全文获取类型
收费全文 | 4531篇 |
免费 | 316篇 |
国内免费 | 32篇 |
专业分类
化学 | 3097篇 |
晶体学 | 45篇 |
力学 | 169篇 |
数学 | 737篇 |
物理学 | 831篇 |
出版年
2023年 | 31篇 |
2022年 | 45篇 |
2021年 | 129篇 |
2020年 | 97篇 |
2019年 | 190篇 |
2018年 | 152篇 |
2017年 | 107篇 |
2016年 | 241篇 |
2015年 | 154篇 |
2014年 | 247篇 |
2013年 | 479篇 |
2012年 | 279篇 |
2011年 | 293篇 |
2010年 | 207篇 |
2009年 | 199篇 |
2008年 | 214篇 |
2007年 | 203篇 |
2006年 | 202篇 |
2005年 | 162篇 |
2004年 | 146篇 |
2003年 | 113篇 |
2002年 | 124篇 |
2001年 | 64篇 |
2000年 | 81篇 |
1999年 | 52篇 |
1998年 | 34篇 |
1997年 | 43篇 |
1996年 | 35篇 |
1995年 | 34篇 |
1994年 | 34篇 |
1993年 | 37篇 |
1992年 | 31篇 |
1991年 | 23篇 |
1990年 | 15篇 |
1989年 | 28篇 |
1988年 | 24篇 |
1987年 | 20篇 |
1986年 | 17篇 |
1985年 | 29篇 |
1984年 | 24篇 |
1983年 | 21篇 |
1982年 | 20篇 |
1981年 | 26篇 |
1980年 | 16篇 |
1979年 | 15篇 |
1978年 | 15篇 |
1977年 | 9篇 |
1976年 | 13篇 |
1975年 | 16篇 |
1959年 | 8篇 |
排序方式: 共有4879条查询结果,搜索用时 15 毫秒
1.
2.
3.
Adel Z. El‐Sonbati Mostafa A. Diab Ahmed M. Eldesoky Shaimaa M. Morgan Omnia L. Salem 《应用有机金属化学》2019,33(5)
Novel polymer complexes of 8‐hydroxyquinoline‐5‐sulfonic acid hydrate ( H 2 L ) with Cu2+, Co2+ and Ni2+ chloride were prepared and characterized. Microanalysis, magnetic susceptibility, IR spectra, electron spin resonance, mass spectra, X‐ray, molar conductance, thermal, and UV–Vis spectra studies have been used to confirm the structure of the prepared polymer complexes. The molecular and electronic structures of the hydrogen bond conformers for ligand ( H 2 L ) were optimized theoretically and the quantum chemical parameters were calculated. On the basis of elemental and IR data, the chemical structure of metal chelates commensurate that the tri‐dentate (H2L) coordinate to metal chlorides through oxygen atom of phenolic OH and oxygen atom of SO3‐H group by replacing H atoms and nitrogen of the quinoline ring. The magnetic studies suggested the octahedral geometrical structure for all produced polymer complexes with general formula {[ML (OH2)3] .xH2O}n (M = Cu2+, x = 1.; Co2+, x = 2 and Ni2+, x = 2) in molar ratio (1:1). Coats–Redfern and Horowitz–Metzger methods have been used for calculating the activation thermodynamic parameters of the thermal decomposition for H 2 L and its polymer complexes. The interaction between H 2 L and its transition metal complexes with the calf thymus DNA (CT‐DNA) was determined by UV–Vis spectra. Binding efficiency between H 2 L with the receptors of the prostate cancer (PDB code 2Q7L Hormone) and the breast cancer (PDB code 1JNX Gene regulation) was studied by molecular docking. The inhibition behaviour of H 2 L against the corrosion of carbon steel / HCl (2 M) solution was studied by weight loss, Tafel polarisation, electrochemical impedance spectroscopy (EIS) and electrochemical frequency modulation (EFM) techniques. The adsorption isotherm was found to be Friendlish isotherm. The morphology of inhibited carbon steel? s surface was studied using scanning electron microscope (SEM) and energy dispersive X‐ray spectroscopy (EDS). 相似文献
4.
