全文获取类型
收费全文 | 4666篇 |
免费 | 236篇 |
国内免费 | 39篇 |
专业分类
化学 | 3233篇 |
晶体学 | 24篇 |
力学 | 116篇 |
数学 | 547篇 |
物理学 | 606篇 |
无线电 | 415篇 |
出版年
2023年 | 52篇 |
2022年 | 58篇 |
2021年 | 91篇 |
2020年 | 115篇 |
2019年 | 111篇 |
2018年 | 85篇 |
2017年 | 65篇 |
2016年 | 150篇 |
2015年 | 132篇 |
2014年 | 172篇 |
2013年 | 252篇 |
2012年 | 323篇 |
2011年 | 382篇 |
2010年 | 179篇 |
2009年 | 152篇 |
2008年 | 352篇 |
2007年 | 335篇 |
2006年 | 334篇 |
2005年 | 285篇 |
2004年 | 232篇 |
2003年 | 201篇 |
2002年 | 169篇 |
2001年 | 39篇 |
2000年 | 36篇 |
1999年 | 44篇 |
1998年 | 39篇 |
1997年 | 46篇 |
1996年 | 63篇 |
1995年 | 37篇 |
1994年 | 31篇 |
1993年 | 28篇 |
1992年 | 25篇 |
1991年 | 27篇 |
1990年 | 28篇 |
1989年 | 16篇 |
1988年 | 13篇 |
1987年 | 15篇 |
1986年 | 18篇 |
1985年 | 25篇 |
1984年 | 28篇 |
1983年 | 14篇 |
1982年 | 15篇 |
1981年 | 15篇 |
1980年 | 19篇 |
1979年 | 10篇 |
1978年 | 22篇 |
1977年 | 12篇 |
1976年 | 16篇 |
1975年 | 9篇 |
1974年 | 10篇 |
排序方式: 共有4941条查询结果,搜索用时 31 毫秒
951.
Fiona H. Scholes Tino Ehlig Michael James Kwan H. Lee Noel Duffy Andrew D. Scully T. Birenda Singh Kevin N. Winzenberg Pete Kemppinen Scott E. Watkins 《Advanced functional materials》2013,23(45):5655-5662
A comprehensive study of the effect of intraphase microstructure on organic photovoltaic (OPV) device performance is undertaken. Utilizing a bilayer device architecture, a small molecule donor (TIPS‐DBC) is deposited by both spin‐coating and by thermal evaporation in vacuum. The devices are then completed by thermal evaporation of C60, an exciton blocking layer and the cathode. This bilayer approach enables a direct comparison of device performance for donor layers in which the same material exhibits subtle differences in microstructure. The electrical performance is shown to differ considerably for the two devices. The bulk and interfacial properties of the donor layers are compared by examination with photoelectron spectroscopy in air (PESA), optical absorption spectroscopy, charge extraction of photo‐generated charge carriers by linearly increasing voltage (photo‐CELIV), time‐resolved photoluminescence measurements, X‐ray reflectometry (XR), and analysis of dark current behavior. The observed differences in device performance are shown to be influenced by changes to energy levels and charge transport properties resulting from differences in the microstructure of the donor layers. Importantly, this work demonstrates that in addition to the donor/acceptor microstructure, the intraphase microstructure can influence critical parameters and can therefore have a significant impact on OPV performance. 相似文献
952.
Kevin van de Ruit Racheli Itzhak Cohen Dirk Bollen Ton van Mol Rachel Yerushalmi‐Rozen René A. J. Janssen Martijn Kemerink 《Advanced functional materials》2013,23(46):5778-5786
The mechanism and magnitude of the in‐plane conductivity of poly(3,4‐ethy‐lenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) thin films is determined using temperature dependent conductivity measurements for various PEDOT:PSS weight ratios with and without a high boiling solvent (HBS). Without the HBS the in‐plane conductivity of PEDOT:PSS is lower and for all studied weight ratios well described by the relation $ \sigma = \sigma _0 {\rm exp}[- \left({{{{T_0}}\over{T}}} \right)^{0.5}] $ with T0 a characteristic temperature. The exponent 0.5 indicates quasi‐one dimensional (quasi‐1D) variable range hopping (VRH). The conductivity prefactor σ0 varies over three orders of magnitudes and follows a power law σ0∝c3.5PEDOT with cPEDOT the weight fraction of PEDOT in PEDOT:PSS. The field dependent conductivity is consistent with quasi‐1D VRH. Combined, these observations suggest that conductance takes place via a percolating network of quasi‐1D filaments. Using transmission electron microscopy (TEM) filamentary structures are observed in vitrified dispersions and dried films. For PEDOT:PSS films with HBS, the conductivity also exhibits quasi‐1D VRH behavior when the temperature is less than 200 K. The low characteristic temperature T0 indicates that HBS‐treated films are close to the critical regime between a metal and an insulator. In this case, the conductivity prefactor scales linearly with cPEDOT, indicating the conduction is no longer limited by a percolation of filaments. The lack of observable changes in TEM upon processing with the HBS suggests that the changes in conductivity are due to a smaller spread in the conductivities of individual filaments, or a higher probability for neighboring filaments to be connected rather than being caused by major morphological modification of the material. 相似文献
953.
