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521.
l-Luciferin can be converted into d-luciferin with an enzyme/co-factor system consisting of firefly luciferase, an esterase, ATP, Mg2+, and coenzyme A. By this means, a new firefly bioluminescence system can be constructed that uses l-luciferin as the substrate. 相似文献
522.
Tabayashi K Yamamoto K Takahashi O Tamenori Y Harries JR Gejo T Iseda M Tamura T Honma K Suzuki IH Nagaoka S Ibuki T 《The Journal of chemical physics》2006,125(19):194307
Inner-shell excitation spectra and fragmentation of small clusters of formic acid have been studied in the oxygen K-edge region by time-of-flight fragment mass spectroscopy. In addition to several fragment cations smaller than the parent molecule, we have identified the production of HCOOH.H+ and H3O+ cations characteristic of proton transfer reactions within the clusters. Cluster-specific excitation spectra have been generated by monitoring the partial ion yields of the product cations. Resonance transitions of O1s(C[double bond]O/OH) electrons into pi(CO)* orbital in the preedge region were found to shift in energy upon clusterization. A blueshift of the O1s(C[double bond]O)-->pi(CO)* transition by approximately 0.2 eV and a redshift of the O1s(OH)-->pi(CO)* by approximately 0.6 eV were observed, indicative of strong hydrogen-bond formation within the clusters. The results have been compared with a recent theoretical calculation, which supports the conclusion that the formic-acid clusters consist of the most stable cyclic dimer andor trimer units. Specifically labeled formic acid-d, HCOOD, was also used to examine the core-excited fragmentation mechanisms. These deuterium-labeled experiments showed that HDO+ was formed via site-specific migration of a formyl hydrogen within an individual molecule, and that HD2O+ was produced via the subsequent transfer of a deuterium atom from the hydroxyl group of a nearest-neighbor molecule within a cationic cluster. Deuteron (proton) transfer from the hydroxyl site of a hydrogen-bond partner was also found to take place, producing deuteronated HCOOD.D+ (protonated HCOOH.H+) cations within the clusters. 相似文献
523.
Arisawa M Terada Y Takahashi K Nakagawa M Nishida A 《The Journal of organic chemistry》2006,71(11):4255-4261
A pure ruthenium hydride complex with N-heterocyclic carbene (NHC) ligand was efficiently generated from the reaction of a second-generation Grubbs ruthenium catalyst with vinyloxytrimethylsilane and unambiguously characterized. This ruthenium hydride complex showed high catalytic activity for the selective isomerization of terminal olefin and for the cycloisomerization of 1,6-dienes. These reactions of N-allyl-o-vinylaniline lead to novel synthetic methods for heterocycles such as indoles and 3-methylene-2,3-dihydroindoles, which are useful synthons for bioactive natural products. These procedures address an important issue in diversity-oriented synthesis. 相似文献
524.
Tetsuya Mochizuki Akihiro Nezu Hiroshi Abe Mitsuhiro Arisawa 《Tetrahedron letters》2010,51(6):977-3363
Indole derivatives 3a and 3b of adenophostin A (2) in which the adenine of 2 was replaced with indole or 4-fluoroindole was designed as potential inositol trisphosphate receptor ligands. These target compounds were successfully synthesized from the key disaccharide unit 6. Biological evaluation showed that 3b selectively activates IP3R1, a subtype of IP3 receptors. 相似文献
525.
Mitsuhiro Kanakubo Takafumi Aizawa Hiroshi Nanjo Yasuo Kameda Yuko Amo Takeshi Usuki 《Fluid Phase Equilibria》2010
X-ray diffraction measurements for the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF4], mixed with CO2 were carried out at high pressures using our developed polymer cell. The intermolecular distribution functions obtained for [BMIM][BF4]–CO2 mixtures showed that CO2 molecules are preferentially solvated to the [BF4]− anion. The similar preferential solvation was previously observed in analogous 1-btuyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], with a different anion, which is in harmony with the present results in [BMIM][BF4]–CO2. 相似文献
526.
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
527.
Sadahito Aoshima Shinji Sugihara Mitsuhiro Shibayama Shokyoku Kanaoka 《Macromolecular Symposia》2004,215(1):151-164
The living cationic polymerization of several functional monomers in the presence of an added base is investigated as a possible preparation of a new series of water-soluble or stimuli-responsive copolymers. Under appropriate conditions, the polymerization allows the selective preparation of polymers with various shapes and different sequence distributions of monomer units, including stimuli-responsive block copolymers, gradient copolymers, poly(vinyl alcohol) graft copolymers, and star-shaped polymers. The stimuli-induced self-association of the diblock copolymers is also examined. An aqueous solution of the diblock copolymer with a thermo-sensitive segment undergoes rapid physical gelation upon warming to the critical temperature to give a transparent gel, and returns sensitively to the solution state upon cooling. The sharp transition of stimuli-responsive segments with highly controlled primary structure turns out to play an important role in the self-association. Small-angle neutron scattering, dynamic light scattering, and electron microscopy studies reveal that the physical gelation involves a thermosensitive micellization of diblock copolymers (core size: 18-20 nm) and subsequent micelle macrolattice formation (bcc symmetry). Based on the gelation mechanism, several stimuli-responsive gelation systems are achieved using other stimuli such as the addition of a selective solvent or compound, cooling, pH change, and irradiation with ultraviolet light. 相似文献
528.
