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31.
Viktor Gutmann Wolfgang Kantner Wolfgang Linert 《Monatshefte für Chemie / Chemical Monthly》1986,117(6-7):739-751
Shifts of the “current free” electrochemical potentials have been measured in the course of mechanical deformation of copper in electrolyte solutions of N,N-dimethylformamide (DMF), N,N-dimethylthioformamide (DMTF) and acetonitrile (An). Shifts towards negative potentials are observed inDMF and inDMTF, towards positive values inAn. By increasing the oxygen concentration the potential shifts are increased inDMF, decreased inDMTF and reversed in sign inAn. As the temperature is increased, the potential shifts are decreased inDMF andDMTF and increased inAn. After cooling to room temperature the potential shifts are found at positive potentials inDMF, whereas inAn the value found at the highest temperature is retained after cooling. The observations suggest characteristic changes in both copper and copperoxide superstructures at the metal-solvent interface. 相似文献
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The interaction of the palladium(II) complex [Pd(hzpy)(H2O)2]2+, where hzpy is 2‐hydrazinopyridine, with purine nucleoside adenosine 5′‐monophosphate (5′‐AMP) was studied kinetically under pseudo‐first‐order conditions, using stopped‐flow techniques. The reaction was found to take place in two consecutive reaction steps, which are both dependent on the actual 5′‐AMP concentration. The activation parameters for the two reaction steps, i.e. ΔH = 32 ±2 kJ mol?1, ΔS = ?168 ±7 J K?1 mol?1, and ΔH = 28 ± 1 kJ mol?1, ΔS = ?126 ± 5 J K?1 mol?1, respectively, were evaluated and suggested an associative mode of activation for both substitution processes. The stability constants and the associated speciation diagram of the complexes were also determined potentiometrically. The isolated solid complex was characterized by C, H, and N elemental analyses, IR, magnetic, and molar conductance measurements. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 42: 132–142, 2010 相似文献
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Absmeier A Bartel M Carbonera C Jameson GN Weinberger P Caneschi A Mereiter K Létard JF Linert W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(8):2235-2243
A new series of [mu-tris-{1,n-bis(tetrazol-1-yl)alkane-N4,N4'}iron(II)] bis(perchlorate) spin-crossover coordination polymers ([Fe(nditz)3](ClO4)2]; n = 4-9) has been synthesised and characterised. The ditetrazole bridging ligands provide octahedral symmetry at the iron(II) centres while allowing the distance between iron(II) centres to be varied. These polymers have therefore been investigated to determine the effects of spacer length on their thermal and light-induced spin-transition behaviour. An increase in the number of carbon atoms in the spacer (n) raises the thermal spin-crossover temperature, while decreasing the stability of the light-induced metastable state generated through the light-induced excited spin state trapping (LIESST) effect by irradiating the sample at 530 nm. Remarkably, however, the parity of the spacer also has an effect, enabling the series of complexes to be divided into two sub-series depending on whether the bridging ligand possesses an even or an odd number of carbon atoms. An explanation at the molecular level using the single configurational coordinate (SCC) model is presented. 相似文献
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Phenomenological characteristics and kinetic and mechanistic aspects of the thermal decomposition of nitrate, chloride, bromide, and iodide complexes of nickel(II) with 4‐N‐(4′‐antipyrylmethylidene)aminoantipyrine have been studied using thermogravimetric (TG) and differential thermogravimetric (DTG) techniques. Kinetic parameters such as activation energy, preexponential factor, and entropy of activation were quantified. The rate‐controlling process in all stages of decomposition was found to be based on random nucleation with one nucleus on each particle according to the Mampel model. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 53–58, 2007 相似文献
40.
Boca M Baran P Boca R Fuess H Kickelbick G Linert W Renz F Svoboda I 《Inorganic chemistry》2000,39(15):3205-3212
The condensation of 2-pyridinecarboxaldehyde N-oxide and triethylenetetramine yields a product with two imidazolidine rings, as proven by a solid-state X-ray structure analysis as well as by NMR solution spectra. This ligand, L1, undergoes a ring-opening reaction on complex formation with Cu(II), yielding [CuL2]2+ where L2 functions as a pentadentate ligand, containing only one imidazolidine ring. On complexation with Zn(II) and Fe(III), both rings are opened and the complexes [ZnL3]2+ and [FeL3]3+ with a hexadentate L3 ligand are formed. The recrystallization of [ZnL3]2+ from DMSO solution results in the complex [ZnL1(DMSO)2]2+ in which L1 behaves as a tetradentate ligand. Thus L1, L2, and L3 are structural isomers with two, one, or no imidazolidine rings, as confirmed by X-ray structure analyses. The intramolecular ring formation is the result of the nucleophilic addition of the N(amino) group to the electrophilic sp2-hybridized -HC delta+=N site. Owing to the absence of the chelate effect on the sp3-hybridized carbon atom belonging to the imidazolidine ring, the ring opening is facilitated and readily observed upon complex formation with Cu(II), Zn(II), and Fe(III). 相似文献