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51.
An on-column trace enrichment method for capillary electrochromatography of dilute samples is described. It involves the sequential use of frontal and elution electrochromatography on a segmented capillary column comprising of two contiguous segments each packed with a different sorbent. While the entering segment is for preconcentration by frontal electrochromatography the second segment is much longer and is meant for separation of the enriched analytes in the subsequent elution electrochromatography step. The preconcentration segment is usually packed with a sorbent that affords the highest affinity towards the solutes of interest while the separation segment is packed with a stationary phase that exhibits the highest selectivity and separation efficiency for the analytes. The detection is performed in the UV using a z-cell configuration for achieving an increased path length for detection. The effectiveness of this on-column trace enrichment is demonstrated on dilute samples of moderately polar solutes (e.g., carbamate insecticides) and nonpolar solutes (e.g., pyrethroid insecticides). Under optimal frontal and elution electrochromatography conditions. 817- and 1100-fold sensitivity increase are achieved for permethrin (a pyrethroid insecticide) and methiocarb (a carbamate insecticide), respectively, with a UV detector. The method is demonstrated with real water samples (e.g., tap and lake water samples) spiked with carbamate and pyrethroid insecticides. The limits of detection for the pesticides achieved in tap and lake waters reached 10(-8) to 10(-9) M. 相似文献
52.
Samples of synthetic hydroxyapatite, Ca(10)(PO(4))(6)(OH)(2), obtained by wet method and calcined at 1173 K in air were used in an adsorption study of some essential amino acids, mainly histidine, methionine, and tryptophan. Adsorption isotherms were obtained using aqueous solutions of concentration range 2.7x10(-2)-1.3x10(-3) M at 303, 318, and 343 K, under near neutral conditions. The mode of adsorption was studied using IR spectroscopy. The results are discussed in terms of the dependence of the adsorption process both on the functional groups on the hydroxyapatite and on the solution chemistry of the aqueous amino acids solutions. Copyright 2001 Academic Press. 相似文献
53.
S. S. Abd El Rehim L. I. Ali N. H. Amin N. F. Mohamed 《Monatshefte für Chemie / Chemical Monthly》1997,128(3):245-254
Summary The electrochemical behaviour of lead in NaOH solution was studied by potentiodynamic and cyclic voltammetric techniques in combination with X-ray diffraction analysis. The active dissolution of lead involves a small shoulderA1 followed by a peakA1 prior to a passive region. The shoulderA1 is assigned to the electroformation of a Pb(OH)2 film, whereas peakA1 is due to the formation of PbO. Beyond the passive region, the current density increases again, forming a small shoulderA2 and a peakA2 prior to the oxygen evolution potential. The shoulderA2 and the peakA2 are correlated to the electrooxidation of PbO to Pb3O4 and PbO2, respectively. The intensity of the anodic peaks increases with increasing alkali concentration, temperature and scan rate. In cyclic voltammetry, the reverse scan shows two cathodic peaksC1 andC2 which are correlated to the electroreduction of PbO and PbO2 respectively, to Pb.
Potentiodynamisches und cyclovoltammetrisches Verhalten einer Bleielektrode in NaOH-Lösung
Zusammenfassung Das elektrochemische Verhalten von Blei in NaOH wurde mittels potentiodynamischer und cyclovoltammetrischer Techniken unter Zuhilfenahme der Röntgenbeugungsanalyse untersucht. Die aktive Auflösung von Blei verläuft über eine SchulterA1, die von einem einer passiven Region vorgelagerten PeakA1 gefolgt wird. Die SchulterA1 wird der elektrochemischen Bildung eines Pb(OH)2-Films, der PeakA1 der Bildung von PbO zugeschrieben. Jenseits der passiven Region steigt die Stromdichte wieder an, und vor Erreichen des Sauerstoffpotentials treten eine kleine SchulterA2 und ein PeakA2 auf, die mit der Elektrooxidation von PbO zu Pb3O4 und PbO2 korrelieren. Analog dazu beobachtet man in der cyclischen Voltammetrie zwei kathodische PeaksC1 undC2, die der Elektroreduktion von PbO und PbO2 zu Pb entsprechen. Die Intensität der anodischen Peaks steigt mit steigender Alkalikonzentration, Temperatur und Scangeschwindigkeit.相似文献
54.