Fumiyoshi Ikkai Mitsuhiro Shibayama 《Journal of Polymer Science.Polymer Physics》1996,34(9):1637-1645
The microstructure and swelling kinetics of ion-exchange resins having sulfonic acid groups were investigated by small-angle neutron scattering (SANS) and swelling experiments as functions of the crosslinking density (CD), pH, and the salt concentration (Csalt). The swelling kinetics was analyzed on the basis of the Tanaka-Fillmore swelling equation for the cooperative diffusion of polymer gels. The swelling behavior was very sensitive to CD, but not to pH and Csalt. The SANS intensity functions, I(q), were independent of CD and well described with a power law function, I(q) ∼ q−D, where q and D are the magnitude of the scattering vector and the mass-fractal dimension, respectively. D was estimated to be ∼2, indicating that the resin consisted of a rather coarsely interconnected domains irrespective of CD at swelling equilibrium. It was found that CD is the most important parameter determining the swelling power of ion-exchange resin. However, no remarkable variations were found in the microstructure in the order of tens to hundreds of angstrom. © 1996 John Wiley & Sons, Inc. 相似文献
529.
Mitsuhiro Nakae Hiroki Uehara Tetsuo Kanamoto Toshio Ohama Roger S. Porter 《Journal of Polymer Science.Polymer Physics》1999,37(15):1921-1930
The drawing behavior of the ultra‐high molecular weight polyethylene (UHMW‐PE) melts has been studied by comparing the stress/strain curves for two types of samples as polymerized using conventional Ziegler and newer metallocene catalyst systems. Two UHMW‐PE samples, having the same viscosity average molecular weight of 3.3 × 106, but different molecular weight distribution, have been drawn from melt at special conditions. The sample films for drawing were prepared by compression molding of reactor powders at 180°C in the melt. Differences in the structural changes during drawing and resultant properties, ascribable to their broad or narrow molecular weight distribution, were estimated from tensile tests, SEM observations, X‐ray measurements and thermal analyses. The metallocene‐catalyzed sample having narrower molecular weight distribution, could be effectively drawn from the melt up to a maximum draw ratio (DR) of 20, significantly lower than that obtained for the Ziegler‐catalyzed sample, ∼ 50. The stress/strain curves on drawing were remarkably influenced by draw conditions, including draw temperature and rate. However, the most effective draw for both was achieved at 150°C and a strain rate of 5 min−1, independent of sample molecular weight distribution. The efficiency of drawing, as evaluated by the resultant tensile properties as a function of DR, was higher for the metallocene‐catalyzed sample having narrower molecular weight distribution. Nevertheless, the maximum achieved tensile modulus and strength for the Ziegler sample, 50–55 and 0.90 GPa, respectively, were significantly higher than those for the metallocene sample, 20 and 0.65 GPa, respectively, reflecting the markedly higher drawability for the former than the latter. The stress/strain behavior indicated that the origin of differences during drawing from the melt could be attributed to the ease of chain relaxation for the lower molecular weight chains in the melt. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1921–1930, 1999 相似文献
530.
Erika Yoshihara Makoto Sasaki Ahmed Nabil Michihiro Iijima Mitsuhiro Ebara 《Molecules (Basel, Switzerland)》2022,27(3)
In this study, temperature-responsive polymer-protein conjugate was synthesized using a “grafting from” concept by introducing a chain transfer agent (CTA) into bovine serum albumin (BSA). The BSA-CTA was used as a starting point for poly(N-isopropylacrylamide) (PNIPAAm) through reversible addition-fragmentation chain transfer polymerization. The research investigations suggest that the thermally responsive behavior of PNIPAAm was controlled by the monomer ratio to CTA, as well as the amount of CTA introduced to BSA. The study further synthesized the human serum albumin (HSA)-PNIPAAm conjugate, taking the advantage that HSA can specifically adsorb indoxyl sulfate (IS) as a uremic toxin. The HSA-PNIPAAm conjugate could capture IS and decreased the concentration by about 40% by thermal precipitation. It was also revealed that the protein activity was not impaired by the conjugation with PNIPAAm. The proposed strategy is promising in not only removal of uremic toxins but also enrichment of biomarkers for early diagnostic applications. 相似文献