全文获取类型
收费全文 | 7683篇 |
免费 | 1537篇 |
国内免费 | 942篇 |
专业分类
化学 | 5435篇 |
晶体学 | 116篇 |
力学 | 442篇 |
综合类 | 89篇 |
数学 | 854篇 |
物理学 | 3226篇 |
出版年
2024年 | 32篇 |
2023年 | 236篇 |
2022年 | 383篇 |
2021年 | 373篇 |
2020年 | 446篇 |
2019年 | 418篇 |
2018年 | 348篇 |
2017年 | 322篇 |
2016年 | 437篇 |
2015年 | 444篇 |
2014年 | 475篇 |
2013年 | 644篇 |
2012年 | 718篇 |
2011年 | 702篇 |
2010年 | 505篇 |
2009年 | 463篇 |
2008年 | 441篇 |
2007年 | 393篇 |
2006年 | 327篇 |
2005年 | 300篇 |
2004年 | 249篇 |
2003年 | 205篇 |
2002年 | 181篇 |
2001年 | 154篇 |
2000年 | 111篇 |
1999年 | 137篇 |
1998年 | 105篇 |
1997年 | 90篇 |
1996年 | 91篇 |
1995年 | 75篇 |
1994年 | 64篇 |
1993年 | 44篇 |
1992年 | 35篇 |
1991年 | 46篇 |
1990年 | 41篇 |
1989年 | 26篇 |
1988年 | 22篇 |
1987年 | 18篇 |
1986年 | 14篇 |
1985年 | 13篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1978年 | 2篇 |
1964年 | 1篇 |
1959年 | 1篇 |
1957年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
151.
Cheng‐Hua Lee Meng‐Rong Tsai Yen‐Tzu Chang Prof. Dr. Long‐Li Lai Dr. Kuang‐Lieh Lu Dr. Kung‐Lung Cheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(32):10573-10579
Three unconventional dendrimers that contained rigid NH? triazine linkages and peripheral tert‐butyl moieties were prepared by using a convergent approach and characterized by 1H and 13C NMR spectroscopy, mass spectrometry, and elemental analysis. Based on a thermogravimetric analysis study, these dendrimers were observed to display thermal stability at about 300 °C. The NH? triazine moiety, which possessed protonated and proton‐free nitrogen sites (like the imidazole unit), displayed the capture of polarizable CO2 molecules through hydrogen‐bond and/or dipole–quadrupole interactions. In addition, the adsorption of various amounts of CO2 and N2 at different pressures suggests that the dendritic pores, which arise from the stacking of the middle co‐planar and rim protuberant dendrimers, G n ‐N~N‐G n (n=1–3), either swell or shrink at high pressure, thus indicating that these dendrimers may have a breathing ability. 相似文献
152.
聚苯并双噁唑酰亚胺的热分解动力学研究 总被引:1,自引:0,他引:1
采用二步法合成了以2,6-二(对-氨基苯)苯[1,2-d;5,4-d’]二噁唑和1,4-二(3,4-二苯氧基)苯四甲酸二酐(HQDPA)为单体的聚苯并双噁唑酰亚胺.该聚酰亚胺的预聚体聚酰胺酸的黏度为1.70 dL/g,经过热环化后能够生成浅黄色的聚酰亚胺薄膜.通过热重分析法研究了聚苯并双噁唑酰亚胺在N2气氛中的热降解机理.采用Flynn-Wall-Ozawa和Friedman法计算了聚苯并双噁唑酰亚胺热降解表观活化能,分别为356.36kJ/mol和370.54 kJ/mol,平均值为363.45 kJ/mol;反应级数为4.22,指前因子为6.44×1016s-1.采用Coast-Redfern法和Phadnis-Deshpande法研究了聚苯并双噁唑酰亚胺的热降解固相反应机理,认为该聚酰亚胺的热降解机理属于反曲线(A3)机理,是成核和增长模式(Avrami equation 2方程)控制的热降解反应,积分形式为g(X)=[-ln(1-X)]3. 相似文献
153.
Analysis of an aggregation‐based algebraic two‐grid method for a rotated anisotropic diffusion problem 下载免费PDF全文
A two‐grid convergence analysis based on the paper [Algebraic analysis of aggregation‐based multigrid, by A. Napov and Y. Notay, Numer. Lin. Alg. Appl. 18 (2011), pp. 539–564] is derived for various aggregation schemes applied to a finite element discretization of a rotated anisotropic diffusion equation. As expected, it is shown that the best aggregation scheme is one in which aggregates are aligned with the anisotropy. In practice, however, this is not what automatic aggregation procedures do. We suggest approaches for determining appropriate aggregates based on eigenvectors associated with small eigenvalues of a block splitting matrix or based on minimizing a quantity related to the spectral radius of the iteration matrix. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
154.
Sheng‐Run Zheng Xi‐Ling Wen Zi‐Meng Liu Tao Xie Jing‐Bo Tan Jun Fan Shuang‐Shuang Hou Wei‐Guang Zhang 《无机化学与普通化学杂志》2014,640(10):2057-2061
Two coordination polymers (CPs), namely, [Cu(Hptz)2(Hhba)2]n ( 1 ) [Hptz = 5‐(4‐pyridyl)‐1H‐tetrazole, H2hba = 2‐hydroxybenzoic acid] and [Zn3(ptz)2(hpa)2]n ( 2 ) (H2hpa = 2‐hydroxy‐2‐phenylacetic acid), were synthesized by solvothermal reactions. Both complexes were characterized by elemental analysis, infrared spectroscopy, powder X‐ray diffraction, thermogravimetric analysis, and single‐crystal X‐ray diffraction analysis. Compound 1 exhibits a 2D (4,4) network, where each layer connects to four adjacent layers to construct a 3D supramolecular framework. Compound 2 has a 3D framework structure composed of 1D SUBs, which are formed by both carboxyl and tetrazole groups. The complexes represent two rare examples of CPs constructed from Hptz and organic carboxyl acid ligands. Complex 2 exhibits intense, red‐shifted emissions in the visible region at room temperature. 相似文献
155.