Waleed A. El‐Said Mona A. Abdel‐Rahman Eman M. Sayed Aboel‐Magd A. Abdel‐Wahab 《Electroanalysis》2019,31(5):829-837
Here, we reported on a one‐step fabrication of magnetite Fe3O4 nanoparticles/indium tin oxide (ITO) electrode based on the direct growing of Fe3O4 nanoparticles on the ITO surface by using a solvothermal process. The modified electrode was used as electrochemical methotrexate (MTX) biosensor with high sensitivity based on cyclic voltammetry and square wave voltammetry techniques. The results demonstrated a linear relationship between the MTX concentration and its oxidation current peak over a wide range from 10?5 to 10?14 mole/L with a limit of detection of 0.4×10?15 M based on the square wave voltammetry (SWV) technique. In addition, Fe3O4/ITO electrode showed a good capability for measuring very low concentrations of MTX drug dissolved in human serum solution. Also, Fe3O4/ITO electrode was used for detecting MTX in blood serum samples collected from patients after their treatment with MTX. The prepared electrode showed the higher sensitivity that higher than the Viva‐E instrument, which opens the door for developing a cheap, simple and higher sensitive MTX sensor. 相似文献
5.
New thiazole derivatives were synthesized and fully characterized, then coordinated with PtCl4 salt. Also, the newly synthesized Pt(IV) complexes were investigated analytically (elemental and thermogravimetric analyses), spectrally (infrared, UV–visible, mass, 1H NMR, 13C NMR, X‐ray diffraction) as well as theoretically (kinetics, modeling and docking). The data extracted led to the establishment of the best chemical and structural forms. Octahedral geometry was the only formula proposed for all complexes, which is favorable for d6 systems. The molecular ion peaks from mass spectral analysis coincide with all analytical data, confirming the molecular formula proposed. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) allowed discrimination of features between crystalline particles and other amorphous morphology. By applying Gaussian09 as well as HyperChem 8.2 programs, the best structural forms were obtained, as well as computed significant parameters. Computed parameters such as softness, hardness, surface area and reactivity led us towards application in two opposing pathways: tumor inhibition and oxidation activation. The catalytic oxidation for CO was conducted over PtO2, which was yielded from calcination of the most reactive complex. The success of catalytic role for synthesized PtO2 was due to its particulate size and surface morphology, which were estimated from XRD patterns and SEM images, respectively. The antitumor activity was tested versus HCT‐116 and HepG‐2 cell lines. Mild toxicity was recorded for two of the derivatives and their corresponding complexes. This degree of toxicity is more favorable in most cases, due to exclusion of serious side effects, which is coherently attached with known antitumor drugs. 相似文献
6.
A new Schiff base hydrazone (Z)‐2‐(2‐aminothiazol‐4‐yl)‐N′‐(2‐hydroxy‐3‐methoxybenzylidene) acetohydrazide (H2L) and its chelates [VO (HL)2]·5H2O, [Cu (HL)Cl(H2O)]·2H2O and [Fe(L)Cl(H2O)2]·3H2O have been isolated and characterized using different physico‐chemical methods, for example infrared (IR), electron paramagnetic resonance (EPR), thermogravimetric analysis and DTG in the solid state, and 1H‐NMR, 13C‐NMR and UV in solution. Magnetic and UV–visible measurements proposed that the coordination environments are square pyramidal, tetrahedral and octahedral geometries for oxovanadium (IV), Cu (II) and Fe (III), respectively. The ligand acts as mono‐negative NO towards oxovanadium (IV) and Cu (II) ions, and bi‐negative ONO for Fe (III) ion. The geometries of the ligand and its complexes were performed using Gaussian 9 program with density functional theory. The EPR spectral data of oxovanadium (IV) and Cu (II) chelates confirmed the mentioned geometries. The molecular modeling was done, and illustrated bond lengths, bond angles, molecular electrostatic potential, Mulliken atomic charges and chemical reactivity for the inspected compounds. Theoretical IR and 1H‐NMR of the free ligand were calculated. Furthermore, thermodynamic and kinetic parameters for thermal decomposition steps were studied. Docking study of H2L was applied against the proteins of both bacterial strains Staphylococcus aureus and Escherichia coli, as well as the protein of xanthine oxidase as antioxidant agent by Schrödinger suite program utilizing XP glide protocol. Furthermore, antimicrobial, antioxidant and DNA‐binding activities of the compounds have been carried out. 相似文献
7.
