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981.
Viktor Reshetnikov Steffen Daum Dr. Christina Janko Weronika Karawacka Dr. Rainer Tietze Prof. Dr. Christoph Alexiou Dr. Solomiya Paryzhak Dr. Tetiana Dumych Prof. Dr. Rostyslav Bilyy Dr. Philipp Tripal Dr. Benjamin Schmid Dr. Ralf Palmisano Prof. Dr. Andriy Mokhir 《Angewandte Chemie (International ed. in English)》2018,57(37):11943-11946
Mitochondrial membrane potential is more negative in cancer cells than in normal cells, allowing cancer targeting by delocalized lipophilic cations (DLCs). However, as the difference is rather small, these drugs affect also normal cells. Now a concept of pro‐DLCs is proposed based on an N‐alkylaminoferrocene structure. These prodrugs are activated by the reaction with reactive oxygen species (ROS) forming ferrocenium‐based DLCs. Since ROS are overproduced in cancer, the high‐efficiency cancer‐cell‐specific targeting of mitochondria could be achieved as demonstrated by fluorescence microscopy in combination with two fluorogenic pro‐DLCs in vitro and in vivo. We prepared a conjugate of another pro‐DLC with a clinically approved drug carboplatin and confirmed that its accumulation in mitochondria was higher than that of the free drug. This was reflected in the substantially higher anticancer effect of the conjugate. 相似文献
982.
Three‐Dimensional Branched and Faceted Gold–Ruthenium Nanoparticles: Using Nanostructure to Improve Stability in Oxygen Evolution Electrocatalysis 下载免费PDF全文
Dr. Lucy Gloag Dr. Tania M. Benedetti Dr. Soshan Cheong Dr. Yibing Li Dr. Xuan‐Hao Chan Prof. Lise‐Marie Lacroix Prof. Shery L. Y. Chang Dr. Raul Arenal Dr. Ileana Florea Dr. Hector Barron Dr. Amanda S. Barnard Dr. Anna M. Henning Prof. Chuan Zhao Prof. Wolfgang Schuhmann Prof. J. Justin Gooding Prof. Richard D. Tilley 《Angewandte Chemie (International ed. in English)》2018,57(32):10241-10245
Achieving stability with highly active Ru nanoparticles for electrocatalysis is a major challenge for the oxygen evolution reaction. As improved stability of Ru catalysts has been shown for bulk surfaces with low‐index facets, there is an opportunity to incorporate these stable facets into Ru nanoparticles. Now, a new solution synthesis is presented in which hexagonal close‐packed structured Ru is grown on Au to form nanoparticles with 3D branches. Exposing low‐index facets on these 3D branches creates stable reaction kinetics to achieve high activity and the highest stability observed for Ru nanoparticle oxygen evolution reaction catalysts. These design principles provide a synthetic strategy to achieve stable and active electrocatalysts. 相似文献
983.
Can a Ketone Be More Reactive than an Aldehyde? Catalytic Asymmetric Synthesis of Substituted Tetrahydrofurans 下载免费PDF全文
Dr. Sunggi Lee Dr. Han Yong Bae Prof. Dr. Benjamin List 《Angewandte Chemie (International ed. in English)》2018,57(37):12162-12166
O‐heterocycles bearing tetrasubstituted stereogenic centers are prepared via catalytic chemo‐ and enantioselective nucleophilic additions to ketoaldehydes, in which the ketone reacts preferentially over the aldehyde. Five‐ and six‐membered rings with both aromatic and aliphatic substituents, as well as an alkynyl substituent, are obtained. Moreover, 2,2,5‐trisubstituted and 2,2,5,5‐tetrasubstituted tetrahydrofurans are synthesized with excellent stereoselectivities. Additionally, the synthetic utility of the described method is demonstrated with a three‐step synthesis of the side chain of anhydroharringtonine. 相似文献
984.
