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991.
Ya-Guang Chen Fan-Xia Meng Hai-Jun Pang Dong-Mei Shi Yu Sun 《Journal of Cluster Science》2007,18(2):396-405
A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na5[(A-α-SiW9O33H3)2K{UO2(H2O)}2], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal
X-ray diffraction. In the anion, two A-α-SiW9O3410− groups share two terminal oxygen atoms Od′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open
mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating
anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement.
Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and
U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the
U–O bonds of the uranyl cation.
Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
992.
Yan Xiao Jian Wang Wang Xia Guang Feng Huai You Wang 《Journal of Analytical Chemistry》2007,62(5):438-443
The maximum emission wavelength of dopamine is 317 nm with excitation at 290 nm. The relative fluorescence intensity of dopamine
decreased in the presence of enoxacin, which showed that fluorescence quenching occurred. The Stern-Volmer (S-V) plot showed
a nonlinear relationship between the relative fluorescence intensity of dopamine and the concentration of enoxain. The quenching
mechanism was studied and the results suggested that both dynamic and static quenching processes were responsible for the
observed positive deviation in the S-V plot. When the S-V plot was modified by logarithm, the linear relationship was obtained
between logF
0/F and C in the range of 0.10 to 13.0 μg/mL (where F
0 is the relative fluorescence intensity of dopamine, F is the relative fluorescence intensity of dopamine in the presence of enoxacin, and C is the concentration of enoxacin). The fluorescence quenching method for the determination of enoxacin was developed. The
linear regression equation of the calibration graph of enoxacin was C = 13.70 (logF
0/F) − 0.5836, with the correlation coefficient 0.9984. The detection limit was 2.0 ng/mL and the relative standard deviation
was 2.52%. The effects of pH, the stability of dopamine in the presence of enoxacin, and foreign ions on the determination
of enoxacin have been examined. The recovery of enoxacin was from 94.9 to 103.0% in a human serum sample and from 94.9 to
108.0% in a urine sample. The method is simple, rapid, and can be used for the determination of enoxacin in human serum and
urine samples with satisfactory results.
The text was submitted by the authors in English. 相似文献
993.
Rosa Maria Rojas K. Petrov G. Avdeev J. M. Amarilla L. Pascual J. M. Rojo 《Journal of Thermal Analysis and Calorimetry》2007,90(1):67-72
Chromium doped spinels LiCrYMn2−YO4 (0.2≤Y≤0.8) has been synthesized by the sucrose-aided combustion procedure. The thermal behaviour, phase homogeneity and structural
characteristics of the samples were studied by thermal analysis, coupled mass spectrometry, and room-and high-temperature
X-ray diffraction methods. It was found that the ‘as prepared’ samples contained residual organic impurities undetectable
for X-ray diffraction, that burn out completely at 400°C. Samples treated between 400 and 750°C are single phase spinels,
whose crystallites size increase from 10 to 50 nm on increasing the temperature. Cr-doping enhances the thermal stability
of the spinels, which augments on increasing the Cr content Y. The enhanced thermal stability of the spinels has been accounted
for based on the high excess stabilization energy of Cr3+ in octahedral ligand field. 相似文献
994.
The factors influencing the electrochemical behaviour of a supercapacitor have been partly examined in this work. The effects
of so-called intrinsic parameters, i.e. exchange current density, unit cell length and double layer (DL) capacitance; as well
as the so-called application parameters, i.e. cell current, on the cell potential discharge time have been considered. The
contributions of each type of capacitors, DL capacitor and faradaic supercapacitor under various states of operation and material
have been analyzed, and the competing (compensating) effects of the two types of capacitors as regards to the discharge and
power characteristics manifested by current–potential and energy–power (Ragone plots) are elucidated. 相似文献
995.
Capillary electrophoresis with wavelength-resolved laser-induced fluorescence detection 总被引:5,自引:0,他引:5
Capillary electrophoresis (CE) enables rapid separations with high separation efficiency and compatibility with small sample volumes. Laser-induced fluorescence detection can result in extremely low limits of detection in CE. Single-channel fluorescence detection, however, furnishes little qualitative information about a species being detected, except for its CE migration time. Use of multidimensional information often enables unambiguous identification of analytes. Combination of CE with information-rich wavelength-resolved fluorescence detection is analogous with ultraviolet-visible diode-array detection and furnishes both qualitative and quantitative chemical information about target species. This review discusses recent advances in wavelength-resolved laser-induced fluorescence detection coupled with CE, with an emphasis on instrument design. 相似文献
996.
