全文获取类型
收费全文 | 528篇 |
免费 | 17篇 |
国内免费 | 4篇 |
专业分类
化学 | 364篇 |
晶体学 | 6篇 |
力学 | 3篇 |
数学 | 73篇 |
物理学 | 103篇 |
出版年
2023年 | 2篇 |
2022年 | 3篇 |
2021年 | 3篇 |
2020年 | 8篇 |
2019年 | 10篇 |
2018年 | 7篇 |
2017年 | 9篇 |
2016年 | 8篇 |
2015年 | 12篇 |
2014年 | 19篇 |
2013年 | 38篇 |
2012年 | 36篇 |
2011年 | 57篇 |
2010年 | 21篇 |
2009年 | 12篇 |
2008年 | 33篇 |
2007年 | 39篇 |
2006年 | 48篇 |
2005年 | 49篇 |
2004年 | 22篇 |
2003年 | 22篇 |
2002年 | 18篇 |
2001年 | 6篇 |
2000年 | 9篇 |
1999年 | 4篇 |
1998年 | 5篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 5篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 6篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 4篇 |
1982年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1966年 | 1篇 |
1962年 | 1篇 |
1955年 | 1篇 |
1951年 | 1篇 |
排序方式: 共有549条查询结果,搜索用时 31 毫秒
11.
P Leroy A Nicolas C Gavriloff M Matt P Netter B Bannwarth B Hercelin M Mazza 《Journal of chromatography. A》1991,564(1):258-265
A simple and fast high-performance liquid chromatographic method was developed for the simultaneous measurement of 2-mercaptopropionylglycine (Tiopronine) and its metabolite (2-mercaptopropionic acid) in human plasma after the administration of a pharmaceutical dosage form (Acadione). The sample treatment before high-performance liquid chromatographic analysis consisted of the reduction of the corresponding disulphides by tri-n-butylphosphine and protein precipitation with ethanol. Separation was achieved by ion-pair high-performance liquid chromatography on a reversed-phase column (LiChrospher RP 18e) with cetrimonium bromide as counter ion and detection by fluorimetry after post-column derivatization with a selective thiol reagent, i.e. pyrenemaleimide. The high frequency of the analyzed samples and validation results make the method suitable for pharmacokinetic studies, and this was demonstrated by the first results obtained after the administration of an oral dose of 500 mg of Tiopronine to two healthy subjects. 相似文献
12.
13.
Cheeseman M Feuillet FJ Johnson AL Bull SD 《Chemical communications (Cambridge, England)》2005,(18):2372-2374
A new way of combining chiral auxiliaries and substrate-directable reactions for asymmetric synthesis is described that employs a three-step sequence of aldol-cyclopropanation-retro-aldol reactions for the stereoselective synthesis of enantiopure cyclopropane carboxaldehydes. 相似文献
14.
The potential of molecules that combine the properties of a conical cavity with those of a covalently-linked transition-metal centre is highlighted through the assessment of cyclodextrin- and calixarene-derived podands ("cavitand" ligands) in coordination chemistry and catalysis. Metallocavitands with coordination sites directed towards the interior of the generic cavity provide interesting systems for studying host-guest complexation processes, their enhanced strength of metal-ion binding allowing for regioselective catalysis in a confined environment, and stabilisation of coordination complexes of unusual forms. Where cavitands have exo-oriented podand arms, the intrinsic dynamics of the cavity can dramatically modify metal chelation behaviour and the catalytic properties of the complexes. Such functionalised cavities are also useful as metal-ion transporters. 相似文献
15.
Frost RL Erickson KL Carmody O Weier ML 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(4):749-754
A suite of torbernites and metatorbernites have been analysed by near-infrared spectroscopy. The spectra of torbernites and metatorbernites in the first HOH fundamental overtone are different and the spectra of torbernites of different origins in the 6000-7500 cm(-1) region vary. NIR spectroscopy provides a method of studying the hydration of cations in the interlayer of torbernite. NIR spectroscopy shows that the spectra of torbernites from different origins in the water HOH first fundamental overtone and combination regions are different. This difference implies the hydration of cations is different for torbernite minerals. The structural arrangement of the water molecules in the interlayer is sample dependent. The NIR spectra of metatorbernites are different from that of torbernites and a similarity of the spectra of metatorbernites suggests that the water structure in metatorbernites is similar. 相似文献
16.
