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991.
Wrona M Mauriala T Bateman KP Mortishire-Smith RJ O'Connor D 《Rapid communications in mass spectrometry : RCM》2005,19(18):2597-2602
The removal of bottlenecks in discovery stage metabolite identification studies is an ongoing challenge for the pharmaceutical industry. We describe the use of an 'All-in-One' approach to metabolite characterization that leverages the fast scanning and high mass accuracy of hybrid quadrupole time-of-flight mass spectrometry (QqToFMS) instruments. Full-scan MS and MS/MS data is acquired using collision energy switching without the preselection, either manually or in a data-dependent manner, of precursor ions. The acquisition of 'clean' MS/MS data is assisted by the use of ultrahigh-performance chromatography. Data acquired using this method can then be mined post-acquisition in a number of ways. These include using narrow window extracted ion chromatograms (nwXICs) for expected biotransformations, XICs for the product ions of the parent compound and/or expected modification of these product ions, and neutral loss chromatograms. This approach has the potential to be truly comprehensive for the determination of in vitro biotransformations in a drug discovery environment. 相似文献
992.
Anhydrous copper(II) furoate and copper(II) thiophene-2-carboxylate have been Synthesized. They are formulated as dimeric species with four carboxylate bridges. The thiophene and furan moieties give rise to polymeric structures. Electron spin resonance spectra and magnetic susceptibility measurements show that the dimers have a singlet ground state and a thermally populated triplet state. The exchange coupling constants, 2J, are ?322 and ?312 cm?1 for the furoate and thiophene-2-carboxylate complexes, respectively. The electronic and infrared spectra are also discussed. 相似文献
993.
Johannes C. S. Malan Jacobus A. Steenkamp Desmond A. Young Daneel Ferreira 《Tetrahedron》1989,45(24):7859-7868
Acid-catalyzed condensation of (+)-mollisacacidin-[(2R, 3S, 4R)-2, 3-trans-3, 4-trans-flavan-3,3′,4,4′,7-pentaol] with an excess of (−)-robinetinidol[(2R,3S)-2,3-trans-flavan-3,3′,4′,5′,7-pentaol] afforded a novel series of bi-, tri-, and tetraflavanoid profisetinidins. They are accompanied by (−)-fisetinidol-(4,2′)-(−)-robinetinidol which results from the pyrogallol B-ring of (−)-robinetinidol serving as nucleophile competing with its resorcinol A-ring in coupling with a C-4 carbocationic intermediate. Similar condensation with (+)-epifisetinidol[(2S,3S)-2,3-cis-flavan-3,3′,4′,7-tetraol] led to the exclusive formation of [4,6]-interflavanyl bonds, these units being ‘linearly’ arranged in the tetraflavanoid analogue in contrast to the ‘branched’ nature of the (−)-robinetinidol homologue. 相似文献
994.
Vincenti M Biazzi S Ghiglione N Valsania MC Richardson SD 《Journal of the American Society for Mass Spectrometry》2005,16(6):803-813
Four highly-fluorinated alkyl and aryl chloroformates, including 2,2,3,3,4,4,5,5-octafluoro-1-pentyl chloroformate (OFPCF), 2,3,4,5,6-pentafluorobenzyl chloroformate (PFBCF), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octyl chloroformate (TDFOCF), and 2-(2,3,4,5,6-pentafluorophenoxy)-ethyl chloroformate (PFPECF), were synthesized and tested as reagents for the direct water derivatization of polar and hydrophilic analytes. The goal of this research was to develop an optimal derivatizing agent to aid in the identification of highly polar ozonation drinking water disinfection by-products (DBPs) that are believed to be missed with current analytical procedures. The chemical properties (reactivity, selectivity, derivatization products, and their chromatographic and spectral features) for the four chloroformates were investigated using a set of highly polar standard analytes, including malic and tartaric acids, hydroxylamine, valine, 2-aminoethanol, resorcinol, 1,3,5-trihydroxybenzene, and 2,4-dihydroxybenzoic acid. Upon derivatization, the analytes were extracted from the aqueous solvent and analyzed by gas chromatography (GC)-mass spectrometry (MS) in the electron capture negative ionization (ECNI) mode. Positive chemical ionization (PCI)-MS was used for confirmation of molecular ions that were weak or absent in ECNI mass spectra. Of the four derivatizing reagents tested, OFPCF showed the best performance, with good reaction efficiency, good chromatographic and spectroscopic properties, low detection limits (10-100 fmol), and a linear response more than two orders of magnitude. Further, the entire procedure from raw aqueous sample to ready-to-inject hexane solutions of the derivatives requires less than 10 min. PFBCF showed ideal applicability for derivatizing aminoalcohols and aminoacids. The two chloroformates with the highest intrinsic stability (TDFOCF and PFPECF) failed to derivatize some of the analytes. Finally, the OFPCF derivatizing agent was tested with simulated ozonated drinking water (aqueous fulvic acid treated with ozone), and three highly polar reaction by-products were determined. 相似文献
995.
