全文获取类型
收费全文 | 808篇 |
免费 | 64篇 |
国内免费 | 1篇 |
专业分类
化学 | 695篇 |
晶体学 | 4篇 |
力学 | 4篇 |
数学 | 55篇 |
物理学 | 69篇 |
无线电 | 46篇 |
出版年
2023年 | 13篇 |
2022年 | 12篇 |
2021年 | 15篇 |
2020年 | 26篇 |
2019年 | 24篇 |
2018年 | 11篇 |
2017年 | 14篇 |
2016年 | 31篇 |
2015年 | 39篇 |
2014年 | 42篇 |
2013年 | 41篇 |
2012年 | 56篇 |
2011年 | 74篇 |
2010年 | 50篇 |
2009年 | 38篇 |
2008年 | 69篇 |
2007年 | 68篇 |
2006年 | 41篇 |
2005年 | 24篇 |
2004年 | 37篇 |
2003年 | 29篇 |
2002年 | 34篇 |
2001年 | 11篇 |
2000年 | 12篇 |
1999年 | 4篇 |
1998年 | 7篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 8篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1986年 | 1篇 |
1985年 | 6篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1968年 | 1篇 |
1925年 | 1篇 |
排序方式: 共有873条查询结果,搜索用时 15 毫秒
851.
852.
853.
Microcapsules are reviewed with special emphasis on the relevance of controlled mechanical properties for functional aspects. At first, assembly strategies are presented that allow control over the decisive geometrical parameters, diameter and wall thickness, which both influence the capsule's mechanical performance. As one of the most powerful approaches the layer-by-layer technique is identified. Subsequently, ensemble and, in particular, single-capsule deformation techniques are discussed. The latter generally provide more in-depth information and cover the complete range of applicable forces from smaller than pN to N. In a theory chapter, we illustrate the physics of capsule deformation. The main focus is on thin shell theory, which provides a useful approximation for many deformation scenarios. Finally, we give an overview of applications and future perspectives where the specific design of mechanical properties turns microcapsules into (multi-)functional devices, enriching especially life sciences and material sciences. 相似文献
854.
Dr. Melanie Chiu Boris H. Tchitchanov Daniel Zimmerli Italo A. Sanhueza Prof. Dr. Franziska Schoenebeck Dr. Nils Trapp Dr. W. Bernd Schweizer Prof. Dr. François Diederich 《Angewandte Chemie (International ed. in English)》2015,54(1):349-354
The formal [2+2] cycloaddition–retroelectrocyclization (CA–RE) reactions between tetracyanoethylene (TCNE) and strained, electron‐rich dibenzo‐fused cyclooctynes were studied. The effect of ring strain on the reaction kinetics was quantified, revealing that the rates of cycloaddition using strained, cyclic alkynes are up to 5500 times greater at 298 K than those of reactions using unstrained alkynes. Cyclobutene reaction intermediates, as well as buta‐1,3‐diene products, were isolated and their structures were studied crystallographically. Isolation of a rare example of a chiral buta‐1,3‐diene that is optically active and configurationally stable at room temperature is reported. Computational studies on the enantiomerization pathway of the buta‐1,3‐diene products showed that the eight‐membered ring inverts via a boat conformer in a ring‐flip mechanism. In agreement with computed values, experimentally measured activation barriers of racemization in these compounds were found to be up to 26 kcal mol?1. 相似文献
855.
Andreas F. Glas Sabine Schneider Dr. Melanie J. Maul Ulrich Hennecke Dr. Thomas Carell Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(40):10387-10396
UV‐light irradiation induces the formation of highly mutagenic lesions in DNA, such as cis‐syn cyclobutane pyrimidine dimers (CPD photoproducts), pyrimidine(6‐4)pyrimidone photoproducts ((6‐4) photoproducts) and their Dewar valence isomers ((Dew) photoproducts). Here we describe the synthesis of defined DNA strands containing these lesions by direct irradiation. We show that all lesions are efficiently repaired except for the T(Dew)T lesion, which cannot be cleaved by the repair enzyme under our conditions. A crystal structure of a T(6‐4)C lesion containing DNA duplex in complex with the (6‐4) photolyase from Drosophila melanogaster provides insight into the molecular recognition event of a cytosine derived photolesion for the first time. In light of the previously postulated repair mechanism, which involves rearrangement of the (6‐4) lesions into strained four‐membered ring repair intermediates, it is surprising that the not rearranged T(6‐4)C lesion is observed in the active site. The structure, therefore, provides additional support for the newly postulated repair mechanism that avoids this rearrangement step and argues for a direct electron injection into the lesion as the first step of the repair reaction performed by (6‐4) DNA photolyases. 相似文献
856.
Stefan Henkel Melanie Ertelt Prof. Dr. Wolfram Sander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7585-7588
4‐Oxocyclohexa‐2,5‐dienylidene is a highly reactive triplet ground state carbene that is hydrogenated in solid H2, HD, and D2 at temperatures as low as 3 K. The mechanism of the insertion of the carbene into dihydrogen was investigated by IR and EPR spectroscopy and by kinetic studies. H or D atoms were observed as products of the reaction with H2 and D2, respectively, whereas HD produces exclusively D atoms. The hydrogenation shows a very large kinetic isotope effect and remarkable isotope selectivity, as was expected for a tunneling reaction. The experiments, therefore, provide clear evidence for both hydrogen tunneling and the rare deuterium tunneling in an intermolecular reaction. 相似文献
857.
