全文获取类型
收费全文 | 1066篇 |
免费 | 56篇 |
国内免费 | 1篇 |
专业分类
化学 | 640篇 |
晶体学 | 4篇 |
力学 | 21篇 |
数学 | 117篇 |
物理学 | 250篇 |
无线电 | 91篇 |
出版年
2023年 | 11篇 |
2022年 | 22篇 |
2021年 | 26篇 |
2020年 | 31篇 |
2019年 | 28篇 |
2018年 | 19篇 |
2017年 | 14篇 |
2016年 | 45篇 |
2015年 | 28篇 |
2014年 | 26篇 |
2013年 | 42篇 |
2012年 | 58篇 |
2011年 | 81篇 |
2010年 | 37篇 |
2009年 | 32篇 |
2008年 | 53篇 |
2007年 | 56篇 |
2006年 | 43篇 |
2005年 | 41篇 |
2004年 | 36篇 |
2003年 | 32篇 |
2002年 | 19篇 |
2001年 | 10篇 |
2000年 | 13篇 |
1999年 | 9篇 |
1998年 | 10篇 |
1997年 | 22篇 |
1996年 | 13篇 |
1995年 | 15篇 |
1994年 | 28篇 |
1993年 | 13篇 |
1992年 | 9篇 |
1991年 | 17篇 |
1990年 | 11篇 |
1989年 | 9篇 |
1988年 | 8篇 |
1987年 | 11篇 |
1986年 | 11篇 |
1985年 | 11篇 |
1983年 | 8篇 |
1978年 | 10篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1973年 | 6篇 |
1969年 | 6篇 |
1968年 | 7篇 |
1967年 | 5篇 |
1966年 | 5篇 |
1958年 | 5篇 |
1957年 | 5篇 |
排序方式: 共有1123条查询结果,搜索用时 0 毫秒
51.
Alexandria N. Bone Chelsea N. Widener Duncan H. Moseley Zhiming Liu Zhengguang Lu Dr. Yongqiang Cheng Dr. Luke L. Daemen Dr. Mykhaylo Ozerov Prof. Joshua Telser Prof. Komalavalli Thirunavukkuarasu Dr. Dmitry Smirnov Samuel M. Greer Prof. Stephen Hill Dr. J. Krzystek Dr. Karsten Holldack Azar Aliabadi Dr. Alexander Schnegg Prof. Kim R. Dunbar Prof. Zi-Ling Xue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(43):11110-11125
Large separation of magnetic levels and slow relaxation in metal complexes are desirable properties of single-molecule magnets (SMMs). Spin-phonon coupling (interactions of magnetic levels with phonons) is ubiquitous, leading to magnetic relaxation and loss of memory in SMMs and quantum coherence in qubits. Direct observation of magnetic transitions and spin-phonon coupling in molecules is challenging. We have found that far-IR magnetic spectra (FIRMS) of Co(PPh3)2X2 ( Co-X ; X=Cl, Br, I) reveal rarely observed spin-phonon coupling as avoided crossings between magnetic and u-symmetry phonon transitions. Inelastic neutron scattering (INS) gives phonon spectra. Calculations using VASP and phonopy programs gave phonon symmetries and movies. Magnetic transitions among zero-field split (ZFS) levels of the S=3/2 electronic ground state were probed by INS, high-frequency and -field EPR (HFEPR), FIRMS, and frequency-domain FT terahertz EPR (FD-FT THz-EPR), giving magnetic excitation spectra and determining ZFS parameters (D, E) and g values. Ligand-field theory (LFT) was used to analyze earlier electronic absorption spectra and give calculated ZFS parameters matching those from the experiments. DFT calculations also gave spin densities in Co-X , showing that the larger Co(II) spin density in a molecule, the larger its ZFS magnitude. The current work reveals dynamics of magnetic and phonon excitations in SMMs. Studies of such couplings in the future would help to understand how spin-phonon coupling may lead to magnetic relaxation and develop guidance to control such coupling. 相似文献
52.
