全文获取类型
收费全文 | 1227篇 |
免费 | 33篇 |
国内免费 | 4篇 |
专业分类
化学 | 750篇 |
晶体学 | 5篇 |
力学 | 46篇 |
数学 | 127篇 |
物理学 | 336篇 |
出版年
2023年 | 8篇 |
2022年 | 7篇 |
2021年 | 19篇 |
2020年 | 24篇 |
2019年 | 19篇 |
2018年 | 19篇 |
2017年 | 22篇 |
2016年 | 29篇 |
2015年 | 29篇 |
2014年 | 40篇 |
2013年 | 126篇 |
2012年 | 56篇 |
2011年 | 70篇 |
2010年 | 51篇 |
2009年 | 50篇 |
2008年 | 48篇 |
2007年 | 60篇 |
2006年 | 49篇 |
2005年 | 47篇 |
2004年 | 37篇 |
2003年 | 30篇 |
2002年 | 23篇 |
2001年 | 18篇 |
2000年 | 13篇 |
1999年 | 17篇 |
1998年 | 12篇 |
1996年 | 12篇 |
1995年 | 10篇 |
1994年 | 11篇 |
1993年 | 7篇 |
1992年 | 14篇 |
1991年 | 7篇 |
1990年 | 10篇 |
1989年 | 7篇 |
1988年 | 11篇 |
1987年 | 14篇 |
1986年 | 10篇 |
1985年 | 19篇 |
1984年 | 24篇 |
1983年 | 13篇 |
1982年 | 13篇 |
1981年 | 18篇 |
1980年 | 26篇 |
1979年 | 13篇 |
1978年 | 20篇 |
1977年 | 19篇 |
1976年 | 6篇 |
1975年 | 7篇 |
1973年 | 7篇 |
1972年 | 7篇 |
排序方式: 共有1264条查询结果,搜索用时 39 毫秒
1.
2.
3.
We have used the condensation method to synthesize 2-acetyl-5-methylsemicarbazone ligand. Manganese(II) and Cobalt(II) complexes having formula [ML2]X2 were synthesized where M = Mn(II) and Co(II), L = ligand, X = Cl−, CH3COO−, NO3−, ½SO42−. The characterization data suggests the octahedral geometry for all the synthesized complexes. Tridentate nature of the 2-acetyl-5-methylsemicarbazone ligand was revealed by IR studies. Molar conductance analysis suggested the electrolytic nature of the complexes. The theoretical study includes geometrical optimization, HOMO-LUMO energy gap, energetic parameters and dipole moment. These results also confirmed the tridentate nature of the ligand and the octahedral geometry of complexes. The molecular electrostatic potential (MEP) study suggested the reactive sites for an electrophilic or nucleophilic attack in the ligand. We tested the synthesized compounds for their antifungal and antibacterial action via well diffusion method and found that parent ligand after the coordination with the metal ion showed more effective inhibition against bacteria and fungi. 相似文献
4.
K.C. Devarayapalli S.V. Prabhakar Vattikuti T.V.M. Sreekanth Ki Soo Yoo P.C. Nagajyothi Jaesool Shim 《应用有机金属化学》2020,34(3):e5376
Herein, cobalt (Co)-based metal–organic zeolitic imidazole frameworks (ZIF-67) coupled with g-C3N4 nanosheets synthesized via a simple microwave irradiation method. SEM, TEM and HR-TEM results showed that ZIF-67 were uniformly dispersed on g-C3N4 surfaces and had a rhombic dodecahedron shape. The photocatalytic properties of g-C3N4/ZIF-67 nanocomposite were evaluated by photocatalytic dye degradation of crystal violet (CV), 4-chlorophenol (4-CP) and photocatalytic hydrogen (H2) production. In presence of visible light illumination, the photocatalytic dye results showed that 95% CV degradation and 53% 4-CP degradation within 80 min. The H2 production of the g-C3N4/ZIF-67 composite was 2084 μmol g−1, which is 3.84 folds greater than that of bare g-C3N4 (541 μmol g−1). 相似文献
5.
