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41.
Kittaka S Iwashita T Serizawa A Kranishi M Takahara S Kuroda Y Mori T Yamaguchi T 《The journal of physical chemistry. B》2005,109(49):23162-23169
The effect of confinement on the phase changes and dynamics of acetonitrile in mesoporous MCM-41 was studied by use of adsorption, FT-IR, DSC, and quasi-elastic neutron scattering (QENS) measurements. Acetonitrile molecules in a monolayer interact strongly with surface hydroxyls to be registered and perturb the triple bond in the C[triple bond]N group. Adsorbed molecules above the monolayer through to the central part of the cylindrical pores are capillary condensed molecules (cc-acetonitrile), but they do not show the hysteresis loop in adsorption-desorption isotherms, i.e., second order capillary condensation. FT-IR measurements indicated that the condensed phase is very similar to the bulk liquid. The cc-acetonitrile freezes at temperatures that depend on the pore size of the MCM-41 down to 29.1 A (C14), below which it is not frozen. In addition, phase changes between alpha-type and beta-type acetonitriles were observed below the melting points. Application of the Gibbs-Thomson equation, assuming the unfrozen layer thickness to be 0.7 nm, gave the interface free energy differences between the interfaces, i.e., Deltagamma(l/alpha) = 22.4 mJ m(-2) for the liquid/pore surface (ps) and alpha-type/ps, and Deltagamma(alpha/beta) = 3.17 mJ m(-2) for alpha-type/ps and beta-type/ps, respectively. QENS experiments substantiate the differing behaviors of monolayer acetonitrile and cc-acetonitrile. The monolayer acetonitrile molecules are anchored so as not to translate. The two Lorentzian analysis of QENS spectra for cc-acetonitriles showed translational motion but markedly slowed. However, the activation energy for cc-acetonitrile in MCM-41 (C18) is 7.0 kJ mol(-1) compared to the bulk value of 12.7 kJ mol(-1). The relaxation times for tumbling rotational diffusion of cc-acetonitrile are similar to bulk values. 相似文献
42.
Novel phosphonylation of the active Me group of pyridine derivatives is described.Reaction of 2 (and 4) -methylpyridine (3 and 5) with PCl5 in POCl3 gave 2 (and 4) -trichloromethylpyridine (4 and 6). Similarly, reaction of 4 (and 6) methyl-3-nitropyridine (7 and 9) afforded the corresponding trichloromethyl derivative (8 and 10). However, the similar reaction of 2-methyl-3-nitropyridine (11) gave dichloro-(3-nitro-2-pyridyl)-methylphosphonic dichloride (12).Mechanisms of the formation of these products are discussed. 相似文献
43.
Fluorous reverse-phase silica gel (FRPSG)-supported Lewis acids which have fluorous ligands acted as effective catalysts of Baeyer-Villiger and Diels-Alder reactions in water. Direct esterification of carboxylic acid with alcohol in organic media was also catalyzed. The FRPSG-supported Lewis acids could be recycled by simple filtration after the reaction. 相似文献
44.
Konarev DV Khasanov SS Otsuka A Yoshida Y Saito G 《Journal of the American Chemical Society》2002,124(26):7648-7649
The ionic multicomponent complex complex: ([Cr(I)(PhH)(2)].+))(2)[Co(II)TPP(C(60)(CN)(2))]-[C(60)(CN)(2)](.-).3(o-C(6)H(4)Cl(2)) (Co(II)TPP: cobalt (II) tetraphenylporphyrin; Cr(PhH)(2): bis(benzene)chromium; o-C(6)H(4)Cl(2): o-dichlorobenzene) containing CoTPP(C(60)(CN)(2)- anion and C(60)(CN)(2).- radical anion was obtained. The complex has the cage structure with channels, which accommodate Cr(I)(PhH)(2)(.+) and o-C(6)H(4)Cl(2) molecules. For the first time the sigma-bonding of Co(II)TPP to the fullerene radical anion with the essentially shortened Co.C(C(60)(CN)(2)) contact of 2.282 A is observed. The sigma-bonding results in the diamagnetism of Co(II)TPP(C(60)(CN)(2))(-) anion. The nonbonded C(60)(CN)(2)(.-) radical anion retains both the C(2)(v)symmetry and the shape of the molecule. The length of the C(triple bond)N bonds is 1.141 and 1.152 A. 相似文献
45.
Tachibana Y Otsuka K Terabe S Arai A Suzuki K Nakamura S 《Journal of chromatography. A》2003,1011(1-2):181-192
A robust and simple interface for microchip electrophoresis-mass spectrometry (MCE-MS) was developed using a spray nozzle connected to the exit of the separation channel of the microchip. The spray nozzle was attached to the microchip using a polyether ether ketone screw without adhesive, thus allowing easy replaced. Sample injection and electrophoretic separation was performed by control of the voltage only. The analysis of a few basic drugs was performed using the optimized MCE-MS system. The separation was improved by using a high-viscosity separation buffer and a spray nozzle with a small bore size. This system was also applied to the separation of peptides and protein-trypsin digests. Sample adsorption was minimized by adding acetonitrile to the separation buffer when using a quartz microchip. 相似文献
46.
