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91.
Dr. Tobias Blockhaus MSc. Fabian L. Zott Dr. Peter M. Zehetmaier Dr. Christian Klein-Heßling Prof. Dr. Karlheinz Sünkel 《无机化学与普通化学杂志》2023,649(1):e202200277
1,2,3- Tricyanoferrocene and 1,3-dibromo-2,4,5-tricyanoferrocene have been synthesized via metallation and usage of dimethylmalononitrile (DMMN) as cyanating agent. They are the first compounds where three nitrile functions could be introduced into the ferrocene sceleton. Further studies on the electrophilic cyanation of lithiated haloferrocenes [Fe(C5HmX4-mLi)(C5H5)] (X=Cl, Br; m=0–3) show the formation of complex mixtures of cyano-halo-ferrocenes [Fe{C5HmX5-m-n(CN)n}(C5H5)] (m=0–3, n=0–3) most likely induced by “halogen-dance” reactions. The molecular and crystal structures of [Fe{C5H2(CN)3}(C5H5)] and [Fe(C5Cl4CN)(C5H5)] are discussed. Cyclic voltametric studies of both tricyanoferrocenes show irreversible oxidations at very high potentials (Eonset≈845 mV and 945 mV, respectively, vs FcH/FcH+). 相似文献
92.
Maite Nößler René Jäger David Hunger Dr. Marc Reimann Tobias Bens Dr. Nicolás I. Neuman Dr. Arijit Singha Hazari Prof. Dr. Martin Kaupp Prof. Dr. Joris van Slageren Prof. Dr. Biprajit Sarkar 《欧洲无机化学杂志》2023,26(19):e202300091
Due to their ability to form stable molecular complexes that have tailor-made properties, terpyridine ligands are of great interest in chemistry and material science. In this regard, we prepared two terpyridine ligands with two different fluorinated phenyl rings on the backbone. The corresponding CoII and FeII complexes were synthesized and characterized by single-crystal X-ray structural analysis, electrochemistry and temperature-dependent SQUID magnetometry. Single crystal X-ray diffraction analyses at 100 K of these complexes revealed Co−N and Fe−N bond lengths that are typical of low spin CoII and FeII centers. The metal centers are coordinated in an octahedral fashion and the fluorinated phenyl rings on the backbone are twisted out of the plane of the terpyridine unit. The complexes were investigated with cyclic voltammetry and UV/Vis-NIR spectroelectrochemistry. All complexes show a reversible oxidation and several reduction processes. Temperature dependent SQUID magnetometry revealed a gradual thermal SCO behavior in two of the complexes, while EPR spectroscopy provided further insights on the electronic structure of the metal complexes, as well as site of reduction. 相似文献
93.
Michael Zirbes Dr. Tobias Graßl Rieke Neuber Prof. Dr. Siegfried R. Waldvogel 《Angewandte Chemie (International ed. in English)》2023,62(14):e202219217
Lignin, the world's largest resource of renewable aromatics, with annually roughly 50 million tons of accruing technical lignin, mainly Kraft lignin, is highly underdeveloped regarding the production of monoaromatics. We demonstrate the oxidative depolymerization of Kraft lignin at 180 °C to produce vanillin 1 in yields up to 6.2 wt % and 92 % referred to the maximum yield gained from the quantification reaction utilizing nitrobenzene. Using peroxodicarbonate (C2O62−) as “green” oxidizer for the degradation, toxic and/or harmful reagents are prevented. Also, the formed waste can serve as makeup chemical in the pulping process. Na2C2O6 is synthesized in an ex-cell electrolysis of aqueous Na2CO3 at BDD anodes, achieving a yield of Na2C2O6 with 41 %. At least, the oxidation and degradation of Kraft lignin is analysis via UV/Vis and NMR spectroscopy. 相似文献
94.
Immanuel Plangger Dr. Tobias Pinkert Dr. Klaus Wurst Prof. Dr. Thomas Magauer 《Angewandte Chemie (International ed. in English)》2023,62(32):e202307719
We present a concise asymmetric total synthesis (5–8 steps) of nine sesquiterpenoid alkaloids featuring four different tetra-/pentacyclic scaffolds. To this end, a novel, bioinspired indole N-terminated cationic tricyclization has been developed, enabling the divergent synthesis of greenwayodendrines and polysin. Subtle variation of the C2-substituted indole cyclization precursor allowed switching between indole N- and C-termination. For the latter, a subsequent Witkop oxidation enabled conversion of the cyclopentene-fused indole into the eight-membered benzolactam to directly furnish the family of greenwaylactams. In addition, a diastereomeric C-termination product has been elaborated to provide access to polyveoline. 相似文献
95.
