全文获取类型
收费全文 | 216篇 |
免费 | 3篇 |
专业分类
化学 | 127篇 |
数学 | 19篇 |
物理学 | 40篇 |
无线电 | 33篇 |
出版年
2022年 | 4篇 |
2021年 | 3篇 |
2020年 | 3篇 |
2019年 | 1篇 |
2018年 | 2篇 |
2017年 | 4篇 |
2016年 | 3篇 |
2015年 | 3篇 |
2014年 | 6篇 |
2013年 | 11篇 |
2012年 | 14篇 |
2011年 | 18篇 |
2010年 | 17篇 |
2009年 | 10篇 |
2008年 | 20篇 |
2007年 | 14篇 |
2006年 | 19篇 |
2005年 | 12篇 |
2004年 | 4篇 |
2003年 | 9篇 |
2002年 | 9篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有219条查询结果,搜索用时 31 毫秒
211.
Pedersen CS Lauritsen FR Sysoev A Viitanen AK Mäkelä JM Adamov A Laakia J Mauriala T Kotiaho T 《Journal of the American Society for Mass Spectrometry》2008,19(9):1361-1366
Ionized acetates were used as model compounds to describe gas-phase behavior of oxygen containing compounds with respect to their formation of dimers in ion mobility spectrometry (IMS). The ions were created using corona discharge at atmospheric pressure and separated in a drift tube before analysis of the ions by mass spectrometry. At the ambient operational temperature and pressure used in our instrument, all acetates studied formed dimers. Using a homolog series of n-alkyl-acetates, we found that the collision cross section of a dimer was smaller than that of a monomer with the same reduced mass. Our experiments also showed that the reduced mobility of acetate dimers with different functional groups increased in the order n-alkyl = branched chain alkyl = cyclo alkyl < aromat. For mixed n-alkyl dimers we found that the reduced mobility of acetate dimers having the same number of carbons, for example a dimer of acetyl acetate and hexyl acetate has the same reduced mobility as a dimer composed of two butyl acetates. The fundamental behavior of acetate monomers and dimers described in this paper will assist in a better understanding of the influence of dimer formation in ion mobility spectrometry. 相似文献
212.
Sikanen T Tuomikoski S Ketola RA Kostiainen R Franssila S Kotiaho T 《Journal of mass spectrometry : JMS》2008,43(6):726-735
We present a detailed optimization and characterization of the analytical performance of SU-8-based emitters for electrospray ionization mass spectrometry (ESI/MS). The improved SU-8 fabrication process presented here enhances patterning accuracy and reduces the time and cost of fabrication. All emitters are freestanding and enable sample delivery by both pressure-driven and spontaneous flows. The optimized emitter design incorporates a sharp, double-cantilevered tip implemented to the outlet of an SU-8 microchannel and provides highly sensitive ESI/MS detection. Moreover, the optimized design allows the use of relatively large microchannel dimensions (up to 200 x 50 microm(2), w x h) without sacrificing the detection sensitivity. This is advantageous with a view of preventing emitter clogging and enabling reproducible analysis. The measured limits of detection for the optimized emitter design were 1 nM for verapamil and 4 nM for Glu-fibrinopeptide B with good quantitative linearities between 1 nM and 10 microM (R(2) = 0.9998) for verapamil and between 4 nM and 3 microM (R(2) = 0.9992) for Glu-fibrinopeptide B. The measured tip-to-tip repeatability for signal intensity was 14% relative standard deviation (RSD) (n = 3; 5 microM verapamil) and run-to-run repeatability 4-11% RSD (n = 4; 5 microM verapamil) for all individual emitters tested. In addition, long-term stability of < 2% RSD was maintained for timescales of 30 min even under free flow conditions. SU-8 polymer was also shown to be chemically stable against most of the tested electrospray solvents. 相似文献
213.
Kauppila TJ Talaty N Jackson AU Kotiaho T Kostiainen R Cooks RG 《Chemical communications (Cambridge, England)》2008,(23):2674-2676
Desorption electrospray ionization mass spectrometry (DESI-MS) is applied to the analysis of carbohydrates and steroids; the detection limits are significantly improved by the addition of low concentrations of salts to the spray solvent. 相似文献
214.
Ari Lehmusvuori Ulla KarhunenAntti-Heikki Tapio Urpo LamminmäkiTero Soukka 《Analytica chimica acta》2012
We introduce a switchable lanthanide luminescence reporter technology based closed-tube PCR for the detection of specific target DNA sequence. In the switchable lanthanide chelate complementation based reporter technology hybridization of two nonfluorescent oligonucleotide probes to the adjacent positions of the complementary strand leads to the formation of a highly fluorescent lanthanide chelate complex. The complex is self-assembled from a nonfluorescent lanthanide chelate and a light-harvesting antenna ligand when the reporter molecules are brought into close proximity by the oligonucleotide probes. Outstanding signal-to-background discrimination in real-time PCR assay was achieved due to the very low background fluorescence level and high specific signal generation. High sensitivity of the reporter technology allows the detection of a lower concentration of amplified DNA in the real-time PCR, resulting in detection of the target at the earlier amplification cycle compared to commonly used methods. 相似文献
215.
