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71.
Pihlainen K Grigoras K Franssila S Ketola R Kotiaho T Kostiainen R 《Journal of mass spectrometry : JMS》2005,40(4):539-545
The suitability of atmospheric pressure desorption/ionization on silicon mass spectrometry (AP-DIOS-MS) and matrix-assisted laser desorption ionization mass spectrometry (AP-MALDI-MS) for the identification of amphetamines and fentanyls in forensic samples was studied. With both ionization techniques, the mass spectra recorded showed abundant protonated molecules, and the background did not disturb the analysis. The use of tandem mass spectrometry (MS/MS) allowed unambiguous identification of the amphetamines and fentanyls. AP-DIOS-MS/MS and AP-MALDI-MS/MS were also successfully applied to the identification of authentic compounds from drug seizures. Common diluents and tablet materials did not disturb the analysis and compounds were unequivocally identified. The limits of detection (LODs) for amphetamines and fentanyls with AP-DIOS-MS/MS were 1-3 pmol, indicating excellent sensitivity of the method. The LODs with AP-MALDI-MS/MS were about 5-10 times higher. 相似文献
72.
Salo PK Salomies H Harju K Ketola RA Kotiaho T Yli-Kauhaluoma J Kostiainen R 《Journal of the American Society for Mass Spectrometry》2005,16(6):906-915
The feasibility of ultra thin-layer chromatography atmospheric pressure matrix-assisted laser desorption ionization mass spectrometry (UTLC-AP-MALDI-MS) has been studied in the analysis of small molecules. Because of a thinner adsorbent layer, the monolithic UTLC plates provide 10-100 times better sensitivity in MALDI analysis than conventional high performance thin-layer chromatography (HPTLC) plates. The limits of detection down to a low picomole range are demonstrated by UTLC-AP-MALDI-MS. Other advantages of UTLC over HPTLC include faster separations and lower solvent consumption. The performances of AP-MALDI-MS and vacuum MALDI-MS have been compared in the analysis of small drug molecules directly from the UTLC plates. The desorption from the irregular surface of UTLC plates with an external AP-MALDI ion source combined with an ion trap instrument provides clearly less variation in measurements of m/z values when compared with a vacuum MALDI-time-of-flight (TOF) instrument. The performance of the UTLC-AP-MALDI-MS method has been applied successfully to the purity analysis of synthesis products produced by solid-phase parallel synthesis method. 相似文献
73.
Raimo A. Ketola Jari T. Kiuru Juha T. Kokkonen Tapio Kotiaho 《Analytica chimica acta》2006,562(2):245-251
A temperature-programmed desorption (TPD) device connected to a mass spectrometer was used to detect volatile organic compounds from air samples. The main aim was to develop an analytical method, by which both non-polar and polar organic components can be detected in the same run. In TPD, the adsorbed compounds are desorbed from the resin more slowly than in the conventional trapping techniques, such as purge-and-trap technique, in which the resin is flash-heated and the compounds are desorbed at the same time to a cryogenic trap or an analytical column. In TPD, the adsorbent resin acts also as an analytical column. In this way it is possible to obtain more rapid analysis, and also a more simple instrumentation, which can be used on-line and on-site. In this work, a new version of TPD device, which uses a resistor for heating and a Peltier element for rapid cooling, was designed and constructed. Various adsorbent resins were tested for their adsorption and desorption properties of both polar and non-polar compounds. When using a mixture of adsorbent resins, Tenax TA and HayeSep D, it was possible to analyze both polar, low-molecular weight compounds, such as methanol and ethanol, and non-polar volatile organic compounds, such as benzene and toluene, in the same run within 15 min including sampling. The same TPD principle was also tested using a Fourier transform infrared spectrometer as an analytical instrument, and the results showed that it was possible to obtain a separation of similar compounds, such as hexane and heptane, and still retaining the same sensitivity as the original on-line FTIR instrument. 相似文献
74.
Jan?KronqvistEmail author Andreas?Lundell Tapio?Westerlund 《Journal of Global Optimization》2016,64(2):249-272
A new deterministic algorithm for solving convex mixed-integer nonlinear programming (MINLP) problems is presented in this paper: The extended supporting hyperplane (ESH) algorithm uses supporting hyperplanes to generate a tight overestimated polyhedral set of the feasible set defined by linear and nonlinear constraints. A sequence of linear or quadratic integer-relaxed subproblems are first solved to rapidly generate a tight linear relaxation of the original MINLP problem. After an initial overestimated set has been obtained the algorithm solves a sequence of mixed-integer linear programming or mixed-integer quadratic programming subproblems and refines the overestimated set by generating more supporting hyperplanes in each iteration. Compared to the extended cutting plane algorithm ESH generates a tighter overestimated set and unlike outer approximation the generation point for the supporting hyperplanes is found by a simple line search procedure. In this paper it is proven that the ESH algorithm converges to a global optimum for convex MINLP problems. The ESH algorithm is implemented as the supporting hyperplane optimization toolkit (SHOT) solver, and an extensive numerical comparison of its performance against other state-of-the-art MINLP solvers is presented. 相似文献
75.
