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11.
Volatile hydrides of As, Se, Sb, Sn and Bi were generated from aqueous sample solutions using a tetrahydroborate reductant. The gaseous analytes were transferred to the inner wall of an electrothermal vaporizer (graphite furnace) and preconcentrated on a 1.25 μg thin-film of reduced palladium at 400°C. The furnace comprised the sample introduction unit of an inductively coupled plasma mass spectrometric detection system. Absolute limits of detection (3σB) were 2.9, 3.3, 54, 5 and 1980 pg for As, Sb, Sn, Bi and Se, respectively. System efficiency for the generation and sequestration of the hydrides averaged, with the exception of Se, better than 75%. Multielement determinations of As, Se and Bi were possible using the same experimental conditions, those for Sn and Sb were accomplished in a separate run. The efficacy of this analytical approach was verified by the analysis of several marine reference materials using simple calibration standards prepared in the same manner as the samples. Good agreement with certified values was achieved for As, Sn, Sb and Se; no reference materials were available for assessment of accuracy in the case of Bi. 相似文献
12.
The major octabromo isomer of technical octabromo diphenyl ether mixture (technical octaBDE) DE-79 was isolated by RP-HPLC. Three serially coupled columns (each 250 mm long) enabled a good separation of the target compound from other congeners using 100% ACN as eluent. Approximately 100 microg of the target compound was isolated with a purity of >90% and investigated by MS for confirmation of the degree of bromination. 1H-NMR and 2-D 1H-13C correlation NMR spectra unequivocally clarified that the octaBDE in question is 2,2',3,3',4,4',6,6'-octabromodiphenyl ether (BDE 197). Based on annual production rates of technical BDE products (1999/2001), approximately 380 tons of BDE 197 were annually produced which, on the long term, may enter the environment. Compared with other individual BDE congeners, BDE 197 has the seventh highest application rate. Reductive debromination of BDE 197 can lead to four hepta-, 15 hexa-, 23 penta-, and 28 tetra-BDE isomers, respectively. This variety includes all known major BDEs of environmental concern (BDE 47, 85, 99, 100, 153, 154, and 183). The identification of BDE 197 in technical octaBDE DE-79 strongly suggests that research on the environmental fate of BDEs should include this key-BDE congener. 相似文献
13.
Samuel K Yin W Stearns RA Tang YS Chaudhary AG Jewell JP Lanza T Lin LS Hagmann WK Evans DC Kumar S 《Journal of mass spectrometry : JMS》2003,38(2):211-221
Metabolic activation of drug candidates to electrophilic reactive metabolites that can covalently modify cellular macromolecules may result in acute and/or idiosyncratic immune system-mediated toxicities in humans. This presents a significant potential liability for the future development of these compounds as safe therapeutic agents. We present here an example of an approach where sites of metabolic activation within a new drug candidate series were rapidly identified using online liquid chromatography/multi-stage mass spectrometry on an ion trap mass spectrometer. This was accomplished by trapping the reactive intermediates formed upon incubation of compounds with rat and human liver microsomes as their corresponding glutathione conjugates and mass spectral characterization of these thiol adducts. Based on the structures of the GSH adducts identified, potential sites and mechanisms of bioactivation within the chemical structure were proposed. These metabolism studies were interfaced with iterative structural modifications of the chemical series in order to block these bioactivation sites within the molecule. This strategy led to a significant reduction in the propensity of the compounds to undergo metabolic activation as evidenced by reductions in the irreversible binding of radioactivity to liver microsomal material upon incubation of tritium-labeled compounds with this in vitro system. With the efficiency and throughput achievable with such an approach, it appears feasible to identify and address the metabolic activation potential of new drug leads during routine metabolite identification studies in an early drug discovery setting. 相似文献
14.
Hiroshi Ito Vladimir Marousek Conrad Schuerch 《Journal of polymer science. Part A, Polymer chemistry》1979,17(5):1299-1307
1,6-Anhydro-2,3,4-tri-O-(p-methylbenzyl)-ß-D -galactopyranose (TXGal,M1) has been copolymerized with 1,6-anhydro-2,3,4-tri-O-benzyl-ß-D -mannopyranose (TBMan,M2), the products characterized by NMR, specific rotation, and viscosity, and the reactivity ratios calculated. The reactivity ratios r1 = 0.37 ± 0.15 and r2 = 38 ± 4 indicate that the anhydromannose derivative is about 100 times as reactive as that of anhydrogalactose. A comparison of glucose, mannose, and galactose copolymerizations suggests that the reactivity differences of the three propagating cations are comparatively small and the reactivity differences of the monomers large. This result is consistent with a mechanism proposed earlier. Methyl substitution on the aromatic rings of the p-xylyl groups inhibits the initiation process significantly relative to benzyl, but propagation only slightly. 相似文献
15.
