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51.
Tiina?J.?Kauppila Andries?P.?BruinsEmail author Risto?Kostiainen 《Journal of the American Society for Mass Spectrometry》2005,16(8):1399-1407
In the novel atmospheric pressure photoionization-mass spectrometry the ionization efficiency has been observed to decrease
when the solvent flow rate is increased. The effect of the flow rate on the ionization efficiency was studied by comparing
the behavior of two analytes, one of which is ionized through charge exchange, the other through proton transfer. Additional
information about the ion loss mechanisms was obtained by comparing results obtained with two different APPI ion sources:
a Sciex prototype and the Agilent/Syagen APPI source. In addition to the measurements done by using the mass analyzer, the
total ion current in the ion source was obtained by measuring the currents of the ions arriving at curtain/end plate and orifice/capillary
of the two mass spectrometers. The total ion current measurements showed a significant decrease at high solvent flow rates.
Loss of dopant radical cations was thought to be the reason for the signal decrease of the analytes formed through charge
exchange. Analytes formed through proton transfer were not as seriously ected by the high solvent flow rates, but some saturation
of their signal was nevertheless observed. Loss of photons through absorption by solvent vapor is another mechanism that can
be held responsible for a reduction of the total number of ions produced by the APPI source. 相似文献
52.
The infrared spectrum of CO2 in the region 540–830 cm?1 has been studied with a Fourier spectrometer at a resolution of 0.010 cm?1. In addition to the fundamental ν2, more than 10 “hot” band transitions of 12C16O2 have been identified. The rotational constants involved have been derived. Special care has been taken in obtaining accurate constants for the level 0110. The ν2 fundamentals of the isotopic molecules 13C16O2, 16O12C18O, and 16O12C17O have also been observed in a natural sample. 相似文献
53.
Electron-beam-mediated postsynthesis doping of boron-nitride nanostructures with carbon atoms [Nature (London) 464, 571 (2010); J. Am. Chem. Soc. 132, 13?692 (2010)] was recently demonstrated, thus opening a new way to control the electronic properties of these systems. Using density-functional theory static and dynamic calculations, we show that the substitution process is governed not only by the response of such systems to irradiation, but also by the energetics of the atomic configurations, especially when the system is electrically charged. We suggest using spatially localized electron irradiation for making carbon islands and ribbons embedded into BN sheets. We further study the magnetic and electronic properties of such hybrid nanostructures and show that triangular carbon islands embedded into BN sheets possess magnetic moments, which can be switched on and off by electrically charging the structure. 相似文献
54.
Jorma Lehtonen Risto Mikkonen Jaakko Paasi 《Physica C: Superconductivity and its Applications》1998,310(1-4):340-344
Stability of a Bi-2223/Ag multifilamentary composite conductor against fast transport current ramps was studied by using a numerical model. The model was based on the two-dimensional magnetic diffusion and heat conduction equations. Calculations were carried out both in an adiabatic mode and pool boiling modes in liquid helium, hydrogen and nitrogen. When estimating the heat load (AC losses), real temperature dependent current density–electric field characteristics were used. The results computed by the finite element method are presented and discussed with special emphasis on differences of the stability considerations between high-temperature and low-temperature superconductors. 相似文献
55.
Maximum likelihood estimates for parameters in a linear functional relationship are derived when the errors are also linearly related for each observation. This is approximately the case, for example, when both variables are smooth functions of time and their values are recorded as an experimental unit reaches a certain state. This kind of model specification was needed to describe how the timing of growth cessation of trees depends on night length and temperature sum. If the slope in the constraint equation for errors varies, then an iterative estimation procedure is needed. The estimation method is extended for a two-phase linear model. 相似文献
56.
Risto S. Laitinen Bruce Randolph Tapani A. Pakkanen 《Journal of computational chemistry》1987,8(5):658-662
A theoretical study of homocyclic sulfur species S6, S7, and S8 was carried out using a molecular valence method involving stepwise approximations for orthogonality and core-valence interactions. The valence shell orbitals are described at the minimal basis level. The geometries of the molecules are predicted well as compared with other theoretical studies and the experimental values. The slight overestimation of the SS bond length is typical to the nonpolarized basis sets. The energies of the valence orbitals are well in accord with the conventional all-electron ab initio results. The trend in the stabilities of the three molecules is discussed. The present method provides an attractive possibility to study homocyclic and heterocyclic systems involving heavier chalcogens with no increase of the computing time. 相似文献
57.
