全文获取类型
收费全文 | 481篇 |
免费 | 8篇 |
国内免费 | 1篇 |
专业分类
化学 | 288篇 |
晶体学 | 11篇 |
力学 | 14篇 |
数学 | 66篇 |
物理学 | 111篇 |
出版年
2022年 | 3篇 |
2021年 | 6篇 |
2020年 | 7篇 |
2019年 | 7篇 |
2018年 | 8篇 |
2017年 | 7篇 |
2016年 | 19篇 |
2015年 | 10篇 |
2014年 | 16篇 |
2013年 | 63篇 |
2012年 | 14篇 |
2011年 | 19篇 |
2010年 | 17篇 |
2009年 | 19篇 |
2008年 | 15篇 |
2007年 | 15篇 |
2006年 | 24篇 |
2005年 | 12篇 |
2004年 | 10篇 |
2003年 | 9篇 |
2002年 | 12篇 |
2001年 | 5篇 |
2000年 | 6篇 |
1999年 | 8篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1994年 | 3篇 |
1992年 | 4篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 3篇 |
1983年 | 3篇 |
1980年 | 4篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1974年 | 4篇 |
1972年 | 3篇 |
1969年 | 5篇 |
1968年 | 3篇 |
1966年 | 4篇 |
1959年 | 4篇 |
1957年 | 11篇 |
1937年 | 8篇 |
1935年 | 7篇 |
1934年 | 3篇 |
排序方式: 共有490条查询结果,搜索用时 46 毫秒
481.
Volná K Holcapek M Kolárová L Lemr K Cáslavský J Kacer P Poustka J Hubálek M 《Rapid communications in mass spectrometry : RCM》2008,22(2):101-108
A library of negative ion electrospray ionization mass spectra and tandem mass spectra (MS/MS) of sulfonated dyes has been developed for fast identification purposes. The uniform protocol has been elaborated and applied to the measurements of more than 50 anionic dyes. Three collision energies are selected in our protocol which ensures that at least one of them provides a suitable ratio of product ions to the precursor ion. The robustness is investigated with altered values of tuning parameters (e.g. the pressure of the nebulizing gas, the temperature and the flow rate of drying gas, and the mobile phase composition). The results of the inter-laboratory comparison of product ion mass spectra recorded on seven different tandem mass spectrometers (three ion traps, two triple quadrupoles and two hybrid quadrupole time of flight instruments) are presented for four representative anionic dyes--azo dye Acid Red 118, anthraquinone dye Acid Violet 43, triphenylmethane dye Acid Blue 1 and Al(III) metal-complex azo dye. The fragmentation patterns are almost identical for all tandem mass analyzers, only the ratios of product ions differ somewhat which confirms the possibility of spectra transfer among different mass analyzers with the goal of library formation. 相似文献
482.
Volný M Sadílek M Jackson KE Diener M Elam WT Turecek F 《Journal of mass spectrometry : JMS》2008,43(9):1265-1273
We report new experiments in which laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF-MS) was applied to detection and characterization of gramicidin S and IgG pentapeptide (DSDPR) that were reactively landed on plasma-treated stainless steel surfaces. The distributions of [M + H](+), [M + Na](+) and [M + K](+) ion species in LDI-TOF for gramicidin S and IgG pentapeptide (DSDPR) were found to be markedly different from those in conventional MALDI-TOF spectra of the same samples. LDI-TOF mass spectra showed a strong preference for [M + K](+) adducts even in the presence of a large excess of sodium cations, or following surface treatment with trifluoroacetic acid. Alkali metal cations (K(+) and Cs(+)) can be exchanged in reactively landed peptide samples to provide the corresponding cationized peptide ions by LDI. Multiple charged trypsin cations were reactively landed into a layer of 2-(4-hydroxyphenylazo)benzoic acid and ionized by LDI. The ionization mechanisms for LDI of surface-deposited peptides are briefly discussed. Copyright (c) 2008 John Wiley & Sons, Ltd. 相似文献
483.
The effect of power ultrasound application on DC hollow needle to plate atmospheric pressure electrical discharge enhanced by the flow of air through the needle electrode was studied experimentally. It was found that applying ultrasound increases discharge volume. In this volume take place plasmachemical processes, used in important ecological applications such as the production of ozone, VOC decomposition and de-NOx processes enhancement. In our experiments we used a negatively biased needle electrode as a cathode and a perpendicularly placed surface of the ultrasonic resonator--horn--as an anode. To demonstrate the effect of ultrasound waves on electrical discharge photographs of the discharge for the needle to the ultrasonic resonator at distances of 4, 6 and 8mm are shown. By varying the distance between needle and the surface of the transducer, we were able to create the node or the antinode at the region around the tip of the needle, where the ionization processes are effective. In our experimental arrangement the amplitude of acoustic pressure at antinode exceeded 10(4) Pa. The photographs reveal that the diameter of the discharge on the surface of the ultrasonic horn is increased when ultrasound is applied. The increase of discharge volume caused by the application of ultrasound can be explained as a combined effect of the change of the reduced electric field E/n (E is electric field strength and n is the neutral particles density), strong turbulence of the particles in the discharge region caused by quick changes of amplitudes of the standing ultrasonic wave and finally by the boundary layer near the ultrasonic transducer perturbations due to vibrations of the transducer surface. 相似文献
484.
