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41.
In this paper, various implementations of the analytic Hartree–Fock and hybrid density functional energy second derivatives are studied. An approximation-free four-centre implementation is presented, and its accuracy is rigorously analysed in terms of self-consistent field (SCF), coupled-perturbed SCF (CP-SCF) convergence and prescreening criteria. The CP-SCF residual norm convergence threshold turns out to be the most important of these. Final choices of convergence thresholds are made such that an accuracy of the vibrational frequencies of better than 5 cm?1 compared to the numerical noise-free results is obtained, even for the highly sensitive low frequencies (<100–200 cm?1). The effects of the choice of numerical grid for density functional exchange–correlation integrations are studied and various weight derivative schemes are analysed in detail. In the second step of the work, approximations are introduced in order to speed up the computation without compromising its accuracy. To this end, the accuracy and efficiency of the resolution of identity approximation for the Coulomb terms and the semi-numerical chain of spheres approximation to the exchange terms are carefully analysed. It is shown that the largest performance improvements are realised if either Hartree–Fock exchange is absent (pure density functionals) and otherwise, if the exchange terms in the CP-SCF step of the calculation are approximated by the COSX method in conjunction with a small integration grid. Default values for all the involved truncation parameters are suggested. For vancomycine (176 atoms and 3593 basis functions), the RIJCOSX Hessian calculation with the B3LYP functional and the def2-TZVP basis set takes ~3 days using 16 Intel® Xeon® 2.60GHz processors with the COSX algorithm having a net parallelisation scaling of 11.9 which is at least ~20 times faster than the calculation without the RIJCOSX approximation. 相似文献
42.
C.-W. Cho J. Ranke J. Arning J. Thöming U. Preiss C. Jungnickel 《SAR and QSAR in environmental research》2013,24(10):863-882
43.
Julia Grandke Lidia Oberleitner Ute Resch-Genger Leif-Alexander Garbe Rudolf J. Schneider 《Analytical and bioanalytical chemistry》2013,405(5):1601-1611
Enzyme immunoassays with optical detection are amongst the most widely used bioanalytical tools. We defined seven parameters for the quality assessment of immunoassays that were addressed in a systematic study of direct and indirect immunoassays, using the enzymes horseradish peroxidase (HRP) and alkaline phosphatase (AP), the chromogenic substrates 3,3′,5,5′-tetramethylbenzidine (TMB) and para-nitrophenyl phosphate, and the fluorescent substrates 3-(4-hydroxyphenyl)propionic acid and 4-methylumbelliferyl phosphate. The same monoclonal antibody against caffeine was used throughout the study. The four quality parameters regarding the standard curve were the test midpoint (sensitivity), the measurement range, the relative dynamic range of the signal, and the goodness of fit of the adjusted four-parameter logistic function. All HRP immunoassays showed a higher sensitivity compared to the AP assays. On the basis of all four criteria, it was established that the direct assay format is superior to the indirect format, the immunoassay using HRP TMB fulfilling all requirements best. In a second step, caffeine concentrations in 24 beverage and cosmetics samples were determined and three more quality parameters were assessed with this application. The direct HRP TMB assay showed one of the best intra- and inter-plate precisions and the best accuracy, defined by the correlation of results with those from the chosen reference method liquid chromatography tandem mass spectrometry (LC-MS/MS). Considering all criteria, HRP TMB seems to be the enzyme substrate system of choice preferably used in the direct assay format. Figure
Overview on the different enzyme immunoassay formats compared 相似文献
44.
Andreja Lesac H. Loc Nguyen Sanja Narančić Ute Baumeister Siegmar Diele Duncan W. Bruce 《Liquid crystals》2013,40(2):167-174
New, bent‐core mesogens are described in which the core of the molecule is a semiflexible, di(4‐aminocyclohexyl)methane spacer. The compounds show nematic, columnar nematic and columnar phases as shown by a combination of X‐ray diffraction and optical microscopy. The potential of these new mesogens as biaxial nematic candidates is considered. 相似文献
45.
Melanie Platzer Sandra Kiese Thomas Herfellner Ute Schweiggert-Weisz Oliver Miesbauer Peter Eisner 《Molecules (Basel, Switzerland)》2021,26(5)
Numerous assays were developed to measure the antioxidant activity, but each has limitations and the results obtained by different methods are not always comparable. Popular examples are the DPPH and ABTS assay. Our aim was to study similarities and differences of these two assay regarding the measured antioxidant potentials of 24 phenolic compounds using the same measurement and evaluation methods. This should allow conclusions to be drawn as to whether one of the assays is more suitable for measuring specific subgroups like phenolic acids, flavonols, flavanones, dihydrochalcones or flavanols. The assays showed common trends for the mean values of most of the subgroups. Some dihydrochalcones and flavanones did not react with the DPPH radical in contrast to the ABTS radical, leading to significant differences. Therefore, to determine the antioxidant potential of dihydrochalcone or flavanone-rich extracts, the ABTS assay should be preferred. We found that the results of the flavonoids in the DPPH assay were dependent on the Bors criteria, whereas the structure–activity relationship in the ABTS assay was not clear. For the phenolic acids, the results in the ABTS assay were only high for pyrogallol structures, while the DPPH assay was mainly determined by the number of OH groups. 相似文献
46.
