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51.
Use of gel-permeation chromatography in the determination of the composition of two-polymer mixtures
Jean-Pierre Menin Ren Roux 《Journal of polymer science. Part A, Polymer chemistry》1972,10(3):855-866
The possibility of evaluating with acceptable accuracy the composition of a two-polymer mixture which is well separated by GPC, was studied by using mixtures of high molecular weight polybutadiene (M?w = 4.5 × 105) and low molecular weight polyiso-butylene (M?n in the range of 103). It was concluded that a satisfactory evaluation of the composition of a polymer mixture can be achieved, provided that the variations of the refractive index with the molecular weight are taken into account for the low molecular weight polymer (the polyisobutylene). 相似文献
52.
14N-NMR. measurements using the Fourier Transform technique are presented and compared to C. W. experiments. The F. T. technique is especially advantageous for relaxation time measurements. However, since 14N-nuclei may have widely different relaxation times, it is often not possible to have optimal gain in sensitivity (as compared to C. W. measurements) in a single F. T. experiment for different 14N-nuclei contained in the same sample. Different experiments have to be performed, optimizing the spectrometer parameters for each 14N-resonance of appreciably different linewidth. The technique is applied to three different problems. 14N-relaxation in symmetrical ammonium salts is shown to arise from reorientation of the water dipoles. The use of a double spin-probe, 13C-14N, allows the determination of the electric field gradients in cyclic ammonium salts. The electronic distribution is especially distorted from tetrahedral symmetry in the highly strained N, N-dimethyl-aziridinium cation. Finally, electric and dynamic effects in ion pairing may be studied as shown on the case of tetrabutylammonium iodide in water and in benzene. 相似文献
53.
Jean-Pierre Labbé 《Mikrochimica acta》1964,52(2-4):298-316
Résumé L'auteur reprend et complète la méthode de dosage microgravimétrique du germanium à l'état de germanimolybdate de tétraphénylarsonium (F
Ge=0,02137). Dans une deuxième partie, il décrit une méthode de préparation des heptagermanates alcalins et de métagermanates de métaux bivalents à partir des solutions d'oxyde GeO2 et d'acétates métalliques. Les courbes de thermolyse et les spectres d'absorption infrarouge sont présentés. Aucun orthogermanate ne précipite des solutions aqueuses.
Mémoire en l'honneur du professeurA. A. Benedetti-Pichler. 相似文献
Summary The author resumes and completes the method for the microgravimetric determination of germanium as the germanium molybdate of tetraphenylarsonium (F Ge=0.02137). In a second part he describes a method for preparing some heptagermanates of divalent metals from solutions of the oxide GeO2 and metal acetates. The thermolysis curves and the infrared absorption curves are given. No orthogermanate precipitates from aqueous solutions.
Zusammenfassung Der Verfasser berichtet über die mikrogravimetrische Bestimmung des Germaniums als Tetraphenylarsonium-Germanium-Molybdat (F Ge=0,02137). Im zweiten Teil der Arbeit wird die Herstellung von Alkaliheptagermanat sowie von Metagermanaten bivalenter Metalle aus Germaniumoxidlösungen und Metallacetaten beschrieben. Die Thermolysekurven und IR-Absorptionsspektren werden vorgelegt. Aus wäßrigen Lösungen fällt kein Orthogermanat aus.
Mémoire en l'honneur du professeurA. A. Benedetti-Pichler. 相似文献
54.
1H-Cyclopropa[b]naphthalene 3c and the 2,7-diphenyl-substituted derivative 3a have been synthesized via cycloaddition of the appropriate isobenzofurans 1a and 1b to 1-bromo-2-chlorocyclopropene and aromatization of the adducts with low-valent Ti. The same procedure afforded the 2,7-dimethyl-H-cyelopropa[g]isoquinoline ( 15 ), but failed for the parent azacompound. Reaction of adducts of furans to 1-bromo-2-chlorocyclopropenes with low-valent Ti produced mixtures of cyclopropabenzenes 19 and 1,6-dihalogeno-1,3,5-cycloheptatrienes 18 . The latter could be converted to cyclopropabenzenes with BuLi. 相似文献
55.
