全文获取类型
收费全文 | 2878篇 |
免费 | 673篇 |
国内免费 | 166篇 |
专业分类
化学 | 572篇 |
晶体学 | 4篇 |
力学 | 197篇 |
综合类 | 19篇 |
数学 | 55篇 |
物理学 | 1378篇 |
无线电 | 1492篇 |
出版年
2024年 | 11篇 |
2023年 | 36篇 |
2022年 | 81篇 |
2021年 | 91篇 |
2020年 | 78篇 |
2019年 | 76篇 |
2018年 | 75篇 |
2017年 | 120篇 |
2016年 | 127篇 |
2015年 | 154篇 |
2014年 | 204篇 |
2013年 | 228篇 |
2012年 | 256篇 |
2011年 | 216篇 |
2010年 | 179篇 |
2009年 | 198篇 |
2008年 | 184篇 |
2007年 | 204篇 |
2006年 | 213篇 |
2005年 | 151篇 |
2004年 | 141篇 |
2003年 | 113篇 |
2002年 | 95篇 |
2001年 | 72篇 |
2000年 | 72篇 |
1999年 | 46篇 |
1998年 | 52篇 |
1997年 | 35篇 |
1996年 | 35篇 |
1995年 | 29篇 |
1994年 | 22篇 |
1993年 | 17篇 |
1992年 | 14篇 |
1991年 | 13篇 |
1990年 | 21篇 |
1989年 | 6篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
排序方式: 共有3717条查询结果,搜索用时 15 毫秒
71.
基于大口径闪烁法和差分到达角起伏法开展了间距为3.95 km近水平路径的大气相干长度测量实验。测量结果表明:在同路径的上下行光传播方向上,闪烁法测量相干长度的相关系数为0.94,而到达角起伏法测量相干长度的相关系数为0.79。路径权重的理论分析揭示了闪烁法对路径中部的湍涡敏感,且路径权重函数关于路径中部呈对称分布;到达角起伏法对接收端附近的湍涡敏感,其路径权重函数从发射端到接收端呈单调递增趋势。因此,实际的长距离光传输实验中,在不能确定路径中湍流强度分布的情况下,采用闪烁法测量路径上的湍流效应更适宜。 相似文献
72.
The MCM‐41 and SiO2 supported TiCl4 and TiCl4/MgCl2 catalysts with different molar ratios of Mg/Ti were synthesized and used for ethylene polymerization under atmospheric pressure. The nanochannels of MCM‐41 serve as nanoscale polymerization reactor and the polyethylene nanofibers were extruded during the reaction. The nanofibers were observed in SEM micrographs of resulting polyethylene. The effect of MgCl2 on catalytic activity and thermal properties of resulting polyethylene is investigated too. In the presence of MgCl2, the catalytic activity increased and more crystalline polyethylene with higher melting points were formed. However, no fibers could be observed in the polyethylene prepared by SiO2 supported catalysts. 相似文献
73.
Raiza Fernández Freddy Galarraga Zully Benzo Gonzalo Márquez M. Gabriela Requiz 《International journal of environmental analytical chemistry》2013,93(3):230-240
Biomonitoring of PAH air pollution using lichens was carried out. Sixteen PAHs were studied in 11 locations along the valley of Caracas (Venezuela). The results of this work indicate that 14 of the 16 analysed PAHs were highly accumulated into the lichen thalli of Pyxine coralligera Malme. PAH levels in the samples revealed that the several volatile PAHs (naphthalene, acenaphtylene, acenaphtene, and fluoranthene) have the highest levels in the majority of the studied locations. The fluoranthene/pyrene and phenantrene/antracene ratios suggested that the major sources of PAHs are anthropogenic, mainly associated with gasoline and diesel combustion (pyrolytic) and unburnt oil derivates (petrogenic). The total PAH concentrations obtained in the present study were in the range of 0.24 to 9.08?µg/g, similar to those reported by other works in European and Asian cities. 相似文献
74.
