全文获取类型
收费全文 | 1613篇 |
免费 | 134篇 |
国内免费 | 1篇 |
专业分类
化学 | 1376篇 |
晶体学 | 6篇 |
力学 | 27篇 |
数学 | 79篇 |
物理学 | 260篇 |
出版年
2023年 | 23篇 |
2022年 | 22篇 |
2021年 | 33篇 |
2020年 | 54篇 |
2019年 | 60篇 |
2018年 | 36篇 |
2017年 | 13篇 |
2016年 | 71篇 |
2015年 | 79篇 |
2014年 | 73篇 |
2013年 | 96篇 |
2012年 | 123篇 |
2011年 | 123篇 |
2010年 | 71篇 |
2009年 | 52篇 |
2008年 | 81篇 |
2007年 | 72篇 |
2006年 | 87篇 |
2005年 | 55篇 |
2004年 | 33篇 |
2003年 | 30篇 |
2002年 | 39篇 |
2001年 | 20篇 |
2000年 | 36篇 |
1999年 | 29篇 |
1998年 | 17篇 |
1997年 | 19篇 |
1996年 | 17篇 |
1995年 | 31篇 |
1994年 | 11篇 |
1993年 | 13篇 |
1992年 | 14篇 |
1991年 | 14篇 |
1990年 | 21篇 |
1989年 | 12篇 |
1988年 | 13篇 |
1987年 | 7篇 |
1986年 | 7篇 |
1985年 | 6篇 |
1984年 | 6篇 |
1982年 | 11篇 |
1981年 | 4篇 |
1979年 | 4篇 |
1978年 | 8篇 |
1977年 | 7篇 |
1975年 | 5篇 |
1973年 | 5篇 |
1972年 | 4篇 |
1970年 | 4篇 |
1951年 | 5篇 |
排序方式: 共有1748条查询结果,搜索用时 15 毫秒
151.
Fragment‐Based De Novo Design Reveals a Small‐Molecule Inhibitor of Helicobacter Pylori HtrA 下载免费PDF全文
Thomas P. Schmidt Dr. Manja Böhm Katharina Stutz Daniel Reker Dr. Bernhard Pfeiffer Prof. Dr. Karl‐Heinz Altmann Prof. Dr. Steffen Backert Prof. Dr. Silja Wessler Prof. Dr. Gisbert Schneider 《Angewandte Chemie (International ed. in English)》2015,54(35):10244-10248
Sustained identification of innovative chemical entities is key for the success of chemical biology and drug discovery. We report the fragment‐based, computer‐assisted de novo design of a small molecule inhibiting Helicobacter pylori HtrA protease. Molecular binding of the designed compound to HtrA was confirmed through biophysical methods, supporting its functional activity in vitro. Hit expansion led to the identification of the currently best‐in‐class HtrA inhibitor. The results obtained reinforce the validity of ligand‐based de novo design and binding‐kinetics‐guided optimization for the efficient discovery of pioneering lead structures and prototyping drug‐like chemical probes with tailored bioactivity. 相似文献
152.
Heterophase Photocatalysts from Water‐Soluble Conjugated Polyelectrolytes: An Example of Self‐Initiation under Visible Light 下载免费PDF全文
Saman Ghasimi Dr. Simon Prescher Zi Jun Wang Prof. Katharina Landfester Dr. Jiayin Yuan Dr. Kai A. I. Zhang 《Angewandte Chemie (International ed. in English)》2015,54(48):14549-14553
We herein report a new design route to stable, heterophase photocatalysts, which function as highly dispersible conjugated polymer nanoparticles and porous monoliths under visible light in aqueous medium. They were constructed by attachment of the ionic‐liquid species 1‐alkyl‐3‐vinylimidazolium bromide onto the side chains of a photoactive polymer. The structure configuration allows not only photocatalysis in aqueous environment but also a unique self‐initiation radical cross‐linking process to transform the water‐soluble photoactive polymer into a heterophase system, either as nanoparticles or a porous monolith. High photocatalytic activity and reusability of the heterophase system were demonstrated in the degradation of organic dyes and reduction of CrVI into CrIII in water under visible‐light irradiation. 相似文献
153.
Ultraviolet Absorption Induces Hydrogen‐Atom Transfer in G⋅C Watson–Crick DNA Base Pairs in Solution 下载免费PDF全文
Dr. Katharina Röttger Hugo J. B. Marroux Dr. Michael P. Grubb Philip M. Coulter Hendrik Böhnke Dr. Alexander S. Henderson Dr. M. Carmen Galan Prof. Friedrich Temps Prof. Andrew J. Orr‐Ewing Dr. Gareth M. Roberts 《Angewandte Chemie (International ed. in English)》2015,54(49):14719-14722
Ultrafast deactivation pathways bestow photostability on nucleobases and hence preserve the structural integrity of DNA following absorption of ultraviolet (UV) radiation. One controversial recovery mechanism proposed to account for this photostability involves electron‐driven proton transfer (EDPT) in Watson–Crick base pairs. The first direct observation is reported of the EDPT process after UV excitation of individual guanine–cytosine (G?C) Watson–Crick base pairs by ultrafast time‐resolved UV/visible and mid‐infrared spectroscopy. The formation of an intermediate biradical species (G[?H]?C[+H]) with a lifetime of 2.9 ps was tracked. The majority of these biradicals return to the original G?C Watson–Crick pairs, but up to 10 % of the initially excited molecules instead form a stable photoproduct G*?C* that has undergone double hydrogen‐atom transfer. The observation of these sequential EDPT mechanisms across intermolecular hydrogen bonds confirms an important and long debated pathway for the deactivation of photoexcited base pairs, with possible implications for the UV photochemistry of DNA. 相似文献
154.
