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51.
52.
Sofia I. Bär Madeleine Gold Sebastian W. Schleser Dr. Tobias Rehm Alexander Bär Leonhard Köhler Lucas R. Carnell Dr. Bernhard Biersack Prof. Dr. Rainer Schobert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(15):5003-5010
Three [1,3-diethyl-4-(p-methoxyphenyl)-5-(3,4,5-trimethoxyphenyl)imidazol-2-ylidene](L)gold(I) complexes, 4 a (L=Cl), 5 a (L=PPh3), and 6 a (L=same N-heterocyclic carbene (NHC)), and their fluorescent [4-(anthracen-9-yl)-1,3-diethyl-5-phenylimidazol-2-ylidene](L)gold(I) analogues, 4 b , 5 b , and 6 b , respectively, were studied for their localisation and effects in cancer cells. Despite their identical NHC ligands, the last three accumulated in different compartments of melanoma cells, namely, the nucleus ( 4 b ), mitochondria ( 5 b ), or lysosomes ( 6 b ). Ligand L was also more decisive for the site of accumulation than the NHC ligand because the couples 4 a / 4 b , 5 a / 5 b , and 6 a / 6 b , carrying different NHC ligands, afforded similar results in cytotoxicity tests, and tests on targets typically found at their sites of accumulation, such as DNA in nuclei, reactive oxygen species and thioredoxin reductase in mitochondria, and lysosomal membranes. Regardless of the site of accumulation, cancer cell apoptosis was eventually induced. The concept of guiding a bioactive complex fragment to a particular subcellular target by secondary ligand L could reduce unwanted side effects. 相似文献
53.
Mechanistic Insights into the Pd‐Catalyzed Direct Amination of Allyl Alcohols: Evidence for an Outer‐Sphere Mechanism Involving a Palladium Hydride Intermediate 下载免费PDF全文
Supaporn Sawadjoon Dr. Per J. R. Sjöberg Dr. Andreas Orthaber Prof. Olle Matsson Dr. Joseph S. M. Samec 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(6):1520-1524
The mechanism of direct amination of allyl alcohol by a palladium triphenylphosphite complex has been explored. Labelling studies show that the reaction proceeds through a π‐allylpalladium intermediate. A second‐order dependence of reaction rate on allyl alcohol concentration was observed. Kinetic isotope effect studies and ESI‐MS studies are in agreement with a reaction proceeding through a palladium hydride intermediate in which both O–H bond and C–O bond cleavages are involved in rate‐determining steps. A stereochemical study supports an outer‐sphere nucleophilic attack of the π‐allylpalladium intermediate giving complete chiral transfer from starting material to product. 相似文献
54.
Suihan Feng Dr. Vibor Laketa Frank Stein Dr. Anna Rutkowska Dr. Aidan MacNamara Dr. Sofia Depner Prof. Ursula Klingmüller Dr. Julio Saez‐Rodriguez Priv.‐Doz. Dr. Carsten Schultz 《Angewandte Chemie (International ed. in English)》2014,53(26):6720-6723
Chemical dimerizers are powerful tools for non‐invasive manipulation of enzyme activities in intact cells. Here we introduce the first rapidly reversible small‐molecule‐based dimerization system and demonstrate a sufficiently fast switch‐off to determine kinetics of lipid metabolizing enzymes in living cells. We applied this new method to induce and stop phosphatidylinositol 3‐kinase (PI3K) activity, allowing us to quantitatively measure the turnover of phosphatidylinositol 3,4,5‐trisphosphate (PIP3) and its downstream effectors by confocal fluorescence microscopy as well as standard biochemical methods. 相似文献
55.
Dr. Sofia Curland Dr. Christoph Allolio Leah Javitt Shiri Dishon Ben-Ami Dr. Isabelle Weissbuch Dr. David Ehre Prof. Dr. Daniel Harries Prof. Dr. Meir Lahav Prof. Dr. Igor Lubomirsky 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(36):15705-15709
Electrofreezing experiments of super-cooled water (SCW) with different ions, performed directly on the charged hemihedral faces of pyroelectric LiTaO3 and AgI crystals, in the presence and in the absence of pyroelectric charge are reported. It is demonstrated that bicarbonate (HCO3−) ions elevate the icing temperature near the positively charged faces. In contrast, the hydronium (H3O+) slightly reduces the icing temperature. Molecular dynamics simulations suggest that the hydrated trigonal planar HCO3− ions self-assemble with water molecules near the surface of the AgI crystal as clusters of slightly different configuration from those of the ice-like hexagons. These clusters, however, have a tendency to serve as embryonic nuclei for ice crystallization. Consequently, we predicted and experimentally confirmed that the trigonal planar ions of NO3− and guanidinium (Gdm+), at appropriate concentrations, elevate the icing temperature near the positive and negative charged surfaces, respectively. On the other hand, the Cl− and SO42− ions of different configurations reduce the icing temperature. 相似文献
56.