Henk C. van der Plas 《Chemistry of Heterocyclic Compounds》1994,30(11-12):1427-1443
In this review attention is paid to two topics, which were of great interest to us during 30 years of studies in pyrimidine chemistry in our laboratory: first, the development of our concepts of the AIYRORC processes, which occur in ring transformation reactions; second, the intra- and intermolecular inverse Diels-Alder reactions in which the pyrimidine ring acts as the electron poor diazadiene system. Their use in synthetic chemistry is illustrated and evidence is presented, based on experiments and molecular mechanics calculations, that in intermolecular Diels-Alder reactions the geometry of the side-chain plays a vital role. 相似文献
997.
A type of high visible-light active titanium oxinitride(TiO2-xNx) powder was prepared by a simple proc-ess:the calcination of the hydrated titanium dioxide at the atmosphere of ammonia-argon using a tu-bular electric furnace at high temperatures. The hydrated titanium dioxide was synthesized as the precursor of TiO2-xNx using titanic acid as raw material,which came from sulfate technique of produc-ing titanium white. The effects of temperature and reaction time on the nitrogen content,grain size and crystal structure were studied. The visible-light activity and photocatalysis capability of the powder were also investigated. 相似文献
998.
Samuel González-Mancebo Javier Lacadena Yolanda García-Alonso Jesús Hernández-Benito Emilio Calle Julio Casado 《Monatshefte für Chemie / Chemical Monthly》2002,133(2):157-166
Summary. Nitrosation reactions of phenol, o-cresol, 2,6-dimethylphenol, o-tert-butylphenol, 2-hydroxyacetophenone, and 2-allylphenol in water and water/acetonitrile were studied. Kinetic monitoring of
the reactions was accomplished by spectrophotometric analysis of the nitrosated products at 345 nm. The dominant reaction
was C-nitrosation via a mechanism consisting of an attack on the nitrosatable substrate by NO+/NO2H2
+ followed by a slow proton transfer. The values of the rate constants of phenolic C-nitrosation were increased by electron
donating substituents, and a good Hammett correlation was observed with ρ = −6.1. The results also revealed the strong effect of pH and the permitivity of the reaction medium on the rate constant, whose maximum values were observed for pH ≈ 3, decreasing strongly for higher pH values. The study in water/acetonitrile with up to 25% acetonitrile showed that it is possible to inhibit the reaction strongly
by increasing the percentage of the organic component. The conclusions drawn show that (i) it is possible to predict the rate of nitrosation of phenolics as a function of the meta-substituents on the phenol ring and (ii) the nitrosation of phenolics can be strongly inhibited by increasing the pH of the reaction medium as well as by lowering its dielectric constant.
Received July 13, 2001. Accepted (revised) September 18, 2001 相似文献
999.
(1R,2R)-1,2-bis-(5-amino-1,3,4-thiadiazole-2-yl)ethane-1,2-diol (L) has been prepared by the reaction of thiosemicarbazide with (2R,3R)-(+)-tartaric
acid (I) and phosphorous oxychloride, and its complexes with Co(II), Ni(II) and Cu(II) have been obtained. The structures
of the ligand and its complexes have been established by i. r., 1H- and 13C-n.m.r. spectra, u.v.–vis–nir spectroscopy, elemental analyses, T.g.-D.t.a. and magnetic susceptibility measurements. 相似文献
1000.
Previous work on the electrochemistry of palladium in aqueous acid solution demonstrated the existence of two multilayer
hydrous oxide reduction peaks, one at ca. 0.24 V and another at ca. 0.55 V vs. RHE, plus the presence of a reversible active
surface state transition at ca. 0.24 V. In the present work with thermally activated palladium it was observed that, in agreement
with the hydrous oxide reduction behaviour of the system, there is a second active state transition at E≥ca. 0.45 V. In most of its reactions in aqueous acid solution, apart from its unusual capacity to absorb hydrogen, palladium
exhibits properties very similar to those of platinum; however, palladium seems to be more prone to dissolution and subsurface
oxygen formation. Also the premonolayer oxidation responses of these two metals are often different as the more active state
of the palladium surface is not as readily generated as that of platinum. The electrocatalytic properties of palladium, as
reported earlier, correlate quite well with the hydrous oxide and premonolayer oxidation behaviour of this electrode system.
Electronic Publication 相似文献