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951.
952.
Michael Kemper Sven Reese Dr. Elric Engelage Prof. Dr. Christian Merten 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202202812
Stabilization of chiral propeller conformations in triaryl compounds is challenging due to generally low racemization barriers. Nonetheless, it was recently found that chiral conformational preferences can be induced to triaryl boranes by incorporating point-chiral alkylether chains to the aryl blades and subsequently locking the structure with ammonia. A four-point interaction, meaning that the cooperative effects of Lewis-adduct formation and three hydrogen bonds, was proposed as stabilizing mechanism. Herein, it was shown that three such strong interactions suffice to introduce a preferential propeller handedness. Although DFT calculations predict no noteworthy preferences for either P- or M-chiral propellers for some of the investigated triarylborane–amine adducts that were prepared with chiral primary amines, vibrational circular dichroism (VCD) spectroscopic characterizations revealed that there is indeed a measurable excess of one propeller handedness. Furthermore, the steric demand of the amine was found to play a key role in the induction process and especially in preventing blade rotations. 相似文献
953.
Philipp Schüler Dr. Helmar Görls Dr. Sven Krieck Prof. Dr. Matthias Westerhausen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(62):15508-15515
In the in situ Grignard metalation method (iGMM), the addition of bromoethane to a suspension of magnesium turnings and cyclopentadienes [C5H6 (HCp), C5H5-Si(iPr)3 (HCpTIPS)] in diethyl ether smoothly yields heteroleptic [(Et2O)Mg(CpR)(μ-Br)]2 (CpR=Cp ( 1 ), CpTIPS ( 2 )). The Schlenk equilibrium of 2 in toluene leads to ligand exchange and formation of homoleptic [Mg(CpR)2] ( 3 ) and [(Et2O)MgBr(μ-Br)]2 ( 4 ). Interfering solvation and aggregation as well as ligand redistribution equilibria hamper a quantitative elucidation of thermodynamic data for the Schlenk equilibrium of 2 in toluene. In ethereal solvents, mononuclear species [(Et2O)2Mg(CpTIPS)Br] ( 2’ ), [(Et2O)nMg(CpTIPS)2] ( 3’ ), and [(Et2O)2MgBr2] ( 4’ ) coexist. Larger coordination numbers can be realized with cyclic ethers like tetrahydropyran allowing crystallization of [(thp)4MgBr2] ( 5 ). The interpretation of the temperature-dependency of the Schlenk equilibrium constant in diethyl ether gives a reaction enthalpy ΔH and reaction entropy ΔS of −11.5 kJ mol−1 and 60 J mol−1, respectively. 相似文献
954.
955.
Jan Beran Sven Möhrle Sucharita Ghosh 《Journal of computational and graphical statistics》2016,25(3):917-934
Statistical inference for time series with long-range dependence is often based on the assumption of Gaussian subordination Xt = G(Zt). Although the Hermite rank m of G plays an essential role for statistical inference in these situations, the question of estimating m or of testing hypotheses about the Hermite rank has not been addressed in the literature. In this article, a method is introduced for testing H0: m = 1 against H1: m > 1. This allows for deciding whether inference based on the usual assumption of m = 1 is appropriate. Simulations and data examples illustrate the method. 相似文献
956.
957.
Clément Lepori Dr. Elise Bernoud Dr. Régis Guillot Dr. Sven Tobisch Dr. Jérôme Hannedouche 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(3):835-844
A comprehensive mechanistic study by means of complementary experimental and computational approaches of the exo-cyclohydroamination of primary aminoalkenes mediated by the recently reported β-diketiminatoiron(II) complex B is presented. Kinetic analysis of the cyclisation of 2,2-diphenylpent-4-en-1-amine ( 1 a ) catalysed by B revealed a first-order dependence of the rate on both aminoalkene and catalyst concentrations and a primary kinetic isotope effect (KIE) (kH/kD) of 2.7 (90 °C). Eyring analysis afforded ΔH≠=22.2 kcal mol−1, ΔS≠=−13.4 cal mol−1 K−1. Plausible mechanistic pathways for competitive avenues of direct intramolecular hydroamination and oxidative amination have been scrutinised computationally. A kinetically challenging proton-assisted concerted N−C/C−H bond-forming non-insertive pathway is seen not to be accessible in the presence of a distinctly faster σ-insertive pathway. This operative pathway involves 1) rapid and reversible syn-migratory 1,2-insertion of the alkene into the Fe−Namido σ bond at the monomer {N^N}FeII amido compound; 2) turnover-limiting Fe−C σ bond aminolysis at the thus generated transient {N^N}FeII alkyl intermediate and 3) regeneration of the catalytically competent {N^N}FeII amido complex, which favours its dimer, likely representing the catalyst resting state, through rapid cycloamine displacement by substrate. The collectively derived mechanistic picture is consonant with all empirical data obtained from stoichiometric, catalytic and kinetics experiments. 相似文献
958.
Sven Henning H. R. Imam Khasim Goerg H. Michler Jörg Brandt 《Macromolecular Symposia》2012,315(1):84-97
The contribution describes the development of a biocompatible nanocomposite material consisting of a resorbable polymeric matrix and osteoinductive nanoparticles that can be used to manufacture compact products, porous scaffolds, hybrid nanofibers, and alternating porous/compact structures. It is shown that the material has a good balance of stiffness, strength and toughness. The material supports osteoblast proliferation. Based on a modular design principle, several prototypes for hierarchical 3D constructs are proposed. 相似文献
959.
Tight-spans of metrics were first introduced by Isbell in 1964 and rediscovered and studied by others, most notably by Dress in 1984, who gave them this name. Subsequently, it has been found that tight-spans can be defined for more general maps, such as directed metrics and distances, and more recently for diversities. In this paper, we show that all of these tight-spans, as well as some related constructions, can be defined in terms of point configurations. This provides a useful way in which to study these objects in a unified and systematic way. We also show that by using point configurations we can recover results concerning one-dimensional tight-spans for all of the maps we consider, as well as extending these and other results to more general maps such as symmetric and asymmetric maps. 相似文献
960.
Okoli C Sanchez-Dominguez M Boutonnet M Järås S Civera C Solans C Kuttuva GR 《Langmuir : the ACS journal of surfaces and colloids》2012,28(22):8479-8485
Magnetic iron oxide nanoparticles (MION) for protein binding and separation were obtained from water-in-oil (w/o) and oil-in-water (o/w) microemulsions. Characterization of the prepared nanoparticles have been performed by TEM, XRD, SQUID magnetometry, and BET. Microemulsion-prepared magnetic iron oxide nanoparticles (ME-MION) with sizes ranging from 2 to 10 nm were obtained. Study on the magnetic properties at 300 K shows a large increase of the magnetization ~35 emu/g for w/o-ME-MION with superparamagnetic behavior and nanoscale dimensions in comparison with o/w-ME-MION (10 emu/g) due to larger particle size and anisotropic property. Moringa oleifera coagulation protein (MOCP) bound w/o- and o/w-ME-MION showed an enhanced performance in terms of coagulation activity. A significant interaction between the magnetic nanoparticles and the protein can be described by changes in fluorescence emission spectra. Adsorbed protein from MOCP is still retaining its functionality even after binding to the nanoparticles, thus implying the extension of this technique for various applications. 相似文献