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91.
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Yasutaka Shimada Kazumasa Usuda Hirokazu Okabe Tsuguru Suzuki Kazutsugu Matsumoto 《Tetrahedron: Asymmetry》2009,20(24):2802-2808
The deracemization of 1,2-diol monotosylate derivatives is achieved by the sequential combination of enzymatic hydrolysis and Mitsunobu inversion using a polymer-bound triphenylphosphine. After the lipase-catalysed hydrolysis of the racemic 2-acetoxyhexyl tosylate, the subsequent Mitsunobu reaction without separation causes an inversion of the resulting (R)-alcohol to give the (S)-enantiomer of the acetate as a single product. In particular, the reaction using the polymer-bound triphenylphosphine also proceeds smoothly, and the product is easily separated by filtration from the polymer-bound reagent and its by-products. This deracemization process is applicable to the preparation of several optically active 1,2-diol monotosylates. 相似文献
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We report the effects of guest particles on the swelling properties of bulk polyacrylamide gels. The guest particles were the spheres of poly(N‐isopropylacrylamide) gel with submicrometer diameter, which were synthesized by an emulsion‐polymerized reaction in water. Polyacrylamide gels were prepared by a free radical polymerization reaction, immobilizing the gel microparticles with different concentrations at gelation. The macroscopic swelling ratio of this hybrid gel in a cylindrical shape was measured as functions of temperature and acetone concentration. The presence of guest particles was found to strongly affect the swelling behavior in the bulk gels when the concentration of incorporated particles exceeded a threshold. The experimental results indicated that the macroscopic volume in response to the temperature change should be determined by the guest particles above the threshold. On the other hand, the hybrid gel could not evidently shrink by adding acetone when the concentration of guest particles exceeded the threshold. To make clear the distribution of guest particles in the bulk networks, the fractured surfaces of dried gels were imaged by tapping mode atomic force microscopy. The guest particles were found to aggregate in the bulk homogeneous networks to form microdomains with densely connected structure, which became larger with increasing particle concentration. The roles of bulk networks as well as guest particles on the swelling behavior of hybrid gels were qualitatively discussed on the basis of the incorporated structure of guest particles, depending on the concentration of guest particles. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1696–1704, 2005 相似文献
96.
Nobuo Yoshida 《Journal of statistical physics》2008,133(6):1033-1058
We consider a discrete-time stochastic growth model on d-dimensional lattice. The growth model describes various interesting examples such as oriented site/bond percolation, directed
polymers in random environment, time discretizations of binary contact path process and the voter model. We study the phase
transition for the growth rate of the “total number of particles” in this framework. The main results are roughly as follows:
If d≥3 and the system is “not too random”, then, with positive probability, the growth rate of the total number of particles is
of the same order as its expectation. If on the other hand, d=1,2, or the system is “random enough”, then the growth rate is slower than its expectation. We also discuss the above phase
transition for the dual processes and its connection to the structure of invariant measures for the model with proper normalization.
Supported in part by JSPS Grant-in-Aid for Scientific Research, Kiban (C) 17540112. 相似文献
97.
Kensuke Okusa Yuki Suita Yukio Otsuka Mineo Tahara Tohru Ikegami Nobuo Tanaka Masayoshi Ohira Masakazu Takahashi 《Journal of separation science》2010,33(3):348-358
The effectiveness of several basic compounds for testing silica‐based stationary phases was reviewed by applying them to recent columns for reversed‐phase HPLC. Most octadecylsilylated (C18) stationary phases, prepared as a base‐deactivated material from high‐purity silica gel with endcapping, provided excellent peak shape and column efficiency for the bases including benzylamine and amitriptyline that once caused problems and were subsequently employed for testing silanol activities. However, a cyclic tertiary amine, dextrometorphan, was eluted as an acceptable peak from only a few columns at neutral pH. Such a more sensitive probe is expected to contribute to further improvement of the stationary phase for reversed‐phase HPLC. 相似文献
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Hisayasu Ishibashi Dr. Manuel Rondelli Hiroki Shudo Prof. Dr. Takehisa Maekawa Prof. Dr. Hideto Ito Prof. Dr. Kiichi Mizukami Prof. Dr. Nobuo Kimizuka Prof. Dr. Akiko Yagi Prof. Dr. Kenichiro Itami 《Angewandte Chemie (International ed. in English)》2023,62(44):e202310613
The active metal template (AMT) strategy is a powerful tool for the formation of mechanically interlocked molecules (MIMs) such as rotaxanes and catenanes, allowing the synthesis of a variety of MIMs, including π-conjugated and multicomponent macrocycles. Cycloparaphenylene (CPP) is an emerging molecule characterized by its cyclic π-conjugated structure and unique properties. Therefore, diverse modifications of CPPs are necessary for its wide application. However, most CPP modifications require early stage functionalization and the direct modification of CPPs is very limited. Herein, we report the synthesis of a catenane consisting of [9]CPP and a 2,2′-bipyridine macrocycle as a new CPP analogue that contains a reliable synthetic scaffold enabling diverse and concise post-modification. Following the AMT strategy, the [9]CPP-bipyridine catenane was successfully synthesized through Ni-mediated aryl-aryl coupling. Catalytic C−H borylation/cross-coupling and metal complexation of the bipyridine macrocycle moiety, an effective post-functionalization method, were also demonstrated with the [9]CPP-bipyridine catenane. Single-crystal X-ray structural analysis revealed that the [9]CPP-bipyridine catenane forms a tridentated complex with an Ag ion inside the CPP ring. This interaction significantly enhances the phosphorescence lifetime through improved intermolecular interactions. 相似文献