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81.
Shongwe MS Al-Rahbi SH Al-Azani MA Al-Muharbi AA Al-Mjeni F Matoga D Gismelseed A Al-Omari IA Yousif A Adams H Morris MJ Mikuriya M 《Dalton transactions (Cambridge, England : 2003)》2012,41(8):2500-2514
The two potentially tridentate and monoprotic Schiff bases acetylpyridine benzoylhydrazone (HL(1)) and acetylpyridine 4-tert-butylbenzoylhydrazone (HL(2)) demonstrate remarkable coordination versatility towards iron on account of their propensity to undergo tautomeric transformations as imposed by the metal centre. Each of the pyridyl aroylhydrazone ligands complexes with the ferrous or ferric ion under strictly controlled reaction conditions to afford three six-coordinate mononuclear compounds [Fe(II)(HL)(2)](ClO(4))(2), [Fe(II)L(2)] and [Fe(III)L(2)]ClO(4) (HL = HL(1) or HL(2)) displaying distinct colours congruent with their intense CT visible absorptions. The synthetic manoeuvres rely crucially on the stoichiometry of the reactants, the basicities of the reaction mixtures and the choice of solvent. Electrochemically, each of these iron compounds exhibits a reversible metal-centred redox process. By all appearances, [Fe(III)(L(1))(2)]ClO(4) is one of only two examples of a crystallographically elucidated iron(III) bis-chelate compound of a pyridyl aroylhydrazone. Several pertinent physical measurements have established that each of the Schiff bases stabilises multiple spin states of iron; the enolate form of these ligands exhibits greater field strength than does the corresponding neutral keto tautomer. To the best of our knowledge, [Fe(III)(L(1))(2)]ClO(4) and [Fe(III)(L(2))(2)]ClO(4) are the first examples of ferric spin crossovers of aroylhydrazones. Whereas in the former the spin crossover (SCO) is an intricate gradual process, in the latter the (6)A(1)?(2)T(2) transition curve is sigmoidal with T(?)~280 K and the SCO is virtually complete. As regards [Fe(III)(L(1))(2)]ClO(4), M?ssbauer and EPR spectroscopic techniques have revealed remarkable dependence of the spin transition on sample type and extent of solvation. In frozen MeOH solution at liquid nitrogen temperature, both iron(III) compounds exist wholly in the doublet ground state. 相似文献
82.
Wang WN An WJ Ramalingam B Mukherjee S Niedzwiedzki DM Gangopadhyay S Biswas P 《Journal of the American Chemical Society》2012,134(27):11276-11281
A facile development of highly efficient Pt-TiO(2) nanostructured films via versatile gas-phase deposition methods is described. The films have a unique one-dimensional (1D) structure of TiO(2) single crystals coated with ultrafine Pt nanoparticles (NPs, 0.5-2 nm) and exhibit extremely high CO(2) photoreduction efficiency with selective formation of methane (the maximum CH(4) yield of 1361 μmol/g-cat/h). The fast electron-transfer rate in TiO(2) single crystals and the efficient electron-hole separation by the Pt NPs were the main reasons attributable for the enhancement, where the size of the Pt NPs and the unique 1D structure of TiO(2) single crystals played an important role. 相似文献
83.
Stępiński D 《Micron (Oxford, England : 1993)》2012,43(8):870-875
Nucleolin and its homologues are multifunctional proteins which reside mainly in nucleoli of yeast, animal and plant cells. Hence, they are generally implicated in many stages of ribosome biosynthesis. In this study nucleolin was identified in root meristematic cell nucleoli of soybean plants subjected to chilling stress, recovered after chilling and under control conditions with the use of the immunogold electron microscopy technique. Soybean nucleoli exhibited various metabolic activities under these conditions (St?piński, 2004). Current studies showed that the level of nucleolin, expressed as a number of gold grains per μm2, varied in particular subnucleolar regions in the soybean root meristematic cell nucleoli. Labeling density changed in these regions when plants were subjected to the given treatment. Most abundantly this protein was present in dense fibrillar component (DFC) around fibrillar centers (FCs) in the nucleoli of recovered plants, while in the nucleoli of stressed plants this region contained the lowest level of nucleolin. It can be supposed that nucleolin participates in ribosome biogenesis and its level is correlated with metabolic activity of soybean nucleoli – the more active nucleoli, the higher level of nucleolin and vice versa. 相似文献
84.
