全文获取类型
收费全文 | 12549篇 |
免费 | 795篇 |
国内免费 | 247篇 |
专业分类
化学 | 8870篇 |
晶体学 | 128篇 |
力学 | 306篇 |
综合类 | 8篇 |
数学 | 1730篇 |
物理学 | 2549篇 |
出版年
2023年 | 120篇 |
2022年 | 176篇 |
2021年 | 273篇 |
2020年 | 286篇 |
2019年 | 279篇 |
2018年 | 277篇 |
2017年 | 247篇 |
2016年 | 490篇 |
2015年 | 441篇 |
2014年 | 467篇 |
2013年 | 902篇 |
2012年 | 872篇 |
2011年 | 1012篇 |
2010年 | 542篇 |
2009年 | 492篇 |
2008年 | 826篇 |
2007年 | 814篇 |
2006年 | 650篇 |
2005年 | 610篇 |
2004年 | 472篇 |
2003年 | 451篇 |
2002年 | 418篇 |
2001年 | 270篇 |
2000年 | 254篇 |
1999年 | 179篇 |
1998年 | 138篇 |
1997年 | 134篇 |
1996年 | 156篇 |
1995年 | 108篇 |
1994年 | 121篇 |
1993年 | 144篇 |
1992年 | 99篇 |
1991年 | 66篇 |
1990年 | 58篇 |
1989年 | 65篇 |
1988年 | 46篇 |
1987年 | 41篇 |
1986年 | 50篇 |
1985年 | 78篇 |
1984年 | 76篇 |
1983年 | 52篇 |
1982年 | 58篇 |
1981年 | 40篇 |
1980年 | 27篇 |
1979年 | 19篇 |
1978年 | 29篇 |
1977年 | 21篇 |
1976年 | 16篇 |
1975年 | 21篇 |
1974年 | 21篇 |
排序方式: 共有10000条查询结果,搜索用时 390 毫秒
151.
J. J. Berzas Nevado J. Rodríguez Flores M. J. Villaseñor Llerena 《Analytical and bioanalytical chemistry》1997,357(7):989-994
Adsorptive stripping voltammetry was used for the determination of trace amounts of the dye Tartrazine (E-102) by square-wave
(SWS) and differential pulse techniques (DPS). Its adsorptive voltammetric behaviour was investigated at different pH media.
NH4Cl/NH3 buffer solution was chosen as the most suitable, taking into account the sensitivity and definition of the reduction peaks
obtained. The effects of the experimental parameters on the determination are discussed. Standard deviations of 3.3% and 2.6%
were obtained by SWS and DPS for 100 and 50 μg/L Tartrazine solutions, respectively (n = 10). Both methods were applied to
determine the dye in several commercial soft drinks, containing very small amounts of it. Measurements were made directly
in the commercial samples. A comparison of the results obtained by the proposed voltammetric methods with those of an HPLC
method was also made. Good correlations between the voltammetric results and the values supplied by the manufacturer were
found, whereas recoveries of the same order of magnitude were obtained by the HPLC method.
Received: 23 May 1996 / Revised: 5 July 1996 / Accepted: 10 July 1996 相似文献
152.
Summary A method is reported for the determination of dibutyltin (DBT), diphenyltin (DPhT), tributyltin (TBT), and triphenyltin (TPhT)
species at the nanogram per litre concentration level in natural water samples. Analytes were isolated from samples by solid-phase
extraction and analysed both off-line and on-line by reversed-phase high-performance liquid chromatography with post-column
derivatization and fluorimetric detection. Several SPE cartridges and eluents were evaluated; C18 enrichment and elution with a mixture of methanol, acetic acid, and water was found most suitable. Preconcentration factors
up to 250 can be achieved when a 500-mL sample is processed. Detection limits, recovery rates, and the precision of the whole
process have been determined. The method has been applied to the determination of organotin species in spiked natural water
samples collected on the NW Mediterranean coast. Recovery rates range from 75 to 110% and detection limits are at the low
ng L−1 level (1–3 ng Sn L−1 for DPhT, DBT, and PhT and 40 ng Sn L−1 for TBT when 250 mL spiked sea water is processed.) 相似文献
153.
A method for the quantitative preconcentration of lead based on an existing batch process was developed for implementation in a flow system including a flame AAS detector. Lead can be quantitatively preconcentrated as pyrrolidinedithiocarbamate or dithizonate on an activated carbon minicolumn. The chelates are eluted in methyl isobutyl ketone and introduced directly into the nebuliser-burner. An enrichment factor of 50 is typically obtained for a preconcentration time of 2 min (lead can be determined at concentrations between 15 and 400 ng/ml), which results in a throughput of ca. 25 samples per hr. The sensitivity achieved with the two reagents is similar, but the selectivity provided by APDC exceeds that of dithizone. Based on the results obtained in the determination of lead in reference materials (minerals and skim milk), the proposed APDC method is applicable to real samples. 相似文献
154.
