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91.
Three of the main oxygen-containing fragments resulting from 3-methyl-2-butyl trifluoroacetate (11) had been identified previously as the 1-triflnoroacetoxyethyl cation (m/z 141, 12, product of simple cleavage), and the products of single (m/z 142) and double hydrogen transfer (m/z 143, protonated ethyl trifluoroacetate). Collisionally activated dissociation of m/z 142 and the isotopomers resulting from 11-2-d, 11-1-d3, 11-5,6-d6, and 11-18O2 has established that m/z 142 is the oxygen protonated 1-trifluoroacetoxyethyl free radical (17) formed by hydrogen shift irom a γ-methyl group to oxygen in the molecular ion, rather than in a complex (18) between 12 and the 2-propyl free radical, as expected based on a mechanistic model existing in the literature. The second hydrogen transferred originates in the other γ-methyl group; its migration may occur, but does not have to, in the complex between 17 and a molecule of propene, prior to dissociation of the two fragments. Collision-activated dissociation has now shown that the m/z 140 ion observed in the spectrum is the molecular ion of vinyl trifluoroacetate, possibly formed by a hydrogen transfer from 12 to the 2-propyl radical in the complex 18. The hydrogen migration to oxygen exhibits no isotope effect, whereas the transfers to carbon atoms exhibit small primary and α secondary kinetic isotope effects. Exclusive migration of the tertiary hydrogen from C(3) occurs in the formation of 2-methylbutene cation radical (m/z 70) from the molecular ion. The hydrocarbon ion fragments and the heteroatom-containing fragments are formed from 11 by disjoint pathways. 相似文献
92.
Wilkie GD Elliott GI Blagg BS Wolkenberg SE Soenen DR Miller MM Pollack S Boger DL 《Journal of the American Chemical Society》2002,124(38):11292-11294
The scope of intramolecular Diels-Alder and a novel tandem Diels-Alder/1,3-dipolar cycloaddition cascade of 1,3,4-oxadiazoles is disclosed. In the cases examined, the tandem cycloadditions construct three new rings with formation of four new C-C bonds and set all six stereocenters about a central six-membered ring in a single step including three contiguous and four total quaternary centers without a trace of a second diastereomer. 相似文献
93.
Heterogeneous fluorescence immunoassays have been automated using flow injection manifolds incorporating thiophilic gel solid phase reactors to separate antibody-bound and unbound analyte molecules. Antibody elution is achieved by changes in ionic strength, thus allowing the use of pH sensitive fluorescent labels. This facilitates the development of dual analyte systems, in which two competitive immunoassays with separate labels are monitored in parallel. Detection of the fluorophores by high speed synchronous fluorescence scanning while the flow is briefly stopped utilises either one synchronous interval which detects both fluorophores, or two separate scans at different wavelength intervals, one for each fluorophore. Simultaneous analyses of serum albumin and transferrin exemplify these novel approaches. Spectroscopic interferences are very small, analyte recoveries are close to 100%, with a relative standard deviation of 5-6% and a sampling rate of 20 h-1. 相似文献
94.
Miller TA Jeffery JC Ward MD Adams H Pope SJ Faulkner S 《Dalton transactions (Cambridge, England : 2003)》2004,(10):1524-1526
Co-crystallisation of the anionic cyanometallate chromophore [Ru(bipy)(CN)4]2- with Yb(III) provides coordination polymers or oligomers containing Ru-CN-Yb bridges; in [K(H2O)4][Yb(H2O)6][Ru(bipy)(CN)4]2.5H2O Ru-->Yb energy-transfer (k > 5 x 10(6) s(-1)) results in partial quenching of the Ru-based luminescence and sensitised near-IR luminescence from the Yb(III) unit. 相似文献
95.
Y. B. Tewari D. E. Martire S. P. Wasik M. M. Miller 《Journal of solution chemistry》1982,11(6):435-445
From thermodynamics and certain assumptions it is shown that, under the usual experimental conditions, the octanol-water partition coefficient (Ko/w) of a given organic liquid should be the same whether the substance is partitioned neat or as part of a mixture. Measurements of several mixtures of n-propylbenzene (log Ko/w=3.71±0.04)+ethylbenzene (log Ko/w=3.16±0.01) clearly confirm this. It is also shown that the aqueous solubility (Sw) of a neat organic liquid can be related to its aqueous solubility (S
w
), when it is present at volume fraction in an organic liquid mixture, by S
w
=Sw, where is its activity coefficient in the organic mixture. The measured S
w
values for n-propylbenzene + ethylbenzene (1), n-hexane + nitrobenzene (>1) and di-isopropyl ether + chloroform (<1) are found to be in good agreement with the predicted values (average differences of, respectively, <2%, 8% and 6%). In general, the bounds on S
w
are expected to be 0w
w. 相似文献
96.
At a pressure of 10?6 Torr the ion cyclotron resonance spectra of p-benzoquinone, methyl-p-benzoquinone, tetramethyl-p-benzoquinone and tetrafluoro-p-benzoquinone are identical to the normal mass spectra. Above 10?5 Torr the spectra show a variety of signals for product ions. From double resonance measurements it was shown that all the product ions are formed by addition of the molecular ion or of a fragment ion to a neutral quinone molecule. In most cases the addition is accompanied by the elimination of carbon monoxide. 相似文献
97.
Walter M. Miller 《Set-Valued Analysis》1995,3(2):181-194
A set-valued dynamical systemF on a Borel spaceX induces a set-valued operatorF onM(X) — the set of probability measures onX. We define arepresentation ofF, each of which induces an explicitly defined selection ofF; and use this to extend the notions of invariant measure and Frobenius-Perron operators to set-valued maps. We also extend a method ofS. Ulam to Markov finite approximations of invariant measures to the set-valued case and show how this leads to the approximation ofT-invariant measures for transformations , whereT corresponds to the closure of the graph of . 相似文献
98.
Jesik R Abramov V Antipov Y Baldin B Crittenden R Dauwe L Davis C Denisov S Dyshkant A Dzierba A Glebov V Goldberg H Gribushin A Koreshev V Krider J Krinitsyn A Li R Margulies S Marshall T Martin J Mendez H Petrukhin A Sirotenko V Smith P Solomon J Sulanke T Sulyaev R Vaca F Zieminski A Blusk S Bromberg C Chang P Choudhary B Chung W de Barbaro L Dlugosz W Dunlea J Engels E Fanourakis G Ginther G Hartman K Huston J Kapoor V Lirakis C Lobkowicz F Mani S Mansour J Maul A Miller R Oh B Pothier E 《Physical review letters》1995,74(4):495-498
99.
100.
Artuso M Gao M Goldberg M He D Horwitz N Moneti GC Mountain R Muheim F Mukhin Y Playfer S Rozen Y Stone S Xing X Zhu G Bartelt J Csorna SE Egyed Z Jain V Gibaut D Kinoshita K Pomianowski P Barish B Chadha M Chan S Cowen DF Eigen G Miller JS O'Grady C Urheim J Weinstein AJ Würthwein F Asner DM Athanas M Bliss DW Brower WS Masek G Paar HP Gronberg J Korte CM Kutschke R Menary S Morrison RJ Nakanishi S Nelson HN Nelson TK Qiao C Richman JD Roberts D Ryd A Tajima H Witherell MS Balest R Cho K 《Physical review letters》1995,75(5):785-789