Niina M. Suni Henni Aalto Tiina J. Kauppila Tapio Kotiaho Risto Kostiainen 《Journal of mass spectrometry : JMS》2012,47(5):611-619
In this article, the effect of spray solvent on the analysis of selected lipids including fatty acids, fat‐soluble vitamins, triacylglycerols, steroids, phospholipids, and sphingolipids has been studied by two different ambient mass spectrometry (MS) methods, desorption electrospray ionization‐MS (DESI‐MS) and desorption atmospheric pressure photoionization‐MS (DAPPI‐MS). The ionization of the lipids with DESI and DAPPI was strongly dependent on the spray solvent. In most cases, the lipids were detected as protonated or deprotonated molecules; however, other ions were also formed, such as adduct ions (in DESI), [M‐H]+ ions (in DESI and DAPPI), radical ions (in DAPPI), and abundant oxidation products (in DESI and DAPPI). DAPPI provided efficient desorption and ionization for neutral and less polar as well as for ionic lipids but caused extensive fragmentation for larger and more labile compounds because of a thermal desorption process. DESI was more suitable for the analysis of the large and labile lipids, but the ionization efficiency for less polar lipids was poor. Both methods were successfully applied to the direct analysis of lipids from pharmaceutical and food products. Although DESI and DAPPI provide efficient analysis of lipids, the multiple and largely unpredictable ionization reactions may set challenges for routine lipid analysis with these methods. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
216.
Toivonen TL Hukka TI Cramariuc O Rantala TT Lemmetyinen H 《The journal of physical chemistry. A》2006,110(44):12213-12221
Spectroscopic properties of a ground state nonbonded porphine-buckminsterfullerene (H2P...C60) complex are studied in several different relative orientations of C60 with respect to the porphine plane by using the density functional (DFT) and time-dependent density functional (TDDFT) theories. The geometries and electronic structures of the ground states are optimized with the B3LYP and PBE functionals and a SVP basis set. Excitation energies and oscillator strengths are obtained from the TDDFT calculations. The relative orientation of C60 is found to affect the equilibrium distance between H2P and C60 especially in the case of the PBE functional. The excitation energies of different H2P...C60 complexes are found to be practically the same for the same excitations when the B3LYP functional is used but to differ notably when PBE is used in calculations. Existence of the states related to a photoinduced electron transfer within a porphyrin-fullerene dyad is also studied. All calculations predict a formation of an excited charge-transfer complex state, a locally excited donor (porphine) state, as well as a locally excited acceptor (fullerene) state in the investigated H2P...C60 complexes. 相似文献
217.
Hannu-Pekka Komsa Tapio Rantala Alfredo Pasquarello 《Physica B: Condensed Matter》2012,407(15):3063-3067
We present a comparison of the most common finite-size supercell correction schemes for charged defects in density functional theory calculations. Considered schemes include those proposed by Makov and Payne (MP), Lany and Zunger (LZ), and Freysoldt, Neugebauer, and Van de Walle (FNV). The role of the potential alignment is also assessed. Supercells of various sizes are considered and the corrected formation energies are compared to the values obtained by extrapolation to large supercells. For defects with localized charge distributions, we generally find that the FNV scheme slightly improves upon the LZ one, while the MP scheme generally overcorrects except for point-charge-like defects. We also encountered more complex situations in which the extrapolated values do not coincide. Inspection of the defect electronic structure indicates that this occurs when the defect Kohn–Sham states are degenerate with band-edge states of the host. 相似文献
218.
Development of fuzzy state controller and its application to a hydraulic position servo 总被引:5,自引:0,他引:5
By combining control theory and fuzzy set theory, a new kind of state controller is proposed. Full order feedback and membership functions, which utilize the experience of experts, are used in the design of the state controller which we call a fuzzy state controller. Hydraulic position servos with a nonsymmetrical cylinder are commonly used in industry. This kind of system is nonlinear in nature and generally difficult to control. For different ending position, moving direction, strokes, and load the system dynamics is totally different. Once the above-mentioned parameters of the system are known, it is relatively straightforward to tune the gains of state controller to obtain good dynamic response. But when these parameters change, especially in case of the load, using the same gains will cause overshoot or even loss of system stability. Adaptive control is not applicable in this case due to the complexity of the algorithm, its rate of convergence, and the fast response characteristic of the system. The fuzzy state controller has been successfully applied to a hydraulic position servo. The system shows excellent robustness against variations of system parameters. 相似文献
219.