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101.
Cihang Yu Dr. Agnes Kütt Prof. Dr. Gerd-Volker Röschenthaler Dr. Tomas Lebl Dr. David B. Cordes Prof. Dr. Alexandra M. Z. Slawin Prof. Dr. Michael Bühl Prof. Dr. David O'Hagan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):20077-20081
We report the synthesis of all-cis 1,2,4,5-tetrakis (trifluoromethyl)- and all-cis 1,2,3,4,5,6-hexakis (trifluoromethyl)- cyclohexanes by direct hydrogenation of precursor tetrakis- or hexakis- (trifluoromethyl)benzenes. The resultant cyclohexanes have a stereochemistry such that all the CF3 groups are on the same face of the cyclohexyl ring. All-cis 1,2,3,4,5,6-hexakis(trifluoromethyl)cyclohexane is the most sterically demanding of the all-cis hexakis substituted cyclohexanes prepared to date, with a barrier (ΔG) to ring inversion calculated at 27 kcal mol−1. The X-ray structure of all-cis 1,2,3,4,5,6-hexakis(trifluoromethyl)cyclohexane displays a flattened chair conformation and the electrostatic profile of this compound reveals a large diffuse negative density on the fluorine face and a focused positive density on the hydrogen face. The electropositive hydrogen face can co-ordinate chloride (K≈103) and to a lesser extent fluoride and iodide ions. Dehydrofluorination promoted decomposition occurs with fluoride ion acting as a base. 相似文献
102.
Guillaume Lafitte Audrey Beillard Sandrine Chambon Catherine Soulet Laurence Dumais Grégoire Mouis Jean-François Fournier Laurence Clary Claire Bouix-Peter Loic Tomas Craig S. Harris 《Tetrahedron letters》2018,59(3):256-259
During our search for novel CGRP antagonists, we had great difficulty in accessing one of our key motifs. Herein, we communicate how we solved the problem by an unprecedented Mitsunobu alkylation using unprotected amino alcohols. 相似文献
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A safe, functional-group-tolerant and high-throughput version of the trimethylaluminium mediated amide bond formation reaction has been developed in a microreactor system; rimonabant and efaproxiral were prepared to illustrate the utility of the method. 相似文献
105.
Light-Responsive Elastin-Like Peptide-Based Targeted Nanoparticles for Enhanced Spheroid Penetration
Dr. Duc H. T. Le Dr. Vusala Ibrahimova Sebastian A. H. van den Wildenberg Dr. Hanglong Wu Alba Fonseca Prof. Dr. Tomas Torres Dr. Elisabeth Garanger Dr. William P. J. Leenders Prof. Dr. Roland Brock Prof. Dr. Sébastien Lecommandoux Prof. Dr. Jan C. M. van Hest 《Angewandte Chemie (International ed. in English)》2023,62(24):e202300511
We describe here a near infrared light-responsive elastin-like peptide (ELP)-based targeted nanoparticle (NP) that can rapidly switch its size from 120 to 25 nm upon photo-irradiation. Interestingly, the targeting function, which is crucial for effective cargo delivery, is preserved after transformation. The NPs are assembled from (targeted) diblock ELP micelles encapsulating photosensitizer TT1-monoblock ELP conjugates. Methionine residues in this monoblock are photo-oxidized by singlet oxygen generated from TT1, turning the ELPs hydrophilic and thus trigger NP dissociation. Phenylalanine residues from the diblocks then interact with TT1 via π-π stacking, inducing the re-formation of smaller NPs. Due to their small size and targeting function, the NPs penetrate deeper in spheroids and kill cancer cells more efficiently compared to the larger ones. This work could contribute to the design of “smart” nanomedicines with deeper penetration capacity for effective anticancer therapies. 相似文献
106.
