全文获取类型
收费全文 | 1454篇 |
免费 | 20篇 |
国内免费 | 18篇 |
专业分类
化学 | 984篇 |
晶体学 | 25篇 |
力学 | 24篇 |
数学 | 248篇 |
物理学 | 211篇 |
出版年
2023年 | 8篇 |
2021年 | 9篇 |
2020年 | 18篇 |
2019年 | 8篇 |
2018年 | 6篇 |
2017年 | 8篇 |
2016年 | 22篇 |
2015年 | 18篇 |
2014年 | 20篇 |
2013年 | 66篇 |
2012年 | 62篇 |
2011年 | 86篇 |
2010年 | 45篇 |
2009年 | 52篇 |
2008年 | 101篇 |
2007年 | 104篇 |
2006年 | 88篇 |
2005年 | 67篇 |
2004年 | 70篇 |
2003年 | 77篇 |
2002年 | 81篇 |
2001年 | 24篇 |
2000年 | 36篇 |
1999年 | 25篇 |
1998年 | 21篇 |
1997年 | 19篇 |
1996年 | 35篇 |
1995年 | 13篇 |
1994年 | 20篇 |
1993年 | 14篇 |
1992年 | 23篇 |
1991年 | 9篇 |
1989年 | 12篇 |
1988年 | 9篇 |
1987年 | 6篇 |
1986年 | 12篇 |
1985年 | 17篇 |
1984年 | 14篇 |
1983年 | 7篇 |
1982年 | 17篇 |
1981年 | 24篇 |
1980年 | 14篇 |
1979年 | 19篇 |
1978年 | 18篇 |
1977年 | 9篇 |
1976年 | 9篇 |
1975年 | 10篇 |
1974年 | 7篇 |
1973年 | 5篇 |
1972年 | 5篇 |
排序方式: 共有1492条查询结果,搜索用时 15 毫秒
91.
We examine the interaction between cytoskeletal F-actin and espin 3A, a prototypical actin bundling protein found in sensory cell microvilli, including ear cell stereocilia. Espin induces twist distortions in F-actin as well as facilitates bundle formation. Mutations in one of the two F-actin binding sites of espin, which have been implicated in deafness, can tune espin-actin interactions and radically transform the system's phase behavior. These results are compared to recent theoretical work on the general phase behavior linker-rod systems. 相似文献
92.
We introduce a new solid-state NMR method, which uses very slow sample rotation to visualize NMR spectra whose width exceeds feasible spectrometer bandwidths. It is based on the idea that if we reorient a tensor by a known angle about a known axis, the shifts in the NMR frequencies observed across the spectral width allow us to reconstruct the entire tensor. Called STREAQI (Slow Turning Reveals Enormous Anisotropic Quadrupolar Interactions), this method allows us to probe NMR nuclei that are intractable to current methods. To prove the concept and demonstrate its promise we have implemented the method for several 79Br containing samples with quadrupolar coupling constants in the range of 10-50 MHz. 相似文献
93.
Poly(ethylene glycol) (PEG) hydrogels have been used to encapsulate fluorescently labeled molecules in order to detect a variety
of analytes. The hydrogels are designed with a mesh size that will retain the sensing elements while allowing for efficient
diffusion of small analytes. Some sensing assays, however, require a conformational change or binding of large macromolecules,
which may be sterically prohibited in a dense polymer matrix. A process of hydrogel microporation has been developed to create
cavities within PEG microspheres to contain the assay components in solution. This arrangement provides improved motility
for large sensing elements, while limiting leaching and increasing sensor lifetime. Three hydrogel compositions, 100% PEG,
50% PEG, and microporated 100% PEG, were used to create pH-sensitive microspheres that were tested for response time and stability.
In order to assess motility, a second, more complex sensor, namely a FITC-dextran/TRITC-Con A glucose-specific assay was encapsulated
within the microspheres. 相似文献
94.
Roos C. W. van Lier Dr. A. Dowine de Bruijn Prof. Dr. Gerard Roelfes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(4):1430-1437
Dehydroalanine (Dha) residues are attractive noncanonical amino acids that occur naturally in ribosomally synthesised and post-translationally modified peptides (RiPPs). Dha residues are attractive targets for selective late-stage modification of these complex biomolecules. In this work, we show the selective photocatalytic modification of dehydroalanine residues in the antimicrobial peptide nisin and in the proteins small ubiquitin-like modifier (SUMO) and superfolder green fluorescent protein (sfGFP). For this purpose, a new water-soluble iridium(III) photoredox catalyst was used. The design and synthesis of this new photocatalyst, [Ir(dF(CF3)ppy)2(dNMe3bpy)]Cl3, is presented. In contrast to commonly used iridium photocatalysts, this complex is highly water soluble and allows peptides and proteins to be modified in water and aqueous solvents under physiologically relevant conditions, with short reaction times and with low reagent and catalyst loadings. This work suggests that photoredox catalysis using this newly designed catalyst is a promising strategy to modify dehydroalanine-containing natural products and thus could have great potential for novel bioconjugation strategies. 相似文献
95.
