Far infrared absorption spectra of amorphous (As2S3)?(Sb2S3) semiconductors and the spatial charge fluctuation

Far infrared absorption spectra of amorphous (As₂S₃)_1–x(Sb₂S₃)_x system (x=0.00.6) were measured in the wavenumber region 725 cm^–1 with Lamellar grating far infrared Fourier Transform Spectrometer, and the spatial fluctuation of charges and its correlation range were estimated with charge fluctuation model. The charge fluctuation of (As₂S₃)_1–x(Sb₂S₃)_x system increases with Sb₂S₃ concentration x. On the other hand, the correlation length of the charge fluctuation decreases from 7 A to 4.5 A with an increase in x. As a result, it can be found that the medium range order of As₂S₃ changes drastically with an incease in Sb₂S₃ concentration x.     

Total synthesis of (+)-tubelactomicin A. 2. Synthesis of the upper-half segment and completion of the total synthesis

[reaction: see text]. We have completed the total synthesis of natural (+)-tubelactomicin A (1), a 16-membered macrolide antibiotic. This Letter presents a highly efficient synthesis of the upper-half segment (C14-C24) and the completion of the total synthesis featuring a high-yielding Stille coupling for the connection of the upper-half and lower-half segments and Mukaiyama macrolactonization for the construction of the entire structure of 1.     

Catalytic specificity exhibited by p-sulfonatocalix[n]arenes in the methanolysis of N-acetyl-l-amino acids

Specific acid catalysis of p-sulfonatocalix[n]arenes (n = 4, Calix-S4; n = 6, Calix-S6; n = 8, Calix-S8) was observed in the alcoholysis of N-acetyl-l-amino acids in methanol. The methanolysis rates of basic amino acid substrates (His, Lys, and Arg) were markedly enhanced in the presence of Calix-Sn, as compared with rates observed with p-hydroxybenzenesulfonic acid (pHBS), which is a noncyclic analogue of Calix-Sn. This catalytic effect of Calix-Sn was not observed for the methanolysis of Phe, Tyr, and Trp substrates. On the other hand, (1)H NMR experiments following the effect of Calix-Sn on N-acetyl-l-amino acid substrates in CD(3)OD showed that the spectrum of a mixture of the His substrate with Calix-Sn was significantly different from the combined spectra of the respective compounds. These changes in spectra support the formation of an inclusion complex of Calix-Sn with basic amino acids. Furthermore, it was obvious that methanolysis of the His substrate catalyzed by Calix-S4 and Calix-S6 obeyed Michaelis-Menten kinetics. These results indicate that the catalytic activity of Calix-Sn originates from its forming a complex with specific substrates (basic amino acids), similar to enzymatic reactions.     

Ligand field modification around Cu2+ ions in sodium borate glass by codoping

Understanding the effect of codoping on the properties of photonic glasses is important for improving their properties. The effect of codoping on the ligand field around Cu(2+) ions in a sodium borate glass is examined using optical absorption spectroscopy, continuous-wave electron paramagnetic resonance, and three-pulse electron-spin-echo envelope-modulation. Glass with a composition of 0.1CuO·5Na(2)O·95B(2)O(3) was codoped with 2 mol % of Al(3+), Si(4+), P(5+), Zr(4+), or La(3+) oxide. Three codoping effects are found: strengthening the ligand field, as observed for Zr-codoping, which induces a large blue shift of the optical absorption peak of Cu(2+); weakening the ligand field, as observed for P-codoping, which causes a red shift of the Cu(2+) absorption peak; and almost no effect on the ligand field, which is observed for Al-, Si-, and La-codoping. Coordination structure models based on local charge neutrality are proposed for the codoped glasses. The mechanism of the codoping effect is revealed by elucidating the local structure around Cu(2+).     

Interaction between human tissue thromboplastin and human antithrombin III

It is known that antithrombin III (ATIII) activity is inhibited by tissue thromboplastin (TP) in the presence of heparin. In our study on the mechanism of the inhibition, however, TP was found to inhibit ATIII activity even in the absence of heparin, indicating an interaction between ATIII and TP. We then studied effect of ATIII on the interaction between factor VII (FVII) and TP using FVII-depleted human plasma. When the mixture of FVII + ATIII + TP was incubated at 37 degrees C and mixed with FVII-depleted plasma, the interaction between FVII and TP was inhibited. Possible complex formation was examined by electrophoretic techniques. In the immunoelectrophoresis, ATIII shifted toward the cathode in the presence of TP and the substance which had changed the mobility of ATIII showed TP activity after zone electrophoresis. The results indicated that TP had shifted toward the anode due to ATIII while ATIII had shifted toward the cathode due to TP. In the immunoblotting analysis, ATIII was separated into several bands in the presence of TP. ATIII antigenicity was altered in the presence of both heparin and TP but not in the presence of TP alone. Our results strongly suggest that TP modulates ATIII activity in the initiation of the TP-mediated coagulation cascade and that in progressing coagulation ATIII participates in the inhibition of the coagulation cascade by blocking not only thrombin activity but also the interaction between TP and FVII.     

