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11.
Heterogeneous structure of silk fibers from Bombyx mori resolved by 13C solid-state NMR spectroscopy
Asakura T Yao J Yamane T Umemura K Ulrich AS 《Journal of the American Chemical Society》2002,124(30):8794-8795
The molecular conformation of silk fibrion is characterized by solid-state 13C NMR before spinning (silk I structure) and after spinning (silk II structure). We compare native silk fibers with the quasi-crystalline Cp-fraction and a synthetic model peptide (Ala-Gly)15, both of which can be converted either into silk I by dialysis from 9 M LiBr or into silk II by treatment with formic acid. Our results demonstrate that silk II fibers are intrinsically heterogeneous, consisting of beta-sheets, distorted beta-turns, and distorted beta-sheets. This higher-order heterogeneity is revealed by the 13C-NMR Cbeta-peak of Ala, indicating that the Ala side chains are stacked partially in parallel and partially face-to-face, at a ratio of 1:2. 相似文献
12.
Kajihara M Sugie T Sano A Fujioka K Urabe Y Tanihara M Imanishi Y 《Chemical & pharmaceutical bulletin》2003,51(1):11-14
Silicone has been utilized as a carrier material for sustained release system of lipophilic drugs. Extensive studies revealed that drug release rate is influenced by factors such as physicochemical properties of the drug and additives.(1-5)) When a lipophilic drug is highly potent at low concentrations, the drug release rate should be strictly controlled so as to avoid side effects. In this study, using vitamin D(3) (VD(3)) as an example of such drugs, we investigated novel method to suppress initial burst and to modify drug release rate from silicone matrix. As a result, it was found that (a). addition of human serum albumin (HSA) suppressed initial burst and enhanced release rate in the later stage, resulting constant release of VD(3), (b). covering a matrix formulation with a membrane of low diffusivity (core-rod formulation) suppressed initial burst and released drug in a constant rate, and (3) using materials for which the drug has high affinity as dissolution solvent (reservoir formulation), the drug release rate was reduced. 相似文献
13.
Double-walled carbon nanotubes (DWNTs) have been synthesized by catalytic chemical vapor deposition (CCVD) over supported metal catalysts decomposed from Fe(CH3COO)2 and Co(CH3COO)2 on mesoporous silica. Bundles of tubes with relatively high percentage of DWNTs, in areas where tubular layered structures could be clearly resolved, have been observed by transmission electron microscopy (TEM). In other areas, crystal-like alignment of very uniform DWNTs was observed for the first time, suggesting that mesoporous silica might play a templating role in guiding the initial nanotube growth. In addition, compatible with nano-electronics research, bridging of catalytic islands by DWNTs has also been demonstrated. 相似文献
14.
Yusuke Kaminaga Takahiro Yamada Hisanori Yamane 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(7):i57-i58
A new quaternary oxide, calcium yttrium stannate, Ca0.8Y2.4Sn0.8O6, is isostructural with Mg3TeO6 (trigonal, R). The empirical formula can be expressed as (Ca0.2667Y0.7333)6(Y0.4Sn0.6)SnO12. The Ca/Y site has a distorted coordination octahedron of O atoms, with Ca/Y—O distances ranging from 2.227 (3) to 2.350 (3) Å, while the octahedra of O atoms that coordinate to the Sn and Y/Sn sites are nearly regular, with an Sn—O distance of 2.066 (2) Å and a Y/Sn—O distance of 2.147 (3) Å. 相似文献
15.
Masayuki Yamane 《Journal of Sol-Gel Science and Technology》1997,8(1-3):483-487
A thick silica gel film, corresponding to the glass film of 10–20 micron in thickness, has been formed at the interface between
two immiscible liquids, hexane and water, using E-40, a partially polymerized silicon alkoxide, as the precursor. The film
formation was possible using both acid- and base-catalyzed water, but was greatly dependent on the type of catalyst. Only
the trace of a film was observed for the system catalyzed with a strong electrolyte such as HCl, HNO3 or NaOH, while a gel film, corresponding to the glass film of several to 10 micron in thickness was formed with a weak electrolyte
such as ammonia, organic acid like acetic acid, citric acid, etc., of similar pH value. The direct introduction of organic
base catalyst like triethylamine in hexane was much more effective than the use of ammonia water, suggesting that the polymerization
of E-40 to form a gel film takes place in the organic phase, where water molecules, as well as undissociated ammonia or organic
acids, can diffuse in. 相似文献
16.
