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141.
Vojinović K McLachlan LJ Hinchley SL Rankin DW Mitzel NW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(12):3033-3042
The simple silylhydrazines F(3)SiN(Me)NMe(2) (1), F(2)Si(N(Me)NMe(2))(2) (2), and F(3)SiN(SiMe(3))NMe(2) (3) have been prepared by reaction of SiF(4) with LiN(Me)NMe(2) and LiN(SiMe(3))NMe(2), while F(3)SiN(SnMe(3))NMe(2) (4) was prepared from SiF(4) and (Me(3)Sn)(2)NNMe(2) (5). The compounds were characterized by gas-phase IR and multinuclear NMR spectroscopy ((1)H, (13)C, (14/15)N, (19)F, (29)Si, (119)Sn), as well as by mass spectrometry. The crystal structures of compounds 1-5 were determined by X-ray crystallography. The structures of free molecules 1 and 3 were determined by gas-phase electron diffraction. The structures of 1, 2, and 4 were also determined by ab initio calculations at the MP2/6-311+G** level of theory. These structural studies constitute the first experimental proof for the presence of strong Si.N beta-donor-acceptor bonds between the SiF(3) and geminal NMe(2) groups in silylhydrazines. The strength of these non-classical Si.N interactions is strongly dependent on the nature of the substituent at the alpha-nitrogen atom of the SiNN unit, and has the order 3>4>1. The valence angles at these extremely deformed alpha-nitrogen atoms, and the Si.N distances are (crystal/gas): 1 104.2(1)/106.5(4) degrees, 2.438(1)/2.510(6) A; 3 83.6(1)/84.9(4) degrees, 2.102(1)/2.135(9) A; 4 89.6(1) degrees, 2.204(2) A. 相似文献
142.
J. Vučina S. Milenković V. Šćepanović 《Journal of Radioanalytical and Nuclear Chemistry》1988,120(1):205-210
The possible effects of several protecting procedures on the quality of99mTc eluates were investigated. The content of99Mo in the eluates (99Mo breakthrough) was expressed in (%) with respect to the total adsorbed99Mo radioactivity and in () i.e. as the ratio of99Mo and99mTc radioactivities in each particular eluate. The radiochemical purity was expressed in (%) of99mTc(VII) in the eluates. The content of Al3+ and Cu2+ as chemical impurities was also determined. 相似文献
143.
Zusammenfassung Bei der Titration von Zink aus dem Niederschlag von Natrium-Zinkuranylacetat wird statt des früher vorgeschlagenen Indikators Eriochromschwarz T der Indikator Dithizon verwendet. Dadurch wird auch bei Titrationen mit 0,001-m Lösungen ein scharfer Umschlag erzielt.
Summary Dithizone is used in place of Eriochrome black T previously suggested as indicator in the titration of zinc contained in the precipitate of sodium-zinc-uranyl acetate. A sharper change is thus observed even with 0.001M solutions.
Résumé Lors du titrage du zinc dans le précipité d'acétate d'uranyle de zinc et de sodium, les auteurs emploient comme indicateur la dithizone au lieu du Noir Eriochrome T qui avait été précédemment recommandé. Il est ainsi possible d'obtenir un virage très net, même pour des titrages effectués avec des solutions 0,001M.相似文献
144.
In the present study we give the results of the ab initio calculations on the vibronic, spin-orbit, and magnetic hyperfine structure in the X (2)Pi electronic state of the NCO radical. The calculations of the potential surfaces and the electronic mean values of the hyperfine coupling constants are carried out by means of the density functional theory approach (B3LYP functional combined with an atomic orbital basis set suitable for calculations of the hyperfine structure). The vibronic levels, spin-orbit splitting, and the vibronic mean values of the components of the hyperfine tensor in the vibronic species are calculated using a variational method. The results of the calculations are in good agreement with the available experimental data. 相似文献
145.