Stefania Sandoval Nitesh Kumar Dr. A. Sundaresan Prof. C. N. R. Rao Prof. Amparo Fuertes Dr. Gerard Tobias 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(38):11999-12003
Nitrogen‐doped reduced graphene oxide (N‐doped RGO) samples with a high level of doping, up to 13 wt. %, have been prepared by annealing graphene oxide under a flow of pure ammonia. The presence of nitrogen within the structure of RGO induces a remarkable increase in the thermal stability against oxidation by air. The thermal stability is closely related with the temperature of synthesis and the nitrogen content. The combustion reaction of nitrogen in different coordination environments (pyridinic, pyrrolic, and graphitic) is analyzed against a graphene fragment (undoped) from a thermodynamic point of view. In agreement with the experimental observations, the combustion of undoped graphene turns out to be more spontaneous than when nitrogen atoms are present. 相似文献
96.
The Origin of Shape Sensitivity in Palladium‐Catalyzed Suzuki–Miyaura Cross Coupling Reactions 下载免费PDF全文
Dr. Gillian Collins Michael Schmidt Dr. Colm O'Dwyer Prof. Justin D. Holmes Dr. Gerard P. McGlacken 《Angewandte Chemie (International ed. in English)》2014,53(16):4142-4145
The shape sensitivity of Pd catalysts in Suzuki–Miyaura coupling reactions is studied using nanocrystals enclosed by well‐defined surface facets. The catalytic performance of Pd nanocrystals with cubic, cuboctahedral and octahedral morphologies are compared. Superior catalytic reactivity is observed for Pd NCs with {100} surface facets compared to {111} facets. The origin of the enhanced reactivity associated with a cubic morphology is related to the leaching susceptibility of the nanocrystals. Molecular oxygen plays a key role in facilitating the leaching of Pd atoms from the surface of the nanocrystals. The interaction of O2 with Pd is itself facet‐dependent, which in turn gives rise to more efficient leaching from {100} facets, compared to {111} facets under the reaction conditions. 相似文献
97.
Ina Vollmer Michael J. F. Jenks Mark C. P. Roelands Robin J. White Toon van Harmelen Paul de Wild Gerard P. van der Laan Florian Meirer Jos T. F. Keurentjes Bert M. Weckhuysen 《Angewandte Chemie (International ed. in English)》2020,59(36):15402-15423
Increasing the stream of recycled plastic necessitates an approach beyond the traditional recycling via melting and re‐extrusion. Various chemical recycling processes have great potential to enhance recycling rates. In this Review, a summary of the various chemical recycling routes and assessment via life‐cycle analysis is complemented by an extensive list of processes developed by companies active in chemical recycling. We show that each of the currently available processes is applicable for specific plastic waste streams. Thus, only a combination of different technologies can address the plastic waste problem. Research should focus on more realistic, more contaminated and mixed waste streams, while collection and sorting infrastructure will need to be improved, that is, by stricter regulation. This Review aims to inspire both science and innovation for the production of higher value and quality products from plastic recycling suitable for reuse or valorization to create the necessary economic and environmental push for a circular economy. 相似文献
98.
Carla Kirschbaum Essa M. Saied Kim Greis Eike Mucha Sandy Gewinner Wieland Schllkopf Gerard Meijer Gert von Helden Berwyck L. J. Poad Stephen J. Blanksby Christoph Arenz Kevin Pagel 《Angewandte Chemie (International ed. in English)》2020,59(32):13638-13642
1‐Deoxysphingolipids are a recently described class of sphingolipids that have been shown to be associated with several disease states including diabetic and hereditary neuropathy. The identification and characterization of 1‐deoxysphingolipids and their metabolites is therefore highly important. However, exact structure determination requires a combination of sophisticated analytical techniques due to the presence of various isomers, such as ketone/alkenol isomers, carbon–carbon double‐bond (C=C) isomers and hydroxylation regioisomers. Here we demonstrate that cryogenic gas‐phase infrared (IR) spectroscopy of ionized 1‐deoxysphingolipids enables the identification and differentiation of isomers by their unique spectroscopic fingerprints. In particular, C=C bond positions and stereochemical configurations can be distinguished by specific interactions between the charged amine and the double bond. The results demonstrate the power of gas‐phase IR spectroscopy to overcome the challenge of isomer resolution in conventional mass spectrometry and pave the way for deeper analysis of the lipidome. 相似文献
99.
Carlos A. Martinez Eric Keller Renzo Meijer Gerard Metselaar Gerlof Kruithof Curtis Moore Pei-Pei Kung 《Tetrahedron: Asymmetry》2010,21(19):2408-2412
An efficient four-step biotransformation-mediated synthesis of (1S)-1-(2,6-dichloro-3-fluorophenyl)ethanol in enantiomerically pure form is described. This compound is a key intermediate required for the preparation of PF-2341066, a potent inhibitor of c-Met/ALK that is currently in clinical development. The described synthesis was used to manufacture 6 kg of the title compound and can also be employed to produce the corresponding (1R)-enantiomer. 相似文献
100.
Venugopal Gandikota Gerard F. Jones Amy S. Fleischer 《Experimental Thermal and Fluid Science》2010,34(5):554-561
This study analyzes the use of a carbon fiber epoxy heat sink for evaporator surface enhancement in a FC-72 thermosyphon. The pin-fin heat sink features 945 small-cross-section (1.27 mm by 0.965 mm) fins fabricated with an integral base plate. These fins have a high thermal conductivity (500 W/m K) along the length of the fin. The influence of heat load, thermosyphon fill volume, and condenser operating temperature on the overall thermal performance is examined. The results of this experiment provide significant insight into the possible implementation and potential benefits of carbon-fiber heat sink technology in two-phase flow leading to significant improvements in thermal management strategies for advanced electronics. 相似文献