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81.
Cobalt (II) phthalocyanine (CoPc) molecules have been encapsulated within the supercage of zeolite-Y. The square-planar complex, being larger than the almost spherical cage, is forced to adopt a distorted geometry on encapsulation. A comparative spectroscopic and magnetic investigation of CoPc encapsulated in zeolite-Y and in the unencapsulated state is reported. These results supported by molecular modeling have been used to understand the nature and extent of the loss of planarity of CoPc on encapsulation. The encapsulated molecule is shown to be the trans-diprotonated species in which the center of inversion is lost due to distortions required to accommodate the square complex within the zeolite. Encapsulation also leads to an enhancement of the magnetic moment of the CoPc. This is shown to be a consequence of the nonplanar geometry of the encapsulated molecule resulting in an excited high-spin state being thermally accessible. 相似文献
82.
Electron diffraction and lattice dynamical calculations are used to investigate the unit cells, space group symmetries and inherent displacive flexibility of the room-temperature average structures of AlPO4-8, AlPO4-16 and AlPO4-tridymite. The zero-frequency rigid unit modes (RUMs) of the idealized high-symmetry polymorphs thereof are also investigated along with their relationship to the lower-temperature polymorphism of these zeotypic aluminophosphates. The clear presence of satellite reflections in addition to the Bragg reflections (G) of the underlying Cmc21 parent structure in the case of AlPO4-8 shows that the true unit cell of the room-temperature polymorph has a doubled c-axis due to a condensed RUM mode. Structured diffuse scattering is also observed which can be related to the thermal excitation of RUM modes. In the case of AlPO4-tridymite, a complex F1 triclinic polymorph is observed and related to soft RUM modes while, in the case of AlPO4-16, a soft q=0 RUM mode is shown to be responsible for an observed phase transition in the case of the all SiO2 analogue of AlPO4-16. A large number of additional zero-frequency RUM modes also exist in the case of AlPO4-16. 相似文献
83.
The leaching of two estrogens, 17β-estradiol and estrone, and two degradation products of non-ionic surfactants, octylphenol and nonylphenol, through a soil column were studied to estimate their transport behavior. Different concentration methods (lyophilization, solid phase extraction, and liquid–liquid extraction) were evaluated for analyzing these compounds in small effluent fractions (30–50 mL) collected. Liquid chromatography-mass spectrometry (LC-MS-MS) and gas chromatography-mass spectrometry (GC-MS) were employed for quantitative analysis of these compounds. After comparison, the lyophilization-LC-MS-MS method was found to be best suited for the analysis of the two estrogen hormones and the liquid–liquid extraction-GC-MS method best for the analysis of the two phenols in small samples in the soil column study. Because of their high sorption capacity, these compounds were mostly sorbed in the upper part of the soil column and were difficult to detect in column effluent. 相似文献
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Cardiolipin is an important phospholipid present in the mitochondrial inner membrane. It plays a key function in mitochondrial respiration by interacting with many enzymes or cofactors related to oxidative phosphorylation complexes. We have determined the concentration of cardiolipin using on-line 10-N-nonyl acridine orange (NAO) dye interaction capillary electrophoresis (CE) and spectrophotometric detection with a sample throughput of 3 min. In addition to the presence of 0.1 mM NAO, the background electrolyte (BGE) composition has been set at 80% methanol-10% acetonitrile-10% H(2)O (all v/v) to provide both good solubility and the maximum absorbance enhancement at 497 nm for the NAO-cardiolipin complex as compared to NAO alone. Sample consumption for each injection is about 57 nL. A calibration curve is established from 0.5 microM to 0.1 mM with R (2) = 0.9912 with a detection limit of 0.05 microM for cardiolipin. In a blind study, actual mitochondrial cell membrane samples in the microL range before or after UV light exposure were analyzed using the CE method. Cardiolipin concentration decreased in the different parts of the membrane sample upon UV photolysis of the cells. Support for the theory that UV light can induce cardiolipin translocation from the inner membrane (IM) to the outer membrane (OM) was indicated by a significant percentage increase of cardiolipin (as measured by the cardiolipin in the OM as compared to the sum total in the OM and IM) from 30.7 +/- 2.4% before UV light photolysis to 38.3 +/- 2.2% after UV irradiation. 相似文献
86.
Rusanova D Forsling W Antzutkin ON Pike KJ Dupree R 《Langmuir : the ACS journal of surfaces and colloids》2005,21(10):4420-4424
The interactions of synthetic chalcocite surfaces with diethyldithiophosphate, potassium salt, K[S2P(OC2H5)2], were studied by means of 31P cross-polarization/magic angle spinning (CP/MAS) NMR spectroscopy and scanning electron microscopy (SEM). To identify the species formed on the Cu2S surfaces, a polycrystalline {CuI6[S2P(OC2H5)2]6} cluster was synthesized and analyzed by SEM, powder X-ray diffraction techniques and solid-state 31P CP/MAS NMR and static 65Cu NMR spectroscopy. 31P chemical shift anisotropy (CSA) parameters, delta(cs) and eta(cs), were estimated and used for assigning the bridging type of diethyldithiophosphate ligands in the {CuI6[S2P(OC2H5)2]6} cluster. The latter data were compared to 31P CSA parameters estimated from the spinning sideband patterns in 31P NMR spectra of the collector-treated mineral surfaces: formation of polycrystalline {CuI6[S2P(OC2H5)2]6} on the Cu2S surfaces is suggested. The second-order quadrupolar line shape of 65Cu was simulated, and the NMR interaction parameters, CQ and etaQ, for the copper(I) diethyldithiophosphate cluster were obtained. 相似文献
87.
Martens WN Kloprogge JT Frost RL Bartlett JR 《Journal of colloid and interface science》2002,247(1):132-137
A model for pseudoboehmite crystallite packing formed during the hydrolysis of trisecbutoxyaluminium is postulated. The model describes platelike crystallites of pseudoboehmite stacked in a sharing edges only configuration. With this type of stacking, the pore sizes detected are approximately equal to the crystallite sizes of the hydrolysates. The hydrolysates age via a dissolution re-precipitation reaction. This increases the size of the crystallite size of the pseudoboehmite formed, speeding peptization by allowing nitrate ions to enter pores and access the surfaces of the crystallites. This type of model also allows an explanation for the peptization kinetics of systems containing sec-butanol formed during the hydrolysis of trisecbutoxyaluminium. 相似文献
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