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991.
Molecular dynamics simulations in the isobaric–isothermal ensemble are used to investigate the structure and dynamics of an ionic liquid confined at ambient temperature and pressure in hydroxylated amorphous silica nanopores. The use of the isobaric–isothermal ensemble allows estimating the effect of confinement and surface chemistry on the density of the confined ionic liquid. The structure of the confined ionic liquid is investigated using density profiles and structural order parameters while its dynamics is assessed by determining the mobility and ionic conductivity of the confined phase. Despite the important screening of the electrostatic interactions (owing to the small Debye length in ionic liquids), the local structure of the confined ionic liquid is found to be mostly driven by electrostatic interactions. We show that both the structure and dynamics of the confined ionic liquid can be described as the sum of a surface contribution arising from the ions in contact with the surface and a bulk-like contribution arising from the ions located in the pore centre; as a result, most properties of the confined ionic liquid are a simple function of the surface-to-volume ratio of the host porous material. In contrast, the ionic conductivity of the confined ionic liquid, which is a collective dynamical property, is found to be similar to the bulk. This study sheds light on the complex behaviour of hybrid materials made up of ionic liquid confined in inorganic porous materials. 相似文献
992.
Elisabeth Schültke Ralf Menk Bernd Pinzer Alberto Astolfo Marco Stampanoni Fulvia Arfelli Laura‐Adela Harsan Guido Nikkhah 《Journal of synchrotron radiation》2014,21(1):242-250
Gold nanoparticles are excellent intracellular markers in X‐ray imaging. Having shown previously the suitability of gold nanoparticles to detect small groups of cells with the synchrotron‐based computed tomography (CT) technique both ex vivo and in vivo, it is now demonstrated that even single‐cell resolution can be obtained in the brain at least ex vivo. Working in a small animal model of malignant brain tumour, the image quality obtained with different imaging modalities was compared. To generate the brain tumour, 1 × 105 C6 glioma cells were loaded with gold nanoparticles and implanted in the right cerebral hemisphere of an adult rat. Raw data were acquired with absorption X‐ray CT followed by a local tomography technique based on synchrotron X‐ray absorption yielding single‐cell resolution. The reconstructed synchrotron X‐ray images were compared with images obtained by small animal magnetic resonance imaging. The presence of gold nanoparticles in the tumour tissue was verified in histological sections. 相似文献
993.
In has been shown in [5] that the NLS approximation makes wrong predictions for the water wave problem in case of small surface tension. We explain that the ideas used in [5] allow to show a similar result for the FWI approximation, too. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
994.
995.
Roberto Ambra Sonia Manca Guido Leoni Barbara Guantario Raffaella Canali Raffaella Comitato 《Molecules (Basel, Switzerland)》2021,26(1)
We previously demonstrated that apoptosis induced by tocotrienols (γ and δT3) in HeLa cells is preceded by Ca2+ release from the endoplasmic reticulum. This event is eventually followed by the induction of specific calcium-dependent signals, leading to the expression and activation of the gene encoding for the IRE1α protein and, in turn, to the alternative splicing of the pro-apoptotic protein sXbp1 and other molecules involved in the unfolded protein response, the core pathway coping with EndoR stress. Here, we showed that treatment with T3s induces the expression of a specific set of miRNAs in HeLa cells. Data interrogation based on the intersection of this set of miRNAs with a set of genes previously differentially expressed after γT3 treatment provided a few miRNA candidates to be the effectors of EndoR-stress-induced apoptosis. To identify the best candidate to act as the effector of the Xbp1-mediated apoptotic response to γT3, we performed in silico analysis based on the evaluation of the highest ∆ in Gibbs energy of different mRNA–miRNA–Argonaute (AGO) protein complexes. The involvement of the best candidate identified in silico, miR-190b, in Xbp1 splicing was confirmed in vitro using T3-treated cells pre-incubated with the specific miRNA inhibitor, providing a preliminary indication of its role as an effector of EndoR-stress-induced apoptosis. 相似文献
996.
997.
Janine George David Waroquiers Davide Di Stefano Guido Petretto Gian‐Marco Rignanese Geoffroy Hautier 《Angewandte Chemie (International ed. in English)》2020,59(19):7569-7575
The Pauling rules have been used for decades to rationalise the crystal structures of ionic compounds. Despite their importance, there has been no statistical assessment of the performances of these five empirical rules so far. Here, we rigorously and automatically test all five Pauling rules for a large data set of around 5000 known oxides. We discuss each Pauling rule separately, stressing their limits and range of application in terms of chemistries and structures. We conclude that only 13 % of the oxides simultaneously satisfy the last four rules, indicating a much lower predictive power than expected. 相似文献
998.
Guido Zichittella Matthias Scharfe Begoa Purtolas Vladimir Paunovi Patrick Hemberger Andras Bodi Lszl Szentmiklsi Núria Lpez Javier Prez‐Ramírez 《Angewandte Chemie (International ed. in English)》2019,58(18):5877-5881
The product distribution in direct alkane functionalization by oxyhalogenation strongly depends on the halogen of choice. We demonstrate that the superior selectivity to olefins over an iron phosphate catalyst in oxychlorination is the consequence of a surface‐confined reaction. By contrast, in oxybromination alkane activation follows a gas‐phase radical‐chain mechanism and yields a mixture of alkyl bromide, cracking, and combustion products. Surface‐coverage analysis of the catalyst and identification of gas‐phase radicals in operando mode are correlated to the catalytic performance by a multi‐technique approach, which combines kinetic studies with advanced characterization techniques such as prompt‐gamma activation analysis and photoelectron photoion coincidence spectroscopy. Rationalization of gas‐phase and surface contributions by density functional theory reveals that the molecular level effects of chlorine are pivotal in determining the stark selectivity differences. These results provide strategies for unraveling detailed mechanisms within complex reaction networks. 相似文献
999.
1000.
Modular Synthesis of Linear Bis‐ and Tris‐monodentate Fused [6]Polynorbornane‐Based Ligands and their Assembly into Coordination Cages 下载免费PDF全文
Mark D. Johnstone Eike K. Schwarze Prof. Dr. Guido H. Clever Dr. Frederick M. Pfeffer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):3948-3955
A modular approach has been developed for the synthesis of rigid linear di‐ and tritopic ligands based on a fused [6]polynorbornane scaffold. The design provides up to three sites for installing functionality, including both “ends” and a “central” position with the advantage that each region can be independently addressed during synthesis. To illustrate the utility of the approach, both pyridyl and picolyl units were incorporated to provide six new ligands, with centers and ends either matched or mismatched. Indeed, both [M2L4] cages with endohedral functionality and [M3L4] complexes were cleanly produced from these ligands with assembled structures confirmed by using 1H NMR spectroscopy, HRMS, and molecular modelling. 相似文献