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141.
By means of differential pulse polarography, Pu ions of different oxidation states have been investigated in 1M Na2CO3 solution. Redox reactions of Pu/III/, Pu/IV/, Pu/V/ and Pu/VI/, which are mostly of irreversible nature, have been observed within the potential range of the dropping mercury electrode /DME/, from 0 to –1.5 V, against a Ag/AgCl/NaCl (3M) reference electrode. Based on the peak potential observed for each reaction, the stability of a given oxidation state in the solution could be ascertained. The redox potential of the Pu/IV/–Pu/III/ pair, which was found to be –1.0 V, indicated that the Pu/IV/ carbonate complex was of high stability. The detection sensitivity of the Pu/IV/ ion was found to be 1×10–6M. 相似文献
142.
Cross-validation of a solid-state NMR-derived membrane polypeptide structure is demonstrated. An initial structure has been achieved directly from solid-state NMR derived orientational restraints based on a variety of anisotropic nuclear spin interactions. Refining the molecular structure involves setting up a penalty function that incorporates all available solid-state NMR experimental data and an energy function. A validation method is required to choose the optimal weighting factor for the total penalty function to balance the contribution from the experimental restraints and the energy function. Complete cross-validation has been used to avoid over-fitting the orientational restraints. Such cross-validation involves partitioning of the experimental data into a test set and a working set followed by checking the free R-value during the refinement process. This approach is similar to the method used in crystallography and solution NMR. Optimizing the weighting factor on the penalty function by cross-validation will increase the quality of the refined structure from solid-state NMR data. The complete cross-validation and R-factor calculation is demonstrated using experimental solid-state NMR data from gramicidin A, a monovalent cation channel in lipid bilayers. 相似文献
143.
A neutron activation analysis for the determination of zinc in bismuth was developed. After irradiating the samples for 44 days at 4·1011n/cm2/sec, zinc was separated quantitatively by hexone extraction and precipitation as quinaldate. The sensitivity of the method was estimated as 0.05 p.p.m. No zinc could be detected in the high purity bismuth samples. An addition method of analysis showed that the precision was 1.2%. 相似文献
144.
E. S. Klimov F. Kim V. Kh. Sabanov T. I. Chulkova O. Yu. Okhlobystin 《Theoretical and Experimental Chemistry》1992,28(1):58-60
1,8-Naphthylenediamine was reacted with 2,6-di-tert-butyl-4-formyl-phenol to produce 2,6-di-tert-butyl-4-(1,3-dihydro-perimidyl) phenol (I). The latter was coverted into 2,6-di-tert-butyl-4-(1H-perimidyl)phenol (II) by oxidizing I with sodium pyrosulfate. When phenol II was oxidized by lead dioxide in toluene and THF, the EPR spectra revealed a 12-component multiplet with perimidyl splitting constants a1
N=a3
N=aH
NH=0.2 mT; aH
6.7=0.6 mT.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 1, pp. 64–67, January, 1992. 相似文献
145.
Asymmetric silyl nitronate cycloadditions with N-acryloyl (2R)-bornane-10,2-sultam, N-acryloyl (2S)-bornane-10,2-sultam, and N-methacryloyl (2R)-bornane-10,2-sultam have been studied. The asymmetric silyl nitronate cycloaddidon/elimination methodology provides a general route for the asymmetric synthesis of 2-isoxazolines. 相似文献
146.
Dong Han Kim 《Journal of heterocyclic chemistry》1976,13(6):1187-1192
1,2,3,4,8,9,10,11-Octahydro[1,4]diazepino[6,5,4-jk]earbazole (VIa) was synthesized from 2,3,4,5-tetrahydro-1H-benzodiazepine (la) via the route shown in Scheme 1. Other compounds which were prepared similarly are 3-acetyl-6-chloro-1,2,3,4,8,9,10,11-octahydro[1,4]diazepino-[6,5,4-jk]carbazole(Vb) and 3-methyl-1,2,3,4,8,9,10,11-octahydro[1,4]diazepino[6,5,4-jk]carb-azole (VIII). Chemical transformations which were carried out with VI and 3-acetyl-1,2,3,4,8,9, 10,11-octahydro[1,4]diazepino[6,5,4-jk]carbazole (Va) are also described. 相似文献
147.
Plasma chromatography detects and identifies compounds in trace quantities at atmospheric pressure through characteristic positive and negative mobility spectra. To facilitate use of the technique to detect gas chromatographic effluents, a number of reference mobility spectra for different classes of compounds have been reported. Reference spectra for two more compounds, heroin and cocaine, are presented in this study. The primary ions found in these mobility spectra were determined to be M+, (M - H2)+, and (M - CH3CO2)+ for heroin and M+, (M - C6H5CO2)+ and (M - C6H5CO2 - CO2CH3)+ for cocaine using a directly interfaced plasma chromatograph-mass spectrometer. The identified ions agree closely with those predicted in the ion mobility spectra using mass-mobility correlation data coupled with chemical ionization mass spectrometry data. Also, an independent check demonstrating the reliability of reduced mobility values reported in earlier reference spectra was made. 相似文献
148.