Spontaneous Formation of Microgroove Arrays on the Surface of p‐Type Porous Silicon Induced by a Turing Instability in Electrochemical Dissolution 下载免费PDF全文
Prof. Dr. Kazuhiro Fukami Tomoko Urata Prof. Dr. Katharina Krischer Prof. Dr. Naoya Nishi Prof. Dr. Tetsuo Sakka Dr. Atsushi Kitada Prof. Dr. Kuniaki Murase 《Chemphyschem》2015,16(8):1613-1618
Self‐organization plays an imperative role in recent materials science. Highly tunable, periodic structures based on dynamic self‐organization at micrometer scales have proven difficult to design, but are desired for the further development of micropatterning. In the present study, we report a microgroove array that spontaneously forms on a p‐type silicon surface during its electrodissolution. Our detailed experimental results suggest that the instability can be classified as Turing instability. The characteristic scale of the Turing‐type pattern is small compared to self‐organized patterns caused by the Turing instabilities reported so far. The mechanism for the miniaturization of self‐organized patterns is strongly related to the semiconducting property of silicon electrodes as well as the dynamics of their surface chemistry. 相似文献
155.
Controlled Formation of Polymer Nanocapsules with High Diffusion‐Barrier Properties and Prediction of Encapsulation Efficiency 下载免费PDF全文
Ines Hofmeister Prof. Dr. Katharina Landfester Dr. Andreas Taden 《Angewandte Chemie (International ed. in English)》2015,54(1):327-330
Polymer nanocapsules with high diffusion‐barrier performance were designed following simple thermodynamic considerations. Hindered diffusion of the enclosed material leads to high encapsulation efficiencies (EEs), which was demonstrated based on the encapsulation of highly volatile compounds of different chemical natures. Low interactions between core and shell materials are key factors to achieve phase separation and a high diffusion barrier of the resulting polymeric shell. These interactions can be characterized and quantified using the Hansen solubility parameters. A systematic study of our copolymer system revealed a linear relationship between the Hansen parameter for hydrogen bonding (δh) and encapsulation efficiencies which enables the prediction of encapsulated amounts for any material. Furthermore EEs of poorly encapsulated materials can be increased by mixing them with a mediator compound to give lower overall δh values. 相似文献
156.
Sonja Kracht Dr. Matthias Messerer Dr. Matthieu Lang Dr. Sonja Eckhardt Dr. Miriam Lauz Prof. Bernard Grobéty Prof. Katharina M. Fromm Prof. Bernd Giese 《Angewandte Chemie (International ed. in English)》2015,54(10):2912-2916
Some microorganisms perform anaerobic mineral respiration by reducing metal ions to metal nanoparticles, using peptide aggregates as medium for electron transfer (ET). Such a reaction type is investigated here with model peptides and silver as the metal. Surprisingly, Ag+ ions bound by peptides with histidine as the Ag+‐binding amino acid and tyrosine as photoinducible electron donor cannot be reduced to Ag nanoparticles (AgNPs) under ET conditions because the peptide prevents the aggregation of Ag atoms to form AgNPs. Only in the presence of chloride ions, which generate AgCl microcrystals in the peptide matrix, does the synthesis of AgNPs occur. The reaction starts with the formation of 100 nm Ag@AgCl/peptide nanocomposites which are cleaved into 15 nm AgNPs. This defined transformation from large nanoparticles into small ones is in contrast to the usually observed Ostwald ripening processes and can be followed in detail by studying time‐resolved UV/Vis spectra which exhibit an isosbestic point. 相似文献
157.
Inside Cover: Spontaneous Formation of Microgroove Arrays on the Surface of p‐Type Porous Silicon Induced by a Turing Instability in Electrochemical Dissolution (ChemPhysChem 8/2015) 下载免费PDF全文
158.
Patrick C. Dolder Matthias E. Liechti Katharina M. Rentsch 《Analytical and bioanalytical chemistry》2015,407(6):1577-1584
159.
160.
Matthias Worm Biao Kang Carsten Dingels Frederik R. Wurm Holger Frey 《Macromolecular rapid communications》2016,37(9):775-780
Poly ((ethylene oxide)‐b‐(propylene oxide)‐b‐(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid‐labile acetal moieties in the backbone of poloxamers to generate acid‐cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate‐protected vinyl ether to introduce acetal units. Three cleavable PEO‐PPO‐PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol−1; Mn,PEO = 2200, 3600, 4750 g·mol−1) have been synthesized using anionic ring‐opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06–1.08). Surface tension measurements reveal surface‐active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid‐triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation “on demand.”