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31.
Maekawa K Shiomi D Ise T Sato K Takui T 《The journal of physical chemistry. B》2005,109(19):9299-9304
Spin alignments in heterospin chains are examined from numerical calculations of model spin Hamiltonians. The Hamiltonians of the heterospin chains mimic an open-shell molecular assemblage composed of an organic biradical in a singlet (S = 0) ground state and a doublet (S = 1/2) monoradical, which are coupled by intermolecular ferromagnetic exchange interactions. It is found from numerical calculations of the spin Hamiltonians that the spin value S2 of the ground-state singlet biradical embedded in the exchange-coupled assemblage deviates from zero and contributes to the bulk magnetization. The alternating chain is found to have two kinds of ground spin states, a high- and a low-spin state. All the spins are parallel to each other in the high-spin state, which is characterized by the spin correlation function of (S(i).S(j)) = 0.25. On the other hand, the spin alignment in the low-spin state is found to be dependent on the topology of the intermolecular exchange interactions. The energy preference of the two states depends on the relative amplitude of the exchange interactions in the chain. The intermolecular ferromagnetic couplings are competing in the ground-state singlet biradical with the intramolecular antiferromagnetic interaction. The appearance of the two kinds of ground states is attributed to a quantum spin frustration effect inherent in the triangular motif of the competing interactions. Magnetic properties of a zigzag chain complex composed of a nitronyl nitroxide biradical with a singlet ground state and Cu(hfac)2 are examined on the basis of the theoretical calculations. The vanishing magnetic moments, or the product of susceptibility and temperature chiT, at low temperatures observed for the complex are consistent with those of the low-spin state predicted in the theoretical calculations. 相似文献
32.
Miyoshi D Matsumura S Nakano S Sugimoto N 《Journal of the American Chemical Society》2004,126(1):165-169
Because of the importance of telomere DNAs, the structures of these DNAs in vivo are currently of great research interest in the medical, pharmaceutical, chemical, and industrial fields. To understand the structure of biomolecules in vivo, their properties studied in vitro are extrapolated to the in vivo condition, while the condition in a living cell is inherently molecularly crowded and a nonideal solution contains various biomolecules. We investigated the effect of molecular crowding, which is one of the most important cellular environmental conditions, on the structure and stability of the telomere and G-rich and C-rich DNAs using circular dichroism (CD) spectra, CD melting curves, and isothermal titration calorimetry (ITC). The CD spectra and CD melting curves of G-rich DNA, C-rich DNA, and the 1:1 mixture of G-rich and C-rich DNAs showed that each G-rich DNA, C-rich DNA, and the 1:1 mixture form the antiparallel G-quadruplex, I-motif, and duplex, respectively, in the noncrowding condition as previously considered. On the contrary, the G-rich and C-rich DNAs individually form the parallel G-quadruplex and I-motif, respectively, in the molecular crowding condition, and the 1:1 mixture folds into the parallel G-quadruplex and I-motif but does not form a duplex. The ITC measurements indicated that the thermodynamic stability (DeltaG degrees (20)) of the duplex formation between the G-rich and C-rich DNAs in the noncrowding condition was -10.2 kcal mol(-)(1), while only a small heat change was observed in the ITC measurements in the molecular crowding condition. These ITC results also demonstrated that the molecular crowding condition prevents any duplex formation between G-rich and C-rich DNAs. These results indicate that a structural polymorphism of the telomere DNAs is induced by molecular crowding in vivo. 相似文献
33.
Sakae Uemura Shin-Ichi Fukuzawa Akio Toshimitsu 《Journal of organometallic chemistry》1983,250(1):203-215
Treatment of olefinic hydrocarbons with phenyltellurium tribromide or a mixture of diphenylditelluride and bromine in alcohol affords (β-alkoxyalkyl)phenyltellurium dibromides in fair to good yield (alkoxytelluration of olefins). Various aryltellurium trichlorides, diphenylditelluride/CuCl2, and phenyltellurocyanate/CuCl2 can be used for the preparation of (β-alkoxyalkyl)aryltellurium dichlorides. Similar reactions in aqueous tetrahydrofuran or aqueous t-butyl alcohol result in the formation of the corresponding β-hydroxy compound (hydroxytelluration of olefins). The reaction is trans stereospecific in the cases of cis-2-butene and cis- and trans-4-octenes and regiospecific in the cases of all terminal olefins examined (1-hexene, 1-octene, 1-decene, styrene, α-methylstyrene, 2-methyl-1-pentene, and isobutylene), tellurium species attacking the terminal carbon solely. The diorganyltellurium dihalide produced is reduced to the corresponding diorganyltelluride by reducing agents such as N2H4, Na2S, Na2S2O3, and NaHSO4 in aqueous solution. Treatment of the diorganyltellurium dibromide with aqueous NaOH affords either an allylic ether (by telluroxide elimination) or a telluroxide depending on the structure of the telluroxide. 相似文献
34.