We present parallelization of a quantum-chemical tree-code for linear scaling computation of the Coulomb matrix. Equal time partition is used to load balance computation of the Coulomb matrix. Equal time partition is a measurement based algorithm for domain decomposition that exploits small variation of the density between self-consistent-field cycles to achieve load balance. Efficiency of the equal time partition is illustrated by several tests involving both finite and periodic systems. It is found that equal time partition is able to deliver 91%-98% efficiency with 128 processors in the most time consuming part of the Coulomb matrix calculation. The current parallel quantum chemical tree code is able to deliver 63%-81% overall efficiency on 128 processors with fine grained parallelism (less than two heavy atoms per processor). 相似文献
17.
Treatment of 4-nitrophenyl chloroformate with alkylammonium hydrochloride salts and solid anhydrous Na2CO3 in either CH2Cl2 or CH3CN gave 4-nitrophenyl N-methylcarbamate and other N-alkylcarbamate analogues in excellent yields. Of particular interest is the observation that 4-nitrophenyl N-methylcarbamate, a safer alternative to the highly toxic methyl isocyanate, is obtained in quantitative yield (?95% pure as determined by 1H NMR) after simple filtration and solvent evaporation. 相似文献
18.
19.
Frost RL Duong L Weier M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(8-9):1853-1859
A series of tungstate bearing minerals including scheelite, stolzite, ferberite, hübnerite, wolframite, russellite, tungstenian wulfenite and cuprotungstite have been analyzed by Raman microscopy. The results of the Raman spectroscopic analysis are compared with published data. These minerals are closely related and often have related paragenesis. Raman microscopy enables the selection of individual crystals of these minerals for spectroscopic analysis even though several of the minerals can be found in the same matrix because of the pargenetic relationships between the minerals. The Raman spectra are assigned according to factor group analysis and related to the structure of the minerals. These minerals have characteristically different Raman spectra. The nu1(Ag) band is observed at 909 cm(-1) and although the corresponding nu1(Bu) vibration should be inactive a minor band is observed around 894 cm(-1). The bands at 790 and 881 cm(-1) are associated with the antisymmetric and symmetric Ag modes of terminal WO2. The band at 695 cm(-1) is interpreted as an antisymmetric bridging mode associated with the tungstate chain. The nu4(Eg) band was absent for scheelite. The bands at 353 and 401 cm(-1) are assigned as either deformation modes or as r(Bg) and delta(Ag) modes of terminal WO2. The band at 462 cm(-1) has an equivalent band in the infrared at 455 cm(-1) assigned as delta(as)(Au) of the (W2O4)n chain. The band at 508 cm(-1) is assigned as nu(sym)(Bg) of the (W2O4)n chain. 相似文献
20.
Solvent extraction of a mixture of PbII, MnII, FeIII, CoII, NiII and CdII in aqueous perchlorate medium by a phosphorylated hexahomotrioxacalix[3]arene (calix‐3) in dichloromethane shows a significant selectivity towards lead ions. The ligand can also be incorporated into a membrane to provide a new lead ion‐selective electrode (PbII‐ISE). A plasticized PVC membrane containing 30% PVC, 53.5% ortho‐nitrophenyloctylether (NPOE), 4.5% sodium tetraphenylborate (NaTPB) and 12% ionophore was directly coated on a graphite rod. This sensor gave a good Nernstian response of 29.7 ± 0.7 mV decade?1 over a concentration range of 1 × 10?8 – 1 × 10?4 M of lead ions, independent of pH in the range 3‐7, with a detection limit of 0.4 × 10?8 M. The dynamic response time of the electrode to achieve a steady potential was very fast and found to be less than 7 s. The selectivity relative to Ag+, NH4+, Li+, Na+, K+, Ca2+, Sr2+, Ba2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Fe3+, La3+, Sm3+, Dy3+, Er3+, Y3+ and Th4+ was examined. The electrode exhibits adequate stability with good reproducibility (with a slope of 29.6 ± 1.5 mV for 8 weeks). The characteristics of the sensor are compared with those of a tetraphosphorylated calix[4]arene (calix‐4) based PbII‐ISE, reported recently. The electrode was successfully used as an indicator electrode for a potentiometric titration of a lead solution using a standard solution of EDTA. The applicability of the sensor for lead ion measurements in various synthetic samples was also investigated. 相似文献