Pascal Röthlisberger Fabienne Levi-Acobas Ivo Sarac Rémy Ricoux Jean-Pierre Mahy Piet Herdewijn Philippe Marlière Marcel Hollenstein 《Tetrahedron letters》2018,59(48):4241-4244
Abasic sites are amongst the most frequent DNA lesions and result from spontaneous hydrolysis of the glycosidic bond or from the removal of damaged nucleobases. These depurination events can also occur on free deoxyribonucleoside triphosphates present in cells and lead to the formation of an abasic site triphosphate of which very little is known. Herein, we report the synthesis and biochemical characterization of the minimal triphosphate dФTP. Unexpectedly, dФTP is tolerated by various DNA polymerases and the incorporation efficiency obeys the A-rule. Single incorporation of dФMP units were also observed opposite abasic sites and the addition of prosthetic molecules mimicking base-pairs do not seem to favor the process. 相似文献
56.
钯(Ⅱ)—组氨酸络合物极谱波的研究 总被引:1,自引:0,他引:1
本用极谱法研究了Pd(Ⅱ)-组氨酸络合物波的形成条件和性质,用线性法和连续变化法确定了Pd(Ⅱ)与组氨酸的络合物比为1:2,络合物的稳定常数β为3.47×10^19。测定钯的线性范围为0.02~0.7μg/ml。 相似文献
57.
Optimized conditions for copper-catalyzed N-arylation of methyl pyroglutamate are described. These studies permitted the synthesis of methyl N-naphthylpyroglutamate, which was then cyclized to a ketone. The known dehydration of amidoketones by PPA was extended to this new scaffold to lead to a novel condensed benzo[de]quinoline with potential antioxidative activity. 相似文献
58.
Bibal B Tinant B Declercq JP Dutasta JP 《Chemical communications (Cambridge, England)》2002,(5):432-433
The new tetra-thiophosphonatocavitand 1 in its iiii configuration extracts quantitatively Ag+ ions from aqueous solutions; the tetranuclear complex [1(2).Ag4Pic4] was selectively formed and characterized in the solid state by X-ray diffraction which revealed the formation of a new dimeric assembly through Ag+ coordination. 相似文献
59.
McSkimming G Tucker JH Bouas-Laurent H Desvergne JP Coles SJ Hursthouse MB Light ME 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(15):3331-3342
Aza-crown ethers 2 and 3 with anthracene-containing pendant arms have been synthesised and characterised. Both compounds bind Group 1 metal cations in solution, forming complexes of 1:1 stoichiometry. The properties of compound 2 and its complexes have been studied by a range of techniques, including NMR, UV and fluorescence spectroscopy and X-ray crystallography. The pendant arms can adopt either a cis or a trans geometry, the cis geometry favoured with larger cations. The geometry of the complex affects the fluorescence properties of the system, with larger cations giving higher excimer/monomer ratios. Upon irradiation at lambda>300 nm, coronand 2 forms the cryptand 5 through a reversible intramolecular [4pi+4pi] cycloaddition reaction. The rates of the forward and reverse reactions of this photochromic process are cation dependent; in particular the rate of the thermal reverse reaction is decreased by smaller cations and increased by larger cations, especially Rb(+). The metal binding constants in methanol for 2 and 5 have been determined, revealing that the cryptand 5 binds Na(+) and Rb(+) more weakly than crown ether 2 by over two orders of magnitude. 相似文献
60.
Leclerc E Buchmann W Taphanel MH Morizur JP 《Rapid communications in mass spectrometry : RCM》2002,16(7):686-695
Ion/molecule reactions between O=P(OCH(3))(2)(+) phosphonium ions and six aromatic hydrocarbons (benzene, toluene, 1,2,4-trimethylbenzene, naphthalene, acenaphthylene and fluorene) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH(3))(2)(+) phosphonium ions, formed by electron impact from neutral trimethyl phosphite, were found to react with aromatic hydrocarbons (ArHs) to give (i) an adduct [ArH, O=P(OCH(3))(2)](+) and (ii) for ArHs which have an ionization energy below or equal to 8.14 eV, a radical cation ArH(+ *) by charge transfer reaction. Collision-induced dissociation experiments, which produce fragment ions other than the O=P(OCH(3))(2)(+) ions, indicate that the adduct ions are covalent species. Isotope-labeled ArHs were used to elucidate fragmentation mechanisms. The charge transfer reactions were investigated using density functional theory at the B3LYP/6-311 + G(3df,2p)//B3LYP/6-31G(d,p) level of theory. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH(3))(2)(+) and benzene is described. 相似文献