全文获取类型
收费全文 | 609篇 |
免费 | 0篇 |
国内免费 | 2篇 |
专业分类
化学 | 418篇 |
晶体学 | 1篇 |
力学 | 10篇 |
数学 | 102篇 |
物理学 | 80篇 |
出版年
2021年 | 6篇 |
2014年 | 3篇 |
2013年 | 12篇 |
2012年 | 16篇 |
2011年 | 13篇 |
2010年 | 12篇 |
2009年 | 7篇 |
2008年 | 18篇 |
2007年 | 15篇 |
2006年 | 15篇 |
2005年 | 9篇 |
2004年 | 22篇 |
2003年 | 18篇 |
2002年 | 8篇 |
2001年 | 7篇 |
1999年 | 8篇 |
1998年 | 12篇 |
1997年 | 17篇 |
1996年 | 12篇 |
1995年 | 15篇 |
1994年 | 11篇 |
1993年 | 22篇 |
1992年 | 7篇 |
1991年 | 10篇 |
1990年 | 16篇 |
1989年 | 13篇 |
1988年 | 19篇 |
1987年 | 12篇 |
1986年 | 13篇 |
1985年 | 13篇 |
1984年 | 7篇 |
1983年 | 12篇 |
1982年 | 13篇 |
1981年 | 6篇 |
1980年 | 19篇 |
1979年 | 10篇 |
1978年 | 12篇 |
1977年 | 7篇 |
1976年 | 5篇 |
1975年 | 18篇 |
1974年 | 11篇 |
1973年 | 10篇 |
1972年 | 10篇 |
1971年 | 14篇 |
1970年 | 19篇 |
1969年 | 11篇 |
1968年 | 3篇 |
1966年 | 4篇 |
1964年 | 4篇 |
1963年 | 4篇 |
排序方式: 共有611条查询结果,搜索用时 281 毫秒
91.
92.
Frömel T Peschka M Fichtner N Hierse W Ignatiev NV Bauer KH Knepper TP 《Rapid communications in mass spectrometry : RCM》2008,22(23):3957-3967
In search of fluorinated functional groups which could undergo defluorination, and therefore be included in novel non-polluting fluorinated surfactants, omega-(bis(trifluoromethyl)amino)alkane-1-sulfonates (BTFMA-AS) with a homologue distribution from seven to thirteen methylene groups were synthesized and investigated for aerobic biodegradation applying both a standardized test and a fixed-bed bioreactor (FBBR). These compounds were prepared as part of a screening study for potentially mineralizable fluorinated endgroups.Application of hybrid triple quadrupole-linear ion trap mass spectrometry (QqQ(LIT)-MS) coupled to high-performance liquid chromatography (HPLC) allowed the tracking of primary degradation as well as the detection and structural elucidation of biotransformation intermediates. An understanding of the fragmentation pathway of the test compounds allowed selective precursor ion scans to reveal the presence of stable fluorinated metabolites. Structures were confirmed by enhanced product ion scans and MS(3) scans in the linear ion trap mode.The primary biodegradation rate and the extent of biodegradation were found to be chain-length dependent, with higher homologues being completely primarily degraded within 10 days. For the first time, two simultaneous metabolic pathways for substituted linear alkane-1-sulfonates were discovered: Desulfonation, oxidation to a carboxylic acid and subsequent chain-length shortening by beta-oxidation dominated the metabolism. This pathway resulted in the formation of 3-(bis(trifluoromethyl)amino)propionic acid and bis(trifluoromethyl)aminoacetic acid, which showed recalcitrance in this experiment. Oxidation of the alkyl chain to the respective carbonyl derivative represents the minor pathway. Only the long-chain homologues of these oxidized species were partially degraded; the short-chain homologues were not attacked. 相似文献
93.
94.
Voss S Fischer R Jung G Wiesmüller KH Brock R 《Journal of the American Chemical Society》2007,129(3):554-561
For the detection of bioanalytes, there is an ongoing search for synthetic sensors to replace enzyme-based assays which are sensitive to contaminants or suboptimal storage conditions. Lipopolysaccharide (LPS), a bacteria-borne endotoxin that may lead to life-threatening conditions such as septic shock, is one such case. Fluorescently labeled analogues of two peptide variants derived from the putative ligand-binding domain of the LPS-binding protein CD14 were developed that detect and discriminate LPS and lipids down to the submicromolar concentration range. Peptides are terminally labeled with carboxyfluorescein and tetramethylrhodamine. For one given peptide, sensitivity and specificity for the detection of LPS and discrimination from other lipids are achieved by spectral signatures that combine changes in the fluorescence resonance energy transfer (FRET) between both dyes and the total emission of tetramethylrhodamine. Alternatively, specificity is obtained by combining the FRET efficiencies of both peptide variants. In comparison to published synthetic LPS sensors, the CD14-derived sensors yield an increase in sensitivity by about 3 orders of magnitude and exhibit specificity for analytes for which the design of synthetic recognition elements is a challenging task. Moreover, one of the sensors enabled the detection of LPS in the presence of up to 50% fetal calf serum, thereby demonstrating the feasibility of this peptide-based approach for clinically relevant samples. 相似文献
95.
