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91.
David S Shucker 《Journal of Functional Analysis》1984,58(3):291-309
The theory of symmetric local semigroups due to A. Klein and L. Landau (J. Funct. Anal.44 (1981), 121–136) is generalized to semigroups indexed by subsets of n for n > 1. The result implies a similar result of A. E. Nussbaum (J. Funct. Anal.48 (1982), 213–223). It is further generalized to semigroups that are symmetric local in some directions and unitary in others. The results are used to give a simple proof of A. Devinatz's (Duke Math. J.22 (1955), 185–192) and N. I. Akhiezer's (“the Classical Moment Problem and Some Related Questions,” Hafner, New York, 1965) generalization of a theorem of Widder concerning the representation of functions as Laplace integrals. This result is extended to the representation as a Laplace integral of a function taking values in (), the set of bounded linear operators on a Hilbert space . Also, a theorem is proved encompassing both the result of Devinatz and Akhiezer, and Bochner's theorem on the representation of positive definite functions as Fourier integrals. 相似文献
92.
Mono- and bis-(tricarbonylchromium) compounds of dibenzo-18-crown-6 have been synthesized. The compounds exhibit a decreased ability to extract alkali metal salts into organic solvents, indicating an overall electron withdrawal from the oxygen crown by the Cr(CO)3 substituents. For the disubstituted compound, the normal selectivity for K+ over Na+ is reversed. 相似文献
93.
94.
Pattarawarapan M Chen J Steffensen M Burgess K 《Journal of combinatorial chemistry》2001,3(1):102-116
Bifunctional linker-scaffolds (compounds 1-3) were designed to meet several criteria for solid-phase syntheses of bivalent ligands. They have two amine-functionalized arms that can be differentially protected. Elaboration of these arms could give ligand-pharmacophore dimers wherein the two active components are held reasonably rigidly at around 10 A separation. Their bifunctional design also enables reactions of libraries with libraries to amplify diversity in a truly combinatorial fashion. Molecules 1-3 are also designed so that cleavage of the linker liberates the scaffold entity into solution under conditions that create only byproducts that should not interfere with biological assays. Thus they contain 2-nitrobenzene sulfonamide components that cleave in the presence of good nucleophiles. In the event, the linker-scaffolds 1-3 were prepared (Schemes 1 and 2). The N-benzyl system 2 was shown to have good stability to the types of conditions that might be used to functionalize the scaffold arms and to be sufficiently labile to the cleavage nucleophile (vide infra). The nucleophiles generally used to cleave nitrobenzene sulfonamides either generate undesirable byproducts (thiophenol or alkane thiols) or proved to be insufficiently reactive for the required solid-phase transformations (n-propylamine). However, sodium sulfide was investigated as a new alternative and shown to be a highly reactive cleavage agent that gives only volatile byproducts and sodium hydroxide. It is suggested that sodium sulfide is a highly desirable nucleophile for cleavage of 2-nitrobenzene sulfonamides, in general. The linker-scaffolds 1-3 were used to prepare a small library of bivalent ligands targeted to a protein receptor having charged cavities separated by approximately 10 A. These systems were made from guanidine, pyridinium, carboxylic acid, and sulfonic acid constituents (Tables 1 and 2). 相似文献
95.
A high pressure thermobalance was assembled by placing a DuPont Model 950 balance into a stainless steel enclosure. The thermobalance is capable of operation to a maximum pressure (of N2) to 500 atm and to a maximum temperature of 500°C. Operation of the instrument is illustrated by the thermogravimetric curves of BaBr2·2H2O, CuSO4·5H20 and NaHCO3 at various pres 相似文献
96.
For the new complex Me3 SiMe2 SiCH2 Fe(CO)2Cp the metalcarbon bond undergoes normal insertion reactions;however, under certain conditions the SiSiCFe framework rearranges to the siliconiron bonded system SiC SiFe. 相似文献
97.
