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91.
Achim Füngerlings Adarsh Koul Maik Dreyer Anna Rabe Dulce M. Morales Wolfgang Schuhmann Malte Behrens Rossitza Pentcheva 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):17145-17158
In a combined experimental and theoretical study we assess the role of Co incorporation on the OER activity of LaCoxFe1−xO3. Phase pure perovskites were synthesized up to in 0.025/0.050 steps. HAADF STEM and EDX analysis points towards FeO2-terminated (001)-facets in LaFeO3, in accordance with the stability diagram obtained from density functional theory calculations with a Hubbard U term (DFT+U). Linear sweep voltammetry conducted in a rotating disk electrode setup shows a reduction of the OER overpotential and a nonmonotonic trend with x, with double layer capacitance measurements indicating an intrinsic nature of activity. This is supported by DFT+U results that show reduced overpotentials for both Fe and Co reaction sites with the latter reaching values of 0.32–0.40 V, ∼0.3 V lower than for Fe. This correlates with a stronger reduction of the binding energy difference of the *O and *OH intermediates towards an optimum value of 1.6 eV for , the OH deprotonation being the potential limiting step in most cases. Significant variations of the magnetic moments of both surface and subsurface Co and Fe during OER demonstrate that the beneficial effect is a result of a concerted action involving many surrounding ions, which extends the concept of the active site. 相似文献
92.
Maik Dreyer Dr. Daniel Cruz Dr. Ulrich Hagemann Dr. Patrick Zeller Dr. Markus Heidelmann Dr. Soma Salamon Dr. Joachim Landers Anna Rabe Dr. Klaus Friedel Ortega Dr. Sharif Najafishirtari Prof. Dr. Heiko Wende Prof. Dr. Nils Hartmann Dr. Axel Knop-Gericke Prof. Dr. Robert Schlögl Prof. Dr. Malte Behrens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):17127-17144
Perovskites are interesting oxidation catalysts due to their chemical flexibility enabling the tuning of several properties. In this work, we synthesized LaFe1−xCoxO3 catalysts by co-precipitation and thermal decomposition, characterized them thoroughly and studied their 2-propanol oxidation activity under dry and wet conditions to bridge the knowledge gap between gas and liquid phase reactions. Transient tests showed a highly active, unstable low-temperature (LT) reaction channel in conversion profiles and a stable, less-active high-temperature (HT) channel. Cobalt incorporation had a positive effect on the activity. The effect of water was negative on the LT channel, whereas the HT channel activity was boosted for x>0.15. The boost may originate from a slower deactivation rate of the Co3+ sites under wet conditions and a higher amount of hydroxide species on the surface comparing wet to dry feeds. Water addition resulted in a slower deactivation for Co-rich catalysts and higher activity in the HT channel state. 相似文献
93.
Garima Ghale Adrienne G. Lanctt Hannah T. Kreissl Maik H. Jacob Helge Weingart Mathias Winterhalter Werner M. Nau 《Angewandte Chemie (International ed. in English)》2014,53(10):2762-2765
The efficacy of drugs and biomolecules relies on their ability to pass through the bilayer. The development of methods to directly and sensitively monitor these membrane transport processes has remained an experimental challenge. A macrocyclic host (p‐sulfonatocalix[4]arene or cucurbit[7]uril) and a fluorescent dye (lucigenin or berberine) are encapsulated as a chemosensing ensemble inside liposomes, which allows for a direct, real‐time fluorescence monitoring of the passage of unlabeled bioorganic analytes. This in vitro assay is transferable to different channel proteins and analytes, has potential for fluorescence‐based screening, e.g., of channel modulators, and yields the absolute kinetics of translocation. Using this new biophysical method, we observed for the first time direct rapid translocation of protamine, an antimicrobial peptide, through the bacterial transmembrane protein OmpF. 相似文献
94.
Ludwig Zapf Sven Peters Dr. Rüdiger Bertermann Prof. Dr. Udo Radius Prof. Dr. Maik Finze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(39):e202200275
The 1-methyl-3-(tricyanoborane)imidazolin-2-ylidenate anion ( 2 ) was obtained in high yield by deprotonation of the B(CN)3-methylimidazole adduct 1 . Regarding charge and stereo-electronic properties, anion 2 closes the gap between well-known neutral NHCs and the ditopic dianionic NHC, the 1,3-bis(tricyanoborane)imidazolin-2-ylidenate dianion ( IIb ). The influence of the number of N-bonded tricyanoborane moieties on the σ-donating and π-accepting properties of NHCs was assessed by quantum chemical calculations and verified by experimental data on 2 , IIb , and 1,3-dimethylimidazolin-2-ylidene (IMe, IIa ). Therefore NHC 2 , which acts as a ditopic ligand via the carbene center and the cyano groups, was reacted with alkyl iodides, selenium, and [Ni(CO)4] yielding alkylated imidazoles 3 and 4 , the anionic selenium adduct 5 , and the anionic nickel tricarbonyl complex 8 , respectively. The results of this study prove that charge, number of coordination sites, buried volume (%Vbur) and σ-donor and π-acceptor abilities of NHCs can be effectively fine-tuned via the number of tricyanoborane substituents. 相似文献
95.