The conventional condensation and refluxing process was employed to synthesize Ni(II) and Cu(II) complexes of Methylcarbamatethiosemicarbazone ligand. Reactions were carried out at the pH of 7. The molar ratio of the ligand and metal salt was 2:1. The structures of the synthesized metal complexes were suggested by different analytical techniques such as magnetic susceptibility, molar conductance, IR, EPR and UV spectroscopy. Experimental studies confirmed the octahedral geometry for all the complexes. The geometry of the ligand and complexes were also confirmed by theoretical studies. The complexes were investigated for biological action against pathogenic fungi (C. krusei, C. albican) and bacteria (S. aureus, E. coli). The antimicrobial results confirmed superior inhibition potential of the metal complexes as compared with the parent ligand. The enhanced antimicrobial activities might be due to the chelation. Molecular-docking assays confirmed the strong interaction of ligand with target antimicrobial protein DNA gyrase-B. 相似文献
6.
Priyadeep Bhutani Rekha U. Shivakumar H. N. Prabhakar K. Ranjanna Atish T. Paul 《Biomedical chromatography : BMC》2020,34(10):e4902
Garcinia cambogia is one of the most commonly used anti-obesity dietary supplements, and hydroxycitric acid (HCA) is a major constituent in the commercial preparations of Garcinia. High doses of HCA are often consumed without much awareness of its pharmacokinetic and toxicokinetic parameters, and therefore, a complete understanding of its effects is lacking. The first step in understanding these parameters is the availability of a reliable bioanalytical method. Here, we present the first report on a UPLC–MS/MS method for analysis of HCA in rat plasma after a simplified and cost-effective protein precipitation. Chromatographic separation of the analytes in the supernatant was achieved using hydrophilic interaction liquid chromatography, where mass parameters were optimized and a rapid 5-min quantitative assay was developed. The method was highly sensitive, accurate, precise and linear in the concentration range of 10.5–5000 ng/mL (validated according to the United States Food and Drug Administration guidelines). Further, the method was successfully used to describe the pharmacokinetic profile of HCA in rat plasma after the administration of pure HCA and commercial Garcinia preparations. 相似文献
7.
8.
This study addresses the magnetic interaction between paramagnetic metal ions and the radical ligands taking the [CuII(hfac)2(imVDZ)] and [MII(hfac)2(pyDTDA)] (imVDZ=1,5-dimethyl-3-(1-methyl-2-imidazolyl)-6-oxoverdazyl; hfac=(1,1,1,5,5,5)hexafluroacetylacetonate; pyDTDA=4-(2′-pyridyl)-1,2,3,5-dithiadiazolyl), (M=Cu, Ni, Co, Fe, Mn) compounds as reference systems. The coupling between the metal and ligand spins is quantified in terms of the exchange coupling constant (J) in the platform of density functional theory (DFT) and the wave function-based complete active space self-consistent field (CASSCF) method. Application of DFT and broken symmetry (BS) formalism results ferromagnetic coupling for all the transition metal complexes except the Mn(II) complex. This DFT-BS prediction of magnetic nature matches with the experimental finding for all the complexes other than the Fe(II)-pyDTDA complex, for which an antiferromagnetic coupling between high spin iron and the thiazyl ligand has been reported. However, evaluation of spin state energetics through the multiconfigurational wave function-based method produces the S=3/2 ground spin state for the iron-thiazyl in parity with experiment. Electronic structure analyses find the overlap between the metal- and ligand-based singly occupied molecular orbitals (SOMOs) to be one of the major reasons attributing to different extent of exchange coupling in the systems under investigation. 相似文献
9.
S. N. V. M. S. Gupta A. K. Nayak U. B. Misra Balaji Rao Yarasi C. Phani Babu G. Kalyanakrishnan 《Journal of Radioanalytical and Nuclear Chemistry》2017,313(3):571-579
The present paper describes a new analytical method developed for direct determination of boron in steels using radio frequency glow discharge optical emission spectrometer. “Single parameter alternative method” technique has been used to optimize the various experimental conditions of glow discharge plasma such as forward power, gas pressure inside plasma chamber, pre-integration time, and integration time. Different emission lines for boron were studied and inter element interference effect is also discussed in the paper. A complete statistical analysis has been done to validate the developed method. A RSD of less than ±5% is achieved for boron in the range of 0.0010–0.020% in Steels using this method. 相似文献
10.
Metal complexes of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) are being used as a chiral catalysts in many organic reactions. This review highlights recent developments on synthesis of metal BINAPs and its application in various organic synthesis. The studies done on the application of metal BINAPs show a unique reactivity, which enables its use in entirely different sets of chemical transformation. 相似文献