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61.
Tomonari Wakabayashi Daisuke Kasuya Haruo Shiromaru Shinzo Suzuki Koichi Kikuchi Yohji Achiba 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,40(1):414-417
Systematic fractional change in the yield of various isomers of fullerenes was revealed to strongly depend on temperature of a buffer gas. A new kinetic consideration is proposed for understanding the observed temperature- and pressure-dependence of yield of fullerenes. The model consists of three competitive reactions in consideration of plausible behaviors of a precursor, (1) decomposition into smaller fragments, (2) isomerization leading to formation of a stable fullerene cage, and (3) growth into a larger carbon cluster. Arrhenius activation energy of formation of stable fullerenes was determined to be 0.8 eV for both C60 and C70, while a higher energy of 2.0?3.3 eV for seven different isomers of higher fullerenes ranging from C76 to C84. Correlation in the activation energy is noted for a series of higher fullerenes with different sizes, suggesting the existence of a specific precursor in their formation processes. 相似文献
62.
Hori R Furukawa D Yamamoto K Kutsumizu S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(24):7346-7350
Binary mixtures were prepared from an azobenzene derivative and a liquid-crystal (LC) compound that exhibits smectic?C (SmC) and bicontinuous cubic (Cub(bi)) LC phases. Reversible switching between the two phases in response to UV-light irradiation was observed. This light-driven SmC-to-Cub(bi) transition is the first example showing the increased dimensionality of molecular ordering with isomerization of azobenzenes (see figure). 相似文献
63.
Reaction pathway and stereoselectivity of asymmetric synthesis of chrysanthemate with the aratani C1-symmetric salicylaldimine-copper catalyst 总被引:2,自引:0,他引:2
The reaction pathway and the mechanism of asymmetric induction in the synthesis of (+)-trans-(1R,3R)-chrysanthemic acid methyl ester from methyl diazoacetate and 2,5-dimethyl-2,4-hexadiene in the presence of a C(1)-chiral salicylaldimine Cu(I) complex has been probed with the aid of hybrid density functional calculations. The key finding is that the alkoxycarbonyl carbene complex intermediate is intrinsically chiral and that the intramolecular hydrogen bonding in the carbene complex transmits the chirality information from the side chain to the carbene complex. Molecular orbital backgrounds of the structure of the carbene complex and the transition state of the cyclopropanation have been elucidated. 相似文献
64.
Cylindrospermopsin determination using 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid (HEPES) as the internal standard 总被引:1,自引:0,他引:1
Cylindrospermopsin (CYN) was determined by liquid chromatography/electrospray ionization-mass spectrometry (LC/ESI-MS) using 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid (HEPES) as the internal standard. In the selected ion monitoring of LC/ESI-MS, m/z 414 for CYN and 237 for HEPES were monitored using the negative mode; the retention times of CYN and HEPES were 12.41 and 14.21 min, respectively. CYN was determined from peak area ratios of m/z 414/237. By the treatment of an anion exchange cartridge using a buffer at pH 10.5, CYN was isolated and condensed. No interfering peak was observed. Linearity of this method was observed at the range of 0.10-31.12 ng. Total coefficients of variation were 5.1 and 2.9% at 104 and 1038 μg CYN L−1. The quantitative limit at a signal-to-noise (S/N) ratio of 10 was 0.16 ng.CYN concentration in natural waters is low. CYN in waters should be condensed for determination. This method including the treatment for isolation and condensation of CYN is useful for determination of CYN in environmental and/or drinking waters. 相似文献
65.
Morino K Watase N Maeda K Yashima E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(19):4703-4707
Poly[(4-carboxyphenyl)acetylene] (poly-1) exhibits an intense induced circular dichroism (ICD) in the UV-visible region upon complexation with excess (R)-1-(1-naphthyl)ethylamine ((R)-2), owing to the formation of a predominantly single-handed helical conformation of the polymer backbone. In the presence of a small amount of (R)-2, poly-1 showed a very weak ICD due to the lack of a single-handed helical conformation. However, we have found that the co-addition of the excess bulky, achiral 1-naphthylmethylamine (5) with a small amount of (R)-2 caused a dramatic increase in the ICD magnitude, comparable to the full ICD induced by excess (R)-2. This indicates that an almost single-handed helix can be induced on poly-1 upon complexation with a small amount of (R)-2 assisted by achiral 5. Furthermore, the induced single-handed helical poly-1 could be successfully memorized by the replacement of (R)-2 and 5 with achiral 2-aminoethanol or n-butylamine. 相似文献
66.
