全文获取类型
收费全文 | 579篇 |
免费 | 21篇 |
国内免费 | 1篇 |
专业分类
化学 | 498篇 |
晶体学 | 7篇 |
力学 | 4篇 |
数学 | 50篇 |
物理学 | 42篇 |
出版年
2023年 | 7篇 |
2022年 | 6篇 |
2021年 | 25篇 |
2020年 | 21篇 |
2019年 | 19篇 |
2018年 | 8篇 |
2017年 | 7篇 |
2016年 | 22篇 |
2015年 | 16篇 |
2014年 | 22篇 |
2013年 | 37篇 |
2012年 | 41篇 |
2011年 | 48篇 |
2010年 | 20篇 |
2009年 | 24篇 |
2008年 | 36篇 |
2007年 | 39篇 |
2006年 | 33篇 |
2005年 | 43篇 |
2004年 | 29篇 |
2003年 | 22篇 |
2002年 | 23篇 |
2001年 | 7篇 |
2000年 | 6篇 |
1999年 | 5篇 |
1998年 | 1篇 |
1997年 | 4篇 |
1996年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1981年 | 5篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有601条查询结果,搜索用时 171 毫秒
81.
Validated multi‐drug determination using liquid chromatography with tandem mass spectrometry for the evaluation of a commercial drug disposal product 下载免费PDF全文
Veronica B. Waybright Stephanie H. Ma Kevin A. Schug 《Journal of separation science》2016,39(9):1666-1674
Currently, there are limited effective means of drug disposal for consumers, and this creates a gateway to illicit use and environmental contamination. Here, we evaluated the efficacy of a new drug disposal product, composed from a slurry of activated carbon, which claims to sequester up to 100% of a drug's active ingredient when the loading capacity is not exceeded, making it safe to dispose in landfill. High‐performance liquid chromatography with tandem mass spectrometry was applied to quantify as many as 24 drugs (opiates, barbiturates, statins, amphetamine, and benzodiazepine drugs) in the residual solvent solution from the product. Calibration curves were established in the concentration ranges of 0.25–7.0 μg/mL and showed good linearity. The limits of detection varied from 0.001 to 0.02 μg/mL, depending on the drug. Accuracy ranged from 80 to 111% for quality control samples, with a few minor exceptions. Precision overall varied between 0.2 to 12.7%. In sample bottles tested, where active ingredient of the loaded drug was below the maximum sorption capacity stated on the label, 98 to >99.9% of the active ingredient was sequestered. Percent active ingredient adsorbed was slightly lower in bottles loaded in excess of label specifications. 相似文献
82.
Zhengjin Yang Rui Guo Richard Malpass‐Evans Mariolino Carta Neil B. McKeown Michael D. Guiver Liang Wu Tongwen Xu 《Angewandte Chemie (International ed. in English)》2016,55(38):11499-11502
The development of polymeric anion‐exchange membranes (AEMs) combining high ion conductivity and long‐term stability is a major challenge for materials chemistry. AEMs with regularly distributed fixed cationic groups, based on the formation of microporous polymers containing the V‐shape rigid Tröger's base units, are reported for the first time. Despite their simple preparation, which involves only two synthetic steps using commercially available precursors, the polymers provide AEMs with exceptional hydroxide conductivity at relatively low ion‐exchange capacity, as well as a high swelling resistance and chemical stability. An unprecedented hydroxide conductivity of 164.4 mS cm?1 is obtained at a relatively a low ion‐exchange capacity of 0.82 mmol g?1 under optimal operating conditions. The exceptional anion conductivity appears related to the intrinsic microporosity of the charged polymer matrix, which facilitates rapid anion transport. 相似文献
83.
In a time of emerging bacterial resistance there is a vital need for new targets and strategies in antibacterial therapy. Using uropathogenic Escherichia coli as a model pathogen we have developed a class of compounds, pilicides, which inhibit the formation of virulence-associated organelles termed pili. The pilicides interfere with a highly conserved bacterial assembly and secretion system called the chaperone-usher pathway, which is abundant in a vast number of Gram-negative pathogens and serves to assemble multi-protein surface fibers (pili/fimbriae). This class of compounds provides a platform to gain insight into important biological processes such as the molecular mechanisms of the chaperone-usher pathway and the sophisticated function of pili. Pili are primarily involved in bacterial adhesion, invasion and persistence to host defenses. On this basis, pilicides can aid the development of new antibacterial agents. 相似文献
84.
The effect of 1,1,1,3,3,3-hexafluoro-2-phenylpropan-2-ol (HFPP) on the persistency of sec-alkyl peroxy radicals has been investigated. The formation of a hydrogen-bonding complex between HFPP and the radical resulted in a large increase in the lifetime of the radical. This variation was accompanied by a decrease in the g-value. An enthalpy change of -3.4 kcal mol-1 was estimated for the formation of the hydrogen-bonded complex. 相似文献
85.
