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51.
The experimental electron density of a chromone derivative was determined from a multipole refinement of 100 K X-ray synchrotron
data and complemented by theoretical calculations with experimental and optimized geometry. Atomic and topological properties
were obtained using the Quantum Theory of Atoms in Molecules approach. The examination of topological parameters unambiguously
showed π-delocalization within the H-bonded ring. The application of source function analysis confirmed the intramolecular
N–H···O hydrogen bond to be a resonance-assisted hydrogen bond. The topological study confirmed the covalent nature of N–H···O
interaction and the electrostatic nature of weak C–H···O interactions. 相似文献
52.
Mechanistic Studies on the Organocatalytic α‐Chlorination of Aldehydes: The Role and Nature of Off‐Cycle Intermediates 下载免费PDF全文
M. Sc. Sebastian Ponath M. Sc. Martina Menger M. Sc. Lydia Grothues Manuela Weber Prof. Dr. Dieter Lentz Prof. Dr. Carsten Strohmann Prof. Dr. Mathias Christmann 《Angewandte Chemie (International ed. in English)》2018,57(36):11683-11687
Herein we report the isolation and characterization of aminal intermediates in the organocatalytic α‐chlorination of aldehydes. These species are stable covalent ternary adducts of the substrate, the catalyst and the chlorinating reagent. NMR‐assisted kinetic studies and isotopic labeling experiments with the isolated intermediate did not support its involvement in downstream stereoselective processes as proposed by Blackmond. By tuning the reactivity of the chlorinating reagent, we were able to suppress the accumulation of rate‐limiting off‐cycle intermediates. As a result, an efficient and highly enantioselective catalytic system with a broad functional group tolerance was developed. 相似文献
53.
Two‐Color Valence‐to‐Core X‐ray Emission Spectroscopy Tracks Cofactor Protonation State in a Class I Ribonucleotide Reductase 下载免费PDF全文
Ryan J. Martinie Dr. Elizabeth J. Blaesi Prof. Dr. J. Martin Bollinger Jr. Prof. Dr. Carsten Krebs Dr. Kenneth D. Finkelstein Dr. Christopher J. Pollock 《Angewandte Chemie (International ed. in English)》2018,57(39):12754-12758
Proton transfer reactions are of central importance to a wide variety of biochemical processes, though determining proton location and monitoring proton transfers in biological systems is often extremely challenging. Herein, we use two‐color valence‐to‐core X‐ray emission spectroscopy (VtC XES) to identify protonation events across three oxidation states of the O2‐activating, radical‐initiating manganese–iron heterodinuclear cofactor in a class I‐c ribonucleotide reductase. This is the first application of VtC XES to an enzyme intermediate and the first simultaneous measurement of two‐color VtC spectra. In contrast to more conventional methods of assessing protonation state, VtC XES is a more direct probe applicable to a wide range of metalloenzyme systems. These data, coupled to insight provided by DFT calculations, allow the inorganic cores of the MnIVFeIV and MnIVFeIII states of the enzyme to be assigned as MnIV(μ‐O)2FeIV and MnIV(μ‐O)(μ‐OH)FeIII, respectively. 相似文献
54.
Hao Yu Dr. Zhen Li Prof. Dr. Carsten Bolm 《Angewandte Chemie (International ed. in English)》2018,57(1):324-327
Free NH‐sulfoximines were directly prepared from sulfoxides through iron catalysis by applying a readily available, shelf‐stable hydroxylamine triflic acid salt. No additional oxidant is needed, and the substrate scope is broad, including a range of heterocyclic compounds. 相似文献
55.
56.
Bolm C Hildebrand JP Muñiz K Hermanns N 《Angewandte Chemie (International ed. in English)》2001,40(18):3284-3308
Addition and substitution reactions with carbon nucleophiles are fundamental processes in organic synthesis, and the development of general catalytic asymmetric variants thereof is still a major challenge today. In contrast to enantioselective alkyl transfer reactions, the corresponding arylations have not yet reached a high level of maturity. The existing protocols are either of no general applicability or are limited in terms of selectivity. This article summarizes established routes for catalytic asymmetric aryl transfer together with the latest developments in this area. The scope and limitations of this reaction are discussed. 相似文献
57.