Interfacial property modulation of thermoresponsive polymer brush surfaces and their interaction with biomolecules 总被引:2,自引:0,他引:2
Nagase K Kobayashi J Kikuchi A Akiyama Y Kanazawa H Okano T 《Langmuir : the ACS journal of surfaces and colloids》2007,23(18):9409-9415
Dense poly(N-isopropylacrylamide) (PIPAAm) brushes were created on silica bead surfaces by surface-initiated atom transfer radical polymerization (ATRP). Interfacial properties of PIPAAm brushes were characterized by thermoresponisve interaction with biomolecules. The grafted amounts of PIPAAm on silica bead surfaces exceeded that from previously reported polymer-hydrogel-modified silica beads prepared by conventional radical polymerization by nearly 1 order of magnitude. Temperature-dependent chromatographic interactions with soluble analytes were modulated by changing the grafted PIPAAm chain lengths. Short PIPAAm-grafted silica beads produce insufficient dehydration and chain aggregation to separate steroids using weak hydrophobic interactions. In contrast, broad unresolved peaks were observed on silica beads column grafted with long PIPAAm chains due to steroid partitioning into thick, densely grafted PIPAAm brush layers. Thus, silica beads column grafted with PIPAAm chains of proper length can demonstrate baseline separation of steroids with relatively high resolution among the tested columns. Relatively longer retention times for steroid analytes were observed on all columns compared to those previously reported for other PIPAAm-grafted silica beads. This indicates that densely PIPAAm-grafted chains enable control of strong hydrophobic interactions with steroids by changing the column temperature. Densely grafted PIPAAm columns were also successful in separating two peptides into two peaks as the column temperature was increased to 40 degrees C. This provides an effective separation alternative for peptides using substantial hydrophobicity without modification of hydrophobic surfaces and/or low mobile phase pH. In conclusion, densely PIPAAm-grafted surfaces exhibit strong, reversible temperature-modulated hydrophobic interactions, facilitating baseline separations of steroids and peptides in aqueous milieu without changes in the mobile phase pH and high ionic strength. 相似文献
67.
Kikuchi H Saito Y Komiya J Takaya Y Honma S Nakahata N Ito A Oshima Y 《The Journal of organic chemistry》2001,66(21):6982-6987
We investigated the constituents of Dictyostelium discoideum to clarify the diversity of secondary metabolites of Dictyostelium cellular slime molds and to explore biologically active substances that could be useful in the development of novel drugs. From a methanol extract of the multicellular fruit body of D. discoideum, we isolated two novel amino sugar analogues, furanodictine A (1) and B (2). They are the first 3,6-anhydrosugars to be isolated from natural sources. Their relative structures were elucidated by spectral means, and the absolute configurations were confirmed by asymmetric syntheses of 1 and 2. These furanodictines potently induce neuronal differentiation of rat pheochromocytoma (PC-12) cells. 相似文献
68.
Five new monoterpene glycosides, ovatolactone 7-O-(6'-O-p-hydroxybenzoyl)-beta-D-glucopyranoside, ovatic acid methyl ester 7-O-(6'-O-p-hydroxybenzoyl)-beta-D-glucopyranoside, 7-O-p-hydroxybenzoylovatol 1-O-(6'-O-p-hydroxybenzoyl)-beta-D-glucopyranoside, 6'-O-p-hydroxybenzoylcatalposide and (2E,6R)-2,6-dimethyl-8-hydroxy-2-octenoic acid 8-O-[6'-O-(E)-p-coumaroyl]-beta-D-glucopyranoside were isolated from the fallen leaves of Catalpa ovata G. Don. Their structures were determined by extensive spectroscopic studies and syntheses. 相似文献
69.
The kainoid amino acids are biologically important compounds because they show remarkable neuroexcitatory and excitotoxic activities. For exhibiting potent activity, the stereochemical relationship of the substituents on the pyrrolidine ring is crucial. We found simple methods for determining the relative stereochemistry of these compounds on the basis of the (1)H NMR chemical shifts of H-2 and H-4 in D(2)O solution. The signals of H-2 appear at fields higher than 4.2 ppm when the compounds have 2,3-trans stereochemistry whereas, in the 2,3-cis compounds, they appear lower than 4.2 ppm, irrespective of the C-4 substituent. This criterion holds when the solution is in the range of pD 3-8. Moreover, when an epimeric pair at C-2 is available and the spectra are recorded at the same or nearly equal pD, the H-2 chemical shift of the 2,3-trans isomer is higher than that of the corresponding 2,3-cis isomer. Similarly, the relative stereochemistry between C-3 and C-4 can be determined from the chemical shift of H-4. The signals of H-4 of the 3,4-cis isomers appear at lower fields than those of the corresponding 3,4-trans isomers in each pair of C-4 epimers when the spectra are recorded at the same or nearly equal pD. This holds for the compounds bearing an unsaturated substituent at C-4. All these phenomena can be rationalized by the anisotropic effect of the pi-electron system in the C-2 and C-4 substituents. 相似文献
70.
Jun-Ichi Kikuchi Yukito Murakami 《Journal of inclusion phenomena and macrocyclic chemistry》1998,32(2-3):209-221
Steroid cyclophanes, bearing four bile acid moieties covalently placed on a tetraazaparacyclophane skeleton, were designed and synthesized as artificial cell-surface receptors. Guest-binding behavior of the steroid cyclophanes embedded in a bilayer membrane formed with a synthetic peptide lipid was clarified by means of fluorescence and circular dichroism spectroscopy. We found that the steroid cyclophane effectively bound aromatic guests in both bilayer membranes and aqueous solution. In addition, copper(II) ions acted as a guest species for the steroid cyclophane and a competitive inhibitor toward a NADH-dependent lactate dehydrogenase (LDH). On these grounds, we constituted a supramolecular assembly as an artificial signaling system in combination with the steroid cyclophane, a cationic peptide lipid, and LDH. As a consequence, the steroid cyclophane acted as an effective artificial cell-surface receptor being capable of transmitting an external signal to the enzyme in collaboration with copper(II) ions as a signal transmitter. 相似文献