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排序方式: 共有5640条查询结果,搜索用时 15 毫秒
1.
BIT Numerical Mathematics - Linear and nonlinear evolution equations have been formulated to address problems in various fields of science and technology. Recently, methods using an exponential... 相似文献
2.
Daisuke Uraguchi Fumito Ueoka Naoya Tanaka Tomohito Kizu Wakana Takahashi Takashi Ooi 《Angewandte Chemie (International ed. in English)》2020,59(28):11456-11461
Catalysis by chiral weakly‐coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non‐nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O‐tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins‐type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis. 相似文献
3.
Suzuka Kinoshita Ryota Yamano Dr. Yu Shibata Yusuke Tanaka Kyoichi Hanada Dr. Takashi Matsumoto Prof. Dr. Kazunori Miyamoto Dr. Atsuya Muranaka Prof. Dr. Masanobu Uchiyama Prof. Dr. Ken Tanaka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):11113-11120
An S-shaped double helicene-like molecule (>99 % ee), possessing stable helical chirality, has been synthesized by the rhodium(I)/difluorphos complex-catalyzed highly diastereo- and enantioselective intramolecular double [2+2+2] cycloaddition of a 2-naphthol- and benzene-linked hexayne. The collision between two terminal naphthalene rings destabilizes the helical chirality of the S-shaped double helicene-like molecule, but the introduction of two additional fused benzene rings significantly increases the configurational stability. Thus, no epimerization and racemization were observed even at 100 °C. The enantiopure S-shaped double helicene-like molecule forms a trimer through the multiple C−H⋅⋅⋅π and C−H⋅⋅⋅O interactions in the solid-state. The trimers stack to form columnar packing structures, in which neighboring stacks have opposite dipole directions. The accumulation of helical structures in the same direction in the S-shaped double helicene-like molecule enhanced the chiroptical properties. 相似文献
4.
Dr. Takaaki Mitsuhashi Dr. Lena Barra Zachary Powers Volga Kojasoy Andrea Cheng Feng Yang Dr. Yoshimasa Taniguchi Dr. Takashi Kikuchi Prof. Dr. Makoto Fujita Prof. Dr. Dean J. Tantillo Prof. Dr. John A. Porco Jr Prof. Dr. Ikuro Abe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23980-23989
Fungal meroterpenoids are a diverse group of hybrid natural products with impressive structural complexity and high potential as drug candidates. In this work, we evaluate the promiscuity of the early structure diversity-generating step in fungal meroterpenoid biosynthetic pathways: the multibond-forming polyene cyclizations catalyzed by the yet poorly understood family of fungal meroterpenoid cyclases. In total, 12 unnatural meroterpenoids were accessed chemoenzymatically using synthetic substrates. Their complex structures were determined by 2D NMR studies as well as crystalline-sponge-based X-ray diffraction analyses. The results obtained revealed a high degree of enzyme promiscuity and experimental results which together with quantum chemical calculations provided a deeper insight into the catalytic activity of this new family of non-canonical, terpene cyclases. The knowledge obtained paves the way to design and engineer artificial pathways towards second generation meroterpenoids with valuable bioactivities based on combinatorial biosynthetic strategies. 相似文献
5.
Jin Su Takashi Hisatomi Tsutomu Minegishi Kazunari Domen 《Angewandte Chemie (International ed. in English)》2020,59(33):13800-13806
Most CdTe photoanodes and photocathodes show positive and negative photocurrent onset potentials for water oxidation and reduction, respectively, and are thus unable to drive photoelectrochemical (PEC) water splitting without external applied biases. Herein, the activity of a CdTe photoanode having an internal p‐n junction during PEC water oxidation was enhanced by applying a CdCl2 annealing treatment together with surface modifications. The resulting CdTe photoanode generated photocurrents of 1.8 and 5.4 mA cm?2 at 0.6 and 1.2 VRHE, respectively, with a photoanodic current onset potential of 0.22 VRHE under simulated sunlight (AM 1.5G). The CdCl2 annealing increased the grain sizes and lowered the density of grain boundaries, allowing more efficient charge separation. Consequently, a two‐electrode tandem PEC cell comprising a CdTe‐based photoanode and photocathode split water without any external bias at a solar‐to‐hydrogen conversion efficiency of 0.51 % at the beginning of the reaction. 相似文献
6.