For the long-range infrared imaging system, the marine atmospheric turbulence degrades seriously the probability of object recognition and tracking. In this study, the angle of arrival fluctuations of an optical wave, which describes the distortion effects of marine atmospheric turbulence on an infrared optical imaging system, is investigated in detail both analytically and numerically. Analytic expressions of the angle of arrival fluctuations are derived for optical plane and spherical waves propagating through weak marine atmospheric turbulence with horizontal path, and they consider simultaneously finite turbulence inner scale, turbulence outer scale, wavelength, and aperture diameters. Numerical calculations are conducted to analyze the influence of marine weak turbulence on the infrared imaging. The results are useful for understanding the potential impact of deviations from the terrestrial turbulence. 相似文献
75.
Pulsed microwave-driven argon plasma jet with distinctive plume patterns resonantly excited by surface plasmon polaritons 下载免费PDF全文
Atmospheric lower-power pulsed microwave argon cold plasma jets are obtained by using coaxial transmission line resonators in ambient air.The plasma jet plumes are generated at the end of a metal wire placed in the middle of the dielectric tubes.The electromagnetic model analyses and simulation results suggest that the discharges are excited resonantly by the enhanced electric field of surface plasmon polaritons.Moreover,for conquering the defect of atmospheric argon filamentation discharges excited by 2.45-GHz of continued microwave,the distinctive patterns of the plasma jet plumes can be maintained by applying different gas flow rates of argon gas,frequencies of pulsed modulator,duty cycles of pulsed microwave,peak values of input microwave power,and even by using different materials of dielectric tubes.In addition,the emission spectrum,the plume temperature,and other plasma parameters are measured,which shows that the proposed pulsed microwave plasma jets can be adjusted for plasma biomedical applications. 相似文献
76.
Assessment of the various ionization methods in the analysis of metal salen complexes by mass spectrometry 下载免费PDF全文
Beata Słomińska Wojciech Chaładaj Witold Danikiewicz 《Journal of mass spectrometry : JMS》2014,49(5):392-399
Metal salen complexes are one of the most frequently used catalysts in enantioselective organic synthesis. In the present work, we compare a series of ionization methods that can be used for the mass spectral analysis of two types of metalosalens: ionic complexes (abbreviated as Com+X?) and neutral complexes (NCom). These methods include electron ionization and field desorption (FD) which can be applied to pure samples and atmospheric pressure ionization techniques: electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) which are suitable for solutions. We found that FD is a method of choice for recording molecular ions of the complexes containing even loosely bonded ligands. The results obtained using atmospheric pressure ionization methods show that the results depend mainly on the structure of metal salen complex and the ionization method. In ESI spectra, Com+ ions were observed, while in APCI and APPI spectra both Com+ and [Com + H]+ ions are observed in the ratio depending on the structure of the metal salen complex and the solvent used in the analysis. For complexes with tetrafluoroborate counterion, an elimination of BF3 took place, and ions corresponding to complexes with fluoride counterion were observed. Experiments comparing the relative sensitivity of ESI, APCI and APPI (with and without a dopant) methods showed that for the majority of the studied complexes ESI is the most sensitive one; however, the sensitivity of APCI is usually less than two times lower and for some compounds is even higher than the sensitivity of ESI. Both methods show very high linearity of the calibration curve in a range of about 3 orders of magnitude of the sample concentration. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
77.
