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61.
Anderson MW Ohsuna T Sakamoto Y Liu Z Carlsson A Terasaki O 《Chemical communications (Cambridge, England)》2004,(8):907-916
This article describes a number of important recent microscopy tools and their application in particular to the study of porous inorganic materials. The authors believe that these new techniques are on the threshold of delivering enormous new power in the chemist's arsenal for understanding new and complex behaviour in multi-component, hierarchical or composite materials. In particular we consider the contribution of electron crystallography, three-dimensional electron tomography, ultra-high resolution scanning electron microscopy as well as the combined application of high-resolution electron microscopy and atomic force microscopy to the study of surfaces and crystal growth. Much of this work has taken on a particular significance owing to the ground breaking work of scientists at Mobil and in Japan 10 years ago in the successful synthesis of materials with porosity on many length scales achieved through the cooperative self-assembly between inorganic and organic phases. This resulted in a series of materials known as M41S of which MCM-41 and MCM-48 were two of the first and most important structures to be synthesised. This has led to a wealth of new porous structures with order over many length scales and has presented new problems in characterisation. Microscopy methods properly executed are particularly important in the study of this new class of material. 相似文献
62.
The ion-pair extraction equilibria of dibenzo-18-crown-6 (DB18C6) complexes of Na+, K+, Rb+ and Cs+ (M+) with picrate ion (Pic−) into 1,2-dichloroethane (1,2-DCE) have been studied at 25.0°C. In the case of the Rb+ and Cs+ systems, the extraction results were interpreted by taking into consideration the formation of a (DB18C6)2 -M+ complex in 1,2-DCE. The thermodynamic constants of extraction,
, and ion-pair formation in 1,2-DCE,
, of ion pairs of the DB18C6-M+ complexes with Pic− were determined. By using the distribution coefficient of M+·Pic− the thermodynamic formation constants of the DB18C6-M+ complexes in 1,2-DCE,
, were evaluated. Consequently the component equilibrium constants of the ion-pair extraction were completely determined and a contribution of these constants to the difference of
value was discussed. The
value in 1,2-DCE is quite high compared with that in solvating solvents and log
decreases linearly with increasing Gutmann donor number of solvents. 相似文献
63.
Sakamoto S Ito A Kudo K Yoshikawa S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3717-3726
The introduction of a flavin chromophore on the myoglobin (Mb) surface and an effective electron-transfer (ET) reaction through the flavin were successfully achieved by utilizing the self-assembly of heterostranded coiled-coil peptides. We have prepared a semiartificial Mb, named Mb-1alphaK, in which an amphiphilic and cationic alpha-helix peptide is conjugated at the heme propionate (Heme-1alphaK). Heme-1alphaK has a covalently bound iron-protoporphyrin IX (heme) at the N terminus of a 1alphaK peptide sequence. This sequence was designed to form a heterostranded coiled-coil in the presence of a counterpart amphiphilic and anionic 1alphaE peptide sequence in a parallel orientation. Two peptides, Fla(1)-1alphaE and Fla(31)-1alphaE, both incorporating a 10-methylisoalloxazine moiety as an artificial flavin molecule, were also prepared (Fla=2-[7-(10-methyl)isoalloxazinyl]-2-oxoethyl). Heme-1alphaK was successfully inserted into apomyoglobin to give Mb-1alphaK. Mb-1alphaK recognized the flavin-modified peptides and a two-alpha-helix structure was formed. In addition, an efficient ET from reduced nicotinamide adenine dinucleotide to the heme center through the flavin unit was observed. The ET rate was faster in the presence of Fla(1)-1alphaE than in the presence of Fla(31)-1alphaE or the equivalent molecule that has no peptide chain. These results demonstrate that the introduction of a functional chromophore on the Mb surface can be achieved by using specific peptide-peptide interactions. Moreover, the dependence of the ET rate on the position of the flavin indicated that the distance between the heme active site and the flavin chromophore was regulated by the three-dimensional structure of the designed polypeptide. 相似文献
64.
Takiue T Hirose D Murakami D Sakamoto H Matsubara H Aratono M 《The journal of physical chemistry. B》2005,109(34):16429-16434
The interfacial tension gamma of the hexane solution of 1H,1H-perfluorononanol (FDFC(9)OH) and its omega-hydrogenated analogue, 1H,1H,9H-perfluorononanol (HDFC(9)OH), against water was measured as a function of pressure and concentration at 298.15 K in order to clarify the effect of omega-dipole on the orientation of fluorononanol molecules from the viewpoint of volume. The adsorbed films of both alcohols exhibit two kinds of phase transitions among three different states: the gaseous, expanded, and condensed states. The partial molar volume changes of adsorption - in the expanded and condensed states were evaluated and compared between the two systems. The - values of both alcohols are negative, and thus the alcohol molecules have smaller volume in the adsorbed film than in the bulk solution. Furthermore, the value was obtained through the evaluation of by the density measurement of the bulk hexane solution. It was found that the value of HDFC(9)OH is smaller than that of FDFC(9)OH in the condensed state. On the basis of three matters concerning the molecular structure of alcohols, the occupied area at the interface, and the orientation of FDFC(9)OH in the adsorbed film deduced from the earlier results of X-ray reflectivity measurement, the mean tilt angle of HDFC(9)OH from the interface normal in the condensed film was estimated to be 15 degrees . The thermodynamic estimation demonstrated here is highly valuable one to provide structure information on an adsorbed film. 相似文献
65.