Highly dispersed molybdena-titania catalyst can be prepared by an equilibrium adsorption method. In this method, molybdate
anions adsorb onto the positively charged titania surfaces via electrostatic attraction by controlling the pH of the impregnating
solution and they increase as an inverse function of the pH. 95Mo-NMR and UV spectroscopic studies of impregnating solution show that the polymeric species like Mo7O24
6-ions are adsorbed on titania in the acidic impregnating solution. XRD, Raman, and XPS data of the calcined samples show that
mono-layer coverage of molybdenum oxide over-layer possesses a highly distorted MoO6 group with a molecular geometry resembling the distorted square pyramid.
The catalytic oxidation of methanol over the surface molybdate species on titania possesses higher turnover numbers and higher
selectivities of partial oxidation products than the catalysts supported on alumina, silica, zirconia, or magnesia. Changes
of the surface properties either after reduction and sulfiding treatment over monolayer catalyst on titania have also been
investigated. The NO chemisorption and XPS studies show that two types of active sites appeared after reduction treatment:
one site is active for hydrogenation of 1,3-butadiene and the other site is active for metathesis of propene. A higher degree
coordinative unsaturations of MO is required for hydrogenation than metathesis. After sulfiding treatments of the catalyst,
hydrogenation of 1,3-butadiene also requires triply coordinative unsaturation, and hydrogenolysis of thiophene requires the
ensemble of doubly or triply coordinative unsaturations. 相似文献
149.
Kang K Bae SJ Kim WM Lee DH Cho U Lee MH Lee MS Nam S Kuettner KE Schwartz DE 《Experimental & molecular medicine》2000,32(3):146-154
Nonsteroidal antiinflammatory drugs(NSAIDs) are known as clinically effective agents for treatment of inflammatory diseases. Inhibition of cyclooxygenase has been thought to be a major facet of the pharmacological mechanism of NSAIDs. However, it is difficult to ascribe the antiinflammatory effects of NSAIDs solely to the inhibition of prostaglandin synthesis. Human neutrophil elastase (HNElastase; HNE, EC 3.4.21.37) has been known as a causative factor in inflammatory diseases. To investigate the specific relationship between HNElastase inhibition and specificity of molecular structure of several NSAIDs, HNElastase was purified by Ultrogel AcA54 gel filtration, CM-Sephadex ion exchange, and HPLC (with TSK 250 column) chromatography. HNElastase was inhibited by aspirin and salicylate in a competitive manner and by naproxen, ketoprofen, phenylbutazone, and oxyphenbutazone in a partial competative manner, but not by ibuprofen and tolmetin. HNElastase-phenylbutazone-complex showed strong Raman shifts at 200, 440, 1124, 1194, 1384, 1506, and 1768 cm(-1). The Raman bands 1194, 1384, and 1768 cm(-1) may represent evidences of the conformational change at -N=N-phi radical, pyrazol ring, and -C=O radical of the elastase-drug complex, respectively. Phenylbutazone might be bound to HNElastase by ionic and hydrophobic interaction, and masked the active site. Inhibition of HNElastase could be another mechanism of action of NSAIDs besides cyclooxygenase inhibition in the treatment of inflammatory diseases. Different inhibition characteristics of HNE-lastase by NSAIDs such as aspirin, phenylbutazone-like drugs and ineffective drugs could be important points for drawing the criteria for appropriate drugs in clinical application. 相似文献
150.
Woo-Jin Lee Su-Il Pyun Tae-Hyun Yang Joong-Do Kim Young-Ho Baek Han-Gyu Kim 《Journal of Solid State Electrochemistry》1997,1(2):120-125
Hydrogen transport through a Pd-Ni alloy electrodeposited on a Pd substrate (Pd-Ni/Pd bilayer symmetric electrode) has been
investigated using cyclic voltammetry and a.c. impedance spectroscopy combined with the electrochemical hydrogen permeation
method. The permeation build-up current transients and the measured impedance spectra were analyzed using the time-lag method
for the bilayer electrode and a complex non-linear least squares data-fitting method based upon the derived Faradaic admittance
for the hydrogen absorption into and diffusion through the bilayer electrode under the permeable boundary condition, respectively.
The value of the hydrogen diffusivity in the Pd-Ni layer was lower than that in the Pd layer. Furthermore, the values of the
charge transfer resistance and equilibrium absorption constant for the Pd-Ni/Pd bilayer electrode were higher than those for
the Pd single layer electrode. From the experimental results, the role of the thin Ni(OH)2 film formed on the Pd-Ni layer surface in the hydrogen transport through the Pd-Ni/Pd bilayer electrode is discussed in terms
of its passivating effect and extremely large hydrogen solubility.
Received: 22 January 1997 / Accepted: 15 April 1997 相似文献