A new method for the high performance liquid chromatographic determination of TA-870, a dopamine prodrug (catechol ester compound)

A new method for the high performance liquid chromatographic (HPLC) determination of N-(N-acetyl-L-methionyl)-O,O-bis(ethoxycarbonyl)dopamine (TA-870), a dopamine prodrug, in biological fluid has been developed. In order to measure with an electrochemical detector (ECD), TA-870 was passed first through an immobilized carboxylesterase column to be converted to the electrochemically active deethoxycarbonylated TA-870 (DEC-TA-870). The properties of this carboxylesterase immobilized on Sepharose 4B were examined by this flow injection system. Hydrolysis of TA-870 with this immobilized carboxylesterase was a maximum at pH 7-8 and 50 degrees C, and the activity decreased in the presence of organic solvent such as acetonitrile. For the determination of TA-870 in biological fluids, an HPLC-immobilized enzyme-ECD system using a column-switching technique was developed. The blood was deproteinized with ethanol, and TA-870 in the ethanol extracts was adsorbed in Bond Elut C18. The dichloromethane eluate from Bond Elut C18 was injected into the HPLC system. The HPLC apparatus was composed of three pumps, two separation columns (LiChrosorb Si 60 and mu Bondasphere), a trap column (Bond Elut), an enzyme column, ECD and the column-switching system. The calibration curve for TA-870 in blood was linear in the range from 2 to 200 ng/mL. This new assay method might be useful also for the determination of other catechol ester compounds.     

Hydrogen Peroxide Formation by Electric Discharge with Fine Bubbles

Pulsed discharge plasma is typical oxidation technology for disposing organic compounds in aqueous solutions. When this electrical discharge plasma was applied in water, it may produce hydrogen peroxide (H₂O₂) without any catalyst or chemical agent. In order to increase H₂O₂ production by electrical discharge plasma in water, fine bubbles were introduced into the electrical discharge plasma in this experiment. Bipolar pulsed voltages were applied to cylindrical electrodes in the water while Ar or O₂ bubbles were introduced, generating a pulsed discharge plasma. The introduction of the bubbles seemed to enhance the dissociation of water molecules and increased H₂O₂ formation, especially with O₂ bubbling. Dissolved oxygen in the water contributed to H₂O₂ formation by pulsed discharge plasma with the bubbles, while dissociation of water molecules was the cause of H₂O₂ formation by pulsed discharge plasma without bubbles. More H₂O₂ was formed by pulsed discharge plasma with O₂ bubbles, because the amount of dissolved oxygen in the water increased upon bubbling with O₂.     

Production of Acetone–Butanol–Ethanol (ABE) in Direct Fermentation of Cassava by Clostridium saccharoperbutylacetonicum N1-4

In this work, acetone–butanol–ethanol (ABE) fermentation characteristics of cassava starch and cassava chips when using Clostridium saccharoperbutylacetonicum N1-4 was presented. The obtained results in batch mode using a 1-L fermenter showed that C. saccharoperbutylacetonicum N1-4 was a hyperamylolytic strain and capable of producing solvents efficiently from cassava starch and cassava chips, which was comparable to when glucose was used. Batch fermentation of cassava starch and cassava chips resulted in 21.0 and 19.4 g/L of total solvent as compared with 24.2 g/L of total solvent when using glucose. Solvent productivity in fermentation of cassava starch was from 42% to 63% higher than that obtained in fermentation using corn and sago starches in the same condition. In fermentation of cassava starch and cassava chips, maximum butanol concentration was 16.9 and 15.5 g/L, respectively. Solvent yield and butanol yield (based on potential glucose) was 0.33 and 0.41, respectively, for fermentation of cassava starch and 0.30 and 0.38, respectively for fermentation using cassava chips.     

Determination of bithionol, bromophen, nitroxynil, oxyclozanide, and tribromsalan in milk with liquid chromatography coupled with tandem mass spectrometry

LC/MS/MS was developed to determine the residues of bithionol (BTN), bromofen (BMF), nitroxynil (NTX), oxyclozanide (OCZ), and tribromsalan (TBS) in milk. Samples were extracted with ethyl acetate and cleaned up by liquid-liquid separation with acetonitrile and n-hexane. The compounds were determined by RP-LC using a C18 column with 0.1% formic acid-methanol. Mass spectral acquisition was performed in the negative mode by applying selected-reaction monitoring. The method was validated in milk spiked with these compounds at 5-600 microg/kg; average recoveries were in the range 83.8-97.1%, with RSD values of 1.4-8.0%. The interassay RSDs were less than 11%. The LODs of these compounds in milk were 0.1 microg/kg. The method was applied to 24 raw milk samples. The concentration of these compounds in all samples was lower than the Japanese maximum residue limits. The method is rapid, sensitive, and specific for monitoring residues of BTN, BMF, NTX, OCZ, and TBS in milk.     

Selection rules for light-induced magnetization of a crystal with threefold symmetry: the case of antiferromagnetic NiO

We propose Raman-induced collinear difference-frequency generation (DFG) as a method to manipulate dynamical magnetization. When a fundamental beam propagates along a threefold rotational axis, this coherent second-order optical process is permitted by angular momentum conservation through the rotational analogue of the umklapp process. As a demonstration, we experimentally obtained polarization properties of collinear magnetic DFG along a [111] axis of a single crystal of antiferromagnetic NiO with micromultidomain structure, which excellently agreed with the theoretical prediction.     