The reaction of conjugated dienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,5-dimethyl-2,4-hexadiene, 1,3-cyclopentadiene, and 1,3-cyclohexadiene, with thallium(III)acetate in acetic acid at 10–65° for 0.5–15 hr affords an isomeric mixture of the corresponding diacetoxyalkenes (1,2- and 1,4-addition products) in 10–92% yields. The 1,2-addition products are predominantly formed in all cases examined except the case of 1,3-cyclopentadiene. The reaction is assumed to proceed through acetoxythallation and dethallation steps, the latter step being accompanied and/or followed by an attack of acetoxyl group. An initial attack of thallium moiety is proposed to occur mainly at C-1 and C-2 carbons in the cases of linear terminal dienes and cyclic dienes, respectively. 相似文献
35.
We report in this study the presence of Janus particles, which are candidates for use with electronic color papers. We used negatively charged polystyrene particles (370 nm) as the core particles, and gold was then sputtered onto their packed monolayer under several conditions. The sputtered particles were next redispersed into the aqueous medium by gentle sonication. Gold nanoparticles localized on one side of the cores could also serve as seeds for subsequent shell growth by electroless gold plating. Through these treatments, a series of well-dispersed Janus particles were obtained with gold nanostructures of different size and shape only on one side. Their dispersions showed different colors originating from the surface plasmon resonance absorption of gold nanoparticles localized on the hemisphere. The particles obtained by this approach have potential applications such as in sensors and electronic color paper. 相似文献
36.
pi-Allyl-nickel complexes initiated addition polymerisation of 2-phenyl-1-methylenecyclopropane to give a polymer with three-membered rings; the formed polymer showed a high Tg and negligible thermal decomposition up to 300 degrees C. 相似文献
37.
Kenjiro Hattori Akira Kenmoku Tsukasa Mizuguchi Daisuke Ikeda Mamoru Mizuno Toshiyuki Inazu 《Journal of inclusion phenomena and macrocyclic chemistry》2006,56(1-2):9-16
A synthetic series of heptakis-galactose-branched cyclodextrins (termed CDs) having a longer spacer arm using two amino-caproic acids as an enlarging unit were prepared. Starting with heptakis-amino-β-CD or heptakis-amino-caproic-amide-β-CD, treated with galactosyl-glucono-amide-caproic acid, the new compounds heptakis (Gal-cap1)-CD (4) or heptakis (Gal-cap2)-CD (5) were obtained. The longer galactose spacer arm extremely favors the PNA association. The effect of branch length on K with PNA was enhanced up to 138-fold 3 as well as with DXR enhanced up to 81-fold. Hexakis (Gal-cap2)-CD (6) was prepared and the association constants with rat liver cells were observed to be 2.5 × 1010 M−1. A multi-high mannose type oligosaccharide branched CD (7) showed a large association constant with DXR up to 1.1 × 109 M−1. The two-dimensional map for the association constants of newly synthesized oligosaccharide-branched CDs toward lectin or liver cells versus the association constants toward a drug (doxorubicin) suggested a method of finding a better targeting drug carrier. The structural effect of the oligosaccharide-CDs showed that the number and length of the branch were dominant factors in designing for enhanced dual recognition. 相似文献
38.
Minato M Sekimizu R Uchida D Ito T 《Dalton transactions (Cambridge, England : 2003)》2004,(21):3695-3698
Treatment of eta(3)-allyl compound [Cp(2)Mo(eta(3)-C(3)H(5))](+)(1; Cp =eta(5)-C(5)H(5)) with MH (M = Li, Na) resulted in reduction of the allyl ligand to give propane. Deuterium-labeling studies were used to trace the origins and fates of the hydrogen atoms. The mechanism is discussed in light of the HSAB principle. The studies showed that the formation of propane can be explained by 1,2-hydrogen migration from the central to the terminal carbon of the allyl ligand, and the subsequent double nucleophilic addition of the hydride at the central carbon. 相似文献
39.
