全文获取类型
收费全文 | 3393篇 |
免费 | 368篇 |
国内免费 | 483篇 |
专业分类
化学 | 1928篇 |
晶体学 | 12篇 |
力学 | 64篇 |
综合类 | 36篇 |
数学 | 81篇 |
物理学 | 851篇 |
无线电 | 1272篇 |
出版年
2024年 | 16篇 |
2023年 | 74篇 |
2022年 | 151篇 |
2021年 | 193篇 |
2020年 | 187篇 |
2019年 | 104篇 |
2018年 | 87篇 |
2017年 | 140篇 |
2016年 | 166篇 |
2015年 | 183篇 |
2014年 | 203篇 |
2013年 | 278篇 |
2012年 | 233篇 |
2011年 | 242篇 |
2010年 | 154篇 |
2009年 | 177篇 |
2008年 | 206篇 |
2007年 | 202篇 |
2006年 | 190篇 |
2005年 | 180篇 |
2004年 | 128篇 |
2003年 | 131篇 |
2002年 | 101篇 |
2001年 | 79篇 |
2000年 | 78篇 |
1999年 | 58篇 |
1998年 | 39篇 |
1997年 | 33篇 |
1996年 | 27篇 |
1995年 | 41篇 |
1994年 | 34篇 |
1993年 | 17篇 |
1992年 | 24篇 |
1991年 | 8篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1988年 | 16篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1984年 | 10篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 3篇 |
排序方式: 共有4244条查询结果,搜索用时 31 毫秒
91.
Sébastien Gagné 《Biomedical chromatography : BMC》2013,27(5):664-668
A novel method for the biological monitoring of benzene‐exposed workers has been developed through ultra‐performance liquid chromatography coupled to tandem mass spectrometry. The method uses trans,trans‐muconic acid in urine as the benzene‐exposure biomarker. The method was developed using a triple quadrupole mass spectrometer with enough sensitivity to facilitate diluting and injecting the urine samples directly, rather than performing a solid‐phase extraction procedure as is common in the available protocols. Moreover, compared with a conventional high‐pressure liquid chromatography system, the separation power provided by the ultra‐performance liquid chromatography system allows a 10‐fold reduction in run time. The method was adjusted to a dynamic range of between 198.9 and 4916.7 µg/L to cover the biological exposure index of trans,trans‐muconic acid in urine. Also, the method demonstrated intra‐day and inter‐day precision at 98%, and accuracy within an acceptable range of 101 ± 8%. The method has been used to quantify various types of urine samples, such as workers' urine and inter‐laboratory proficiency tests. Depending on the sample, the quantified levels ranged from less than the limit of quantitation to 3836.7 µg/L. No levels exceeding the calibration range were detected in the urine of workers, and the reported concentrations in urine for the proficiency tests were, as expected, based on known values. Moreover, the new method using sample dilution and faster chromatographic run was more effective, facilitating fast communication of results, as needed, to decision‐makers. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
92.
93.
The enhanced biological activities of three Zn (II) complexes based on different 1,2,4‐triazole fungicides
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Guo‐yu Ren Jie Li Xu‐zhan Wei Jin‐hua Zhou Biao Yan Zhao‐qi Guo Ying‐hui Ren Xiao‐hong Sun Hai‐xia Ma 《应用有机金属化学》2018,32(9)
In order to screen effective fungicides, three Zn (II) complexes, [Zn L 1 4 (NO3)2]·2H2O·2EtOH ( 1 ), [Zn L 2 4 (NO3)2] ( 2 ), and [Zn L 3 4 (DMF)2](NO3)2 ( 3 ), ( L 1 = paclobutrazol, L 2 = diniconazole, and L 3 = hexaconazole), were synthesized and characterized by elemental analysis, FT‐IR spectroscopy, and single‐crystal XRD. The antifungal activities of these complexes were then evaluated against four selected fungi using the mycelial growth rate method. The resulting data indicate that all the complexes show the enhanced antifungal activities than the corresponding ligand and mixtures. And, the interactions between the metal salt and ligands in the three complexes seem to be synergistic. According to the study of the influence of the structures on the activity, complex 2 with C=C linkage and 2,4‐dichlorophenyl moieties enhances the bioactivity significantly, especially against Wheat gibberellic ( II ). Density functional theory (DFT) calculations were carried out to help explain the enhanced bioactivity of the Zn (II) complexes. Meanwhile, all complexes are excellent grow‐regulators, especially complex 3 . The resulting data show that the complexes based on triazole fungicides have the potential applications in agriculture. 相似文献
94.
In this letter, a comparison between three types (two linear and one nonlinear) of models of skeletal muscle stiffness is shown. Results are compared with experimental data for biceps brachii in the case of muscle stretching and with the Hill equation for a biological muscle. It is shown that results for nonlinear stiffness model in case of length-force relationship fits to the experimental data. 相似文献
95.
