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151.
Simpson EJ Hickey JL Breadner D Luyt LG 《Dalton transactions (Cambridge, England : 2003)》2012,41(10):2950-2958
Histidine is a convenient tridentate chelator used in the synthesis of technetium-99m radiopharmaceuticals, as it can be pendantly attached to a biomolecule for molecular imaging applications. Once coordinated, it forms a neutral complex that is capable of forming diastereomers at the alpha amine of the histidine. This is demonstrated through the synthesis and characterization of four different histidine chelators; three small molecule chelators, which consist of a benzylated histidine at the alpha amine, and one modified dipeptide, containing a phenylalanine derivative at the C-terminus and a histidine at the N-terminus. Upon rhenium coordination, two products are observed, each having the desired exact mass of the metal-containing species. The two products have been characterized through LC-MS, (1)H, gCOSY, NOESY and ROESY NMR experiments, and the relative stereochemistry determined. The implications of diastereomer formation when using this chelation system for creating molecular imaging agents is also discussed. 相似文献
152.
Deep-ultraviolet resonance Raman (DUVRR) spectra is sensitive to secondary structural motifs but, similar to circular dichroism (CD) and infrared spectroscopy, requires the application of multivariate and advanced statistical analysis methods to resolve the pure secondary structure Raman spectra (PSSRS) for determination of secondary structure composition. Secondary structure motifs are selectively enhanced by different excitation wavelengths, a characteristic that inspired the first methods for quantifying secondary structures by DUVRR. This review traces the evolution of multivariate methods and their application to secondary structure composition analyses of proteins by DUVRR spectroscopy from the first experiments using two-wavelengths, and culminating with recent studies utilizing time-resolved DUVRR measurements. 相似文献
153.
Time-delayed control in a balancing problem may be a nonsmooth function for a variety of reasons. In this paper we study a
simple model of the control of an inverted pendulum by either a connected movable cart or an applied torque for which the
control is turned off when the state of the pendulum is located within certain regions of phase space. Without applying a
small angle approximation for deviations about the vertical position, we see structurally stable periodic orbits which may
be attracting or repelling. Due to the nonsmooth nature of the control, these periodic orbits originate in various discontinuity-induced
bifurcations. We also show that a coincidence of switching events can produce complicated periodic and aperiodic solutions. 相似文献
154.
T Ohtsubo NJ Stone JR Stone IS Towner CR Bingham C Gaulard U Köster S Muto J Nikolov K Nishimura GS Simpson G Soti M Veskovic WB Walters F Wauters 《Physical review letters》2012,109(3):032504
The nucleus ^{49}Sc, having a single f_{7/2} proton outside doubly magic ^{48}Ca (Z=20, N=28), is one of the very few isotopes which makes possible testing of the fundamental theory of nuclear magnetism. The magnetic moment has been measured by online β NMR of nuclei oriented at milli-Kelvin temperatures to be (+)5.616(25) μ_{N}. The result is discussed in terms of a detailed theory of the structure of the magnetic moment operator, showing excellent agreement with calculated departure from the f_{7/2} Schmidt limit extreme single-particle value. The measurement completes the sequence of moments of Sc isotopes with even numbers of f_{7/2} neutrons: the first such isotopic chain between two major shells for which a full set of moment measurements exists. The result further completes the isotonic sequence of ground-state moments of nuclei with an odd number of f_{7/2} protons coupled to a closed subshell of f_{7/2} neutrons. Comparison with a recent shell-model calculation of the latter sequence is made. 相似文献
155.
Vinh NB Simpson JS Scammells PJ Chalmers DK 《Journal of computer-aided molecular design》2012,26(4):409-423
We have used virtual screening to develop models for the binding of aryl substituted heterocycles to p38α MAPK. Virtual screening
was conducted on a number of p38α MAPK crystal structures using a library of 46 known p38α MAPK inhibitors containing a heterocyclic
core substituted by pyridine and fluorophenyl rings (structurally related to SB203580) and a set of decoy compounds. Multiple
protonation states and tautomers of active and decoy compounds were considered. Each docking model was evaluated using receiver
operating characteristic (ROC) curves and enrichment factors. The two best performing single crystal structures were found
to be 1BL7 and 2EWA, with enrichment factors of 14.1 and 13.0 at 2 % of the virtual screen respectively. Ensembles of up to
four receptors of similar conformations were generated, generally giving good or very good performances with high ROC AUCs
and good enrichment. The 1BL7-2EWA ensemble was able to outperform each of its constituent receptors and gave high enrichment
factors of 17.3, 12.0, 8.0 at 2, 5 and 10 % respectively, of the virtual screen. A ROC AUC of 0.94 was obtained for this ensemble.