Dohnálek Z Kim J Bondarchuk O White JM Kay BD 《The journal of physical chemistry. B》2006,110(12):6229-6235
Physisorption of N(2), O(2), and CO was studied on fully oxidized TiO(2)(110) using beam reflection and temperature-programmed desorption (TPD) techniques. Sticking coefficients for all three molecules are nearly equal (0.75 +/- 0.05) and approximately independent of coverage suggesting that adsorption occurs via a precursor-mediated mechanism. Excluding multilayer coverages, the TPD spectra for all three adsorbates exhibit three distinct coverage regimes that can be interpreted in accord with previous theoretical studies of N(2) adsorption. At low coverages (0-0.5 N(2)/Ti(4+)), N(2) molecules bind head-on to five-coordinated Ti(4+) ions. The adsorption occurs preferentially on the Ti(4+) sites that do not have neighboring adsorbates. This arrangement minimizes the repulsive interactions between the adsorbed molecules along the Ti(4+) rows resulting in a relatively small shift of the TPD peak (105 --> 90 K) with increasing coverage. At higher N(2) coverages (0.5-1.0 N(2)/Ti(4+)) the nearest-neighbor Ti(4+) sites become occupied. The close proximity of the adsorbates results in strong repulsion thus giving rise to a significant shift of the TPD leading edges (90 --> 45 K) with increasing coverage. For N(2)/Ti(4+) > 1, an additional low-temperature peak (approximately 43 K) is present and is ascribed to N(2) adsorption on bridge-bonded oxygen rows. The results for O(2) and CO are qualitatively similar. The repulsive adsorbate-adsorbate interactions are largest for CO, most likely due to alignment of CO dipole moments. The coverage-dependent binding energies of O(2), N(2), and CO are determined by inverting TPD profiles. 相似文献
485.
Babica P Kohoutek J Bláha L Adamovský O Marsálek B 《Analytical and bioanalytical chemistry》2006,385(8):1545-1551
The efficiencies of conventional extraction techniques and analytical methods (HPLC–DAD and ELISA) were investigated for analyses
of microcystins (MCs) in sediments. Our results showed several limitations. First, the extraction efficiency strongly depends
on the extraction solvent, and extraction with 5% acetic acid in 0.2% trifluoroacetic acid (TFA)–methanol was confirmed as
being the most appropriate for three different sediments (recovery: 33.1–44.9% of total MCs according to HPLC analyses). Second,
the recovery of MCs was affected by the type of sediment but did not clearly correlate with the content of organic carbon.
These results suggest that the sorption of MCs onto inorganic materials such as clay minerals is probably a more important
process than interactions of the MCs with organic sediment matter. Third, the structure of the MCs is another crucial factor
that affects the sorption of MCs and their recovery from sediments. Hydrophilic MC-RR gave much lower recoveries (20.0–38.8%)
than MC-YR (44.1–59.5%) or MC-LR (55.3–77.8%) from three different types of spiked sediments. Recovery results analysed with
HPLC–DAD correlated well with ELISA analyses. Further, extraction with 5% acetic acid in 0.2% TFA–methanol was used for analyses
of MCs in 34 natural sediment samples collected from Brno reservoir (Czech Republic) from April to October 2005. Concentrations
of MCs in sediments ranged from 0.003 to 0.380 μg/g sediment d.m. (ELISA results) or 0.016–0.474 μg/g d.m. (HPLC results).
These values are equivalent to 0.63–96.47 μg/L of sediment (ELISA) or 4.67–108.68 μg/L (HPLC), respectively. Concentrations
of sediment MCs showed both temporal and spatial variability, with the highest MC contents observed in the spring (April and
May) and the lowest concentrations in July and August. Our results demonstrate the suitability of the methods described here
for studying the occurrence, fate and ecological role of MCs in the aquatic environment.
相似文献
486.