The Kinetic Method (KM), applied commonly for thermochemical determinations, is used here for sterically-controlled isomeric determination of N- versus C-terminal Arg-containing dipeptide isomers (ArgX versus XArg; where X = His, Leu, Lys, Pro, Ser, Phe, and Tyr). The KM is offered as an alternate approach to direct collision-induced dissociation (CID) procedures. Through formation, isolation, and dissociation of a sterically-encumbered, metal-centered complex with electrospray ionization ion trap mass spectrometry technology, reference dipeptide molecules are screened to quantitatively differentiate a mixture of isomers based on their arrangement about the metal center. Arg-containing dipeptide molecules are chosen because of their contribution in a wide array of protein and peptide functions. Additionally, problems cited previously for evaluation of systems containing Arg residues (due to the incorporation of the guanidinium moiety) by the KM are addressed. The method is shown to be successful for highlighting favorable reference analytes (e.g., ArgPhe, ArgLeu, ProArg, PheArg, among others) for exceptional discrimination (R(iso) > 2.0) of the majority of N- and C-terminal Arg-containing peptides tested. 相似文献
954.
Gooding KB Higgs R Hodge B Stauffer E Heinz B McKnight K Phipps K Shapiro M Winkler M Ng WL Julian RK 《Journal of the American Society for Mass Spectrometry》2004,15(6):884-892
Approximately 300,000 compounds from selected libraries were screened against a subdomain of a hepatitis C viral (HCV) RNA using a high throughput flow injection mass spectrometry (FIA-MS) method with automated data storage and analysis. Samples contained 2 microM RNA target and 10 microM of each of up to ten ligands. Preliminary studies to optimize operational parameters used the binding of aminoglycosides to the A44 subdomain of bacterial RNA. Binding (confirmed by titration) and sensitivity were maximized within the constraints of the library and throughput. The mobile phase of 5 mM ammonium acetate in 50% isopropanol maintained the noncovalent complexes and provided good detection by electrospray mass spectrometry. Additionally, this composition maximized general solubility of the various classes of compounds including the oligonucleotide and organic library molecules. Cation adduction was insignificant in this screen although some solute and target dependent acetate adduction was observed. The ion trap mass spectrometer provided sufficient mass resolution to identify complexes of RNA with known components of the library. Converted mass spectral data (netCDF) were subjected to two types of statistical evaluation based on binding. The first algorithm identified noncovalent complexes that correlated with the molecular weights of the injected compounds. The second yielded the largest peak in the noncovalent complex region of the spectrum; this spectrum may or may not correlate with expected well components. Sixty-three compounds were confirmed to bind by more stringent secondary testing. Titrations, which were carried out with selected binding compounds, yielded a range of dissociation constants. Biological activity was observed for eleven confirmed binders. 相似文献
955.
Walker AK Land CM Kinsel GR Nelson KD 《Journal of the American Society for Mass Spectrometry》2000,11(1):62-68
Polymer surface-peptide binding interactions have been shown previously to lead to reductions in peptide matrix assisted laser desorption/ionization (MALDI) ion signals. In previous studies, increases in surface-peptide binding were characterized by the increases in both the initially adsorbed and retained quantities of 125I-radiolabeled peptides. The present studies establish a specific correlation between the peptide retention properties of the polymer surface and the reduction in the peptide MALDI ion signal. This correlation is demonstrated by obtaining MALDI mass spectra of angiotensin I applied to various polymer surfaces having a range of peptide adsorption and retention properties. In addition, the use of a MALDI based method of standard additions is shown to allow the quantitation of the polymer surface-peptide retention affinity for angiotensin I and porcine insulin. The MALDI standard additions method for measurement of surface-peptide retention affinities offers a number of significant advantages over conventional radiolabeled peptide binding methods and promises to be a valuable tool for the determination of this important biomaterial characteristic. 相似文献
956.
Christopher Kerestes Yi Wang Kevin Shreve James Mutitu Tim Creazzo Paola Murcia Allen Barnett 《Progress in Photovoltaics: Research and Applications》2013,21(4):578-587
Transparent silicon solar cells can lead to an increased efficiency of silicon‐based multi‐junction assemblies by transmitting near and below band gap energy light for conversion in a low band gap solar cell. This analysis shows that the maximum efficiency gain for a low band gap solar cell beneath silicon at a concentration of 50 suns is 5.8%, based on ideal absorption and conversion of the photons. This work analyzes the trade‐offs between increased near band edge absorption in the silicon and silicon solar cell transparency. Application of these results to real cases including a germanium bottom solar cell is analyzed, leading to a range of cases with increased system efficiency. Non‐ideal surfaces and real silicon and germanium solar cell device performance are presented. The range of practical system gains may be as low as 2.2 – 1% absolute when compared with the efficiency of a light‐trapped silicon solar cell for 1‐sun operation, based on this work. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
957.
