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941.
Lehmann WD Wei J Hung CW Gabius HJ Kirsch D Spengler B Kübler D 《Rapid communications in mass spectrometry : RCM》2006,20(16):2404-2410
In an analysis of a combined chymotrypsin/AspN digest of galectin-3 by positive ion nano-electrospray ionisation mass spectrometry (nanoESI-MS) several peptides were observed which showed metal adduct ions as their most abundant ion signals. The most prominent adduct ions were observed at m/z values corresponding to [M+40]2+, [M+41]3+, and [M+42]4+ ions. Detailed investigation of the [M+40]2+ ion of the peptide GAPAGPLIVPY showed that it was not, as originally expected, a [M+H+39K]2+ adduct ion but had the composition [M+40Ca]2+. This was verified by several approaches: (i) nanoESI-MS/MS of the [M+Ca]2+ adduct ions resulted in the virtually exclusive formation of doubly charged fragment ions; (ii) mass determination by quadrupole time-of-flight (QTOF)-MS provided a preliminary identification; and (iii) accurate mass measurement using nanoESI Fourier transform ion cyclotron resonance (FTICR)-MS at a mass resolving power of 500 000 allowed the specific detection and identification of the isobaric ion pairs [M+40Ca]2+/[M+H+39K]2+ and [M+24Mg]2+/[M+H+23Na]2+. All peptides in the chymotryptic galectin-3 digest without a basic residue (K or R) showed addition of calcium as the most prominent ionisation principle. A further common feature of these nonbasic peptides was the presence of several proline residues, which is assumed to be a factor promoting the intense addition of calcium. It was observed that the common trace levels of sodium and calcium in analytical grade solvents (about 1-10 microM) are sufficient to generate the [M+H+23Na]2+ and [M+40Ca]2+ ions as the most prominent species of the peptide GAPAGPLIVPY. We conclude that the sequence motifs P-XX-P and P-XXX-P favour the solvation of alkaline earth ions in ESI-MS. In view of the successful detection of physiological Ca/protein interactions by ESI-MS, this finding may point to a solvation of Ca2+ by galectin in solution. The findings open new routes of research in the study of metal/protein and metal/peptide interactions 相似文献
942.
Microfabrication processes, especially in silicon, are not compatible with biomolecules. Silicon and metal-based materials having crystalline structures are manipulated under harsh conditions with acids, bases, and organic solvents at high temperature. In comparison, organic biomolecules such as DNA and proteins have complex, three-dimensional structures and are sensitive to denaturation, oxidation, hydrolysis, and thermal destruction. Here, we report on the integration of DNA and the biotin-binding protein NeutrAvidin into microfabrication processes by using a novel approach based on a gold passivation mask. Our data show that this passivation method preserves approximately 84% of the biofunctionality of DNA and approximately 30% of that of NeutrAvidin under harsh process conditions. This novel technology enables the integration of DNA, proteins, and potentially other biological molecules into mass scalable microfabrication processes for biomedical devices, biochips, biosensors, and microelectromechanical systems with biomolecules (BioMEMS). 相似文献
943.
Lud SQ Steenackers M Jordan R Bruno P Gruen DM Feulner P Garrido JA Stutzmann M 《Journal of the American Chemical Society》2006,128(51):16884-16891
We have investigated the formation of self-assembled monolayers (SAMs) of 4'-nitro-1,1-biphenyl-4-diazonium tetrafluoroborate (NBD) onto ultrananocrystalline diamond (UNCD) thin films. In contrast to the common approach to modify diamond and diamond-like substrates by electrografting, the SAM was formed from the saturated solution of NBD in acetonitrile by pure chemical grafting. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and near edge X-ray absorption fine structure spectroscopy (NEXAFS) have been used to verify the direct covalent attachment of the 4'-nitro-1,1-biphenyl (NB) SAM on the diamond substrate via stable C-C bonds and to estimate the monolayer packing density. The results confirm the presence of a very stable, homogeneous and dense monolayer. Additionally, the terminal nitro group of the NB SAM can be readily converted into an amino group by X-ray irradiation as well as electrochemistry. This opens the possibility of in situ electrochemical modification as well as the creation of chemical patterns (chemical lithography) in the SAM on UNCD substrates and enables a variety of consecutive chemical functionalization for sensing and molecular electronics applications. 相似文献
944.
