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41.
Antonio Tognazzi Arduino M. Dattilo Luca Bracchini Claudio Rossi Davide Vione 《International journal of environmental analytical chemistry》2013,93(15):1679-1688
It is known that the compound 2,4-dichloro-6-nitrophenol (2,4DC6NP) is formed upon nitration of 2,4-dichlorophenol, which in turn is a transformation intermediate of the herbicide dichlorprop. However, the chemical and spectroscopic characteristics of 2,4DC6NP, as well as its toxicity, are poorly known. This work shows that 2,4DC6NP behaves as a diprotic acid in aqueous solutions, with pKa values of 3.0?±?0.9 and 4.9?±?0.5. At pH?<?3, 2,4DC6NP would undergo protonation. The absorption spectra suggest that anionic 2,4DC6NP, which prevails at pH?>?5 would have an ortho-quinoid structure that is responsible for the absorption peak centred at 428?nm. Considering that 2,4DC6NP has been detected in the brackish lagoons of the Rhône delta (southern France), where its levels are comparable to those of the parent herbicide, it is necessary to examine the possible effects of 2,4DC6NP on the species living in that environment. For this reason, the acute toxicity of the anionic form of 2,4DC6NP was assessed for the brine shrimp Artemia salina, a zooplankton species that lives both in brackish and in saline aquatic environments. The toxicity test yielded a LC20 value of 8?±?2?mg?L?1 and a LC50 value of 18.7?±?0.8?mg?L?1. Such values are safely higher than the maximum detected concentration of 2,4DC6NP in the Rhône delta lagoons. Further studies should be concentrated on the long-term effects of 2,4DC6NP, and in particular on its potential genotoxicity. 相似文献
42.
Dr. Alessandro Barge Marina Caporaso Prof. Giancarlo Cravotto Dr. Katia Martina Dr. Paolo Tosco Prof. Silvio Aime Dr. Carla Carrera Dr. Eliana Gianolio Dr. Giorgio Pariani Dr. Davide Corpillo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(36):12086-12092
We report the synthesis and characterization of a water‐soluble, star‐shaped macromolecular platform consisting of eight β‐cyclodextrin (β‐CD) units anchored to the narrower rim of a γ‐CD core through bis(triazolyl)alkyl spacers. The efficient synthetic protocol is based on the microwave (MW)‐promoted Cu‐catalyzed 1,3‐dipolar cycloaddition of CD monoazides to CD monoacetylenes. The ligand‐hosting capability of the construct has been assessed by relaxometric titration and nuclear magnetic relaxation dispersion (NMRD) profiling, which showed it to be good, and this was supported by molecular dynamics simulations. To demonstrate the feasibility of obtaining supramolecular structures with high hosting ability, we designed a dimeric platform, formed by joining two nonamers through the γ‐CD cores through a bis(lithocholic acid) linker. With a view to the potential biological applications, cytotoxicity and extent of binding to human serum albumin were assessed. The properties of this dendrimeric multicarrier make it suitable for pharmaceutical and diagnostic purposes, ranging from targeted drug delivery to molecular imaging. 相似文献
43.
Elisabetta Massolo Maurizio BenagliaDavide Parravicini Davide BrennaRita Annunziata 《Tetrahedron letters》2014
Starting from (E)-β-substituted-β-nitroacrylates and α,β-unsaturated ketones, a stereoselective organocatalyzed one-pot methodology allowed to synthesize highly decorated chiral 2-nitro-cyclohexane carboxylic esters. The reaction is promoted by Cinchona alkaloid-derived primary amines in the presence of an acidic co-catalyst and affords two diastereoisomers, in good yields and high enantiomeric excess (often higher than 90% ee). By replacing conventional heating with microwave irradiation, cleaner reactions in shortened times (from 48 h to 30 min) were obtained, with improved dr (80:20) and high ee (up to 94%). The application of microwave technology to this organocatalytic methodology allowed also employing C1 substituted enones, leading to cyclohexanones with four contiguous stereocenters in two isomers only, and up to 99% enantioselectivity. 相似文献
44.
The effect of the Reynolds number in a supersonic isothermal channel flow is studied using a direct numerical simulation (DNS). The bulk Mach number based on the wall temperature is 1.5, and the bulk Reynolds number is increased up to Reτ ≈︁ 1000. The use of van Driest velocity transformation in the presence of heated walls has been questioned due to the poor accuracy at low Reynolds number. For this reason alternative transformations of the velocity profile and turbulence statistics have been proposed, as, for instance, semi-local scalings. We show that the van Driest transformation recovers its accuracy as the Reynolds number is increased. The Reynolds stresses collapse on the incompressible ones, when properly scaled with density, and very good agreement with the incompressible stresses is found in the outer layer. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
45.
Lorenzo Di Terlizzi Prof. Stefano Protti Prof. Davide Ravelli Prof. Maurizio Fagnoni 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(26):e202200313
With the aim of generating new, thermally inaccessible diradicals, potentially able to induce a double-strand DNA cleavage, the photochemistry of a set of chloroaryl-substituted carboxylic acids in polar media was investigated. The photoheterolytic cleavage of the Ar−Cl bond occurred in each case to form the corresponding triplet phenyl cations. Under basic conditions, the photorelease of the chloride anion was accompanied by an intramolecular electron-transfer from the carboxylate group to the aromatic radical cationic site to give a diradical species. This latter intermediate could then undergo CO2 loss in a structure-dependent fashion, according to the stability of the resulting diradical, or abstract a hydrogen atom from the medium. In aqueous environment at physiological pH (pH=7.3), both a phenyl cation and a diradical chemistry was observed. The mechanistic scenario and the role of the various intermediates (aryl cations and diradicals) involved in the process was supported by computational analysis. 相似文献
46.