Shingo KomatsuYouichi Sakamoto Toshiyasu Suzuki Shizuo Tokito 《Journal of solid state chemistry》2002,168(2):470-473
Perfluoro-1,3,5-tris(p-quaterphenyl)benzene (PF-13Y) and perfluoro-1,3,5-tris(p-quinquephenyl)benzene (PF-16Y) have been synthesized and characterized. They showed higher glass transition temperatures compared with perfluoro-1,3,5-tris(p-terphenyl)benzene (PF-10Y). Organic light-emitting diodes were fabricated using these materials as the electron-transport layers. PF-13Y and -16Y are better electron transporters than PF-10Y. The electron mobilities of PF-10Y and Alq3 were measured by the time-of-flight technique. PF-10Y showed higher electron mobilities (10−4 cm2/V s) and weaker electric field dependence compared with Alq3. 相似文献
66.
67.
Kobayashi K Ishii K Sakamoto S Shirasaka T Yamaguchi K 《Journal of the American Chemical Society》2003,125(35):10615-10624
The guest- or solvent-induced assembly of a tetracarboxyl-cavitand 1 and a tetra(3-pyridyl)-cavitand 2 into a heterodimeric capsule 1.2 in a rim-to-rim fashion via four intermolecular CO(2)H.N hydrogen bonds has been investigated both in solution and in the solid state. In the (1)H NMR study, a 1:1 mixture of1a and 2a (R = (CH(2))(6)CH(3)) in CDCl(3) gave a mixture of various complicated aggregates, whereas this mixture in CDCl(2)CDCl(2) or p-xylene-d(10) exclusively produced the heterodimeric capsule 1a.2a. It was found that an appropriate 1,4-disubstituted-benzene is a suitable guest for inducing the exclusive formation of 1a.2a in CDCl(3). The ability of a guest to induce the formation of guest-encapsulating heterodimeric capsule, guest@(1a.2a), increased in the order p-ethyltoluene < 1-ethyl-4-methoxybenzene < or = 1-ethyl-4-iodobenzene < or = 1,4-dibromobenzene < 1-iodo-4-methoxybenzene < or= 1,4-dimethoxybenzene < or = 1,4-diiodobenzene. The (1)H NMR study revealed that a CH-halogen interaction between the inner protons of the methylene-bridge rims (-O-H(out)CH(in)-O-) of the 1a and 2a units and the halogen atoms of 1,4-dihalobenzenes and a CH-pi interaction between the methoxy protons of 1,4-dimethoxybenzene and the aromatic cavities of the 1a and 2a units play important roles in the formation of 1,4-dihalobenzene@(1a.2a) and 1,4-dimethoxybenzene@(1a.2a), respectively. A preliminary single-crystal X-ray diffraction analysis of guest@(1b.2b) (R = (CH(2))(2)Ph; guest = 1-iodo-4-methoxybenzene or p-xylene) confirmed that the guest encapsulated in 1b.2b is oriented with the long axis of the guest along the long axis of 1b.2b and that the iodo and the methoxy groups of the encapsulated 1-iodo-4-methoxybenzene are specifically oriented with respect to the cavities of the 2b and 1b units, respectively. 相似文献
68.
Porous polymer spherical particles for column packings in nonaqueous size-exclusion chromatography (SEC) were prepared from 1,2-syndiotactic polybutadiene by suspension and evaporation method. The polymer microbeads obtained were crosslinked by radical reaction between 2-vinyl groups in polybutadiene with ultraviolet radiation, to render them insoluble. These microbeads have wider chromatographic separation width than polystyrene column packings. In addition, the polybutadiene microbeads did not show the excessive retention observed with commercial polystyrene columns for polycyclic aromatic compounds. Therefore, a close correlation between the elution volume and M, for polycyclic aromatic compounds was observed with polybutadiene microbeads columns. 相似文献
69.
Nakatani K Hagihara S Sando S Sakamoto S Yamaguchi K Maesawa C Saito I 《Journal of the American Chemical Society》2003,125(3):662-666
The binding of a dimeric form of the 2-amino-1,8-naphthyridine derivative (naphthyridine dimer) to a human telomeric sequence, TTAGGG, was investigated by UV melting, CD spectra, and CSI-MS measurements. Both the 9-mer d(TTAGGGTTA) and the 15-mer d(TTAGGGTTAGGGTTA) showed apparent melting temperatures (T(m)) of 45.6 and 63.6 degrees C, respectively, in the presence of naphthyridine dimer (30 microM) in sodium cacodylate buffer (50 mM, pH 7.0) containing 100 mM NaCl. The CD spectra at 235 and 255 nm of the 9-mer increased in intensity accompanied with strong induced CDs at 285 and 340 nm upon complex formation with naphthyridine dimer. UV titration of the binding of naphthyridine dimer to the 9-mer at 320 nm showed a hypochromism of the spectra. A Scatchard plot of the data showed the presence of multiple binding sites with different association constants. Cold spray ionization mass spectrometry of the complex between naphthyridine dimer and the 9-mer clearly showed that one to three molecules of the ligand bound to the dimer duplex of the 9-mer. Telomeric repeat elongation assay showed that the binding of naphthyridine dimer to the telomeric sequence inhibits the elongation of the sequence by telomerase. 相似文献
70.
Junzo Otera Masaki Kishi Koichi Kanehira Shigeaki Suzuki Manzo Shiono Yoshiji Fujita 《合成通讯》2013,43(4):347-352
A sequence of ene-type chlorination, palladium catalyzed dehydrochlorination, and the intramolecular Diels-Alder reaction afforded a new method for conversion of prenyl derivatives into bicyclic compounds. 相似文献