全文获取类型
收费全文 | 704篇 |
免费 | 56篇 |
国内免费 | 4篇 |
专业分类
化学 | 572篇 |
晶体学 | 1篇 |
力学 | 24篇 |
数学 | 63篇 |
物理学 | 104篇 |
出版年
2024年 | 3篇 |
2023年 | 12篇 |
2022年 | 12篇 |
2021年 | 14篇 |
2020年 | 30篇 |
2019年 | 16篇 |
2018年 | 9篇 |
2017年 | 6篇 |
2016年 | 30篇 |
2015年 | 35篇 |
2014年 | 34篇 |
2013年 | 38篇 |
2012年 | 81篇 |
2011年 | 86篇 |
2010年 | 43篇 |
2009年 | 35篇 |
2008年 | 49篇 |
2007年 | 46篇 |
2006年 | 34篇 |
2005年 | 36篇 |
2004年 | 31篇 |
2003年 | 17篇 |
2002年 | 13篇 |
2001年 | 9篇 |
2000年 | 5篇 |
1999年 | 4篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 4篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1976年 | 3篇 |
1975年 | 1篇 |
1972年 | 1篇 |
1968年 | 1篇 |
1890年 | 2篇 |
排序方式: 共有764条查询结果,搜索用时 15 毫秒
81.
Flower KR Khalifa I Bassan P Démoulin D Jackson E Lockyer NP McGown AT Miles P Vaccari L Gardner P 《The Analyst》2011,136(3):498-507
Recently a new di-gold(I) organometallic complex [1,3-(Ph(3)PAu)(2)-C(6)H(4)] (KF0101) has been synthesised and found to exhibit cytotoxic activity in vitro. Subsequently it has been demonstrated that KF0101 shows little or no cross-resistance against a number of the cisplatin resistant ovarian cancer cell lines in vitro suggesting a different mode of action for the drug. In this study, syncrotron radiation infrared microspectroscopy (SR-IRMS) has been used on drug treated single A2780 cells in order to determine if this different mode of action can be identified spectroscopically. The aim of the study was to establish: (i) if single cell SR-IRMS could be used to give insight into the cellular response on treatment with different cytotoxic agents relative to non-treated cells (control) and (ii) that if the cytotoxic drugs elicit a different biochemical response these responses could be distinguished from each other. The most striking features obtained after Principal Components Analysis (PCA) of Resonant Mie Scattering (RMieS) corrected single cell spectra of drug treated ovarian A2780 cells are: (i) The spectra obtained for the control are quite heterogeneous and several hundred spectra are required to adequately define the nature of the control; (ii) after drug treatment at the IC50 level for 24 h with cisplatin, KF0101, methotrexate, paclitaxel or 5-fluorouracil the cell spectra, as represented on a PCA scores plot, generally concentrate in certain well defined areas of the control, there are however a small number of spectra that fall outside of the area defined by the control; and (iii) a differentiation between cell spectra obtained on treatment with different drugs is observed which fits well with different in vitro cell culture behaviour and a flow cytometry cell cycle analysis of the control and drug treated cells. Inspection of the loading plots shows that PC1 is essentially the same for all plots and reflects changes in cell biochemistry related to the cell cycle. PC2, however, on comparison of the control versus cisplatin or cisplatin versus KF0101 is indicative of differences induced by drug treatment and has been termed as cell cycle-plus behaviour. These data are shown to be consistent with that obtained using bench-top IRMS by averaging a number of single cell spectra and carrying out a PCA, but SR-IRMS offers more insight into how the drug is affecting the cell population. More importantly, this approach enables the influence of the cell cycle on both the control and drug treated samples to be taken into consideration when evaluating the drug-cell interaction. 相似文献
82.
