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71.
Cyano-bridged Mn(III)-M(III) single-chain magnets with M(III)=Co(III), Fe(III), Mn(III), and Cr(III)
Miyasaka H Madanbashi T Saitoh A Motokawa N Ishikawa R Yamashita M Bahr S Wernsdorfer W Clérac R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(13):3942-3954
A series of isostructural cyano-bridged Mn(III)(h.s.)-M(III)(l.s.) alternating chains, [Mn(III)(5-TMAMsalen)M(III)(CN)(6)]?4H(2)O (5-TMAMsalen(2-)=N,N'-ethylenebis(5-trimethylammoniomethylsalicylideneiminate), Mn(III)(h.s.)=high-spin Mn(III), M(III)(l.s.)=low-spin Co(III), Mn-Co; Fe(III), Mn-Fe; Mn(III), Mn-Mn; Cr(III), Mn-Cr) was synthesized by assembling [Mn(III)(5-TMAMsalen)](3+) and [M(III)(CN)(6)](3-). The chains present in the four compounds, which crystallize in the monoclinic space group C2/c, are composed of an [-Mn(III)-NC-M(III)-CN-] repeating motif, for which the -NC-M(III)-CN- motif is provided by the [M(III)(CN)(6)](3-) moiety adopting a trans bridging mode between [Mn(III)(5-TMAMsalen)](3+) cations. The Mn(III) and M(III) ions occupy special crystallographic positions: a C(2) axis and an inversion center, respectively, forming a highly symmetrical chain with only one kind of cyano bridge. The Jahn-Teller axis of the Mn(III)(h.s.) ion is perpendicular to the N(2)O(2) plane formed by the 5-TMAMsalen tetradentate ligand. These Jahn-Teller axes are all perfectly aligned along the unique chain direction without a bending angle, although the chains are corrugated with an Mn-N(axis) -C angle of about 144°. In the crystal structures, the chains are well separated with the nearest inter-chain M???M distance being relatively large at 9?? due to steric hindrance of the bulky trimethylammoniomethyl groups of the 5-TMAMsalen ligand. The magnetic properties of these compounds have been thoroughly studied. Mn-Fe and Mn-Mn display intra-chain ferromagnetic interactions, whereas Mn-Cr is characterized by an antiferromagnetic exchange that induces a ferrimagnetic spin arrangement along the chain. Detailed analyses of both static and dynamic magnetic properties have demonstrated without ambiguity the single-chain magnet (SCM) behavior of these three systems, whereas Mn-Co is merely paramagnetic with S(Mn)=2 and D/k(B)=-5.3?K (D being a zero-field splitting parameter). At low temperatures, the Mn-M compounds with M=Fe, Mn, and Cr display remarkably large M versus H hysteresis loops for applied magnetic fields along the easy magnetic direction that corresponds to the chain direction. The temperature dependence of the associated relaxation time for this series of compounds systematically exhibits a crossover between two Arrhenius laws corresponding to infinite-chain and finite-chain regimes for the SCM behavior. These isostructural hetero-spin SCMs offer a unique series of alternating [-Mn-NC-M-CN-] chains, enabling physicists to test theoretical SCM models between the Ising and Heisenberg limits. 相似文献
72.
Ayumi Narita Yuji BabaTetsuhiro Sekiguchi Iwao ShimoyamaNorie Hirao Tsuyoshi Yaita 《Applied Surface Science》2012,258(6):2034-2037
Chemical states of the interfaces between octadecyl-triethoxy-silane (ODTS) molecules and sapphire surface were measured by X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) using synchrotron soft X-rays. The nearly self-assembled monolayer of ODTS was formed on the sapphire surface. For XPS and NEXAFS measurements, it was elucidated that the chemical bond between silicon alkoxide in ODTS and the surface was formed, and the alkane chain of ODTS locates upper side on the surface. As a result, it was elucidated that the silicon alkoxide is a good anchor for the immobilization of organic molecules on oxides. 相似文献
73.
