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61.
Hara T Hirayama F Arima H Yamaguchi Y Uekama K 《Chemical & pharmaceutical bulletin》2006,54(3):344-349
2-(N-Cyanoimino)-5-[(E)-4-styrylbenzylidene]-4-oxothiazolidine (FPFS-410) is a newly synthesized thiazolidine derivative having not only antidiabetic but also lipid-lowering activities. However, this compound has an extremely low aqueous solubility (2.8 (+/-0.33) x 10(-8) M (0.0094+/-0.0011 microg/ml) in 1.0 M phosphate buffer (pH 7.0) at 25 degrees C). In this study, we investigated the effect of various hydrophilic cyclodextrins (CyDs) on the solubility of FPFS-410 to select a CyD suitable for formulations of the compound. Among various CyDs, 2-hydroxypropyl-beta-CyD (HP-beta-CyD) had the highest solubilizing ability to FPFS-410, e.g., the solubility of the compound was increased 200000-fold by the addition of 40 mM HP-beta-CyD, which was attributable to the formation of the 1 : 2 (guest : host) inclusion complexes. The interaction of HP-beta-CyD with FPFS-410 was studied using 1H-nuclear magnetic resonance (NMR) spectroscopies including ROESY spectroscopy and a molecular modeling calculation. These results suggested that HP-beta-CyD forms a 1:2 (guest : host) inclusion complex with FPFS-410 by including both the stilbene and thiazolidine moieties. FPFS-410/HP-beta-CyD solid complexes with various stoichiometries were prepared by the spray drying and cogrinding methods, and confirmed by powder X-ray diffractometry that these complexes are in an amorphous state. The dissolution of FPFS-410 in water was significantly accelerated by the complexation with HP-beta-CyD. In vivo studies revealed that HP-beta-CyD markedly increases the bioavailability of FPFS-410 after oral administration in dogs. The present results suggest that HP-beta-CyD is useful for improvement of the extremely low bioavailability of FPFS-410. 相似文献
62.
We experimentally demonstrated remote sensing of the constituents of microparticles in air by combining laser-induced breakdown spectroscopy (LIBS) and lidar, using femtosecond terawatt laser pulses. Laser pulses of 70 fs duration and 130 mJ energy generated filaments when focused at a focal length of 20 m and the pulses irradiated artificial saltwater aerosols in air at a 10 Hz pulse repetition rate. Na fluorescence was observed remotely at a distance of 16 m using a 318 mm diameter Newtonian telescope, a spectrometer, and an intensified CCD camera. These results show the possibility of remote measurement of the constituents of atmospheric particles, such as aerosols, clouds, and toxic materials, by LIBS-lidar using femtosecond terawatt laser pulses. 相似文献
63.
Matsuda Y Hoki K Maeda S Hanaue K Ohta K Morokuma K Mikami N Fujii A 《Physical chemistry chemical physics : PCCP》2012,14(2):712-719
Ionization dynamics of acetone and its dimer in supersonic jets is investigated by a combination of experimental and theoretical techniques, both of which have recently been developed. In experiments, the neutral and the cationic structures are explored by infrared predissociation spectroscopy with the vacuum-ultraviolet photoionization detection schemes. Reaction paths following the one-photon ionization of the acetone monomer and its dimer have been studied by the joint use of several theoretical methods including the ab initio molecular dynamics, the global reaction route mapping, the intrinsic reaction coordinate, and the artificial force induced reaction calculations. Upon one-photon ionization, the dimer isomerizes to the H-bonded form, in which the enol cation of acetone is bound to the neutral molecule, while this enolization is energetically forbidden in the acetone monomer. The enolization of the dimer cation occurs through a two-step proton-transfer from the methyl group of the ionized moiety, and is catalyzed by the neutral moiety within the dimer cation. 相似文献
64.
A cobalt-N-heterocyclic carbene catalyst, in combination with an appropriate Grignard reagent, promotes a chelation-assisted aromatic C-H functionalization reaction via addition to an aromatic aldimine. 相似文献
65.
