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Palladium(II)-catalyzed oxidations constitute a paramount reaction class but have remained immature over the past few decades. Recently, this field has reappeared at the forefront of organometallic catalysis. This emerging area article outlines recent developments in palladium(II)-catalyzed oxidation chemistry with discussion of potential future growth. 相似文献
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The molecular structure of 4,4′-sulfanidyl-bis-thiophenol (C12H10S3) has been determined by gas electron diffraction. Assuming identical geometry and D2h local symmetry for ---SC6H4S--- moieties, the following bond lengths (rg) and bond angles were obtained: C---H = 1.101 ± 0.005, S---H = 1.388 ± 0.019, (C---C)mean = 1.400 ± 0.003, (S---C)mean = 1.778 ± 0.004 Å, Car---S---Car = 103.5 ± 1.3, C---C(S)---C = 120.4 ± 0.3, C(H)---C(H)---H = 119.1 ± 0.9 and C---S---H = 94.6 ± 3.1°. Two ratational forms were found to reproduce the experimental data, characterized by dihedral angles of the benzene rings with respect to the CarSCar plane; 1 = 67.8 ± 2.0°, 2 = 4.5 ± 7.2°, and 1 = 69.4 ± 2.0δ, 2 = −26.6 ± 7.1°. Identical signs of 1 and 2 indicate that the two benzene rings are rotated in the same direction about the respective Scentral---C axes. 相似文献
7.
Jan F. Keij Jan Th . M. Jansen Frank W. Schultz Jan W. M. Visser 《Photochemistry and photobiology》1994,60(5):503-509
Abstract-During the development of a photodamage cell sorter several photosensitizers were tested for their ability to photoinactivate more than 90% of the sensitized cells after a brief irradiation with a fluence of 10 kJ/m2 . In pilot experiments, yeast cells sensitized with 10-dodecyl acridine orange (DAO) were effectively photoinactivated after receiving a fluence of 10 kJ/m2 delivered in 8 s. However, when the same fluence was delivered in 3 μ s during passage through a focused laser beam in the cell sorter, all cells survived.
Computer simulations of the relevant photophysical and chemical reactions inside the irradiated cell were used to investigate the cause of this phenomenon. The results indicated that the absence of photoinactivation by DAO, after flash irradiations, was caused by the combined effects of (1) limited oxygen diffusion into the cell and (2) a reduced number of collisions between photosensitizer triplet and oxygen molecules during the irradiation due to saturation of the intracellular photosensitizer triplet concentration. The contributions of triplet-triplet annihilation and triplet quenching by ground state photosensitizer molecules were found to be minimal and not significant. These findings indicate that Type II photosensitizers are incapable of rapid selective photoinactivation in cell sorters. 相似文献
Computer simulations of the relevant photophysical and chemical reactions inside the irradiated cell were used to investigate the cause of this phenomenon. The results indicated that the absence of photoinactivation by DAO, after flash irradiations, was caused by the combined effects of (1) limited oxygen diffusion into the cell and (2) a reduced number of collisions between photosensitizer triplet and oxygen molecules during the irradiation due to saturation of the intracellular photosensitizer triplet concentration. The contributions of triplet-triplet annihilation and triplet quenching by ground state photosensitizer molecules were found to be minimal and not significant. These findings indicate that Type II photosensitizers are incapable of rapid selective photoinactivation in cell sorters. 相似文献
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Studies directed at a synthesis of dihydrothiepin 1b have resulted in the elucidation of several factors which effect cyclobutene ring opening in the 3-heterobicyclo[3.2.0]hept-6-ene ring system. We report the unexpected rearrangement of 4a, 4b, 13b and 13c to the synthetically useful a-vinyl-2,5-dihydrothiophenes 7a, 7b, 15a and 15b, respectively. Conversion of 4a to 6 is suggested to occur by a 1,3-rearrangement of 4a to isomeric 3-thiabicyclo[3.2.0]hept-6-ene 19 followed by cyclobutene ring opening in 19. 相似文献
9.
Schultz György Hargittai István Rot Nicolette Bickelhaupt Friedrich 《Structural chemistry》1998,9(3):209-214
The molecular structure of 1,3,5-tris (trimethylstannyl) benzene has been determined by gas-phase electron diffraction. The C — C bond length is in good agreement with that in benzene. In agreement with the somewhat electron-releasing character of the substituents, the endocyclic bond angles at the substituents are somewhat smaller than 120°. The mean value of Sn — C bond lengths is greater than that in tetraphenyltin and tetramethyltin. The SnMe3 groups appear freely rotating around the Caryl — Sn bonds. The following bond lengths (r
g) and bond angles were determined: (Sn — C)mean 2.150 ± 0.007 Å, C — C 1.399 ± 0.005 Å, (C — H)mean 1.105 ± 0.006 Å, < C — C(Sn) — C 117.7 ± 1.7º, < Caryl — Sn — Cmethyl 106.7 ± 0.7º < Sn — C — H 111.5 ± 0.9º. 相似文献
10.
Summary The advantages and disadvantages of high performance precipitation liquid chromatography have been demonstrated for polystyrene
homopolymers. Depending on the mobile phase composition at the dissolution point of the polymeric sample and surface properties
of the stationary phase, elution is governed either by a solution process or by adsorption. A contribution by adsorption was
noticed on silica as well as on reversed phases based on silica with a normal phase gradient of increasing polarity (heptane
to dichloromethane). Elution was solely governed by solubility of the polymers on both types of stationary phase for polystyrenes
with a molecular weight above 35 000 and reversed phase gradient of decreasing polarity (methanol to dichloromethane). Under
these conditions an identical dependence of elution solvent composition on sample size was found as for turbidity titrations.
Due to differences in the velocity of the eluent front and the polymeric sample with porous stationary phases the polymers
can be eluted as colloidal solutions Non-porous stationary phases are superior in this respect because the velocities of eluent
and solutes are identical. 相似文献