Use of cheaper metal than Rh, CHCl3-free Pd catalyst, in 1,2-addition of aromatic aldehydes with arylboronic acids

Pd(OAc)₂-(±)-tol-BINAP-catalyzed arylation reaction of aromatic aldehydes with arylboronic acids in the absence of CHCl₃ is described.     

N-linked oligosaccharide analysis of rat brain Thy-1 by liquid chromatography with graphitized carbon column/ion trap-Fourier transform ion cyclotron resonance mass spectrometry in positive and negative ion modes

We have previously described the site-specific glycosylation analysis of rat brain Thy-1 by LC/multistage tandem mass spectrometry (MS(n)) using proteinase-digested Thy-1. In the present study, detailed structures of oligosaccharides released from Thy-1 were elucidated by mass spectrometric oligosaccharide profiling using LC/MS with a graphitized carbon column (GCC-LC/MS). First, using model oligosaccharides, we improved the oligosaccharide profiling by ion trap mass spectrometry (IT-MS) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Sequential scanning of a full MS(1) scan with FT-ICR-MS followed by data-dependent MS(n) with IT-MS in positive ion mode, and a subsequent full MS(1) scan with FT-ICR-MS followed by data-dependent MS(n) with IT-MS in negative ion mode enabled the monosaccharide composition analysis as well as profiling and sequencing of both neutral and acidic oligosaccharides in a single analysis. The improved oligosaccharide profiling was applied to elucidation of N-linked oligosaccharides from Thy-1 isolated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. It was demonstrated that Thy-1 possesses a significant variety of N-linked oligosaccharides, including Lewis a/x, Lewis b/y, and disialylated structure as a partial structure. Our method could be applicable to analysis of a small abundance of glycoproteins, and could become a powerful tool for glycoproteomics.     

Layered hydride CaNiGeH with a ZrCuSiAs-type structure: crystal structure, chemical bonding, and magnetism induced by Mn doping

Stimulated by the discovery of the iron oxypnictide superconductor with ZrCuSiAs-type structure in 2008, extensive exploration of its isostructural and isoelectronic compounds has started. These compounds, including oxides, fluorides, and hydrides, can all be simply recognized as valence compounds for which the octet rule is valid. We report herein the first example of a ZrCuSiAs-type hydride, CaNiGeH, which violates the octet rule. This hydride was synthesized by hydrogenation of the CeFeSi-type compound CaNiGe under pressurized hydrogen. Powder diffraction and theoretical simulation confirm that H enters into the interstitial position of the Ca(4) tetrahedron, leading to notable anisotropic expansion of the unit cell along the c axis. Density functional theory calculations indicate the modification of the chemical bonding and formation of ionic Ca-H bond as a result of hydrogen insertion. Furthermore, CaNiGeH shows Pauli paramagnetism and metallic conduction similar to that of CaNiGe, but its carrier type changes to hole and the carrier density is drastically reduced as compared to CaNiGe. Mn-doping at the Ni site introduces magnetism to both the parent compound and the hydride. The measurement demonstrates that hydrogenation of CaNi(1-x)Mn(x)Ge reduces ferromagnetic ordering of Mn ions and induces huge magnetic hysteresis, whereas the spin glass state observed for the parent compound is preserved in the hydride. The hydrogenation-induced changes in the electric and magnetic properties are interpreted in terms of development of two-dimensionality in crystal structure as well as electronic state.     

Long-term observation of fluorescence of free single molecules to explore protein-folding energy landscapes

A method was developed to detect fluorescence intensity signals from single molecules diffusing freely in a capillary cell. A unique optical system based on a spherical mirror was designed to enable quantitative detection of the fluorescence intensity. Furthermore, "flow-and-stop" control of the sample can extend the observation time of single molecules to several seconds, which is more than 1000 times longer than the observation time available using a typical confocal method. We used this method to scrutinize the fluorescence time series of the labeled cytochrome c in the unfolded state. Time series analyses of the trajectories based on local equilibrium state analysis revealed dynamically differing substates on a millisecond time scale. This system presents a new avenue for experimental characterization of the protein-folding energy landscape.