Single-particle kinetic studies of the reaction between oleic acid and O 3 have been conducted on two different types of core particles: polystyrene latex (PSL) and silica. Oleic acid was found to adsorb to both particle types in multilayer islands that resulted in an adsorbed layer of a total volume estimated to be less than one monolayer. The rate of the surface reaction between surface-adsorbed oleic acid and O 3 has been shown for the first time to be influenced by the composition of the aerosol substrate in a mixed organic/inorganic particle. A Langmuir-Hinshelwood mechanism was applied to the observed dependence of the pseudo-first-order rate constant with [O 3], and the resulting fit parameters for the ozone partition coefficient ( K O 3 ) and maximum first order rate constant ( k 1,max ) suggest that the reaction proceeded faster on the less polar PSL core at lower [O 3] due to the increased residence time of O 3 on the PSL surface, but the reaction was ultimately more efficient on the silica surface at high [O 3]. Values for the uptake coefficient, gamma oleic , for reaction of oleic acid on PSL spheres decrease from 2.5 x 10 (-5) to 1 x 10 (-5) with increasing [O 3] from 4 to 25 ppm and overlap at high [O 3] with the estimated values for gamma oleic on silica, which decrease from 1.6 x 10 (-5) to 1.3 x 10 (-5). The relationship between gamma oleic and the more common expression for gamma O 3 is discussed. 相似文献
107.
Anirudra Parajuli Daniel H. Kwak Luca Dalponte Dr. Niina Leikoski Tomas Galica Ugochukwu Umeobika Dr. Laurent Trembleau Andrew Bent Prof. Kaarina Sivonen Matti Wahlsten Dr. Hao Wang Dr. Ermanno Rizzi Prof. Gianluca De Bellis Prof. James Naismith Prof. Marcel Jaspars Prof. Xinyu Liu Dr. Wael Houssen Dr. David Peter Fewer 《Angewandte Chemie (International ed. in English)》2016,55(11):3596-3599
Cyanobactins are a rapidly growing family of linear and cyclic peptides produced by cyanobacteria. Kawaguchipeptins A and B, two macrocyclic undecapeptides reported earlier from Microcystis aeruginosa NIES‐88, are shown to be products of the cyanobactin biosynthetic pathway. The 9 kb kawaguchipeptin (kgp) gene cluster was identified in a 5.26 Mb draft genome of Microcystis aeruginosa NIES‐88. We verified that this gene cluster is responsible for the production of the kawaguchipeptins through heterologous expression of the kgp gene cluster in Escherichia coli. The KgpF prenyltransferase was overexpressed and was shown to prenylate C‐3 of Trp residues in both linear and cyclic peptides in vitro. Our findings serve to further enhance the structural diversity of cyanobactins to include tryptophan‐prenylated cyclic peptides. 相似文献
108.
The aim of this note is to discuss some issues posed by the emergency of universal interfaces able to decide on the truth of geometric statements. More specifically, we consider a recent GeoGebra module allowing general users to verify standard geometric theorems. Working with this module in the context of Varignon’s theorem, we were driven—by the characteristics of the GeoGebra interface—to perform a quite detailed study of the very diverse fate of attempting to automatically prove this statement, when using two different construction procedures. We highlight the relevance—for the theorem proving output—of expression power of the dynamic geometry interface, and we show that the algorithm deciding about the truth of some—even quite simple—statements can fall into a not true and not false situation, providing a source of confusion for a standard user and an interesting benchmark for geometers interested in discovering new geometric facts. 相似文献
109.
110.
Ausra Peciulyte Juris Kiskis Per Tomas Larsson Lisbeth Olsson Annika Enejder 《Cellulose (London, England)》2016,23(3):1521-1536
Enzymatic hydrolysis of cellulose provides a renewable source of monosaccharides for production of variety of biochemicals and biopolymers. Unfortunately, the enzymatic hydrolysis of cellulose is often incomplete, and the reasons are not fully understood. We have monitored enzymatic hydrolysis in terms of molecular density, ordering and autofluorescence of cellulose structures in real time using simultaneous CARS, SHG and MPEF microscopy with the aim of contributing to the understanding and optimization of the enzymatic hydrolysis of cellulose. Three cellulose-rich substrates with different supramolecular structures, pulp fibre, acid-treated pulp fibre and Avicel, were studied at microscopic level. The microscopy studies revealed that before enzymatic hydrolysis Avicel had the greatest carbon-hydrogen density, while pulp fibre and acid-treated fibre had similar density. Monitoring of the substrates during enzymatic hydrolysis revealed the double exponential SHG decay for pulp fibre and acid-treated fibre indicating two phases of the process. Acid-treated fibre was hydrolysed most rapidly and the hydrolysis of pulp fibre was spatially non-uniform leading to fractioning of the particles, while the hydrolysis of Avicel was more than an order of magnitude slower than that of both fibres. 相似文献