Prof. Isao Fujii Dr. Makoto Hashimoto Kaori Konishi Akiko Unezawa Haruka Sakuraba Kenta Suzuki Harue Tsushima Miho Iwasaki Satsuki Yoshida Akane Kudo Rina Fujita Aika Hichiwa Koharu Saito Dr. Takashi Asano Dr. Jun Ishikawa Dr. Daigo Wakana Dr. Yukihiro Goda Ayumi Watanabe Mamoru Watanabe Yui Masumoto Dr. Junichiro Kanazawa Dr. Hajime Sato Prof. Masanobu Uchiyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(22):8542-8548
Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark. 相似文献
7.
Jianyu Wang Huabin Sun Yun Sheng Fan Gao Yao Yin Yun Li Lijia Pan Youdou Zheng Yi Shi Takashi Sekiguchi 《固体物理学:研究快报》2015,9(8):466-469
Surface‐diffusion‐induced spontaneous Ga incorporation process is demonstrated in ZnO nanowires grown on GaN substrate. Crucially, contrasting distributions of Ga atoms in axial and radial directions are experimentally observed. Ga atoms uniformly distribute along the ~10 μm long ZnO nanowire and show a rapidly gradient distribution in the radial direction, which is attributed substantially to the difference between surface and volume diffusion. The understanding on the incorporation process can potentially modulate doping and properties in semiconductor nanomaterials.
8.
Dr. Shintaro Ishida Dr. Takashi Abe Dr. Fumiya Hirakawa Tomoyuki Kosai Katsuhiro Sato Prof. Dr. Mitsuo Kira Prof. Dr. Takeaki Iwamoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15100-15103
A persistent dialkylsilanone was synthesized by the dehydrobromination of a dialkylbromosilanol with tris(trimethylsilyl)silyl potassium in solution at ?80 °C: It was characterized by NMR and IR spectroscopy, and was tested in several reactions. In 29Si NMR spectrum in [D8]toluene, the signal due to the unsaturated silicon nuclei was observed at 128.7 ppm. Reactions of the dialkylsilanone with water and mesitonitrile oxide gave a silanediol and a [2+3] cycloadduct, respectively. The silanone remains intact in [D8]toluene below ?80 °C for at least two days, while it undergoes unprecedented isomerization to give a siloxysilene by means of 1,3‐silyl migration at higher temperatures. 相似文献
9.
Xin Wang Takashi Hisatomi Zheng Wang Jun Song Junle Qu Tsuyoshi Takata Kazunari Domen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(31):10776-10780
LaTaON2 is a photocatalyst with intense visible light absorption up to 650 nm, but exhibits low H2 evolution activity owing to uncontrolled facets and high defect densities. In this work, core–shell‐structured plate‐like LaKNaTaO5/LaTaON2 was synthesized by nitriding a layered perovskite‐type LaKNaTaO5. The volatilization of K and Na species during the nitridation promoted the rapid transformation of LaKNaTaO5 into LaTaON2 along [010] direction with the plate‐like shape retained. This yielded high‐quality LaTaON2 shells exposing (010) facets on the lattice‐matched LaKNaTaO5 cores. After loading with a Rh co‐catalyst, LaKNaTaO5/LaTaON2 showed photocatalytic H2 evolution activity four times greater than that obtained from conventional irregular‐shaped LaTaON2 powders and utilized visible light up to 620 nm. This work provides a novel strategy yielding oxynitrides with well‐defined facets and low defect densities by selecting lattice‐matched oxide precursors containing volatile components. 相似文献
10.
Dr. Hiromi Oshita Takashi Suzuki Kyohei Kawashima Prof. Dr. Hitoshi Abe Prof. Dr. Fumito Tani Prof. Dr. Seiji Mori Prof. Dr. Tatsuo Yajima Prof. Dr. Yuichi Shimazaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(32):7649-7658
In order to gain new insights into the effect of the π–π stacking interaction of the indole ring with the CuII–phenoxyl radical as seen in the active form of galactose oxidase, we have prepared a CuII complex of a methoxy-substituted salen-type ligand, containing a pendent indole ring on the dinitrogen chelate backbone, and characterized its one-electron-oxidized forms. The X-ray crystal structures of the oxidized CuII complex exhibited the π–π stacking interaction of the indole ring mainly with one of the two phenolate moieties. The phenolate moiety in close contact with the indole moiety showed the characteristic phenoxyl radical structural features, indicating that the indole ring favors the π–π stacking interaction with the phenoxyl radical. The UV/Vis/NIR spectra of the oxidized CuII complex with the pendent indole ring was significantly different from those of the complex without the side-chain indole ring, and the absorption and CD spectra exhibited a solvent dependence, which is in line with the phenoxyl radical–indole stacking interaction in solution. The other physicochemical results and theoretical calculations strongly support that the indole ring, as an electron donor, stabilizes the phenoxyl radical by the π–π stacking interaction. 相似文献