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11.
Capillaries made of fluorinated ethylene propylene (FEP) with an inner diameter of 50 microm have been employed in capillary zone electrophoresis with UV-Vis absorbance detection. The capillaries were made in the laboratory with a recently developed technique using fluoropolymer heat shrink/melt tubing and a tungsten wire as a template for the channel. An electroosmotic flow was obtained in the channels and it is shown that an FEP capillary is more effective for a cationic test solute than a fused-silica capillary. The compatibility of FEP capillaries with optical detection is evaluated briefly. 相似文献
12.
Dai QH Tommos C Fuentes EJ Blomberg MR Dutton PL Wand AJ 《Journal of the American Chemical Society》2002,124(37):10952-10953
The use of side chains as catalytic cofactors for protein mediated redox chemistry raises significant mechanistic issues as to how these amino acids are activated toward radical chemistry in a controlled manner. De novo protein design has been used to examine the structural basis for the creation and maintenance of a tryptophanyl radical in a three-helix bundle protein maquette. Here we report the detailed structural analysis of the protein by multidimensional NMR methods. An interesting feature of the structure is an apparent pi-cation interaction involving the sole tryptophan and a lysine side chain. Hybrid density functional calculations support the notion that this interaction raises the reduction potential of the W degrees /WH redox pair and helps explain the redox characteristics of the protein. This model protein system therefore provides a powerful model for exploring the structural basis for controlled radical chemistry in protein. 相似文献
13.
Margareta Zehnder 《Helvetica chimica acta》1979,62(8):2854-2859
Polynuclear Cobalt Complexes. V. Preparation of tetrakis (ethylenediamine)-μ-peroxo-μ-amido and μ-peroxo-μ-thiocyanato-dicobalt (III) complexes starting from tetrakis (ethylenediamine)bis-(ammine)-μ-peroxo-dicobalt (III)-tetraperchlorate Racemic tetrakis (ethylenediamine)-μ-peroxo-μ-amido-dicobalt (III) thiocyanate and its corresponding hydroperoxo- and superoxo-complexes have been isolated from [(en)2(NH3)Co(O2)(NH3)(en)2](ClO4)4. A new binuclear peroxo complex containing thiocyanate as bridging ligand was prepared by the same method. The stretching frequencies of the CN- and CS-group as well as the NCS-bending frequence in the IR. spectrum of [(en)2Co(O2, SCN)Co(en)2](NO3)3 suggest that the μ-thiocyanato group is N-bonded (2050, 750, 475 cm?1). A comparison of IR. spectra of known singly and doubly bridged μ-peroxo complexes is made. Characteristic absorption bands, assignable to ν(O? O) and ν(Co? O) are given. 相似文献
14.
Synthesis, Crystal Structure, and Magnetic Properties of Bis(1,2-benzoquinonediimide)-1,2-benzosemiquinonediimidocobalt (II)-tetraphenylborate-pentahydrate Co (II)-salts catalyze the autoxidation of 1,2-diaminobenzene in slightly alkaline solution. Deeply coloured metal complexes are formed during the reaction suggesting intermediate radical or semiquinonediimide stages of the aromatic ligands. Starting from [CoII (1,2-diaminobenzene)3] (ClO4)2 two different intermediate complexes can be isolated, the magnetic properties of which point to a high-spin cobalt (II)-complex and a low-spin cobalt (II)-complex with a radical ligand respectively. The X-ray structure determination of the latter complex yielded a square pyramidal arrangement, the Co-N4-plane distance being only 0.5 Å. The dark blue coloured complex is diamagnetic. Two of the aromatic ligands have the oxidation state of a benzoquinonediimide while the third, coordinated by one amino group only, is pseudosemiquinonoid. Crystals of C42H48BCoN6O5 are monoclinic, a = 14.493 (5), b = 18.341 (7), c = 15.492 (5) Å, β = 99.198 (5), space group P21/n. Dobs. = 1.290, Dcalc. = 1.289 g/cm3 for Z = 4. The structure was solved by Patterson's method and refined by least-squares techniques to R = 0.088 for 2866 of 5014 independent reflexions. 相似文献
15.
Polynuclear Cobalt Complexes. IV. Preparation and Structure of [(papd)Co(O2)Co(papd)](S2O6)(NO3)2 · 4 H2O The binuclear peroxo complex [(papd)Co(O2)Co(papd)](S2O6)(NO3)2 · 4 H2O I crystallizes in the triclinic space group P1 . Lattice constants are a = 9.405(4), b = 9.270(4), c = 12.218(6)Å, α = 89.58(5), β = 99.08(6), γ = 114.79(5)° for Z = 1. The binuclear cation has a center of symmetry, so the Co? O? O? Co unit is planar. Three chelate rings have a common plane, the ligand configuration is δ. 相似文献
16.