With impressive progress in carbon capture and renewable energy, carbon dioxide (CO2) conversion into useful chemicals has become a potential tool against climate change. Electrochemical CO2 conversion into C2 products (ethylene and ethanol) is an especially economically promising approach and an active research area. Nonetheless, catalyst layer design for CO2 conversion is challenging because of the complex CO2-to-C2 reaction pathways. In this review, we highlight key ideas in catalyst layer design for CO2 conversion to C2 in the past few years. We identify three fundamental principles to control catalyst selectivity—local CO2 and CO concentration, local pH, and intermediate–catalyst interaction. To achieve these goals, we introduce design strategies for both catalytic materials and overall catalyst layer morphology. 相似文献
53.
Chhavi Bhardwaj Jerry F. Moore Yang Cui Gerald L. Gasper Hans C. Bernstein Ross P. Carlson Luke Hanley 《Analytical and bioanalytical chemistry》2013,405(22):6969-6977
Laser desorption postionization mass spectrometry (LDPI-MS) imaging is demonstrated with a 10.5 eV photon energy source for analysis and imaging of small endogenous molecules within intact biofilms. Biofilm consortia comprised of a synthetic Escherichia coli K12 coculture engineered for syntrophic metabolite exchange are grown on membranes and then used to test LDPI-MS analysis and imaging. Both E. coli strains displayed many similar peaks in LDPI-MS up to m/z 650, although some observed differences in peak intensities were consistent with the appearance of byproducts preferentially expressed by one strain. The relatively low mass resolution and accuracy of this specific LDPI-MS instrument prevented definitive assignment of species to peaks, but strategies are discussed to overcome this shortcoming. The results are also discussed in terms of desorption and ionization issues related to the use of 10.5 eV single-photon ionization, with control experiments providing additional mechanistic information. Finally, 10.5 eV LDPI-MS was able to collect ion images from intact, electrically insulating biofilms at ~100 μm spatial resolution. Spatial resolution of ~20 μm was possible, although a relatively long acquisition time resulted from the 10 Hz repetition rate of the single-photon ionization source. Figure
Neutral species laser desorbed from cocultured biofilms undergo single photon ionization by VUV radiation and resultant ions are detected by time-of-flight mass spectrometry 相似文献
54.
Monika Michel Luke Chimuka Tomasz Kowalkowski Ewa M. Cukrowska Bogusław Buszewski 《Journal of separation science》2013,36(5):986-991
An artificial neural network model of supported liquid membrane extraction process with a stagnant acceptor phase is proposed. Triazine herbicides and phenolic compounds were used as model compounds. The model is able to predict the compound extraction efficiency within the same family based on the octanol–water partition coefficient, water solubility, molecular mass and ionisation constant of the compound. The network uses the back‐propagation algorithm for evaluating the connection strengths representing the correlations between inputs (octanol–water partition coefficients logP, acid dissociation constant pKa, water solubility and molecular weight) and outputs (extraction efficiency in dihexyl ether and undecane as organic solvents). The model predicted results in good agreement with the experimental data and the average deviations for all the cases are found to be smaller than ±3%. Moreover, standard statistical methods were applied for exploration of relationships between studied parameters. 相似文献
55.
Arthur J. Banister Anthony W. Luke 《Journal of polymer science. Part A, Polymer chemistry》1992,30(12):2653-2656
Mono-, bis- and tris-(1,3,2,4-dithiadiazolium) salts [R-(CNSNS +)n]n+[AsF-6]n (R = aryl, n = 1, 2, 3) were found to initiate the cationic ring-opening polymerization of tetrahydrofuran (THF) at room temperature to give clear gels from which the pure polymer was precipitated. 1,3,2,4-Dithiadiazolium cations associated with the hard [AsF6]- anion thus constitute a new class of cationic polymerization initiators. The poly(THF) formed by initiation with 1,3,2,4-dithiadiazolium cation was characterized by gel permeation chromatography, infrared spectrophotometry, and 13C-NMR spectroscopy. Number-average molecular weights of 198 700 g mol-1 (polydispersity 1.96) and 190 000 g mol-1 (polydispersity 1.61) were obtained using [PhCNSNS ] [AsF6] and [C6H3-1,3,5-(CNSNS )3][AsF6]3, respectively, as initiators. The use of multifunctional dithiadiazolium salts as initiators suggests that they may be useful in the preparation of starburst and dendritic polymers. © 1992 John Wiley & Sons, Inc. 相似文献
56.
