全文获取类型
收费全文 | 56531篇 |
免费 | 7721篇 |
国内免费 | 6423篇 |
专业分类
化学 | 26444篇 |
晶体学 | 1142篇 |
力学 | 10043篇 |
综合类 | 640篇 |
数学 | 14861篇 |
物理学 | 17545篇 |
出版年
2024年 | 159篇 |
2023年 | 679篇 |
2022年 | 1750篇 |
2021年 | 1717篇 |
2020年 | 2031篇 |
2019年 | 1674篇 |
2018年 | 1574篇 |
2017年 | 2018篇 |
2016年 | 2423篇 |
2015年 | 1996篇 |
2014年 | 2881篇 |
2013年 | 4336篇 |
2012年 | 3478篇 |
2011年 | 3699篇 |
2010年 | 3176篇 |
2009年 | 3528篇 |
2008年 | 3470篇 |
2007年 | 3520篇 |
2006年 | 3247篇 |
2005年 | 3012篇 |
2004年 | 2649篇 |
2003年 | 2415篇 |
2002年 | 2032篇 |
2001年 | 1714篇 |
2000年 | 1637篇 |
1999年 | 1472篇 |
1998年 | 1360篇 |
1997年 | 1112篇 |
1996年 | 918篇 |
1995年 | 810篇 |
1994年 | 733篇 |
1993年 | 556篇 |
1992年 | 574篇 |
1991年 | 419篇 |
1990年 | 325篇 |
1989年 | 274篇 |
1988年 | 218篇 |
1987年 | 165篇 |
1986年 | 123篇 |
1985年 | 154篇 |
1984年 | 135篇 |
1983年 | 64篇 |
1982年 | 84篇 |
1981年 | 73篇 |
1980年 | 50篇 |
1979年 | 62篇 |
1978年 | 42篇 |
1977年 | 47篇 |
1976年 | 21篇 |
1975年 | 13篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
941.
An air-segmented continuous-flow method has been developed for the determination of molybdenum at ultra trace levels using
the catalytic effect of molybdate during the oxidation of L-ascorbic acid by hydrogen peroxide. Incorporation of an on-line
ion exchange column improved the tolerance limit for various ions. The detection limits with and without the column were 64 pmol L−1 and 17 pmol L−1, and the reproducibilities at 10 nmol L−1 were 2.1% and 0.2%, respectively. The proposed method was applied to the determination of molybdenum in seawater and lake
water as well as in rock and sediment samples. This method has the highest sensitivity among the available literature to our
knowledge, and is also convenient for routine analysis of molybdenum in various natural samples.
Author for correspondence. E-mail: masahito.sugiyama@ sojin0206.mbox.media.kyoto-u.ac.jp
Received October 23, 2002; accepted January 28, 2003
Published online May 19, 2003 相似文献
942.
用等压法研究了273.15 K下Li2B4O7-LiCl-H2O体系不同质量摩尔浓度分数的等压平衡浓度和水活度; 计算了LiCl和Li2B4O7混合盐溶液的渗透系数等热力学性质. 用273.15 K下的实验数据对Pitzer离子相互作用模型进行了参数化研究, 拟合求取了273.15 K下Pitzer离子相互作用参数, 用获得的参数计算了LiCl和Li2B4O7在Li2B4O7-LiCl-H2O体系中的活度系数. 273.15 K下由相应的Pitzer模型计算的渗透系数值与实验结果一致. 这对完善含锂、硼盐湖卤水体系的热力学模型具有重要意义. 相似文献
943.