This method may be applied to other proteins where there are a large number of inhibitor classes with different binding site
conformations. 相似文献
156.
We study how the degree of fluorine substitution for hydrogen atoms in ethene affects its reactivity in the gas phase. The reactions of a series of small fluorocarbon cations (CF(+), CF(2)(+), CF(3)(+), and C(2)F(4)(+)) with ethene (C(2)H(4)), monofluoroethene (C(2)H(3)F), 1,1-difluoroethene (CH(2)CF(2)), and trifluoroethene (C(2)HF(3)) have been studied in a selected ion flow tube. Rate coefficients and product cations with their branching ratios were determined at 298 K. Because the recombination energy of CF(2)(+) exceeds the ionization energy of all four substituted ethenes, the reactions of this ion produce predominantly the products of nondissociative charge transfer. With their lower recombination energies, charge transfer in the reactions of CF(+), CF(3)(+), and C(2)F(4)(+) is always endothermic, so products can only be produced by reactions in which bonds form and break within a complex. The trends observed in the results of the reactions of CF(+) and CF(3)(+) may partially be explained by the changing value of the dipole moment of the three fluoroethenes, where the cation preferentially attacks the more nucleophilic part of the molecule. Reactions of CF(3)(+) and C(2)F(4)(+) are significantly slower than those of CF(+) and CF(2)(+), with adducts being formed with the former cations. The reactions of C(2)F(4)(+) with the four neutral titled molecules are complex, giving a range of products. All can be characterized by a common first step in the mechanism in which a four-carbon chain intermediate is formed. Thereafter, arrow-pushing mechanisms as used by organic chemists can explain a number of the different products. Using the stationary electron convention, an upper limit for Δ(f)H°(298)(C(3)F(2)H(3)(+), with structure CF(2)═CH-CH(2)(+)) of 628 kJ mol(-1) and a lower limit for Δ(f)H°(298)(C(2)F(2)H(+), with structure CF(2)═CH(+)) of 845 kJ mol(-1) are determined. 相似文献
157.
G E Reid S E Tichy J Pérez R A O'Hair R J Simpson H I Kentt?maa 《Journal of the American Chemical Society》2001,123(6):1184-1192
The gas-phase ion-molecule reactions of neutral alanylglycine have been examined with various mass-selected acylium ions RCO(+) (R= CH(3), CD(3), C(6)H(5), C(6)F(5) and (CH(3))( 2)N), as well as the transacylation reagent O-benzoylbenzophenone in a Fourier transform ion cyclotron resonance mass spectrometer. Reactions of the gaseous dipeptide with acylium ions trapped in the ICR cell result in the formation of energized [M + RCO](+) adduct ions that fragment to yield N-terminal b-type and C-terminal y-type product ions, including a modified b(1) ion which is typically not observed in the fragmentation of protonated peptides. Judicious choice of the acylium ion employed allows some control over the product ion types that are observed (i.e., b versus y ions). The product ion distributions from these ion--molecule reactions are similar to those obtained by collision-activated dissociation in a triple quadrupole mass spectrometer of the authentic N-acylated alanylglycine derivatives. These data indicate that derivatization of the peptide in the gas-phase occurs at the N-terminal amine. Ab initio molecular orbital calculations, performed to estimate the thermochemistry of the steps associated with adduct formation as well as product ion formation, indicate that (i) the initially formed adduct is energized and hence likely to rapidly undergo fragmentation, and (ii) the likelihood for the formation of modified b(1) ions in preference to y(1) ions is dependent on the R substituent of the acylium ion. The reaction of the tetrapeptide valine--alanine--alanine--phenylalanine with the benzoyl cation was also found to yield a number of product ions, including a modified b(1) ion. This result suggests that the new experimental approach described here may provide a tool to address one of the major limitations associated with traditional mass spectrometric peptide sequencing approaches, that is, determination of the identity and order of the two N-terminal amino acids. Analogies are made between the reactions observed here and the derivatization and N-terminal cleavage reactions employed in the condensed-phase Edman degradation method. 相似文献
158.
