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151.
Kiyoshi Kikukawa Shun-Ichi Nozakura Shunsuke Murahashi 《Journal of polymer science. Part A, Polymer chemistry》1972,10(1):139-149
Divinyl esters of dibasic acids, CH2?CHOCO(CH2)n?2COOCH?CH2, n = 2–10, were synthesized and polymerized with a radical initiator, and the structure of poly(vinyl alcohol)(PVA) derived from the polymers were studied. The cyclopolymerizability of these monomers was nearly equal to or less than that of divinyl carbonate which was previously reported, and the extent of cyclization was 15–65%. All the monomers yielded gelled polymers. The monomers which are to yield even-membered rings tend to cyclopolymerize more easily than those of odd-membered rings. PVA derived from these polymers showed a similar structure with respect to 1,2-glycol content and stereoregularity to that from poly(vinyl acetate). 相似文献
152.
Yasushi Joh Heimei Yuki Shunsuke Murahashi 《Journal of polymer science. Part A, Polymer chemistry》1970,8(10):2775-2790
The polymerization of isobutyl vinyl ether by the VCln–AIR3 system was carefully studied. The vanadium components were prepared by the reaction between VCl4 and AlEt3 or n-BuLi as a reducing agent. VCl3·LiCl and VCl2·2LiCl are the effective catalysts for the stereospecific polymerization of isobutyl vinyl ether. When VCl3·LiCl is combined with AlR3, a new catalytic system is formed. The effect of the preparative conditions of the various vanadium component in the AlR3–VCln system shows that the effective vanadium component is trivalent. In the polymerization by VCl3·LiCl–Al (i-Bu)3 system, a change of the polymerization mechanism may occur at Al(i-Bu)3/VCl3·LiCl ratio at around 5. When the ratio is lower than 5, a cationic polymerization by VCl3·LiCl takes place predominantly, while at ratios higher than 5, it is suggested that the polymerization proceeds by means of a VCl3·LiClA–Al(i-Bu)3 complex by a coordinated anionic mechanism. The polymers obtained by these catalysts are highly crystalline. Styrene was also polymerized by using the same catalysts. VCl3·LiCl and VCl3·LiCl–THF complex yielded amorphous polymer by cationic polymerization. When VCl3·LiCl was combined with 6 mole-eq of Al(i-Bu)3, the resulting polystyrene was highly crystalline and had an isotactic structure, while the VCl2·2LiCl–Al(i-Bu)3 (1:6) system yielded traces of polymer of extremely low stereoregularity. The results indicate that the effective vanadium component at Al/V ≧ 6 is trivalent and that the mechanism is a coordinated anionic one. 相似文献
153.
Nano-architectural silica thin films with two-dimensionally connected cagelike pores synthesized from vapor phase 总被引:2,自引:0,他引:2
Tanaka S Nishiyama N Oku Y Egashira Y Ueyama K 《Journal of the American Chemical Society》2004,126(15):4854-4858
Novel mesostructured silica thin films were prepared on a Si substrate by a vapor-phase synthesis. Vapor of tetraethoxysilane (TEOS) was infiltrated into a surfactant film consisting of a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer. Nanophase transition from a lamellar structure to a two-dimensional cage structure of a silica-surfactant nanocomposite was found under vapor infiltration. The rearrangement into the cage structure implies high mobility of the silica-surfactant composites in solid phase. The silica thin films have two-dimensionally connected cagelike mesopores and are isotropic parallel to the film surface. The structure of pores of the films is advantageous for next-generation low-k films. The mesoporous structure has a large lattice parameter d of approximately 102 A, silica layer thickness of approximately 58 A, pillar diameter in the middle of approximately 60 A, pore size of approximately 72 A, BET surface area of approximately 729 m(2)/g, and pore volume of approximately 1.19 cm(3)/g. The films synthesized by the vapor infiltration show a lower concentration of residual Si-OH groups compared to the films prepared by a conventional sol-gel method. The films show high thermal stability up to 900 degrees C and high hydrothermal stability. This method is a simpler process than conventional sol-gel techniques and attractive for mass production of a variety of organic-inorganic composite materials and inorganic porous films. 相似文献
154.
Kenshu Fujiwara Yu-ichi Aki Fuyuki Yamamoto Mariko Kawamura Masanori Kobayashi Azusa Okano Daisuke Awakura Shunsuke Shiga Akio Murai Hidetoshi Kawai Takanori Suzuki 《Tetrahedron letters》2007,48(26):4523-4527
In this study, we synthesized the C8-C20 and C21-C30 segments of the diarrhetic shellfish toxin pectenotoxin 2. The C8-C20 segment was assembled from a phosphonate corresponding to the C8-C15 segment (prepared from l-malic acid in 19 steps) and an aldehyde corresponding to the C16-C20 segment (synthesized from 3-methyl-3-butenol in nine steps) by a twelve-step process including the Horner-Wadsworth-Emmons reaction, regio- and stereoselective reduction of the resulting enone, diastereoselective epoxidation, and 5-exo epoxide cleavage forming the C-ring. The C21-C30 segment was constructed in 13 steps from (S)-glycidol via a route involving E-ring formation by 5-exo epoxide cleavage and stereoselective methylation at C27 by the Evans method. 相似文献
155.