Liu JM Hu SR He XM Li XL Zhan FP Zeng LQ Li LD Zhu GH Huang XM 《Analytical and bioanalytical chemistry》2005,382(7):1507-1512
Silicon dioxide nano-particles, diameter 50 nm, containing morin (morin–SiO2) have been synthesized by the sol–gel method. They emit strong and stable room-temperature phosphorescence (SS-RTP) on filter paper as substrate, and bismuth can quench the intensity of the SS-RTP. On this basis a new morin–SiO2 solid-substrate room-temperature phosphorescence-quenching method has been established for determination of traces of bismuth. Reduction of phosphorescence intensity (Ip) is directly proportional to the concentration of bismuth in the working range 0.16–14.4 ag spot–1 (sample volume 0.40 L spot–1, corresponding to the concentration range 0.40–36.0 fg mL–1). The regression equation of the working curve is Ip=14.86+5.279×[Bi3+] (ag spot–1) (n=6, r=0.9982). The detection limit of this method is 0.026 ag spot–1 (corresponding to a concentration of 6.5×10–17 g mL–1).This sensitive, reproducible and accurate method has been used for successful analysis of real samples. 相似文献
944.
Pilar Campíns-Falcó Adela Sevillano-Cabeza Luisa Gallo-Martínez Francisco Bosch-Reig Isidro Monzó-Mansanet 《Mikrochimica acta》1997,126(3-4):207-215
This paper discusses the spectrophotometric determination of cephalexin as the intact cephalexin or as its acid-induced degradation product. Cephalexin can be determined in the range 1 × 10–5–18 × 10–5
M with relative standard deviations of 5-1%. The limits of quantitation and detection were 10–5 and 0.3 × 10–5
M, respectively. These procedures were compared with reversed-phase HPLC determination. No interference was observed in the presence of common pharmaceutical adjuvants. The H-point standard additions method was applied in order to correct for the possible presence of the cephalexin precursor, 7-aminocephalosporanic acid; this improves the selectivity of the UV-vis spectrophotometric method. 相似文献
945.
To understand the cation-pi interaction in aromatic amino acids and peptides, the binding of M(+) (where M(+) = Li(+), Na(+), and K(+)) to phenylalanine (Phe) is studied at the best level of density functional theory reported so far. The different modes of M(+) binding show the same order of binding affinity (Li(+)>Na(+)>K(+)), in the approximate ratio of 2.2:1.5:1.0. The most stable binding mode is one in which the M(+) is stabilized by a tridentate interaction between the cation and the carbonyl oxygen (O[double bond]C), amino nitrogen (--NH(2)), and aromatic pi ring; the absolute Li(+), Na(+), and K(+) affinities are estimated theoretically to be 275, 201, and 141 kJ mol(-1), respectively. Factors affecting the relative stabilities of various M(+)-Phe binding modes and conformers have been identified, with ion-dipole interaction playing an important role. We found that the trend of pi and non-pi cation bonding distances (Na(+)-pi>Na(+)-N>Na(+)-O and K(+)-pi>K(+)-N>K(+)-O) in our theoretical Na(+)/K(+)-Phe structures are in agreement with the reported X-ray crystal structures of model synthetic receptors (sodium and potassium bound lariat ether complexes), even though the average alkali metal cation-pi distance found in the crystal structures is longer. This difference between the solid and the gas-phase structures can be reconciled by taking the higher coordination number of the cations in the lariat ether complexes into account. 相似文献
946.
A new parameter set (referred to as 45A4) is developed for the explicit-solvent simulation of hexopyranose-based carbohydrates. This set is compatible with the most recent version of the GROMOS force field for proteins, nucleic acids, and lipids, and the SPC water model. The parametrization procedure relies on: (1) reassigning the atomic partial charges based on a fit to the quantum-mechanical electrostatic potential around a trisaccharide; (2) refining the torsional potential parameters associated with the rotations of the hydroxymethyl, hydroxyl, and anomeric alkoxy groups by fitting to corresponding quantum-mechanical profiles for hexopyranosides; (3) adapting the torsional potential parameters determining the ring conformation so as to stabilize the (experimentally predominant) (4)C(1) chair conformation. The other (van der Waals and nontorsional covalent) parameters and the rules for third and excluded neighbors are taken directly from the most recent version of the GROMOS force field (except for one additional exclusion). The new set is general enough to define parameters for any (unbranched) hexopyranose-based mono-, di-, oligo- or polysaccharide. In the present article, this force field is validated for a limited set of monosaccharides (alpha- and beta-D-glucose, alpha- and beta-D-galactose) and disaccharides (trehalose, maltose, and cellobiose) in solution, by comparing the results of simulations to available experimental data. More extensive validation will be the scope of a forthcoming article. (c) 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1400-1412, 2005. 相似文献
947.