Summary In order to prepare a large single crystal, tetraoxymethylene recrystallized by distilled water adjusted to pH 8 was sealed
in an ampoule at a reduced pressure of 1 mm Hg and was crystallized in a furnace with the temperature gradient of 6 °C/cm.
The lowering rate of the ampoule was required to be 6 cm/day for preparing the single crystal with 1 cm diameter and to be
3 cm/day for one with 2 cm diameter. The optimum angle at the pointing end of the ampoule, where a seed crystal is formed,
was about 40°. The b-axis of the obtained single crystal was parallel to the direction of the crystal growth i. e. the wall
of the ampoule. It was polymerized byγ-ray under conditions which prevent the growth of the twin crystal. The obtained polyoxymethylene was porous, because the
polymerization yield of 100% could not be attained. However, it was so tough that a specimen for measurements could be cut
down by a diamond cutter. Its fiber axis was parallel to the direction of the wall of the ampoule. It did not contain the
so-called amorphous regions, although it did contain defects. It was characterized with the extremely high orientation of
the polymer chains.
We are greatly indebted to Dr.Y. Miyake of Mitsui Toatsu Co., Ltd. for providing the tetraoxymethylene. Thanks are to due Dr.M. Nishii of Osaka Laboratories, Japan Association for Radiation Research on Polymer for the radiation polymerization, to Mr.T. Tsukihara for the X-ray measurement, and to Mrs.H. Tanaka for the help with the electron microscopy. We are also grateful to Prof.S. Seki for offering the use of differential scanning calorimeter. 相似文献
Zusammenfassung Zur Pr?parierung gro?er Einkristalle wurde rekristallisiertes Tetraoxymethylen in destilliertem Wasser von pH 8 in eine Ampulle bei einem reduzierten Quecksilberdruck von 1 mm eingefüllt und in einem Ofen mit einem Temperaturgradienten von 6 °C/cm kristallisiert. Die Abkühlgeschwindigkeit der Ampulle betrug etwa 6 cm/Tag für die Pr?paration eines Einkristalls mit 1 cm ? und 3 cm/Tag für einen solchen mit 2 cm ?. Der optimale Winkel am spitzen Ende der Ampulle, wo der Keimkristall gebildet wird, betrug etwa 40°. Dieb-Achse des Einkristalls war parallel zur Wachstumsrichtung, d. h. zur Wand der Ampulle. Der Kristall wurde durch R?ntgenstrahlen polymerisiert unter Bedingungen, die das Wachsen eines Zwillingskristalls vermeiden. Das erhaltene Polyoxymethylen war por?s, doch konnte eine Polymerisationsausbeute von 100% nicht erhalten werden. Doch war der Einkristall so z?h, da? für Messungen eine Probe mit dem Diamantschneider abgeschnitten werden konnte. Die Faserachse war parallel zur Wandrichtung der Ampulle. Das kristalline Material enthielt keine sogenannten amorphen Bereiche, allerdings Defekte. Es war durch extrem hohe Orientierungen der Polymerketten charakterisiert.
We are greatly indebted to Dr.Y. Miyake of Mitsui Toatsu Co., Ltd. for providing the tetraoxymethylene. Thanks are to due Dr.M. Nishii of Osaka Laboratories, Japan Association for Radiation Research on Polymer for the radiation polymerization, to Mr.T. Tsukihara for the X-ray measurement, and to Mrs.H. Tanaka for the help with the electron microscopy. We are also grateful to Prof.S. Seki for offering the use of differential scanning calorimeter. 相似文献
40.
Inada Y Nishibayashi Y Hidai M Uemura S 《Journal of the American Chemical Society》2002,124(51):15172-15173
A novel cationic methanethiolate-bridged diruthenium complex [Cp*RuCl(mu2-SMe)2RuCp*(OH2)]OTf (1e) has been disclosed to promote the catalytic propargylic substitution reaction of propargylic alcohols bearing not only terminal alkyne group but also internal alkyne group with thiols. It is noteworthy that neutral thiolate-bridged diruthenium complexes (1a-1c), which were known to promote the propargylic substitution reactions of propargylic alcohols bearing a terminal alkyne group with various heteroatom- and carbon-centered nucleophiles, did not work at all. The catalytic reaction described here provides a general and environmentally friendly preparative method for propargylic sulfides, which are quite useful intermediates in organic synthesis, directly from the corresponding propargylic alcohols and thiols. 相似文献