155.
María Luisa Moyá Setefilla Escalera Cristina Martín Amalia Rodríguez María Mu?oz María del Mar Graciani 《Reaction Kinetics and Catalysis Letters》2006,89(1):177-182
Summary The reaction methyl 4-nitrobenzenesulfonate + Br- was studied in water-formamide tetradecyltrimethylammonium bromide micellar solutions. A pseudophase kinetic model was used
to quantitatively rationalize the kinetic micellar effects observed 相似文献
156.
Aviñó A Cubero E González C Eritja R Orozco M 《Journal of the American Chemical Society》2003,125(51):16127-16138
The structural, dynamical, and recognition properties of antiparallel DNA triplexes formed by the antiparallel d(G#G.C), d(A#A.T), and d(T#A.T) motifs (the pound sign and dot mean reverse-Hoogsteen and Watson-Crick hydrogen bonds, respectively) are studied by means of "state of the art" molecular dynamics simulations. Once the characteristics of the helix are defined, molecular dynamics and thermodynamic integration calculations are used to determine the expected stabilization of the antiparallel triplex caused by the introduction of 8-aminopurines. Finally, oligonucleotides containing 8-aminopurine derivatives are synthesized and tested experimentally using several approaches in a variety of systems. A very large stabilization of the triplex is found experimentally, as predicted by simulations. These results open the possibility for the use of oligonucleotides carrying 8-aminopurines to bind single-stranded nucleic acids by formation of antiparallel triplexes. 相似文献
157.
The main features of transition structures associated with eight-electron electrocyclic reactions have been studied with Density Functional Theory. It is found that conrotatory electrocyclization reaction of (3Z,5Z)-octa-1,3,5,7-tetraenes takes place via M?bius aromatic transition structures of helical conformation. The reaction is completely periselective. In general, transition structures having outward substituents are preferred with respect to the inward transition structures, irrespective of the pi-donor or pi-acceptor character of the substituent. In contrast with four-electron thermal conrotatory electrocyclic reactions, there is no satisfactory correlation between the difference in energy of activation between inward and outward substituents and the Taft resonance sigma(R) parameter. 相似文献
158.
A stochastic method of optimization, which combines simulated annealing with simplex, is implemented to fit the parameters of a simple model potential. The main characteristic of the method is that it explores the whole space of the parameters of the model potential, and therefore it is very efficient in locating the global minimum of the cost function, in addition to being independent of the initial guess of the parameters. The method is employed to fit the complex intermolecular potential energy surface of the dimer of water, using as a reference the spectroscopic quality anisotropic site-site potential of Feller et al. The simple model potential chosen for its reparameterization is the MCY model potential of Clementi et al. The quality of the fit is assessed by comparing the geometry of the minimum, the harmonic frequencies, and the second virial coefficients of the parameterized potential with the reference one. Finally, to prove more rigorously the robustness of this method, it is compared with standard nonstochastic methods of optimization. 相似文献
159.
González-Núñez ME Mello R Royo J Asensio G Monzó I Tomás F López JG Ortiz FL 《The Journal of organic chemistry》2005,70(9):3450-3457
[reaction: see text] Data on the apparent dipole moment of thianthrene-5-oxide (1) and (1)H NMR spectra in different solvents support the conformational mobility of 1, which flaps between two limit boat conformations with the sulfinyl group in pseudoequatorial and pseudoaxial positions, respectively. The conformational equilibrium of 1 occurs too fast for the (1)H NMR (500 MHz) time-scale even at -130 degrees C, and the equilibrium constant has not been determined. The apparent dipole moments of 1 in n-hexane and 1,4-dioxane and the (1)H NMR spectra of 1 and the model compounds cis- and trans-thianthrene-5,10-dioxides (2) and thianthrene (5) in different solvents and at various temperatures confirm that the relative position of the conformational equilibrium of 1 is solvent-dependent, and more polar solvents favor the conformation with the sulfoxide group in the pseudoaxial position (1(')(ax)). Variable-temperature (1)H NMR spectra have established the interconversion barrier of trans-2 and confirmed that the conformational equilibrium of cis-2 is strongly displaced toward the conformation with both sulfinyl groups in the pseudoequatorial position. The (1)H NMR data support the transannular interaction of the functional groups in 1 and trans-2. 相似文献
160.
J. Rodriguez-Añón J. Prouupin M. González-Añón L. Núñez-Regueira 《Journal of Thermal Analysis and Calorimetry》1998,52(3):1005-1012
The heating values of municipal solid waste generated in three towns with a population of less than 50 000, situated in Galicia
(Spain), were measured with a static bomb calorimeter. Samples of raw refuse were burnt either as received or after sorting
of the different combustible components. A study was made of samples from controlled and uncontrolled landfills.
The calorific values were compared with those corresponding to a commercial residual derived fuel in order to study the possibility
of using municipal solid waste as a source of recovered energy.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献