'Herbal highs' have been advertised as legal and natural substitutes to cannabis, but a detailed examination of these products has revealed that the herbal matrix is laced with synthetic substances that mimic the effects of marijuana. Producers select the ingredients based on the results of scientific studies on the affinities of different chemicals to cannabinoid receptors. Naphthoylindoles have turned out to be the most popular class of substances identified in the products. Legal actions taken in order to tackle the problem of uncontrolled access to one substance have usually resulted in the marketing of derivatives or analogues. In the study, the mass spectral behavior of twelve synthetic cannabinoids from the naphthoylindole family under electrospray ionization (ESI) was investigated. LC-QTOFMS experiments were performed in three modes (low fragmentor voltage, high fragmentor voltage with/without collision energy), and they enabled the identification of protonated molecules and main ions. A general fragmentation pattern under this ionization method was proposed, and mechanisms of ion formation were discussed. The developed procedure allowed the determination of substituent groups of the core naphthoylindole structure and distinction between positional isomers. The obtained results were used for the prediction of the ESI-MS spectra for many naphthoylindoles with a high affinity to cannabinoid receptors. Similarities and differences between ESI-MS and electron impact-MS spectra of naphthoylindoles were discussed. The developed identification process was presented on an example of an analysis of an unknown herbal material, in which JWH-007 was finally identified. Knowledge of the fragmentation mechanisms of naphthoylindoles could also be used by other researchers for identification of unknown substances in this chemical family. 相似文献
85.
Dariusz Szychowski Barbara Pacewska 《Journal of Thermal Analysis and Calorimetry》2012,109(2):789-795
The purpose of this study was to determine the possibility of producing hydrophobic mesoporous mineral-carbon sorbents from aluminum hydroxide and coal-tar pitch-polymer compositions by carbonization at 600?°C in an nitrogen atmosphere. The method of homogenization was optimized using different solvents. Blends of aluminum hydroxide and coal-tar pitch with a definite composition or the products of co-precipitation of aluminum hydroxide in the coal-tar pitch-polymer medium were subjected to carbonization process. The hydrophilic?Chydrophobic properties were evaluated by adsorption of water vapors. The highest value of BET surface area about 370?m2/g, was achieved for the carbonization product obtained from co-precipitated raw components with 10?wt% coal-tar pitch-polymer compositions. 相似文献
86.
MS Shongwe UA Al-Zaabi F Al-Mjeni CS Eribal E Sinn IA Al-Omari HH Hamdeh D Matoga H Adams MJ Morris AL Rheingold E Bill DJ Sellmyer 《Inorganic chemistry》2012,51(15):8241-8253
Several potentially tridentate pyridyl and phenolic Schiff bases (apRen and HhapRen, respectively) were derived from the condensation reactions of 2-acetylpyridine (ap) and 2'-hydroxyacetophenone (Hhap), respectively, with N-R-ethylenediamine (RNHCH(2)CH(2)NH(2), Ren; R = H, Me or Et) and complexed in situ with iron(II) or iron(III), as dictated by the nature of the ligand donor set, to generate the six-coordinate iron compounds [Fe(II)(apRen)(2)]X(2) (R = H, Me; X(-) = ClO(4)(-), BPh(4)(-), PF(6)(-)) and [Fe(III)(hapRen)(2)]X (R = Me, Et; X(-) = ClO(4)(-), BPh(4)(-)). Single-crystal X-ray analyses of [Fe(II)(apRen)(2)](ClO(4))(2) (R = H, Me) revealed a pseudo-octahedral geometry about the ferrous ion with the Fe(II)-N bond distances (1.896-2.041 ?) pointing to the (1)A(1) (d(π)(6)) ground state; the existence of this spin state was corroborated by magnetic susceptibility measurements and M?ssbauer spectroscopy. In contrast, the X-ray structure of the phenolate complex [Fe(III)(hapMen)(2)]ClO(4), determined at 100 K, demonstrated stabilization of the ferric state; the compression of the coordinate bonds