Controlling Proton and Electron Transfer Rates to Enhance the Activity of an Oxygen Reduction Electrocatalyst 下载免费PDF全文
Rajendra P. Gautam Yi Teng Lee Gabriel L. Herman Cynthia M. Moreno Prof. Dr. Edmund C. M. Tse Prof. Dr. Christopher J. Barile 《Angewandte Chemie (International ed. in English)》2018,57(41):13480-13483
An electrochemical approach is developed that allows for the control of both proton and electron transfer rates in the O2 reduction reaction (ORR). A dinuclear Cu ORR catalyst was prepared that can be covalently attached to thiol‐based self‐assembled monolayers (SAMs) on Au electrodes using azide–alkyne click chemistry. Using this architecture, the electron transfer rate to the catalyst is modulated by changing the length of the SAM, and the proton transfer rate to the catalyst is controlled with an appended lipid membrane modified with proton carriers. By tuning the relative rates of proton and electron transfer, the current density of the lipid‐covered catalyst is enhanced without altering its core molecular structure. This electrochemical platform will help identify optimal thermodynamic and kinetic parameters for ORR catalysts and catalysts of other reactions that involve the transfer of both protons and electrons. 相似文献
985.
Dr. Werner Fudickar Prof. Dr. Torsten Linker 《Angewandte Chemie (International ed. in English)》2018,57(39):12971-12975
The generation of reactive singlet oxygen under mild conditions is of current interest in chemistry, biology, and medicine. We were able to release oxygen from dipyridylanthracene endoperoxides (EPOs) by using a simple chemical trigger at low temperature. Protonation and methylation of such EPOs strongly accelerated these reactions. Furthermore, the methyl pyridinium derivatives are water soluble and therefore serve as oxygen carriers in aqueous media. Methylation of the EPO of the ortho isomer affords the parent form directly without increasing the temperature under very mild conditions. This exceptional behavior is ascribed to the close contact between the nitrogen atom and the peroxo group. Singlet oxygen is released upon this reaction, and can be used to oxygenate an acceptor such as tetramethylethylene in the dark with no heating. Thus, a new chemical source of singlet oxygen has been found, which is triggered by a simple stimulus. 相似文献
986.
Superoxide Stabilization and a Universal KO2 Growth Mechanism in Potassium–Oxygen Batteries 下载免费PDF全文
Wanwan Wang Dr. Nien‐Chu Lai Zhuojian Liang Yu Wang Prof. Yi‐Chun Lu 《Angewandte Chemie (International ed. in English)》2018,57(18):5042-5046
Rechargeable potassium–oxygen (K‐O2) batteries promise to provide higher round‐trip efficiency and cycle life than other alkali–oxygen batteries with satisfactory gravimetric energy density (935 Wh kg?1). Exploiting a strong electron‐donating solvent, for example, dimethyl sulfoxide (DMSO) strongly stabilizes the discharge product (KO2), resulting in significant improvement in electrode kinetics and chemical/electrochemical reversibility. The first DMSO‐based K‐O2 battery demonstrates a much higher energy efficiency and stability than the glyme‐based electrolyte. A universal KO2 growth model is developed and it is demonstrated that the ideal solvent for K‐O2 batteries should strongly stabilize superoxide (strong donor ability) to obtain high electrode kinetics and reversibility while providing fast oxygen diffusion to achieve high discharge capacity. This work elucidates key electrolyte properties that control the efficiency and reversibility of K‐O2 batteries. 相似文献
987.
Nika Mahne Sara E. Renfrew Prof. Bryan D. McCloskey Dr. Stefan A. Freunberger 《Angewandte Chemie (International ed. in English)》2018,57(19):5529-5533
Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal‐O2 batteries, and are believed to form and decompose reversibly in metal‐O2/CO2 cells. In these cathodes, Li2CO3 decomposes to CO2 when exposed to potentials above 3.8 V vs. Li/Li+. However, O2 evolution, as would be expected according to the decomposition reaction 2 Li2CO3→4 Li++4 e?+2 CO2+O2, is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen (1O2) forms upon oxidizing Li2CO3 in an aprotic electrolyte and therefore does not evolve as O2. These results have substantial implications for the long‐term cyclability of batteries: they underpin the importance of avoiding 1O2 in metal‐O2 batteries, question the possibility of a reversible metal‐O2/CO2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition‐metal cathodes with residual Li2CO3. 相似文献
988.
