全文获取类型
收费全文 | 223篇 |
免费 | 2篇 |
国内免费 | 1篇 |
专业分类
化学 | 157篇 |
力学 | 1篇 |
数学 | 23篇 |
物理学 | 45篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 2篇 |
2020年 | 4篇 |
2019年 | 2篇 |
2018年 | 2篇 |
2017年 | 2篇 |
2016年 | 2篇 |
2015年 | 4篇 |
2014年 | 3篇 |
2013年 | 5篇 |
2012年 | 15篇 |
2011年 | 10篇 |
2010年 | 8篇 |
2009年 | 10篇 |
2008年 | 13篇 |
2007年 | 25篇 |
2006年 | 10篇 |
2005年 | 19篇 |
2004年 | 13篇 |
2003年 | 9篇 |
2002年 | 8篇 |
2001年 | 2篇 |
2000年 | 4篇 |
1999年 | 4篇 |
1998年 | 1篇 |
1997年 | 4篇 |
1996年 | 7篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1988年 | 1篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 5篇 |
1978年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1961年 | 1篇 |
1960年 | 1篇 |
1958年 | 1篇 |
1930年 | 2篇 |
排序方式: 共有226条查询结果,搜索用时 0 毫秒
101.
102.
103.
Steven R. Kass Hangzhou Guo Gregg D. Dahlke 《Journal of the American Society for Mass Spectrometry》1990,1(5):366-371
The thiomethyl anion (1) has been generated by fluorodesilylation of trimethylsilylmethanethiol in a variable-temperature flowing afterglow device. The proton affinity (1649 ± 12 kJ mol?1) and electron affinity (0.67 ± .13 eV) were determined and compared to a previously reported molecular orbital calculation. Isomerization via a 1,2-proton shift does not take place between ?40° and 100°C despite a 156 kJ mol?1 driving force. Ion-molecule reactions of 1 were examined with a number of reagents including N20, O2, CS2, COS, and CO2, Hydride ion transfer was observed in every case, along with other products, and thermodynamic information has been derived. 相似文献
104.
Cellulase adsorption and an evaluation of enzyme recycle during hydrolysis of steam-exploded softwood residues 总被引:1,自引:0,他引:1
Lu Yanpin Yang Bin Gregg David Saddler John N. Mansfield Shawn D. 《Applied biochemistry and biotechnology》2002,98(1-9):641-654
The sugar yield and enzyme adsorption profile obtained during the hydrolysis of SO2-catalyzed steam-exploded Douglas-fir and posttreated steamexploded Douglas-fir substrates were determined. After hot alkali
peroxide posttreatment, the rates and yield of hydrolysis attained from the posttreated Douglas-fir were significantly higher,
even at lower enzyme loadings, than those obtained with the corresponding steam-exploded Douglas-fir. The enzymatic adsorption
profiles observed during hydrolysis of the two substrates were significantly different. Ultrafiltration was employed to recover
enzyme in solution (supernatant) and reused in subsequent hydrolysis reactions with added, fresh substrate. These recycle
findings suggested that the enzyme remained relatively active for three rounds of recycle. It is likely that enzyme recovery
and reuse during the hydrolysis of posttreated softwood substrates could lead to reductions in the need for the addition of
fresh enzyme during softwood-based bioconversion processes. 相似文献
105.