Tuija Jokinen Dr. Mikko Sipilä Stefanie Richters Prof. Veli‐Matti Kerminen Dr. Pauli Paasonen Dr. Frank Stratmann Dr. Douglas Worsnop Prof. Markku Kulmala Dr. Mikael Ehn Prof. Hartmut Herrmann Dr. Torsten Berndt 《Angewandte Chemie (International ed. in English)》2014,53(52):14596-14600
Gas‐phase oxidation routes of biogenic emissions, mainly isoprene and monoterpenes, in the atmosphere are still the subject of intensive research with special attention being paid to the formation of aerosol constituents. This laboratory study shows that the most abundant monoterpenes (limonene and α‐pinene) form highly oxidized RO2 radicals with up to 12 O atoms, along with related closed‐shell products, within a few seconds after the initial attack of ozone or OH radicals. The overall process, an intramolecular ROO→QOOH reaction and subsequent O2 addition generating a next R′OO radical, is similar to the well‐known autoxidation processes in the liquid phase (QOOH stands for a hydroperoxyalkyl radical). Field measurements show the relevance of this process to atmospheric chemistry. Thus, the well‐known reaction principle of autoxidation is also applicable to the atmospheric gas‐phase oxidation of hydrocarbons leading to extremely low‐volatility products which contribute to organic aerosol mass and hence influence the aerosol–cloud–climate system. 相似文献
78.
Gunasekaran Manonmani Lakshmanan Sandhiya Kittusamy Senthilkumar 《International journal of quantum chemistry》2020,120(11):e26182
The hydrolysis of sulfonylamine (HNSO2) results in the formation of sulfuric acid along with ammonia, and is of significant interest due to their negative impact on environment and life on Earth. The formation of H2SO4 through the reaction of HNSO2 with (H2O)2-4 has been studied using high level electronic structure calculations. This hydrolysis reaction is a step-wise process, in the first step a H-atom from H2O is transferred to the N-atom of HNSO2 which results in the formation of NH2, and in the next step, H2SO4, NH3 and water molecule(s) are formed. The results show that the energy barrier associated with the formation of intermediates and product complexes is reduced by 7 to 10 kcal/mol when the number of water molecules is increased from 2 to 4. The rate constant was calculated using canonical variational transition state theory with small curvature tunneling correction over the temperature range of 200 to 1000 K. At 298 K, the calculated rate constant for the formation of intermediate in the first step is 2.24 × 10−16, 1.03 × 10−12, and 2.10 × 10−11 cm3 mol−1 s−1, respectively, for the reaction with water dimer, trimer and tetramer. The calculated enthalpy and free energy show that the reaction corresponding to the formation of H2SO4 is highly exothermic and exoergic in nature. 相似文献
79.
硝酰氯(nitryl chloride,ClNO2)是大气中一种重要的气态污染物,对大气氧化性、一次污染物的降解和二次污染物的生成具有重要影响,并在全球氮循环和氯循环中扮演着不可忽视的角色。本文归纳了ClNO2的基本物理化学性质及其在大气中的生成和去除机制,并介绍了实验室研究和外场观测中ClNO2的主要测量方法。在此基础上,本文总结了过去十几年报道的ClNO2在实际大气中的时空分布特征,通过分析实验室模拟和外场观测的研究结果系统讨论了ClNO2非均相生成的机制、产率及其影响因素,探讨了ClNO2对氯自由基、大气氧化性以及臭氧和硝酸盐形成的影响。我们指出,ClNO2既耦合了气相化学和非均相化学,又耦合了夜间大气化学和日间光化学,在我国大气复合污染中可能起着非常重要的作用。最后,本文提出了ClNO2大气化学研究中尚待解决的关键科学问题,并简要讨论了该领域的未来发展方向。 相似文献
80.
Xiaoyang Shi Hang Xiao Habib Azarabadi Juzheng Song Xiaolong Wu Xi Chen Klaus S. Lackner 《Angewandte Chemie (International ed. in English)》2020,59(18):6984-7006
The urgency to address global climate change induced by greenhouse gas emissions is increasing. In particular, the rise in atmospheric CO2 levels is generating alarm. Technologies to remove CO2 from ambient air, or “direct air capture” (DAC), have recently demonstrated that they can contribute to “negative carbon emission.” Recent advances in surface chemistry and material synthesis have resulted in new generations of CO2 sorbents, which may drive the future of DAC and its large‐scale deployment. This Review describes major types of sorbents designed to capture CO2 from ambient air and they are categorized by the sorption mechanism: physisorption, chemisorption, and moisture‐swing sorption. 相似文献