Synthesis of chiral 1,3-diamines derived from cis-2-benzamidocyclohexanecarboxylic acid and their application in the Cu-catalyzed enantioselective Henry reaction.

In this study, 13 different chiral 1,3-diamines were synthesized from (-)-cis-2-benzamidocyclohexanecarboxylic acid. They were successfully applied as ligands in the Cu-catalyzed asymmetric Henry reaction between benzaldehyde and nitromethane. It was confirmed that the enantioselectivity of the product could be controlled by the substituents on the two amino groups. A time-course study revealed a decrease in product enantioselectivity caused by spontaneous retro-Henry reaction, which was suppressed by conducting the reaction at 0 °C. This versatile reaction afforded various ß-nitroalcohols in excellent yields and enantioselectivities (up to 98% yield, 91% enantiomeric excess) under the optimized reaction conditions. The chiral induction mechanism was explained on the basis of a previously proposed transition-state model.

Switching of enantioselectivity in the catalytic addition of diethylzinc to aldehydes by regioisomeric chiral 1,3-amino sulfonamide ligands.

Twenty chiral 1,3-amino sulfonamides of two classes (2a-i and 3a-k) have been prepared from (-)-cis-2-benzamidocyclohexanecarboxylic acid (1) and studied as ligands for catalytic enantioselective addition of Et(2)Zn to a variety of aromatic and aliphatic aldehydes. The ligands 2 and 3 are regioisomers in which the position of the amine and sulfonamide groups is exchanged. Each class of ligands with the same chirality was shown to afford sec-alcohols with the opposite stereochemistry. Structural surveys revealed that the combination of tertiary amino and p-toluenesufonylamido groups works most effectively for the reaction. Through optimization of the structural and reaction conditions, the best ligands quantitatively provided both enantiomeric secondary alcohols in good to excellent enantioselectivity of up to 94% and 98% ee for (S)- and (R)-enantiomers, respectively.

Quantitative Evaluation of the Movement Distance of Deep Fascia and Change of Muscle Shape Related to Chain Response in Fascia Tissue of Lower Limb.

By using ultrasonography, we measured the longitudinal movement distance of the deep fascia (LMDDF), change of the pennation angle (PA) and muscle thickness (MT) in both the tensor fasciae latae muscle (TFL) and the gluteus medius muscle (G-Med) during passive movement of the toes/ankle joints. 21 right lower limbs of 21 healthy males were evaluated in this study. We measured the LMDDF of the TFL and G-Med by measuring distance between the designated landmark on skin and the intersection of the major deep-fascia (D-fascia) and the fascial bundle. We also measured change of the PA and MT of both muscles. Additionally, we also measured the reliability of the measurement and the measurement error. The measurement was performed during three manual positions on the toes/ankle; manual holding of the toes and ankle joint in neutral, toes flexion and ankle plantar flexion/inversion position, toes extension and ankle extension/valgus position. The existence of muscle contraction of both the muscles during passive motion was monitored by active surface electrodes. This study confirmed mobility of the D-fascia in which the TFL's D-fascia moves and change of muscle shape in the distal direction during no muscle contraction due to passive movement. This fact suggests the possibility that passive tension on fascia tissue of the ankle extends to the proximal part of the limb, i.e., to the D-fascia of the TFL.

Increased serum levels of interleukin-6 in malnourished patients with colorectal cancer.

Peri-operative serum levels of interleukin-6 (IL-6) were determined in 62 patients who underwent resection of colorectal cancer to clarify the relationship between nutritional status and IL-6 response. Patients were divided into two groups based on creatinine height index: malnourished group (n=13) and normally nourished group (n=49). The preoperative median serum level of IL-6 in the malnourished group was significantly higher than in the normally nourished group (P=0.041). The postoperative median serum level of IL-6 in the malnourished group also tended to be higher. In conclusion, the peri-operative IL-6 response may be activated in malnourished colorectal cancer patients.

The relationship between circulating interleukin-6 and carcinoembryonic antigen in patients with colorectal cancer.

PURPOSE: The purpose of this study was to clarify whether or not preoperative serum levels of interleukin-6 (IL-6) correlate with well-established prognostic variables (serum level of carcinoembryonic antigen (CEA), stage, histological grade, lymphatic and venous invasion) in colorectal cancer patients. PATIENTS AND METHODS: Serum levels of IL-6 and CEA were determined in 62 patients who underwent resection of colorectal cancer. The patients were divided into two groups based on a selected cut-off value: high and low IL-6 and CEA groups. RESULTS: The median serum level of IL-6 in colorectal cancer patients was significantly higher than the median level in normal controls (p = 0.0014). Multivariate logistic regression analysis showed that a high serum level of CEA is an independent predictor for a high serum level of IL-6 (odds ratio, 4.10; p = 0.046). CONCLUSION: A high serum level of IL-6 is significantly associated with a high serum level of CEA in preoperative colorectal cancer patients.

Electric charging/discharging characteristics of super capacitor, using de-alloying and anodic oxidized Ti-Ni-Si amorphous alloy ribbons.

Charging/discharging behaviors of de-alloyed and anodic oxidized Ti-Ni-Si amorphous alloy ribbons were measured as a function of current between 10 pA and 100 mA, using galvanostatic charge/discharging method. In sharp contrast to conventional electric double layer capacitor (EDLC), discharging behaviors for voltage under constant currents of 1, 10 and 100 mA after 1.8 ks charging at 100 mA show parabolic decrease, demonstrating direct electric storage without solvents. The supercapacitors, devices that store electric charge on their amorphous TiO2-x surfaces that contain many 70-nm sized cavities, show the Ragone plot which locates at lower energy density region near the 2nd cells, and RC constant of 800 s (at 1 mHz), which is 157,000 times larger than that (5 ms) in EDLC.