Efficient esterification of carboxylic acids and phosphonic acids with trialkyl orthoacetate in ionic liquid

An operationally simple, inexpensive, efficient, and environmentally friendly esterification of various carboxylic acids, phosphonic acids, and phosphinic acids with triethyl orthoacetate or trimethyl orthoacetate under neutral conditions in a typical room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate, was successfully carried out to provide the corresponding ethyl esters or methyl esters in high yields.     

Chemical conversion of various celluloses to glucose and its derivatives in supercritical water

The supercritical water biomass conversion system was designed and developed in our laboratory. The reaction vessel with cellulose sample was treated with this system at supercritical state of water for a designated period (3–105s) under the conditions of a tin bath temperature of 500°C and pressure of 35MPa. The recovered products of hydrolysates were then analyzed by high performance liquid chromatography. The obtained results indicated that a high amount of glucose and levoglucosan can be achieved from both celluloses I and II for 5–10s supercritical treatment, while that from starch for 3–5s treatment. Although this difference could be due to a difference in the molecular structure between cellulose and starch, a difference between celluloses I and II was not significant. Instead, an accessibility of the water towards cellulose molecules seemed to be significant for their chemical conversion. With the longer treatment, amounts of these compounds observed were decreased due to decomposition. Therefore, it may be concluded that, compared with acid hydrolysis or enzymatic saccharification, cellulose may be hydrolyzed to glucose and its derivatives more or less to the same degree as in corn starch under supercritical state. This finding suggests that the supercritical treatment can overcome the difficulties in hydrolyzing cellulose to glucose, found in the acid hydrolysis or enzymatic saccharification techniques.     

Synthesis of 4-fluorinated UDP-MurNAc pentapeptide as an inhibitor of bacterial growth

4-Fluorinated UDP-MurNAc pentapeptide, 2, has been synthesized. In our previous study, UDP-MurNAc pentapeptide analogue 1 was found to be incorporated into the bacterial cell wall through biosynthesis. Compound 2 showed growth-inhibition activity against Gram-positive bacteria when it was added to growth media at 0.01 mg/mL. [structure--see text]     

Chemical reaction dynamics of PeCB and TCDD decomposition: A tight‐binding quantum chemical molecular dynamics study with first‐principles parameterization

The decomposition reaction dynamics of 2,3,4,4′,5‐penta‐chlorinated biphenyl (2,3,4,4′,5‐PeCB), 3,3′,4,4′,5‐penta‐chlorinated biphenyl (3,3′,4,4′,5‐PeCB), and 2,3,7,8‐tetra‐chlorinated dibenzo‐p‐dioxin (2,3,7,8‐TCDD) was clarified for the first time at atomic and electronic levels, using our novel tight‐binding quantum chemical molecular dynamics method with first‐principles parameterization. The calculation speed of our new method is over 5000 times faster than that of the conventional first‐principles molecular dynamics method. We confirmed that the structure, energy, and electronic states of the above molecules calculated by our new method are quantitatively consistent with those by first‐principles calculations. After the confirmation of our methodology, we investigated the decomposition reaction dynamics of the above molecules and the calculated dynamic behaviors indicate that the oxidation of the 2,3,4,4′,5‐PeCB, 3,3′,4,4′,5‐PeCB, and 2,3,7,8‐TCDD proceeds through an epoxide intermediate, which is in good agreement with the previous experimental reports and consistent with our static density functional theory calculations. These results proved that our new tight‐binding quantum chemical molecular dynamics method with first‐principles parameterization is an effective tool to clarify the chemical reaction dynamics at reaction temperatures. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Affinity transformation from hydrophilicity to hydrophobicity of water molecules on the basis of adsorption of water in graphitic nanopores

The interaction of water with hydrophobic surfaces is quite important in a variety of chemical and biochemical phenomena. The coexistence of water and oil can be realized by introduction of surfactants. In the case of water vapor adsorption on graphitic nanopores, plenty of water can be adsorbed in graphitic nanopores without surfactants, although the graphitic surface is not hydrophilic. Why are water molecules adsorbed in hydrophobic nanopores remarkably? This work can give an explicit insight to water adsorption in hydrophobic graphite nanopores using experimental and theoretical approaches. Water molecules are associated with each other to form the cluster of 1 nm in size, leading to a significant stabilization of the cluster in the graphitic nanopores. This mechanism can be widely applied to interfacial phenomena relating to coexistence of water and nanostructural materials of hydrophobicity.     

A new Zn(II) coordination polymer with 4-pyridylthioacetate: assemblies of homo-chiral helices with sulfide sites

A coordination polymer [Zn(pyta)(OH)] (pyta = 4-pyridylthioacetate), was synthesized and structurally characterized; it is constructed by an alternating assembly of two types of homo-chiral helices, [Zn-OH] and [Zn-pyta], in which the sulfide moieties are fastened in the latter columns.     

Color adjustment algorithm adapted to the spectral reflectance estimation method

We are developing a daily health monitoring system that uses mobile phones with cameras and analyzes physiological conditions from R, G, and B intensity levels. However, since it is affected by various imaging conditions of the image input, color correction is required for accurate health monitoring. Therefore, we developed and validated a colorcorrection algorithm to derive reliable color information by correcting the spectral reflectance using the Wiener estimation and a color chart.     

Magnetic structures of exchange bias Ni/FeF2(1 1 0) interface

Electronic and magnetic structures of ferromagnetic (FM)/antiferromagnetic (AFM), Ni/FeF₂(1 1 0), with a compensated AFM interface are investigated by using the full-potential linearized augmented plane-wave method. We find that magnetic structures at the AFM interface are perturbed by a contact with the FM material, where the superexchange interaction through the interface F excites and induces a small net moment at the AFM interface. These results predicted may play an important role for explaining the exchange bias in this system, and rule out the exchange bias mechanisms with the spin-flop coupling and the magnetic moment reorientation.     

Changes in diffusion tensor imaging (DTI) eigenvalues of skeletal muscle due to hybrid exercise training

Several studies have proposed the cell membrane as the main water diffusion restricting factor in the skeletal muscle cell. We sought to establish whether a particular form of exercise training (which is likely to affect only intracellular components) could affect water diffusion. The purpose of this study is to characterise prospectively the changes in diffusion tensor imaging (DTI) eigenvalues of thigh muscle resulting from hybrid training (HYBT) in patients with non-alcoholic fatty liver disease (NAFLD). Twenty-one NAFLD patients underwent HYBT for 30 minutes per day, twice a week for 6 months. Patients were scanned using DTI of the thigh pre- and post-HYBT. Fractional anisotropy (FA), apparent diffusion coefficient (ADC), the three eigenvalues lambda 1 (λ1), λ2, λ3, and the maximal cross sectional area (CSA) were measured in bilateral thigh muscles: knee flexors (biceps femoris (BF), semitendinosus (ST), semimembranous (SM)) and knee extensors (medial vastus (MV), intermediate vastus (IV), lateral vastus (LV), and rectus femoris (RF)), and compared pre- and post-HYBT by paired t-test. Muscle strength of extensors (P < 0.01), but not flexors, increased significantly post-HYBT. For FA, ADC and eigenvalues, the overall picture was of increase. Some (P < 0.05 in λ2 and P < 0.01 in λ1) eigenvalues of flexors and all (λ1-λ3) eigenvalues of extensors increased significantly (P < 0.01) post-HYBT. HYBT increased all 3 eigenvalues. We suggest this might be caused by enlargement of muscle intracellular space.