全文获取类型
收费全文 | 390篇 |
免费 | 13篇 |
专业分类
化学 | 334篇 |
晶体学 | 1篇 |
力学 | 3篇 |
数学 | 28篇 |
物理学 | 37篇 |
出版年
2024年 | 1篇 |
2023年 | 1篇 |
2022年 | 8篇 |
2021年 | 10篇 |
2020年 | 10篇 |
2019年 | 8篇 |
2018年 | 4篇 |
2017年 | 7篇 |
2016年 | 8篇 |
2015年 | 11篇 |
2014年 | 14篇 |
2013年 | 23篇 |
2012年 | 32篇 |
2011年 | 31篇 |
2010年 | 27篇 |
2009年 | 11篇 |
2008年 | 22篇 |
2007年 | 15篇 |
2006年 | 17篇 |
2005年 | 13篇 |
2004年 | 22篇 |
2003年 | 17篇 |
2002年 | 13篇 |
2001年 | 4篇 |
2000年 | 8篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 7篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 1篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 8篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1961年 | 1篇 |
排序方式: 共有403条查询结果,搜索用时 31 毫秒
81.
82.
Ines Mancini Graziano Guella Helmut Zibrowius Francesco Pietra 《Helvetica chimica acta》2000,83(7):1561-1575
Eunicellane diterpenes with a C(7)=C(16) (Δ7,16; see 17 – 19 ), (Z)‐C(7)=C(8) ((7Z)Δ7,8; see 20 – 23 ), and (Z)‐C(6)=C(7) ((6Z)Δ6,7; see 10 ) bond, an uncommon feature in the case of extensive functionalization at the cyclohexane ring and the latter exhibiting uncommon configurations, were isolated from the gorgonian Eunicella cavolinii from Marseille (Figs. 5 and 2). The gorgonian Eunicella singularis (=Eunicella stricta) from the same area gave (7Z)Δ7,8, Δ7,16, and (6E)Δ6,7 analogs 24 , 25 , and 13 , respectively (Fig. 5 and Scheme). The (6E)Δ6,7 moiety of 13 – characterized by a slow 180° conformational flipping (Fig. 3) that results in broadening of NMR signals – makes the macrocycle highly strained. This may explain the spontaneous conversion of 13 to the 6‐methoxy‐7‐hydroxy derivative 14 in the presence of MeOH at −20° in the dark (Scheme). The isomeric, deacylated analogue 10 showed only little broadening of NMR signals and proved stable, in accordance with the less strained nature of this compound (Fig. 4). 相似文献
83.
Ines Mancini Graziano Guella Helmut Zibrowius Dominique Laurent Francesco Pietra 《Helvetica chimica acta》1999,82(10):1681-1689
Massileunicellins A ( 7 ), B ( 9 ), and C ( 11 ) – which show a novel type of a second epoxy bridge in eunicellane diterpenes – were isolated from the gorgonian Eunicella cavoliniii collected near Marseille. Structural assignments are based on NMR and MS data of these compounds and of their ketal derivatives 8 , 10 , and 12 . Negligible activity of the massileunicellins on L1210 and KB tumor cell lines, and similar results for related known compounds, cast doubt on high cytotoxicity reported for the latter by other authors. 相似文献
84.
Rossi B Verrocchio P Viliani G Scarduelli G Guella G Mancini I 《The Journal of chemical physics》2006,125(4):44511
Vibrational properties of inclusion complexes with cyclodextrins are studied by means of Raman spectroscopy and numerical simulation. In particular, Raman spectra of the nonsteroidal, anti-inflammatory drug indomethacin undergo notable changes in the energy range between 1600 and 1700 cm(-1) when inclusion complexes with cyclodextrins are formed. By using both ab initio quantum chemical calculations and molecular dynamics, we studied how to relate such changes to the geometry of the inclusion process, disentangling single-molecule effects, from changes in the solid state structure or dimerization processes. 相似文献
85.