Résumé Nous étudions la vitesse de convergence du théorème de la limite centrale pour des champs de d, faiblement dépendants: m-dépendant ou -fortement mélangeant. Dès que le champ est dans L
2+, >0, la vitesse de convergence obtenue est
n
– (1)
avec un facteur (log
n
)
a
qui intervient quand est à décroissance exponentielle et dans le cas m-dépendant quand 1. Le cas où est à décroissance puissance est aussi étudié. Ces résultats ne font intervenir ni la stationarité, ni la géométrie des domaines sur lesquels le T.L.C. est étudié. 相似文献
996.
Hearns NG Preuss KE Richardson JF Bin-Salamon S 《Journal of the American Chemical Society》2004,126(32):9942-9943
The 4-(2'-pyridyl)-1,2,3,5-dithiadiazolyl neutral radical 1 has been prepared for use as a spin-bearing bidentate ligand. The coordination of this ligand to bis(hexafluoroacetylacetonato)cobalt affords a thermally stable complex 2. Magnetic susceptibility measurements of the crystalline complex indicate ferromagnetic coupling between the ligand-centered spin and the unpaired electrons of the high-spin Co(II). 相似文献
997.
A detailed mechanism for the oxidation of aryl sulfides by peroxymonocarbonate ion in cosolvent/water media is described. Kinetic studies were performed to characterize the transition state, including a Hammett correlation and variation of solvent composition. The results are consistent with a charge-separated transition state relative to the reactants, with an increase of positive charge on the sulfur following nucleophilic attack of the sulfide at the electrophilic oxygen of peroxymonocarbonate. In addition, an average solvent isotope effect of 1.5 +/- 0.2 for most aryl sulfide oxidations is consistent with proton transfer in the transition state of the rate-determining step. Activation parameters for oxidation of ethyl phenyl sulfide in tert-butyl alcohol/water are reported. From the pH dependence of oxidation rates and (13)C NMR equilibrium experiments, the estimated pK(a) of peroxymonocarbonate was found to be approximately 10.6. 相似文献
998.
Chia-En Lin Stewart K. Richardson Weiheng Wang Tiansheng Wang David S. Garvey 《Tetrahedron》2006,62(35):8410-8418
The development and preparation of five series of tertiary thiols and nitrosothiols as nitric oxide releasing molecules functionalized with acid, alcohol, or amine groups for future conjugation are reported. 相似文献
999.
P. J. Richardson J. H. D. Eland P. Lablanquie 《Journal of mass spectrometry : JMS》1986,21(5):289-294
Photoion-photoion coincidence spectra of benzene and benzene-d6 photoionized by He(II) light and synchrotron radiation show the existence of six major and eight minor charge-separation reactions of the [C6H6]2+ ion. Three main groups of ion pairs are related to [C3H3]+ + [C3H3]+, [C2H3]+ + [C4H3]+ and [CH3]+ + [C5H3]+, with appearance energies of 32.2 ± 0.5 eV, 31.3 ± 0.5 eV and 28.4 ± 0.3 eV. The kinetic energy release is the same for all pairs within a group, irrespective of hydrogen number, but differs from group to group. Results are interpreted in terms of fast, direct charge separation of [C6H6]2+, and subsequent hydrogen loss by the singly charged fragments. 相似文献
1000.
R. T. Richardson 《Journal of Thermal Analysis and Calorimetry》1994,42(4):771-780
A thermobalance has been converted to allow interactive control of the heating rate from the rate of mass loss of the sample (Constrained Rate Thermogravimetry). The interfacing of the balance and temperature controller both to an ACORN RISC microcomputer and to a PC microcomputer is described along with an outline of the software required. This provides an economic route for the conversion of existing thermobalances. Problems of achieving effective control and acceptable data recording are outlined. The nature of the TG curves obtained from interactive temperature control and the influence of control parameters is discussed. 相似文献