全文获取类型
收费全文 | 205篇 |
免费 | 9篇 |
国内免费 | 1篇 |
专业分类
化学 | 191篇 |
晶体学 | 7篇 |
力学 | 2篇 |
数学 | 5篇 |
物理学 | 10篇 |
出版年
2023年 | 5篇 |
2022年 | 2篇 |
2021年 | 23篇 |
2020年 | 7篇 |
2019年 | 6篇 |
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 12篇 |
2015年 | 9篇 |
2014年 | 5篇 |
2013年 | 15篇 |
2012年 | 13篇 |
2011年 | 19篇 |
2010年 | 6篇 |
2009年 | 10篇 |
2008年 | 12篇 |
2007年 | 11篇 |
2006年 | 11篇 |
2005年 | 6篇 |
2004年 | 5篇 |
2003年 | 2篇 |
2002年 | 5篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1995年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1981年 | 2篇 |
1977年 | 1篇 |
排序方式: 共有215条查询结果,搜索用时 359 毫秒
161.
Isolation and Versatile Derivatization of an Unsaturated Anionic Silicon Cluster (Siliconoid) 下载免费PDF全文
Philipp Willmes Dr. Kinga Leszczyńska Yannic Heider Dr. Kai Abersfelder Dr. Michael Zimmer Dr. Volker Huch Prof. Dr. David Scheschkewitz 《Angewandte Chemie (International ed. in English)》2016,55(8):2907-2910
The characteristic features of bulk silicon surfaces are echoed in the related partially substituted—and thus unsaturated—neutral silicon clusters (siliconoids). The incorporation of siliconoids into more‐extended frameworks is promising owing to their unique electronic features, but further developments in this regard are limited by the notable absence of functionalized siliconoid derivatives until now. Herein we report the isolation and full characterization of the lithium salt of an anionic R5Si6‐siliconoid, thus providing the missing link between silicon‐based Zintl anions and siliconoid clusters. Proof‐of‐principle for the high potential of this species for the efficient transfer of the intact unsaturated R5Si6 moiety is demonstrated by clean reactions with representative electrophiles of Groups 13, 14, and 15. 相似文献
162.
Katarzyna Solarska-
ciuk Kinga Adach Sylwia Cyboran-Mikoajczyk Dorota Bonarska-Kujawa Agnieszka Rusak ucja Cwynar-Zajc Tomasz Machaowski Teofil Jesionowski Katarzyna Grzywacz Mateusz Fijakowski 《Molecules (Basel, Switzerland)》2021,26(5)
Silicon dioxide, in the form of nanoparticles, possesses unique physicochemical properties (size, shape, and a large surface to volume ratio). Therefore, it is one of the most promising materials used in biomedicine. In this paper, we compare the biological effects of both mesoporous silica nanoparticles extracted from Urtica dioica L. and pyrogenic material. Both SEM and TEM investigations confirmed the size range of tested nanoparticles was between 6 and 20 nanometers and their amorphous structure. The cytotoxic activity of the compounds and intracellular ROS were determined in relation to cells HMEC-1 and erythrocytes. The cytotoxic effects of SiO2 NPs were determined after exposure to different concentrations and three periods of incubation. The same effects for endothelial cells were tested under the same range of concentrations but after 2 and 24 h of exposure to erythrocytes. The cell viability was measured using spectrophotometric and fluorimetric assays, and the impact of the nanoparticles on the level of intracellular ROS. The obtained results indicated that bioSiO2 NPs, present higher toxicity than pyrogenic NPs and have a higher influence on ROS production. Mesoporous silica nanoparticles show good hemocompatibility but after a 24 h incubation of erythrocytes with silica, the increase in hemolysis process, the decrease in osmotic resistance of red blood cells, and shape of erythrocytes changed were observed. 相似文献
163.
164.
Kulon K Valensin D Kamysz W Nadolny R Gaggelli E Valensin G Kozłowski H 《Dalton transactions (Cambridge, England : 2003)》2008,(39):5323-5330
Waglerin I is a 22 amino acid snake venom toxin. Its three fragments (GGKPDLRPCHP-NH2, PCHYIPRPKPR-NH2, PCHPPCHYIPR-NH2), due to the presence of two Cys and His residues, are potentially very attractive ligands for transition metal ions. The main aim of this work was to establish the impact of these two adjacent residues on Ni2+ ion binding, especially because this kind of motif is very common in nature, and the study of low molecular weight models could be helpful in understanding larger systems. In this work waglerin fragments and their N-protected analogues were studied with Ni2+ (and Cu2+ for peptides with disulfide bridges) ions using combined potentiometric and spectroscopic measurements (UV-Vis, CD, EPR and NMR). In all peptides, except PCHPPCHYIPR-NH2 with a disulfide bridge, the Cys-His motif was found to be crucial for the coordination of Ni2+ ions. In the case of the N-unprotected analogues, the N-terminal amino group participates in the coordination as well. 相似文献
165.