Nagwa Rashed Abdel Moneim El Massry El Sayed H. El Ashry Adel Amer Hans Zimmer 《Journal of heterocyclic chemistry》1990,27(3):691-694
A series of 1-aryl-s-triazolo[4,3-a]quinoxalin-4-ones, 3 , were synthesized via the pyrolysis of the corresponding hydrazones, 6 . Thus, the cyclodehydrogenation occurred by refluxing them in an inert solvent (e.g. ethylene glycol) to give the triazoloquinoxalin-4-ones in a satisfactory yield. Using DMSO as a solvent for the above transformation afforded as a minor by-product an S-ylid. In contrast to earlier findings, annelation of a six-membered ring was successful and achieved through the pyrolysis of the pyruvate hydrazones derived of the quinoxalin-4-ones at ?230° to give the as-triazino[4,3-a]quinoxalin-5-ones, 4 . The reaction of 5 with acetylacetone afforded 3-(3′,5′-dimethylpyrazol-1-yl)-2(1H)-quinoxalinone, 10 . The structural assignments for the new compounds were based on their elemental analysis and spectroscopic data as well as an independent synthesis. 相似文献
55.
Mohamed El Guendouzi Abderrahim Dinane Abdelfetah Mounir 《Journal of solution chemistry》2002,31(2):119-129
The mixed aqueous electrolyte system of ammonium and lithium chlorides has been studied by the hygrometric method at 25°C. The relative humidities of this system are measured at total molalities from 0.3 to 6 mol-kg– 1 for different ionic-strength fractions y of NH4Cl with y = 0.33, 0.50, and 0.67. The data obtained allow the deduction of new water activities and osmotic coefficients. The experimental results are compared with the predictions of the ECA (extended composed additivity) law proposed in our previous work. The Zdanovskii–Stokes–Robinson (ZSR), the Robinson–Stokes (RS), Reilly–Wood–Robinson (RWR), the Pitzer, and the Lietzke–Stoughton (LS II) models are also compared with our results. Predictions made using these models are, in general, consistent with our results. From these measurements, new Pitzer mixing ionic parameters are determined and used to predict the solute activity coefficients in the mixture for different ionic-strength fractions. 相似文献
56.
57.
Atomic hydrogen electrosorption is reported at crystallite sites of polyacrylate-capped Pt nanoparticles (d = 2.5 +/- 0.6 nm), by assembling nanostructured electrodes of polyacrylate-Pt nanocrystallites layer-by-layer in a cationic polyelectrolyte, poly(diallyldimethylammonium chloride). Cyclic voltammetry in 1 M H2SO4 revealed a strongly adsorbed hydrogen state and a weakly adsorbed hydrogen state assigned to adsorption at (100) and (110) sites of the modified nanocrystallites, respectively. Resolving hydrogen adsorption states signifies that surface capping by the carboxylate groups is not irreversibly blocking hydrogen adsorption sites at the modified Pt nanoparticle surface. Adsorption peak currents increased with increasing the number of layers up to 16 bilayers, indicating the feasibility of nanoparticle charging via interparticle charge hopping and the accessibility of adsorption states within the thickness of the nanoparticle/polyelectrolyte multilayers. Despite similarity in hydrogen adsorption in the cyclic voltammorgrams in 1 M H2SO4, negative shifts in adsorption potentials were measured at the nanocrystallite Pt-polyelectrolyte multilayers relative to a polycrystalline bulk Pt surface. This potential shift is attributed to a kinetic limitation in the reductive hydrogen adsorption as a result of the Pt nanoparticle surface modification and the polyelectrolyte environment. 相似文献
58.
Zusammenfassung Zu den schwierigsten Aufgaben der toxikologischen Analyse gehört die rasche und sichere Isolierung und Identifizierung organischer Basen aus dem Untersuchungsmaterial. Mit einem entsprechenden Extraktionsverfahren oder durch Fällung mit Tetraphenylborat in einem systematischen Analysengang können sehr günstige Ausbeuten erzielt werden. Die Reinigung der Rohextrakte oder -fällungen erfolgt prinzipiell mittels Dünnschichtchromatographie. Aus den Tetraphenylboratkomplexen werden dabei auf den Kieselgelschichten die reinen Basen in Freiheit gesetzt. An Hand derR
f- Wert-Tabellen ist eine Identifizierung möglich, wobei Substanzen mit gleichemR
f- Wert durch fraktionierte Extraktion bei verschiedenem pH getrennt werden können. Eine weitere Identifizierung kann mit Hilfe der UV-Spektren erfolgen.