Mayara da Silva Santos Dr. Robert Medel Max Flach Olesya S. Ablyasova Martin Timm Prof. Dr. Bernd von Issendorff Dr. Konstantin Hirsch Dr. Vicente Zamudio-Bayer Prof. Dr. Sebastian Riedel Prof. Dr. J. Tobias Lau 《Chemphyschem》2023,24(22):e202300390
The tetraoxido ruthenium(VIII) radical cation, [RuO4]+, should be a strong oxidizing agent, but has been difficult to produce and investigate so far. In our X-ray absorption spectroscopy study, in combination with quantum-chemical calculations, we show that [RuO4]+, produced via oxidation of ruthenium cations by ozone in the gas phase, forms the oxygen-centered radical ground state. The oxygen-centered radical character of [RuO4]+ is identified by the chemical shift at the ruthenium M3 edge, indicative of ruthenium(VIII), and by the presence of a characteristic low-energy transition at the oxygen K edge, involving an oxygen-centered singly-occupied molecular orbital, which is suppressed when the oxygen-centered radical is quenched by hydrogenation of [RuO4]+ to the closed-shell [RuO4H]+ ion. Hydrogen-atom abstraction from methane is calculated to be only slightly less exothermic for [RuO4]+ than for [OsO4]+. 相似文献
96.
Beatrice Lansbergen Srija Tewari Ireneusz Tomczyk Maik Seemann Henning Louis Buchholz Mike Rippegarten Daniel Chamier Cieminski Dr. Fabio Juliá Prof. Dr. Tobias Ritter 《Angewandte Chemie (International ed. in English)》2023,62(52):e202313659
We report the first reductive vinylation of alkyl iodides. The reaction uses a vinyl thianthrenium salt, a palladium catalyst, and an alkyl zinc intermediate formed in situ to trap the LnPdII(vinyl) complex formed after oxidative addition before it undergoes undesired homocoupling to form butadiene. 相似文献
97.
98.
Substitution reactions between gaseous ions and neutral substrate molecules are of ongoing high interest. To investigate these processes in a qualitative and quantitative manner, we have constructed a device, with which a defined amount of a volatile substrate can be mixed with a defined amount of helium gas and added into a three‐dimensional quadrupole ion trap. From the known inner volume of the device, the known ratio nsubstrate:nHe of the mixture, and the determined absolute partial pressure of helium in the ion trap, we can derive the partial pressure of the substrate in the ion trap and, thus, convert the directly observable pseudo–first‐order rate constants of the substitution reactions into absolute bimolecular rate constants. We have tested the device by investigating a series of SN2 reactions of Br ? and CF3CH2O ? anions as well as ligand exchange reactions of ligated Na+ cations. As the obtained results suggest, the described device makes it possible to determine the bimolecular rate constants of substitution reactions as well as other ion‐molecule reactions with satisfactory accuracy and reliability. 相似文献
99.
Klaus Albert Markus Dachtler Tobias Glaser Heidi Hndel Tanja Lacker Gtz Schlotterbeck Sabine Strohschein Li-Hong Tseng Ulrich Braumann 《Journal of separation science》1999,22(3):135-143
The hyphenation of chromatographic separation techniques with NMR spectroscopy is one of the most powerful and time-saving methods for the separation and structural elucidation of unknown compounds and molecular compositions of mixtures. Most of the routinely used NMR flow-cells have detection volumes between 40–180 μL for conventional separations with analytical columns, and the newest designs employ detection volumes in the order of 200 nL for capillary separations. The low flow rates used in capillary chromatography permit the use of deuterated solvents. Unequivocal structural assignment of unknown chromatographic peaks is possible by two-dimensional stopped-flow capillary HPLC-NMR experiments. 相似文献
100.
Prof. Dr. Petra Schwille Prof. Dr. Joachim Spatz Prof. Dr. Katharina Landfester Prof. Dr. Eberhard Bodenschatz Prof. Dr. Stephan Herminghaus Prof. Dr. Victor Sourjik Dr. Tobias J. Erb Prof. Dr. Philippe Bastiaens Prof. Dr. Reinhard Lipowsky Prof. Dr. Anthony Hyman Prof. Dr. Peter Dabrock Dr. Jean‐Christophe Baret Dr. Tanja Vidakovic‐Koch Dr. Peter Bieling Dr. Rumiana Dimova Dr. Hannes Mutschler Dr. Tom Robinson Dr. T.‐Y. Dora Tang Dr. Seraphine Wegner Prof. Dr. Kai Sundmacher 《Angewandte Chemie (International ed. in English)》2018,57(41):13382-13392
A large German research consortium mainly within the Max Planck Society (“MaxSynBio”) was formed to investigate living systems from a fundamental perspective. The research program of MaxSynBio relies solely on the bottom‐up approach to synthetic biology. MaxSynBio focuses on the detailed analysis and understanding of essential processes of life through modular reconstitution in minimal synthetic systems. The ultimate goal is to construct a basic living unit entirely from non‐living components. The fundamental insights gained from the activities in MaxSynBio could eventually be utilized for establishing a new generation of biotechnological processes, which would be based on synthetic cell constructs that replace the natural cells currently used in conventional biotechnology. 相似文献