全文获取类型
收费全文 | 78337篇 |
免费 | 332篇 |
国内免费 | 375篇 |
专业分类
化学 | 24452篇 |
晶体学 | 792篇 |
力学 | 6727篇 |
数学 | 31979篇 |
物理学 | 15094篇 |
出版年
2018年 | 10434篇 |
2017年 | 10264篇 |
2016年 | 6059篇 |
2015年 | 843篇 |
2014年 | 295篇 |
2013年 | 320篇 |
2012年 | 3796篇 |
2011年 | 10521篇 |
2010年 | 5634篇 |
2009年 | 6059篇 |
2008年 | 6607篇 |
2007年 | 8774篇 |
2006年 | 261篇 |
2005年 | 1329篇 |
2004年 | 1567篇 |
2003年 | 1997篇 |
2002年 | 1029篇 |
2001年 | 248篇 |
2000年 | 290篇 |
1999年 | 154篇 |
1998年 | 194篇 |
1997年 | 147篇 |
1996年 | 202篇 |
1995年 | 115篇 |
1994年 | 78篇 |
1993年 | 93篇 |
1992年 | 53篇 |
1991年 | 65篇 |
1990年 | 50篇 |
1989年 | 59篇 |
1988年 | 60篇 |
1987年 | 62篇 |
1986年 | 60篇 |
1985年 | 57篇 |
1984年 | 50篇 |
1983年 | 36篇 |
1982年 | 52篇 |
1981年 | 45篇 |
1980年 | 52篇 |
1979年 | 49篇 |
1978年 | 36篇 |
1977年 | 25篇 |
1973年 | 25篇 |
1914年 | 45篇 |
1913年 | 40篇 |
1912年 | 40篇 |
1909年 | 41篇 |
1908年 | 40篇 |
1907年 | 32篇 |
1904年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Mixed micelles formed by zwitterionic surfactant dimethyldodecylammniopropane sulfonate and short-chain phospholipid 1,2-diheptanoyl-sn-glycero-3-phosphocholine in different proportions in an aqueous medium have been studied physicochemically at an air/water interface and in the bulk by using interfacial tension and pyrene fluorescence intensity measurements, respectively. The critical micellar concentration and free energies of micellization and of interfacial adsorption have been determined. The interfacial study reveals that a mixed monolayer is formed at the air/water interface by the adsorption of surfactant and phospholipid monomers. This has been confirmed by evaluating the interfacial parameters; the maximum surface excess, the minimum area per molecule of a surface-active compound, and the Gibbs surface excess related to surface pressure. The nonideality of mixing, expressed in the terms of the regular solution interaction parameter, #, has negative values over the whole mole fraction range. The negative # values indicate the mutual synergism between the surfactant and phospholipid monomers. The equilibrium distribution of components between micelle and monomer phases was evaluated using a theoretical treatment based on excess thermodynamics quantities evaluated by Motomura's formulation. 相似文献
992.
Shin-ichi NayaMakoto Nitta 《Tetrahedron》2003,59(23):4157-4165
The synthesis and properties of a novel type of bis(heteroazulen-3-yl)methyl cations, bis(2-oxo-2H-cyclohepta[b]furan-3-yl)methyl cation salt and nitrogen analogues, (9a-c·PF6−) and (9a-c·BF4−), as well as bis(heteroazulen-3-yl)ketones (12a-d) are studied. The synthetic method was based on a TFA-catalyzed electrophilic aromatic substitution on the heteroazulenes (6a-d) with paraformaldehyde to afford the corresponding disubstituted methane derivatives 7a-d, followed by oxidative hydrogen abstraction with DDQ, and subsequent exchange of the counter-anion by using aq. HPF6 or aq. HBF4. In addition, the reaction of 7a-d with 2.2 equiv. amounts of DDQ afforded carbonyl compounds 12a-d. The delocalization of the positive charge of 9a-c was evaluated by the 1H and 13C NMR spectral data. The thermodynamic stability of cations 9a-c was evaluated to be in the order 9a<9b<9c on the basis of their reduction potentials measured by cyclic voltammetry (CV) and pKR+ values (2.6-10.3) obtained spectrophotometrically. The reduction waves of cations 9a-c were irreversible, suggesting the dimerization of the radical species generated by one-electron reduction. This was demonstrated by the reduction of 9a·BF4− with Zn powder to give dimerized product 14a. In addition, the quenching of 9a·BF4− with MeOH/NaHCO3 gives ether derivative 15a, which is proposed for the precursor for synthesizing tris(heteroazulene)-substituted methyl cations bearing two different heteroazulene-units. 相似文献
993.
With P(CH3)3 as the probe molecule adsorbed on titanium silicalite (TS-1) zeolite, the special and important role of T12 site in MFI-type zeolite was clearly elucidated. There are altogether three active sites present in TS-1 zeolite with Ti at the T12 site. Owing to the preferential adsorption of probe molecules on the first Brönsted acidic site, the Ti12 center will probably fail to show Lewis acidity. The ionic [HP(CH3)3]+ species can be stabilized by the first or second Brönsted acidic site, with the former energetically favored. The latter was formed through the transfer of the ionic [HP(CH3)3]+ species from the first to the second Brönsted acidic site. 相似文献
994.
Young Hyun Cho Wanno Lee Kun Ho Chung Geun Sik Choi Chang Woo Lee 《Journal of Radioanalytical and Nuclear Chemistry》2007,274(3):531-538
The seasonal variation of the 7Be activities in air and the size distribution of the 7Be aerosols were studied by using a continuous air sampler and a five stage cascade impactor. The mean monthly activity level
of 7Be at the Korea Atomic Energy Research Institute (KAERI) site varied from 0.5 to 4.8 Bq·m−3 and revealed a seasonal variation, in which the 7Be activity levels were high in winter and low in summer. The mass size distribution showed a bi-modal distribution with a
higher peak around 0.49 μm and a smaller peak between 3 μm and 7.2 μm. The activity median aerodynamic diameter (AMAD) decreased
with increasing ambient 7Be concentrations. The mean residence times by using a mean growth rate of 0.004 μm·h−1 were estimated to be 2.5–6.4 days. The AMAD has an increasing tendency with higher relative humidity. It seemed that the
high humidity condition facilitated the growth of the aerosol, resulting in increased deposition rates of the aerosols and
the low 7Be content in the surface air. The AMAD of the 7Be aerosols increased with an increasing temperature, but the temperature dependency of AMAD should be explained with geological
and meteorological conditions. 相似文献
995.
996.
Different from C60 dianion which readily reacts with electrophiles, supramolecular C60 dianion (2) generated from gamma-cyclodextrin-bicapped C60 (1) and NaBH4 (or diborate) in DMSO-H2O (9:1, v/v) is able to reduce N-N+, C=C-EWG and C=O bonds to provide the respective dihydro derivatives; 1-mediated reduction of acetophenone with NaBH4 in the presence of (Me2N)2CH2 and EtONa gives turn over frequency (TOF)/h of 400. 相似文献
997.
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
998.
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
999.
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
1000.
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