全文获取类型
收费全文 | 989篇 |
免费 | 29篇 |
国内免费 | 7篇 |
专业分类
化学 | 489篇 |
晶体学 | 17篇 |
力学 | 30篇 |
数学 | 139篇 |
物理学 | 350篇 |
出版年
2020年 | 8篇 |
2019年 | 15篇 |
2018年 | 10篇 |
2017年 | 12篇 |
2016年 | 13篇 |
2015年 | 16篇 |
2014年 | 24篇 |
2013年 | 60篇 |
2012年 | 32篇 |
2011年 | 47篇 |
2010年 | 15篇 |
2009年 | 22篇 |
2008年 | 39篇 |
2007年 | 41篇 |
2006年 | 43篇 |
2005年 | 48篇 |
2004年 | 29篇 |
2003年 | 30篇 |
2002年 | 29篇 |
2001年 | 25篇 |
2000年 | 18篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 12篇 |
1996年 | 21篇 |
1995年 | 13篇 |
1994年 | 11篇 |
1993年 | 17篇 |
1992年 | 13篇 |
1991年 | 14篇 |
1990年 | 15篇 |
1989年 | 24篇 |
1988年 | 15篇 |
1987年 | 19篇 |
1985年 | 28篇 |
1984年 | 18篇 |
1983年 | 8篇 |
1982年 | 14篇 |
1981年 | 13篇 |
1980年 | 19篇 |
1979年 | 7篇 |
1978年 | 18篇 |
1977年 | 15篇 |
1976年 | 14篇 |
1975年 | 12篇 |
1974年 | 10篇 |
1973年 | 7篇 |
1972年 | 8篇 |
1971年 | 8篇 |
1969年 | 8篇 |
排序方式: 共有1025条查询结果,搜索用时 531 毫秒
991.
Dr. Jared B. DeCoste Dr. Mitchell H. Weston Patrick E. Fuller Trenton M. Tovar Gregory W. Peterson Dr. M. Douglas LeVan Dr. Omar K. Farha 《Angewandte Chemie (International ed. in English)》2014,53(51):14092-14095
We present a systematic study of metal–organic frameworks (MOFs) for the storage of oxygen. The study starts with grand canonical Monte Carlo simulations on a suite of 10 000 MOFs for the adsorption of oxygen. From these data, the MOFs were down selected to the prime candidates of HKUST‐1 (Cu‐BTC) and NU‐125, both with coordinatively unsaturated Cu sites. Oxygen isotherms up to 30 bar were measured at multiple temperatures to determine the isosteric heat of adsorption for oxygen on each MOF by fitting to a Toth isotherm model. High pressure (up to 140 bar) oxygen isotherms were measured for HKUST‐1 and NU‐125 to determine the working capacity of each MOF. Compared to the zeolite NaX and Norit activated carbon, NU‐125 has an increased excess capacity for oxygen of 237 % and 98 %, respectively. These materials could ultimately prove useful for oxygen storage in medical, military, and aerospace applications. 相似文献
992.
Sambhy V Peterson BR Sen A 《Langmuir : the ACS journal of surfaces and colloids》2008,24(14):7549-7558
We demonstrate a versatile methodology combining both covalent surface anchoring and polymer cross-linking that is capable of forming long-lasting coatings on reactive and nonreactive surfaces. Polymers containing reactive methoxysilane groups form strong Si-O-Si links to oxide surfaces, thereby anchoring the polymer chains at multiple points. The interchain cross-linking of the methoxysilane groups provides additional durability to the coating and makes the coatings highly resistant to solvents. By tailoring the chemical structure of the polymer, we were able to control the surface energy (wetting) of a variety of surfaces over a wide range of water contact angles of 30-140 degrees . In addition, we synthesized covalently linked layer-by-layer polymeric assemblies from these novel methoxysilane polymers. Finally, antibacterial agents, such as silver bromide nanoparticles and triiodide ions, were introduced into these functional polymers to generate long-lasting and renewable antiseptic coatings on glass, metals, and textiles. 相似文献
993.
Anderson AW Marois R Colson ER Peterson BS Duncan CC Ehrenkranz RA Schneider KC Gore JC Ment LR 《Magnetic resonance imaging》2001,19(1):1-5
The objective of this study was to detect auditory cortical activation in non-sedated neonates employing functional magnetic resonance imaging (fMRI). Using echo-planar functional brain imaging, subjects were presented with a frequency-modulated pure tone; the BOLD signal response was mapped in 5 mm-thick slices running parallel to the superior temporal gyrus. Twenty healthy neonates (13 term, 7 preterm) at term and 4 adult control subjects. Blood oxygen level-dependent (BOLD) signal in response to auditory stimulus was detected in all 4 adults and in 14 of the 20 neonates. FMRI studies of adult subjects demonstrated increased signal in the superior temporal regions during auditory stimulation. In contrast, signal decreases were detected during auditory stimulation in 9 of 14 newborns with BOLD response. fMRI can be used to detect brain activation with auditory stimulation in human infants. 相似文献
994.
Neutron powder diffraction (NPD) offers many advantages in the analysis of battery materials. Understanding the relationship
between the structural transformations of electrode materials and their electrochemical performance within lithium-ion batteries
is crucial for further development of these technologies and is the overall goal of in situ NPD experiments. In this work,
we present NPD data of electrode materials within batteries that are collected in situ during electrochemical cycling, including
the commercially available materials LiCoO2, LiMn2O4, LiFePO4 and graphite and the YFe(CN)6 and FeFe(CN)6 materials that are not commercially available. Using these data, we illustrate the experimental approach and requirements
for the collection of in situ NPD data of sufficient quality for detailed structural analyses of the electrode components
of interest within batteries. 相似文献
995.