Matrix-assisted laser desorption/ionization (MALDI) is a soft ionization technique which can be used in mass spectrometry to produce ions from biomolecules without inducing the fragmentation associated with traditional methods of ionization. When used with small molecules, the lack of fragmentation allows identification of specific molecules against a background of alternative signals; thus, for example, the presence of drug molecules and metabolites can be distinguished from a range of alternative biomolecules present within a tissue sample. Using highly collimated lasers in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) allows imaging of a tissue sample whereby the laser is rastered across the sample and individual mass spectra are collected in a serial manner. Thus, the distribution of the molecules within the tissue sample can be presented in the form of a 2D image. While the detection of specific drug molecules and metabolites within biological samples has its uses, quantification of those same molecules would be of greater benefit in a clinical setting. However, accurate quantification presents additional challenges. We present an overview of the MALDI-MS technique followed by recent progress in profiling drugs and their metabolites through imaging drug distributions within tissues and finish with recent developments in the quantification of drugs in tissues by MALDI-MSI. 相似文献
96.
97.
Coordination compounds of Fe(III), Zn(II), Ni(II), Co(II), Cu(II), Cd(II) and Mn(II) ions were synthesized from the ligand [4,4′‐((((ethane‐1,2‐diylbis(oxy))bis(2,1‐phenylene))bis(methanylylidene))bis(azanylylidene))diphenol]ethane (H2L) derived from the condensation of bisaldehyde and 4‐aminophenol. Microanalysis, magnetic susceptibility, infrared, 1H NMR and mass spectroscopies, molar conductance, X ray powder diffraction and thermal analysis were used to confirm the structure of the synthesized chelates. According to the data obtained, the composition of the 1:1 metal ion–bis‐Schiff base ligand was found to be [M(H2L)(H2O)2]Cln (M = Zn(II), Ni(II), Co(II), Cu(II), Cd(II) and Mn(II), n = 2; Fe(III), n = 3). Magnetic susceptibility measurements and reflectance spectra suggested an octahedral geometry for the complexes. Central metals ions and bis‐Schiff base coordinated together via O2 and N2 donor sites which as evident from infrared spectra. The Gaussian09 program was applied to optimize the structural formula for the investigated Schiff base ligand. The energy gaps and other important theoretical parameters were calculated applying the DFT/B3LYP method. Molecular docking using AutoDock tools was utilized to explain the experimental behaviour of the Schiff base ligand towards proteins of Bacillus subtilis (5 h67), Escherichia coli (3 t88), Proteus vulgaris (5i39) and Staphylococcus aureus (3ty7) microorganisms through theoretical calculations. The docked protein receptors were investigated and the energies of hydrogen bonding were calculated. These complexes were then subjected to in vitro antibacterial studies against several organisms, both Gram negative (P. vulgaris and E. coli) and Gram positive (S. pyogones and B. subtilis). The ligand and metal complexes exhibited good microbial activity against the Gram‐positive and Gram‐negative bacteria. 相似文献
98.
Due to the relatively large structures in the Oil and Gas industry, original equipment manufacturers (OEMs) have been implementing custom-designed laser vision sensor (LVS) surface profiling systems as part of quality control in their manufacturing processes. The rough manufacturing environment and the continuous movement and misalignment of these custom-designed tools adversely affect the accuracy of laser-based vision surface profiling applications. Accordingly, Oil and Gas businesses have been raising the demand from the OEMs to implement practical and robust LVS calibration techniques prior to running any visual inspections. This effort introduces an LVS calibration technique representing a simplified version of two known calibration techniques, which are commonly implemented to obtain a calibrated LVS system for surface profiling applications. Both calibration techniques are implemented virtually and experimentally to scan simulated and three-dimensional (3D) printed features of known profiles, respectively. Scanned data is transformed from the camera frame to points in the world coordinate system and compared with the input profiles to validate the introduced calibration technique capability against the more complex approach and preliminarily assess the measurement technique for weld profiling applications. Moreover, the sensitivity to stand-off distances is analyzed to illustrate the practicality of the presented technique. 相似文献
99.
100.
《应用有机金属化学》2017,31(11)
A novel azo dye ligand, 2,2′‐(1,3‐phenylenebis(diazene‐2,1‐diyl))bis(4‐chlorophenol), was synthesized from the diazotization of m ‐phenelyenediamine and coupling with p ‐chlorophenol in alkaline medium. Mononuclear Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes of the azo ligand (H2L) were prepared and characterized using elemental analyses, infrared spectroscopy, electron spin resonance, magnetic susceptibility, conductance measurements and thermal analyses. The UV–visible, 1H NMR and mass spectra of the ligand and its chelates were also recorded. The analytical data showed that the metal‐to‐ligand ratio in the mononuclear azo complexes was 1:1. Diffuse reflectance and magnetic moment measurements revealed the complexes to have octahedral geometry. The infrared spectral data showed that the chelation behaviour of the ligand towards transition metal ions was through phenolic oxygen and azo nitrogen atoms. The electronic spectral results indicated the existence of π → π* (phenyl rings) and n → π* (─N═N) and confirmed the mentioned structure. Molar conductivity revealed the non‐electrolytic nature of all chelates. The presence of water molecules in all complexes was supported by thermal studies. Molecular docking was used to predict the binding between H2L and the receptors of breast cancer mutant 3hb5‐oxidoreductase, crystal structure of Escherichia coli (3 t88) and crystal structure of Staphylococcus aureus (3q8u). The molecular and electronic structure of H2L was optimized theoretically and the quantum chemical parameters were calculated. In addition, the effects of the H2L azo ligand and its complexes on the inhibition of bacterial or fungal growth were evaluated. The prepared complexes had enhanced activity against bacterial or fungal growth compared to the H2L azo ligand. 相似文献