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101.
Miyoko Kamigauchi Yuko Noda Kinuko Iwasa Zjujiro Nishijo Thoshimasa Ishida Yasuko In 《Helvetica chimica acta》1995,78(1):80-86
The crystal structure of (±)-7,8,13β,14α-tetrahydro-N7-(13C)methylcorysaminium iodide (13C- 3a ·I) was investigated by X-ray analysis and thus the relative configuration (7S*,13S*,14S*) established (Fig. 1). The conformation of 3a was shown to have a cis-junction of the B/C rings and the rings A and D in an antiperiplanar position relative to the C(13)? C(14) bond (‘anti-cis’), a twisted half-chair for ring B, and a half-chair for ring C (Figs. 2 and 3). Conformation analysis by 1H-NMR data indicated that the crystal conformation of 3a is also the preferred one in MeOH solution. 相似文献
102.
Okamoto Y Masum SM Miyazawa H Yamazaki M 《Langmuir : the ACS journal of surfaces and colloids》2008,24(7):3400-3406
Cubic biomembranes, nonbilayer membranes with connections in three-dimensional space that have a cubic symmetry, have been observed in various cells. Interconversion between the bilayer liquid-crystalline (L(alpha)) phase and cubic phases attracted much attention in terms of both biological and physicochemical aspects. Herein we report the pH effect on the phase and structure of dioleoylphosphatidylserine (DOPS)/monoolein (MO) membranes under a physiological ion concentration condition, which was revealed by small-angle X-ray scattering (SAXS) measurement. At neutral pH, DOPS/MO membranes containing high concentrations of DOPS were in the L(alpha) phase. First, the pH effect on the phase and structure of the multilamellar vesicles (MLVs) of the DOPS/MO membranes preformed at neutral pH was investigated by adding various low-pH buffers into the MLV suspension. For 20%-DOPS/80%-MO MLVs, at and below pH 2.9, a transition from the L(alpha) to cubic (Q(224)) phase occurred within 1 h. This phase transition was reversible; a subsequent increase in pH to a neutral one in the membrane suspension transformed the cubic phase into the original L(alpha) phase. Second, we found that a decrease in pH transformed large unilamellar vesicles of DOPS/MO membranes into the cubic phase under similar conditions. We have proposed the mechanism of the low-pH-induced phase transition and also made a quantitative analysis on the critical pH of the phase transition. This finding is the first demonstration that a change in pH can induce a reversible phase transition between the L(alpha) and cubic phases of lipid membranes within 1 h. 相似文献
103.
104.
Dr. Akihito Konishi Koki Horii Haruna Iwasa Yui Okada Dr. Ryohei Kishi Prof. Dr. Masayoshi Nakano Prof. Dr. Makoto Yasuda 《化学:亚洲杂志》2021,16(12):1553-1561
The singlet open-shell character and antiaromaticity are intriguing features in π-conjugated carbocycles. These two exhibit similar chemical and physical properties. However, they rarely coexist in the same molecule. Understanding the interrelation between the open-shell and antiaromatic characteristics in the same molecule is crucial to control the electronic properties. Herein we describe the synthesis and characterization of a new member of diareno[a,f]pentalene, benzo[a]naphtho[2,3-f]pentalene 6 . Unlike its isomer 5 with a closed-shell ground state, 6 exhibits an appreciable open-shell character and a moderate antiaromatic feature. The behaviors of the open-shell index (y0) against the difference of the proton chemical signal (Δδ(H1)) between pentalenide dianions/neutral pentalenes for our reported pentalenes 1 , 4 , 5 , and 6 give a thought-provoking conclusion about the interrelation between open-shell and antiaromatic characteristics in this series. The mode of the incorporated quinoidal moiety and the formal molecular symmetry are critical to balance these two characteristics. 相似文献
105.
With the application of machine learning to large-material data sets, models are being developed that allow us to better predict novel materials with designed properties. Advances in artificial intelligence and its subclasses, as well as compute infrastructure, are making it possible to rapidly compute material properties, to access time/length scales and chemical spaces beyond the current capabilities of density functional theory and to outperform humans in interpretation and characterization of the data. This review highlights the latest developments in the field with special interest to energy storage materials. 相似文献
106.