Alicja Kowalska Krystian Pluta Kinga Suwiska 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(4):o211-o213
In the title compound, C9H13N4O2+·I−·0.5H2O, the non‐H atoms of the ionic components lie on a mirror plane in Cmca, with the O atom of the partial water molecule lying on a twofold rotation axis. Whereas one of the methoxy methyl groups is directed away from the adjacent N‐methyl group, the other methoxy methyl group is directed towards its adjacent N‐methyl group. The conformation of the methoxy methyl groups provides an explanation for the outcomes of intramolecular thermal rearrangements of 2,6‐dialkoxy‐7,9‐dimethylpurinium salts. 相似文献
166.
167.
168.
Kinga Wzgarda-Raj Justyna Dominikowska Sławomir Wojtulewski Agnieszka J. Rybarczyk-Pirek 《Acta Crystallographica. Section C, Structural Chemistry》2023,79(2):52-60
The results of the X-ray structure analysis of three novel 3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine cocrystals are presented. These are 3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine–2,4,6-tribromophenol (1/2), C12H8N6·2C6H3Br3O, 3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine–isonicotinic acid N-oxide (1/2), C12H8N6·2C6H5NO3, and 3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine–4-nitrobenzenesulfonamide (1/1), C12H8N6·C6H6N2O4S. Special attention is paid to a conformational analysis of the title tetrazine molecule in known crystal structures. Quantum chemistry methods are used to compare the energetic parameters of the investigated conformations. A structural analysis of the hydrogen and halogen bonds with acceptor aromatic tetrazine and pyrazine rings is conducted in order to elucidate factors responsible for conformational stability. 相似文献
169.
Maria Nowakowska Kinga Nawalany Mariusz Kępczyński Zdzisław Krawczyk 《Macromolecular Symposia》2009,279(1):132-137
Photodynamic theraphy (PDT) is a clinically approved method for treatment of cancer and some other diseases. It employs the combination of a drug (photosensitizer) and light to induce photoxicity towards the cancerous cells. The efficiency of currently used photosensitizers is limited due to their aggregation in aqueous media and low chemical purity; usually a mixture of various isomers is used. This paper presents the results of our studies on the development of nanostructural materials for PDT. They are constructed from porphyrin (Po) which is covalently attached to the chain of hydrophylic polymer such as poly(methacrylic acid) (PMA) or poly(ethylene glycol) (PEG) and solubilized in lipid bilayer of liposome vesicles. The attachment of Po to the polymer chain improves its solubility in water while the solubilization in liposome carriers helps the dye to penetrate the cell membranes. Physicochemical and photophysical properties of those systems were determined. The in vitro studies on cancer cell lines demonstrated that the photosensitizers are efficiently accumulated in the cells. Their dark toxicity is negligible, while phototoxicity is very high. 相似文献
170.
Semiconductor photocatalysis is considered one of the most promising technologies for water purification from toxic organic dyes. However, to reliably evaluate the possibility of using a given material as a photocatalyst, it is crucial to investigate not only the photocatalytic activity but also its affinity towards various dyes and reusability. In this work, we studied the adsorptive/photocatalytic properties of hollow-spherical raspberry-like SnO2 and its SnO2/SnS2 heterostructures that were obtained via a chemical conversion method using three different concentrations of a sulfide precursor (thioacetamide). The adsorptive/photocatalytic properties of the samples towards cationic rhodamine B (RhB) and anionic indigo carmine (IC) were analyzed using uncommon wall zeta potential measurements, hydrodynamic diameter studies, and adsorption/photodecomposition tests. Moreover, after conducting cyclic experiments, we investigated the (micro)structural changes of the reused photocatalysts by scanning electron microscopy and Fourier-transform infrared spectroscopy. The obtained results revealed that the sensitization of SnO2 resulted not only in the significantly enhanced photocatalytic performance of the heterostructures, but also completely changed their affinity towards dyes. Furthermore, despite the seemingly best photocatalytic performance, the sample with the highest SnS2 content was unstable due to its (micro)structure. This work demonstrates that dye adsorption/desorption processes may overlap the results of cyclic photodecomposition kinetics. 相似文献