Dr. Jean‐François Létard Dr. Saket Asthana Helena J. Shepherd Dr. Philippe Guionneau Dr. André E. Goeta Naohiko Suemura Ryuta Ishikawa Prof. Sumio Kaizaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(19):5924-5934
A comprehensive study of the magnetic and photomagnetic behaviors of cis‐[Fe(picen)(NCS)2] (picen=N,N′‐bis(2‐pyridylmethyl)1,2‐ethanediamine) was carried out. The spin‐equilibration was extremely slow in the vicinity of the thermal spin‐transition. When the cooling speed was slower than 0.1 K min?1, this complex was characterized by an abrupt thermal spin‐transition at about 70 K. Measurement of the kinetics in the range 60–70 K was performed to approach the quasi‐static hysteresis loop. At low temperatures, the metastable HS state was quenched by a rapid freezing process and the critical T(TIESST) temperature, which was associated with the thermally induced excited spin‐state‐trapping (TIESST) effect, was measured. At 10 K, this complex also exhibited the well‐known light‐induced excited spin‐state‐trapping (LIESST) effect and the T(LIESST) temperature was determined. The kinetics of the metastable HS states, which were generated from the freezing effect and from the light‐induced excitation, was studied. Single‐crystal X‐ray diffraction as a function of speed‐cooling and light conditions at 30 K revealed the mechanism of the spin‐crossover in this complex as well as some direct relationships between its structural properties and its spin state. This spin‐crossover (SCO) material represents a fascinating example in which the metastability of the HS state is in close vicinity to the thermal spin‐transition region. Moreover, it is a beautiful example of a complex in which the metastable HS states can be generated, and then compared, either by the freezing effect or by the LIESST effect. 相似文献
66.
Yuri Hirayama Naohiko Anzai Hiroyuki Kinouchi Schuichi Koizumi 《Molecules (Basel, Switzerland)》2022,27(12)
A sub-lethal ischemic episode (preconditioning [PC]) protects neurons against a subsequent lethal ischemic injury. This phenomenon is known as ischemic tolerance. PC itself does not cause brain damage, but affects glial responses, especially astrocytes, and transforms them into an ischemia-resistant phenotype. P2X7 receptors (P2X7Rs) in astrocytes play essential roles in PC. Although P2X7Rs trigger inflammatory and toxic responses, PC-induced P2X7Rs in astrocytes function as a switch to protect the brain against ischemia. In this review, we focus on P2X7Rs and summarize recent developments on how astrocytes control P2X7Rs and what molecular mechanisms they use to induce ischemic tolerance. 相似文献
67.
68.
Based on the resonating group method, transfer reaction form factors are derived in distorted wave Born approximation. As a direct consequence of antisymmetrization, renormalization operators of relative motion in entrance and exit channels are automatically included. These operators, when used in the passive core approximation, change the conventional reduced width amplitudes into those advocated by Fliessbach. In the present paper, however, his results are derived in a way which avoids the problematic use of non-orthogonal intermediate states in the cluster transfer approximation. It is proposed to use the conventional reduced width amplitudes, together with proper renormalization kernels, in order to separate structure effects from reaction dynamics (energy dependence, absorption etc.) which determines the actual importance of the renormalization operators in entrance and exit channels. 相似文献
69.
Cobalt‐Catalyzed Intramolecular Reactions between a Vinylcyclopropane and an Alkyne: Switchable [5+2] Cycloaddition and Homo‐Ene Pathways 下载免费PDF全文
Dr. Chunlin Wu Prof. Dr. Naohiko Yoshikai 《Angewandte Chemie (International ed. in English)》2018,57(22):6558-6562
Cobalt–diphosphine catalysts have been found to promote intramolecular reactions between a vinylcyclopropane and an alkyne to selectively afford either the [5+2] cycloaddition product or the homo‐ene reaction product under solvent control. The former product is exclusively formed in noncoordinating 1,2‐dichloroethane, whereas the latter is dominant in coordinating solvents, such as acetonitrile and dimethylacetamide. Furthermore, a highly enantioselective variant of the homo‐ene reaction afforded chiral tetrahydrofuran, pyrrolidine, and cyclopentane derivatives bearing 1,3‐diene and alkylidene substituents. 相似文献
70.
Nakano K Suemura N Kawata S Fuyuhiro A Yagi T Nasu S Morimoto S Kaizaki S 《Dalton transactions (Cambridge, England : 2003)》2004,(7):982-988
The synthesis and characterization of new spin-crossover pyrazolato bridged dinuclear [(FeII(NCS)(py))2(mu-bpypz)2] and the corresponding cyanotrihydroborato-kappaN complexes are described together with the X-ray crystal analysis of the latter in both the high-spin and low-spin states as well as the variable temperature magnetic susceptibility and/or Mossbauer spectra demonstrating the spin-crossover which exhibits an one-step process, but not a two-step one characteristic of the known bpym bridged dinuclear complexes. 相似文献