全文获取类型
收费全文 | 14693篇 |
免费 | 1359篇 |
国内免费 | 4732篇 |
专业分类
化学 | 15526篇 |
晶体学 | 531篇 |
力学 | 536篇 |
综合类 | 161篇 |
数学 | 1675篇 |
物理学 | 2355篇 |
出版年
2024年 | 10篇 |
2023年 | 133篇 |
2022年 | 164篇 |
2021年 | 378篇 |
2020年 | 426篇 |
2019年 | 344篇 |
2018年 | 369篇 |
2017年 | 449篇 |
2016年 | 560篇 |
2015年 | 455篇 |
2014年 | 689篇 |
2013年 | 1216篇 |
2012年 | 1505篇 |
2011年 | 837篇 |
2010年 | 720篇 |
2009年 | 929篇 |
2008年 | 1055篇 |
2007年 | 1159篇 |
2006年 | 1060篇 |
2005年 | 1036篇 |
2004年 | 959篇 |
2003年 | 800篇 |
2002年 | 691篇 |
2001年 | 545篇 |
2000年 | 561篇 |
1999年 | 463篇 |
1998年 | 402篇 |
1997年 | 369篇 |
1996年 | 347篇 |
1995年 | 365篇 |
1994年 | 331篇 |
1993年 | 242篇 |
1992年 | 290篇 |
1991年 | 212篇 |
1990年 | 169篇 |
1989年 | 125篇 |
1988年 | 96篇 |
1987年 | 67篇 |
1986年 | 72篇 |
1985年 | 50篇 |
1984年 | 35篇 |
1983年 | 19篇 |
1982年 | 24篇 |
1981年 | 14篇 |
1980年 | 9篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1975年 | 4篇 |
1972年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance. 相似文献
22.
Julián Bravo-Castillero Ariel Ramírez-Torres Catherine García-Reimbert Raúl Guinovart-Díaz Reinaldo Rodríguez-Ramos 《Waves in Random and Complex Media》2020,30(4):593-613
ABSTRACT The asymptotic homogenization method is applied to complex dielectric periodic composites. An equivalence to coupled dielectric problems with real coefficients is shown. This is similar to a piezoelectric problem: an out-plane mechanical displacement and an in-plane electric potential establishing a correspondence principle. Closed-form formulas for the complex dielectric effective tensor in the case of a square array of circular inclusions embedded in a matrix are given. These formulas are written in terms of a real and symmetric matrix which facilitates the implementation of the computational scheme. We also get similar formulas for multilayered complex dielectric composites. The real closed-form formulas are advantageous for estimating gain and loss enhancement properties of active and passive composites in certain volume fraction intervals. Numerical computations are performed and the results are compared with other approaches showing the usefulness of the obtained formulas. This may be of interest in the context of metamaterials. 相似文献
23.
24.
Qi-Jun Li Ya-Jie Ren Qin Xie Min Wu Hua-Xing Feng Li-Mei Zheng Hua-Xin Zhang Jin-Qiao Long Tian-Shun Wang 《应用有机金属化学》2020,34(10):e5813
Two nickel complexes, [Ni(tpen)](ClO4)2.0.5CH3COCH3 ( 1 ) and [Ni(tpbn)](ClO4)2 ( 2 ), of tetrapyridyl ligands N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,2-ethanediamine (tpen) and N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,4-butanediamine (tpbn) were prepared and their catalysis for water oxidation reaction (WOR) studied. In 0.1 M phosphate buffer solution (PBS) of pH 8.0, complex 1 is a homogeneous molecular catalyst with an overpotential of ~440 mV and a Faradaic efficiency of 89%. At pH ≥ 9.0, complex 1 degraded gradually during the catalytic process and formed NiOx composite (nickel oxide with general formula NixOyHz) active for WOR. In contrast, complex 2 deteriorated under measured conditions (pH 8.0–12.0) and formed NiOx composite active for WOR. The NiOx composite derived from 1 in 0.1 M PBS at pH 11.0 showed an activity with an overpotential of ~500 mV, a Tafel slope of ~90 mV/decade and a Faradaic efficiency of 97%. Mechanisms were proposed for water oxidation catalyzed by 1 and 2 . This work revealed that the catalytic activity of the nickel complexes was related to the flexibility of the tetrapyridyl ligands and the adaptability of the coordination sphere of the nickel(II) center. 相似文献
25.
Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)2] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2. 相似文献
26.