Many workers and also the general population are exposed to polycyclic aromatic hydrocarbons (PAHs), and benzo[a]pyrene (BaP) was recently classified as carcinogenic for humans (group 1) by the International Agency for Research on Cancer. Biomonitoring of PAHs exposure is usually performed by urinary 1-hydroxypyrene (1-OHP) analysis. 1-OHP is a metabolite of pyrene, a non-carcinogenic PAH. In this work, we developed a very simple but highly sensitive analytical method of quantifying one urinary metabolite of BaP, 3-hydroxybenzo[a]pyrene (3-OHBaP), to evaluate carcinogenic PAHs exposure. After hydrolysis of 10 mL urine for two hours and concentration by automated off-line solid phase extraction, the sample was injected in a column-switching high-performance liquid chromatography fluorescence detection system. The limit of quantification was 0.2 pmol L(-1) (0.05 ng L(-1)) and the limit of detection was estimated at 0.07 pmol L(-1) (0.02 ng L(-1)). Linearity was established for 3-OHBaP concentrations ranging from 0.4 to 74.5 pmol L(-1) (0.1 to 20 ng L(-1)). Relative within-day standard deviation was less than 3% and relative between-day standard deviation was less than 4%. In non-occupationally exposed subjects, median concentrations for smokers compared with non-smokers were 3.5 times higher for 1-OHP (p<0.001) and 2 times higher for 3-OHBaP (p<0.05). The two urinary biomarkers were correlated in smokers (ρ=0.636; p<0.05; n=10) but not in non-smokers (ρ=0.09; p>0.05; n=21). 相似文献
83.
Quinton D Girard A Thi Kim LT Raimbault V Griscom L Razan F Griveau S Bedioui F 《Lab on a chip》2011,11(7):1342-1350
In this work we report on the design, microfabrication and analytical performances of a new electrochemical sensor array (ESA) which allows for the first time the simultaneous amperometric detection of nitric oxide (NO) and peroxynitrite (ONOO(-)), two biologically relevant molecules. The on-chip device includes individually addressable sets of gold ultramicroelectrodes (UMEs) of 50 μm diameter, Ag/AgCl reference electrode and gold counter electrode. The electrodes are separated into two groups; each has one reference electrode, one counter electrode and 110 UMEs specifically tailored to detect a specific analyte. The ESA is incorporated on a custom interface with a cell culture well and spring contact pins that can be easily interconnected to an external multichannel potentiostat. Each UME of the network dedicated to the detection of NO is electrochemically modified by electrodepositing thin layers of poly(eugenol) and poly(phenol). The detection of NO is performed amperometrically at 0.8 V vs. Ag/AgCl in phosphate buffer solution (PBS, pH = 7.4) and other buffers adapted to biological cell culture, using a NO-donor. The network of UMEs dedicated to the detection of ONOO(-) is used without further chemical modification of the surface and the uncoated gold electrodes operate at -0.1 V vs. Ag/AgCl to detect the reduction of ONOOH in PBS. The selectivity issue of both sensors against major biologically relevant interfering analytes is examined. Simultaneous detection of NO and ONOO(-) in PBS is also achieved. 相似文献
84.
Jeffs L Arquier D Kariuki B Bethell D Page PC Hutchings GJ 《Organic & biomolecular chemistry》2011,9(4):1079-1084
By synthesising S-2-phenyl-N-(4-nitrophenyl)aziridine from S-phenylglycinol, it has been demonstrated that the aziridination of styrene by [N-(4-nitrobenzenesulfonyl)imino]phenyliodinane (nosyliminophenyliodinane, PhINNs) in the presence of S,S-2,2'-isopropylidene-bis(4-phenyl-2-oxazoline), catalysed by copper(II) triflate in CH(3)CN solution or heterogeneously by CuHY, has predominantly an R-configuration. The enantioselectivity of the aziridination of styrene by [N-arenesulfonylimino]-phenyliodinanes catalysed by copper-exchanged zeolite Y (CuHY), in conjunction with a chiral bis-oxazoline ligand, has been re-examined. In the case of PhINNs, it is shown that the product mixture of enantiomeric aziridines, on treatment with hexane, gives rise to a solid phase of low enantiomeric excess (ee) and a solution phase of high ee. Separation of the solid phase and recrystallisation afforded a true racemate (racemic compound), which has been confirmed by X-ray crystallography. The aziridine obtained from the solution phase could be recrystallised to produce the pure enantiomer originally in excess. A consequence of the new findings is that previous reports on the enantioselectivity of copper-catalysed aziridination, both in heterogeneous and homogeneous conditions, should be regarded with caution if the analytical procedure involved HPLC with injection of the enantiomeric mixture in a hexane-rich solvent. Such a method has been used in previous work from this laboratory, but has also been used elsewhere, following the procedure developed by Evans and co-workers when the (homogeneous) copper-catalysed aziridination by PhINTs was first discovered. Evidently, the change of substituent in the benzenesulfonyl group reduces the solubility in hexane, affording a solution phase of enhanced ee. 相似文献
85.
