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81.
82.
Fred L. Tobiason Greg H. Cain Steve M. Gregory 《Journal of polymer science. Part A, Polymer chemistry》1978,16(3):659-666
Rotational isomeric-state chain-configurational calculations have been applied to the novolac phenol–formaldehyde structure. Steric interference allows the chain to be considered with a twofold potential energy barrier model. Computations that fit the observed dipole-moment data over a range of molecular weights indicate that the conformational angle is near ±80°, with the g±g= states on the average being 155 cal/mole below the g±g± states. The limiting dipole-moment ratio is computed to be 1.47, compared to the experimental value of 1.48. A negative temperature coefficient agrees in sign with the experimental value, and the characteristic ratio of the end-to-end molecular dimensions is calculated to be 3.27, as compared to the experimental value of 4.76. 相似文献
83.
84.
Alan R. Fersht Jian-Ping Shi Anthony J. Wilkinson David M. Blow Paul Carter Mary M. Y. Waye Greg P. Winter 《Angewandte Chemie (International ed. in English)》1984,23(7):467-473
Structure-activity relationships of enzymes can now be analyzed for the first time by the systematic alteration of protein structure. Recent developments in the chemical synthesis of DNA fragments and recombinant DNA technology enable the facile modification of proteins by highly specific mutagenesis of their genes. Kinetic analysis of the mutant enzymes combined with high-resolution structural data from protein X-ray crystallography allow direct measurements on the relationships between structure and function. In particular, the strength and nature of enzyme-substrate interactions and their detailed roles in catalysis and specificity can now be studied. We have developed such analysis of enzyme structure-function by site-directed mutagenesis of the tyrosyl-tRNA synthetase from Bacillus stearothermophilus, concentrating so far on the subtle role of hydrogen bonding in both substrate specificity and catalysis. We find that the energetics of tyrosine and ATP binding must be analyzed in terms of an exchange reaction with solvent water. Based on this idea and structural data, we have engineered an enzyme of improved enzyme-substrate affinity, and there thus appear to be real prospects of engineering proteins of new specificities, activities, and structural properties. We are also using protein engineering to gather direct information on the nature of enzyme catalysis. For example, we find the catalysis of formation of Tyr-AMP from Tyr and ATP is due largely to electrostatic and hydrogen bonding interactions that are stronger in the transition state than in the ground state—a “strain” mechanism rather than acid-base or covalent catalysis. 相似文献
85.
In Oman and Salminen [19], the authors introduce and study residually small rings, defined as follows: an infinite commutative ring R with identity is residually smallif for every r∈R?{0}, there exists an ideal Ir of R such that r?Ir and |R∕Ir|<|R|. The purpose of this note is to extend our study. In particular, we continue our investigation of residually small rings and then generalize this notion to modules. 相似文献
86.
According to a common line of criticism, Donald Davidson’s argument in “On the Very Idea of a Conceptual Scheme” is invalid because it moves illicitly from the relatively weak thesis that conceptual schemes cannot be incommensurable to the stronger thesis that the idea of a conceptual scheme itself is incoherent. I argue in this paper that such objections fail because they misunderstand the position that Davidson’s argument is intended to rule out. According to the “scheme-content dualism” Davidson targets, conceptual schemes differ only if they are incommensurable with one another. Thus, if Davidson has successfully shown the idea of incommensurability to be incoherent (as the critics in question grant), then he has shown “the very idea of a conceptual scheme” to be incoherent, as well. 相似文献
87.
88.
Kasat RB Zvinevich Y Hillhouse HW Thomson KT Wang NH Franses EI 《The journal of physical chemistry. B》2006,110(29):14114-14122
The sorbent-solvent interactions for amylose tris(3, 5-dimethylphenylcarbamate) (ADMPC) with five commonly used solvents, hexane, methanol, ethanol, 2-propanol (IPA), and acetonitrile (ACN), are studied using attenuated total reflection infrared spectroscopy (ATR-IR) of thin sorbent films, X-ray diffraction (XRD) of thin films, (13)C cross polarization/magic angle spinning (CP/MAS) and MAS solid state NMR of polymer-coated silica beads (commercially termed "Chiralpak AD"), and DFT modeling. The ADMPC-polymer-coated silica beads are used commercially for analytical and preparative scale separations of chiral enantiomers. The polymer forms helical rods with intra- and inter-rod hydrogen bonds (H-bonds). There are various nm-sized cavities formed between the polymer side-chains and rods. The changes in the H-bonding states of the C=O and NH groups of the polymer upon absorption of each of the five solvents at 25 degrees C are determined with ATR-IR. The IR wavenumbers, the H-bonding interaction energies, and the H-bonding distances of the polymer side-chains with each of the solvent molecules are predicted using the DFT/B3LYP/6-311+g(d,p) level of theory. The changes in the polymer crystallinity upon absorption of each solvent are characterized with XRD. The changes in the polymer crystallinity and the H-bonding states of C=O groups are also probed with (13)C CP/MAS solid-state NMR. The changes in the polymer side-chain mobility are detected using (13)C MAS solid-state NMR. The H-bonding states of the polymer change upon absorption of each polar solvent and usually result in an increase in the polymer crystallinity and the side-chain mobility. The polymer rods are reorganized upon solvent absorption, and the distance between the rods increases with the increase in the solvent molecular size. These results have implications for understanding the role of the solvent in modifying the structure and behavior of the polymer sorbents. 相似文献
89.
Greg Michalski Michelle Kolanowski Krystin M. Riha 《Isotopes in environmental and health studies》2013,49(3):382-391
Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ15N values of synthetic and natural nitrates were 0?±?2?‰ similar to the air N2 from which they are derived. The δ18O values of synthetic nitrates were 23?±?3?‰, similar to air O2, and natural nitrate fertilizer δ18O values (55?±?5?‰) were similar to those observed in atmospheric nitrate. The Δ17O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ17O values of 18?±?2?‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models. 相似文献
90.
The removal of the native oxides from the In0.53Ga0.47As surface by exposure to atomic hydrogen has been investigated by highly surface sensitive synchrotron radiation based photoelectron spectroscopy. This shows that it is possible to fully remove the arsenic oxides at low temperatures, while still leaving a low concentration of stable Ga2O and In2O at the surface, and no evidence of indium loss from the substrate. The removal of surface carbon contamination is also seen, however full removal is only detected in the absence of prior substrate annealing. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献