Dr. Melanie Rauschenberg Dr. Sateesh Bandaru Dr. Mark P. Waller Prof. Dr. Bart Jan Ravoo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(10):2770-2782
A broad spectrum of physiological processes is mediated by highly specific noncovalent interactions of carbohydrates and proteins. In a recent communication we identified several cyclic hexapeptides in a dynamic combinatorial library that interact selectively with carbohydrates with high binding constants in water. Herein, we report a detailed investigation of the noncovalent interaction of two cyclic hexapeptides (Cys‐His‐Cys (which we call HisHis) and Cys‐Tyr‐Cys (which we call TyrTyr)) with a selection of monosaccharides and disaccharides in aqueous solution. The parallel and antiparallel isomers of HisHis or TyrTyr were synthesized separately, and their interaction with monosaccharides and disaccharides in aqueous solution was studied by isothermal titration calorimetry, NMR spectroscopic titrations, and circular dichroism spectroscopy. From these measurements, we identified particularly stable complexes (Ka>1000 M ?1) of the parallel isomer of HisHis with N‐acetylneuraminic acid and with methyl‐α‐D ‐galactopyranoside as well as of both isomers of TyrTyr with trehalose. To gain further insight into the structure of the peptide–carbohydrate complexes, structure prediction was performed using quantum chemical methods. The calculations confirm the selectivity observed in the experiments and indicate the formation of multiple intermolecular hydrogen bonds in the most stable complexes. 相似文献
858.
Wong VW Rustad KC Glotzbach JP Sorkin M Inayathullah M Major MR Longaker MT Rajadas J Gurtner GC 《Macromolecular bioscience》2011,11(11):1458-1466
Cell-based therapies for wound repair are limited by inefficient delivery systems that fail to protect cells from the acute inflammatory environment. Here, a biomimetic hydrogel system is described that is based on the polymer pullulan, a carbohydrate glucan known to exhibit potent antioxidant capabilities. It is shown that pullulan hydrogels are an effective cell delivery system and improve mesenchymal stem cell survival and engraftment in high-oxidative-stress environments. The results suggest that glucan hydrogel systems may prove beneficial for progenitor-cell-based approaches to skin regeneration. 相似文献
859.
Trnka TM Morgan JP Sanford MS Wilhelm TE Scholl M Choi TL Ding S Day MW Grubbs RH 《Journal of the American Chemical Society》2003,125(9):2546-2558
This paper reports the synthesis and characterization of a variety of ruthenium complexes coordinated with phosphine and N-heterocyclic carbene (NHC) ligands. These complexes include several alkylidene derivatives of the general formula (NHC)(PR(3))(Cl)(2)Ru=CHR', which are highly active olefin metathesis catalysts. Although these catalysts can be prepared adequately by the reaction of bis(phosphine) ruthenium alkylidene precursors with free NHCs, we have developed an alternative route that employs NHC-alcohol or -chloroform adducts as "protected" forms of the NHC ligands. This route is advantageous because NHC adducts are easier to handle than their free carbene counterparts. We also demonstrate that sterically bulky bis(NHC) complexes can be made by reaction of the pyridine-coordinated precursor (NHC)(py)(2)(Cl)(2)Ru=CHPh with free NHCs or NHC adducts. Two crystal structures are presented, one of the mixed bis(NHC) derivative (H(2)IMes)(IMes)(Cl)(2)Ru=CHPh, and the other of (PCy(3))(Cl)(CO)Ru[eta(2)-(CH(2)-C(6)H(2)Me(2))(N(2)C(3)H(4))(C(6)H(2)Me(3))], the product of ortho methyl C-H bond activation. Other side reactions encountered during the synthesis of new ruthenium alkylidene complexes include the formation of hydrido-carbonyl-chloride derivatives in the presence of primary alcohols and the deprotonation of ruthenium vinylcarbene ligands by KOBu(t). We also evaluate the olefin metathesis activity of NHC-coordinated complexes in representative RCM and ROMP reactions. 相似文献
860.
Dr. Fan Xie Dr. Wenhao Sun Dr. Pablo Pinacho Prof. Dr. Melanie Schnell 《Angewandte Chemie (International ed. in English)》2023,62(14):e202218539
The initial stages of the gas-phase nucleation between CO2 and monoethanolamine were investigated via broadband rotational spectroscopy with the aid of extensive theoretical structure sampling. Sub-nanometer-scale aggregation patterns of monoethanolamine-(CO2)n, n=1–4, were identified. An interesting competition between the monoethanolamine intramolecular hydrogen bond and the intermolecular interactions between monoethanolamine and CO2 upon cluster growth was discovered, revealing an intriguing CO2 binding priority to the hydroxyl group over the amine group. These findings are in sharp contrast to the general results for aqueous solutions. In the quinary complex, a cap-like CO2 tetramer was observed cooperatively surrounding the monoethanolamine. As the cluster approaches the critical size of new particle formation, the contribution of CO2 self-assembly to the overall stability increases. 相似文献