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131.
Kinumi T Goto M Eyama S Kato M Kasama T Takatsu A 《Analytical and bioanalytical chemistry》2012,404(1):13-21
A certified reference material (CRM) is a higher-order calibration material used to enable a traceable analysis. This paper describes the development of a C-peptide CRM (NMIJ CRM 6901-a) by the National Metrology Institute of Japan using two independent methods for amino acid analysis based on isotope-dilution mass spectrometry. C-peptide is a 31-mer peptide that is utilized for the evaluation of β-cell function in the pancreas in clinical testing. This CRM is a lyophilized synthetic peptide having the human C-peptide sequence, and contains deamidated and pyroglutamylated forms of C-peptide. By adding water (1.00 ± 0.01) g into the vial containing the CRM, the C-peptide solution in 10 mM phosphate buffer saline (pH 6.6) is reconstituted. We assigned two certified values that represent the concentrations of total C-peptide (mixture of C-peptide, deamidated C-peptide, and pyroglutamylated C-peptide) and C-peptide. The certified concentration of total C-peptide was determined by two amino acid analyses using pre-column derivatization liquid chromatography-mass spectrometry and hydrophilic chromatography-mass spectrometry following acid hydrolysis. The certified concentration of C-peptide was determined by multiplying the concentration of total C-peptide by the ratio of the relative area of C-peptide to that of the total C-peptide measured by liquid chromatography. The certified value of C-peptide (80.7 ± 5.0) mg/L represents the concentration of the specific entity of C-peptide; on the other hand, the certified value of total C-peptide, (81.7 ± 5.1) mg/L can be used for analyses that does not differentiate deamidated and pyroglutamylated C-peptide from C-peptide itself, such as amino acid analyses and immunochemical assays. 相似文献
132.
Kouichi Ohe Tomomi Yokoi Koji Miki Fumiaki Nishino Sakae Uemura 《Journal of the American Chemical Society》2002,124(4):526-527
The reaction of cis vicinal acetylethynylcyclopropanes 1 with a catalytic amount of M(CO)5(THF) (M = Cr or W) in the presence of Et3N at room temperature gave ortho-substituted phenols 7 in good yields as valence isomerized products. In the absence of Et3N the reactions did not work at all. The reaction of a cyclopropane having an ester or an amide instead of an acetyl moiety with M(CO)5(THF) did not take place, whereas an ethynylvinylcyclopropane gave a mixture of 1- and 2-substituted 1,3,5-cycloheptatrienes. These valence isomerization reactions are assumed to proceed via the formation of vinylidene-metal intermediates 2 from terminal alkynyl moieties followed by [3,3]sigmatropy of 2 to give seven-membered carbene complexes 3. 相似文献
133.
Axially chiral benzamides and anilides were prepared by enantiotopic lithiation at the distinguished benzylic methyl of prochiral tricarbonylchromium complexes of N,N-diethyl 2,6-dimethylbenzamide (1) and N-methyl-N-acyl 2,6-dimethylaniline (14 and 21) with a chiral lithium amide base followed by electrophilic substitution in good yields with high optical purity. The resulting axially chiral chromium-complexed benzamides and anilides were oxidized under air to give chromium-free axially chiral benzamides and anilides in an enantiomerically active form without axial bond rotation at room temperature. 相似文献
134.
The complete structure of palytoxin (1) was elucidated by us in 1982.1 Our continuous interests in palytoxin led us to examine minor constituents of Okinawan Palythoa tuberculosa. In this paper, we describe successful isolation and structural elucidation of four minor toxins, which were named homopalytoxin (2), bishomopalytoxin (3), neopalytoxin (4) and deoxypalytoxin (5). 相似文献
135.
Akio Toshimitsu Toshiaki Aoai Hiroto Owada Sakae Uemura Masaya Okano 《Tetrahedron》1985,41(22):5301-5306
The reaction of phenylselenenyl chloride with olefins in aqueous acetonitrile affords β-hydroxyalkyl phenyl selenides in excellent yields, providing the most convenient method for hydroxyselenation of olefins so far reported. When the reaction was applied to conjugated dienes, monohydroxyselenated products were obtained in good to excellent yields. From non-conjugated dienes, on the other hand, cyclic ethers containing two phenylseleno groups were produced in good to excellent yields, the first step of this reaction being the hydroxyselenation of one double bond. 相似文献
136.
