全文获取类型
收费全文 | 2219篇 |
免费 | 106篇 |
国内免费 | 32篇 |
专业分类
化学 | 1362篇 |
晶体学 | 13篇 |
力学 | 133篇 |
数学 | 336篇 |
物理学 | 272篇 |
无线电 | 241篇 |
出版年
2024年 | 3篇 |
2023年 | 15篇 |
2022年 | 46篇 |
2021年 | 82篇 |
2020年 | 98篇 |
2019年 | 108篇 |
2018年 | 134篇 |
2017年 | 105篇 |
2016年 | 176篇 |
2015年 | 115篇 |
2014年 | 164篇 |
2013年 | 264篇 |
2012年 | 183篇 |
2011年 | 161篇 |
2010年 | 136篇 |
2009年 | 121篇 |
2008年 | 106篇 |
2007年 | 76篇 |
2006年 | 50篇 |
2005年 | 39篇 |
2004年 | 30篇 |
2003年 | 16篇 |
2002年 | 21篇 |
2001年 | 12篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 4篇 |
1995年 | 5篇 |
1994年 | 3篇 |
1993年 | 7篇 |
1992年 | 9篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1974年 | 1篇 |
1971年 | 1篇 |
1970年 | 2篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有2357条查询结果,搜索用时 14 毫秒
31.
Samira Dadkhah-Tehrani Mehdi Shabani-Nooshabadi Mohsen Moradian 《Journal of the Iranian Chemical Society》2018,15(1):171-179
The electrochemical synthesis of some new 2-[(4-methyl-2-pyridyl)amino)-1,4-benzenediol derivatives was performed via the electrochemical oxidation of hydroquinones in the presence of 2-amino-4-methylpyridine in an aqueous solution. The results demonstrate that electrogenerated p-benzoquinone participated in the Michael-type addition reaction via an electrochemical–chemical (EC) reaction mechanism pathway and converted to the corresponding 2-[(4-methyl-2-pyridyl)amino)-1,4-benzenediol derivatives. These new compounds have been synthesized in high yields and purity without using any toxic reagents or catalyst at the surface of carbon electrode. 相似文献
32.
Effects of Zr addition on solidification characteristics of Al–Zn–Mg–Cu alloy using thermal analysis
Saman Mostafapoor Mehdi Malekan Masoud Emamy 《Journal of Thermal Analysis and Calorimetry》2018,134(3):1457-1469
The effect of Zr as a grain refiner on the solidification behavior, micro- and macrostructure of a new Al–Zn–Mg–Cu aluminum super-high strength alloy containing high Zn content was studied. The addition of 2 mass% Zr reduced the grain size from 1500 to 190 μm. Moreover, the dendritic structure of the alloy altered from a coarse, elongated and non-uniform morphology to a rosette-like shape and more uniform one. The parameters of liquidus region of cooling curve obtained from thermal analysis were in a good correlation with grain size results. The maximum of first derivative in the liquidus region was introduced beside recalescence undercooling which could predict the grain refinement level even after disappearing of recalescence in the cooling curve. Furthermore, the addition of 1 mass% Zr enhanced fraction of solid in dendrite coherency point from 21 to 31% and lessened the amounts of porosity from 2.3 to 1.4%. 相似文献
33.
Morteza Hosseini Mehdi Khoobi Roghayeh Tarasi Mohammad Reza Ganjali 《Research on Chemical Intermediates》2018,44(9):5031-5042
A rhodamine-conjugated coumarin (L) was used in designing a selective fluorescence chemosensor for the determination of trace amounts of Cr3+ ions in acetonitrile–water (MeCN/H2O (90:10, %v/v) solutions. The intensity of the fluoresce emission of the chemosensor is intensified upon addition of Cr3+ ions in MeCN/H2O (90:10, %v/v) solutions, due to the formation of a selective 1:1 complex between L and Cr3+ ions. The fluorescence enhancement versus Cr3+ concentration has been found to be linear from 1.0?×?10?7 to 1.8?×?10?5 M and a detection limit of 7.5?×?10?8 M. The proposed fluorescent probe proved to be highly selective towards Cr3+ ions as compared to other common metal ions and could be successfully applied to the determination of Cr3+ concentrations in some water and wastewater samples. 相似文献
34.
