全文获取类型
收费全文 | 1099篇 |
免费 | 218篇 |
国内免费 | 115篇 |
专业分类
化学 | 831篇 |
晶体学 | 13篇 |
力学 | 29篇 |
数学 | 66篇 |
物理学 | 493篇 |
出版年
2024年 | 3篇 |
2023年 | 32篇 |
2022年 | 34篇 |
2021年 | 43篇 |
2020年 | 63篇 |
2019年 | 57篇 |
2018年 | 42篇 |
2017年 | 39篇 |
2016年 | 56篇 |
2015年 | 70篇 |
2014年 | 69篇 |
2013年 | 87篇 |
2012年 | 105篇 |
2011年 | 104篇 |
2010年 | 76篇 |
2009年 | 59篇 |
2008年 | 71篇 |
2007年 | 64篇 |
2006年 | 51篇 |
2005年 | 40篇 |
2004年 | 32篇 |
2003年 | 29篇 |
2002年 | 23篇 |
2001年 | 18篇 |
2000年 | 11篇 |
1999年 | 18篇 |
1998年 | 16篇 |
1997年 | 22篇 |
1996年 | 17篇 |
1995年 | 7篇 |
1994年 | 11篇 |
1993年 | 13篇 |
1992年 | 11篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 1篇 |
1987年 | 4篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1969年 | 1篇 |
1966年 | 1篇 |
1955年 | 1篇 |
排序方式: 共有1432条查询结果,搜索用时 31 毫秒
141.
Hu X Dou W Xu C Tang X Zheng J Liu W 《Dalton transactions (Cambridge, England : 2003)》2011,40(13):3412-3418
A bi-phosphonate ligand tetraethyl-(2,3,5,6-tetramethyl-1,4-phenylene) bis(methylene)diphosphonate has been designed and synthesized. The bi-phosphonate as a bridging ligand reacts with lanthanide nitrates forming four different types of 1D coordination complexes: ribbon polymer (type I), semi-ribbon polymer (type II), zigzag polymer (type III), and dinuclear-triligand short chain (type IV), which changed according to the decrease of the radius of the lanthanide. They have been characterized by IR spectroscopy, elemental analysis, and X-ray diffraction spectroscopy. The photophysical properties of Sm(3+), Eu(3+), Tb(3+) and Dy(3+) complexes at room temperature were also investigated. They exhibit strong fluorescence by excitation of the Ln(3+) ion absorption bands and the quantum yield values of Eu(3+) and Tb(3+) complexes are no less than 20%. 相似文献
142.
Zhang AJ Wang YW Dou W Dong M Zhang YL Tang Y Liu WS Peng Y 《Dalton transactions (Cambridge, England : 2003)》2011,40(12):2844-2851
Six new homodinuclear lanthanide(III) complexes with a flexible tripodal carboxylate ligand (H(3)L), of formulae [Ln(2)L(2)(DMF)(4)]·4DMF (Ln = La (1), Nd (2), Eu (3), Gd (4), Tb (5), Dy (6), DMF = N, N-Dimethylformamide) have been synthesized. Among them, 1, 2, 3, 4, 6 were characterized by single-crystal X-ray diffraction, which crystallized in the monoclinic space group P2(1)/n with a = 13.309(2) ?, b = 27.404(4) ?, c = 16.686(3) ?, β = 105.115(2) and V = 5875.2(17) ?(3) for 1, a = 13.3016(5) ?, b = 27.1952(12) ?, c = 16.6339(7) ?, β = 105.030(2) and V = 5811.3(4) ?(3) for 2, a = 13.2797(10) ?, b = 27.072(2) ?, c = 16.6564(13) ?, β = 104.9390(10) and V = 5785.7(8) ?(3) for 3, a = 13.2855(3) ?, b = 27.0074(6) ?, c = 16.6357(3) ?, β = 104.9790(10) and V = 5766.2(2) ?(3) for 4, a = 13.2837(5) ?, b = 26.9105(10) ?, c = 16.6066(6) ?, β = 104.917(2) and V = 5736.3(4) ?(3) for 6. The crystal structures reveal that these complexes are isostructural, and molecules are connected from 0D to 3D supramolecular structures by hydrogen bonds. All of them were characterized by elemental analysis, IR spectroscopy, XRD and TGA. Unusually, non-luminescent Tb(III) complex was obtained. The photophysical property of the Eu(III) complex and the magnetic property of Gd(III) complex are investigated and discussed in detail. 相似文献
143.