We investigate the thermal conductivity of single-wall carbon nanotubes (SWCNT) either isolated or in contact with external media by using equilibrium molecular dynamics and the Boltzmann transport equation. We show that, contrary to existing controversies, both methods yield a finite value of the thermal conductivity for infinitely long tubes, as opposed to the case of 1D, momentum-conserving systems. Acoustic and flexure modes with mean free paths of the order of a few microns are identified as major contributors to the high value of SWCNT conductivity. We also find that the interaction with an external medium may substantially decrease the lifetime of the low-frequency vibrations, reducing the thermal conductivity by up to 2 orders of magnitude. 相似文献
47.
Christian Gentzsch Kerstin Seier Antonios Drakopoulos Dr. Marie-Lise Jobin Dr. Yann Lanoiselée Dr. Zsombor Koszegi Dr. Damien Maurel Dr. Rémy Sounier Dr. Harald Hübner Prof. Dr. Peter Gmeiner Dr. Sébastien Granier Prof. Dr. Davide Calebiro Prof. Dr. Michael Decker 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(15):6014-6020
μ-Opioid receptors (μ-ORs) play a critical role in the modulation of pain and mediate the effects of the most powerful analgesic drugs. Despite extensive efforts, it remains insufficiently understood how μ-ORs produce specific effects in living cells. We developed new fluorescent ligands based on the μ-OR antagonist E-p-nitrocinnamoylamino-dihydrocodeinone (CACO), that display high affinity, long residence time and pronounced selectivity. Using these ligands, we achieved single-molecule imaging of μ-ORs on the surface of living cells at physiological expression levels. Our results reveal a high heterogeneity in the diffusion of μ-ORs, with a relevant immobile fraction. Using a pair of fluorescent ligands of different color, we provide evidence that μ-ORs interact with each other to form short-lived homodimers on the plasma membrane. This approach provides a new strategy to investigate μ-OR pharmacology at single-molecule level. 相似文献
48.
Dr. Luka Ðorđević Cataldo Valentini Dr. Nicola Demitri Cécile Mézière Magali Allain Prof. Dr. Marc Sallé Dr. Andrea Folli Prof. Dr. Damien Murphy Samuel Mañas-Valero Prof. Dr. Eugenio Coronado Prof. Dr. Davide Bonifazi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(10):4135-4143
Herein we report an efficient synthesis to prepare O-doped nanographenes derived from the π-extension of pyrene. The derivatives are highly fluorescent and feature low oxidation potentials. Using electrooxidation, crystals of cationic mixed-valence (MV) complexes were grown in which the organic salts organize into face-to-face π-stacks, a favorable solid-state arrangement for organic electronics. Variable-temperature electron paramagnetic resonance (EPR) measurements and relaxation studies suggest a strong electron delocalization along the longitudinal axis of the columnar π-stacking architectures. Electric measurements of single crystals of the MV salts show a semiconducting behavior with a remarkably high conductivity at room temperature. These findings support the notion that π-extension of heteroatom-doped polycyclic aromatic hydrocarbons is an attractive approach to fabricate nanographenes with a broad spectrum of semiconducting properties and high charge mobilities. 相似文献
49.
IRMPD Spectra of Protonated Hydroxybenzaldehydes: Evidence of Torsional Barriers in Carboxonium Ions
Prof. Barbara Chiavarino Prof. Otto Dopfer Prof. Maria Elisa Crestoni Dr. Davide Corinti Dr. Philippe Maître Prof. Simonetta Fornarini 《Chemphyschem》2020,21(8):749-761
Protonation at the formyl oxygen atom of benzaldehydes leading to the formation of carboxonium ions yields two distinct isomers, depending on the relative orientation of the proton either cis or trans with respect to the hydrogen atom on the adjacent carbon. In this context, the IR multiple photon dissociation (IRMPD) spectra of protonated ortho, meta, and para-hydroxybenzaldehydes ( OH−BZH+ ), delivered into the gas phase by electrospray ionization of hydro-alcoholic solutions, are reported in the 3200–3700 cm−1 spectral range. This range is characteristic of O−H stretching modes and thus able to differentiate cis and trans carboxonium isomers. Comparison between IRMPD spectra and DFT calculations at the B3LYP/6-311++G(2df2p) level suggests that for both p- OH−BZH+ and m- OH−BZH+ only cis conformers are present in the ion population analyzed. For o- OH−BZH+ , IRMPD spectroscopy points to a mixture comprising one trans and more than one cis conformers. The energy barrier for cis–trans isomerization calculated for each OH−BZH+ isomer is a measure of the degree of π-electron delocalization. Furthermore, IRMPD spectra of p- OH−BZH+ , m- OH−BZH+ and protonated phenol (this last used as reference) were recorded also in the fingerprint range. Both the observed C−O and O−H stretching vibrations appear to be a measure of π-electron delocalization in the ions. 相似文献
50.
Roberta Sanna Davide Sanna Valeria Alzari Daniele Nuvoli Sergio Scognamillo Massimo Piccinini Massimo Lazzari Emilia Gioffredi Giulio Malucelli Alberto Mariani 《Journal of polymer science. Part A, Polymer chemistry》2012,50(19):4110-4118
Thermoresponsive poly(N‐vinylcaprolactam) nanocomposite hydrogels containing graphene were successfully prepared by frontal polymerization. High concentration of graphene (5.0 mg/mL) was obtained by direct graphite sonication in the self‐same liquid monomer, thus avoiding any chemical manipulation and obtaining “real” graphene as nanofiller instead of one of its more or less oxidized derivative, which is what generally reported in published reports. Furthermore, the corresponding nanocomposites were obtained without using any solvent to be eventually removed. The materials were fully characterized by RAMAN, SEM, and TEM, and their swelling behavior and rheological properties were investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献