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81.
Case studies of the Baeyer-Villiger reaction applied to diand trifluoromethylketone derivatives and the effect of the fluoromethyl groups on the Baeyer-Villiger reaction, are described. 相似文献
82.
Synthetic routes for the branching pentasaccharides 4 and 5 of glycoproteins are described in a regio- and stereo- controlled way. 相似文献
83.
We report the synthesis of optically active 2-aryl-2-fluoropropionic acids 2 as non-epimerizable mimics of 2-arylpropionic acids 1, a class of compounds which have been widely used as non-steroidal anti-inflammatory drugs (NSAIDs). This is a continuation of our research involving the design, synthesis, and evaluation of chiral fluorine-containing organic molecules as effective analogues of pharmacologically important compounds. 相似文献
84.
Zhao Y Higashihara T Sugiyama K Hirao A 《Journal of the American Chemical Society》2005,127(41):14158-14159
Novel 3-arm ABC, 4-arm ABCD, and 5-arm ABCDE asymmetric star polymers comprising the conductive polyacetylene precursor, poly(4-methylphenyl vinyl sulfoxide) (PMePVSO), and other segments, such as polystyrene, poly(alpha-methylstyrene), poly(4-methoxystyrene), poly(4-trimethylsilylstyrene), and poly(4-methylstyrene), were synthesized by the methodology based on living anionic polymerization using DPE-functionalized polymers. This methodology involves the addition reaction of a DPE-functionalized polymer to a living anionic polymer followed by the living anionic polymerization of MePVSO initiated from the in situ formed polymer anion with two, three, or four polymer segments. The resultant asymmetric star polymers possessed predetermined molecular weights, narrow molecular weight distributions (Mw/Mn < 1.03), and desired compositions as confirmed by SEC, 1H NMR, SLS, and elemental analysis. After thermal treatment, the PMePVSO segment in the star polymer could be completely converted into a conductive polyacetylene segment, evident from TGA and elemental analysis. These asymmetric star polymers are expected to exhibit interesting solution properties and unique microphase-separated morphological suprastructures with potential applications in nanoscopic conductive materials. Moreover, this methodology can afford the target asymmetric star polymers with arm segments varying in a wide range and enables the synthesis of more complex macromolecular architectures. 相似文献
85.
Tomoya Ito Koji Suda Takuya Kumamoto Waka Nakanishi Toshiko Watanabe Tsutomu Ishikawa Hiroko Seki Masatoshi Kawahata Kentaro Yamaguchi Yasumitsu Ogura Kazuo T. Suzuki 《Molecular diversity》2010,14(1):131-145
The role of o-bisguanidinobenzenes (BGBs) as new Brønsted base ligands for arsenic and phosphoric acids was examined. In solution state, complexation was evaluated by Job’s plot in 1H NMR experiment, indicating a 1:1 complex formation, whereas in solid state crystalline structures of complexes obtained were addressed by X-ray crystallographic analysis and/or solid state 13C NMR experiment, in which 1:2 complexes between the BGB and the acid components were normally formed. Based on these results, Merrifield and Hypogel® resin-anchored BGBs were designed and prepared as the corresponding polymer-supported host ligands. Evaluation of their coordination ability with metal salts (ZnCl2 and CoCl2) and arsenic acid in aqueous media by ICP-MS showed that the latter Hypogel® resin-anchored BGBs acted as effective immobilized base ligands. 相似文献
86.
87.
We establish the Stein phenomenon in the context of two-step, monotone incomplete data drawn from , a (p+q)-dimensional multivariate normal population with mean and covariance matrix . On the basis of data consisting of n observations on all p+q characteristics and an additional N−n observations on the last q characteristics, where all observations are mutually independent, denote by the maximum likelihood estimator of . We establish criteria which imply that shrinkage estimators of James-Stein type have lower risk than under Euclidean quadratic loss. Further, we show that the corresponding positive-part estimators have lower risk than their unrestricted counterparts, thereby rendering the latter estimators inadmissible. We derive results for the case in which is block-diagonal, the loss function is quadratic and non-spherical, and the shrinkage estimator is constructed by means of a nondecreasing, differentiable function of a quadratic form in . For the problem of shrinking to a vector whose components have a common value constructed from the data, we derive improved shrinkage estimators and again determine conditions under which the positive-part analogs have lower risk than their unrestricted counterparts. 相似文献
88.
This study presents the novel concept of a transformable protecting group, which changes its properties through structural transformation. Based on this concept, we developed a 2-(2-ethynylphenyl)-2-(5-methylfuran-2-yl)-ethoxycarbonyl (Epoc) group. The Epoc group was transformed into an Fmoc-like structure with gold(iii)-catalyzed fluorene formation and was removable under Fmoc-like mild basic conditions post-transformation even though it was originally stable under strongly basic conditions. As an application for organic synthesis, the Epoc group provides the novel orthogonality of gold(iii)-labile protecting groups in solid-phase peptide synthesis. In addition, the high turnover number of fluorene formation in aqueous media is suggestive of the applicability of the Epoc group to biological systems.A protecting group removable with gold(iii)-catalyzed fluorene formation and the subsequent addition of piperidine was developed. 相似文献
89.
90.
Hikari Jinnouchi Hisanori Nambu Kanae Takahashi Tomoya Fujiwara Takayuki Yakura 《Tetrahedron》2019,75(16):2436-2445
Dirhodium(II)-catalyzed oxonium ylide formation–[2,3]-sigmatropic rearrangement of 6-allyloxy-2-diazo-3-ketoesters possessing a C-6 substituent is described. The reaction of 6-alkyl- or 6-aryl-substituted 6-allyloxy-2-diazo-3-ketoesters with a catalytic amount of Rh2(S-PTTL)4 proceeded in a chemoselective and stereoselective manner to provide 6-substituted 2-allyl-3-oxotetrahydropyran-2-carboxylates in good yields and with high diastereoselectivities. To demonstrate the utility of this sequential reaction, we conducted the total synthesis of (+)-tanikolide, in which the construction of the δ-lactone skeleton was achieved by employing a 2-iodobenzamide-catalyzed oxidative cleavage of tetrahydropyran-2-methanol. 相似文献