Ben Jadi S. El Guerraf A. Bazzaoui E.A. Wang R. Martins J.I. Bazzaoui M. 《Journal of Solid State Electrochemistry》2019,23(8):2423-2433
Journal of Solid State Electrochemistry - Due to their distinctive chemical, electronic, and environmental properties, polypyrrole is used as a blocking barrier for methanol leakage in direct... 相似文献
8.
Gouda A. A. El Sheikh R. El Sayed H. M. Khedr A. M. Al Ezz Sh. Abo Gamil W. Hamdy M. 《Journal of Applied Spectroscopy》2022,89(3):567-578
Journal of Applied Spectroscopy - A new, green, simple, and validated ultrasound-assisted dispersive microsolid-phase extraction method applying unprecedented adsorbent-modified multiwalled carbon... 相似文献
9.
Yang Chunxiao Taralova Ina El Assad Safwan Loiseau Jean-Jacques 《Nonlinear dynamics》2022,109(3):2103-2127
Nonlinear Dynamics - Nonlinear dynamic systems and chaotic systems have been quite exhaustively researched in the domain of cryptography. However, the possibility of using fractional chaotic... 相似文献
10.
Heavy metal ions are harmful to aquatic life and humans owing to their high toxicity and non‐biodegradability, so their removal from wastewater is an important task. Therefore, this work focuses on designing suitable, simple and economical nanosensors to detect and remove these metal ions with high selectivity and sensitivity. Based on this idea, different types of mesoporous materials such as hexagonal SBA‐15, cubic SBA‐16 and spherical MCM‐41, their chloro‐functionalized derivatives, as well as 4‐(4‐nitro‐phenylazo)‐naphthalen‐1‐ol (NPAN) azo dye have been synthesized, with the aim of designing some optical nanosensors for metal ions sensing applications. The mentioned azo dye has been anchored into the chloro‐functionalized mesoporous materials. The designed nanosensors were characterized using scanning and transmission electron microscopy as well as Fourier transform infrared and UV–visible spectral analysis, nitrogen adsorption–desorption isotherms, low‐angle X‐ray diffraction and thermogravimetric analyses. Their optical sensing to various toxic metal ions such as Cd (II), Hg (II), Mn (II), Fe (II), Zn (II) and Pb (II) at different values of pH (1.1, 4.9, 7 and 12) was investigated. The optimization of experimental conditions, including the effect of pH and metal ion concentration, was examined. The experimental results showed that the solution pH had a major impact on metal ion detection. The optical nanosensors respond well to the tested metal ions, as reflected by the enhancement in both absorption and emission spectra upon adding different concentrations of the metal salts and were fully reversible on adding ethylene diamine tetra acetic acid or citric acid to the formed complexes. High values of the binding constants for the designed nanosensors were observed at pHs 7 and 12, confirming the strong chelation of different metals to the nanosensor at these pHs. Also, high binding constants and sensitivity were observed for NPAN‐MCM‐41 as a nanosensor to detect the different metal ions. From the obtained results, we succeeded in transforming the harmful azo dye into an environmentally friendly form via designing of the optical nanosensors used to detect toxic metal ions in wastewater with high sensitivity. 相似文献