现实生活中,与国计民生密切相关的基础设施网络大多不是独立存在的,而是彼此之间相互联系或依赖的,于是用于研究这些系统的多层网络模型随之产生.多层网络中的节点在失效或者遭受攻击后会因"层内"和"层间"的相互作用而产生级联效应,从而使得失效能够在网络层内和层间反复传播并使得失效规模逐步放大.因此,多层网络比单个网络更加脆弱.多层网络级联失效产生的影响和损失往往是非常巨大的,所以对多层网络级联失效的预防和恢复的研究具有重大意义.就多层网络级联失效的预防而言,主要包含故障检测,保护重要节点,改变网络耦合机制和节点备份等策略.就多层网络发生级联失效后的恢复策略而言,主要包含共同边界节点恢复、空闲连边恢复、加边恢复、重要节点优先恢复、更改拓扑结构、局域攻击修复、自适应边修复等策略. 相似文献
27.
The Burton-Miller boundary integral formulation is solved by a complex variable boundary element-free method (CVBEFM) for the boundary-only meshless analysis of acoustic problems with arbitrary wavenumbers. To regularize both strongly singular and hypersingular integrals and to avoid the computation of the solid angle and its normal derivative, a weakly singular Burton-Miller formulation is derived by considering the normal derivative of the solid angle and adopting the singularity subtraction procedures. To facilitate the implementation of the CVBEFM and the approximation of gradients of the boundary variables, a stabilized complex variable moving least-square approximation is selected in the meshless discretization procedure. The results show the accuracy and efficiency of the present CVBEFM and reveal that the method can produce satisfactory results for all wavenumbers, even for extremely large wavenumbers such as k = 10 000. 相似文献
28.
《Current Applied Physics》2020,20(7):853-861
Among the conventional metallic inks used in the printing process, silver exhibits high conductivity and thermal stability. Nevertheless, due to the high cost of silver, it cannot be extensively used for the fabrication of inks. As a competitive alternative, copper can be considered as a substitute for silver; however, copper ink oxidizes under certain atmospheric conditions. To meet these shortcomings, a cost effective, highly conductive, and oxidation-free copper-based ink has been synthesized in this study, wherein, oxidation of the copper particles in the copper-based ink was prevented by using copper complexes. The copper ink thus fabricated was printed on chemically treated Si/SiO2 substrates followed by the characterization of the printed copper films. The results of this study confirmed that the synthesized copper ink exhibited properties suitable for its use in the inkjet printing process for fabrication of various electronic devices. 相似文献
29.
Investigation of Suzuki–Miyaura catalyst‐transfer polycondensation of AB‐type fluorene monomer using coordination‐saturated aryl Pd(II) halide complexes as initiators 下载免费PDF全文
Zilong Zhang Pan Hu Xiao Li Hongmei Zhan Yanxiang Cheng 《Journal of polymer science. Part A, Polymer chemistry》2015,53(12):1457-1463
Novel triarylamine‐based coordination‐saturated aryl Pd(II) halide complexes ligated by PEt3, PCy3, and P(o‐tol)3 were successfully synthesized by direct oxidative addition of aryl halide to the corresponding Pd(0) precursors. Suzuki–Miyaura coupling polymerization of 2‐(7‐halide‐9,9‐dioctylfluoren‐2‐yl)?1,3,2‐dioxaborinane with these Pd(II) complexes as initiators was investigated for the synthesis of poly(fluorene)s with triarylamine end group. Pd(II) complexes with PCy3 or P(o‐tol)3 exhibited catalytic activity and realized the catalyst‐transfer polycondensation at 75 °C and room temperature, respectively, while the polymerization using Pd(II) catalyst ligated by PEt3 did not proceed, which indicated that the bulky phosphine ligands could facilitate the reductive elimination and further promote the polymerization. In addition, the dimeric Pd(II) complex with P(o‐tol)3 can convert into monomeric Pd(II) intermediate with an open coordination site, which had a higher activity. The end groups of the afforded polyfluorene were analyzed by matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry, in which the Ar/H end groups are indicative of the catalyst‐transfer polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1457–1463 相似文献
30.
A new dinuclear iron(Ⅲ) complex has been synthesized and structurally characterized by X-ray crystallography: [FeⅢ2(L)(C6H5COO)(SO4)(CH3OH)2]·CH3CN·CH3OH(1, H3 L = N,N'-bis(salicylidene)-1,3-diamino-2-propanol). Complex 1 belongs to orthorhombic space group Pna21 with a = 11.4400(8), b = 22.9705(2), c = 12.5712(9) , V = 3303.5(4) 3, Z = 4, F(000) = 1576, Dc = 1.531 g·cm–3, Mr = 761.36, μ = 1.007 mm–1, S = 1.014, the final R = 0.0505 and wR = 0.1018. The crystal packing is stabilized by intermolecular O–H···O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters of J = 19.7 cm-1, g = 1.89 and R2 = 0.9999. 相似文献