This work examines the relationship between the physical properties of agarose and dextran-grafted agarose cation exchangers and protein adsorption equilibrium and rates. Four different sulfopropyl (SP) matrices were synthesized using a neutral agarose base material--two based on a short ligand chemistry and two obtained by grafting 10 and 40kDa dextran polymers. The pore accessibility, determined by inverse size exclusion chromatography (iSEC) with dextran probes, decreases dramatically as a result of the combined effects of crosslinking, dextran grafting, and the introduction of ionic ligands, with pore radii decreasing from 19nm for the base matrix to 6.1nm for the 40kDa dextran-grafted SP-matrix. In spite of this reduction, while the adsorption isotherms were similar, protein uptake rates were greatly increased with the dextran-grafted SP-matrices, compared to SP-matrices based on the short ligand chemistry. The effective pore diffusivities were 4-10 times higher than free solution diffusivity for the dextran-grafted matrices, indicating that the charged dextran grafts result in enhanced protein mass transfer rates. 相似文献
86.
Cornel VM 《The Journal of organic chemistry》2007,72(14):5466-5476
Reviews are listed in order of appearance in the sources indicated. In multidisciplinary review journals, only those reviews which fall within the scope of this Journal are included. Sources are listed alphabetically in three categories: regularly issued review journals and series volumes, contributed volumes, and other monographs. Titles are numbered serially, and these numbers are used for reference in the index. Major English-language sources of critical reviews are covered. Encyclopedic treatises, annual surveys such as Specialist Periodical Reports, and compilations of symposia proceedings are omitted. This installment of Recent Reviews covers principally the early part of the 2007 literature. Previous installment: J. Org. Chem. 2007, 72 (7), 2699-706. 相似文献
87.
Wasserman V Kizelsztein P Garbuzenko O Kohen R Ovadia H Tabakman R Barenholz Y 《Langmuir : the ACS journal of surfaces and colloids》2007,23(4):1937-1947
The piperidine nitroxide tempamine (TMN) is a cell-permeable, stable radical having antioxidant, anticancer, and proapoptotic and/or pronecrotic activities, as was demonstrated by us in cell cultures. We also demonstrated synergism between TMN and doxorubicin in doxorubicin-sensitive and doxorubicin-resistant cell lines. Treatment of the C26 mouse colon carcinoma model in vivo also demonstrated synergism between TMN and doxorubicin in sterically stabilized liposomes (SSLs) containing TMN (SSL-TMN) and those containing doxorubicin. The above effects of TMN and SSL-TMN motivated us to develop and optimize the SSL-TMN formulation so that it will be able to reach the disease site with a sufficiently high TMN level and a release rate needed to achieve a therapeutic effect. Because TMN is an amphipathic weak base, it was remote loaded by an intraliposome high/extraliposome low transmembrane ammonium sulfate gradient. The kinetics and level of TMN loading were monitored by cyclic voltammetry (CV) and electron paramagnetic resonance (EPR); the latter also indicates TMN precipitation in the intraliposomal aqueous phase. The regeneration of the original CV and EPR signals by the ionophore nigericin indicates that TMN remained fully intact during loading and release. The cardinal role of the transmembrane ammonium ion gradient in the loading process was proven by the use of the selective ionophores nonactin (for NH4+) and nigericin (for H+). The anion of the ammonium salts affects loading stability and the rate of TMN release, both mediated through the TMN state of aggregation in the intraliposomal aqueous phase. The greater the TMN salt precipitation, the slower the TMN release rate. This was supported by measurement of osmolality, which is inversely related to TMN salt precipitate. Precipitation is in the order SO4(-2)>Cl-1>glucuronate-1. Liposome lipid composition, magnitude of the transmembrane ammonium ion gradient, and type of anion of the ammonium salt determine the amount of TMN loaded and its release rate. 相似文献
88.
This communication reports on rapid, efficient synthesis of the metal‐organic chemical vapor deposition (MOCVD) precursor (methylcyclopentadienyl)allylplatinum. The compound is shown to be an effective precursor for the deposition of platinum thin films giving deposits of high quality and purity, probably due to the nature of ligands which seems to be good leaving <?tw=99%>groups as confirmed by mass spectrometric path‐way. Copyright © 1999 John Wiley & Sons, Ltd. 相似文献
89.
Mariolino Carta 《Tetrahedron letters》2009,50(43):5954-6479
The synthesis of novel monomers based upon the rigid 1,1′-spiro-bis(1,2,4,5-tetrahydro-6,7-dihydroxynaphthalene) framework is reported. These monomers can be used for the synthesis of polymers of intrinsic microporosity (PIMs) due to their reactive catechol units and nonlinear shape, which introduces the necessary sites of contortion into the resulting PIM. 相似文献
90.
Veronica Mugnaini Mauro Fabrizioli Imma Ratera Matteo Mannini Andrea Caneschi Dante Gatteschi Yishay Manassen Jaume Veciana 《Solid State Sciences》2009,11(5):956-960
The Electron Spin Noise Scanning Tunnelling Microscopy (ESN-STM) technique is one of the most promising techniques detecting one single spin, combining the spatial resolution of the STM with the ability of spectral resolution and spin manipulation of Electron Spin Resonance. After its first observation, the effectiveness of this technique has been tested by different groups to study the properties of small aggregates or single organic radical molecules.We report on the ongoing ESN-STM study on nano-aggregates of tris(2,4,6-thrichlorophenyl)methyl radical (TTM) derivatives, whose possibility to be used as wires, switches and memory devices has already been investigated in bulk. After deposition on Au(111), TTM radicals preserved their magnetism. To treat the collected noise data we followed a statistical approach; some peculiar characteristics of this analysis will be addressed. 相似文献