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61.
Boskovic C Brechin EK Streib WE Folting K Bollinger JC Hendrickson DN Christou G 《Journal of the American Chemical Society》2002,124(14):3725-3736
The reaction of (NBu(n)(4))[Mn(8)O(6)Cl(6)(O(2)CPh)(7)(H(2)O)(2)] (1) with 2-(hydroxymethyl)pyridine (hmpH) or 2-(hydroxyethyl)pyridine (hepH) gives the Mn(II)(2)Mn(III)(10) title compounds [Mn(12)O(8)Cl(4)(O(2)CPh)(8)(hmp)(6)] (2) and [Mn(12)O(8)Cl(4)(O(2)CPh)(8)(hep)(6)] (3), respectively, with X = Cl. Subsequent reaction of 3 with HBr affords the Br(-) analogue [Mn(12)O(8)Br(4)(O(2)CPh)(8)(hep)(6)] (4). Complexes 2.2Et(2)O.4CH(2)Cl(2), 3.7CH(2)Cl(2), and 4.2Et(2)O.1.4CH(2)Cl(2) crystallize in the triclinic space group P1, monoclinic space group C2/c, and tetragonal space group I4(1)/a, respectively. Complexes 2 and 3 represent a new structural type, possessing isomeric [Mn(III)(10)Mn(II)(2)O(16)Cl(2)] cores but with differing peripheral ligation. Complex 4 is essentially isostructural with 3. A magnetochemical investigation of complex 2 reveals an S = 6 or 7 ground state and frequency-dependent out-of-phase signals in ac susceptibility studies that establish it as a new class of single-molecule magnet. These signals occur at temperatures higher than those observed for all previously reported single-molecule magnets that are not derived from [Mn(12)O(12)(O(2)CR)(16)(H(2)O)(x)]. A detailed investigation of forms of complex 2 with different solvation levels reveals that the magnetic properties of 2 are extremely sensitive to the latter, emphasizing the importance to the single-molecule magnet properties of interstitial solvent molecules in the samples. In contrast, complexes 3 and 4 are low-spin molecules with an S = 0 ground state. 相似文献
62.
Brechin EK Sañudo EC Wernsdorfer W Boskovic C Yoo J Hendrickson DN Yamaguchi A Ishimoto H Concolino TE Rheingold AL Christou G 《Inorganic chemistry》2005,44(3):502-511
The reaction of 2-(hydroxyethyl)pyridine (hepH) with a 2:1 molar mixture of [Mn3O(O2CMe)6(py)3]ClO4 and [Mn3O(O2CMe)6(py)3] in MeCN afforded the new mixed-valent (16Mn(III), 2Mn(II)), octadecanuclear complex [Mn18O14(O2CMe)18(hep)4(hepH)2(H2O)2](ClO4)2 (1) in 20% yield. Complex 1 crystallizes in the triclinic space group P. Direct current magnetic susceptibility studies in a 1.0 T field in the 5.0-300 K range, and variable-temperature variable-field dc magnetization studies in the 2.0-4.0 K and 2.0-5.0 T ranges were obtained on polycrystalline samples. Fitting of magnetization data established that complex 1 possesses a ground-state spin of S = 13 and D = -0.18 K. This was confirmed by the value of the in-phase ac magnetic susceptibility signal. Below 3 K, the complex exhibits a frequency-dependent drop in the in-phase signal, and a concomitant increase in the out-of-phase signal, consistent with slow magnetization relaxation on the ac time scale. This suggests the complex is a single-molecule magnet (SMM), and this was confirmed by hysteresis loops below 1 K in magnetization versus dc field sweeps on a single crystal. Alternating current and direct current magnetization data were combined to yield an Arrhenius plot from which was obtained the effective barrier (U(eff)) for magnetization reversal of 21.3 K. Below 0.2 K, the relaxation becomes temperature-independent, consistent with relaxation only by quantum tunneling of the magnetization (QTM) through the anisotropy barrier via the lowest-energy MS = +/-13 levels of the S = 13 spin manifold. Complex 1 is thus the SMM with the largest ground-state spin to display QTM. 相似文献
63.
Quantum tunneling of magnetization in a new [Mn18]2+ single-molecule magnet with s = 13 总被引:3,自引:0,他引:3
Brechin EK Boskovic C Wernsdorfer W Yoo J Yamaguchi A Sañudo EC Concolino TR Rheingold AL Ishimoto H Hendrickson DN Christou G 《Journal of the American Chemical Society》2002,124(33):9710-9711
The reaction between 2-(hydroxyethyl)pyridine (hepH) and a 2:1 molar mixture of [Mn3O(O2CMe)6(py)3](ClO4) and [Mn3O(O2CMe)6(py)3](py) in MeCN leads to isolation of [Mn18O14(O2CMe)18(hep)4(hepH)2(H2O)2](ClO4)2 (1) in 10% yield. The complex is 2MnII,16MnIII and consists of a Mn4O6 central unit to either side of which is attached a Mn7O9 unit. Magnetization data collected in the 2.0-4.0 K and 20-50 kG ranges were fit to yield S = 13, g = 1.86, and D = -0.13 cm-1 = -0.19 K, where D is the axial zero-field splitting parameter. AC susceptibility studies in the 0.04-4.0 K range at frequencies up to 996 Hz display out-of-phase (chiM' ') signals, indicative of a single-molecule magnet (SMM). Magnetization vs applied DC field scans exhibit hysteresis at <1.0 K, confirming 1 to be a SMM. DC magnetization decay data were collected on both a microcrystalline sample and a single crystal, and the combined data were used to construct an Arrhenius plot. Between 3.50 and 0.50 K, the relaxation rate is temperature-dependent with an effective barrier to relaxation (Ueff) of 14.8 cm-1 = 21.3 K. Below ca. 0.25 K, the relaxation rate is temperature-independent at 1.3 x 10-8 s-1, indicative of quantum tunneling of magnetization (QTM) between the lowest energy Ms = +/-13 levels of the S = 13 state. Complex 1 is both the largest spin and highest nuclearity SMM to exhibit QTM. 相似文献
64.