Introducing Fe2+ into Nickel–Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity 下载免费PDF全文
Zhao Cai Daojin Zhou Maoyu Wang Seong‐Min Bak Yueshen Wu Zishan Wu Yang Tian Xuya Xiong Dr. Yaping Li Dr. Wen Liu Prof. Samira Siahrostami Dr. Yun Kuang Prof. Xiao‐Qing Yang Dr. Haohong Duan Prof. Zhenxing Feng Prof. Hailiang Wang Prof. Xiaoming Sun 《Angewandte Chemie (International ed. in English)》2018,57(30):9392-9396
Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Herein we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe‐LDHs) by partially substituting Ni2+ with Fe2+ to introduce Fe‐O‐Fe moieties. These Fe2+‐containing NiFe‐LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA cm?2, which is among the best OER catalytic performance to date. In‐situ X‐ray absorption, Raman, and electrochemical analysis jointly reveal that the Fe‐O‐Fe motifs could stabilize high‐valent metal sites at low overpotentials, thereby enhancing the OER activity. These results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts. 相似文献
989.
Interfacial Nanoprecipitation toward Stable and Responsive Microbubbles and Their Use as a Resuscitative Fluid 下载免费PDF全文
Dr. Yifeng Peng Dr. Raymond P. Seekell Alexis R. Cole Jemima R. Lamothe Andrew T. Lock Sarah van den Bosch Xiaoqi Tang Prof. Dr. John N. Kheir Prof. Dr. Brian D. Polizzotti 《Angewandte Chemie (International ed. in English)》2018,57(5):1271-1276
A new approach has been developed to prepare stable microbubbles (MBs) by interfacial nanoprecipitation of bioabsorbable polymers at air/liquid interfaces. This facile method offers robust control over the morphology and chemophysical properties of MBs by simple chemical modifications. This approach is amenable to large‐scale manufacturing, and is useful to develop functional MBs for advanced biomedical applications. To demonstrate this, a MB‐based intravenous oxygen carrier was created that undergoes pH‐triggered self‐elimination. Intravenous injection of previous MBs increased the risk of pulmonary vascular obstruction. However, we show, for the first time, that our current design is superior, as they 1) yielded no evidence of acute risks in rodents, and 2) improved the survival in a disease model of asphyxial cardiac arrest (from 0 to 100 %), a condition that affects more than 100 000 in‐hospital patients, and carries a mortality of about 90 %. 相似文献
990.
Visualization of Heterogeneous Oxygen Storage Behavior in Platinum‐Supported Cerium‐Zirconium Oxide Three‐Way Catalyst Particles by Hard X‐ray Spectro‐Ptychography 下载免费PDF全文
Makoto Hirose Dr. Nozomu Ishiguro Kei Shimomura Dr. Nicolas Burdet Dr. Hirosuke Matsui Prof. Dr. Mizuki Tada Prof. Dr. Yukio Takahashi 《Angewandte Chemie (International ed. in English)》2018,57(6):1474-1479
The cerium density and valence in micrometer‐size platinum‐supported cerium–zirconium oxide Pt/Ce2Zr2Ox (x=7–8) three‐way catalyst particles were successfully mapped by hard X‐ray spectro‐ptychography (ptychographic‐X‐ray absorption fine structure, XAFS). The analysis of correlation between the Ce density and valence in ptychographic‐XAFS images suggested the existence of several oxidation behaviors in the oxygen storage process in the Ce2Zr2Ox particles. Ptychographic‐XAFS will open up the nanoscale chemical imaging and structural analysis of heterogeneous catalysts. 相似文献