全文获取类型
收费全文 | 27250篇 |
免费 | 2785篇 |
国内免费 | 2676篇 |
专业分类
化学 | 21009篇 |
晶体学 | 210篇 |
力学 | 973篇 |
综合类 | 87篇 |
数学 | 3306篇 |
物理学 | 7126篇 |
出版年
2024年 | 33篇 |
2023年 | 385篇 |
2022年 | 567篇 |
2021年 | 818篇 |
2020年 | 761篇 |
2019年 | 738篇 |
2018年 | 598篇 |
2017年 | 554篇 |
2016年 | 1098篇 |
2015年 | 934篇 |
2014年 | 1094篇 |
2013年 | 1992篇 |
2012年 | 2298篇 |
2011年 | 2423篇 |
2010年 | 1472篇 |
2009年 | 1687篇 |
2008年 | 1735篇 |
2007年 | 1623篇 |
2006年 | 1401篇 |
2005年 | 1370篇 |
2004年 | 1535篇 |
2003年 | 1150篇 |
2002年 | 1028篇 |
2001年 | 590篇 |
2000年 | 519篇 |
1999年 | 480篇 |
1998年 | 423篇 |
1997年 | 377篇 |
1996年 | 397篇 |
1995年 | 336篇 |
1994年 | 259篇 |
1993年 | 264篇 |
1992年 | 220篇 |
1991年 | 153篇 |
1990年 | 164篇 |
1989年 | 122篇 |
1988年 | 115篇 |
1987年 | 101篇 |
1986年 | 94篇 |
1985年 | 118篇 |
1984年 | 105篇 |
1983年 | 76篇 |
1982年 | 71篇 |
1981年 | 67篇 |
1980年 | 57篇 |
1979年 | 34篇 |
1978年 | 28篇 |
1977年 | 35篇 |
1976年 | 26篇 |
1974年 | 27篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
991.
Variations of densities and viscosities with temperature and composition are reported for binary liquid mixtures containing propionic acid+aniline (I),+o-toluidine (II),+o-anisidine (III), and+o-chloroaniline (IV). Entropies S
m and enthalpies H
m of activation as functions of the composition of the mixtures, as well as free energies of activation G
m at 10, 20, 30, 40, and 50°C and different compositions were calculated by means of Eyring's equation. The formation of activated complexes between the components of these binary mixtures is postulated and claimed to result from acid-base and hydrogen bonding exchange interactions. 相似文献
992.
I. B. Plećaš A. D. Perić J. D. Drljača A. M. Kostadinović 《Journal of Radioanalytical and Nuclear Chemistry》1992,157(1):95-104
An optimization of mortar (as matrix), improved with bentonite clay, used for immobilization of radionuclides60Co,137Cs,85Sr and54Mn, is presented. A relatively simple mathematical model is given, which permits minimization of leach rate and permeability and maximization of compressive strength. An optimal solution, based on experimental data, is given. These results will be used for a future Yugoslav radioactive waste storing center. 相似文献
993.
María L. Dell'Arciprete Carlos J. Cobos Dr. Jorge P. Furlong Dr. Daniel O. Mártire Dr. Mónica C. Gonzalez Dr. 《Chemphyschem》2007,8(17):2498-2505
The kinetics of the oxidation of pyridine, 3‐chloropyridine, 3‐cyanopyridine, 3‐methoxypyridine and 3‐methylpyridine mediated by SO4 < M ‐> radicals are studied by flash photolysis of peroxodisulphate, S2O82?, at pH 2.5 and 9. The absolute rate constants for the reactions of both, the basic and acid forms of the pyridines, are determined and discussed in terms of the Hammett correlation. The monosubstituted pyridines react about 10 times faster with sulphate radicals than their protonated forms, the pyridine ions. The organic intermediates are identified as the corresponding hydroxypyridine radical adducts and their absorption spectra compared with those estimated employing the time‐dependent density functional theory with explicit account for bulk solvent effects. A reaction mechanism which accounts for the observed intermediates and the pyridinols formed as products is proposed. 相似文献
994.