Nirmala Ramanujam Michele Follen Mitchell Anita Mahadevan-Jansen Sharon L. Thomson Gregg Staerkel Anais Malpica Thomas Wright Neely Atkinson Rebecca Richards-Kortum 《Photochemistry and photobiology》1996,64(4):720-735
Abstract— A portable fluorimeter was developed and utilized to acquire fluorescence spectra from 381 cervical sites in 95 patients at 337, 380 and 460 nm excitation immediately prior to colposcopy. A multivariate statistical algorithm was used to extract clinically useful information from tissue spectra acquired in vivo. Two full-parameter algorithms were developed using tissue fluorescence emission spectra at all three excitation wavelengths (161 excitation-emission wavelength pairs) for cervical precancer (squamous intraepithelial lesion [SIL]) detection: a screening algorithm that discriminates between SIL and non-SIL with a sensitivity of 82 ± 1.4% and specificity of 68 ± 0.0%, and a diagnostic algorithm that differentiates high-grade SIL from non-high-grade SIL with a sensitivity and specificity of 79 ± 2% and 78 ± 6%, respectively. Multivariate statistical analysis was also employed to reduce the number of fluorescence excitation-emission wavelength pairs needed to redevelop algorithms that demonstrate a minimum decrease in classification accuracy. Two reduced-parameter algorithms that employ fluorescence intensities at only 15 excitation-emission wavelength pairs were developed: the screening algorithm differentiates SIL from non-SIL with a sensitivity of 84 ± 1.5% and specificity of 65 ± 2% and the diagnostic algorithm discriminates high-grade SIL from non-high-grade SIL with a sensitivity and specificity of 78 ± 0.7% and 74 ± 2%, respectively. Both the full-parameter and reduced-parameter screening algorithms discriminate between SIL and non-SIL with a similar specificity (±5%) and a substantially improved sensitivity relative to Pap smear screening. A comparison of the full-parameter and reduced-parameter diagnostic algorithms to colposcopy in expert hands indicates that all three have a very similar sensitivity and specificity for differentiating high-grade SIL from non-high-grade SIL. 相似文献
106.
Brewer Christopher M. Bujalski Duane R. Parent Virginia E. Su Kai Zank Gregg A. 《Journal of Sol-Gel Science and Technology》1999,14(1):49-68
We have undertaken a systematic study of the oxidation chemistry for a range of SiOC ceramics derived from silsesquioxane polymeric precursors. This study examines the oxidation for 500 hours at 600, 800, 1000 and 1200°C for four SiOC powders. The material changes upon oxidation were characterized qualitatively by color change and optical microscopy and quantitatively by weight and composition change. In this study we employ a very easy method that uses the weight change upon oxidation and a carbon analysis after oxidation to arrive at the composition of the oxidized SiOC. Combined these qualitative and quantitative techniques have shown that on oxidation at 800 and 600°C the SiOC composition is more rapidly changed to that of silica than oxidation over the same time frame at 1000 or 1200°C. The data indicates that this difference is due to the relative rates of oxidation of the excess carbon versus the Si—C bonds in the SiOC. At lower temperatures initially the carbon oxidation predominates which leads to higher porosity throughout the material and an increase in the surface area with eventually complete oxidation to silica. At higher temperatures the Si—C bond oxidation rate is comparable to the rate of oxidation of carbon. This allows a silica-like surface to build up on the SiOC, which slows all subsequent reactions due to the necessity to diffuse O2 in and COx out of the bulk. Under these oxidation conditions materials that originally contain high amounts of excess carbon are more quickly oxidized to silica than those that contain minimal amounts of excess carbon, as confirmed by elemental analysis and optical microscopy. Regardless of the time or temperature of the oxidation conditions no materials were found to be completely stable to oxidation. SiOC materials with low levels of excess carbon showed the best resistance to change upon oxidation. 相似文献
107.
Mehlstäubl M Kottas GS Colella S De Cola L 《Dalton transactions (Cambridge, England : 2003)》2008,(18):2385-2388
A tetrametallic iridium-ytterbium complex has been synthesised that shows sensitized near-infrared emission (lambda(max) = 976 nm) upon excitation of the iridium unit in the visible region (400 nm) due to efficient energy transfer from the iridium units to the Yb(III) ion. The iridium phosphorescence is quenched nearly quantitatively while the ytterbium ion emits brightly in the NIR. 相似文献
108.
Dhanpat Rai Mikazu Yui Dean A. Moore Gregg J. Lumetta Kevin M. Rosso Yuanxian Xia Andrew R. Felmy Frances N. Skomurski 《Journal of solution chemistry》2008,37(12):1725-1746
No thermodynamic data for Th complexes with aqueous Si are available. To obtain such data, extensive studies on ThO2(am) solubility were carried out as functions of: (1) a wide range of aqueous silica concentrations (0.0004 to 0.14 mol⋅L−1) at fixed pH values of about 10, 11, 12, and 13; and (2) and variable pH (ranging from 10 to 13.3) at fixed aqueous Si concentrations
of about 0.006 mol⋅L−1 or 0.018 mol⋅L−1. The samples were equilibrated over long periods (ranging up to 487 days), and the data showed that steady-state concentrations
were reached in < 29 days. X-ray diffraction, FTIR, and Raman analyses of the equilibrated solid phases showed that the Th
solids were amorphous ThO2(am) containing some adsorbed Si. The solubility of ThO2(am) at pH values ranging from 10 to 13.3 at fixed 0.018 mol⋅L−1 aqueous Si concentrations decreases rapidly with an increase in pH, and increases dramatically with an increase in Si concentrations
beyond about 0.003 mol⋅L−1 at fixed pH values > 10. The data were interpreted using both the Pitzer and SIT models, and required only the inclusion
of one mixed-hydroxy-silica complex of Th [Th(OH)3(H3SiO4)32−]. Both models provided similar complexation constant values for the formation of this species. Density functional theory
calculations predict complexes of this stoichiometry, having six-fold coordination of the Th cation, to be structurally stable.