Structure and Bonding in Bis(1‐naphthyl) Diselenide and Bis{[2‐(N,N‐dimethylamino)methyl]phenyl} Tetraselenide,and Their Brominated Derivatives
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Esther M. Takaluoma Teemu T. Takaluoma Raija Oilunkaniemi Risto S. Laitinen 《无机化学与普通化学杂志》2015,641(5):772-779
The formation and crystal structures of bis(1‐naphthyl) diselenide ( 1 ) and bis{[2‐(N,N‐dimethylamino)methyl]phenyl} tetraselenide ( 2 ) are described. Whereas 1 can be produced in good yields, 2 is formed only as a minor product together with the known main product, bis{[2‐(N,N‐dimethylamino)methyl]phenyl} diselenide. The composition of the reaction mixture is semi‐quantitatively estimated by 77Se NMR spectroscopy and DFT calculations. The effect of the n2→σ*(Se–Se) and π→σ*(Se–Se) secondary bonding interactions on the Se–Se bonds is discussed both by DFT calculations and comparison with literature, as available. The bromination of 1 yields monomeric (1‐naphthyl)selenenyl bromide ( 3 ) in good yields. That of the reaction mixture of (C6H4CH2NMe2)Sex (x = 2–4) and Se8 afforded (C6H4CH2NMe2H)2[SeBr4] ( 4 ) and (C6H4CH2NMe2H)2[SeBr6] ( 5 ) in addition to (C6H4CH2NMe2)SeBr, which has been previously reported. 相似文献
58.
Tiina Sikanen Susanna Aura Sami Franssila Tapio Kotiaho Risto Kostiainen 《Analytica chimica acta》2012
We present rapid (<5 min) and efficient intact protein analysis by mass spectrometry (MS) using fully microfabricated and monolithically integrated capillary electrophoresis–electrospray ionization (CE–ESI) microchips. The microchips are fabricated fully of commercial inorganic–organic hybrid material, Ormocomp, by UV-embossing and adhesive Ormocomp–Ormocomp bonding (CE microchannels). A sheath-flow ESI interface is monolithically integrated with the UV-embossed separation channels by cutting a rectangular emitter tip in the end with a dicing saw. As a result, electrospray was produced from the corner of chip with good reproducibility between parallel tips (stability within 3.8–9.2% RSD). Thanks to its inherent biocompatibility and stable (negative) surface charge, Ormocomp microchips enable efficient intact protein analysis with up to ∼104 theoretical separation plates per meter without any chemical or physical surface modification before analysis. The same microchip setup is also feasible for rapid peptide sequencing and mass fingerprinting and shows excellent migration time repeatability from run to run for both peptides (5.6–5.9% RSD, n = 4) and intact proteins (1.3–7.5% RSD, n = 3). Thus, the Ormocomp microchips provide a versatile new tool for MS-based proteomics. Particularly, the feasibility of the Ormocomp chips for rapid analysis of intact proteins with such a simple setup is a valuable increment to the current technology. 相似文献
59.
Linda Ahonen Pekka Keski-Rahkonen Taija Saarelainen Jenni Paviala Raimo A. Ketola Seppo Auriola Matti Poutanen Risto Kostianen 《Analytica chimica acta》2012
The feasibility of a microfluidic-based liquid chromatography-electrospray ionization/mass spectrometric system (HPLC-Chip/ESI/MS) was studied and compared to a conventional narrow-bore liquid chromatography-electrospray ionization/mass spectrometric (LC-ESI/MS) system for the analysis of steroids. The limits of detection (LODs) for oxime derivatized steroids, expressed as concentrations, were slightly higher with the HPLC-Chip/MS system (50–300 pM) using an injection volume of 0.5 μL than with the conventional LC-ESI/MS (10–150 pM) using an injection volume of 40 μL. However, when the LODs are expressed as injected amounts, the sensitivity of the HPLC-Chip/MS system was about 50 times higher than with the conventional LC-ESI/MS system. The results indicate that the use of HPLC-Chip/MS system is clearly advantageous only in the analysis of low-volume samples. Both methods showed good linearity and good quantitative and chromatographic repeatability. In addition to the instrument comparisons with oxime derivatized steroids, the feasibility of the HPLC-Chip/MS system in the analysis of non-derivatized and oxime derivatized steroids was compared. The HPLC-Chip/MS method developed for non-derivatized steroids was also applied to the quantitative analysis of 15 mouse plasma samples. 相似文献
60.
We present the first monolithically integrated silicon/glass liquid chromatography-electrospray ionization microchip for mass spectrometry. The microchip is fabricated by bonding a silicon wafer, which has deep reactive ion etched micropillar-filled channels, together with a glass lid. Both the silicon channel and the glass lid have a through-wafer etched sharp tip that produces a stable electrospray. The microchip is also compatible with laser induced fluorescence (LIF) detection, due to the glass lid. Separation of drugs in less than 5 minutes using either SiO(2) (normal phase) or C(18) coated (reversed-phase) pillars with good sensitivity was demonstrated with mass spectrometric detection as well as separation of fluorescent compounds with LIF detection. 相似文献