinflammatory drugs(NSAIDs) are known as clinically effective agents for treatment of inflammatory diseases. Inhibition of cyclooxygenase has been thought to be a major facet of the pharmacological mechanism of NSAIDs. However, it is difficult to ascribe the antiinflammatory effects of NSAIDs solely to the inhibition of prostaglandin synthesis. Human neutrophil elastase (HNElastase; HNE, EC 3.4.21.37) has been known as a causative factor in inflammatory diseases. To investigate the specific relationship between HNElastase inhibition and specificity of molecular structure of several NSAIDs, HNElastase was purified by Ultrogel AcA54 gel filtration, CM-Sephadex ion exchange, and HPLC (with TSK 250 column) chromatography. HNElastase was inhibited by aspirin and salicylate in a competitive manner and by naproxen, ketoprofen, phenylbutazone, and oxyphenbutazone in a partial competative manner, but not by ibuprofen and tolmetin. HNElastase-phenylbutazone-complex showed strong Raman shifts at 200, 440, 1124, 1194, 1384, 1506, and 1768 cm(-1). The Raman bands 1194, 1384, and 1768 cm(-1) may represent evidences of the conformational change at -N=N-phi radical, pyrazol ring, and -C=O radical of the elastase-drug complex, respectively. Phenylbutazone might be bound to HNElastase by ionic and hydrophobic interaction, and masked the active site. Inhibition of HNElastase could be another mechanism of action of NSAIDs besides cyclooxygenase inhibition in the treatment of inflammatory diseases. Different inhibition characteristics of HNE-lastase by NSAIDs such as aspirin, phenylbutazone-like drugs and ineffective drugs could be important points for drawing the criteria for appropriate drugs in clinical application.     

Free-electron attachment to coronene and corannulene in the gas phase

Electron attachment to the polyaromatic hydrocarbons coronene and corannulene is studied in the electron energy range of about 0-14 eV using a high-resolution crossed electron-neutral beam setup. The major anions observed are the parent anions peaking at about 0 eV with cross sections of 3.8 x 10(-20) and 1 x 10(-19) m(2), respectively. The only fragment anions formed in coronene and corannulene are the dehydrogenated coronene and corannulene anions. Other anions observed in the negative mass spectra at about 0 eV can be ascribed to impurities of the sample. High-level quantum-mechanical studies are carried out for the determination of electron affinities, hydrogen binding energies, and structures of both molecules. The behavior of coronene and corannulene upon electron attachment is compared with that of other polyaromatic hydrocarbons studied previously.     

Creatinine biosensor based on ammonium ion selective electrode and its application in flow-injection analysis

A new, highly sensitive, fast responding and stable potentiometric biosensor for creatinine determination is developed. The biosensor is based on an ammonium ion-selective electrode. Creatinine deiminase (EC 3.5.4.21) is chemically immobilized on the surface of the polymeric ion-sensitive membrane in the form of monomolecular layer using a simple, one-step carbodiimide covalent attachment method. The resulting enzyme electrodes are useful for measurement under flow injection analysis (FIA) conditions. The biosensors exhibit excellent operational and storage stability. The enzyme electrodes retain over 70% of initial sensitivity after ten weeks of work under FIA conditions. The storage stability at 4 °C is longer than half a year without loss of sensitivity. Under optimized conditions near 30 samples per hour can be analyzed and the determination range (0.02-20.0 mmol l⁻¹) fully covers creatinine concentrations important from clinical and biomedical point of view. The simple biosensor/FIA system has been successfully used for determination of creatinine in urine, serum and posthemodialysate samples.     

Modification of bovine beta-lactoglobulin by glycation in a powdered state or in aqueous solution: adsorption at the air-water interface

The adsorption at the air-water interface of native and various glycated forms of beta-Lactoglobulin B (beta-LG), prepared under two different experimental conditions, was investigated by ellipsometry, surface tension and shear elastic constant measurements. The measurements were performed in 0.1 M phosphate buffer, 0.1 M NaCl, pH 6.8. It was found that the interfacial properties of beta-LG were more affected when the glycation was performed in solution than in the dry-way system. Dry-way glycated beta-LG, despite a higher glycation extent, affected slightly its interfacial behaviour. Solution glycated beta-LG exhibited a higher adsorption and more rigid interface as expressed by shear elastic constant measurement at saturation (16.5 mN/m against 8.7 and 11.5 mN/m for native and control treated beta-LG, respectively). These results were attributed to the specific molecular species induced during glycation in solution, which includes monomers and unfolded covalent homodimers of beta-LG molecules with a high tendency to self-association via non-covalent interactions.     