The growth of amorphous solid water (ASW) films on Pt(111) is investigated using rare gas (e.g., Kr) physisorption. Temperature programmed desorption of Kr is sensitive to the structure of thin water films and can be used to assess the growth modes of these films. At all temperatures that are experimentally accessible (20-155 K), the first layer of water wets Pt(111). Over a wide temperature range (20-120 K), ASW films wet the substrate and grow approximately layer by layer for at least the first three layers. In contrast to the ASW films, crystalline ice films do not wet the water monolayer on Pt(111). Virtually identical results were obtained for ASW films on epitaxial Pd(111) films grown on Pt(111). The desorption rates of thin ASW and crystalline ice films suggest that the relative free energies of the films are responsible for the different growth modes. However, at low temperatures, surface relaxation or "transient mobility" is primarily responsible for the relative smoothness of the films. A simple model of the surface relaxation semiquantitatively accounts for the observations. 相似文献
487.
n-alkanes on Pt(111) and on C(0001)Pt(111): chain length dependence of kinetic desorption parameters
We have measured the desorption of seven small n-alkanes (C(N)H(2N+2), N=1-4,6,8,10) from the Pt(111) and C(0001) surfaces by temperature programed desorption. We compare these results to our recent study of the desorption kinetics of these molecules on MgO(100) [J. Chem. Phys. 122, 164708 (2005)]. There we showed an increase in the desorption preexponential factor by several orders of magnitude with increasing n-alkane chain length and a linear desorption energy scaling with a small y-intercept value. We suggest that the significant increase in desorption prefactor with chain length is not particular to the MgO(100) surface, but is a general effect for desorption of the small n-alkanes. This argument is supported by statistical mechanical arguments for the increase in the entropy gain of the molecules upon desorption. In this work, we demonstrate that this hypothesis holds true on both a metal surface and a graphite surface. We observe an increase in prefactor by five orders of magnitude over the range of n-alkane chain lengths studied here. On each surface, the desorption energies of the n-alkanes are found to increase linearly with the molecule chain length and have a small y-intercept value. Prior results of other groups have yielded a linear desorption energy scaling with chain length that has unphysically large y-intercept values. We demonstrate that by allowing the prefactor to increase according to our model, a reanalysis of their data resolves this y-intercept problem to some degree. 相似文献
488.
Miroslav Bulíček Eduard Feireisl Josef Málek 《Nonlinear Analysis: Real World Applications》2009,10(2):992-1015
We consider a complete thermodynamic model for unsteady flows of incompressible homogeneous Newtonian fluids in a fixed bounded three-dimensional domain. The model comprises evolutionary equations for the velocity, pressure and temperature fields that satisfy the balance of linear momentum and the balance of energy on any (measurable) subset of the domain, and is completed by the incompressibility constraint. Finding a solution in such a framework is tantamount to looking for a weak solution to the relevant equations of continuum physics. If in addition the entropy inequality is required to hold on any subset of the domain, the solution that fulfills all these requirements is called the suitable weak solution. In our setting, both the viscosity and the coefficient of the thermal conductivity are functions of the temperature. We deal with Navier’s slip boundary conditions for the velocity that yield a globally integrable pressure, and we consider zero heat flux across the boundary. For such a problem, we establish the large-data and long-time existence of weak as well as suitable weak solutions, extending thus Leray [J. Leray, Sur le mouvement d’un liquide visquex emplissant l’espace, Acta Math. 63 (1934) 193–248] and Caffarelli, Kohn and Nirenberg [L. Caffarelli, R. Kohn, L. Nirenberg, Partial regularity of suitable weak solutions of the Navier–Stokes equations, Comm. Pure Appl. Math. 35 (6) (1982) 771–831] results, that deal with the problem in a purely mechanical context, to the problem formulated in a fully thermodynamic setting. 相似文献
489.
Changtong Hao Luke E. Adams Xinli Yang Martin Sadílek Frantiek Ture
ek 《International journal of mass spectrometry》2009,280(1-3):136
Experiments are reported that utilize surface neutralization of hyperthermal organic ions to obtain hyperthermal neutral species that are reionized on oxygen-activated rhenium surface and detected by mass spectrometry. A special Ping–Pong mass spectrometer was designed and coupled to a double-focusing mass spectrometer to allow energy and angle-resolved measurements. Neutralization of pyridine and benzene ions on gold, copper, and aluminum surfaces generated substantial ion currents into the collecting plate. The ion currents obtained on gold surfaces were found to depend on the recombination energy of the ion projectile. Hyperthermal neutrals coming off the first surface were found to mainly originate from hydrocarbon adsorbates. 相似文献
490.
We discuss the existence of solutions with oblique asymptotes to a class of second order nonlinear ordinary differential equations by means of Lyapunov functions. The approach is new in this field and allows for simpler proofs of general results regarding Emden-Fowler like equations. 相似文献