In this study, the biologically active configurations composed of Thiazolidinedione–Uracil (TU) and Rhodanine–Uracil (RU) have been fully investigated from the energetic and structural points of view, employing B3LYP and M062X functionals in combination with the different basis sets. Dispersion corrections to the interaction energy using M062X–GD3 and double hybrid density functionals (B2PLYP–GD2, B2PLYP–GD3 and mPW2PLYP–GD2) are also taking into account. The basis set superposition error-corrected interaction energy for hydrogen bonded configurations ranges from ??5.27 to ??13.53 and ??5.25 to ??12.93 kcal/mol for TU and RU complexes respectively as calculated at M062X/6–311++G(df,pd) level. The charge transfer process within all of the TU and RU configurations were analyzed using Natural Bond Orbital (NBO) calculations. The nature of the interactions is analyzed with NBO and Atoms in Molecules (AIM) analysis at M062X/6–311++G(df,pd) and energy decomposition analysis at BP86–D3/TZ2P(ZORA)//M062X/6–311++G(df,pd) level of theory. The results confirm that the nature of the interactions is nearly electrostatic, with a contribution of about 51–56% of the total interaction energy. The orbital interactions (ΔEorb) for the considered TU and RU complexes have a contribution of about 24–38% of the total interaction energy. Based on the AIM and NBO results, the interactions were defined as electrostatic H-bonds with partially covalent character. In addition, correlation between interaction energies and vibrational frequency changes was investigated. 相似文献
35.
Catalytic one‐pot condensation of benzil, aldehyde and ammonium acetate have been successfully carried out using 2‐hydroxyethylammonium formate (HEAF) grafted on a magnetic nanoparticles as a new heterogeneous catalyst. The as‐prepared catalyst was characterized by FT‐IR, TEM, FESEM, VSM, TGA and XRD. This catalyst indicated significant advantages, such as excellent yields, shorter reaction time, reusability of the catalyst and easy workup process. 相似文献
36.
A heterogeneous and recyclable catalyst with a high loading of silver nanoparticles was synthesized via the silver nanoparticles being supported onto the surface of magnetic nanoparticles coated with poly(4‐vinylpyridine). The synthesized catalyst was used in the dehydrogenation of alcohols to corresponding carbonyl compounds. A broad diversity of alcohols was converted into their corresponding carbonyl compounds in excellent yields. The catalyst was easily recovered by applying an external magnetic field and reused for seven reaction cycles without considerable loss of activity. The catalyst was fully characterized using various techniques. 相似文献
37.
Ali Shokuhi Rad Sadegh Mehdi Aghaei Elaheh Aali Majid Peyravi Mohsen Jahanshahi 《应用有机金属化学》2018,32(2)
The interactions of the nucleobases thymine (C5H6N2O2) and uracil (C4H4N2O2) with Cr‐doped C20 fullerene (C19Cr) are investigated by performing density functional theory calculations. The adsorption of these nucleobases on C19Cr leads to two distinct geometries (P1 and P2) differing in the orientation of the nucleobases. The interaction of the nucleobases with the C19Cr nanocluster is highly exothermic, revealing that they are chemically adsorbed on C19Cr. The results show that the binding energy of the thymine–C19Cr complex is slightly higher than that of the uracil–C19Cr complex. In addition, the P2 geometry is more stable compared to P1 due to the higher binding energy in the former configuration. However, based on the results of natural bond orbital and frontier molecular orbitals analyses, the C19Cr nanocage has higher reactivity with the nucleobases in P1 geometry in comparison with P2 due to the larger charge transfer and orbital hybridization in the former geometry. Moreover, the band gap of the C19Cr nanocage decreases after interaction with the nucleobases, and interestingly the impact is more pronounced for P1 geometry, confirming the higher sensitivity of C19Cr to the nucleobases in P1 geometry. Our findings reveal the promising potential of C19Cr as an organometallic carrier for nucleobases thymine and uracil. 相似文献
38.