Miao Wan Zhilin Meng Hongxiang Lou Lei Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(50):14065-14069
A trityl ion mediated C H functionalization of ethers with a wide range of nucleophiles at ambient temperature has been developed. The reaction displays high chemoselectivity and good functional group tolerance. The protocol also exhibits excellent regio‐ and diastereoselectivities for the unsymmetric ethers, thus stereoselectively generating highly functionalized disubstituted 2,5‐trans tetrahydrofurans (THF), 2,6‐trans tetrahydropyrans (THP), 2,6‐trans dihydropyrans (DHP), and 1,3‐trans isochromans, and highlighting the capacity of the protocol in complex molecule synthesis. 相似文献
156.
Nickel(I) complexes were generated in situ from Ni (PPh3)2Cl2 using activated iron and the complexes combined with N,N′-bis(4-fluorobenzylidene) ethane-1,2-diamine (BFBED) were then used as a catalyst for the 1,4-addition reaction of arylboronic acids to α,β-unsaturated substrates. The reaction proceeded to completion and did not require the addition of a base but the addition of potassium iodide is crucial to this cross-coupling reaction. Moreover, experimental observations suggested a possible Ni(I)–Ni(III) catalytic cycle mechanism. 相似文献
157.
Ningbo Zhang Yonggang Du Meng Cui Zhiqiang Liu Shuying Liu 《Analytical and bioanalytical chemistry》2014,406(15):3537-3549
Platinum drugs have become one of the most important kinds of chemotherapy agents, and the interactions of these drugs with proteins play very important roles in their side effects and drug resistance. However, it is still a challenge to determine the binding sites of platinum drugs in proteins with multiple disulfide bonds and stable three-dimensional structures using mass spectrometry. Here, the interaction between cisplatin and hen egg white lysozyme (HEWL), a multi-disulfide-bond-containing protein with a stable three-dimensional structure, was investigated using Fourier transform ion cyclotron resonance mass spectrometry. Typical disulfide bond reduction with dithiothreitol/tris(2-carboxyethyl)phosphine before trypsin digestion destroyed the binding of cisplatin to HEWL, and no platination sites were found. Efficient trypsin digestion methods for HEWL–cisplatin adducts were developed to avoid the loss of platinum binding to protein. At 55 °C, platinated HEWL was digested directly by trypsin in 6 h, and multiple platinated peptides were observed. In 60 % acetonitrile, the digestion time of platinated HEWL was shortened to 2 h, and most of the platinated peptides were observed. In addition, the reduction of the disulfide bonds of HEWL greatly accelerated the reaction between HEWL and cisplatin, and the potential binding sites of cisplatin in reduced HEWL could be easily recognized. On the basis of the above-mentioned methods, multiple binding sites of cisplatin in HEWL were first identified by mass spectrometry. Figure
Digestion methods for HEWL-cisplatin adducts 相似文献
158.
Jiang Zhao Meng Lian Yue Yu Xiaogang Yan Xianbin Xu Xiaolong Yang Guijiang Zhou Zhaoxin Wu 《Macromolecular rapid communications》2015,36(1):71-78
A series of novel red phosphorescent polymers is successfully developed through Suzuki cross‐coupling among ambipolar units, functionalized IrIII phosphorescent blocks, and fluorene‐based silane moieties. The photophysical and electrochemical investigations indicate not only highly efficient energy‐transfer from the organic segments to the phosphorescent units in the polymer backbone but also the ambipolar character of the copolymers. Benefiting from all these merits, the phosphorescent polymers can furnish organic light‐emitting diodes (OLEDs) with exceptional high electroluminescent (EL) efficiencies with a current efficiency (η L) of 8.31 cd A−1, external quantum efficiency (η ext) of 16.07%, and power efficiency (η P) of 2.95 lm W−1, representing the state‐of‐the‐art electroluminescent performances ever achieved by red phosphorescent polymers. This work here might represent a new pathway to design and synthesize highly efficient phosphorescent polymers.
159.
160.
The flexible stretchable sensors have great potential for implementation in various applications, such as intelligent soft robots, health monitoring, and motion detection. However, most of the flexible stretchable sensors with microstructures and high sensitivities are fabricated by expensive templates and complex processes. In consideration of large-scale fabrication, a low cost and efficient way is in great demand. Herein, electroless plating on Nafion films with decent swelling ratios are proposed to fabricate stretchable sensors with wrinkle-structured electrodes. By adding isopropanol (IPA) to the electroless plating process, the H2O-IPA sensor with larger swelling ratio shows deeper surface wrinkles, higher surface roughness, and better sensitivity to strain. At the same time, the H2O-IPA sensor exhibit good durability (500 cycles). By mounting the sensor on the joint of human finger, the motion of the finger bending and even the bending degree can be accurately detected, indicating the potential use in the field of wearable devices and soft electronic skins. 相似文献