Spanka C Wentworth P Janda KD 《Combinatorial chemistry & high throughput screening》2002,5(3):233-240
Soluble polymers have emerged as viable alternatives to resin supports across the broad spectrum of high-throughput organic chemistry. As the application of these supports become more widespread, issues such as broad-spectrum solubility and loading are becoming limiting factors and therefore new polymers are required to overcome such limitations. This article details the approach made within our group to new soluble polymer supports and specifically focuses on parallel libraries of block copolymers, de novo poly(styrene-co-chloromethylstyrene), PEG- stealth stars, and substituted poly(norbornylene)s. 相似文献
58.
Bolm C Palazzi C Franciò G Leitner W 《Chemical communications (Cambridge, England)》2002,(15):1588-1589
The aerobic Baeyer-Villiger oxidation of a wide range of ketones, both cyclic and acyclic to the corresponding esters or lactones can be efficiently carried out in compressed carbon dioxide in the presence of an aldehyde as co-reductant. 相似文献
59.
Carsten Jaeschke Marta Padilla Johannes Glckler Inese Polaka Martins Leja Viktors Veliks Jan Mitrovics Marcis Leja Boris Mizaikoff 《Molecules (Basel, Switzerland)》2021,26(12)
Exhaled breath analysis for early disease detection may provide a convenient method for painless and non-invasive diagnosis. In this work, a novel, compact and easy-to-use breath analyzer platform with a modular sensing chamber and direct breath sampling unit is presented. The developed analyzer system comprises a compact, low volume, temperature-controlled sensing chamber in three modules that can host any type of resistive gas sensor arrays. Furthermore, in this study three modular breath analyzers are explicitly tested for reproducibility in a real-life breath analysis experiment with several calibration transfer (CT) techniques using transfer samples from the experiment. The experiment consists of classifying breath samples from 15 subjects before and after eating a specific meal using three instruments. We investigate the possibility to transfer calibration models across instruments using transfer samples from the experiment under study, since representative samples of human breath at some conditions are difficult to simulate in a laboratory. For example, exhaled breath from subjects suffering from a disease for which the biomarkers are mostly unknown. Results show that many transfer samples of all the classes under study (in our case meal/no meal) are needed, although some CT methods present reasonably good results with only one class. 相似文献
60.
Prof. Dr. René T. Boeré Christoph Bolli Prof. Dr. Maik Finze Dr. Alexander Himmelspach Prof. Dr. Carsten Knapp Dr. Tracey L. Roemmele 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(5):1784-1795
The range of electrochemical stability of a series of weakly coordinating halogenated (Hal=F, Cl, Br, I) 1‐carba‐closo‐dodecaborate anions, [1‐R‐CB11X5Y6]? (R=H, Me; X=H, Hal, Me; Y=Hal), has been established by using quantum chemical calculations and electrochemical methods. The structures of the neutral and dianionic radicals, as well as the anions, have been optimized by using DFT calculations at the PBE0/def2‐TZVPP level. The calculated structures are in good agreement with existing experimental data and with previous calculations. Their gas‐phase ionization energies and electron affinities were calculated based on their optimized structures and were compared with experimental (cyclic and square‐wave) voltammetry data. Electrochemical oxidation was performed in MeCN at room temperature and in liquid sulfur dioxide at lower temperatures. All of the anions show a very high resistance to the onset of oxidation (2.15–2.85 V versus Fc0/+), with only a minor dependence of the oxidation potential on the different halogen substituents. In contrast, the reduction potentials in MeCN are strongly substituent dependent (?1.93 to ?3.32 V versus Fc0/+). The calculated ionization energies and electron affinities correlate well with the experimental redox potentials, which provide important verification of the thermodynamic validity of the mostly irreversible redox processes that are observed for this series. The large electrochemical windows that are afforded by these anions indicate their suitability for electrochemical applications, for example, as supporting electrolytes. 相似文献