全文获取类型
收费全文 | 292篇 |
免费 | 38篇 |
国内免费 | 22篇 |
专业分类
化学 | 172篇 |
晶体学 | 5篇 |
力学 | 2篇 |
物理学 | 173篇 |
出版年
2023年 | 1篇 |
2022年 | 6篇 |
2021年 | 4篇 |
2020年 | 8篇 |
2019年 | 9篇 |
2018年 | 12篇 |
2017年 | 9篇 |
2016年 | 10篇 |
2015年 | 13篇 |
2014年 | 15篇 |
2013年 | 13篇 |
2012年 | 17篇 |
2011年 | 23篇 |
2010年 | 26篇 |
2009年 | 42篇 |
2008年 | 22篇 |
2007年 | 23篇 |
2006年 | 10篇 |
2005年 | 18篇 |
2004年 | 12篇 |
2003年 | 13篇 |
2002年 | 9篇 |
2001年 | 11篇 |
2000年 | 7篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1991年 | 1篇 |
1988年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1981年 | 1篇 |
排序方式: 共有352条查询结果,搜索用时 17 毫秒
1.
Vanessa A. Béland Zhiqiang Wang Tsun-Kong Sham Paul J. Ragogna 《Journal of polymer science. Part A, Polymer chemistry》2022,60(16):2508-2517
In this work, we show that polymer networks composed of tertiary alkyl phosphines can be cleanly functionalized with phosphino-phosphonium or triphosphenium cations. Methods for functionalizing the polymers range from halide abstraction of commercially available reagents, to ligand exchange from simple to make reported compounds, and finally, macromolecular ligand design guided by observations made at the molecular level to accommodate the formation of kinetically favored triphosphenium cation functionalized networks. The synthesis, comprehensive characterization, and comparison of the new polymers to molecular analogues is outlined. It is shown the addition of the low valent phosphorus centers to the polymer network has the effect of tuning material physical properties. 相似文献
2.
Dr. Maria Petrosino Dr. Francesco Stellato Prof. Roberta Chiaraluce Prof. Valerio Consalvi Dr. Giovanni La Penna Dr. Alessandra Pasquo Dr. Olivier Proux Prof. Giancarlo Rossi Prof. Silvia Morante 《ChemistryOpen》2021,10(11):1133-1141
We present in this work a first X-ray Absorption Spectroscopy study of the interactions of Zn with human BST2/tetherin and SARS-CoV-2 orf7a proteins as well as with some of their complexes. The analysis of the XANES region of the measured spectra shows that Zn binds to BST2, as well as to orf7a, thus resulting in the formation of BST2-orf7a complexes. This structural information confirms the the conjecture, recently put forward by some of the present Authors, according to which the accessory orf7a (and possibly also orf8) viral protein are capable of interfering with the BST2 antiviral activity. Our explanation for this behavior is that, when BST2 gets in contact with Zn bound to the orf7a Cys15 ligand, it has the ability of displacing the metal owing to the creation of a new disulfide bridge across the two proteins. The formation of this BST2-orf7a complex destabilizes BST2 dimerization, thus impairing the antiviral activity of the latter. 相似文献
3.
Yingyot Poo‐arporn Surachai Thachepan Rungtiva Palangsuntikul 《Journal of synchrotron radiation》2015,22(1):86-90
Evidence of internal sulfate attack in field exposure was demonstrated by the damaged interior wall of a three‐year‐old house situated in Nakhon Ratchasima Province, Thailand. Partial distension of the mortar was clearly observed together with an expansion of a black substance. Removal of the black substance revealed a dense black layer. This layer was only found in the vicinity of the damaged area, suggesting that this black material is possibly involved in the wall cracking. By employing synchrotron‐based X‐ray photoelectron spectroscopy (XPS) and X‐ray absorption near‐edge structure (XANES) techniques, the unknown sample was chemically identified. The S 2p and O 1s XPS results mutually indicated the existence of sulfate species in the materials collected from the damaged area. The XANES results indicated the presence of ferrous (II) sulfate, confirming sulfate‐induced expansion and cracking. The sulfate attack in the present case appeared to physically affect the structure whereas the chemical integrity at the molecular level of the calcium silicate hydrate phase was retained since there was a lack of spectroscopic evidence for calcium sulfate. It was speculated that internal sulfate probably originated from the contaminated aggregates used during the construction. The current findings would be beneficial for understanding the sulfate‐attack mechanism as well as for future prevention against sulfate attack during construction. 相似文献
4.
Extended X‐ray absorption fine structure and multiple‐scattering simulation of nickel dithiolene complexes Ni[S2C2(CF3)2]2n (n = −2, −1, 0) and an olefin adduct Ni[S2C2(CF3)2]2(1‐hexene) 下载免费PDF全文
A series of Ni dithiolene complexes Ni[S2C2(CF3)]2n (n = ?2, ?1, 0) ( 1 , 2 , 3 ) and a 1‐hexene adduct Ni[S2C2(CF3)2]2(C6H12) ( 4 ) have been examined by Ni K‐edge X‐ray absorption near‐edge structure (XANES) and extended X‐ray absorption fine‐structure (EXAFS) spectroscopies. Ni XANES for 1 – 3 reveals clear pre‐edge features and approximately +0.7 eV shift in the Ni K‐edge position for `one‐electron' oxidation. EXAFS simulation shows that the Ni—S bond distances for 1 , 2 and 3 (2.11–2.16 Å) are within the typical values for square planar complexes and decrease by ~0.022 Å for each `one‐electron' oxidation. The changes in Ni K‐edge energy positions and Ni—S distances are consistent with the `non‐innocent' character of the dithiolene ligand. The Ni—C interactions at ~3.0 Å are analyzed and the multiple‐scattering parameters are also determined, leading to a better simulation for the overall EXAFS spectra. The 1‐hexene adduct 4 presents no pre‐edge feature, and its Ni K‐edge position shifts by ?0.8 eV in comparison with its starting dithiolene complex 3 . Consistently, EXAFS also showed that the Ni—S distances in 4 elongate by ~0.046 Å in comparison with 3 . The evidence confirms that the neutral complex is `reduced' upon addition of olefin, presumably by olefin donating the π‐electron density to the LUMO of 3 as suggested by UV/visible spectroscopy in the literature. 相似文献
5.