Feng D Lv Y Wu Z Dou Y Han L Sun Z Xia Y Zheng G Zhao D 《Journal of the American Chemical Society》2011,133(38):15148-15156
We report for the first time the synthesis of free-standing mesoporous carbon films with highly ordered pore architecture by a simple coating-etching approach, which have an intact morphology with variable sizes as large as several square centimeters and a controllable thickness of 90 nm to ~3 μm. The mesoporous carbon films were first synthesized by coating a resol precursors/Pluronic copolymer solution on a preoxidized silicon wafer and forming highly ordered polymeric mesostructures based on organic-organic self-assembly, followed by carbonizing at 600 °C and finally etching of the native oxide layer between the carbon film and the silicon substrate. The mesostructure of this free-standing carbon film is confirmed to be an ordered face-centered orthorhombic Fmmm structure, distorted from the (110) oriented body-centered cubic Im3?m symmetry. The mesoporosity of the carbon films has been evaluated by nitrogen sorption, which shows a high specific BET surface area of 700 m(2)/g and large uniform mesopores of ~4.3 nm. Both mesostructures and pore sizes can be tuned by changing the block copolymer templates or the ratio of resol to template. These free-standing mesoporous carbon films with cracking-free uniform morphology can be transferred or bent on different surfaces, especially with the aid of the soft polymer layer transfer technique, thus allowing for a variety of potential applications in electrochemistry and biomolecule separation. As a proof of concept, an electrochemical supercapacitor device directly made by the mesoporous carbon thin films shows a capacitance of 136 F/g at 0.5 A/g. Moreover, a nanofilter based on the carbon films has shown an excellent size-selective filtration of cytochrome c and bovine serum albumin. 相似文献
144.
Sun Z Kim JH Zhao Y Bijarbooneh F Malgras V Lee Y Kang YM Dou SX 《Journal of the American Chemical Society》2011,133(48):19314-19317
Controlling the morphology and size of titanium dioxide (TiO(2)) nanostructures is crucial to obtain superior photocatalytic, photovoltaic, and electrochemical properties. However, the synthetic techniques for preparing such structures, especially those with complex configurations, still remain a challenge because of the rapid hydrolysis of Ti-containing polymer precursors in aqueous solution. Herein, we report a completely novel approach-three-dimensional (3D) TiO(2) nanostructures with favorable dendritic architectures-through a simple hydrothermal synthesis. The size of the 3D TiO(2) dendrites and the morphology of the constituent nano-units, in the form of nanorods, nanoribbons, and nanowires, are controlled by adjusting the precursor hydrolysis rate and the surfactant aggregation. These novel configurations of TiO(2) nanostructures possess higher surface area and superior electrochemical properties compared to nanoparticles with smooth surfaces. Our findings provide an effective solution for the synthesis of complex TiO(2) nano-architectures, which can pave the way to further improve the energy storage and energy conversion efficiency of TiO(2)-based devices. 相似文献
145.
A seeded approach was developed to synthesize high-silica EU-1 zeolite via inhibiting the co-crystallization of ZSM-48 in the presence of hexamethonium (HM) ions. A systematic study was carried out to determine factors such as seed content and SiO(2)/Al(2)O(3) ratio, which influenced the crystallization of high-silica EU-1 and transformation of EU-1 into ZSM-48. Using EU-1 seeds, not only well-crystallized pure EU-1 zeolites with SiO(2)/Al(2)O(3) ratios more than 500 were synthesized, but also the co-crystalline of ZSM-48/EU-1 or pure ZSM-48 was obtained in control from silica-rich mixture gels. Furthermore, the kinetic features of the seeded synthesis of EU-1 zeolites with SiO(2)/Al(2)O(3) ratios of 55, 190, and 500 were examined. It was found that seeds played crucial roles in the decrease of apparent activation energy of EU-1 nucleation and inhibiting the transformation of EU-1 into ZSM-48. The HM and Al species performed synergistic roles to inhibit the formation ZSM-48 during high-silica EU-1 nucleation and crystal growth. 相似文献
146.