Demetrio De la Calle García Manfred Reichenbcher Klaus Danzer Christian Hurlbeck Christine Bartzsch Karl-Heinz Feller 《Journal of separation science》1998,21(7):373-377
Headspace solid-phase microextraction (HS/SPME) was studied and optimized for the capillary gas chromatographic (CGC) analysis of wine aroma compounds. The results were compared with those obtained using the direct sampling mode (DI/SPME) and using liquid/liquid extraction with Kaltron. The aromatic patterns obtained by HS/SPME-CGC were applied to the chemometric classification of wine varieties. The HS/SPME-CGC standard additional method is an appropriate technique for the quantitative analysis of volatile wine aroma compounds. 相似文献
96.
97.
Alemani M Peters MV Hecht S Rieder KH Moresco F Grill L 《Journal of the American Chemical Society》2006,128(45):14446-14447
The electric field applied between the tip of a scanning tunneling microscope and a metallic surface is shown to induce the reversible trans-cis isomerization of single azobenzene derivatives adsorbed on a Au(111) surface. The investigated molecule is symmetrically equipped with four tert-butyl groups, which decouple the azobenzene core from the metallic surface, facilitating the formation of highly ordered islands. Due to the spatial extension of the electric field, it is possible to switch many molecules within the same island simultaneously. 相似文献
98.
Certified reference materials (CRMs) of different origin were used to validate the direct determination of total mercury by solid sampling Zeeman atomic absorption spectrometry (SS-ZAAS) and a specially designed furnace. The temperature program provides only for one step. Atomisation of mercury and pyrolysis of the matrix is performed at a constant temperature in the range of 900–1000 °C. Calibration points achieved by CRMs and aqueous solutions are covered by one calibration line, indicating the absence of matrix effects. Relatively high amounts of chlorine, known for causing problems in mercury determination do not influence analytical results. The excellent accuracy of the method results in a very good agreement with the certified values. The precision of SS-ZAAS measurements in a range from 0.5 to 50 ng Hg does not exceed 3% R.S.D. A limit of quantification of 0.008 μg g−1 Hg was achieved. 相似文献
99.
Hamidreza?SalimiEmail author Karl-Heinz?Wolf Johannes?Bruining 《Transport in Porous Media》2012,91(2):391-422
This article deals with developing a solution approach, called the non-isothermal negative saturation (NegSat) solution approach.
The NegSat solution approach solves efficiently any non-isothermal compositional flow problem that involves phase disappearance,
phase appearance, and phase transition. The advantage of the solution approach is that it circumvents using different equations
for single-phase and two-phase regions and the ensuing unstable procedure. This paper shows that the NegSat solution approach
can also be used for non-isothermal systems. The NegSat solution approach can be implemented efficiently in numerical simulators
to tackle modeling issues for mixed CO2–water injection in geothermal reservoirs, thermal recovery processes, and for multicontact miscible and immiscible gas injection
in oil reservoirs. We illustrate the approach by way of example to cold mixed CO2–water injection in a 1D geothermal reservoir. The solution is compared with an analytical solution obtained with the wave-curve
method (method of characteristics) and shows excellent agreement. A complete set of simulations is carried out, which identifies
six bifurcations. The two main bifurcations are (1) when the most downstream compositional wave is replaced by a compositional
shock and (2) when an extra Buckley–Leverett rarefaction appears. The plot of the useful energy (exergy) versus the CO2 storage capacity shows a Z-shape. The top horizontal part represents a branch of high exergy recovery/relatively lower storage capacity, whereas the
bottom part represents a branch of lower exergy recovery/higher storage capacity. 相似文献
100.
A good knowledge of the luminosity spectrum is mandatory for many measurements at future $\mathrm {e}^{+}\mathrm {e}^{-}$ colliders. As the beam-parameters determining the luminosity spectrum cannot be measured precisely, the luminosity spectrum has to be measured through a gauge process with the detector. The measured distributions, used to reconstruct the spectrum, depend on Initial State Radiation, cross-section, and Final State Radiation. To extract the basic luminosity spectrum, a parametric model of the luminosity spectrum is created, in this case the spectrum at the 3 TeV compact linear collider. The model is used within a reweighting technique to extract the luminosity spectrum from measured Bhabha event observables, taking all relevant effects into account. The centre-of-mass energy spectrum is reconstructed within 5 % over the full validity range of the model. The reconstructed spectrum does not result in a significant bias or systematic uncertainty in the exemplary physics benchmark process of smuon pair production. 相似文献