Dinda J Liatard S Chauvin J Jouvenot D Loiseau F 《Dalton transactions (Cambridge, England : 2003)》2011,40(14):3683-3688
This work describes the synthesis and characterization of two new bis-terdentate Ru(II) complexes. Compound 1 is a homoleptic complex containing two CNC N-heterocyclic carbene (NHC) based ligands, whereas compound 2 bears one CNC ligand and an ancillary terpyridine ligand. The redox and photophysical properties of both compounds have been investigated and their X-ray crystal structures determined. Complex 1 displays a close-to-perfect octahedral coordination geometry and is not luminescent at room temperature while complex 2 features room temperature and 77 K luminescence despite its partially distorted geometry. The presence of the NHC moieties brings a significant amount of electronic density to the metal centre therefore lowering its oxidation potential with respect to that of analogous polypyridyl complexes. 相似文献
86.
Pieters G Gaucher A Marrot J Maurel F Naubron JV Jean M Vanthuyne N Crassous J Prim D 《Organic letters》2011,13(16):4450-4453
The synthesis and properties of new chiral polycyclic architectures that display both helicity and a saddle-type shape are described. The enantiomers have been separated, and their absolute configuration was determined by VCD and ECD. The unprecedented molecular architecture is based on a cyclooctatriene core surrounded by an association of benzo[c]fluorene and ortho-phenylene units. 相似文献
87.
A novel type of photodeprotection reaction of simple aromatic acetals and ketals is described. The deprotection is highly efficient under optimized conditions. The aromatic ring confers the photoreactivity to the compounds. The efficiency of the process depends on the structure of the acetal moiety. The common minor side reaction, the photooxidation, becomes the major reaction pathway in the cases of cyclic acetals. The use of photon as only reagent makes this procedure especially attractive for acetal deprotection. 相似文献
88.
Pieters G Gaucher A Prim D Besson T Giner Planas J Teixidor F Viñas C Light ME Hursthouse MB 《Chemical communications (Cambridge, England)》2011,47(27):7725-7727
Valuable amino benzo[g,h,i]perylenes have been obtained through a one pot electrophilic aromatic substitution--Scholl reaction sequence. Novel molecular architectures combining 3D-o-carborane and planar amino benzo[g,h,i]perylene units are described. Photophysical properties of amino benzo[g,h,i]perylene and the carborane-appended derivatives are discussed. 相似文献
89.
Alberola A Carter E Constantinides CP Eisler DJ Murphy DM Rawson JM 《Chemical communications (Cambridge, England)》2011,47(9):2532-2534
The β-sheet structure associated with chlorinated aromatics (d(Cl···Cl)≈ 4.0 ?) has been implemented to drive formation of π-stacked structures of dithiadiazolyl radicals. Both title compounds exhibit an increase in paramagnetism above 150 K but solid-state EPR studies indicate that the origin of the paramagnetism in these two systems is different. 相似文献
90.
The strict application of IUPAC rules for the numbering of tropane alkaloids is not always applied by authors and there is hence a lot of confusion in the literature. In most cases, the notation of 3, 6/7-disubstituted derivatives has been chosen arbitrarily, based on NMR and MS data, without taking into account the absolute configuration of these two carbons. This paper discusses the problem and the relevance of CD and NMR to determine molecular configurations. We report on the use of (1)H-NMR anisochrony (Δδ) induced by the Mosher's chiral auxiliary reagents (R)-(-)- and (S)-(+)-α-methoxy-α-trifluoromethyl-phenylacetyl chlorides (MTPA-Cl), to determine the absolute configuration of (3R,6R)-3α-hydroxy-6β-senecioyloxytropane, a disubstituted tropane alkaloid isolated from the aerial parts of Schizanthus grahamii (Solanaceae). These analytical tools should help future works in correctly assigning the configuration of additional 3, 6/7 disubstituted tropane derivatives. 相似文献