Summary Among the most difficult problems of toxicological analysis are the rapid and reliable isolation and identification of organic bases from the material under examination. Very satisfactory yields can be obtained by means of a suitable extraction procedure or through precipitation with tetraphenyl borate in a systematic scheme of analysis. The purification of the crude extracts or precipitates is accomplished fundamentally by thin layer chromotography. The pure bases are liberated on the silica layers from the tetraphenyl borate complexes. An identification is possible through reference toR f- tables; substances with likeR f value can be separated by fractional extraction at different pH values. A further identification can be made with the aid of UV spectra.
Résumé L'isolement rapide et sûr des bases organiques dans une substance à l'étude et leur identification représentent l'un des problèmes les plus difficiles de l'analyse toxicologique. On peut atteindre des rendements très satisfaisants avec un procédé d'extraction analogue ou par précipitation par le tétraphénylborure dans un processus d'analyse systématique. La purification de l'extrait brut ou des produits de précipitation s'effectue principalement au moyen de la chromatographie en couche mince. Les bases pures sont libérées des complexes au tétraphénylborure en opérant sur couches en gel de silice. On peut faire une identification en se servant des valeurs desR f figurant dans les tables, ce qui permet de séparer les substances de mêmeR f par extraction fractionnée à des pH différents. Une identification plus poussée peut avoir lieu à l'aide des spectres UV.相似文献
59.
Odile Merdrignac-Conanec Khadija El Badraoui Paul L’Haridon 《Journal of solid state chemistry》2005,178(1):218-223
Vanadium pentoxide gels have been obtained from decavanadic acid prepared by ion exchange on a resin from ammonium metavanadate solution. The progressive removal of water by solvent exchange in supercritical conditions led to the formation of high surface area V2O5, 1.6H2O aerogels. Heat treatment under ammonia has been performed on these aerogels in the 450-900 °C temperature range. The oxide precursors and oxynitrides have been characterized by XRD, SEM, TGA, BET. Nitridation leads to divided oxynitride powders in which the fibrous structure of the aerogel is maintained. The use of both very low heating rates and high surface area aerogel precursors allows a higher rate and a lower threshold of nitridation than those reported in previous works. By adjusting the nitridation temperature, it has been possible to prepare oxynitrides with various nitrogen enrichment and vanadium valency states. Whatever the V(O,N) composition, the oxidation of the oxynitrides in air starts between 250 and 300 °C. This determines their potential use as chemical gas sensors at a maximum working temperature of 250 °C. 相似文献
60.
Talukder P Datta A Mitra S Rosair G El Fallah MS Ribas J 《Dalton transactions (Cambridge, England : 2003)》2004,(24):4161-4167
A new tridentate Schiff base ligand HL (L = C14H19N2O), derived from the condensation of benzoylacetone and 2-dimethylaminoethylamine in a 1:1 ratio, reacts with copper(ii) acetate and cyanate, thiocyanate or azide, to give rise to several end-to-end polymeric complexes of formulae [CuL(mu(1,3)-NCO)]n 1, [CuL(mu(1,3)-NCS)]n 2 and the complex 3 has two crystallographically independent units of formula [CuL(N3)] in the asymmetric unit cell. Complex 3 exists in dimeric form rather than as a polymeric chain. Compound 1 is the first report of a singly end-to-end cyanate bridged polymeric chain of Cu(II) with a Schiff base as a co-ligand. There are many examples of double NCS bridged polymeric chains, but fewer singly bridged ones such as compound 2. We have characterized these complexes by analytical, spectroscopic, structural and variable temperature magnetic susceptibility measurements. The coordination geometry around the Cu(II) centers is distorted square pyramidal for 1 and 2 and square planar for complex 3. The magnetic susceptibility data show slight antiferromagnetic coupling for the polymers having J values -0.19 and -0.57 cm(-1) for complexes 1 and 2 respectively. The low values of J are consistent with the equatorial-axial disposition of the bridges in the polymers. 相似文献