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111.
112.
Sara Ongay Jos Hermans Andries P. Bruins Adrianus M. C. H. Nieuwendijk Hermen Overkleeft Rainer Bischoff 《Journal of the American Society for Mass Spectrometry》2013,24(1):83-91
Electron transfer dissociation (ETD) has attracted increasing interest due to its complementarity to collision-induced dissociation (CID). ETD allows the direct localization of labile post-translational modifications, which is of main interest in proteomics where differences and similarities between ETD and CID have been widely studied. However, due to the fact that ETD requires precursor ions to carry at least two charges, little is known about differences in ETD and CID of small molecules such as metabolites. In this work, ETD and CID of desmosine (DES) and isodesmosine (IDS), two isomers that due to the presence of a pyridinium group can carry two charges after protonation, are studied and compared. In addition, the influence of DES/IDS derivatization with propionic anhydride and polyethyleneglycol (PEG) reagents on ETD and CID was studied, since this is a common strategy to increase sensitivity and to facilitate the analysis by reversed-phase chromatography. Clear differences between ETD and CID of non-derivatized and derivatized-DES/IDS were observed. While CID is mainly attributable to charge-directed fragmentation, ETD is initiated by the generation of a hydrogen atom at the initial protonation site and its subsequent transfer to the pyridinium ring of DES/IDS. These differences are reflected in the generation of complex CID spectra dominated by the loss of small, noninformative molecules (NH3, CO, H2O), while ETD spectra are simpler and dominated by characteristic side-chain losses. This constitutes a potential advantage of ETD in comparison to CID when employed for the targeted analysis of DES/IDS in biological samples. Figure
A mechanistic study of electron transfer dissociation (ETD) and collision-induced dissociation (CID) of labeled and free desmosine and isodesmosine provides evidence that CID is mainly due to charge-directed fragmentation while ETD is initiated by the generation of a hydrogen atom at the initial protonation site, and its subsequent transfer to the pyridinium ring. 相似文献
113.
Agnieszka Kraj Hendrik-Jan Brouwer Nico Reinhoud Jean-Pierre Chervet 《Analytical and bioanalytical chemistry》2013,405(29):9311-9320
A novel electrochemical (EC) method for fast and efficient reduction of the disulfide bonds in proteins and peptides is presented. The method does not use any chemical agents and is purely instrumental. To demonstrate the performance of the EC reactor cell online with electrospray mass spectrometry, insulin and somatostatin were used as model compounds. Efficient reduction is achieved in continuous infusion mode using an EC reactor cell with a titanium-based working electrode. Under optimized conditions, the presented method shows almost complete reduction of insulin and somatostatin. The method does not require any special sample preparation, and the EC reactor cell makes it suitable for automation. Online EC reduction followed by collision-induced dissociation fragmentation of somatostatin showed more backbone cleavages and improved sequence coverage. By adjusting the settings, the EC reaction efficiency was gradually changed from partial to full disulfide bonds reduction in α-lactalbumin, and the expected shift in charge state distribution has been demonstrated. The reduction can be controlled by adjusting the square-wave pulse, flow rate or mobile phase composition. We have shown the successful use of an EC reactor cell for fast and efficient reduction of disulfide bonds for online mass spectrometry of proteins and peptides. The possibility of online and gradual disulfide bond reduction adds a unique dimension to characterization of disulfide bonds in mid- and top-down proteomics applications. Figure
Principle of electrochemical reduction of disulfide bonds in proteins 相似文献
114.
The non-equilibrium Richards equation is solved using a moving finite element method in this paper. The governing equation is discretized spatially with a standard finite element method, and temporally with second-order Runge–Kutta schemes. A strategy of the mesh movement is based on the work by Li et al. [R.Li, T.Tang, P.W. Zhang, A moving mesh finite element algorithm for singular problems in two and three space dimensions, Journal of Computational Physics, 177 (2002) 365–393]. A Beckett and Mackenzie type monitor function is adopted. To obtain high quality meshes around the wetting front, a smoothing method which is based on the diffusive mechanism is used. With the moving mesh technique, high mesh quality and high numerical accuracy are obtained successfully. The numerical convergence and the advantage of the algorithm are demonstrated by a series of numerical experiments. 相似文献
115.
M. Luft T. Meyer W. D. Kraeft H. H. Brouwer P. P. J. M. Schram B. Strege 《等离子体物理论文集》1990,30(3):369-383
The stopping power and the stopping number, respectively, of charged particles are determined in the frame of the dielectric formalism in random phase approximation. The high and low velocity limits are disscussed. Numerical evalution is given for arbitrary masses of the projectile particle using a dielectric function ?(κ, ω) valid for all values of degeneracy. The connection with transport (e.g. electrical resistivity) is considered. 相似文献
116.
117.
It is proved that the minimum cardinality of a subset of AG(k, q) which intersects all hyperplanes is k(q ? 1) + 1. In case k = 2 this settles a conjecture of J. Doyen. 相似文献
118.
Jagesar DC Hartl F Buma WJ Brouwer AM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(6):1935-1946
The macrocycle in rotaxane 1 is preferentially hydrogen bonded to the succinamide station in the neutral form, but can be moved to the naphthalimide station by one-electron reduction of the latter. The hydrogen bonding between the amide NH groups of the macrocycle and the C double bond O groups in the binding stations in the thread was studied with IR spectroscopy in different solvents in both states. In addition, the solvent effect on the vibrational frequencies was analyzed; a correlation with the solvent acceptor number (AN) was observed. The conformational switching upon reduction could be detected by monitoring the hydrogen-bond-induced shifts of the nu(CO) frequencies of the C double bond O groups of the succinamide and the reduced naphthalimide stations. The macrocycle was found to shield the encapsulated station from the solvent: wavenumbers of nu(CO) bands of the C double bond O groups residing inside the macrocycle cavity remain unaffected by the solvent polarity. 相似文献
119.
(1)H magic-angle spinning (MAS) NMR spectra of p-tert-butylcalix[4]arene inclusion compounds with toluene and pyridine show large complexation-induced shifts of the guest proton resonances arising from additional magnetic shielding caused by the aromatic rings of the cavities of the host calixarene lattice. In combination with ab initio calculations, these observations can be employed for NMR crystallography of host-guest complexes, providing important spatial information about the location of the guest molecules in the host cavities. 相似文献
120.
Benisvy L Gamez P Fu WT Kooijman H Spek AL Meijerink A Reedijk J 《Dalton transactions (Cambridge, England : 2003)》2008,(24):3147-3149
The first examples of lanthanide complexes with a 2-hydroxyisophthalate ligand are reported; the blue-emitting ligand acts as a very efficient sensitizer of the Tb(III) green emissions and does so in the near-UV region. 相似文献