Christoph M. Hendrich Sebastian Senn Lea Haas Marvin T. Hoffmann Dr. Ute Zschieschang Luca C. Greiner Dr. Frank Rominger Dr. Matthias Rudolph Dr. Hagen Klauk Prof. Dr. Andreas Dreuw Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(59):14778-14784
Herein, we describe a gold-catalyzed cascade cyclization of Boc-protected benzylamines bearing two tethered alkyne moieties in a domino reaction initiated by a 6-endo-dig cyclization. The reaction was screened intensively, and the scope was explored, resulting in nine new Boc-protected dihydrobenzo[c]phenanthridines with yields of up to 98 %; even a π-extension and two bidirectional approaches were successful. Furthermore, thermal cleavage of the Boc group and subsequent oxidation gave substituted benzo[c]phenanthridines in up to quantitative yields. Two bidirectional approaches under the optimized conditions were successful, and the resulting π-extended molecules were tested as organic semiconductors in organic thin-film transistors. 相似文献
47.
Gerardo Algara‐Siller Dr. Nikolai Severin Samantha Y. Chong Dr. Torbjörn Björkman Dr. Robert G. Palgrave Andrea Laybourn Prof. Dr. Markus Antonietti Prof. Yaroslav Z. Khimyak Dr. Arkady V. Krasheninnikov Prof. Dr. Jürgen P. Rabe Prof. Dr. Ute Kaiser Prof. Andrew I. Cooper Prof. Dr. Arne Thomas Dr. Michael J. Bojdys 《Angewandte Chemie (International ed. in English)》2014,53(29)
48.
Tetracyanoquinodimethane Reduction by Complexed Guanidinyl‐Functionalized Aromatic Compounds
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Hendrik Herrmann Alexandra Ziesak Ute Wild Simone Leingang David Schrempp Norbert Wagner Prof. Dr. Johannes Beck Dr. Elisabeth Kaifer Prof. Dr. Hubert Wadepohl Prof. Dr. Hans‐Jörg Himmel 《Chemphyschem》2014,15(2):351-365
In this work, we report on the reduction of tetracyanoquinodimethane (TCNQ) with dicationic complexes of guanidinyl‐functionalized aromatic (GFA) electron donors. In contrast to reduction with free GFAs, milder reduction conditions were achieved, and this led to semiconducting materials with extended TCNQ π stacking. The charge on the TCNQ units was estimated from the structural data obtained by single‐crystal X‐ray diffraction analysis and from IR spectroscopic data. The electrical conductivity was studied and the activation energy of the semiconducting materials was estimated from the temperature dependence of the conductivity. 相似文献
49.
Sabine Apelt Susanne Höhne Petra Uhlmann Ute Bergmann 《Surface and interface analysis : SIA》2020,52(12):1150-1155
Active deicing of technical surfaces, such as for wind turbines and heat exchangers, currently requires the usage of heat or chemicals. Passive coating strategies that postpone the freezing of covering water would be beneficial in order to save costs and energy. One hypothesis is that pyroelectric active materials can achieve this because of the surface charges generated on these materials when they are subject to a temperature change. High-quality poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) thin films with a high crystallinity, prefererd edge-on orientation, low surface roughness, and comprised of the β-analogous ferroelectric phase were deposited by spin-coating. Freezing experiments with a cooling rate of 1 K min−1 were made on P(VDF-TrFE) coatings in order to separate the effect of different parameters such as the poling direction, film thickness, used solvent, deposition process, underlying substrate, and annealing temperature on the achievable supercooling. The topography and the underlying substrate significantly changed the distribution of freezing temperatures of water droplets in contact with these thin films. In contrast, no significant effect of the thickness, morphology, or pyroelectric effect of the as-prepared domain-state on the freezing temperatures was found. 相似文献
50.
Zhenping Wang Qirong Yao Christof Neumann Felix Brrnert Julian Renner Ute Kaiser Andrey Turchanin Harold J. W. Zandvliet Siegfried Eigler 《Angewandte Chemie (International ed. in English)》2020,59(32):13657-13662
The thermal decomposition of graphene oxide (GO) is a complex process at the atomic level and not fully understood. Here, a subclass of GO, oxo‐functionalized graphene (oxo‐G), was used to study its thermal disproportionation. We present the impact of annealing on the electronic properties of a monolayer oxo‐G flake and correlated the chemical composition and topography corrugation by two‐probe transport measurements, XPS, TEM, FTIR and STM. Surprisingly, we found that oxo‐G, processed at 300 °C, displays C?C sp3‐patches and possibly C?O?C bonds, next to graphene domains and holes. It is striking that those C?O?C/C?C sp3‐separated sp2‐patches a few nanometers in diameter possess semiconducting properties with a band gap of about 0.4 eV. We propose that sp3‐patches confine conjugated sp2‐C atoms, which leads to the local semiconductor properties. Accordingly, graphene with sp3‐C in double layer areas is a potential class of semiconductors and a potential target for future chemical modifications. 相似文献