A case of Budd-Chiari syndrome: Gd-EOB-DTPA-enhanced MR findings

Budd-Chiari syndrome (BCS) is a rare disorder caused by the obstruction of hepatic venous outflow, leading to sinusoidal congestion, ischemic injury to liver cells and portal hypertension. Long-term survival largely depends on whether hepatocellular carcinoma occurs. A recently available liver-specific contrast medium, gadolinium-ethoxybenzyl-diethylenetriamine penta-acetic acid (Gd-EOB-DTPA), reportedly has high diagnostic capability for detection of malignant liver tumors. However, there has been no report of the sue of Gd-EOB-DTPA-enhanced magnetic resonance imaging (MRI) for BCS. We present a case of chronic BCS who underwent both gadopentetate dimeglumine (Gd-DTPA) and Gd-EOB-DTPA-enhanced MRI. Hepatic congestion and edema were seen as slightly hypointense areas on Gd-EOB-DTPA-enhanced hepatobiliary-phase images, although these areas were observed as slightly hyperintense on previously obtained Gd-DTPA-enhanced delayed-phase image. Reduced uptake of Gd-EOB-DTPA by hepatocytes in the region of congestion or edema may account for this difference, which should be recognized in image interpretations.     

Procyanidins are potent inhibitors of LOX-1: a new player in the French Paradox

Lectin-like oxidized LDL receptor-1 (LOX-1) is an endothelial receptor for oxidized LDL (oxLDL) and plays multiple roles in the development of cardiovascular diseases. We screened more than 400 foodstuff extracts for identifying materials that inhibit oxLDL binding to LOX-1. Results showed that 52 extracts inhibited LOX-1 by more than 70% in cell-free assays. Subsequent cell-based assays revealed that a variety of foodstuffs known to be rich in procyanidins such as grape seed extracts and apple polyphenols, potently inhibited oxLDL uptake in Chinese hamster ovary (CHO) cells expressing LOX-1. Indeed, purified procyanidins significantly inhibited oxLDL binding to LOX-1 while other ingredients of apple polyphenols did not. Moreover, chronic administration of oligomeric procyanidins suppressed lipid accumulation in vascular wall in hypertensive rats fed with high fat diet. These results suggest that procyanidins are LOX-1 inhibitors and LOX-1 inhibition might be a possible underlying mechanism of the well-known vascular protective effects of red wine, the French Paradox.     

Spontaneous ignition temperature for the compacted mixture of Ni–Al system: Experiment,theory, and comparisons

Spontaneous ignition of compacted mixture has been examined not only experimentally but also theoretically, relevant to materials synthesis for Ni–Al system. Spontaneous ignition temperature, determined from the inflection-point of the temporal variation of surface temperature, is found to decrease at first, reach the minimum, and then increase gradually, with increasing size ratio, being defined as the ratio of compact and particle diameters and reported to be useful in correlating experimental results. The lowest temperature observed is as low as that, more than 200 K below the melting point 934 K of Al, at the size ratio of c.a. 700. While its decrease is attributed to the increase in the particle surface per unit spatial volume of compacted mixture, as reported in the literature, its increase found in the course of the present study can fairly be correlated to an enhancement of heat loss from each particle in the compacted mixture, by conducting a theoretical consideration. As for the dependence of spontaneous ignition temperature on the mixture ratio, a shifting occurs from a decreasing trend with increasing mixture ratio at small size ratios, less than about 700, to an insensitive trend to the mixture ratio, had not been reported in the literature. In addition, a fair degree of agreement, shown in experimental comparisons with theoretical results, indicates that the present formulation has captured the essential features of the spontaneous ignition of compacted mixture, especially for size ratios with large values. Since this kind of particle size effects, relevant to the spontaneous ignition of the compacted mixtures, has not been captured in the previous studies, its elucidation can be considered not only notable but also useful, in manipulating combustion process in materials synthesis, especially, in choosing a specific condition for the lowest spontaneous ignition temperature by varying the size ratio.     

Analysis of liquid structure without construction of any structure models by the X-ray scattering method.

A simple approach for determining a liquid structure using X-ray scattering data, in which a liquid structure is uniquely evaluated without construction of any plausible structure models, has been applied to liquid acetonitrile, acetone and cyclohexane. For a pair of molecules, a given point within a molecule is located at the origin with a given molecular orientation. The site of the given point of another molecule is defined by the polar coordinates and the molecular orientation is treated by three Eulerian angles. These parameters are optimized by a non-linear least-squares calculation applied to X-ray scattering data. The reliability of the method was examined by determining the liquid structure of polar acetonitrile and the obtained intermolecular interatomic distances are in good agreement with the previously reported values. The method was then successfully applied to the determination of the liquid structure of acetone and cyclohexane. Especially for nonpolar cyclohexane, the construction of a variety of plausible structural models is very difficult. It was revealed that acetone has an ordered liquid arrangement similar to that found in its crystal, although the intermolecular distances in liquid acetone are different from those in the crystal. On the other hand, the liquid structure of cyclohexane is disordered.