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121.
Kauppila TJ Wiseman JM Ketola RA Kotiaho T Cooks RG Kostiainen R 《Rapid communications in mass spectrometry : RCM》2006,20(3):387-392
The performance of desorption electrospray ionization (DESI) in the analysis of a group of pharmaceuticals and their glucuronic acid conjugates is reported. The suitability of different sprayer solvents and different surfaces was examined. In the positive ion mode, water/methanol/trifluoroacetic acid performed best, whereas, in the negative ion mode, water/methanol/ammonium hydroxide was found to be the most suitable spray solvent. Of the surfaces investigated, polymethylmethacrylate (PMMA) was found to give the best performance in terms of sensitivity. Spray solution flow rate and the distance of the sprayer tip from the surface were also found to have significant effects on the signal intensity. Analytes with basic groups efficiently formed the corresponding protonated molecules in the positive ion mode, whereas acidic analytes, such as the glucuronic acid conjugates, formed intense signals due to the deprotonated molecules in the negative ion mode. Ionization of neutral compounds was less efficient and in many cases it was achieved through adduct formation with simple anions or cations. 相似文献
122.
Ostman P Pakarinen JM Vainiotalo P Franssila S Kostiainen R Kotiaho T 《Rapid communications in mass spectrometry : RCM》2006,20(24):3669-3673
We performed a systematic study using a set of compounds with different proton affinities (PAs) on the ionization in atmospheric pressure desorption/ionization on silicon mass spectrometry (AP-DIOS-MS). The compounds studied included various aromatic molecules of different sizes. The PAs of these compounds were calculated using ab initio and hybrid density functional theory calculations at the B3LYP/6-31G(d) level of theory. We observed that only compounds with relatively high PAs above a threshold value of 920-950 kJ/mol were efficiently ionized as protonated molecules under AP-DIOS conditions and produced very clean mass spectra. 相似文献
123.
Holappa J Nevalainen T Safin R Soininen P Asplund T Luttikhedde T Másson M Järvinen T 《Macromolecular bioscience》2006,6(2):139-144
Novel synthesis methods for the preparation of quaternary piperazine derivatives of chitosan were developed. Quaternary ammonium moiety can be selectively inserted into either one or both of the piperazine nitrogens, yielding structurally uniform chitosan derivative structures. Water-soluble end products were thoroughly characterized with FT-IR, 1H NMR, 13C NMR and 2D 1H-13C HSQC NMR. The molecular weights of the end products were determined by GPC with triple detection. 相似文献
124.
We investigate the dynamics of DNA translocation through a nanopore using 2D Langevin dynamics simulations, focusing on the dependence of the translocation dynamics on the details of DNA sequences. The DNA molecules studied in this work are built from two types of bases A and C, which have been shown previously to have different interactions with the pore. We study DNA with repeating blocks A(n)C(n) for various values of n and find that the translocation time depends strongly on the block length 2n as well as on the orientation of which base enters the pore first. Thus, we demonstrate that the measurement of translocation dynamics of DNA through a nanopore can yield detailed information about its structure. We have also found that the periodicity of the block sequences is contained in the periodicity of the residence time of the individual nucleotides inside the pore. 相似文献
125.
Retinal blood flow quantification by retinal vessel segmentation with Doppler optical coherence angiography is presented. Vessel diameter, orientation, and position are determined in an en face vessel image and two representative cross-sectional flow images of the vessel. Absolute blood flow velocity is calculated with the help of the measured Doppler frequency shift and determined vessel angle. The volumetric flow rate is obtained with the position and the region of the vessel lumen. The volumetric blood flow rate of retinal arteries before and after a bifurcation is verified in a healthy human eye. 相似文献
126.
A linear programming-based optimization algorithm for solving nonlinear programming problems 总被引:1,自引:0,他引:1
In this paper a linear programming-based optimization algorithm called the Sequential Cutting Plane algorithm is presented. The main features of the algorithm are described, convergence to a Karush–Kuhn–Tucker stationary point is proved and numerical experience on some well-known test sets is showed. The algorithm is based on an earlier version for convex inequality constrained problems, but here the algorithm is extended to general continuously differentiable nonlinear programming problems containing both nonlinear inequality and equality constraints. A comparison with some existing solvers shows that the algorithm is competitive with these solvers. Thus, this new method based on solving linear programming subproblems is a good alternative method for solving nonlinear programming problems efficiently. The algorithm has been used as a subsolver in a mixed integer nonlinear programming algorithm where the linear problems provide lower bounds on the optimal solutions of the nonlinear programming subproblems in the branch and bound tree for convex, inequality constrained problems. 相似文献
127.