Yokozawa T Ogawa M Sekino A Sugi R Yokoyama A 《Journal of the American Chemical Society》2002,124(51):15158-15159
Poly(p-benzamide) with a defined molecular weight and a low polydispersity and a block copolymer containing this well-defined aramide was synthesized. Phenyl 4-aminobenzoate, which would yield poly(p-benzamide), did not polymerize under the conditions of chain-growth polycondensation. However, phenyl 4-(4-octyloxybenzylamino)benzoate (1b) polymerized at room temperature in the presence of base and phenyl 4-nitrobenzoate (2) as an initiator in a chain-growth polycondensation manner to give well-defined aromatic polyamides having the 4-octyloxybenzyl groups as a protecting group on nitrogen in an amide. It was confirmed by a model reaction that deprotection of this protecting group proceeded completely with trifluoroacetic acid (TFA) without breaking the amide linkage. The utility of this approach to poly(p-benzamide) with a low polydispersity was demonstrated by the synthesis of block copolymers. Thus, phenyl 4-(octylamino)benzoate (1a) polymerized in the presence of 2 and base, followed by addition of 1b and base to the reaction mixture of the prepolymer to yield the block copolymer of 1a and 1b with a controlled molecular weight and a low polydispersity. The block copolymer was treated with TFA, resulting in a soluble block copolymer of poly(N-octyl-p-benzamide) and poly(p-benzamide). The SEM images of the supramolecular assemblies of the block copolymer showed mum-sized bundles and aggregates of flake structures. 相似文献
47.
We provide a classification method of weighing matrices based on a classification of self‐orthogonal codes. Using this method, we classify weighing matrices of orders up to 15 and order 17, by revising some known classification. In addition, we give a revised classification of weighing matrices of weight 5. A revised classification of ternary maximal self‐orthogonal codes of lengths 18 and 19 is also presented. © 2011 Wiley Periodicals, Inc. J Combin Designs 20:40–57, 2012 相似文献
48.
Yuka Yamazaki Akihiro Yokoyama Tsutomu Yokozawa 《Journal of polymer science. Part A, Polymer chemistry》2012,50(17):3648-3655
Well‐defined (AB)3 type star block copolymer consisting of aromatic polyether arms as the A segment and polystyrene (PSt) arms as the B segment was prepared using atom transfer radical polymerization (ATRP), chain‐growth condensation polymerization (CGCP), and click reaction. ATRP of styrene was carried out in the presence of 2,4,6‐tris(bromomethyl)mesitylene as a trifunctional initiator, and then the terminal bromines of the polymer were transformed to azide groups with NaN3. The azide groups were converted to 4‐fluorobenzophenone moieties as CGCP initiator units by click reaction. However, when CGCP was attempted, a small amount of unreacted initiator units remained. Therefore, the azide‐terminated PSt was then used for click reaction with alkyne‐terminated aromatic polyether, obtained by CGCP with an initiator bearing an acetylene unit. Excess alkyne‐terminated aromatic polyether was removed from the crude product by means of preparative high performance liquid chromatography (HPLC) to yield the (AB)3 type star block copolymer (Mn = 9910, Mw/Mn = 1.10). This star block copolymer, which contains aromatic polyether segments with low solubility in the shell unit, exhibited lower solubility than A2B or AB2 type miktoarm star copolymers. In addition, the obtained star block copolymer self‐assembled to form spherical aggregates in solution and plate‐like structures in film. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
49.
Dr. Yusaku Nomura Dr. Frédéric Thuaud Dr. Daisuke Sekine Prof. Dr. Akihiro Ito Satoko Maeda Dr. Hiroyuki Koshino Dr. Daisuke Hashizume Dr. Atsuya Muranaka Dr. Thomas Cruchter Prof. Dr. Masanobu Uchiyama Prof. Dr. Satoshi Ichikawa Prof. Dr. Akira Matsuda Prof. Dr. Minoru Yoshida Prof. Dr. Go Hirai Prof. Dr. Mikiko Sodeoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8387-8392
A synthetic methodology to access all possible stereoisomers of spectomycin A1 (SMA1) and A2 (SMA2) has been established through late-stage diversification. The key reaction for the construction of all four diastereomers is an intramolecular cyclization based on the umpolung of π-allyl palladium species with bis(pinacolato)diborane (B2(pin)2). Silyl group assisted direct benzylic oxidation of each isomer enabled construction of the fragile β-hydroxytetralone skeleton to provide the SMAs. The relative and absolute stereochemistry of SMA2 was also determined, and the absolute stereochemistry of SMA1 was extrapolated based on the optical rotation of SMA2. The axial chirality of SMAs is discussed based on circular dichroism spectra and DFT calculations, and it is concluded that the M isomer is predominant in solution. Biochemical assessment of all isomers in vitro revealed that the C9 hydroxyl group and dimeric structure were both important for protein SUMOylation-inhibitory activity. 相似文献
50.