Fradi I Servais AC Pedrini M Chiap P Iványi R Crommen J Fillet M 《Electrophoresis》2006,27(17):3434-3442
The enantiomeric separation of a series of acidic pharmaceuticals (mostly nonsteroidal anti-inflammatory drugs) has been investigated in NACE systems using single-isomer amino beta-CD derivatives. The first part of this study consisted of the selection of the basic experimental conditions to separate efficiently the enantiomers of acidic drugs. Several parameters, such as the nature of the ionic BGE components, were studied and a methanolic solution of ammonium acetate containing the cationic CD was selected as BGE. A D-optimal design with 20 experimental points was then applied and the nature and concentration of the CD were found to have a significant effect on the enantiomeric resolution for all studied compounds. Resolution (R(s)) values were always higher with 6-monodeoxy-6-mono(3-hydroxy)propylamino-beta-CD (PA-beta-CD) compared to those obtained with 6-monodeoxy-6-mono(2-hydroxy)propylamino-beta-CD (IPA-beta-CD). However, the latter led to shorter migration times. Generic NACE conditions were then selected by means of the multivariate approach in order to obtain the highest R(s) values in a minimum amount of time. Finally, dependence of separation selectivity, resolution, as well as mobility difference on chiral selector concentration was discussed and binding constants with PA-beta-CD were estimated for the two enantiomers of one of the model compounds, suprofen in these NACE systems. 相似文献
86.
Influences of nanoparticles and chain length on thermodynamic and electrical behavior of fluorine liquid crystals
下载免费PDF全文
![点击此处可从《中国物理 B》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Ines Ben Amor Lotfi Saadaoui Abdulaziz N. Alharbi Talal M. Althagafi and Taoufik Soltani 《中国物理 B》2022,31(10):104202-104202
Hydrogen-bonded polar nematic liquid crystal series with the general formula nOBAF (n = 7—12) is studied. The mesomorphic characterization is demonstrated through differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The complexes with short alkyl chains (n=7, 8) present a wide nematic range and monotropic smectic F mesophase, whereas the longer alkyl chain (n=10—12) analogues show high melting and low clearing mesomorphic liquid crystals. The thermal range of the mesophase and the birefringence increase with chain length decreasing. Furthermore, the effect of the nanoparticles (LiNbO3) on the thermal and the electrical behavior of 8OBAF are investigated. The presence of LiNbO3 nanoparticles increases the conductivity and reduces the resistivity of the complex. 相似文献
87.
Ferse I Langlitz M Kleigrewe K Rzeppa S Lenczyk M Harrer H Cramer B Humpf HU 《Natural product research》2012,26(20):1914-1921
In this study, 10 already described secondary metabolites and 2 unknown metabolites were identified in an extract of Monascus purpureus by high-performance liquid chromatography-diode array detection. The unknown metabolites were isolated and their chemical structures were elucidated. The new metabolites possess the molecular formulas C(21)H(27)NO(4) and C(23)H(31)NO(4). They were named monascopyridines E and F due to their pyridine backbone. The cytotoxicity of the new compounds was studied using immortalised human kidney epithelial cells displaying IC(50) values in the micromolar range. 相似文献
88.
Möller I Thomas A Wingender A Machnik M Schänzer W Thevis M 《European journal of mass spectrometry (Chichester, England)》2012,18(4):407-412
Erythropoietin (EPO) and its recombinant analogues are suspected to be illicitly administered to horses for performance enhancing purposes and, consequently, prohibited in equine sports. Recently, a new erythropoiesis-stimulating agent, peginesatide (Omontys, formerly referred to as Hematide), belonging to the upcoming class of EPO-mimetic peptides, received approval for the treatment of anaemia in humans with chronic kidney disease on dialysis. As the pegylated dimeric peptide of approximately 45 kDa without sequence homology to EPO is not detectable by conventional EPO detection assays, specific methods are bound to be established for horse sports drug testing. Thus, by fortifying equine serum with peginesatide, an approach consisting of a proteolytic digestion with subtilisin after protein precipitation was developed, eventually targeting a proteotypic and xenobiotic pentapeptide which is easily accessible to liquid chromatography- tandem mass spectrometry analysis. The method was validated for qualitative purposes and demonstrated to be specific, precise (relative standard deviations below 14%), sensitive (limit of detection 10 ng mL(-1)) and linear. Being simple, cost-effective and readily transferable to other doping control laboratories, a mass spectrometric assay for the detection of therapeutic concentrations of peginesatide in equine serum is, in terms of preventive doping research, applicable to routine analysis shortly after approval of the drug. 相似文献
89.