The aim of this study was to characterize the influence of plasma spraying on the point of zero charge (PZC) of Al2O3-, Cr2O3- and TiO2-based materials. PZC is one of the most important parameter, which describes the acidity of oxide material in aqueous environments. PZC values of several plasma sprayed oxides were determined using mass titration method. Studies were performed for initial spray powders and plasma sprayed coating materials. In addition, mass titration experiments were performed for water-washed and nonwashed samples. It was found that mass titration is a suitable method to estimate the surface acidity of relatively coarse sample powders. It was found for most of the studied materials that the limiting pH values (assumed to be close PZC) were close to those reported in literature for the PZC values of traditionally manufactured oxide materials. On the other hand, mass titration curves of some oxide samples showed unexpected deviation in curve shapes and limiting pH. These deviations were probably due to selective dissolution of sample contaminations or sample material. 相似文献
128.
Saario SM Salo OM Nevalainen T Poso A Laitinen JT Järvinen T Niemi R 《Chemistry & biology》2005,12(6):649-656
We have previously reported that the endocannabinoid, 2-arachidonoyl-glycerol (2-AG), is hydrolyzed in rat cerebellar membranes by monoglyceride lipase (MGL)-like enzymatic activity. The present study shows that, like MGL, 2-AG-degrading enzymatic activity is sensitive to inhibition by sulfhydryl-specific reagents. Inhibition studies of this enzymatic activity by N-ethylmaleimide analogs revealed that analogs with bulky hydrophobic N-substitution were more potent inhibitors than hydrophilic or less bulky agents. Interestingly, the substrate analog N-arachidonylmaleimide was found to be the most potent inhibitor. A comparison model of MGL was constructed to get a view on the cysteine residues located near the binding site. These findings support our previous conclusion that the 2-AG-degrading enzymatic activity in rat cerebellar membranes corresponds to MGL or MGL-like enzyme and should facilitate further efforts to develop potent and more selective MGL inhibitors. 相似文献
129.
Thorsteinsson T Másson M Jarvinen T Nevalainen T Loftsson T 《Chemical & pharmaceutical bulletin》2002,50(4):554-557
Various 4,5-dihydroisoxazol-3-yl fatty acid ester derivatives of cycloserine were synthesized to improve skin permeation of cycloserine. The ester derivatives were prepared by using the tert-butoxycarbonyl (t-Boc) protection strategy. The 4,5-dihydroisoxazol-3-yl esters were readily hydrolysed in an aqueous buffer solution, and the degradation profiles showed both specific acid and specific base catalysis. In 50% human serum the formation of cycloserine was observed, but enzymatic catalysis was limited. Delivery through hairless mouse skin was investigated, and the apparent permeability coefficient was measured based on the flux of cycloserine into the receptor phase. The skin permeation of cycloserine across the hairless mouse skin was increased up to 20-fold by the fatty acid esters. The 4,5-dihydroisoxazol-3-yl fatty acid esters of cycloserine can therefore be considered as new topical prodrugs with the potential use in treatment of various skin infections. 相似文献
130.
Tapio Salmi 《国际化学动力学杂志》1989,21(10):885-908
Generalized models for steady state catalytic processes are presented in matrix form. Multistep reaction rate control is assumed. Numerical algorithms for solving of the created linear and nonlinear equation systems are developed and tested. Four examples are considered: an Eley–Rideal-mechanism, a Langmuir–Hinshelwood mechanism, a dual route, dual site mechanism, and a monomolecular decomposition with steady state multiplicity. The overall reaction rates are simulated as a function of the reactant concentrations. A maximum reaction rate is obtained in the case of a Langmuir–Hinshelwood mechanism (example 2), the location of the rate maximum in the concentration domain is shifted towards the concentration of the reactant with the lowest adsorption constants. An Eley–Rideal mechanism (example 1) has always monotonously increasing rate curves. In the case of steady state multiplicity (example 4) all steady states could be simulated with the proposed algorithm. The computation of reaction rate surfaces is important in investigating the behavior of complicated catalytic systems (e.g., systems with multistep rate control and/or steady state multiplicity), in planning of experiments and in chemical reactor simulation. 相似文献