Alvarez CM Alvarez MA García-Vivó D García ME Ruiz MA Saáez D Falvello LR Soler T Herson P 《Dalton transactions (Cambridge, England : 2003)》2004,(24):4168-4179
The new hydride complexes [Mo2Cp2(mu-H)(mu-PHR)(CO)4] having bulky substituents (R = 2,4,6-C(6)H2tBu3= Mes*, R = 2,4,6-C6H2Me3= Mes) have been prepared in good yield by addition of Li[PHR] to the triply bonded [Mo2Cp2(CO)4] and further protonation of the resulting anionic phosphide complex [Mo2Cp2(mu-PHR)(CO)4]-. Protonation of the Mes* compound with either [H(OEt2)2][B{3,5-C6H3(CF3)2}4] or HBF4.OEt2 gives the cationic phosphinidene complex [Mo2Cp2(mu-H)(mu-PMes*)(CO)4]+ in high yield. In contrast, protonation of the analogous hydride compounds with Mes or Cy substituents on phosphorus give the corresponding unsaturated tetracarbonyls [Mo2Cp2(mu-PHR)(CO)4]+, which are unstable at room temperature and display a cis geometry. Decomposition of the latter give the electron-precise pentacarbonyls [Mo2Cp2(mu-PHR)(mu-CO)(CO)4]+, also displaying a cis arrangement of the metal fragments. In the presence of BF4- as external anion, fluoride abstraction competes with carbonylation to yield the neutral fluorophosphide hydrides [Mo2Cp2(mu-H)(mu-PFR)(CO)4]. Similar results were obtained in the protonation reactions of the hydride compounds having a Ph substituent on phosphorus. In that case, using HCl as protonation reagent gave the chloro-complex [Mo2ClCp2(mu-PHPh)(CO)4] in good yield. The structures and dynamic behaviour of the new compounds are analyzed on the basis of solution IR and 1H, 31P, 19F and 13C NMR data as well as the X-ray studies carried out on [Mo2Cp2(mu-H)(mu-PHMes)(CO)4](cis isomer), [Mo2Cp2(mu-H)(mu-PFMes)(CO)4](trans isomer), [Mo2Cp2(mu-PHCy)(mu-CO)(CO)4](BF4) and [Mo2ClCp2(mu-PHPh)(CO)4]. 相似文献
995.
996.
Barron JA Glazier S Bernhard S Takada K Houston PL Abruña HD 《Inorganic chemistry》2003,42(5):1448-1455
The absorption and emission spectra, excited-state lifetimes, quantum yields, and electrochemical measurements have been obtained for a new series of chiral complexes based on three different chiral 2,2':6',2' '-terpyridine ligands, (-)-ctpy, (-)-[ctpy-x-ctpy], and (-)-[ctpy-b-ctpy], with one, two, or multiple Ru metal centers. The room-temperature absorption and emission maxima of [[((-)-ctpy)Ru]-(-)-[ctpy-b-ctpy]-[Ru((-)-ctpy)]](PF(6))(4) and ((-)-[ctpy-b-ctpy])-[[Ru((-)-[ctpy-b-ctpy])](PF(6))(2)](n) were shifted to lower energies and also exhibited significantly longer luminescence lifetimes when compared to [Ru((-)-ctpy)(2)](PF(6))(2), [[((-)-ctpy)Ru]-(-)-[ctpy-x-ctpy]-[Ru((-)-ctpy)]](PF(6))(4), and ((-)-[ctpy-x-ctpy])-[[Ru((-)-[ctpy-x-ctpy])](PF(6))(2)](n). In terms of their electrochemical behavior, all of the complexes studied exhibited one Ru-centered and two ligand-centered redox waves and the [[((-)-ctpy)Ru]-(-)-[ctpy-x-ctpy]-[Ru((-)-ctpy)]](PF(6))(4), ((-)-[ctpy-x-ctpy])-[[Ru((-)-[ctpy-x-ctpy])](PF(6))(2)](n), and ((-)-[ctpy-b-ctpy])-[[Ru((-)-[ctpy-b-ctpy])](PF(6))(2)](n)() complexes were found to electrodeposit upon ligand-based reduction. The difference between the formal potentials of the Ru-centered and the first ligand-centered (least negative) waves corresponded linearly with the changes in the observed emission energies. The shifts in energy are discussed using a particle-in-a-box model, and the luminescence lifetimes are discussed in terms of the structure of the excited-state manifold. 相似文献
997.