Paul Gesche Franois Klinger Andreas Riesen Thophile Tschamber Margareta Zehnder Jacques Streith 《Helvetica chimica acta》1987,70(8):2087-2097
Saponification of homodiazepine 1a and 1b , in the absence of any proton donors, led to the formation of the 6π electron anionic species A which, by virtue of a 1,5-electrocyclization, is in equilibrium with the allylic anion B . This latter tricyclic species is thermodynamically less favoured than its bicyclic isomer A . Nevertheless, B could be trapped by acylation and led tupe- 2 compounds which are the major reaction products. This is due to the fact that B is more nucleophilic and, therefore, much more reactive than A . The transoid topology of the tricyclic products 2 was demonstrated by 1H-NMR and by an X-ray diagram of 2d . The transoid geometry of 2 is a consequence of a torquospecific 1,5-electrocyclization (of A ), which is due to a steric, and possibly even to an electronic factor. 相似文献
17.
Advances in wide bandgap SiC for optoelectronics 总被引:1,自引:0,他引:1
Haiyan Ou Yiyu Ou Aikaterini Argyraki Saskia Schimmel Michl Kaiser Peter Wellmann Margareta K. Linnarsson Valdas Jokubavicius Jianwu Sun Rickard Liljedahl Mikael Syväjärvi 《The European Physical Journal B - Condensed Matter and Complex Systems》2014,87(3):1-16
Silicon carbide (SiC) has played a key role in power electronics thanks to its unique physical properties like wide bandgap, high breakdown field, etc. During the past decade, SiC is also becoming more and more active in optoelectronics thanks to the progress in materials growth and nanofabrication. This paper will review the advances in fluorescent SiC for white light-emitting diodes, covering the poly-crystalline doped SiC source material growth, single crystalline epitaxy growth of fluorescent SiC, and nanofabrication of SiC to enhance the extraction efficiency for fluorescent SiC based white LEDs. 相似文献
18.
Peak compression in CEC is a phenomenon that can generate very narrow peaks with extremely high efficiencies that defy current chromatographic theory. This review article summarises the content of publications in this area up to this date. Two main types of peak compression effects have been observed in the literature. First, an irreproducible and hard to control focusing effect of unclear origin, observed on strong cation exchangers. Second, a reproducible continuous stacking effect caused by sample composition induced system zones demonstrated on several types of stationary phases. 相似文献
19.
Almqvist F Manner S Thornqvist V Berg U Wallin M Frejd T 《Organic & biomolecular chemistry》2004,2(21):3085-3090
The formylated spirobyclic alcohol was computer modeled to be a mimetic of paclitaxel. In this model, the formyl group was used as a truncated paclitaxel side chain in order to reduce the computational work. Compound , carrying the paclitaxel side chain, was synthesized in six steps from optically active 1,3-diketone . Microtubule stabilization was not observed for , indicating that the model needs to be adjusted. 相似文献
20.
Irena Blute Martin Svensson Krister Holmberg Margareta Bergh Ann-Therese Karlberg 《Colloids and surfaces. A, Physicochemical and engineering aspects》1999,150(1-3):105-113
It has previously been shown that alcohol ethoxylates readily undergo autoxidation and that one of the major oxidation products is the surfactant aldehyde, i.e. an ethoxylate carrying a –CH2CHO group at the terminal end of the polyoxyethylene chain. In this work the cloud point, phase behavior and aggregation characteristics of the surfactant aldehyde produced by oxidation of C12H25(OCH2CH2)5OH (C12E5) are determined and compared with the values obtained with the parent surfactant. It was found that the physico–chemical behavior of the two species was very similar, which indicates that a considerable portion of the aldehyde group is in hydrated state, i.e. the surfactant aldehyde consists of a mixture of aldehyde in carbonyl form and the corresponding geminal diol. The cloud point of the surfactant aldehyde decreased rapidly with time, even when it was stored at low temperature. Also the parent surfactant and its homologue C12E6 exhibited a decrease in cloud point during storage. For instance, a 1% aqueous solution of C12E6 showed a cloud point decrease from 62 to 32°C after 4 months storage at 40°C. Such a change in solution behavior can have important practical implications. 相似文献