Marzieh Haghverdi Naeimeh Bahri-Laleh Mehdi Nekoomanesh Haghighi 《Journal of Coordination Chemistry》2018,71(8):1180-1192
Five 2-(1H-benzimidazol-2-yl)-phenol derivatives including 1H (HL1), 5-chloro-(HL2), 5-methyl-(HL3), 5,6-dichloro-(HL4), and 5,6-dimethyl-(HL5) were synthesized by the reaction of their corresponding benzene-1,2-diamine precursors and 2-hydroxybenzaldehyde which subsequently was employed in complexation with Fe(II) to prepare complexes C1–C5, respectively. Indeed, in all complexes, the ligands were coordinated as bidentate, via the C=N nitrogen and hydroxy oxygen atom of benzimidazole moiety and phenol ring, respectively. The compounds were characterized by FTIR, UV–vis, 1H- and 13C-NMR spectropscopy, ICP, and elemental analysis (C, H, and N). The purity of these compounds was determined by melting point (m.p )and TLC. The synthesized ligands and complexes were geometrically optimized by Gaussian09 software at B3LYP/TZVP level of theory and satisfactory theoretical–experimental agreement was achieved for analysis of IR data of the compounds. Catalytic behavior of the iron(II) complexes was investigated for ethylene reactivity. On activation with diethylaluminum chloride (Et2AlCl), iron(II) complex (C4) showed the highest activity (1686 kg oligomers.mol?1(Fe).h?1) for ethylene oligomerization when it contains chlorine substituents and exhibits good selectivity for linear 1-butene. The steric and electronic effects of ligands were investigated in detail on the influence of their catalytic activities. 相似文献
39.
Can Coordination‐Driven Supramolecular Self‐Assembly Reactions Be Conducted from Fully Aliphatic Linkers? 下载免费PDF全文
Dr. Mehdi Elsayed Moussa Dr. Sloane Evariste Barbara Krämer Prof. Dr. Régis Réau Prof. Dr. Manfred Scheer Dr. Christophe Lescop 《Angewandte Chemie (International ed. in English)》2018,57(3):795-799
The reaction between a preassembled CuI bimetallic molecular clip with a short intermetallic distance and a series of fully aliphatic cyano‐capped ditopic linkers with increasing lengths was investigated. It is shown that, depending on the length of the ditopic linkers, the rational design of unprecedented supramolecular compact metallacycles containing fully aliphatic walls is possible. The specific preorganized molecular arrangement of the molecular clip used favors stabilizing interlinker London dispersion interactions, which allow, as the length of the linkers increases, the selective formation of discrete compact metallacycles at the expense of 1D coordination polymers. The generalizability of this approach was demonstrated by the reaction of fully aliphatic cyano‐capped linkers with two other types of preassembled CuI bimetallic molecular clips that also had short intermetallic distances. 相似文献
40.
Mehdi Baghayeri Reza Ansari Marzieh Nodehi Hojat Veisi 《International journal of environmental analytical chemistry》2018,98(9):874-888
In this article, a highly sensitive electrochemical sensor is introduced for direct electro-oxidation of bisphenol A (BPA). The novel nanocomposite was prepared based on multi-walled carbon nanotube/thiol functionalised magnetic nanoparticles (Fe3O4-SH) as an immobilisation platform and gold nanoparticles (AuNPs) as an amplifying electrochemical signal. The chemisorbed AuNPs exhibited excellent electrochemical activity for the detection of BPA. Some analysing techniques such as Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy and energy-dispersive x-ray diffraction exposed the formation of nanocomposite. Under optimum conditions (pH 9), the sensor showed a linear range between 0.002–240 μM, with high sensitivity (0.25 μA μM?1) along with low detection limit (6.73 × 10?10 M). Moreover, nanocomposites could efficiently decrease the effect of interfering agents and remarkably enhance the utility of sensor at detection of BPA in some real samples. 相似文献