The excitation and emission luminescence spectra of the complex compounds of manganese (II) chloride with the hydrochlorides of pyridine, 2-methyl- and 2-ethylpiperidine have been studied. It has been established that the crystals of these complex compounds appear in tetrahedral and octahedral configurations. The excitation spectra in both configurations contain bands originating from the4G,4P,4D and4F terms, the position of which is determined by configuration. From the excitation spectra the Racah parametersB andC and the ligand field strength parameter 10Dq have been determined.The emission luminescence spectra also depend on configuration of the complex compound. The character of these spectra is expressed in terms of the following characteristic parameters: the position of the maximum of the functionG(v), the half-width of the emission luminescence band, and the constants andm. From the excitation and emission luminescence spectra it has been established that the emission in both configurations is due to the4T1(G)6A1 transition. 相似文献
146.
D. Šokčević Z. Lenac R. Brako M. Šunjić 《Zeitschrift für Physik B Condensed Matter》1977,28(4):273-281
We develop a theory of low energy electron loss spectroscopy of vibrational modes of molecules adsorbed on metal surfaces. Differential and total cross sections are calculated in the Distorted Wave Born Approximation, assuming i) strong elastic scattering on the metal surface, ii) direct electron-molecule interaction via the electric dipole field associated with the molecular vibration. The angular distributions are calculated and discussed for molecules adsorbed at various distances above the metal surface and for several electron energies and impact angles. The influence of electronic screening of dipolar oscillations is discussed and the consequences of the classical induced image dipoles are explored. It is shown that the metal surface selection rule known in IR spectroscopy is only approximately valid in electron scattering. Finally, we give numerical estimates of the inelastic scattering cross sections for the stretching vibrations of CO molecule adsorbed on transition metal surfaces, in reasonable agreement with experiments. 相似文献
147.
Stable dispersions of fine (< 0.05m) needle-type copper(II) hydroxide particles were prepared at room temperature by admixing sodium acetate and ammonia to copper sulfate solution. The particle length and width could be altered with the concentration of reactants. The rate of dissolution of copper(II) hydroxide particles in doubly distilled water at room temperature is time dependent, which is due in part to the formation of a mononuclear complex solute (CuOH+). After extended times (e.g., 18 h), the particles underwent phase transformation, resulting in longer needles of higher degree of crystallinity.Supported by the Griffin Corp., Valdosta, Georgia. 相似文献
148.
Eudragit RS microspheres containing chitosan hydrochloride were prepared by the solvent evaporation method using acetone/liquid paraffin solvent system and their properties were compared with Eudragit RS microspheres without chitosan, prepared in our previous study. Different stirring rates were applied (400-1200 rpm) and drug content, Higuchi dissolution rate constant, surface and structure characteristics of the microspheres were determined for each size fraction. An increase in average particle size with a reduction of stirring rate appeared in limited interval in both series. The average particle size of microspheres without chitosan, prepared at the same stirring rate, was smaller. Pipemidic acid content increased with increasing fraction particle size, but not with increasing stirring rate as it was observed for microspheres without chitosan. We presume that high pipemidic acid content in larger microspheres is a consequence of cumulation of undissolved pipemidic acid particles in larger droplets during microspheres preparation procedure. Pipemidic acid release was faster from microspheres with chitosan and no correlation between Higuchi dissolution rate constant and stirring rate or fraction particle size was found, though it existed in the system without chitosan. Structure and surface characteristics of microspheres observed by scanning electron microscope (SEM) were not changed significantly by incorporation of chitosan. But in contrast with microspheres without chitosan, the surface of chitosan microspheres was more porous after three hours of dissolution. It is supposed that the influence of particle size fraction and stirring rate on release characteristics is expressed to a great extent through porosity and indirectly through total effective surface area, but the incorporation of highly soluble component i.e. chitosan salt hides these effects on drug release. In conclusion, changes in biopharmaceutical properties due to varying stirring rate and fraction particle size exhibited the same direction as those reported for the microspheres without chitosan, although they are less expressed because of increased experimental variability, likely caused by chitosan. 相似文献
149.