at the metal center is in accord with the (2)T(2) (d(π)(5)) ground state. Magnetic susceptibility measurements along with EPR and M?ssbauer spectroscopic techniques have shown that the iron(III) complexes are spin-crossover (SCO) materials. The spin transition within the [Fe(III)N(4)O(2)](+) chromophore was modulated with alkyl substituents to afford two-step and one-step (6)A(1) ? (2)T(2) transformations in [Fe(III)(hapMen)(2)]ClO(4) and [Fe(III)(hapEen)(2)]ClO(4), respectively. Previously, none of the X-salRen- and X-sal(2)trien-based ferric spin-crossover compounds exhibited a stepwise transition. The optical spectra of the LS iron(II) and SCO iron(III) complexes display intense d(π) → p(π)* and p(π) → d(π) CT visible absorptions, respectively, which account for the spectacular color differences. All the complexes are redox-active; as expected, the one-electron oxidative process in the divalent compounds occurs at higher redox potentials than does the reverse process in the trivalent compounds. The cyclic voltammograms of the latter compounds reveal irreversible electrochemical generation of the phenoxyl radical. Finally, the H(2)salen-type quadridentate ketimine H(2)hapen complexed with an equivalent amount of iron(III) to afford the μ-oxo-monobridged dinuclear complex [{Fe(III)(hapen)}(2)(μ-O)] exhibiting a distorted square-pyramidal geometry at the metal centers and considerable antiferromagnetic coupling of spins (J ≈ -99 cm(-1)). 相似文献
87.
Niko Guskos Spiros Glenis Janusz Typek Grzegorz Zolnierkiewicz Pawel Berczynski Kamil Wardal Aleksander Guskos Daniel Sibera Dariusz Moszyński Witold Lojkowski Urszula Narkiewicz 《Central European Journal of Physics》2012,10(2):470-477
Fine particles of ZnFe2O4 were synthesized by a wet chemical method in the (80 wt.% Fe2O3 + 20 wt.% ZnO) system. The morphological and structural properties of the mixed system were investigated by scanning electron microscopy, X-ray diffraction, inductively coupled plasma atomic emission, and X-ray photoelectron spectroscopy. The major phase was determined to be the ZnFe2O4 spinel with particle size of 11 nm. The magnetic properties of the material were investigated by ferromagnetic resonance (FMR) in the temperature range from liquid helium to room temperature. A very intense, asymmetric FMR signal from ZnFe2O4 nanoparticles was recorded, which has been analyzed in terms of two Callen-lineshape lines. Temperature dependence of the FMR parameters was obtained from fitting the experimental lines with two component lines. Analysis of the FMR spectra in terms of two separate components indicates the presence of strongly anisotropic magnetic interactions. 相似文献
88.
Dariusz Gawin Francesco Pesavento Bernhard A. Schrefler 《International Journal of Solids and Structures》2008,45(25-26):6241-6268
The second part of the paper presents numerical solutions of the mathematical model of hydro-chemo-mechanical behavior of cementitious materials exposed to contact with deionized water of part 1. The model defines kinetics of the calcium leaching process instead of a direct application of a curve describing equilibrium between solid calcium in the material skeleton and the calcium dissolved in the pore solution. It further takes into account the advective flux of calcium ions. Both aspects are new as compared to previous models. The weak form of the governing equations of the model is derived first using the Galerkin method. Then, the equations are discretized in space with finite elements and in time domain with finite differences, and finally the procedures used for numerical solution of their discretized form are presented. Three numerical examples are solved to test the numerical solution procedure proposed and demonstrate its robustness for solution of 1D and 2D problems concerning fast and slow leaching of cement-based materials. The effect of various factors on the results concerning chemical degradation of structures made of cementitious materials is analyzed as well. 相似文献
89.
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