Luke Garcia Carolyn Saba Gabriela Manocchio Gordon A. Anderson Eric Davis Brian H. Clowers 《International Journal for Ion Mobility Spectrometry》2017,20(3-4):87-93
Excluding the ion source, an ion mobility spectrometer is fundamentally comprised of drift chamber, ion gate, pulsing electronics, and a mechanism for amplifying and recording ion signals. Historically, the solutions to each of these challenges have been custom and rarely replicated exactly. For the IMS research community few detailed resources exist that explicitly detail the construction and operation of ion mobility systems. In an effort to address this knowledge gap we outline a solution to one of the key aspects of a drift tube ion mobility system, the ion gate pulser. Bradbury-Nielsen or Tyndall ion gates are found in nearly every research-grade and commercial IMS system. While conceptually simple, these gate structures often require custom, high-voltage, floating electronics. In this report we detail the operation and performance characteristics of a wifi-enabled, MOSFET-based pulser design that uses a lithium-polymer battery and does not require high voltage isolation transformers. Currently, each output of this circuit follows a TTL signal with ~20 ns rise and fall times, pulses up to +/? 200 V, and is entirely isolated using fiber optics. Detailed schematics and source code are provided to enable continued use of robust pulsing electronics that ease experimental efforts for future comparison. 相似文献
57.
Zhiyuan Qian Luke Galuska William W. McNutt Michael U. Ocheje Youjun He Zhiqiang Cao Song Zhang Jie Xu Kunlun Hong Rene B. Goodman Simon Rondeau‐Gagn Jianguo Mei Xiaodan Gu 《Journal of Polymer Science.Polymer Physics》2019,57(23):1635-1644
Thermomechanical properties of polymers highly depend on their glass transition temperature (T g). Differential scanning calorimetry (DSC) is commonly used to measure T g of polymers. However, many conjugated polymers (CPs), especially donor–acceptor CPs (D–A CPs), do not show a clear glass transition when measured by conventional DSC using simple heat and cool scan. In this work, we discuss the origin of the difficulty for measuring T g in such type of polymers. The changes in specific heat capacity (Δc p) at T g were accurately probed for a series of CPs by DSC. The results showed a significant decrease in Δc p from flexible polymer (0.28 J g?1 K?1 for polystyrene) to rigid CPs (10?3 J g?1 K?1 for a naphthalene diimide‐based D–A CP). When a conjugation breaker unit (flexible unit) is added to the D–A CPs, we observed restoration of the Δc p at T g by a factor of 10, confirming that backbone rigidity reduces the Δc p. Additionally, an increase in the crystalline fraction of the CPs further reduces Δc p. We conclude that the difficulties of determining T g for CPs using DSC are mainly due to rigid backbone and semicrystalline nature. We also demonstrate that physical aging can be used on DSC to help locate and confirm the glass transition for D‐A CPs with weak transition signals. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1635–1644 相似文献
58.
James O. Jensen Pallassana N. Krishnan Luke A. Burke 《Journal of Molecular Structure》1996,370(2-3):245-252
Twenty-two structures with the empirical formula H3CNO are presented. These structures are examined since they have the same formula as the H2O…HCN complex. The H2O…HCN potential energy surface is of interest to chemists studying the water catalyzed polymerization of HCN. Structures, thermodynamics, and vibrational spectra are examined. 相似文献
59.
Aoife M. Foley Declan P. Gavin Rebecca E. Deasy Sinéad E. Milner Thomas S. Moody Kevin S. Eccles Simon E. Lawrence Anita R. Maguire 《Tetrahedron》2018,74(13):1435-1443
Efforts to combine the intramolecular nitroaldol reaction with lipase-catalysed resolution of the resulting nitroaldol adduct in a one-pot dynamic kinetic resolution (DKR) are described. Significant challenges were encountered in the combination of the two systems. trans-2-Methyl-2-nitrocyclohexyl acetate (±)-3b was isolated in excellent enantiopurity (>98% ee) via a sequential DKR sequence where the lipase-mediated resolution and base-mediated interconversion of 2-methyl-2-nitrocyclohexanol 2 were effected alternately, demonstrating the feasibility of this approach initially. Further work showed, for the first time, evidence that a DKR-type system is possible for 2. Reaction engineering allowed the design of a sequential one-pot reaction system which furnished the products with excellent enantioselectivity, and good diastereoselectivity. 相似文献
60.