Queen WL Bloch ED Brown CM Hudson MR Mason JA Murray LJ Ramirez-Cuesta AJ Peterson VK Long JR 《Dalton transactions (Cambridge, England : 2003)》2012,41(14):4180-4187
The hydrogen storage properties of Fe(2)(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and an oxidized analog, Fe(2)(O(2))(dobdc), have been examined using several complementary techniques, including low-pressure gas adsorption, neutron powder diffraction, and inelastic neutron scattering. These two metal-organic frameworks, which possess one-dimensional hexagonal channels decorated with unsaturated iron coordination sites, exhibit high initial isosteric heats of adsorption of -9.7(1) and -10.0(1) kJ mol(-1), respectively. Neutron powder diffraction has allowed the identification of three D(2) binding sites within the two frameworks, with the closest contacts corresponding to Fe-D(2) separations of 2.47(3) and 2.53(5) ?, respectively. Inelastic neutron scattering spectra, obtained from p-H(2) (para-H(2)) and D(2)-p-H(2) mixtures adsorbed in Fe(2)(dobdc), reveal weak interactions between two neighboring adsorption sites, a finding that is in opposition to a previous report of possible 'pairing' between neighboring H(2) molecules. 相似文献
996.
Sharma N Guo X Du G Guo Z Wang J Wang Z Peterson VK 《Journal of the American Chemical Society》2012,134(18):7867-7873
Lithium-ion batteries power many portable devices and in the future are likely to play a significant role in sustainable-energy systems for transportation and the electrical grid. LiFePO(4) is a candidate cathode material for second-generation lithium-ion batteries, bringing a high rate capability to this technology. LiFePO(4) functions as a cathode where delithiation occurs via either a solid-solution or a two-phase mechanism, the pathway taken being influenced by sample preparation and electrochemical conditions. The details of the delithiation pathway and the relationship between the two-phase and solid-solution reactions remain controversial. Here we report, using real-time in situ neutron powder diffraction, the simultaneous occurrence of solid-solution and two-phase reactions after deep discharge in nonequilibrium conditions. This work is an example of the experimental investigation of nonequilibrium states in a commercially available LiFePO(4) cathode and reveals the concurrent occurrence of and transition between the solid-solution and two-phase reactions. 相似文献
997.
998.
Fluorination of fluorophores can substantially enhance their photostability and improve spectroscopic properties. To facilitate access to fluorinated fluorophores, bis(2,4,5-trifluorophenyl)methanone was synthesized by treatment of 2,4,5-trifluorobenzaldehyde with a Grignard reagent derived from 1-bromo-2,4,5-trifluorobenzene, followed by oxidation of the resulting benzyl alcohol. This hexafluorobenzophenone was subjected to sequential nucleophilic aromatic substitution reactions, first at one or both of the more reactive 4,4'-fluorines, and second by cyclization through substitution of the less reactive 2,2'-fluorines, using a variety of oxygen, nitrogen, and sulfur nucleophiles, including hydroxide, methoxide, amines, and sulfide. This method yields symmetrical and asymmetrical fluorinated benzophenones, xanthones, acridones, and thioxanthones and provides scalable access to known and novel precursors to fluorinated analogues of fluorescein, rhodamine, and other derivatives. Spectroscopic studies revealed that several of these precursors are highly fluorescent, with tunable absorption and emission spectra, depending on the substituents. This approach should allow access to a wide variety of novel fluorinated fluorophores and related compounds. 相似文献
999.
Bushuyev OS Brown P Maiti A Gee RH Peterson GR Weeks BL Hope-Weeks LJ 《Journal of the American Chemical Society》2012,134(3):1422-1425
Energetic materials have been used for nearly two centuries in military affairs and to cut labor costs and expedite laborious processes in mining, tunneling, construction, demolition, and agriculture, making a tremendous contribution to the world economy. Yet there has been little advancement in the development of altogether new energetic motifs despite long-standing research efforts to develop superior materials. We report the discovery of new energetic compounds of exceptionally high energy content and novel polymeric structure which avoid the use of lead and mercury salts common in conventional primary explosives. Laboratory tests indicate the remarkable performance of these Ni- and Co-based energetic materials, while DFT calculations indicate that these are possibly the most powerful metal-based energetic materials known to date, with heats of detonation comparable with those of the most powerful organic-based high explosives currently in use. 相似文献
1000.
Enhanced stability of Cu-BTC MOF via perfluorohexane plasma-enhanced chemical vapor deposition 总被引:1,自引:0,他引:1
Decoste JB Peterson GW Smith MW Stone CA Willis CR 《Journal of the American Chemical Society》2012,134(3):1486-1489
Metal organic frameworks (MOFs) are a leading class of porous materials for a wide variety of applications, but many of them have been shown to be unstable toward water. Cu-BTC (1,3,5 benzenetricarboxylic acid, BTC) was treated with a plasma-enhanced chemical vapor deposition (PECVD) of perfluorohexane creating a hydrophobic form of Cu-BTC. It was found that the treated Cu-BTC could withstand high humidity and even submersion in water much better than unperturbed Cu-BTC. Through Monte Carlo simulations it was found that perfluorohexane sites itself in such a way within Cu-BTC as to prevent the formation of water clusters, hence preventing the decomposition of Cu-BTC by water. This PECVD of perfluorohexane could be exploited to widen the scope of practical applications of Cu-BTC and other MOFs. 相似文献