6.
Ali M. Abdel‐Mageed Alexander Klyushin Azita Rezvani Axel Knop‐Gericke Robert Schlgl R. Jürgen Behm 《Angewandte Chemie (International ed. in English)》2019,58(30):10325-10329
The electronic and structural properties of Au/ZnO under industrial and idealized methanol synthesis conditions have been investigated. This was achieved by kinetic measurements in combination with time‐resolved operando infrared (DRIFTS) as well as in situ near‐ambient pressure X‐ray photoelectron spectroscopy (NAP‐XPS) and X‐ray absorption near‐edge spectroscopy (XANES) measurements at the O K‐edge together with high‐resolution electron microscopy. The adsorption of CO during the reaction revealed the presence of negatively charged Au nanoparticles/Au sites during the initial phase of the reaction. Near‐ambient‐pressure XPS and XANES demonstrate the build‐up of O vacancies during the reaction, which goes along with a substantial increase in the rate of methanol formation. The results are discussed in comparison with previous findings for Cu/ZnO and Au/ZnO catalysts. 相似文献
7.
8.
Shogo Morisako Seiya Watanabe Satoru Ikemoto Satoshi Muratsugu Mizuki Tada Makoto Yamashita 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(42):15173-15177
A pincer‐iridium complex bearing a Lewis‐base‐free X‐type alumanyl ligand has been synthesized. X‐ray diffraction, NMR and IR spectroscopy, as well as XANES analysis confirmed its tetrahydrido‐IrV structure and Lewis acidity at the Al center as supported by DFT calculations. The resulting complex was applied as a catalyst for the transfer dehydrogenation of cyclooctane. 相似文献
9.
Tris‐amidoximate uranyl complexes via η2 binding mode coordinated in aqueous solution shown by X‐ray absorption spectroscopy and density functional theory methods 下载免费PDF全文
Linjuan Zhang Meiying Qie Jing Su Shuo Zhang Jing Zhou Jiong Li Yu Wang Shitong Yang Shuao Wang Jingye Li Guozhong Wu Jian-Qiang Wang 《Journal of synchrotron radiation》2018,25(2):514-522
The present study sheds some light on the long‐standing debate concerning the coordination properties between uranyl ions and the amidoxime ligand, which is a key ingredient for achieving efficient extraction of uranium. Using X‐ray absorption fine structure combined with theoretical simulation methods, the binding mode and bonding nature of a uranyl–amidoxime complex in aqueous solution were determined for the first time. The results show that in a highly concentrated amidoxime solution the preferred binding mode between UO22+ and the amidoxime ligand is η2 coordination with tris‐amidoximate species. In such a uranyl–amidoximate complex with η2 binding motif, strong covalent interaction and orbital hybridization between U 5f/6d and (N, O) 2p should be responsible for the excellent binding ability of the amidoximate ligand to uranyl. The study was performed directly in aqueous solution to avoid the possible binding mode differences caused by crystallization of a single‐crystal sample. This work also is an example of the simultaneous study of local structure and electronic structure in solution systems using combined diagnostic tools. 相似文献
10.
Solid energy calibration standards for P K‐edge XANES: electronic structure analysis of PPh4Br 下载免费PDF全文
Anastasia V. Blake Haochuan Wei Courtney M. Donahue Kyounghoon Lee Jason M. Keith Scott R. Daly 《Journal of synchrotron radiation》2018,25(2):529-536
P K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy is a powerful method for analyzing the electronic structure of organic and inorganic phosphorus compounds. Like all XANES experiments, P K‐edge XANES requires well defined and readily accessible calibration standards for energy referencing so that spectra collected at different beamlines or under different conditions can be compared. This is especially true for ligand K‐edge X‐ray absorption spectroscopy, which has well established energy calibration standards for Cl (Cs2CuCl4) and S (Na2S2O3·5H2O), but not neighboring P. This paper presents a review of common P K‐edge XANES energy calibration standards and analysis of PPh4Br as a potential alternative. The P K‐edge XANES region of commercially available PPh4Br revealed a single, highly resolved pre‐edge feature with a maximum at 2146.96 eV. PPh4Br also showed no evidence of photodecomposition when repeatedly scanned over the course of several days. In contrast, we found that PPh3 rapidly decomposes under identical conditions. Density functional theory calculations performed on PPh3 and PPh4+ revealed large differences in the molecular orbital energies that were ascribed to differences in the phosphorus oxidation state (III versus V) and molecular charge (neutral versus +1). Time‐dependent density functional theory calculations corroborated the experimental data and allowed the spectral features to be assigned. The first pre‐edge feature in the P K‐edge XANES spectrum of PPh4Br was assigned to P 1s → P‐C π* transitions, whereas those at higher energy were P 1s → P‐C σ*. Overall, the analysis suggests that PPh4Br is an excellent alternative to other solid energy calibration standards commonly used in P K‐edge XANES experiments. 相似文献