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91.
92.
We develop a statistical theory of growing domain structures in quenched systems with multiple-degenerate ground states where the order parameter is not conserved. Exact formulas are derived for the non-equilibrium structure functions for growing domains. As concrete examples the theory is applied to the p-state Johnson-Mehl model and the p-state cell model where the structure functions of the growing domains and the volume fraction of the metastable domain are calculated explicitly. 相似文献
93.
H. Katsuura H. Kawamura M. Manabe H. Kawasaki H. Maeda 《Colloid and polymer science》2002,280(1):30-37
The binding of a cationic surfactant, dodecylpyridinium (C12Py) chloride, with a low-charge-density poly (methacrylic acid)
(PMA) was investigated in buffer solutions under the condition of constant pH. The binding isotherms with PMA consisted of
two and three steps at a pH lower and higher than 3.2, respectively. Bindings in the first step were independent of pH and
this step was considered to correspond to the solubilization of the hydrocarbon chains of C12Py into the nonpolar region of
the compact form of PMA. This is the indication of the compact form from the binding isotherm. At pH higher than 3.2, the
second step was discriminated and it depended on the pH. In the third step, a sharp rise in the degree of binding (β) was
observed accompanying the solubilization of the precipitates of the PMA–C12Py complex. The binding with poly(acrylic acid)
(PAA) and PMA in conventional unbuffered NaCl solutions was also examined and the pH profile of the solution during the binding
process was determined. In the case of unbuffered NaCl solutions, the binding with PAA took place cooperatively at the critical
association concentration (cac). The binding isotherm consisted of two steps and the pH decreased with the increase in β.
The binding isotherm of PMA, on the other hand, consisted of three steps: the pH decreased slightly in the first step and
considerably in the second step with the increase in β but it increased with β in the third step, exhibiting a pH minimum
around 3.2. The binding in the first step coincided with that obtained in the buffered solutions. Linear relationships between
β and the pH were found for both polymers. In the case of PMA, no cac was observed in both buffered and unbuffered NaCl solutions.
Received: 24 January 2001 Accepted: 23 May 2001 相似文献
94.
A new simplified structural model and its governing equations for beams on elastic foundations with elastic coupling are proposed. This modeling system is simple but appropriate for the initial structural design of large-scale submerged floating-beam structures moored by tension legs spaced at uniform interval along the beam. The model is actually for beam on discrete elastic supports rather than on continuous elastic foundations. Therefore, the governing equations are based on finite difference calculus and solutions for beams on discrete elastic supports with elasticity coupling are also proposed. To clarify the applicability limit of the proposed model, the equivalence between a beam on discrete elastic supports and that on continuous elastic foundation is investigated by comparisons of characteristic solutions. 相似文献
95.
Dr. Hideya Kawasaki Teruyuki Yao Takashi Suganuma Kouji Okumura Dr. Yuichi Iwaki Prof. Tetsu Yonezawa Tatsuya Kikuchi Prof. Ryuichi Arakawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(35):10832-10843
We report a new and facile method for synthesizing 3D platinum nanoflowers (Pt Nfs) on a scratched silicon substrate by electroless galvanic displacement and discuss the applications of the Pt Nfs in surface‐assisted laser desorption/ionization‐mass spectrometry (SALDI‐MS). Surface scratching of n‐type silicon is essential to induce Pt Nf growth on a silicon substrate (to obtain a Pt Nf silicon hybrid plate) by the galvanic displacement reaction. The Pt Nf silicon hybrid plate showed excellent SALDI activity in terms of the efficient generation of protonated molecular ions in the absence of a citrate buffer. We propose that the acidity of the Si? OH moieties on silicon increases because of the electron‐withdrawing nature of the Pt Nfs; hence, proton transfer from the Si? OH groups to the analyte molecules is enhanced, and finally, thermal desorption of the analyte ions from the surface occurs. Signal enhancement was observed for protonated molecular ions produced from a titania nanotube array (TNA) substrate on which Pt nanoparticles had been photochemically deposited. Moreover, surface modification of the Pt Nf silicon hybrid plate by perfluorodecyltrichlorosilane (FDTS) (to obtain an FDTS‐Pt Nf silicon hybrid plate) was found to facilitate soft SALDI of labile compounds. More interestingly, the FDTS‐Pt Nf silicon hybrid plate acts 1) as a high‐affinity substrate for phosphopeptides and 2) as a SALDI substrate. The feasibility of using the FDTS‐Pt Nf silicon hybrid plate for SALDI‐MS has been demonstrated by using a β‐casein digest and various analytes, including small molecules, peptides, phosphopeptides, phospholipids, carbohydrates, and synthetic polymers. The hybridization of Pt Nfs with a scratched silicon substrate has been found to be important for achieving excellent SALDI activity. 相似文献
96.
