Structure-activity relationships of alkylxanthines: alkyl chain elongation at the N1- or N7-position decreases cardiotonic activity in the isolated guinea pig heart

Relationships between the alkyl substitutions (C1-C6) and cardiac inotropic activities of xanthine derivatives were studied in isolated guinea pig heart muscles. Most of the alkylxanthines exhibited positive inotropic activity on the left atrium, which was increased with an elongation of alkyl chain at the N3-position but decreased by substitution of a long alkyl group at the N1- or N7-position of the xanthine skeleton. Although positive inotropic activity in the right ventricular papillary muscle was also increased by longer alkyl groups at the N3-position, the inotropic activity became negative with an increment in alkyl chain length at the N1- or N7-position. The positive inotropic activity of alkylxanthines was correlated with their inhibitory activity on the phosphodiesterase (PDE) III isoenzyme. Adenosine A1 antagonism and PDE IV inhibitory activity were also partly associated with the inotropic activity because H-89, an inhibitor of cyclic AMP-dependent protein kinase, diminished the positive inotropic action and potentiated the negative inotropic action. These results indicate that the positive inotropic activity of alkylxanthines becomes weak with elongation of alkyl chains at the N1- and N7-positions; In particular, xanthines having two long alkyl chains show a negative inotropic activity on the right ventricular papillary muscle, an effect that could not be elucidated from their cyclic AMP-dependent action.     

Superhydrophobic/superhydrophilic micropatterning on a carbon nanotube film using a laser plasma-type hyperthermal atom beam facility

Superhydrophobic/superhydrophilic micropatterning on a carbon nanotube (CNT) film has been achieved using a laser plasma-type hyperthermal atom beam facility, which produces a small amount of damage and generates a highly anisotropic beam. Fluorination and oxidation on CNT films by exposure to fluorine-atom and oxygen-atom beams caused superhydrophobic and superhydrophilic surfaces, respectively, while maintaining the as-grown fibrous forms of the CNT films. Micropatterned oxidation on CNT films without using photoresists created superhydrophilic microdots and microchannels.     

Friction Properties of Carbon Nano-Onions from Experiment and Computer Simulations

The carbon nano-onion can be considered as a new kind of interesting lubricating nanoparticle. Used as lubricant additives, carbon nano-onions lead to a strong reduction of both friction and wear, even at low temperature. To better elucidate the mechanisms by which these processes occur, coupled experimental and computational investigations are carried out. In addition, it is found that lubricious iron oxide nanoparticles are generated in the core of the steel contact through mechanisms that are not yet known. The molecular dynamics simulations of carbon onions placed between sliding diamond-like carbon surfaces at high contact pressure indicate that the lubrication mechanism of the onions is based on a coupled process of rolling and sliding inside the contact area. We conclude that most of carbon onions seem to remain intact under friction processes and do not generate graphitic planes, which is in contrast to the previously determined behavior of MoS₂ fullerenes that are mainly exfoliated inside the contact area and liberate lubricating lamellar sheets of h-MoS₂.     

Effect of Oxygen Adsorption on Adhesion of W to Au Studied by Field Ion Microscopy

A field ion microscope has been used to investigate the influence of oxygen adsorption on adhesion of W to Au. An adhesion contact in ultrahigh vacuum of the field ion microscope was carried out using a W tip either with or without oxygen adsorption. It was found that adhesion force decreased with increasing oxygen exposures up to 60 Langmuirs (L). With an oxygen exposure of 16 L, an intermediate adhesion resulted. Adhesion is thus dependent upon the coverage of oxygen. The depth of adhesion-induced lattice defects was studied using the field evaporation technique. Over 200 L, adhesion force was not detectable, nor was distortion of W atoms.     