Hauptvogel IM Bon V Grünker R Baburin IA Senkovska I Mueller U Kaskel S 《Dalton transactions (Cambridge, England : 2003)》2012,41(14):4172-4179
Five new coordination polymers, namely, [Zn(2)(H(2)O)(2)(BBC)](NO(3))(DEF)(6) (DUT-40), [Zn(3)(H(2)O)(3)(BBC)(2)] (DUT-41), [(C(2)H(5))(2)NH(2)][Zn(2)(BBC)(TDC)](DEF)(6)(H(2)O)(7) (DUT-42), [Zn(10)(BBC)(5)(BPDC)(2)(H(2)O)(10)](NO(3))(DEF)(28)(H(2)O)(8) (DUT-43), and [Co(2)(BBC)(NO(3))(DEF)(2)(H(2)O)](DEF)(6)(H(2)O) (DUT-44), where BBC--4,4',4'-(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))tribenzoate, TDC--2,5-thiophenedicarboxylate, BPDC--4,4'-biphenyldicarboxylate, DEF--,N-diethylformamide, were obtained under solvothermal conditions and structurally characterized. It has been shown that compounds DUT-40, DUT-41 and DUT-44 exhibit 2D layered structures with large hexagonal channels. Utilization of additional angular dicarboxylic TDC linker led to the formation of the DUT-42 compound with the structure consisting of three interpenetrated 3D networks. Using the linear co-linker dicarboxylic BPDC, DUT-43 was obtained which forms a complicated 3D architecture arising from the polycatenation of triple-layered 2D building units and 2D single layer units. The pore accessibility of the synthesized compounds in the liquid phase was proved by the adsorption of dye molecules. 相似文献
90.
Metal-metabolomics of microalga Chlorella sorokiniana growing in selenium- and iodine-enriched media
Veronica Gómez-Jacinto Tamara García-Barrera Ines Garbayo-Nores Carlos Vilchez-Lobato José-Luis Gómez-Ariza 《Chemical Papers》2012,66(9):821-828
The microalga Chlorella sorokiniana has been used to accumulate selenium and iodine from culture media enriched with these elements as a first stage in the production of supplemented foods. The microalgal colony was grown in a conventional culture medium containing iodine (KI) at concentrations in the range of 150?C4000 ??g mL?1. Similar experiments were performed with selenium (SeO 4 2? ) at concentrations in the range of 20?C500 ??g mL?1. The concentration of iodine and selenium in the culture medium was analytically monitored daily and the viability of the colony was checked by biomass concentration measurement and by evaluation of the total content of chlorophyll and carotenoids. In addition, photosynthetic activity and the number of cells were also monitored. Iodine accumulation in the algal biomass increased rapidly with time and reached a steady state after 4 h of exposure. With Se exposure the colony viability decreased, although the culture grew well with concentrations of the element of 50 ??g mL?1 in the culture medium; this experiment produced Se-enrichment in the alga (3 ??g g?1) within 100 h. Sequential extraction of an algal pellet was performed in order to separate Se compounds according to their affinity with the following solvents: hot water to recover low molecular mass Se species, enzymatic extraction with driselase for species associated with the cell wall, sodium dodecyl sulphate (SDS) for water insoluble selenoproteins and, finally, enzymolysis with lipase and pronase that release and fragment residual selenoproteinsproducing compounds with low molecular mass. Size-exclusion chromatography (SEC) coupled with an ICP-MS detector showed the preponderance of Se-containing molecules with low molecular mass, possibly seleno-amino acids. Only a peak of low intensity located at 10 min was observed in the SDS extract that could be associated with a protein with molecular mass of 67 kDa. Finally, analysis of the aqueous extract of alga by reverse-phase chromatography with inductively-coupled plasma mass-spectrometry (RPC-ICP-MS) detection revealed the presence of selenocysteine (SeCys2), selenomethylselenocysteine (SeMetSeCys), selenomethionine (SeMet), and Se(VI), particularly the last two species. 相似文献