Sarath P. Gunasekera Sofia Kokkaliari Ranjala Ratnayake Thomas Sauvage Larissa A. H. dos Santos Hendrik Luesch Valerie J. Paul 《Molecules (Basel, Switzerland)》2022,27(5)
Dysidazirine carboxylic acid (1) was isolated from the lipophilic extract of a collection of the benthic marine cyanobacterium Caldora sp. from reefs near Fort Lauderdale, Florida. The planar structure of this new compound was determined by spectroscopic methods and comparisons between HRMS and NMR data with its reported methyl ester. The absolute configuration of the single chiral center was determined by the conversion of 1 to the methyl ester and the comparison of its specific rotation data with the two known methyl ester isomers, 2 and 3. Molecular sequencing with 16S rDNA indicated that this cyanobacterium differs from Caldora penicillata (Oscillatoriales) and represents a previously undocumented and novel Caldora species. Dysidazirine (2) showed weak cytotoxicity against HCT116 colorectal cancer cells (IC50 9.1 µM), while dysidazirine carboxylic acid (1) was non-cytotoxic. Similar cell viability patterns were observed in RAW264.7 cells with dysidazirine only (2), displaying cytotoxicity at the highest concentration tested (50 µM). The non-cytotoxic dysidazirine carboxylic acid (1) demonstrated anti-inflammatory activity in RAW264.7 cells stimulated with LPS. After 24 h, 1 inhibited the production of NO by almost 50% at 50 µM, without inducing cytotoxicity. Compound 1 rapidly decreased gene expression of the pro-inflammatory gene iNOS after 3 h post-LPS treatment and in a dose-dependent manner (IC50 ~1 µM); the downregulation of iNOS persisted at least until 12 h. 相似文献
57.
Ana Sofia Almeida Brbara Silva Paula Guedes de Pinho Fernando Remio Carla Fernandes 《Molecules (Basel, Switzerland)》2022,27(7)
New psychoactive substances represent a public health threat since they are not controlled by international conventions, are easily accessible online and are sold as a legal alternative to illicit drugs. Among them, synthetic cathinones are widely abused due to their stimulant and hallucinogenic effects. To circumvent the law, new derivatives are clandestinely synthesized and, therefore, synthetic cathinones keep emerging on the drug market, with their chemical and toxicological properties still unknown. In this review, a literature assessment about synthetic cathinones is presented focusing on the recent developments, which include more than 50 derivatives since 2014. A summary of their toxicokinetic and toxicodynamic properties are also presented. Furthermore, synthetic cathinones are chiral compounds, meaning that they can exist as two enantiomeric forms which may present different biological and toxicological activities. To analyze the enantiomers, the development of enantiomeric resolution methods for synthetic cathinones is crucial. Many methods have been reported over the years that include mostly chromatographic and electromigration techniques, with liquid chromatography using chiral stationary phases being the technique of choice. This review intended to present an overview of enantioselectivity studies and enantioseparation analysis regarding synthetic cathinones, highlighting the relevance of chirality and current trends. 相似文献
58.
The task of reconstructing the system’s state from the measurements results, known as the Pauli problem, usually requires repetition of two successive steps. Preparation in an initial state to be determined is followed by an accurate measurement of one of the several chosen operators in order to provide the necessary “Pauli data”. We consider a similar yet more general problem of recovering Feynman’s transition (path) amplitudes from the results of at least three consecutive measurements. The three-step histories of a pre- and post-selected quantum system are subjected to a type of interference not available to their two-step counterparts. We show that this interference can be exploited, and if the intermediate measurement is “fuzzy”, the path amplitudes can be successfully recovered. The simplest case of a two-level system is analysed in detail. The “weak measurement” limit and the usefulness of the path amplitudes are also discussed. 相似文献
59.
Elisabet Öberg Andreas Orthaber Marie-Pierre Santoni Fredrick Howard Sascha Ott 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-3):152-158
Abstract Attempts to utilize C-ethylenic phosphaalkenes in metathesis reactions are discussed. Unprecedented reactivity is observed where the vinylphosphaalkene undergoes the first step of the catalytic cycle and cross-metathesis with the phenylmethylene moiety of Grubbs 2nd generation catalyst. However, homo-metathesis reaction to form 1,6-diphosphahexa-1,3,5-triene is not observed, presumably due to steric constraints. 相似文献
60.
Erik Allard Rikard Åslund Tröger Björn Arvidsson Per Johan Ragnar Sjöberg 《Rapid communications in mass spectrometry : RCM》2010,24(4):429-435
Precision, reproducibility and lower limit of quantitation (LLOQ) are important characteristics of a quantitative method. We have investigated these properties for Ximelagatran (Xi), which has a high tendency to form doubly charged ions in electrospray ionization (ESI), by studying the percentage of doubly charged species formed when varying the formic acid (FA) concentration, analyte concentration, amount of organic modifier and flow rate. It was found that the percentage of [Xi + 2H]2+ can be controlled to be more than 90% or less than 10% by varying the amount of FA present, and that the change between these values is dramatic. Furthermore, the percentage of [Xi + 2H]2+ formed decreases with increased analyte concentration and increased flow rate. No apparent relationship with the amount of organic modifier was found. The results have the implication that, by carefully controlling the selected parameters, the LLOQ, precision and reproducibility can be improved. We have compared the fragmentation of the singly and doubly charged species and concluded that the [Xi + 2H]2+ ion is more inclined to undergo fragmentation than [Xi + H]+. As a consequence, unusual instrumental settings had to be used for the experiments. The fragmentation patterns are to a great extent similar, but the doubly charged species is more inclined to generate low‐mass product ions. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献