Evaluation of amorphous ursodeoxycholic acid by thermal methods

PURPOSE: The purpose of this study was to characterize the amorphous state of ursodeoxycholic acid (UDCA) samples by using isothermal microcalorimetry, X-ray diffraction, infrared (IR) spectroscopy and solid state carbon 13 nuclear magnetic resonance (13C-NMR) spectroscopy, and to demonstrate the application of the thermal methods (microcalorimetry and differential scanning calorimetry (DSC) for studying the amorphous state and clarifying the dissolution mechanism of UDCA. METHODS: Amorphous UDCA was prepared by grinding and rapid cooling of the melts. The heat of solution of UDCA was measured by an isothermal heat-conduction twin microcalorimeter at 25.0 degrees C. Some physicochemical properties of amorphous UDCA were also studied. RESULTS: The intensities of X-ray diffraction peaks of crystalline UDCA decreased with an increase in grinding time. The heat levels of solution of crystalline UDCA and UDCA ground for 1 min were endothermic, and became exothermic with an increase in grinding time. A good correlation was obtained between the heat of solution and the heat of crystallization determined from the peak area in DSC. Although no significant difference was observed in X-ray diffraction patterns of amorphous UDCA prepared by the two methods, significant differences were recognized in DSC, IR and 13C-NMR, and the heat of solution indicated different values among the two samples. The stability of amorphous UDCA samples stored under 74.5% relative humidity at 40 degrees C was found to depend upon the preparation methods. CONCLUSIONS: Different states of amorphous UDCA were obtained depending on the preparation method. The application of thermal methods to evaluate the amorphous state was demonstrated. The mechanism of dissolution of UDCA was discussed from the results of the heat of solution examination.     

The effect of slip amplitude on fretting

The effect of slip amplitude on the mechanism of fretting was investigated. Measurements of wear volume, frictional coefficient and of electrical contact resistance were carried out to clarify the wear mechanism. X-ray microdiffraction was used to observe the difference of wear behaviour, and scanning electron microscopic observations were made.At small slip amplitudes wear damage was small compared with that at larger amplitudes the transition being in the region of 70 μ.At smaller slip amplitudes fretting oxidation, a mild type of wear occurs. At larger slip amplitudes, adhesion and abrasion together with oxidation cause fretting wear. At much larger slip amplitudes, wear similar to reciprocating sliding wear occurs.     

Keratanase II-catalyzed synthesis of keratan sulfate oligomers by using sugar oxazolines as transition-state analogue substrate monomers: a novel insight into the enzymatic catalysis mechanism

Keratan sulfate (KS) oligomers with well-defined structures were synthesized by keratanase II (KSase II)-catalyzed transglycosylation. N-Acetyllactosamine [Galbeta(1-->4)GlcNAc; LacNAc] oxazoline derivatives with sulfate groups at the C-6 (1 a) and both the C-6 and the C-6' (1 b) were prepared as transition-state analogue substrate monomers for KSase II. Monomer 1 a was effectively oligomerized by the enzyme under weak alkaline conditions, to give alternating 6-sulfated KS oligomers (2 a) in good yields, and with total control of regioselectivity and stereochemistry. KSase II also recognized 1 b, which provided fully 6-sulfated KS oligomers (2 b) in good yields under similar conditions. Nonsulfated LacNAc oxazoline was difficult to oligomerize enzymatically. These results imply that the catalysis mechanism of KSase II involves a sugar oxazolinium ion that requires the 6-sulfate group in the GlcNAc residue not only in hydrolysis of KS chains, but also in oligomerization of oxazoline monomers. This is the first report of KSase II-catalyzed transglycosylation to form beta(1-->3)-glycosidic bond through a substrate-assisted mechanism.     

Diamond-derived carbon onions as lubricant additives

Among all the new carbon forms like fullerenes or nanotubes, carbon onions are of particular interest for tribological applications because of their spherical and tiny shape, and their chemical inertness. Used as additives blended to a synthetic base oil, they present excellent anti-wear and friction-reducing properties. In this paper, we compare tribological performances of two kinds of carbon onions with different structural features. Due to the synthesis method used, carbon onions present or not a residual diamond core inside the graphitic shells. Carbon onions without the diamond core present better anti-wear properties.     

Direct conversion of methane into methanol over MoO3/SiO2 catalyst in an excess amount of water vapor

Well-dispersed MoO₃ on SiO₂ showed a high activity for partial oxidation of methane (mixed with oxygen in a molar ratio of 9:1) into methanol and formaldehyde at 873 K in an excess amount of water vapor, which is attributed to the formation of silicomolybdic acid (SMA) on the catalyst surface during reaction. One of the roles of SMA for the partial oxidation of methane is proved to depress the successive oxidation of methanol and formaldehyde into carbon oxides.