Tanaka Y Kasai Y Mochizuki S Wakisaka A Morita EH Kojima C Toyozawa A Kondo Y Taki M Takagi Y Inoue A Yamasaki K Taira K 《Journal of the American Chemical Society》2004,126(3):744-752
We have studied the interaction between metal ions and the metal ion-binding motif in hammerhead ribozymes, as well as the functions of the metal ion at the motif, with heteronuclear NMR spectroscopy. In this study, we employed model RNA systems which mimic the metal ion-binding motif and the altered motif. In Co(NH3)6(III) titrations, we observed large 1H and 31P chemical shift perturbations for the motif and found that outer-sphere complexation of Co(NH3)6(III) is possible for this motif. From the reinvestigation of our previous 15N chemical shift data for Cd(II) binding, in comparison with those of organometallic compounds, we conclude that Cd(II) can form an inner-sphere complex with the nucleobase in the motif. Therefore, the A9/G10.1 site was found to accept both inner-sphere and outer-sphere complexations. The Mg(II) titration for a slightly different motif from the A9/G10.1 site (G10.1-C11.1 to A10.1-U11.1) revealed that its affinity to Mg(II) was drastically reduced, although the ribozyme with this altered motif is known to retain enzymatic activities. This observation suggests that the metal ion at these motifs is not a catalytic center of hammerhead ribozymes. 相似文献
156.
Shun-Ichi Nozakura Yotaro Morishima Shunsuke Murahashi 《Journal of polymer science. Part A, Polymer chemistry》1972,10(10):2853-2866
The branching reaction in the radical polymerization of vinyl acetate was studied kinetically. Branching occurs by polymer transfer as well as terminal double-bond copolymerization. The chain-transfer constants to the main chain (Cp,2) and to the acetoxy methyl group (Cp,1) on the polymer were calculated on the basis of the experimental data described in the preceding paper giving Cp,2 = 3.03 × 10?4, Cp,1 = 1.27 × 10?4 at 60°C, and Cp,2 = 2.48 × 10?4, Cp,1 = 0.52 × 10?4 at 0°C. Chain transfer to monomer is important with respect to the formation of the terminal double bond. The total values of transfer constants to the α- or β-position in the vinyl group and the acetoxymethyl group in vinyl acetate was determined to be 2.15 × 10?4 at 60°C. The transfer constant to the acetyl group in the monomer (Cm,1) was also evaluated to be 2.26 × 10?4 at 60°C from the quantitative determination of the carboxyl terminals in PVA. These facts suggest that the chain-transfer constant to the α- or β-position in the monomer (Cm,2) is nearly equal to zero within experimental error. Copolymerization reactivity parameters of the terminal double bond were also estimated. In conclusion, it has become clear that the formation of nonhydrolyzable branching by the terminal double-bond reaction can be almost neglected, and hence that the long branching in PVA is formed only by the polymer transfer mechanism. On the other hand, a large number of hydrolyzable branches in PVAc are prepared by the terminal double-bond reaction rather than by polymer transfer. 相似文献
157.
Epifanio BagarinaoJr. K. Pakdaman Taishin Nomura Shunsuke Sato 《Physica D: Nonlinear Phenomena》1999,130(3-4):211-231
We consider the problem of reconstructing bifurcation diagrams (BDs) of maps using time series. This study goes along the same line of ideas presented by Tokunaga et al. [Physica D 79 (1994) 348] and Tokuda et al. [Physica D 95 (1996) 380]. The aim is to reconstruct the BD of a dynamical system without the knowledge of its functional form and its dependence on the parameters. Instead, time series at different parameter values, assumed to be available, are used. A three-layer fully-connected neural network is employed in the approximation of the map. The task of the network is to learn the dynamics of the system as function of the parameters from the available time series. We determine a class of maps for which one can always find a linear subspace in the weight space of the network where the network’s bifurcation structure is qualitatively the same as the bifurcation structure of the map. We discuss a scheme in locating this subspace using the time series. We further discuss how to recognize time series generated by this class of maps. Finally, we propose an algorithm in reconstructing the BDs of this class of maps using predictor functions obtained by neural network. This algorithm is flexible so that other classes of predictors, apart from neural networks, can be used in the reconstruction. 相似文献
158.
Tetsuo Hino Shunsuke Taniguchi Noriyuki Kuramoto 《Journal of polymer science. Part A, Polymer chemistry》2006,44(2):718-726
Conductive composites consisted of epoxy resin and polyanilines (PANIs) doped with dodecylbenzenesulfonic acid ( 1 ), dodecylsulfonic acid (2), di(2‐ethylhexyl)sulfosuccinic acid (3), and HCl were synthesized by use of N‐tert‐butyl‐5‐methylisoxazolium perchlorate (5) under various reaction conditions. It was found that the composites with PANI doped with acid 2 (PANI‐2) prepared by curing with 10 mol % of reagent 5 at 80 °C for 12 h showed high electroconductivity along with the low conducting percolation threshold (3 wt % of PANI‐2). Furthermore, the composite with even ?10 wt % of PANI‐2 exhibited ?10?1 S/cm of electroconductivity. The UV–vis and IR measurements indicated that the conductive emeraldine salt form of PANI‐2 in the composite was maintained after the curing reaction. The thermal stability was studied by TGA and DSC measurements, and then, the Td10 and Tg of the composite with 5 and 10 wt % of PANI‐2 were found to be similar to those with the cured epoxy resin itself. In addition, the similar investigation with an oxetane resin instead of the epoxy resin was also carried out. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 718–726, 2006 相似文献
159.
Shunsuke Takagi 《Mathematische Zeitschrift》2008,259(2):321-341
We introduce a new variant of tight closure and give an interpretation of adjoint ideals via this tight closure. As a corollary,
we prove that a log pair (X, Δ) is plt if and only if the modulo p reduction of (X, Δ) is divisorially F-regular for all large p ≫ 0. Here, divisorially F-regular pairs are a class of singularities in positive characteristic introduced by Hara and Watanabe
(J Algebra Geom 11:363–392, 2002) in terms of Frobenius splitting.
The author was partially supported by Grant-in-Aid for Young Scientists (B) 17740021 from JSPS. 相似文献
160.