Summary The conditions fox coulometric determination of small quantities of hydrazine, phenylhydrazine and isoniazid in glacial acetic acid with electrogenerated manganese(III) acetate and lead(IV) acetate were investigated. With the direct coulometric method at room temperature, good results were obtained in the determination of hydrazine and isoniazid with lead(IV) acetate and in the determination of phenylhydrazine with manganese(III) acetate. Hydrazine and isoniazid can also be determined by the coulometric back-titration method if the oxidation with manganese(III) acetate is performed at elevated temperature.
Zusammenfassung Die Bedingungen für die coulometrische Bestimmung kleiner Mengen Hydrazin, Phenylhydrazin und Isoniazid mit elektrolytisch erzeugtem Mangan(III)-Acetat und Blei(IV)-Acetat in Eisessig wurden untersucht. Bei Zimmertemperatur wurden gute Resultate durch direkte coulometrische Titration des Hydrazins und Isoniazids mit Blei(IV)-Acetat und bei Titration des Phenylhydrazins mit Mangan(III)-Acetat erhalten. Durch coulometrische Rücktitration können bei höheren Temperaturen Hydrazin und Isoniazid mit Mangan(III)-Acetat erfolgreich bestimmt werden.相似文献
150.
I. Kraljić 《Mikrochimica acta》1960,48(4):586-591
Zusammenfassung Silberionen wirken katalytisch auf die Zersetzung des Hexacyanoferrates(II); in Gegenwart von 2,2-Dipyridyl entsteht als Reaktionsprodukt ein intensiv gefärbter Eisen(II)-Dipyridylkomplex. Bei erhöhter Temperatur und in schwach saurem Medium ist die Wirkung des Silbers sehr stark.Dieser katalytische Effekt wurde für die photometrische Silber-bestimmung verwendet. Der Einfluß der Versuchsbedingungen wurde photometrisch verfolgt und daraus die optimalen Bedingungen abgeleitet. Die Methode ist sehr empfindlich und ermöglicht die Bestimmung von Submikrogrammengen Silber. Die Extinktion wurde mit grünem Filter (oder spektralphotometrisch bei 522 nm) gemessen. Die Eichkurve ist schwach gekrümmt und umfaßt das Konzentrationsbereich von 2 · 10–7 bis 2· 10–6 M AgNO3/l. Bei Einhaltung der genauen Arbeitsbedingungen sind die Resultate innerhalb der Fehlergrenzen photometrischer Bestimmungen reproduzierbar.
II. Croat. Chem. Acta; im Druck. 相似文献
Summary Silver ions have a catalytic action on the decomposition of hexacyano-ferrate(II); in the presence of 2,2-dipyridyl, the reaction product is an intensively colored iron(II)-dipyridyl complex. The action of the silver is very marked at elevated temperatures and in a weakly acid medium.This catalytic effect was employed, for the photometric determination of silver. The influence of the experimental conditions was followed photometrically and the optimal conditions were derived from these findings. The method is very sensitive and permits the determination of submicrogram amounts of silver. The extinction was measured with a green filter (or spectrophotometrically at 522 nm). The calibration curve is slightly bent and includes the concentration range from 2 · 10–7 to 2 · 10–6 M AgNO3 per liter. If the working conditions are strictly maintained, the results are reproducible within the limits of error of photometric determinations.
Résumé Les ions argent ont une action catalytique sur la décomposition du ferrocyanure; en présence du dipyridyle-2,2, il se forme, comme produit de réaction, un complexe dipyridyle-fer-II, intensément coloré. A température plus élevée et en milieu faiblement acide, l'action de l'argent est très forte.On a appliqué cet effet catalytique au dosage photométrique de l'argent. On a suivi, par photométrie, l'influence des conditions expérimentales et l'on a déduit de ces données les conditions optimales. La méthode est très sensible et permet le,dosage de quantités d'argent submicro. On a mesuré l'extinction avec un filtre vert (ou spectrophotométriquement à 522 nm). La courbe d'étalonnage présente une faible courbure et englobe le domaine de concentration de 2 · 10–7 à 2 · 10–6 M AgNO3/l. Si l'on observe les conditions précises du mode opératoire, les résultats sont reproductibles dans les limites d'erreurs des dosages photométriques.
II. Croat. Chem. Acta; im Druck. 相似文献