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11.
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
12.
Pekka Korhonen Margareta Soismaa 《The Journal of the Operational Research Society》1981,32(7):577-585
In this paper we are concerned with ranking various orderings of a set of alternatives to a composite order as a multiple criteria problem. The orderings (called preference orderings) can be real preference orderings or any natural orderings. The objective is to find the most preferred order of the decision maker using the preference orderings as criteria.In principle, the problem can be formulated as a multiple objective linear programming problem using the model of Bowman and Colantoni and then solved with the interactive method proposed by Zionts and Wallenius. However, the fact that we are dealing with integer variables prohibits us from applying this approach as such. We discuss the problem formulation and propose a modified approach to that of Zionts and Wallenius for solving the problem. 相似文献
13.
In this paper we consider a non-trivial link between Baskakov type operators and their genuine Durrmeyer type modification as well as the kth order Kantorovich variant. Recursion formulas for the moments and the images of monomials are proved in order to derive asymptotic expansions. Furthermore we investigate convexity properties of the linking operators and the limiting behavior for certain function spaces. 相似文献
14.
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
15.
Jacques Streith Arnaud Boiron Jean-Louis Paillaud Elsa-Maria Rodriguez-Perez Christiane Strehler Thophile Tschamber Margareta Zehnder 《Helvetica chimica acta》1995,78(1):61-72
Asymmetric methylation and phenylation of the chiral pyridinium salt 7 , as well as methylation of chiral pyridinium salt 18 , with Grignard reagents occurred in good yield and with good-to-excellent diastereoselectivities (Schemes 2 and 3, resp.). These results are best explained by assuming chelate control to govern the asymmetric alkylation/arylation process. The minimum-energy conformations of the out-of-plane twisted pyridinium salts 7 and 18 , as determined by the ‘Molecular Simulations Cerius-Dreiding II’ program, are in good agreement with the postulated asymmetric chelate-control mechanism. 相似文献
16.
The concentrations of the species present during the procedure of Boulègue for determination of sulphide, thiols, thiosulphate and sulphite in mineral waters by titration with mercury(II) chloride have been calculated and functions suitable for the evaluation of the equivalence points have been derived. It is shown that the halide ions in seawater interfere only in the titration of sulphite. 相似文献
17.
Carsten Bolm Konrad Weickhardt Margareta Zehnder Dorothea Glasmacher 《Helvetica chimica acta》1991,74(4):717-726
The synthesis of the complexes 3 of various metals ligated to chiral 4,5-dihydro-2-(2′-oxidophenyl-?O)oxazoles-?N is described (Scheme). Three of them, i.e. 3a , 3e , and 3f containing CuII, ZnII and NiII, respectively, were analyzed by X-ray diffraction studies. A series of CuII complexes ( 6a – d ) with differently substituted dihydrooxazoles have been synthesized. 相似文献
18.
Pelmenschikov V Blomberg MR Siegbahn PE Crabtree RH 《Journal of the American Chemical Society》2002,124(15):4039-4049
The mechanism for methane formation in methyl-coenzyme M reductase (MCR) has been investigated using the B3LYP hybrid density functional method and chemical models consisting of 107 atoms. The experimental X-ray crystal structure of the enzyme in the inactive MCR(ox1)(-)(silent) state was used to set up the initial model structure. The calculations suggest a mechanism not previously proposed, in which the most remarkable feature is the formation of an essentially free methyl radical at the transition state. The reaction cycle suggested starts from a Michaelis complex with CoB and methyl-CoM coenzymes bound and with a squareplanar coordination of the Ni(I) center in the tetrapyrrole F(430) prosthetic group. In the rate-limiting step the methyl radical is released from methyl-CoM, induced by the attack of Ni(I) on the methyl-CoM thioether sulfur. In this step, the metal center is oxidized from Ni(I) to Ni(II). The resulting methyl radical is rapidly quenched by hydrogen-atom transfer from the CoB thiol group, yielding the methane molecule and the CoB radical. The estimated activation energy is around 20 kcal/mol, which includes a significant contribution from entropy due to the formation of the free methyl. The mechanism implies an inversion of configuration at the reactive carbon. The size of the inversion barrier is used to explain the fact that CF(3)-S-CoM is an inactive substrate. Heterodisulfide CoB-S-S-CoM formation is proposed in the final step in which nickel is reduced back to Ni(I). The suggested mechanism agrees well with experimental observations. 相似文献
19.
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
20.
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