A chiral stationary phase (CSP) based on (-)-(18-crown-6)-2,3,11,12-tetracarboxylic acid was evaluated for the direct resolution of the enantiomers of dipeptides and tripeptides. The type and concentration of the acid and the methanol content were optimized with regard to retention time and resolution using Ala-Phe as model peptide. A mobile phase consisting of 10 mM sulfuric acid in 70% aqueous methanol was applied to the separation of a set of 16 structurally diverse dipeptides and tripeptides. Generally, the configuration of the amino acid at the N-terminus determined the enantiomer elution order. With a few exceptions the LL- and LD-enantiomers interacted stronger with the CSP compared to the corresponding DD- or DL-enantiomers. The experimental conditions also allowed the simultaneous separation of all four stereoisomers of Ala-Phe. Addition of ammonium sulfate generally reduced retention times and enantiomer resolution. Addition of triethylamine as modifier led to an overall increase of the retention times while the resolution did not show a general trend, increasing in the case of Ala-Ala but decreasing in the case of Ala-Phe. 相似文献
16.
Firouz Matloubi-Moghandam Peter Rüedi Conrad Hans Eugster 《Helvetica chimica acta》1984,67(1):209-215
Preparation of the First Spiro[(methylcyclopropan)-phenanthrene]-1,3-dione Derivatives by 1,6-Elimination Reactions of Spirocoleons Spirocoleons, e.g. coleon J ( 1 ), on treatment with 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) in aprotic solvents, undergo enolization followed by a rapid 1,6-elimination with formation of the hitherto unknown 2-methyl-spiro[cyclopropane-1,2′(1′H)-phenanthrene]-1′,3′(4′bH)-dione system, e.g. 3 . In protic solvents, base-catalyzed solvolysis of the spirocyclopropane predominates. 相似文献
17.
Tilson JL Naleway C Seth M Shepard R Wagner AF Ermler WC 《The Journal of chemical physics》2004,121(12):5661-5675
A valence full configuration interaction study with a polarized double-zeta quality basis set has been carried out for the lowest 49 electronic states of AmCl(+). The calculations use a pseudopotential treatment for the core electrons and incorporate a one-electron spin-orbit interaction operator. Electrons in the valence s, p, d, and f subshells were included in the active space. The resulting electronic potential energy curves are largely repulsive. The chemical bonding is ionic in character with negligible participation of 5f electrons. The molecular f-f spectroscopy of AmCl(+) arises essentially from an in situ Am(2+) core with states slightly redshifted by the presence of chloride ion. Am(+)+Cl asymptotes which give rise to the few attractive potential energy curves can be predicted by analysis of the f-f spectroscopy of isolated Am(+) and Am(2+). The attractive curves have substantial binding energies, on the order of 75-80 kcal/mol, and are noticeably lower than recent indirect measurements on the isovalent EuCl(+). An independent empirical correlation supports the predicted reduction in AmCl(+) binding energy. The energies of the repulsive curves are strongly dependent on the selection of the underlying atomic orbitals while the energies of the attractive curves do not display this sensitivity. The calculations were carried out using our recently developed parallel spin-orbit configuration interaction software. 相似文献
18.
Adams MR Aïd S Anthony PL Averill DA Baker MD Baller BR Banerjee A Bhatti AA Bratzler U Braun HM Breidung H Busza W Carroll TJ Clark HL Conrad JM Davisson R Derado I Dhawan SK Dietrich FS Dougherty W Dreyer T Eckardt V Ecker U Erdmann M Faller F Fang GY Figiel J Finlay RW Gebauer HJ Geesaman DF Griffioen KA Guo RS Haas J Halliwell C Hantke D Hicks KH Hughes VW Jackson HE Jancso G Jansen DM Jin Z Kaufman S Kennedy RD Kinney ER Kirk T Kobrak HG Kotwal AV Kunori S Lancaster S Lord JJ Lubatti HJ 《Physical review letters》1995,74(9):1525-1529
19.
McFarland KS Naples D Arroyo CG Auchincloss P de Barbaro P Bazarko AO Bernstein RH Bodek A Bolton T Budd H Conrad J Drucker RB Harris DA Johnson RA Kim JH King BJ Kinnel T Koizumi G Koutsoliotas S Lamm MJ Lefmann WC Marsh W McNulty C Mishra SR Nienaber P Nussbaum M Oreglia MJ Perera L Quintas PZ Romosan A Sakumoto WK Schumm BA Sciulli FJ Seligman WG Shaevitz MH Smith WH Spentzouris P Steiner R Stern EG Vakili M Yang UK 《Physical review letters》1995,75(22):3993-3996
20.
Conrad Newton Per Osland Tai Tsun Wu 《Zeitschrift fur Physik C Particles and Fields》1994,61(3):441-447
As a method of regularization, point splitting has played an essential role in the recent theoretical determination of the masses of the Higgs boson and the top quark. It is the purpose of this paper to put this pointsplitting regularization on a firm basis. The result turns out to be extremely simple: replace the usual vertex factor-ieγ µ in quantum electrodynamics by $$ - ie(\gamma _\mu - \frac{{\not p}}{{p \cdot \delta }}\delta _\mu ),$$ wherep is the momentum of the photon line, andδ µ is the distance for point splitting. No additional vertices are needed. 相似文献