Experimental data for a two-dimensional (2-D) turbulent boundary layer (TBL) flow and a three-dimensional (3-D) pressure-driven
TBL flow outside of a wing/body junction were obtained for an approach Reynolds number based on momentum thickness of Re
θ
=23,200. The wing shape had a 3:2 elliptical nose, NACA 0020 profiled tail, and was mounted on a flat wall. Some Reynolds
number effects are examined using fine spatial resolution (Δy
+=1.8) three-velocity-component laser-Doppler velocimeter measurements of mean velocities and Reynolds stresses at nine stations
for Re
θ
=23,200 and previously reported data for a much thinner boundary layer at Re
θ
=5,940 for the same wing shape. In the 3-D boundary layers, while the stress profiles vary considerably along the flow due
to deceleration, acceleration, and skewing, profiles of the parameter
correlate well and over available Reynolds numbers. The measured static pressure variations on the flat wall are similar
for the two Reynolds numbers, so the vorticity flux and the measured mean velocities scaled on wall variables agree closely
near the wall. The stresses vary similarly for both cases, but with higher values in the outer region of the higher Re
θ
case. The outer layer turbulence in the thicker high Reynolds number case behaves similarly to a rapid distortion of the
flow, since stream-wise vortical effects from the wall have not diffused completely through the boundary layer at all measurement
stations.
Received: 9 June 2000/Accepted: 26 January 2001 相似文献
159.
Qusai Hassan Rudraksha Dutta Majumdar Bing Wu Daniel Lane Maryam Tabatabaei-Anraki Ronald Soong Myrna J. Simpson Andre J. Simpson 《Magnetic resonance in chemistry : MRC》2019,57(2-3):69-81
Proton nuclear magnetic resonance (NMR) spectra of intact biological samples often show strong contributions from lipids, which overlap with signals of interest from small metabolites. Pioneering work by Diserens et al. demonstrated that the relative differences in diffusivity and relaxation of lipids versus small metabolites could be exploited to suppress lipid signals, in high-resolution magic angle spinning (HR-MAS) NMR spectroscopy. In solution-state NMR, suspended samples can exhibit very broad water signals, which are challenging to suppress. Here, improved water suppression is incorporated into the sequence, and the Carr-Purcell-Meiboom-Gill sequence (CPMG) train is replaced with a low-power adiabatic spinlock that reduces heating and spectral artefacts seen with longer CPMG filters. The result is a robust sequence that works well in both HR-MAS as well as static solution-state samples. Applications are also extended to include in vivo organisms. For solution-state NMR, samples containing significant amount of fats such as milk and hemp hearts seeds are used to demonstrate the technique. For HR-MAS, living earthworms (Eisenia fetida) and freshwater shrimp (Hyalella azteca) are used for in vivo applications. Lipid suppression techniques are essential for non-invasive NMR-based analysis of biological samples with a high-lipid content and adds to the suite of experiments advantageous for in vivo environmental metabolomics. 相似文献
160.
Andrew J. Carrod Francesco Graglia Dr. Louise Male Dr. Cécile Le Duff Peter Simpson Dr. Mohamed Elsherif Dr. Zubair Ahmed Dr. Haider Butt Guang-Xi Xu Prof. Kenneth Kam-Wing Lo Dr. Paolo Bertoncello Prof. Zoe Pikramenou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(4):e202103541
Dual detection systems are of interest for rapid, accurate data collection in sensing systems and in vitro testing. We introduce an IrIII complex with a boronic acid receptor site attached to the 2-phenylpyridine ligand as an ideal probe with photo- and electrochemical signals that is sensitive to monosaccharide binding in aqueous solution. The complex displays orange luminescence at 618 nm, which is reduced by 70 and 40 % upon binding of fructose and glucose, respectively. The electro-chemiluminescent signal of the complex also shows a direct response to monosaccharide binding. The IrIII complex shows the same response upon incorporation into hydrogel matrices as in solution, thus demonstrating the potential of its integration into a device, as a nontoxic, simple-to-use tool to observe sugar binding over physiologically relevant pH ranges and saccharide concentrations. Moreover, the complex's luminescence is responsive to monosaccharide presence in cancer cells. 相似文献