Magdalena Kurdziel Elżbieta Szczepaniec-Cieciak Monika Watorczyk Barbara Dabrowska 《Journal of solution chemistry》2004,33(5):453-464
The solubility of solid 2-methyl-1,3-butadiene (isoprene) in liquid argon at a temperature of 87.3 K and in liquid nitrogen at 77.4 K has been measured by the filtration method. The hydrocarbon contents in solutions were determined using gas chromatography. GC–MS was used to identify impurities in the solute. The experimental value of the mole fraction solubility of solid isoprene in liquid argon at 87.3 K is (1.41 ± 0.27) × 10–6 and (1.56 ± 0.36) × 10–7 in liquid nitrogen at 77.4 K. The Preston–Prausnitz method was used for calculation of the solubilities of solid hydrocarbon in liquid argon in the temperature range 84.0–110.0 K and in liquid nitrogen from 64.0 to 90.0 K. The solvent–solute interaction parameters l
12 were also calculated. At 90.0 K liquid argon is a better solvent for isoprene than is liquid nitrogen. The experimental values of the solubilities of isoprene in liquid argon and nitrogen were compared with results obtained for selected unsaturated and aromatic hydrocarbons. 相似文献
948.
Equilibrium molecular dynamics (MD) simulations have been performed in both the NVT and NPT ensembles to study the structural and dynamical properties of fully occupied methane clathrate hydrates at 50, 125, and 200 K. Five atomistic potential models were used for water, ranging from fully flexible to rigid polarizable and nonpolarizable. A flexible and a rigid model were utilized for methane. The phonon densities of states were evaluated and the localized rattling modes for the methane molecules were found to couple to the acoustic phonons of the host lattice. The calculated methane density of states was found to be in reasonable agreement with available experimental data. 相似文献
949.
The anomeric effect has been studied for a variety of compounds using the MM4 force field, and also using MP2/6-311++G(2d,2p) ab initio calculations and experimental data for reference purposes. Geometries and energies, including conformational, rotational barriers, and heats of formation were examined. Overall, the agreement of MM4 with the experimental and ab initio data is good, and significantly better than the agreement obtained with the MM3 force field. The anomeric effect is represented in MM4 by various explicit terms in the force constant matrix. The bond length changes are accounted for with torsion-stretch elements. The angle changes are accounted for with torsion-bend elements. The energies are taken into account with a number of torsional terms in the usual way. A torsion-torsion interaction is also of some importance. With all of these elements included in the calculation, the MM4 results now appear to be adequately accurate. The heats of formation were examined for a total of 12 anomeric compounds, and the experimental values were fit by MM4 with an RMS error of 0.42 kcal/mol. 相似文献
950.
T. A. Isaev N. S. Mosyagin A. V. Titov A. B. Alekseyev R. J. Buenker 《International journal of quantum chemistry》2002,88(5):687-690
The correlation calculation of the electronic structure of PbH is carried out with the generalized relativistic effective core potential (GRECP) and multireference single‐ and double‐excitation configuration interaction (MRD‐CI) methods. The 22‐electron GRECP for Pb is used and the outer core 5s, 5p, and 5d pseudospinors are frozen using the level‐shift technique, so only five external electrons of PbH are correlated. A new configuration selection scheme with respect to the relativistic multireference states is employed in the framework of the MRD‐CI method. The [6, 4, 3, 2] correlation spin–orbit basis set is optimized in the coupled cluster calculations on the Pb atom using a recently proposed procedure, in which functions in the spin–orbital basis set are generated from calculations of different ionic states of the Pb atom and those functions are considered optimal that provide the stationary point for some energy functional. Spectroscopic constants for the two lowest‐lying electronic states of PbH (2Π1/2, 2Π3/2) are found to be in good agreement with the experimental data. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献