Yasuyuki Matsushita Ayumi Suzuki Takuya Sekiguchi Kaori Saito Takanori Imai Kazuhiko Fukushima 《Applied Surface Science》2008,255(4):1022-1024
Cationic starch (CS) is routinely used in the papermaking process to improve the dry strength or printability of paper. The effectiveness depends on the distribution of the starch on the pulp fiber, and in this study, time-of-flight secondary ion mass spectrometry was used to investigate this distribution. The characteristic peak at 58m/z was applied to map the CS. Based on the imaging analysis of the handsheets with the CS as an internal additive, the distribution of CS became more uniform with decreasing freeness. The amount of adsorbed CS increased with increasing fiber length and was lower on vessels than on other fibers. These results were related to fibrillation. From the analysis of handsheets with CS as an external additive, the penetration depth of the starch into base paper increased with decreases in the sizing degree of the base paper. 相似文献
74.
A new glass capillary microelectrode for L-glutamate is described using pulled glass capillaries (tip size, approximately 12.5 microm) with a very small volume (approximately 2 microl) of inner solution containing glutamate oxidase (GluOx) and ascorbate oxidase. The operation of the electrode is based on capillary action that samples L-glutamate into the inner solution. The enzyme reaction by GluOx generates hydrogen peroxide that is detected at an Os-gel-HRP polymer modified Pt electrode in a three-electrode configuration. The amperometric response behavior of the electrode was characterized in terms of the capillarity, response time, sensitivity and selectivity for measurements of L-glutamate. The currents at 0 V vs. Ag/AgCl increased linearly with the L-glutamate concentration from 10 to 150 microM for in vitro and in situ calibrations. The response was highly selective to L-glutamate over ascorbate, dopamine, serotonin and other amino acids. The detection of L-glutamate in the extracellular fluids of different regions of mouse hippocampal slices under stimulation of KCl was demonstrated. 相似文献
75.
Nakamura N Negishi K Hirano A Sugawara M 《Analytical and bioanalytical chemistry》2005,383(4):660-667
Real-time monitoring of L-glutamate release from various neuronal regions of mouse hippocampal slices under ischemia (a glucose-free hypoxia condition)
is described. A glass capillary microelectrode with a tip size of ∼10 μm containing a very small volume (∼2 μL) of a solution
of glutamate oxidase (GluOx) and ascorbate oxidase was used. First, the amperometric response behavior of the electrode at
0 V versus Ag/AgCl was characterized with a standard glutamate solution in terms of continuous measurements, effect of oxygen,
viscosity of solution and concentration dependence. The electrode was applied to the real-time monitoring of L-glutamate released from different neuronal regions of acute hippocampal slices submerged in a hypoxia solution. The time-resolved
amounts of L-glutamate released at various neuronal regions (CA1, CA3 and DG) of mouse hippocampal slices were quantified and compared
with the reported L-glutamate fluxes using difference-image analysis during ischemia. 相似文献
76.
Ayumi Yoshida Aranya Manosroi Jiradej Manosroi Hitoshi Yamauchi Masahiko Abe 《Colloids and surfaces. B, Biointerfaces》1995,4(6):423-432
Molecular interactions between phospholipids and mangostin in a lipid bilayer have been investigated in terms of the maximum additive concentration (MAC) of mangostin in liposomes, the surface potential, particle size, microscopic-viscosity and microscopic-polarity of liposomes, and the permeability of glucose. The mangostin used is a natural product extract: 1,3,6-trihydroxy-7-methoxy-2,8-bis(3-methyl-2-butenyl)-9-xanthenenone.
The MAC of mangostin was fairly dependent upon the nature of the liposomes (uncharged, negatively charged or positively charged). Solubilization of mangostin in the liposomal bilayer resulted in both an increase in the negative charge on the liposomal surface, strenghthening the state of the bilayer membrane, and a depression in the release of the glucose involved. Mangostin was found to temporarily stabilize the liposomal bilayer, although the bilayer membrane is still unstable in the long run. 相似文献
77.
