Key role of the Lewis base position in asymmetric bifunctional catalysis: design and evaluation of a new ligand for chiral polymetallic catalysts

New chiral ligands for asymmetric polymetallic catalysts were designed on the basis of the assumption that the higher-order assembly structure is stabilized by modifying the modular unit. The designed ligands 6 and 7 contained a scaffolding cyclohexane ring with a Lewis base phosphine oxide directly attached to the scaffold. A module in the polymetallic complex contains two metals per ligand, and a stable 6-, 5-, 5-membered fused chelation ring system should be generated. Synthesis of these ligands is simple and high yielding, using a catalytic dynamic kinetic resolution promoted by the Trost catalyst as a key step. Ligand function was assessed in a catalytic asymmetric ring-opening reaction of meso-aziridines with TMSCN, a useful reaction for the synthesis of optically active beta-amino acids. The Gd complex generated from Gd(OiPr)3 and the ligand was a highly active and enantioselective catalyst in this reaction. Enantioselectivity was reversed compared to the previously reported d-glucose-derived catalyst containing the same chirality of the individual module. ESI-MS analysis and X-ray crystallographic studies indicate that the assembly state of the modules in the polymetallic catalysts differs depending on the chiral ligand. The difference in the higher-order structure stems from a subtle change (one carbon) in the position of the Lewis base relative to the Gd metal. The change in the higher-order structure of the polymetallic complex led to a dramatic reversal of the enantioselectivity and increased catalyst activity.     

Structure-activity relationships of neuromedin U. V. study on the stability of porcine neuromedin U-8 at the C-terminal asparagine amide under mild alkaline and acidic conditions

Porcine neuromedin U-8 (X-Asn-NH(2), X=H-Tyr-Phe-Leu-Phe-Arg-Pro-Arg) is occasionally unstable in the biological fluids used for bioassay as well as in the acidic solutions used for purification of synthetic peptides. In this study, HPLC examination of an incubate solution of X-Asn-NH(2) revealed that the main decomposition products in Tyrode's solution (pH 7.4) were either alpha- or beta-monocarboxylic acid analogs (X-Asn-OH or X-Asp-NH(2)), and that no dicarboxylic acid analog (X-Asp-OH) was produced. Further investigation, employing a model peptide (Y-Asn-NH(2), Y=Benzoyl-Pro-Arg) incubated in a 0.1 M sodium bicarbonate solution at 60 degrees C, revealed that the decomposition of C-terminal Asn-NH(2) occurred through the formation of an aminosuccinimide intermediate (Y-Asu), at a rate faster than that of Y-Asn-Ser peptide but slower than that of Y-Asn-Gly peptide. Mild acid hydrolysis of X-Asn-NH(2) examined in a 1 M HCl solution at 60 degrees C yielded X-Asn-OH and X-Asp-NH(2), which further decomposed to yield X-Asp-OH. The C-terminal degradation of X-Asn-NH(2) resulted in reduced biological and immunochemical binding activities.     

Tetrahedral Co(II) coordination in alpha-type cobalt hydroxide: Rietveld refinement and X-ray absorption spectroscopy

We report a Rietveld refinement analysis and X-ray absorption study on a green-color Cl(-)-intercalated alpha-type cobalt hydroxide phase. The refinement clearly demonstrated that one-fifth to one-sixth of the Co(II) at octahedral sites was replaced by pairs of tetrahedrally coordinated Co(II) on each side of the hydroxide plane, represented by a structural formula of [Co(octa)(0.828)Co(tetra)(0.348)(OH)2](0.348+)Cl(0.348).0.456H2O. X-ray absorption spectroscopy also indicated that the divalent cobalt were in local neighboring environments of both octahedral and tetrahedral coordination. Furthermore, UV-vis spectroscopic measurements elucidate the typical green/blue color of an alpha-type cobalt hydroxide.     

Community responses to road traffic noise in Hanoi and Ho Chi Minh City

Vietnam is a developing country in southeast Asia, and its environment has been seriously affected by industrialization and urbanization. In large cities like Hanoi (northern Vietnam) and Ho Chi Minh City (southern Vietnam), noise emission from road traffic has been found to be a serious concern among general public. In 2005 and 2007, two large-scale socio-acoustic surveys of community response to road traffic noise were conducted to investigate human reactions to road traffic noise in these cities; the sample sizes were 1503 people in Hanoi and 1471 in Ho Chi Minh City. The noise exposure levels (L_den) were 70–83 dB in Hanoi and 75–83 dB in Ho Chi Minh City. Noise annoyance was estimated using standardized annoyance scales. For both cities, dose–response relationships were established between L_den and the percentage of highly annoyed respondents. Compared to annoyance responses of European people, Vietnamese were less annoyed by road traffic noise by about 5 dB. Hanoi respondents seemed to be more annoyed by noise than Ho Chi Minh City respondents. Conversation and sleep disturbances were not as serious as expected in either city. Furthermore, window orientation in the home was found to affect activity disturbances.     

“Molecular Rope Curtain” Type of Liquid Crystals Based on a Sliding Graft Copolymer Having Mobile PEG Side Chains

A sliding graft copolymer having a polyrotaxane main chain and side chains of polyethylene glycol with a molecular weight of 2000 (PEG2000) was found to be a novel “molecular rope curtain” type of liquid crystalline material, which displayed a smectic A mesophase between 51 °C and 250 °C without any rigid mesogenic moieties.     

Changes in Repetitive Firing Rate Related to Phase Response Curves for Andronov-Hopf Bifurcations

We study specific changes in repetitive firing in the two-dimensional Hindmarsh-Rose （2dHR） oscillatory sys- tem that undergoes a bifurcation transition from the supercritical Andronov-Hopf （All） type to the subcritical Andronov-Hopf （SAH） type. We identify dynamical mechanisms which are responsible for changes of the repeti- tive firing rate during the AH to SAH bifurcation transitions. These include frequency-shift functions in response to small perturbations of a timescale parameter, its multiplicative parameter, and an external input current in the 2dHR oscillatory system. The frequency-shift functions are explicitly represented as functions relating to the phase response curves （PRCs）. Then, we demonstrate that when the timescale is normal and relatively fast, the repetitive firing rate slightly increases and decreases respectively during the AH to SAH bifurcation transition with a change of the intrinsic parameter, whereas it decreases during the SAH to AH bifurcation transition with an increase in the timescale. By analyzing the three different frequency-shift functions, we show that such changes of the repetitive firing rate depend largely on changes of the PRC size. The PRC size for the SAH bifurcation shrinks to the PRC size for the AH bifurcation.     

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.     

Identification of unknown surfactants using electrospray mass spectrometry and NMR spectroscopy preceded by liquid ionization mass spectrometry

Commercially available but completely unknown surfactants used in the tin-lead plating industry were successfully identified by using electrospray mass spectrometry and NMR spectroscopy techniques, preceded by liquid ionization mass spectrometry used to obtain the preliminary information. The mass spectral data suggested that ethoxylated nonionic surfactants having a homologous distribution of molecular weights like 520, 564, 608, 652, 696, etc. were present. The NMR data suggested the presence of two aromatic rings and a quaternary carbon for the hydrophobe moiety instead of the well-known alkyl chains or alkylphenols. The unknown surfactants were finally concluded to be novel nonionic 4-(alpha,alpha-dimethylbenzyl)-phenol ethoxylates.