The reactions of four flexible tetradentate ligands, 1,3-bis(2-pyridylthio)propane (L1), 1,4-bis(2-pyridylthio)butane (L2), 1,5-bis(2-pyridylthio)pentane (L3) and 1,6-bis(2-pyridylthio)hexane (L4) with AgX (X = BF4-, ClO4-, PF6-, or CF3SO3-) lead to the formation of seven new complexes: [AgL1(BF4)]2 (1), [[AgL2](ClO4)]infinity (2), [[AgL2(CH3CN)](PF6)]infinity (3), [[AgL3](BF4)(CHCl3)]2 (4), [[AgL3(CF3SO3)](CH3OH)(0.5)]infinity (5), [[Ag2L4(2)](BF4)2]infinity (6), and [[AgL4](PF6)]infinity (7), which have been characterized by elemental analyses, IR spectroscopy, and X-ray crystallography. Single-crystal X-ray analyses show that complexes 1 and 4 possess dinuclear macrometallacyclic structures, and complexes 2, 3 and 5-7 take chain structures. In all the complexes, the nitrogen atoms of ligands preferentially coordinate to silver atoms to form normal coordination bonds, while the sulfur atoms only show weak interactions with silver atoms and the intermolecular AgS weak contacts connect the low-dimensional complexes into high-dimensional supramolecular networks. Additional weak interactions, such as pi-pi stacking, F...F weak interactions, Ag...O contacts or C-H...O hydrogen bonds, also help to stabilize the crystal structures. It was found that the parity of the -(CH2)n- spacers (n = 3-6) affect the orientation of the two terminal pyridyl rings, thereby significantly influence the framework formations of these complexes. The coordination features of ligands and their conformation changes between free and coordination states have been investigated by DFT calculations. 相似文献
998.
999.
1000.
Bismuth as BiCl4− and BH4− ware successively retained in a column (150 mm × 4 mm, length × i.d.) packed with Amberlite IRA-410 (strong anion-exchange resin). This was followed by passage of an injected slug of hydrochloric acid resulting in bismuthine generation (BiH3). BiH3 was stripped from the eluent solution by the addition of a nitrogen flow and the bulk phases were separated in a gas–liquid separator. Finally, bismutine was atomized in a quartz tube for the subsequent detection of bismuth by atomic absorption spectrometry. Different halide complexes of bismuth (namely, BiBr4−, BiI4− and BiCl4−) were tested for its pre-concentration, being the chloride complexes which produced the best results. Therefore, a concentration of 0.3 mol l−1 of HCl was added to the samples and calibration solutions. A linear response was obtained between the detection limit (3σ) of 0.225 and 80 μg l−1. The R.S.D.% (n = 10) for a solution containing 50 μg l−1 of Bi was 0.85%. The tolerance of the system to interferences was evaluated by investigating the effect of the following ions: Cu2+, Co2+, Ni2+, Fe3+, Cd2+, Pb2+, Hg2+, Zn2+, and Mg2+. The most severe depression was caused by Hg2+, which at 60 mg l−1 caused a 5% depression on the signal. For the other cations, concentrations between 1000 and 10,000 mg l−1 could be tolerated. The system was applied to the determination of Bi in urine of patients under therapy with bismuth subcitrate. The recovery of spikes of 5 and 50 μg l−1 of Bi added to the samples prior to digestion with HNO3 and H2O2 was in satisfactory ranges from 95.0 to 101.0%. The concentrations of bismuth found in six selected samples using this procedure were in good agreement with those obtained by an alternative technique (ETAAS). Finally, the concentration of Bi determined in urine before and after 3 days of treatment were 1.94 ± 1.26 and 9.02 ± 5.82 μg l−1, respectively. 相似文献