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61.
George Hohlneicher Harald Pulm Hans-Joachim Freund 《Journal of Electron Spectroscopy and Related Phenomena》1985,37(2):209-224
First, we show that the quantity Δβ(i) = ΔEA(kii) + 2ΔEB(i) — ΔEB(k) is directly related to the final state relaxation contribution ΔER(i) of the binding energy shift ΔEB(i). ΔEA(kii) is the kinetic energy shift of the Auger transition which corresponds to the decay of a hole state with a hole in level k into a final state with two holes in level i. The shift parameter Δβ(i), which is based on information on two binding energies, is conceptually similar to Wagner's Auger parameter. To establish the relation between Δβ(i) and ΔR(i) one needs, however, less drastic approximations than in the case of Auger parameter shifts. The only approximation necessary is the assumption that ΔR(i) is determined by coulomb contributions.Secondly, we use Δβ (i) to analyse the experimental data of eighteen gaseous phosphorus-containing compounds obtained by Sodhi and Cavell1. It is shown that ΔR(P2p) is strongly related to changes in the polarizability of the ligands. The initial state effects derived from our study deviate from those expected on the basis of simple electronegativity considerations. 相似文献
62.
63.
Sagi D Peter-Katalinic J Conradt HS Nimtz M 《Journal of the American Society for Mass Spectrometry》2002,13(9):1138-1148
Application of the negative mode electrospray ionization-quadrupole time-of-flight mass spectrometry (ESI QTOF) tandem MS for determination of substitution patterns by sialic acid and/or fucose and extention by additional LacNAc disaccharide units in single branches of multianternary N-glycans from biological samples is described. Fragmentation patterns which can be obtained by low energy collision-induced dissociation (CID) using the QTOF instrument include cleavage ions, diagnostic for determination of antennarity and for specific structural features of single antennae. Systematic fragmentation studies in the negative ion mode were focussed toward formation of the D diagnostic ion relevant for assignment of 3- and 6-antennae in complex N-glycans carrying three and four antennae in combination with epitope-relevant B- and C-type ions. For validation of this approach ESI QTOF fragmentation of the permethylated analogues was carried out in the positive ion mode. Using this strategy, products of in vitro glycosylation reactions were investigated in order to clarify some general aspects of N-glycan acceptor specificity during biosynthesis. Alpha1-3fucosylation using GDP-fucose along with a soluble form of the recombinant human alpha1-3fucosyltransferase VI was carried out on tri- and tetraantennary precursors to test structural requirements for formation of Le(x) versus sLe(x) motifs. 相似文献
64.
A rigid terpyridine ligand containing chiral alkyl chains has been synthesized, characterized and subsequently complexed with ruthenium(II) ions. The product was characterized by MALDI-TOF-MS, UV-vis and NMR. Circular dichroism showed the appearance of extended helical columnar aggregates. 相似文献
65.
Cyclic α-trimethylsilylketones are synthesized from cyclic vinyltrimethylsilanes via the epoxides , and the alcohols . 相似文献
66.
Formation of CoAl3Cl11 at higher Al2Cl6 Pressures The reaction of CoCl2,f with Al2Cl6,g (≈ 3 atm) is investigated considering every component of the gas phase (Al2Cl6, AlCl3, Al3Cl9, CoAlCl5, CoAl2Cl8, CoAl3Cl11) and the deviation from the ideal behaviour. The conclusion is derived that at 600 K from CoCl2,s and larger pressures of Al2Cl6 besides CoAl2Cl8 a small amount of CoAl3Cl11 is formed. 相似文献
67.