The key transformation in the total synthesis of (+)-elaeokanine A was accomplished by asymmetric deprotonation of N-Boc pyrrolidine, followed by the reaction of the in situ generated enantioenriched stereogenic cuprate reagent with (E)-4-bromo-1-iodo-1-trimethylsilyl-1-butene with retention of configuration. N-Boc deprotection, followed by a one-pot olefin isomerization and intramolecular amine alkylation afforded a bicyclic vinyl bromide that was converted into (+)-elaeokanine A by sequential halogen metal exchange and reaction of the organolithium reagent with N-butanoylmorpholine. 相似文献
945.
Livshits VA Kurad D Marsh D 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2006,180(1):63-71
Simulations are performed of 34- and 9-GHz EPR spectra, together with 94-GHz EPR spectra, from phospholipid probes spin-labelled at the C4-C14 positions of the sn-2 chain, in liquid-ordered and gel-phase membranes of dimyristoyl phosphatidylcholine with high and low cholesterol contents. The multifrequency simulation strategy involves: (i) obtaining partially averaged spin-Hamiltonian tensors from fast-motional simulations of the 94-GHz spectra; (ii) performing slow-motional simulations of the 34- and 9-GHz spectra by using these pre-averaged tensors with the stochastic Liouville formalism; (iii) constructing, by simulation, slow-motional calibrations for the differences, DeltaA(zz)(qx) and Deltag(zz)(qx), in effective A(zz)-hyperfine splittings and g(zz)-values between 34- (or 94-GHz) and 9-GHz spectra; (iv) using such calibrations for DeltaA(zz)(qx) and Deltag(zz)(qx) and dynamic parameters from stage (ii) as a guide to adjust the extent of pre-averaging of the spin-Hamiltonian tensors; and (v) repeating the 34- and 9-GHz simulations of stage (ii). By using this scheme it is possible to obtain consistent values of the rotational diffusion coefficients, D(R perpendicular) and D(R//), and the long-axis order parameter, S(zz), that characterize the slow axial motion of the lipid chains, from spectra at both 34 and 9GHz. Inclusion of spectra at 34GHz greatly improves precision in determining the D(R//) element of the slow diffusion tensor in these systems. 相似文献
946.
Ebel A Dreher W Leibfritz D 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2006,182(2):330-338
The influence of noise on the standard deviation of spectral integrals is examined. Calculations assuming discrete Fourier-transform data are compared with Monte-Carlo simulations. The effects of zero-filling and apodization are examined for free-induction-decay (FID) signals and for symmetric spin-echo signals in one and two dimensions, with particular attention to features not previously presented in the literature. Findings suggest that for mild apodization, the known sensitivity enhancement due to zero-filling in either the real or the imaginary part signal [E. Bartholdi, R.R. Ernst, Fourier spectroscopy and the causality principle, J. Magn. Reson., 11 (1973) 9-19] is maintained; however, for stronger apodization filters, this enhancement can be obliterated completely. It is shown that results obtained by analysis of one-dimensional signals can be readily applied to multi-dimensional data. Furthermore, zero-filling has a negligible effect for symmetric spin-echo signals with implications for signal averaging in magnetic resonance imaging and spectroscopic imaging. 相似文献
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948.
949.
950.
Magic-angle sample spinning (MAS) nuclear magnetic resonance (NMR) measurements are treated for heterogeneous systems with nanometer dimensions. An appreciable line narrowing in the MAS NMR spectra of the embedded molecules may be achieved also in the cases when the molecules still possess an appreciable local mobility. It appears that the MAS frequencies are of comparable order of magnitude as the frequencies which characterize the random molecular motional processes and which compete with MAS. It will be shown that this behavior may occur if inhomogeneous local magnetic fields due to susceptibility effects have a dominating influence on the widths and shapes of the resonance NMR lines. Properties of these local fields are described. Spectra simulations are carried for molecules embedded in these heterogeneous systems when the coherent averaging by MAS is superimposed by random local motions. This situation may occur for molecules contained in nanoporous solids and also for heterogeneous systems like membranes and biological tissues with flexible components like water, lipids, and small peptides. Several examples are treated which reveal advantages and limitations of these experiments and their theoretical interpretation. 相似文献