Introduction of carbohydrate auxiliary into enanine-based catalyst provided a novel enantiocontrol for aqueous aldol reaction. Methyl 2-(l-prolyl)amido-2-deoxy-α-d-glucopyranosides led to the enantiocontrol as parent amino acids did in the reaction of acetone with 4-nitrobenzaldehyde, and provided R-aldol in an improved efficiency compared with that of l-proline in aqueous media. The enantioreversal control of that with parent amino acid was observed in the reaction with methyl 2-(l-tert-leucyloxy)-α-d-glucopyranoside, which provided S-aldol predominantly in moderate efficiency. The novel enantiocontrol system was proposed to occur as a result of the generation of the transition state through the reaction of enamine with hydroxyl group on glucoside auxiliary. 相似文献
78.
Akimoto S Yokono M Ohmae M Yamazaki I Tanaka A Higuchi M Tsuchiya T Miyashita H Mimuro M 《The journal of physical chemistry. B》2005,109(25):12612-12619
Ultrafast excitation relaxation dynamics and energy-transfer processes in the light-harvesting complex II (LHC II) of Arabidopsis thaliana were examined at physiological temperature using femtosecond time-resolved fluorescence spectroscopy. Energy transfer from lutein to Chl a proceeded with a rate constant of k(ET) = 1.8-1.9 x 10(13) s(-1) and a yield of approximately Phi(ET) = 0.70, whereas that from neoxanthin to Chl a had a rate constant of k(ET) = 6.5 x 10(11) s(-1) and a yield at the most of Phi(ET) = 0.09. Fluorescence anisotropic decay of lutein in LHC II showed a value larger than 0.4 at the initial state and decayed to approximately 0.1 in 0.3 ps, indicating that two lutein molecules interact with each other in LHC II. In solution, anisotropy of lutein remained constant (0.38) independent of time, and thus a new excited state inferred between the S(2) (1B(u)) state and the S(1) (2A(g)) state was not applicable for lutein in solution. Energy migration processes among Chl a or Chl b molecules were clearly resolved by kinetic analysis. On the basis of these results, relaxation processes and energy-transfer kinetics in LHC II of A. thaliana are discussed. 相似文献
79.
Ogoshi T Inagaki A Yamagishi TA Nakamoto Y 《Chemical communications (Cambridge, England)》2008,(19):2245-2247
Single-walled carbon nanotubes (SWCNTs) were suspended in aqueous media with cucurbit[7]uril (CB7), while SWCNTs were insoluble with cucurbit[5]uril (CB5). Moreover, defection-selective solubilization of SWCNTs with CB7 was demonstrated. 相似文献
80.
Nishimura K Higashi T Yoshimatsu A Hirayama F Uekama K Arima H 《Chemical & pharmaceutical bulletin》2008,56(5):701-706
The purpose of this study is to reveal whether Coenzyme Q10 (CoQ10) forms pseudorotaxane-like supramolecular complex with gamma-cyclodextrin (gamma-CyD). The poorly soluble complex of CoQ10 with gamma-CyD in water was prepared by the solubility method. The X-ray diffraction pattern of the CoQ10/gamma-CyD complex was different from that of the physical mixture, but almost the same as that of polypropylene glycol (PPG)/gamma-CyD polypseudorotaxane. Also, the differential scanning calorimetrical study and FT-IR study demonstrated the interaction between CoQ10 and gamma-CyD in the solid state. The 1H-NMR study and the yield study of the supramolecular complex of CoQ10 with gamma-CyD demonstrated that the stoichiometry was 5 : 1 (gamma-CyD : CoQ10). The dispersion rate of CoQ10 was markedly increased by the formation of the supramolecular complex with gamma-CyD, possibly due to submicron-ordered particle formulation. In fact, CoQ10 was found to form submicron-sized supramolecular particles with gamma-CyD, when prepared by the solubility method. Consequently, the present study showed that CoQ10 forms the pseudorotaxane-like supramolecular complex with gamma-CyD in water. 相似文献