Colette Deschamps-Vallet Michle Meyer-Dayan Jean Andrieux Jacques Riboulleau Bernard Bodo Darius Molho 《Journal of heterocyclic chemistry》1977,14(3):489-492
5-Oxo-5H,7H-[2]benzopyrano[4,3-b][1]benzopyran ( 2 ) has been synthesized from 3-(o-hydroxybenzylidene)isochroman-1,4-dione ( 3 ) by reductive cyclization, and from 5H,7H[2]benzo-pyrano[4,3-b][1]benzopyran-5,7-dione ( 4 ) by selective hydro-genation. This second method affords the dihydro compound 6 or 6a,12a-dihydro-5H,7H-[2]benzopyrano[4,3-b] [1 ]benzopyran-5-one as reaction time increases. 相似文献
65.
Gilbert Michel Breuil Colette Yaguchi Makoto Saddler J. N. 《Applied biochemistry and biotechnology》1992,(1):247-259
Thielavia terrestris 255B, a thermophilic ascomycete, produced two major forms of xylanase with pIs of 4.6 (xylanase I) and 6.1 (xylanase II).
The latter enzyme could be purified to > 99% homogeneity using anion-exchange chromatography and gel filtration. Xylanase
II had a mol wt of 25.7 kDa (SDS-PAGE) and a pH and a temperature optimum of 3.6–4.0 and 60–65°C, respectively. The ratio
of the enzyme’s activity against xylan and carboxymethylcellulose was 500–1000 to 1, indicating a possible application of
this enzyme in biobleaching processes. The amino acid sequence of this protein is being determined, and initial data suggest
that the enzyme belongs to a group of low-mol wt xylanases that have been isolated from both bacteria and fungi. 相似文献
66.
Philippe Demont Daniel Chatain Colette Lacabanne Michel Glotin 《Macromolecular Symposia》1989,25(1):167-186
The retardation and relaxation behaviour of poly(ether-block-amide)s PEBA copolymers was investigated as a function of hard polyamide sequence length by using thermally stimulated creep (TSCr) and Current (TSCu). Two primary TSCr and TSCu peaks, called ßPE and ßPA were observed in the temperature range 150–300 K. The “low temperature” peak ßPE was characterized by a peak position T ßPE which depends poorly upon hard segment content as the corresponding DSC glass transition temperature TgPE. The peak position TßPA of the “high temperature” relaxation showed a progressive shift towards higher temperatures as the hard segment average length was increased as it is observed in series of pure polyamide oligomers. So, complex spectra suggest that an amorphous phase separation occurs in PEBA copolymers. The TSCr ßPE and ßPA modes were analysed by thermal sampling method (TS). The elementary TSCr processes isolated in the ßPE and ßPA distributed retardation modes were characterized by retardation times following a compensation law. The comparison of activation and compensation parameters confirmed the existence of a biphasic amorphous phase in PEBA. In TSCr spectra, an additional peak, noted α, is observed at a temperature close to the DSC melting point TmPE of the poly(tetramethylene glycol) segments. 相似文献
67.
68.
In this paper we prove some existence results of semilinear Dirichlet problems in nonsmooth domains in presence of lower and upper solutions well-ordered or not. We first prove existence results in an abstract setting using degree theory. We secondly apply them for domains with conical points. 相似文献
69.
Golnaz Jafarpour Frédéric Roig Eric Dantras Alain Boudet Colette Lacabanne 《Journal of Non》2009,355(34-36):1669-1672
The influence of hydration on cellulose molecular mobility is investigated by two dielectric methods at different molecular scale. The mobility of side groups, assigned to γ mode, for dried cellulose increases. The water molecules have an anti-plasticizer effect on γ mode due to the water–polymer hydrogen bonding. For the β relaxation mode, only observed by the Thermo Stimulated Current technique, the hydration plays a role of plasticizer. The α relaxation mode assigned to the delocalized cooperative mobility of long chain segments of cellulose is plasticized by water. The study of activated parameters deduced from fractional polarization procedure, shows an increase of the activation enthalpy range with dehydration. It permits to conclude that reduction of hydrogen bonds density leading to a more extended cooperative mobility. 相似文献
70.
Previous research has shown that increases in the rate of stimulation on a single electrode yield changes in pitch perception until the rate is increased beyond a given critical rate, after which changes in rate are only perceived as changes in loudness. The critical rate beyond which a rate increase no longer elicits a pitch change in most subjects is approximately 300 Hz, although a small number of subjects have been observed to have critical rates up to approximately 1000 Hz. In this article, we sought to determine if increasing the rate of stimulation beyond the critical rate (up to 12.8 kHz) would eventually result in new changes of perception (other than loudness.) Our data replicate the previously observed results that rates between approximately 300 and 1500 Hz are indistinguishable from each other. However, we observed the finding that a rate of stimulation well above the critical rate (starting between 1500 Hz and 12.8 kHz, depending on electrode and subject) can elicit changes in perception. The perceptual differences between these high rates were sometimes but not always labeled as pitch changes. This phenomenon needs further research to assess its potential relevance to speech perception using high rates of stimulation. 相似文献