Nanami Uemura Tsubasa Kobayashi Shintaro Yoshida Ya-xin Li Karel Goossens Xiangbing Zeng Go Watanabe Takahiro Ichikawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(22):8523-8528
We report a new molecular-design principle for creating double-gyroid nanostructured molecular assemblies based on atropisomerization. Ionic amphiphiles containing two imidazolium rings close to each other were designed and synthesized. NMR data revealed that the rotation of the imidazolium rings is restricted, with an activation energy as high as 63 kJ mol−1 in DMSO-d6 solution (DFT prediction for a model compound in the vacuum: 90–100 kJ mol−1). Due to the restricted rotation, the amphiphiles feature “double” atropisomeric axes in their ionic segments and form three stable atropisomers: meso, R, and S. These isomers co-organize into -type bicontinuous cubic liquid-crystalline mesophases through nanosegregation of the ionic and non-ionic parts. Considering the intrinsic characteristic of -type bicontinuous cubic structures that they are composed of intertwined right- and left-handed single gyroids, we propose that the simultaneous presence of both R- and S-atropisomers is an important contributor to the formation of double-gyroid structures. 相似文献
137.
G.M. Luke K. Kojima M. Larkin J. Merrin B. Nachumi Y.J. Uemura G.M. Kalvius A. Brückl K. Neumaier K. Andres G. Nakamoto M. Sirasi H. Tanaka T. Takabatake H. Fujii M. Ishikawa 《Hyperfine Interactions》1997,104(1-4):199-203
We present zero and longitudinal field μ SR measurements of single crystal and polycrystalline specimens of the heavy fermion
compound CePt2Sn2. Above 1 K the behaviour of the two samples is indistinguishable; the muon 1/T_1 increases with decreasing temperature until
25 K when it plateaus. The 1/T_1 relaxation rate differs strongly for the two cases below \sim\,0.8\ K. At 0.1 K a rate of
about 20 μ s-1 is seen in the polycrystal while in the single crystal it is only about 5 μ s-1. Even more revealing is the fact that longitudinal field decoupling spectra at very low temperatures demonstrate an essentially
static spin system to be present in the polycrystalline material while the single crystal shows definite dynamic spin properties.
We conclude that, in the presence of the distortion, long range magnetic order occurs below 0.9 K while in tetragonal symmetry
long range order is suppressed (probably due to frustration) and spin fluctuations remain for T\rightarrow0.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
138.
B. Nachumi A. Keren K. Kojima M. Larkin G.M. Luke J. Merrin O. Tchernyshöv W.D. Wu Y.J. Uemura Y. Fukuzumi K. Mizuhashi K. Takenaka S. Uchida 《Hyperfine Interactions》1997,105(1-4):125-130
We report the muon spin rotation experiments on Zn substituted La1-x Srx CuO4, for four zinc concentrations y=0.0,0.0025,0.005,0.01, at strontium concentrations x=0.15,0.20. We find that T_ c in the
optimally doped (x=0.15) and overdoped (x=0.20) 2:1:4 decreases linearly with increasing zinc concentration. Plotted against
the planar zinc concentration, the Tc’s of both series seem to fall on the same line. The superconducting carrier density/effective mass ratio, n_ s/m*, at first decreases linearly, rising above this line for higher zinc concentrations. This behavior may result from the localization
of carriers in an area \xiab around each zinc atom.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
139.
M. Mekata T. Asano H. Nakamura M. Shiga K. Kojima G.M. Luke A. Keren W.D. Wu Y.J. Uemura S. Dunsinger M. Gingras 《Hyperfine Interactions》1997,104(1-4):337-342
The relaxation rate of muon polarization of Y0.97Sc0.03Mn2 with a magnetic lattice composed of corner‐shared tetrahedrons shows a broad peak around 2.5 K indicating a random spin freezing
at low temperatures. The substitution by nonmagnetic Al atoms for 10% Mn atoms raises the spin freezing temperature to 45
K. The present work shows clearly that due to the strong geometrical frustration, the ground state of the system is singlet
tetrahedrons mixed with frozen paramagnetic tetrahedrons.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
140.
S.R. Dunsiger R.F. Kiefl K.H. Chow B.D. Gaulin M.J.P. Gingras J.E. Greedan A. Keren K. Kojima G.M. Luke W.A. MacFarlane N.P. Raju J.E. Sonier Y.J. Uemura W.D. Wu 《Hyperfine Interactions》1997,104(1-4):275-280
In a system where magnetic ions occupy the vertices of edge or corner sharing triangular units, the natural antiferromagnetic
coupling between ions is geometrically frustrated. A wide variety of interesting magnetic behaviour has been observed in pyrochlores,
where magnetic ions form a network of corner sharing tetrahedra. The low temperature spin dynamics of a number of pyrochlores
A2B2O7 have been investigated using the technique of μ SR. For example, Y2Mo2O7 shows a transition to a disordered magnetic state similar to a spin glass at TF=22 K. However, unlike conventional metallic spin glasses, a non‐zero muon spin depolarization rate is observed to persist
well below 0.1\ TF. These results suggest that there is a finite density of states for magnetic excitations in this system near zero energy.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献