A sensitive and rapid method is presented for the determination of vanadium at ng to sub-ng ml(-1) levels in natural waters, in which in-line preconcentration/separation is directly coupled with catalytic detection of vanadium in a flow-injection system. Vanadium was adsorbed on a small column packed with Sephadex G-25 gel and desorbed with a small volume of 0.010 M HCl. The catalytic action of vanadium on the oxidation of chromotropic acid (1,8-dihydroxy-3,6-naphthalenedisulphonic acid) by bromate in pH 3.8 buffered media was used in the sensitive determination of vanadium. Effective preconcentration/separation of trace vanadium can be achieved from Fe(III), Cu(II) and a large excess of sodium chloride in seawater sample. A linear calibration using a 5 m sample loop was obtained for vanadium in the range 0-2.5 ng ml(-1). The limit of detection was 0.02 ng ml(-1) and the relative standard deviation was 1.2% for 1.0 ng ml(-1) vanadium (n=5). The present FIA system is rapid and sensitive and can be readily applied to river water and coastal seawater samples. 相似文献
17.
A method for synthesizing substituted quinolines using ruthenium-catalyzed ring-closing metathesis as a key step has been developed. Substituted 1,2-dihydroquinolines, 4-silyloxy-1,2-dihydroquinoline and 4-methoxy-1,2-dihydroquinoline, were successfully synthesized in excellent yields via ene-ene metathesis and silyl or alkyl enol ether-ene metathesis, respectively. The synthetic intermediates of the antimalarial agents quinine, chloroquine, and PPMP-quinine hybrid were efficiently synthesized by this methodology. 相似文献
18.
Kimura T Yoshino M Yamane T Yamato M Tobita M 《Langmuir : the ACS journal of surfaces and colloids》2004,20(14):5669-5672
A diamagnetic particle with magnetic susceptibilities chi3 < chi2 = chi1 < 0 was subjected to a rotating magnetic field to obtain an alignment of the chi3 axis (the smallest susceptibility axis) in the direction perpendicular to the plane of the rotating magnetic field. A polymer short fiber, whose fiber axis coincides with the chi3 axis, was suspended in a fluid with the same density, and then a rotating magnetic field generated by a rotation of a pair of permanent magnets was applied. The fiber axis, rotating following the applied field, finally ended up with an alignment perpendicular to the plane of the rotating magnetic field. The experimental data on the time course of the alignment was in good agreement with the numerical calculation based on the equation of rotation. 相似文献
19.
Muranaka A Okuda M Kobayashi N Somers K Ceulemans A 《Journal of the American Chemical Society》2004,126(14):4596-4604
Oxo-titanium phthalocyanine (TiOPc) derivatives of catechin and hematoxylin (natural ortho-diol type chiral compounds) have been prepared and characterized by spectral and chromatographic techniques. It is demonstrated that the TiOPc unit is an excellent template for chiral recognition through its isolated Q-transitions. The formation of a helical dimeric complex with hematoxylin induces strong CD-activity in the Q-band region. Ab initio geometry optimizations were combined with a Kuhn-Kirkwood coupled-oscillator mechanism to obtain the absolute configuration of hematoxylin. In addition, it is shown that the described chiroptical recognition method is sensitive to slight conformational changes. 相似文献
20.
Angle-resolved photoelectron spectra were measured for a single-domain monolayer film of naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA) prepared on a cleaved GeS(0 0 1) surface using synchrotron radiation. The observed photoelectron angular distributions were analyzed by a calculation using the single-scattering approximation combined with molecular orbital calculation. With the help of the low-energy electron diffraction pattern, the structure of the NTCDA monolayer on GeS(0 0 1) was estimated quantitatively. 相似文献