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43.
Hirakawa Y Suzuto M Ohnishi H Shingaki T Eyring EM Tokunaga M Masujima T 《The Analyst》2003,128(6):676-680
The nano-kinetic movement of a single DNA molecule was observed and analyzed by a newly developed video-microscope system with an optical fiber, called a pin-fiber video scope. A single lambda-DNA molecule was put in focus using fiber-illumination, and the stretching and shrinking motion was measured. The molecule's kinetics were analyzed by numerical calculations and are discussed. A photocleavage phenomenon of DNA molecules was also visualized by the pin-fiber video scope. The new video-microscope system has the potential to observe and analyze the nano-kinetics of a single molecule. 相似文献
44.
Nobutaka Yamaoka Kohei Sumida Itsuki Itani Hiroko Kubo Yusuke Ohnishi Sho Sekiguchi Dr. Toshifumi Dohi Prof. Dr. Yasuyuki Kita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):15004-15011
Metal‐free oxidative C? C coupling by using polyalkoxybenzene‐derived diaryliodonium(III) salts as both the oxidant and aryl source has been developed. These salts can induce single‐electron‐transfer (SET) oxidation to yield electron‐rich arenes and subsequently transfer the polyalkoxyphenyl group into in situ generated aromatic radical cations to produce biaryl products. The reaction is promoted by a Lewis acid that activates the iodonium salts. It has been revealed that the reactivity of the salts under acidic conditions is quite different to their known behavior under basic conditions. The reactivity preference of a series of iodonium salts in the SET oxidation and their ligand transfer abilities have been systematically investigated and the results are summarized in this report. 相似文献
45.
Naofumi Naga Takeshi Shiono Tomiki Ikeda 《Journal of molecular catalysis. A, Chemical》1999,150(1-2):155-162
Ethylene polymerization was conducted with bis(cyclopentadienyl)zirconium dichloride (1) and rac-dimethylsilylenebis(indenyl)zirconium dichloride (2) combined with trialkylaluminum (AlR3; R=methyl (Me), ethyl (Et), isobutyl (iBu))/triphenylcarbenium tetrakis(pentafluorophenyl)borate (Ph3CB(C6F5)4) or tris(pentafluorophenyl)borane (B(C6F5)3) to study the effect of cocatalysts on polymerization rate (Rp). When AlMe3 was used, no activity or very low activity was observed with both zirconocenes regardless of the borane compounds used. The replacement of AlMe3 to AlEt3 or AliBu3 with 1–AlR3/Ph3CB(C6F5)4 caused polymerization and induction time was observed to reach the maximum Rp. Especially in the case of using AlEt3, it took about 30 min to show the activity. When B(C6F5)3 was used, AlEt3 was not effective but AliBu3 gave the highest activity among all the combinations of AlR3 and the borane compounds. In the case of polymerization with 2 using Ph3CB(C6F5)4, high activity was observed with both AlEt3 and AliBu3 without any induction period. When B(C6F5)3 was used instead of Ph3CB(C6F5)4, very low activity was observed with AlEt3. On the other hand, high activity was observed with AliBu3, and the maximum Rp was found at the beginning of the polymerization. The effect of AlR3 on the formation of active species was discussed based on these results. 相似文献
46.
Takahiro Nakae Ryuji Ohnishi Yoshiharu Kitahata Tatsuya Soukawa Hisako Sato Shigeki Mori Tetsuo Okujima Hidemitsu Uno Hiroshi Sakaguchi 《Tetrahedron letters》2012,53(13):1617-1619
6,13-Diiododibenzo[a,h]anthracene and 5,8-diiodopicene were synthesized by AuCl-catalyzed double cyclization. The highly selective reaction yielded a new class of peri-halogenated fused aromatics. 相似文献
47.
The universal occurrence of a hierarchical structure and its dynamic behavior in various types of group, living or abstract, are discussed. Here the word “group” refers not only to tangible aggregation but also to invisible aggregation of social psychological and of geopolitical meaning. The evolution of these groups is simulated using a model of agents distributed on the lattices of cellular grids. It is assumed that agents, fearing isolation, interact asymmetrically with each other with regard to exchange of “power”. As an indicator of hierarchy, the Gini coefficient is introduced. Example calculations are made for the aggregation, fusion and fission of animal groups, and for the appearance of a powerful empire and the rise and fall of supremacy. It is shown that such abstract objects evolve with time in accordance with the universal rules of groups common to birds and fish. 相似文献
48.
Theoretical and computational methods are powerful in studying transition metal complexes. Our theoretical studies of C–H σ‐bond activation of benzene by Pd(II)–formate complex and that of methane by Ti(IV)‐imido complex successfully disclosed that these reactions are understood to undergo heterolytic σ‐bond activation and the driving force is the formation of strong O–H and N–H bonds in the former and the latter, respectively. Orbital interactions are considerably different from those of σ‐bond activation by oxidative addition. The transmetallation, which is a key process in the cross‐coupling reaction, is understood to be heterolytic σ‐bond activation. Our theoretical study clarified how to accelerate this transmetallation. Also, we wish to discuss weak points in theoretical and computational studies of large systems including transition metal elements, such as the necessity to incorporate solvation effect and to present quantitatively correct numerical results. The importance of solvation effects is discussed in the oxidative addition of methyliodide to Pt(II) complex which occurs in a way similar to an SN2 substitution. To apply the CCSD(T) (coupled cluster singles and doubles with perturbative triples correction) method, which is the gold standard of electronic structure theory, to large system, we need to reduce the size of the system by employing a small model. But, such modeling induces neglects of electronic and steric effects of substitutents which are replaced in the small model. Frontier‐orbital‐consistent quantum‐capping potential (FOC‐QCP) was recently proposed by our group to incorporate the electronic effects of the substituents neglected in the modeling. The CCSD(T) calculation with the FOC‐QCP was successfully applied to large systems including transition metal elements. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 10: 000–000; 2010: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900019 相似文献
49.
Y. Todate N. Ohnishi M. Tanaka K. Nishiyama K. Nagamine 《Hyperfine Interactions》1997,104(1-4):375-380
Zero and longitudinal field μSR measurements on diluted triangular‐lattice antiferromagnet LuFeMgO4 have revealed gradual and highly anisotropic slowing‐down of spin fluctuation. Relaxation rate \lambda in the condition with
initial muon spins perpendicular to the hexagonal c‐plane shows divergent behavior while that in the parallel configuration
remains finite. At certain temperature range the fluctuation of spins is suppressed by a small external magnetic field. Monte
Carlo calculation suggests that the correlation time for z(c)‐component of spins diverges first on cooling.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
50.
A series of star-shaped pyrrole-fused tetrathiafulvalene (TTF) oligomers 1-3 was synthesized via an S(N)Ar reaction of fluorinated benzenes with the pyrrolyl sodium salts. Electrochemical and chemical oxidations of 1-3 revealed that a radical cation moiety on each TTF unit was successfully accumulated in all oligomers. Self-assembled structures of neutral and oxidized species were characterized by SEM and XRD, and their conductive properties of the iodine-doped 1-3 as well as an intermolecular mixed-valence ion radical salt were investigated. 相似文献