全文获取类型
收费全文 | 333篇 |
免费 | 6篇 |
国内免费 | 1篇 |
专业分类
化学 | 261篇 |
晶体学 | 3篇 |
力学 | 3篇 |
数学 | 43篇 |
物理学 | 30篇 |
出版年
2024年 | 1篇 |
2023年 | 8篇 |
2022年 | 4篇 |
2021年 | 14篇 |
2020年 | 15篇 |
2019年 | 19篇 |
2018年 | 12篇 |
2017年 | 11篇 |
2016年 | 10篇 |
2015年 | 9篇 |
2014年 | 7篇 |
2013年 | 31篇 |
2012年 | 21篇 |
2011年 | 29篇 |
2010年 | 32篇 |
2009年 | 20篇 |
2008年 | 18篇 |
2007年 | 15篇 |
2006年 | 14篇 |
2005年 | 10篇 |
2004年 | 9篇 |
2003年 | 4篇 |
2002年 | 7篇 |
2001年 | 13篇 |
2000年 | 2篇 |
1999年 | 3篇 |
1997年 | 1篇 |
1994年 | 1篇 |
排序方式: 共有340条查询结果,搜索用时 15 毫秒
51.
Quantitative determination of omega-6 and omega-3 polyunsaturated fatty acids in human plasma and urine with high accuracy and precision provides significant information to monitor the underlying etiology of several diseases. In this regard, liquid chromatography-mass spectrometry is a good choice owing to its great selectivity and sensitivity. Additionally, the hybrid quadrupole–time of flight–mass spectrometer systems provides easy identification of target compounds with superior mass measurements. In this study, an analytical method has been developed for simple, accurate and simultaneous determination of linoleic acid, arachidonic acid, docosahexaenoic acid and eicosapentaenoic acid in a short chromatographic analysis period. The developed method is suitable for the quantitative detection of these four compounds with detection limits ranging between 1.1–3.0 ng ml−1 and its applicability was assessed in human urine and plasma samples. As a result, acceptable accuracy (between 83 and 111%) and good precision (<6%) were obtained for target compounds using matrix matching calibration strategy. 相似文献
52.
The decolorisation process of a synthetic textile dye, direct violet 51, was investigated in an aqueous solution using an electrochemical method in a batch electrochemical cell. Graphite electrodes were used as the anode and cathode for the decolorisation process. The parameters such as applied current, initial pH, solution conductivity, interfering ions, and effect of electrodes were optimised. It was found that the dye with an initial concentration of 20 mg L?1 could be removed after 50 min using a current of 100 mA with colour removal of up to 94 %. The UV-VIS spectra of the dye were analysed prior to and after treatment and these confirmed that the conjugated systems were decomposed at a current of 100 mA. The optimised method was successfully applied to real wastewater samples. 相似文献
53.
Densities and speeds of sound of three ionic liquids (ILs), 1-ethyl-3-methyl imidazoliumtetrafluoroborate (C2mimBF4), 1-butyl-3-methylimidazoliumtetrafluoroborate (C4mimBF4) and 1-hexyl-3-methylimidazoliumtetrafluoroborate (C6mimBF4) were measured in aqueous solutions at (288.15, 293.15, 298.15, 303.15 and 308.15) K. These data were used to calculate the volumetric properties apparent molar volume and apparent molar isentropic compression as a function of molality. Infinite dilution values for these properties were evaluated by an extrapolation procedure based on Redlich–Meyer type equations. Apparent molar isobaric expansions at infinite dilution were also obtained from the slopes of the apparent molar volume at infinite dilution versus temperature. All these properties are interpreted in terms of IL–water interactions. The hydrolysis of the \( {\text{BF}}_{4}^{ - } \) anion of the ILs and its effects on the results is discussed. 相似文献
54.
Elif Gacal Serpil Denizaltı Armağan Kınal Aytaç Gürhan Gökçe Hayati Türkmen 《Tetrahedron》2018,74(47):6829-6838
A series of N-aryl (2a,b) or benzyl (2c,d) substituted piperidoimidazolinium salts and their palladium complexes (3a-d) were prepared and characterized by 1H, 13C NMR, IR spectroscopy and elemental analysis. The crystal structures of 3a and 3c have been determined by X-ray crystallography. Thermogravimetric analysis (TGA) was applied to complexes (3a–d). The palladium complexes have been employed as catalyst for Suzuki-Miyaura cross coupling. The N-aryl substituted complex 3b was a highly efficient precatalyst and successfully employed in Suzuki-Miyaura cross coupling reactions of (hetero)aryl chlorides with arylboronic acids in air. In addition, the oxidative addition step of the reaction mechanism involving chlorobenzene and the catalysts 3a, 3b, 3c and 3d were computationally investigated by the DFT--B97X-D method and complete agreement were obtained with the catalytic results. To measure σ-donating and π-acceptor properties of the new ligands, the rhodium carbonyl complexes were also prepared. 相似文献
55.