Shibatomi K Soga Y Narayama A Fujisawa I Iwasa S 《Journal of the American Chemical Society》2012,134(24):9836-9839
Highly enantioselective chlorination of β-oxo esters and subsequent stereospecific substitution of tertiary chlorides are described. Enantioselective chlorination of β-keto esters and malonates was performed using a chiral Lewis acid catalyst prepared from Cu(OTf)(2) and the newly developed spirooxazoline ligand 2 to yield the desired α-chlorinated products with high enantioselectivity (up to 98% ee). Nucleophilic substitution of the resulting chlorides proceeded smoothly to afford a variety of chiral molecules such as α-amino, α-alkylthio, and α-fluoro esters, without loss of enantiopurity. The results of X-ray crystallographic analysis proved that Walden inversion occurs at the chlorinated tertiary carbon center. These results supported the fact that the substitution proceeds via an S(N)2 mechanism. 相似文献
107.
Chanthamath S Phomkeona K Shibatomi K Iwasa S 《Chemical communications (Cambridge, England)》2012,48(62):7750-7752
The Ru(II)-Pheox complex is an efficient catalyst for the intermolecular cyclopropanation of various terminal olefins with succinimidyl diazoacetate. This catalytic system can perform under mild conditions, and the desired cyclopropane products are obtained in high yields with excellent diastereoselectivity and enantioselectivity. 相似文献
108.
Shibatomi K Kobayashi F Narayama A Fujisawa I Iwasa S 《Chemical communications (Cambridge, England)》2012,48(3):413-415
Highly enantioselective Diels-Alder reactions of β-fluoromethylacrylates were carried out in the presence of a Lewis acid activated chiral oxazaborolidine catalyst. These reactions yielded fluoromethylated cyclohexenes, including trifluoromethyl-, difluoromethyl-, and monofluoromethyl cyclohexenes, as nearly pure enantiomers. The resulting fluoromethyl cyclohexenes were converted into potential synthetic intermediates for bioactive compounds. 相似文献
109.
Tanabe K Iida H Haruna K Kamei T Okamoto A Nishimoto S 《Journal of the American Chemical Society》2006,128(3):692-693
Amperometry was employed to characterize the anthraquinone (AQ)-photoinjected hole transport through a 20-mer oligodeoxynucleotide (ODN) duplex, as immobilized on the surface of a gold electrode, and its triplex forms converted by association with several third oligopyrimidine (OPD) short strands. While the cathodic photocurrent was observed upon irradiation at 365 nm of the AQ photosensitizer linked to the end of DNA duplex, a marked lowering of the current density was identified to occur by the triplex formation of a duplex with a given third OPD short strand. The photocurrent through the DNA duplex showed a reversible fall-rise response concomitant with alternating association-dissociation cycle of the OPD short-strand, as regulated by temperature change around the corresponding melting temperature of the DNA triplex. Both the switched photoirradiation and the thermally alternating duplex-triplex conversion could provide tools of regulating the DNA hole transport. 相似文献
110.
Margadonna S Prassides K Iwasa Y Taguchi Y Craciun MF Rogge S Morpurgo AF 《Inorganic chemistry》2006,45(26):10472-10478
We report the synthesis of potassium phthalocyanine (KPc) and its structural characterization by synchrotron X-ray powder diffraction. We find that while KPc adopts the beta-polymorphic structural type (monoclinic space group P21/a) common for many MPc solids, its structure is characterized by unique features. The K+ ions, which are statistically disordered over two symmetry-equivalent positions, reside in the intrastack spacing of the rodlike molecular assemblies and strongly bond equidistantly to selected N atoms of the two neighboring Pc rings along the chain direction with an unusual 5-fold coordination. The K+-stuffed slipped stacks of Pc units display much greater intrastack and slippage distances than those of other beta-MPc polymorphs. They may be thought as comprising disordered dimeric (Pc)22- units; this leads to electron pairing and is consistent with the observed nonmagnetic response of the system. 相似文献