Tsuneomi Kawasaki 《Journal of fluorine chemistry》2010,131(4):525-1118
Amplification of enantiomeric enrichment is a key feature for the chemical evolution of biological homochirality from the origin of chirality. The aggregations of the enantiomers by diastereomeric interactions enable the modification of their enantiomeric excess during some chemical processes. Fluorine-containing chiral compounds possess large amplification effect via distillation, sublimation and achiral chromatography by self-disproportionation. Asymmetric amplifications in enantioselective catalysis occur by the differential formation and reactivity between homochiral and heterochiral aggregate in solution.We described the amplification of ee in asymmetric autocatalysis of 5-pyrimidyl alkanol in the reaction between diisopropylzinc and pyrimidine-5-carbaldehdye. During the reactions extremely low ee (ca. 0.00005% ee) can be amplified to achieve more than 99.5% ee. Since the proposed origins of chirality such as CPL, quartz, chiral organic crystals of achiral compounds and statistical fluctuation of ee can initiate the asymmetric autocatalysis with amplification of ee, the proposed origin of chirality can be linked with enantiopure organic compound in conjunction with amplification of ee by asymmetric autocatalysis. In addition, we described that the carbon isotopically chiral compound triggers the asymmetric autocatalysis of 5-pyrimiodyl alkanol to afford the enantioenriched product with the absolute configuration correlated with that of carbon isotope chirality, that is, isotope chirality including hydrogen isotopes can control the enantioselectivity of asymmetric addition of alkyl metal reagent to aldehyde. 相似文献
97.
Evaluation of thermodynamic and kinetic stability of CuAlO<Subscript>2</Subscript> and CuGaO<Subscript>2</Subscript> 总被引:1,自引:0,他引:1
Yuh Kumekawa Motohiro Hirai Yuhki Kobayashi Satoshi Endoh Eri Oikawa Takuya Hashimoto 《Journal of Thermal Analysis and Calorimetry》2010,100(1):57-63
Thermodynamic and kinetic stabilities of CuAlO2 and CuGaO2 have been evaluated by using thermogravimetry and thermodynamic calculations. It has been revealed that CuAlO2 and CuGaO2 are not thermodynamically stable in air below 800 °C and 1,200 °C, respectively, and that the oxidation reaction, 4CuMO2 + O2 → 2CuO + 2CuM2O4 (M = Al, Ga), should occur if the reaction kinetics are high enough. However, rate constants and activation energies indicated
slow kinetics of the oxidation reaction, showing kinetic stability of CuMO2 even under some thermodynamically unstable temperatures and atmospheres. It was also concluded that CuAlO2 showed higher thermodynamic and kinetic stability than CuGaO2. 相似文献
98.
Emi Evangelio Dr. Marie‐Laure Bonnet Dr. Miquel Cabañas Dr. Motohiro Nakano Dr. Jean‐Pascal Sutter Dr. Andrea Dei Prof. Vincent Robert Dr. Daniel Ruiz‐Molina Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(22):6666-6677
The different thermally induced intermolecular electron transfer (IET) processes that can take place in the series of complexes [M(Cat‐N‐BQ)(Cat‐N‐SQ)]/[M(Cat‐N‐BQ)2], for which M=Co ( 2 ), Fe ( 3 ) and Ni( 4 ), and Cat‐N‐BQ and Cat‐N‐SQ denote the mononegative (Cat‐N‐BQ?) or dinegative (Cat‐N‐SQ2?) radical forms of the tridentate Schiff‐base ligand 3,5‐di‐tert‐butyl‐1,2‐quinone‐1‐(2‐hydroxy‐3,5‐di‐tert‐butylphenyl)imine, have been studied by variable‐temperature UV/Vis and NMR spectroscopies. Depending on the metal ion, rather different behaviors are observed. Complex 2 has been found to be one of the few examples so far reported to exhibit the coexistence of two thermally induced electron transfer processes, ligand‐to‐metal (IETLM) and ligand‐to‐ligand (IETLL). IETLL was only found to take place in complex 3 , and no IET was observed for complex 4 . Such experimental studies have been combined with ab initio wavefunction‐based CASSCF/CASPT2 calculations. Such a strategy allows one to solicit selectively the speculated orbitals and to access the ground states and excited‐spin states, as well as charge‐transfer states giving additional information on the different IET processes. 相似文献
99.
100.