Synthesis of the Polyketide (E)-Olefin of the Jamaicamides

The jamaicamides, isolated in Jamaica from the cyanobacterium Lyngbya majuscula, are new mixed polyketide-peptides that are known to be sodium channel blockers. The polyketide moiety contains an (E)-vinyl chloride, an undetermined methyl stereocenter (C9), and an (E)-olefin. Herein, we report the synthesis of the (E)-olefin moiety of the polyketide of the jamaicamides utilizing a Kocienski–Julia coupling.

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氟催化废弃硅基还原剂与CO2还原转化反应

CO2是最重要的可再生碳源之一.为了将CO2转化为有用的有机化合物,我们研究了二种模型硅基"废"材料—乙硅烷和硅粉的反应活性.在这些反应中,氟盐的催化活性最高,在常压、在质子源水和硅基还原剂的存在下,CO2可转化为甲酸.原位NMR和动力学分析表明,含氢硅烷和五配位的硅物种分别是反应中间物和活性物种.     

Iron content and temperature dependences of diffuse scattering in Ti–(50–x)Ni–xFe (6 ≤ x ≤ 10) alloys

Diffuse scatterings appearing in electron diffraction patterns of Ti–(50???x)Ni–xFe (x?=?6, 7, 8, 10, in at.%) alloys were investigated. In the alloys, martensitic (R-phase) transformation is suppressed down to 4.2 K, but the electrical resistivity exhibits a local minimum at T _min (210 K, 195 K, 180 K and 140 K for x?=?6, 7, 8, 10, respectively). The following results were obtained for all the alloys. Diffuse scattering appears below T _min and its intensity maximum is located at an incommensurate position of g?+??ζζ0?*, where g is a reciprocal lattice vector of the B2-phase. The value?ζ?at T _min is significantly smaller than 1/3 and increases with decreasing temperature; it decreases with increasing Fe content. The value of?ζ?at T _min agrees with the length of nesting vector obtained by a band calculation, suggesting that the diffuse scattering is caused by the nesting effect of the Fermi surface in the B2-type structure.     

Lanthanum(III) isopropoxide catalyzed chemoselective transesterification of dimethyl carbonate and methyl carbamates

A practical transesterification of less reactive dimethyl carbonate and much less reactive methyl carbamates with primary (1°), secondary (2°), and tertiary (3°) alcohols was established with the use of a lanthanum(III) complex, which was prepared in situ from lanthanum(III) isopropoxide (3 mol %) and 2-(2-methoxyethoxy)ethanol (6 mol %). In particular, corresponding carbonates and carbamates obtained were of synthetic utility from the viewpoint of the selective protection and/or deprotection of 1°-, 2°-, and 3°-alcohols.     

High-pressure synthesis and correlation between structure, magnetic, and dielectric properties in LiNbO(3)-type MnMO3 (M=Ti, Sn)

LiNbO(3)-type MnMO(3) (M = Ti, Sn) were synthesized under high pressure and temperature; their structures and magnetic, dielectric, and thermal properties were investigated; and their relationships were discussed. Optical second harmonic generation and synchrotron powder X-ray diffraction measurements revealed that both of the compounds possess a polar LiNbO(3)-type structure at room temperature. Weak ferromagnetism due to canted antiferromagnetic interaction was observed at 25 and 50 K for MnTiO(3) and MnSnO(3), respectively. Anomalies in the dielectric permittivity were observed at the weak ferromagnetic transition temperature for both the compounds, indicating the correlation between magnetic and dielectric properties. These results indicate that LiNbO(3)-type compounds with magnetic cations are new candidates for multiferroic materials.     

Strained and unstrained macrocycles composed of carbazole and butadiyne units: electronic state and optical properties

Cu(OAc)(2) catalyzes dehydrogenative condensation of 3,6-bis(2-ethynylphenyl)carbazole in the presence of O(2) to afford the cyclization product 1 and cyclodimer 2. Compound 1 contains bent carbazole and butadiyne groups, while 2 has a less strained structure with Z shape around the two parallel butadiyne groups. Optical properties of the compounds are discussed based on the electronic states estimated from electrochemical measurement and density functional theory calculation.     

Moments of a Single Entry of Circular Orthogonal Ensembles and Weingarten Calculus

Consider a symmetric unitary random matrix V = (v _ij )_{1 ≤ i, j ≤ N} from a circular orthogonal ensemble. In this paper, we study moments of a single entry v _ij . For a diagonal entry v _ii , we give the explicit values of the moments, and for an off-diagonal entry v _ij , we give leading and subleading terms in the asymptotic expansion with respect to a large matrix size N. Our technique is to apply the Weingarten calculus for a Haar-distributed unitary matrix.     

Fe2+ localized excitations in the random antiferromagnet with competing spin anisotropies, Fe(1−x)CoxBr2

The Fe²⁺ localized magnetic excitations observed in the Co-rich antiferromagnetic phase of the randomly mixed system with competing Ising and XY spin anisotropies, Fe(_1?x)Co_xBr₂ have been analyzed quantitatively. The calculated frequency-field diagram reproduces well the experiments. The expectation values of the Fe²⁺ spin components in the ground state are calculated. It is shown that even in the Co-rich antiferromagnetic phase Fe²⁺ spins make an angle with the c-plane of the crystal in which Co²⁺ spins are confined.     

Tritium level in Japanese diet and human tissue

Tritium concentrations are reported for diet and human tissue samples collected in the Akita district of northern Japan. Sixteen separate food group samples and a total diet sample were collected for Akita City during April and May 1987. Six samples of heart and nine samples of kidney tissue were collected from 10 decreased individuals in Akita Prefecture from January to July 1986. Five serum and four blood samples were also obtained in Akita Prefecture from December 1985 to June 1986. Free water³H concentration as well as tissue-bound³H were determined separately. Specific activity ratios of tissue-bound³H to free water³H in the samples were almost between 1.0 and 2.0 and were similar to our previous results for food samples and other tissue samples. The specific activity ratio was also found to be lower than that reported in the U.S.A. and significantly lower than in Europe.     

Syntheses of functional condensation polymer. I. Polyesters having pendant functional groups such as hydroxyl,formyl, aldoxime,aminomethyl and hydroxymethyl

Unsaturated polyesters having pendant functional groups such as hydroxyl, formyl, aldoxime, aminomethyl and hydroxymethyl, have been prepared and characterized, and some of their properties were investigated. Reaction conditions for the epoxidation of unsaturated polyesters and hydrolysis of the epoxy groups in the polyesters were established to control the amount of pendant diol groups. It was possible to incorporate up to 90 mole-% of formyl side groups into the unsaturated polyester by the hydroformylation with the rhodium catalyst. In addition, the formyl side groups of the modified polyester were converted into hydroxymethyl or aldoxime groups and were then converted to amino groups. The melting points of the modified polyesters decreased with increasing the pendant group content of the polyesters, as expected. Aliphatic polyesters having pendant hydroxyl or amino groups had a high affinity for moisture, which might be ascribed to the participation of the hydrophilic pendant groups in the modified polyesters.