Raffaelli B Pohjoispää M Hase T Cardin CJ Gan Y Wähälä K 《Organic & biomolecular chemistry》2008,6(14):2619-2627
Various conflicting data on the rearrangement and absolute stereochemistry of hydroxylignano-9,7'-lactones are resolved using 18O labeled compounds, also confirmed by an X-ray analysis of a pure lignano-9,7'-lactone enantiomer, obtained for the first time. Under NaH/DMF rearrangement conditions a silyl protected hydroxylignano-9,9'-lactone underwent an unexpected silyl migration. 相似文献
76.
Ruuska H Arola E Kannus K Rantala TT Valkealahti S 《The Journal of chemical physics》2008,128(6):064109
Feasibility of density functional theory (DFT) to predict dielectric properties such as polarizability of saturated polymers is investigated. Small saturated molecules, methane and propane, which is a monomer of polypropylene chain, are used in testing the methods. Results for polarizabilities based on several density functionals together with different basis sets are compared and contrasted with each other, with results by Hartree-Fock and second-order Moller-Plesset perturbation theory, as well as experimental data. The generalized gradient approximation PW91 method together with the 6-311++G(**) basis set is found to be the most suitable method, in terms of sufficient accuracy and computational efficiency, to calculate polarizabilities for large oligomers of polypropylene. The dielectric constant is then determined using the calculated polarizabilities and the Clausius-Mossotti equation. The molecular DFT methods at the PW916-311++G(**) level together with the Clausius-Mossotti equation give dielectric constants for saturated polymers such as polypropylene in good accordance with the experimental values. 相似文献
77.
Harju M Järn M Dahlsten P Nikkanen JP Rosenholm JB Mäntylä T 《Journal of colloid and interface science》2008,326(2):403-410
The influence of water exposure on the surface properties of plasma-sprayed Cr(2)O(3) and Cr(2)O(3)-25 wt% TiO(2) was studied. It was shown that both plasma-sprayed materials contained Cr(VI) hydrous oxide phases, which dissolved rapidly at the beginning of water exposure. The dissolution continued slowly during the whole water exposure time. The Cr(VI) dissolution was accompanied by a rapid increase in surface IEP value. Both Cr(2)O(3) and Cr(2)O(3)-25 wt% TiO(2) showed similar dissolution, zeta potential, and surface oxidation states. Thus the addition of TiO(2) did not influence the surface properties of the plasma-sprayed Cr(2)O(3). 相似文献
78.
Desorption atmospheric pressure photoionization high‐resolution mass spectrometry: a complementary approach for the chemical analysis of atmospheric aerosols 下载免费PDF全文
79.
Jaakko Laakia Christian Schack Pedersen Alexey Adamov Jyrki Viidanoja Alexey Sysoev Tapio Kotiaho 《Rapid communications in mass spectrometry : RCM》2009,23(19):3069-3076
Negative corona discharge atmospheric pressure chemical ionization (APCI) was used to investigate phenols with varying numbers of tert‐butyl groups using ion mobility spectrometry–mass spectrometry (IMS‐MS). The main characteristic ion observed for all the phenolic compounds was the deprotonated molecule [M–H]−. 2‐tert‐Butylphenol showed one main mobility peak in the mass‐selected mobility spectrum of the [M–H]− ion measured under nitrogen atmosphere. When air was used as a nebulizer gas an oxygen addition ion was seen in the mass spectrum and, interestingly, this new species [M–H+O]− had a shorter drift time than the lighter [M–H]− ion. Other phenolic compounds primarily produced two IMS peaks in the mass‐selected mobility spectra measured using the [M–H]− ion. It was also observed that two isomeric compounds, 2,4‐di‐tert‐butylphenol and 2,6‐di‐tert‐butylphenol, could be separated with IMS. In addition, mobilities of various characteristic ions of 2,4,6‐trinitrotoluene were measured, since this compound was previously used as a mobility standard. The possibility of using phenolic compounds as mobility standards is also discussed. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
80.
In this paper a new approach for the global solution of nonconvex MINLP (Mixed Integer NonLinear Programming) problems that contain signomial (generalized geometric) expressions is proposed and illustrated. By applying different variable transformation techniques and a discretization scheme a lower bounding convex MINLP problem can be derived. The convexified MINLP problem can be solved with standard methods. The key element in this approach is that all transformations are applied termwise. In this way all convex parts of the problem are left unaffected by the transformations. The method is illustrated by four example problems. 相似文献