Çiğdem Özay Elif Beyza Gencer Azim Gökçe 《Journal of Thermal Analysis and Calorimetry》2018,134(1):23-33
A non-commercial Al4Cu0.5Mg alloy has been used for investigating the effects of the elemental Sn additions. Uniaxial die compaction response of the alloys in terms of green density was examined, and the results showed that Sn addition has no effect when compacting conducted under high pressures. In total, 93–95% green density was achieved with an applied pressure of 400 MPa. Thermal events occurring during the sintering of the emerging alloys were studied by using differential scanning calorimetry (DSC). First thermal event on the DSC analysis of the Al4Cu0.5Mg1Sn alloy is the melting of elemental Sn, whereas for Al4Cu0.5Mg alloy, it is the formation of Al–Mg liquid nearly at 450 °C. Also it is clearly seen on the DSC analysis that Sn addition led to an increase in the formation enthalpy of Al–Mg liquid phase. High Sn content and high sintering temperature (620 °C), therefore high liquid-phase content, caused decrease on the mechanical properties due to thick intergranular phases and grain coarsening. Highest transverse rupture strength and hardness values were obtained from Al4Cu0.5Mg0.1Sn alloy sintered at 600 °C and measured as 390 MPa and 73 HB, respectively. 相似文献
56.
Tezcan H Uzluk E Aksu ML 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,70(5):973-982
In this study, new 1:2 Ni complexes of 1,3-substituted phenyl-5-phenylformazans were synthesized with -Cl, -Br substituents in the o-, m-, p-positions of the 1-phenyl ring and -NO(2) group in the m-position of the 3-phenyl ring. Their structures were elucidated and spectral behaviors were investigated with the use of elemental analysis, GC-Mass, (1)H NMR, (13)C NMR, FTIR, UV-vis spectra. Furthermore electrochemical properties such as number of electrons transferred (n), diffusion coefficients (D) and possible reaction mechanism of the compounds were determined with the use of cyclic voltammetry, ultramicrodisc electrode and chronoamperometry. The relation between their absorption properties and electrochemical properties was examined. A linear correlation was obtained between Hammett substituent coefficients with lambda(max) values. 相似文献
57.
Teslime Erşan Didem Giray Dilgin Elif Kumrulu Umur Kumrulu Yusuf Dilgin 《Electroanalysis》2023,35(4):e202200295
This work describes the sensitive voltammetric determination of favipiravir (FAV) based on its reduction for the first time with a low-cost and disposable pencil graphite electrode (PGE). In addition, the determination of FAV was also performed based on its oxidation. Differential pulse (DP) voltammograms recorded in 0.5 M H2SO4 for the reduction of FAV show that peak currents increase linearly in the range of 1.0 to 600.0 μM with a limit of detection of 0.35 μM. The acceptable recovery values (98.9–106.0 %) obtained from a pharmaceutical tablet, real human urine, and artificial blood serum samples spiked with FAV confirm the high accuracy of the proposed method. 相似文献
58.
The γ-hydroxypropyl-functionalised diiron dithiolate complex [Fe2(CO)6(μ-SCH2CH2CH2OH)2] is prepared upon thermolysis of Fe3(CO)12 and HO(CH2)3SH and further reaction with dppm (dppm = Ph2PCH2PPh2) affords [Fe2(CO)4(μ-dppm)(μ-SCH2CH2CH2OH)2]. From the reaction of Fe3(CO)12 with dppm(S2) a minor product is the tetrairon cluster, [{Fe2(CO)6(μ-SCH2CH2CH2OH)}2(μ4-S)], the mode of formation of which is unclear. It has been crystallographically characterised and adopts a μ4-S bridged double butterfly structure which is compared with other crystallographically characterised complexes of this type.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
59.
Eylem Turan Serkan Demirci Tuncer Caykara 《Journal of Polymer Science.Polymer Physics》2008,46(16):1713-1724
Dual temperature‐ and pH‐sensitive hydrogels composed of N‐isopropylacrylamide (NIPAM) and 2‐acrylamido‐2‐methyl‐propanosulfonic acid (AMPS) were prepared by free‐radical crosslinking copolymerization in aqueous solution at 22 °C. The mole percent of AMPS in the comonomer feed was varied between 0.0 and 7.5, while the crosslinker ratio was fixed at 5.0/100. The effect of AMPS content on thermo‐ and pH‐ induced phase transitions as well as equilibrium swelling/deswelling, interior morphology and network structure was investigated. The volume phase transition temperature (VPT‐T) was determined by both swelling/deswelling measurements and differential scanning calorimetry (DSC) technique. In addition, the volume phase transition pH (VPT‐pH) was detected from the derivative of the curves of the swelling ratio (dQv/dpH) versus pH. The polymer‐solvent interaction parameter (χ) and the average molecular mass between crosslinks ( ) of hydrogels were calculated from swelling ratios in buffer solutions at various pHs. The enthalpy (ΔH) and entropy (ΔS) changes appearing in the χ parameter of hydrogels were also determined by using the modified Flory–Rehner equation. The negative values for ΔH and ΔS indicated that the hydrogels had a negative temperature‐sensitive property in water, that is, swelling at a lower temperature and shrinking at a higher temperature. It was observed that the experimental swelling data of hydrogels at different temperature agreed with the modified Flory‐Rehner approach based on the affine network model. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1713–1724, 2008 相似文献