Wiskur SL Lavigne JJ Metzger A Tobey SL Lynch V Anslyn EV 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3792-3804
The thermodynamics of guanidinium and boronic acid interactions with carboxylates, alpha-hydroxycarboxylates, and diols were studied by determination of the binding constants of a variety of different guests to four different hosts (7-10). Each host contains a different combination of guanidinium groups and boronic acids. The guests included molecules with carboxylate and/or diol moieties, such as citrate, tartrate, and fructose, among others. The Gibbs free energies of binding were determined by UV/Vis absorption spectroscopy, by use of indicator displacement assays. The receptor based on three guanidinium groups (7) was selective for the tricarboxylate guest. The receptors that incorporated boronic acids (8-10) had higher affinities for guests that included alpha-hydroxycarboxylate and catechol moieties over guests containing only carboxylates or alkanediols. Isothermal titration calorimetry revealed the enthalpic and entropic contributions to the Gibbs free energies of binding. The binding of citrate and tartrate was investigated with hosts 7-10, for which all the binding events were exothermic, with positive entropy. Because of the selectivity of hosts 8-10, a simple boronic acid (14) was also investigated and determined to be selective for alpha-hydroxycarboxylates and catechols over amino acids and alkanediols. Further, the cooperativity of 8 and 9 in binding tartrate was also investigated, revealing little or no cooperativity with 8, but negative cooperativity with 9. A linear entropy/enthalpy compensation relationship for all the hosts 7-10, 14, and the carboxylate-/diol-containing guests was also obtained. This relationship indicates that increasing enthalpy of binding is offset by similar losses in entropy for molecular recognition involving guanidinium and boronic acid groups. 相似文献
98.
Henri Brunner Manfred Muschiol Ivan Bernal George M. Reisner 《Journal of organometallic chemistry》1980,198(2):169-178
C7H7Mo(CO)(PN★)I (I) (PN★ (S)(+)-(C6H5)2PN(CH3)CH(CH3)(C6H5)) is prepared in 90% yield by reaction of C7H7Mo(CO)2I and PN★. The two diastereo-isomers Ia and Ib differing only in the Mo-configuration exhibit chemical shift differences of their C7H7 and CH3 signals. Ia and Ib can be separated by fractional crystallization. In solution Ia epimerizes with respect to the Mo configuration. The half lives in benzene for the equilibration Ia ? Ib are 5.5, 30, and 104 min at 60, 50, and 40°C, respectively. Phosphine exchange experiments show that the epimerization proceeds via PN★ dissociation.An X-ray structure analysis was carried out on a single crystal of Ia. The absolute configuration at Mo was determined to be (R). 相似文献
99.
Dioctylarsinic acid (HDOAA) in chloroform solution has been investigated as a reagent for the extraction of Hg(II), Ag(I), Co(II), and Cd(II). Silver, cobalt and cadmium are not extracted below pH 7. An extraction coefficient of 1.1, constant over the pH range 1–6.5, was observed for Hg(II). With HCl concentrations of 1–8 M the extractability of mercury decreased slowly, reaching Ea0 = 0.05 at 8 M HCl. Silver formed a silver dioctylarsinate precipitate which collected at the interface. The extraction coefficients for Hg(II), Co(II) and Cd(II) increased above pH 7 to values of 20 (pH 9.1), 30 (pH 8.0), and 23 (pH 10), respectively. Reagent- and pH-dependence studies indicated that Co(II) and Cd(II) are extracted as M(DOAA)2 or M(DOAA)Cl through interaction of HDOAA with M(OH)2 or M(OH)+. Mercury was extracted from solutions of pH 1–6.5 as HgCl2 (HDOAA)2.5. 相似文献
100.
Cowley AH 《Chemical communications (Cambridge, England)》2004,(21):2369-2375
Donor-acceptor bonding between group 13 elements seems counter-intuitive because one normally thinks of e.g. boron and aluminium compounds as classical Lewis acids. Indeed, many such compounds have achieved industrial prominence in this regard. Recently, however, it has become possible to stabilize these and other group 13 elements in the +1 oxidation state as opposed to the archetypical +3 oxidation state. Moreover, it turns out that in the +1 oxidation state these species are excellent donors--hence the formation of these unprecedented donor-acceptor bonds. The discovery of such bonds has led, albeit indirectly, to the development of triple-decker main group cations. This aspect is also covered in the review. 相似文献