Preparation of Secondary Carbinamines via Alkylation of N-Boryl Imines Generated from Partial Reduction of Nitriles with NABH4-Carboxylic Acid

Secondary carbinamines have been prepared from alkylation of N-boryl imines which were generated in situ from partial reduction of nitriles with sodium brohydride modified by carboxylic acid.     

Numerical visualization of free surface oscillation predicted with arbitrary Lagrangian-Eulerian method

A numerical prediction method has been proposed to predict non-linear free surface oscillation in a three-dimensional container. The fluid motions are numerically predicted with Navier-Stokes equations discretized in a Lagrangian scheme with sufficient numerical accuracy. The profile of a free surface is precisely represented with three-dimensional body-fitted coordinates (BFC), which are regenerated in each computational step on the basis of the arbitrary Lagrangian-Eulerian (ALE) formulation. The computational method was applied to non-linear sloshings and transitions from sloshing to swirling motions. The predicted free surface motions were visualized as sequential image files and animations to understand their dynamic futures     

Parallel computation and numerical visualization for non-uniform particles included in gas and liquid flows

A parallel computation method has been proposed for the mixing and segregation of granular mixture included in gas and liquid flows. In this method, a three-dimensional (3D) computational volume is decomposed into multiple sub-blocks and their geometries are represented by 3D body-fitted coordinates. The fluid-particle interactions are treated by two types of models: a two-way model for liquid-solid flows and a one-way model in case of gas-solid flows. The computations of the particle motions in the multiple sub-blocks are executed simultaneously on the basis of the distinct element method (DEM). Since a graphic process is also executed as one of the parallel jobs, the particle distributions can be visualized during the computations. The computational method was applied to the gas-solid flows consisting of different diameters and densities in the horizontal and inclined cylinders rotating around their axes. From the comparison with the experimental results, nearly uniform mixing and particle segregation are successfully predicted in the oscillating liquid flows. In addition, it has been indicated that the particle pathline is very effective to visualize and understand the flow patterns of the particles with different properties. The result of the computations for the liquid-solid flows demonstrated that the vertical segregation of the non-uniform particles is reasonably reproduced.     

Mechahism of the base promoted fragmentatiom of chloroacetylhydrazide

Experiments are described supporting the positions that the visible transient intermediate occurring during the fragmentation of chloroacetylhydrazide is the anion of acetyldiazene, and that the concurrent reduction is not a simple recombination reaction.     

Identification of oligosaccharides from histopathological sections by MALDI imaging mass spectrometry

Direct tissue analysis using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) provides the means for in situ molecular analysis of a wide variety of biomolecules. This technology—known as imaging mass spectrometry (IMS)—allows the measurement of biomolecules in their native biological environments without the need for target-specific reagents such as antibodies. In this study, we applied the IMS technique to formalin-fixed paraffin-embedded samples to identify a substance(s) responsible for the intestinal obstruction caused by an unidentified foreign body. In advance of IMS analysis, some pretreatments were applied. After the deparaffinization of sections, samples were subjected to enzyme digestion. The sections co-crystallized with matrix were desorbed and ionized by a laser pulse with scanning. A combination of α-amylase digestion and the 2,5-dihydroxybenzoic acid matrix gave the best mass spectrum. With the IMS Convolution software which we developed, we could automatically extract meaningful signals from the IMS datasets. The representative peak values were m/z 1,013, 1,175, 1,337, 1,499, 1,661, 1,823, and 1,985. Thus, it was revealed that the material was polymer with a 162-Da unit size, calculated from the even intervals. In comparison with the mass spectra of the histopathological specimen and authentic materials, the main component coincided with amylopectin rather than amylose. Tandem MS analysis proved that the main components were oligosaccharides. Finally, we confirmed the identification of amylopectin by staining with periodic acid-Schiff and iodine. These results for the first time show the advantages of MALDI-IMS in combination with enzyme digestion for the direct analysis of oligosaccharides as a major component of histopathological samples.     

Magnetic resonance differentiation between T2 and T1 gallbladder carcinoma: significance of subserosal enhancement on the delayed phase dynamic study

Purpose

The aim of this study is to investigate whether subserosal enhancement on the delayed-phase dynamic magnetic resonance (MR) study (SED) can differentiate T2 from T1 gallbladder carcinoma (GBC).

Methods

The institutional research board approved this retrospective study. Between 1997 and 2006, there were surgically proven 11 T1 and 21 T2 GBC in 30 patients, all of whom had undergone preoperative contrast enhanced dynamic MR study, either with a 2D sequence (n=17) or 3D sequences (n=15). All images were reviewed by two radiologists for the presence of SED, and receiver operating characteristic (ROC) curve analysis was performed. Sensitivity, specificity, positive and negative predictive values were calculated by consensus.

Results

The areas under the ROC curves of the two readers were 0.91 and 0.86, and the kappa value was 0.78. Of the 21 T2 GBC, 18 and 3 showed positive and negative SED, respectively. Of the 11 T1 GBC, 1 and 10 showed positive and negative SED, respectively. The sensitivity, specificity, positive and negative predictive values of SED for diagnosing T2 lesions were 86%, 88%, 91% and 77%, respectively.

Conclusions

In conclusion, SED may be a useful sign to differentiate T2 from T1 GBC, which would affect the preoperative surgical planning of the patients.     

Facile preparation of aromatic ketones from aromatic bromides and arenes with aldehydes

Aromatic ketones were efficiently prepared in good yields by the reactions of aryl bromides with n-BuLi, followed by the reactions with aromatic aldehydes or aliphatic aldehydes and the subsequent treatment with molecular iodine and K₂CO₃, in a one-pot method. The same treatment of arenes, instead of aromatic bromides, also provided the corresponding aromatic ketones in good yields. Using these methods, various diaryl ketones and alkyl aryl ketones bearing electron-rich aromatics and electron-deficient aromatics could be prepared efficiently by a simple, transition-metal-free, and therefore environmentally benign experimental procedure.     

Vacuum lithography—A completely dry lithography using plasma processing

The purpose of this paper is to describe a thoroughly dry lithography using plasma polymerization and plasma etching. The new lithography is named vacuum lithography because all processes are performed at reduced pressures. Resist films were formed in bell-jar-type and argon-flow-type reactors. The controllability of plasma polymerization is discussed with respect to the type of reactor and gas mixture. A pattern was delineated in the resist using an electron beam, and it was developed by plasma etching with a mixture of argon and oxygen. It was found that the quality of the plasma-polymerized resist depends strongly on the polymer structure and on the plasma etching conditions. In this experiment, the recorded values of sensitivity and value of plasma-polymerized methyl methacrylate were 700 µC/cm² and 1, respectively.     

Prediction of thermal stratification in a curved duct with 3D body-fitted co-ordinates

This paper concerns a numerical prediction method for buoyancy-influenced flows using three-dimensional non-orthogonal curvilinear co-ordinates. The numerical analysis of the transformed governing equations for thermal hydraulics is based on a Lagrangian method, in which advected physical values are evaluated by local cubic spline interpolations with third-order accuracy in the three-dimensional computational domain. In addition, the buoyancy and diffusion terms are discretized in the Lagrangian scheme so as to have second-order accuracy with respect to time and space. The Neumann boundary conditions, which have been rather difficult for non-orthogonal co-ordinates to deal with, can be implemented by making use of normal vectors on the physical boundary surfaces and cubic spline interpolations. The developed numerical method is applied to the steady isothermal flow in a curved pipe and the unsteady stratified flow in a curved duct. Both of the predicted values are in good agreement with the experimental results and the validity of the prediction method is confirmed.