Predictions based on the fitted value of log 10
K
0=−18.5±0.7 for the ThO2(am) solubility reaction involving Th(OH)3(H3SiO4)32−[ThO2(am)+3H4SiO4+H2O↔Th(OH)3(H3SiO4)32−+2H+], along with the thermodynamic data for aqueous Si species reported in the literature, agreed closely with the extensive
experimental data and showed that under alkaline conditions aqueous Si makes very strong complexes with Th. 相似文献
109.
Walsh MR Rainey JD Lafond PG Park DH Beckham GT Jones MD Lee KH Koh CA Sloan ED Wu DT Sum AK 《Physical chemistry chemical physics : PCCP》2011,13(44):19951-19959
Interest in describing clathrate hydrate formation mechanisms spans multiple fields of science and technical applications. Here, we report findings from multiple molecular dynamics simulations of spontaneous methane clathrate hydrate nucleation and growth from fully demixed and disordered two-phase fluid systems of methane and water. Across a range of thermodynamic conditions and simulation geometries and sizes, a set of seven cage types comprises approximately 95% of all cages formed in the nucleated solids. This set includes the ubiquitous 5(12) cage, the 5(12)6(n) subset (where n ranges from 2-4), and the 4(1)5(10)6(n) subset (where n also ranges from 2-4). Transformations among these cages occur via water pair insertions/removals and rotations, and may elucidate the mechanisms of solid-solid structural rearrangements observed experimentally. Some consistency is observed in the relative abundance of cages among all nucleation trajectories. 5(12) cages are always among the two most abundant cage types in the nucleated solids and are usually the most abundant cage type. In all simulations, the 5(12)6(n) cages outnumber their 4(1)5(10)6(n) counterparts with the same number of water molecules. Within these consistent features, some stochasticity is observed in certain cage ratios and in the long-range ordering of the nucleated solids. Even when comparing simulations performed at the same conditions, some trajectories yield swaths of multiple adjacent sI unit cells and long-range order over 5 nm, while others yield only isolated sI unit cells and little long-range order. The nucleated solids containing long-range order have higher 5(12)6(2)/5(12) and 5(12)6(3)/4(1)5(10)6(2) cage ratios when compared to systems that nucleate with little long-range order. The formation of multiple adjacent unit cells of sI hydrate at high driving forces suggests an alternative or addition to the prevailing hydrate nucleation hypotheses which involve formation through amorphous intermediates. 相似文献
110.
Jet propellant 8 (JP-8) is a complex mixture of compounds that varies from batch to batch. Quantification of various compound classes of JP-8, including BTEX, PAHs and VOCs, has been accomplished. Very few papers have tackled total JP-8 quantification because of its complexity. The components in JP-8 tend to co-elute and present at low concentrations, often nondetectable. JP-8 is the major source of chemical exposure for Department of Defense personnel and a potential hazard for civilians and marine animals. Some components of JP-8 have been identified as possible human carcinogens and have been studied extensively. Development of analytical methods to analyze the components of this fuel are essential to measure the extent of exposure, as well as the short-term and long-term exposure in rodents, humans and marine life. To date, JP-8 has been examined in urine, blood, contaminated water and fish tissue. This paper reviews methods currently utilized in the literature for the analysis of JP-8 and its components. This paper also discusses extraction methods and detectors commonly used in JP-8 and hydrocarbon analysis in general. Finally, the effects of exposure and the future of JP-8 and petroleum analysis with respect to human health are discussed. 相似文献