Burgess KM Korobkov I Bryce DL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(18):5748-5758
Multinuclear ((31)P and (79/81)Br), multifield (9.4, 11.75, and 21.1 T) solid-state nuclear magnetic resonance experiments are performed for seven phosphonium bromides bearing the triphenylphosphonium cation, a molecular scaffold found in many applications in chemistry. This is undertaken to fully characterise their bromine electric field gradient (EFG) tensors, as well as the chemical shift (CS) tensors of both the halogen and the phosphorus nuclei, providing a rare and novel insight into the local electronic environments surrounding them. New crystal structures, obtained from single-crystal X-ray diffraction, are reported for six compounds to aid in the interpretation of the NMR data. Among them is a new structure of BrPPh(4), because the previously reported one was inconsistent with our magnetic resonance data, thereby demonstrating how NMR data of non-standard nuclei can correct or improve X-ray diffraction data. Our results indicate that, despite sizable quadrupolar interactions, (79/81)Br magnetic resonance spectroscopy is a powerful characterisation tool that allows for the differentiation between chemically similar bromine sites, as shown through the range in the characteristic NMR parameters. (35/37)Cl solid-state NMR data, obtained for an analogous phosphonium chloride sample, provide insight into the relationship between unit cell volume, nuclear quadrupolar coupling constants, and Sternheimer antishielding factors. The experimental findings are complemented by gauge-including projector-augmented wave (GIPAW) DFT calculations, which substantiate our experimentally determined strong dependence of the largest component of the bromine CS tensor, δ(11), on the shortest Br-P distance in the crystal structure, a finding that has possible application in the field of NMR crystallography. This trend is explained in terms of Ramsey's theory on paramagnetic shielding. Overall, this work demonstrates how careful NMR studies of underexploited exotic nuclides, such as (79/81)Br, can afford insights into structure and bonding environments in the solid state. 相似文献
958.
An enantioselective strategy for the synthesis of phomactin natural products is described. The Lewis acid triggered cyclization of a β-iodoallenolate embedded in a 12-membered macrocycle was used to obtain a highly functionalized bicyclo[9.3.1]pentadecane in good yield and high diastereoselectivity. This iodoenone contains the substituents of the AD ring system of the phomactin family of natural products, appropriate for further functionalization. Synthesis of the oxadecalin core of phomactin A from the AD iodoenone intermediate was achieved. In this unusual strategy, rings A and B are both fashioned within a macrocyclic precursor. 相似文献
959.
Tardiff BJ Hesp KD Ferguson MJ Stradiotto M 《Dalton transactions (Cambridge, England : 2003)》2012,41(26):7883-7885
Treatment of [(IPr)Pd(Cl)(2)(PR(2)H)] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; R = Cy, tBu, or 1-Ad) with NaN(SiMe(3))(2) generated isolable [(IPr)Pd(PR(2)Cl)] complexes (68-75%) that have been crystallographically characterized. The formation of these mixed-ligand Pd(0) species in this manner corresponds to an unusual net dehydrohalogenation/P-Cl reductive elimination sequence. 相似文献
960.
X Yi K Bernot F Pointillart G Poneti G Calvez C Daiguebonne O Guillou R Sessoli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(36):11379-11387
The reaction of [Ln(hfac)(3) ]?2?H(2) O and pyridine-N-oxide (PyNO) leads to isostructural dimers of the formula [Ln(hfac)(3) (PyNO)](2) (Ln=Eu, Gd, Tb, Dy). The Dy derivative shows a remarkable single-molecule magnet behavior with complex hysteresis at 1.4?K. The dynamics of the magnetization features are two relaxation regimes: a thermally activated one at high temperature (τ(0) =(5.62±0.4)×10(-11) s and Δ=(167±1)?K) and a quantum tunneling regime at low temperature with a tunneling frequency of 0.42?Hz. The analysis of the Gd derivative evidences intradimer antiferromagnetic interactions (J=(-0.034±0.001)?cm(-1) ). Moreover, the Eu, Tb, and Dy derivatives are luminescent with quantum yield of 51, 53, and 0.1?%, respectively. The thermal investigation of [Dy(hfac)(3) (PyNO)](2) shows that the dimers can be sublimated intact, suggesting their possible exploit as active materials for surface-confined nanostructures to be investigated by fluorimetry methods. 相似文献