As part of our ongoing project involving the study of (1-C(n)H(2n+1)NH(3))(2)MCl(4)(s) (where M is a divalent metal ion and n = 8-18), we have synthesized the compounds (1-C(n)H(2n+1)NH(3))(2)ZnCl(4)(s) (n = 8, 10, 12, and 13), and the details of the structures are reported herein. All of the compounds were crystallized in the monoclinic form with the space group P2(1)/n for (1-C(8)H(17)NH(3))(2)ZnCl(4)(s), P21/c for (1-C(10)H(21)NH(3))(2)ZnCl(4)(s), P2(1)/c for (1-C(12)H(25)NH(3))(2)ZnCl(4)(s), and P2(1)/m for (1-C(13)H(27)NH(3))(2)ZnCl(4)(s). The lattice potential energies and ionic volumes of the cations and the common anion of the title compounds were obtained from crystallographic data. Molar enthalpies of dissolution of the four compounds at various molalities were measured at 298.15 K in the double-distilled water. According to Pitzer's theory, molar enthalpies of dissolution of the title compounds at infinite dilution were obtained. Finally, using the values of molar enthalpies of dissolution at infinite dilution (Δ(s)H(m)(∞)) and other auxiliary thermodynamic data, the enthalpy change of the dissociation of [ZnCl(4)](2-)(g) for the reaction [ZnCl(4)](2-)(g)→ Zn(2+)(g) + 4Cl(-)(g) was obtained, and then the hydration enthalpies of cations were calculated by designing a thermochemical cycle. 相似文献
147.
Mechanics of Composite Materials - The effect of reinforcement configuration (steel fibers and a rebar) on the mechanical performance of a multiribbed composite slab (MCS) has been investigated.... 相似文献
148.
In this paper, we investigate the asymptotic behaviors of the critical branching process with immigration {Z_n, n ≥ 0}. First we get some estimation for the probability generating function of Zn. Based on it, we get a large deviation for Z_(n+1)/Z_n. Lower and upper deviations for Zn are also studied. As a by-product, an upper deviation for max_(1≤i≤n) Z_i is obtained. 相似文献
149.
Guo Mei Yang Ran Zhang Meng Liu Renyuan Zhu Yongliang Dou Gang 《Nonlinear dynamics》2021,105(1):877-886
Nonlinear Dynamics - In this paper, a novel memcapacitor is designed by the SBT ( $$\hbox {Sr}_{0.95}\hbox {Ba}_{0.05}\hbox {TiO}_{{3}}$$ ) memristor and two capacitors. A fifth-order memcapacitor... 相似文献
150.
Wenjie Sui Shunqin Li Xiaodan Zhou Zishan Dou Rui Liu Tao Wu Hongyu Jia Guanhua Wang Min Zhang 《Molecules (Basel, Switzerland)》2021,26(13)
In this work, steam explosion (SE) was exploited as a potential hydrothermal-humification process of vegetable wastes to deconstruct their structure and accelerate their decomposition to prepare humified substances. Results indicated that the SE process led to the removal of hemicellulose, re-condensation of lignin, degradation of the cellulosic amorphous region, and the enhancement of thermal stability of broccoli wastes, which provided transformable substrates and a thermal-acidic reaction environment for humification. After SE treatment, total humic substances (HS), humic acids (HAs), and fulvic acids (FAs) contents of broccoli samples accounted for up to 198.3 g/kg, 42.3 g/kg, and 166.6 g/kg, and their purification were also facilitated. With the increment of SE severity, structural characteristics of HAs presented the loss of aliphatic compounds, carbohydrates, and carboxylic acids and the enrichment of aromatic structures and N-containing groups. Lignin substructures were proved to be the predominant aromatic structures and gluconoxylans were the main carbohydrates associated with lignin in HAs, both of their signals were enhanced by SE. Above results suggested that SE could promote the decomposition of easily biodegradable matters and further polycondensation, aromatization, and nitrogen-fixation reactions during humification, which were conducive to the formation of HAs. 相似文献