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811.
The effects of pressure at gel preparation on the inhomogeneities were investigated by small-angle neutron scattering. Poly(N-isopropylacrylamide) (PNIPA) gels, known as thermosensitive polymer gels undergoing volume transition, were prepared at various pressures ranging from 0.1 to 300 MPa. The scattering intensity increased with increasing Pprep, up to 200 MPa, then decreased by further increase in Pprep. The degree of inhomogeneities evaluated by the ratio of the static and dynamic correlators exhibited a similar behavior to that of the ensemble average light scattered intensity, <I>E. The physical meaning of the gel inhomogeneities is discussed from the viewpoint of swelling thermodynamics. It will be shown that the increase in the swelling degree is due not to an increase in the miscibility of PNIPA with water but to the increase in inhomogeneities. 相似文献
812.
Takashi Ikeda Dr. Keishiro Tahara Dr. Ryoichi Ishimatsu Prof. Toshikazu Ono Dr. Luxia Cui Momoka Maeda Prof. Yoshiki Ozawa Prof. Masaaki Abe 《Angewandte Chemie (International ed. in English)》2023,62(21):e202301109
This study reports an effective peripheral decoration of organic donor-acceptor diads with B(C6F5)3 for stabilizing electrogenerated radical ions. By employing a common p-type organic semiconductor benzothienobenzothiophene (BTBT) as the donor, tetracoordinate boron complexes showed improved solution electrochemiluminescence (ECL) intensity, reaching a 156-fold increase compared to that of the parent diad. The unprecedented Lewis-pairing-induced ECL enhancement is attributed to the multiple roles of B(C6F5)3: 1) redistributing frontier orbitals, 2) facilitating electrochemical excitation, and 3) restricting molecular motions. Furthermore, B(C6F5)3 converted the molecular arrangement of BTBT from conventional 2D herringbones into 1D π-stacks. This robust, highly ordered columnar nanostructure allowed red-shifting of the crystalline film ECL with electrochemical doping through the electronic coupling pathways of BTBT. Our approach will facilitate the development of elaborate metal-free ECL systems. 相似文献
813.
Toshikazu Hirao 《Macromolecular Symposia》2002,186(1):75-80
A combination of transition metals and π-conjugated molecules or polymers as redox-active ligands affords the hybrid conjugated complexes. A variety of structural design is possible based on the coordination number and geometry to construct an efficient multi-redox system. 相似文献
814.
815.
Prof. Dr. Toshikazu Takata Prof. Dr. Koji Yamamoto Kazuki Higuchi Dr. Masahiro Ogawa Ayumi Kawasaki Shunya Mizuno Hikaru Iwasaki Masaki Nagashima Prof. Dr. Yoshihiro Hayashi Prof. Dr. Susumu Kawauchi Prof. Dr. Kazuko Nakazono Prof. Dr. Yasuhito Koyama 《Angewandte Chemie (International ed. in English)》2023,62(24):e202303494
Post-synthesis modification of polymers streamlines the synthesis of functionalized polymers, but is often incomplete due to the negative polymer effects. Developing efficient polymer reactions in artificial systems thus represents a long-standing objective in the fields of polymer and material science. Here, we show unprecedented macrocycle-metal-complex-catalyzed systems for efficient polymer reaction that result in 100 % transformation of the main chain functional groups presumably via a processive mode reaction. The complete polymer reactions were confirmed in not only intramolecular reaction (hydroamination) but also intermolecular reaction (hydrosilylation) by using Pd- and Pt-macrocycle-catalyzed systems. The most fascinating feature of the both reactions is that higher-molecular-weight polymers reach completion faster. Various studies suggested that the reactions occur in the catalyst cavity via the formation of a supramolecular complex between the macrocycle catalyst and polymer substrate like pseudorotaxane, which should be of characteristic of the efficient polymer reactions progressing in a processive mode. 相似文献
816.
817.
Dr. Yosuke Akae Prof. Dr. Toshikazu Takata 《European journal of organic chemistry》2023,26(12):e202300171
The acylation of a cyclodextrin-based [3]rotaxane was implemented with anhydride reagents following a facile procedure. Methacrylic anhydride facilitated the introduction of a vinyl-group into the rotaxane structure toward achieving a crosslinker. Interestingly, only a few methacrylic units were attached to the cyclodextrin at reaction temperatures of up to 60 °C even with an excess amount of the reagent, probably due to steric hindrance. Therefore, the number of vinyl groups on the [3]rotaxane framework was easily controlled to be approximately two units via a simple random acylation, which worked effectively as a facile synthesis route for the rotaxane crosslinker. The acylation behavior was investigated in detail by NMR and MALDI-TOF-MS analyses. Such a proposed approach will help overcome the trade-off between convenience and utility associated with the mono-modification of cyclodextrins. 相似文献
818.
819.
Hirosuke Watanabe Masashi Furukawa Tadahiko Takata Masahide Yamamoto 《Macromolecular Symposia》2000,159(1):131-142
The application of the low‐temperature plasma method, the excimer laser treatment method and the corona‐discharge method to aramid) were discussed, presenting an overview of current trends and developments in this area. 相似文献
820.
Akiya Ogawa Noriaki Takami Masahito Sekiguchi Noboru Sonoda Toshikazu Hirao 《Heteroatom Chemistry》1998,9(6):581-584
Elemental sulfur can be reduced to the corresponding thiolate anion species (S2− and S2−2) selectively by samarium diiodide in the presence and absence of HMPA, respectively. The subsequent alkylation of the thiolate anion species provides a useful synthetic route to dialkyl sulfides and disulfides. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9: 581–584, 1998 相似文献