Roy A. M. van Beekveld Maik G. N. Derks Raj Kumar Leanna Smid Thorben Maass Dr. João Medeiros-Silva Dr. Eefjan Breukink Dr. Markus Weingarth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202202472
Specific interactions with phospholipids are often critical for the function of proteins or drugs, but studying these interactions at high resolution remains difficult, especially in complex membranes that mimic biological conditions. In principle, molecular interactions with phospholipids could be directly probed by solid-state NMR (ssNMR). However, due to the challenge to detect specific lipids in mixed liposomes and limited spectral sensitivity, ssNMR studies of specific lipids in complex membranes are scarce. Here, by using purified biological 13C,15N-labeled phospholipids, we show that we can selectively detect traces of specific lipids in complex membranes. In combination with 1H-detected ssNMR, we show that our approach provides unprecedented high-resolution insights into the mechanisms of drugs that target specific lipids. This broadly applicable approach opens new opportunities for the molecular characterization of specific lipid interactions with proteins or drugs in complex fluid membranes. 相似文献
96.
Andreas Czulucki Dr. Gudrun Auffermann Dr. Michal Bednarski Łukasz Bochenek Maik Böhme Tomasz Cichorek Dr. Rainer Niewa Prof. Dr. Niels Oeschler Dr. Marcus Schmidt Dr. Frank Steglich Prof. Dr. Rüdiger Kniep Prof. Dr. 《Chemphyschem》2010,11(12):2639-2644
Single crystals of HfAs1.7Se0.2 are grown by chemical transport reaction and their chemical composition characterized in detail by various analytical methods. Chemical analyses and crystal structure investigations by single‐crystal X‐ray diffraction as well as powder diffraction with synchrotron radiation reveal a tetragonal PbFCl structure type with strong disorder caused by a significant arsenic deficiency (As0.9) on the 2a site and mixed occupancy of the 2c site (As0.8Se0.2). HfAs1.7Se0.2 is a diamagnetic metal which transforms into a superconducting state at Tc=0.52 K. Similar to other PbFCl‐type arsenide selenides, the title compound displays a magnetic‐field‐independent ?AT1/2 term in the low‐temperature electrical resistivity. This unusual term presumably originates from the electron scattering of structural two‐level systems. According to the experimental results, HfAs1.7Se0.2 appears to be a rare example of a nonmagnetic Kondo material. 相似文献
97.
Noya Loew Ulla Wollenberger Frieder W. Scheller Martin Katterle 《Bioelectrochemistry (Amsterdam, Netherlands)》2009,76(1-2):28
In this contribution the substitution of the central protoporphyrin IX iron complex of horseradish peroxidase by the respective osmium porphyrin complex is described. The direct electrochemical reduction of the Os containing horseradish peroxidase (OsHRP) was achieved at ITO and modified glassy carbon electrodes and in combination with spectroscopy revealed the three redox couples OsIIIHRP/OsIVHRP, OsIVHRP/OsVHRP and OsVHRP/OsVIHRP. The midpoint potentials differ dependent on the electrode material used with E1/2 (OsIII/IV) of − 0.4 V (ITO) and − 0.25 V (GC), E1/2 (OsIV/V) of − 0.16 V (ITO) and + 0.10 V (GC), and E1/2 (OsV/VI)of + 0.18 V (ITO), respectively. Moreover, with immobilised OsHRP the direct electrocatalytic reduction of hydrogen peroxide and tert-butyl hydroperoxide was observed. In comparison to electrodes modified with native HRP the sensitivity of the OsHRP-electrode for tert-butyl hydroperoxide is higher. 相似文献
98.
99.
Considerations on antibody-phage display methodology 总被引:2,自引:0,他引:2
For almost 15 years phage display is being used for the selection of specific antigen-binders from artificial libraries of single chain antibodies. Filamentous phages have been developed in a way to express foreign proteins on the surface and at the same time carrying the genetic information of the surface expressed molecule within the phage capsid. This property guarantees the coupling of phenotype and genotype during phage amplification and affinity selection. The possibility to generate large antibody libraries and the simplified antibody-backbone of a single chain antibody has made antibody-phage display to a powerful tool for the development of new therapeutics against various human diseases. In this review we discuss the general principles and latest developments and applications in antibody phage display technology. 相似文献
100.