Heats of adsorption of linear CO species adsorbed on the Au degrees and Ti+delta sites of a 1% Au/TiO2 catalyst using in situ FTIR spectroscopy under adsorption equilibrium

The heats of adsorption of two linear CO species adsorbed on the Au degrees particles (denoted L(Au degrees)) and on the Ti(+delta) sites (denoted L(Ti+delta)) of a 1% Au/TiO(2) catalyst are determined as the function of their respective coverage by using the AEIR procedure (adsorption equilibrium infrared spectroscopy) previously developed. Mainly, the evolutions of the IR band area of each adsorbed species (2184 cm(-1) for L(Ti+delta) and at 2110 cm(-1) for L(Au degrees)) as a function of the adsorption temperature T(a), at a constant CO adsorption pressure P(CO), provide the evolutions of the coverages theta(LTi+delta) and theta(LAu degrees ) of each adsorbed CO species with T(a) in isobar conditions that give the individual heats of adsorption. It is shown that they linearly vary from 74 to 47 kJ/mol for L(Au degrees ) and from 50 to 40 kJ/mol for L(Ti+delta) at coverages 0 and 1, respectively. These values are consistent with literature data on model Au particles and TiO(2). In particular, it is shown that the mathematical formalism supporting the AEIR procedure can be applied to literature data on Au-containing solids (single crystals and model particles).     

Polyphospha

The Eglinton reaction of diethynyl(2,4,6-tri-tert-butylphenyl)phosphane (7a), that is, the oxidative coupling of 3, 4, 5, or 6 of these phosphane units, affords a mixture of the 15-, 20-, 25-, and 30-membered macrocycles 8, 9, 10, and 11. Pure triphosphacyclopentadecahexayne 8 and pentaphosphacyclopentacosadecayne 10 were isolated by HPLC, while the mixture of 9 and 11 could not be separated. Multistep syntheses of open-chain polyphosphapolyynes are described, whose intra- or intermolecular coupling yields the phosphamacrocycles 8, 9, and 11. Eglinton coupling of bis(ethynylphosphanyl)butadiyne (17) gave a mixture of the 20-membered tetraphosphacycloicosaoctayne 9, the 30-membered hexaphosphacyclotriacontadodecayne 11, and the 40-membered octaphosphacyclotetracontahexadecayne 23 as result of a di-, tri-, and tetramerization, respectively. Intramolecular coupling of bis[(ethynylphosphanyl)butadiynyl]phosphane 25a gave 8, while intermolecular coupling gave 11; these two compounds were isolated by chromatography to give yields of 70 and 5%, respectively. The open-chain tetraphosphaeikosaoctayne 28 couples intramolecularly to give 9 and intermolecularly to give the 40-membered octaphosphacyclotetracontahexadecayne 23, which was isolated in the pure form. Octaphosphatetracontahexadecayne 32 cyclized to give 23, exclusively. The temperature-dependent 1H and 31P NMR spectra of the open-chain and cyclic ethynylphosphanes indicated a lowering of the inversion barrier of the tertiary phosphanes from the usual 130-140 kJ mol(-1) to 65-75 kJ mol(-1). Ab initio calculations proved that the dramatic reduction of the inversion barriers results from the interaction of the lone pair on phosphorus with the pi orbitals of the triple bonds in the planar transition state during inversion. The situation is comparable with the dramatic reduction of the P inversion barrier in phospholes, because of the planar, aromatic transition state. The polyphospha[m]cyclo[n]carbons may be considered as precursors to cyclic PmCn systems.     

Complex formation equilibria between 1-hydroxy-7-sulpho-2-naphthoic or 1-hydroxy-4,7-disulpho-2-naphthoic acid and iron(III) in 0.1M NaClO4 medium

The equilibria for formation of iron(III) complexes with 1-hydroxy-7-sulpho-2-naphthoic and 1-hydroxy-4,7-disulpho-2-naphthoic acids in aqueous 0.1M sodium perchlorate medium at 25 degrees have been studied by spectrophotometric and potentiometric methods. The data are well described in terms of a series of stepwise complexes, FeL((3-rn)+)(r) in both systems (L(n-) denotes the unprotonated ligand anion).     

CH2CHOH2+ + PN: a proton-transfer triple play

Quantum chemical calculations are used to explore the proton-transfer reactivity of O-protonated vinyl alcohol, CH2CHOH2+, with phosphorus nitride, PN. This reaction is relevant to the chemical evolution of interstellar clouds, since O-protonated vinyl alcohol has been postulated (and tentatively identified) as a product of the association reaction between interstellar H3O+ and C2H2, while PN is the most widespread and abundant phosphorus-containing molecule seen in astrophysical environments. Furthermore, the reaction exhibits an unusual mechanistic feature, namely, an extended "proton-transport catalysis" mechanism, which we characterize here as a "proton-transfer triple play". The reaction proceeds initially by proton transfer from CH2CHOH2+ to PN, then from PNH+ to CH2CHOH, and finally from CH3CHOH+ to PN, where the emphasized atom indicates the resultant site of protonation/deprotonation. Thus, the ultimate overall bimolecular proton-transfer reaction is expected to occur as CH2CHOH2+ + PN --> CH3CHO + PNH+; that is, the apparent favored product channel exhibits not only proton transfer but also keto/enol tautomerization. The triple-play mechanism can be rationalized in terms of the proton affinities of vinyl alcohol, acetaldehyde, and phosphorus nitride, which here are satisfactorily reproduced by high-level ab initio calculations. Other neutrals with a proton affinity appropriate for the possible triple-play mechanism converting CH2CHOH2+ to CH3CHO are also identified, with a view to encouraging experimental investigation of this mechanism.