Jianhua WangElo Harald Hansen 《Analytica chimica acta》2002,456(2):283-292
An automated sequential injection (SI) on-line solvent extraction-back extraction separation/preconcentration procedure is described. Demonstrated for the assay of cadmium by electrothermal atomic absorption spectrometry (ETAAS), the analyte is initially complexed with ammonium pyrrolidinedithiocarbamate (APDC) in citrate buffer and the chelate is extracted into isobutyl methyl ketone (IBMK), which is separated from the aqueous phase by means of a newly designed dual-conical gravitational phase separator. A metered amount of the organic eluate is aspirated and stored in the PTFE holding coil (HC) of the SI-system. Afterwards, it is dispensed and mixed with an aqueous back extractant of dilute nitric acid containing Hg(II) ions as stripping agent, thereby facilitating a rapid metal-exchange reaction with the APDC ligand and transfer of the Cd into the aqueous phase. The aqueous phase is separated in a second dual-conical gravitational phase separator, and 30 μl of it is entrapped and metered in a sample loop (SL) and subsequently introduced via air segmentation into the graphite tube for analyte quantification. The ETAAS determination is performed in parallel with the separation/preconcentration process of the ensuing sample. An enrichment factor of 21.4, a detection limit of 2.7 ng l−1, along with a sampling frequency of 13 h−1 were obtained at a sample flow rate of 6.0 ml min−1. The precision (R.S.D.) at the 0.4 μg l−1 level was 1.8% as compared to 3.2% when quantifying the organic extractant directly. The applicability of the procedure is demonstrated for the determination of trace levels of cadmium in three certified reference materials. 相似文献
68.
Ti7Cl16 and Ti7Br16 and Further Investigations with Titanium Halides. Al2X6 as a Complex Forming Agent TiCl3,s can be transported with Al2Cl6 via TiAlCl6,g in a temperature gradient. The equilibrium of this reaction was studied by mass spectroscopy. There is no indication of the existence of a TiAl2Cl9 molecule as assumed in the literature. β-TiBr3 was prepared from the elements in the presence of the transporting agent Al2Br6,g. The transport of TiCl2 with Al2Cl6,g involves, as an important step, the disproportionation which is favoured by the reaction of Ti with the glass wall. If the disproportionation is made impossible by addition of Ti the novel compound Ti7Cl16 is obtained. Independent of Ti7Cl16, a phase TiCl(2 + x) with a broad range of homogeneity exists. The compound Ti7Br16, being isostructural with Ti7Cl16, was also prepared. Results of magnetic measurements and observations on the thermal decomposition of the compounds are reported. 相似文献
69.
Kai Li Harald D. H. Stver 《Journal of polymer science. Part A, Polymer chemistry》1993,31(10):2473-2479
Narrow disperse microparticles are formed by dispersion polymerization of commercial divinylbenzene in acetonitrile or ethanol solution in the presence of 2,2′-azobis(2-methylpropionitrile) initiator and polyvinylpyrrolidone stabilizer. The particles have average diameters between 1 and 9 μm depending on monomer concentration, solvent, and temperature. While the smaller particles are relatively smooth, surface texture increases with diameter to give popcorn shapes at 9 μm diameter. High crosslinker concentration is shown to be essential for particle formation. © 1993 John Wiley & Sons, Inc. 相似文献
70.
Abdellah Ziadi Harald Hillebrecht Brahim Elouadi 《Journal of solid state chemistry》2004,177(12):4777-4784
The crystal structure of Na3DySi6O15 has been solved and refined to an R1=2.97% (wR2=8.25%) for 1311 independent reflections. The compound was found to crystallize within the orthorhombic system with the space group Cmca (Z=8) and the lattice parameters: a=14.590(7) Å, b=17.813(4) Å, c=10.519(2) Å, V=2734.0 Å3, Dcal=3.11 g/cm3. The structure of Na3DySi6O15 is a filled variant of the zektzerite with S like corrugated double chains of [SiO4] tetrahedral, connected via Na+ and Dy3+ cations and running parallel to c-axis. The three-dimensional network results from the packing of these chains along [100] by skewering them in rods represented by the tunnels delimited by the S shape of the silicate chains. One of the main peculiar features of the Na3DySi6O15 structure is the location of Na+ in tetrahedral sites with rather short Na-O bond lengths (2×2.243 and 2×2.262 Å). 相似文献