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101.
Vibronic sub‐bands in the electronic absorption spectra of symmetrical cyanine dyes (see picture) are attributed to the symmetric C? C valence vibration of the polymethine chain in the excited state. The 3J(H,H) coupling constants in the polymethine chain can be used to characterize the bond localization within the chain in the ground state and thus to explain the intensity distribution of the sub‐bands.

  相似文献   

102.
A new labeling strategy is presented that greatly facilitates the measurement of 2H spin relaxation rates in RNA molecules as a probe of pico- to nanosecond time scale dynamics. In this labeling scheme the sugar positions are uniformly 13C-labeled, with position 2' protonated and all other sites on the sugar deuterated. Pulse sequences are presented for measurement of 2H R1 and R2 relaxation rates at positions 1', 3', and 4' with sensitivity gains that are on the order of 5-fold relative to previous methods that employed random fractional deuteration. The improved sensitivity is transformative and facilitates the study of motion in moderately sized RNA molecules with good sensitivity. The utility of the approach is demonstrated with an application to HIV-2 TAR, where the site-specific measures of molecular dynamics at sugar positions obtained here complement previous studies of dynamics at aromatic sites in the molecule.  相似文献   
103.
The analysis of acylated proteins by mass spectrometry (MS) has largely been overshadowed in proteomics by the analysis of glycosylated and phosphorylated proteins; however, lipid modifications on proteins are proving to be of increasing importance in biomedical research. In order to identify the marker ions and/or neutral loss fragments that are produced upon collision-induced dissociation, providing a means to identify the common lipid modifications on proteins, peptides containing an N-terminally myristoylated glycine, a palmitoylated cysteine and a farnesylated cysteine were chemically synthesized. Matrix-assisted laser desorption/ionization time-of-flight time-of-flight (MALDI-TOF-TOF), electrospray ionization quadrupole time-of-flight (ESI Q-TOF), and electrospray ionization hybrid triple-quadrupole/linear ion trap (ESI QqQ(LIT)) mass spectrometers were used for the analysis. The peptide containing the N-terminally myristoylated glycine, upon CID, produced the characteristic fragments a1 (240.4 Th) and b1 (268.4 Th) ions as well as a low-intensity neutral loss of 210 Da (C14H26O). The peptides containing a farnesylated cysteine residue fragmented to produce a marker ion at a m/z of 205 Th (C15H25) as well as other intense farnesyl fragment ions, and a neutral loss of 204 Da (C15H24). The peptides containing a palmitoylated cysteine moiety generated neutral losses of 238 Da (C16H30O) and 272 Da (C16H32OS); however, no marker ions were produced. The neutral losses were more prominent in the MALDI-TOF-TOF spectra, whereas the marker ions were more abundant in the ESI QqQ(LIT) and Q-TOF mass spectra.  相似文献   
104.
Long-range scalar 5J(H1',F) couplings were observed in 5-fluoropyrimidine-substituted RNA. We developed a novel S3E-19F-alpha,beta-edited NOESY experiment for quantitation of these long-range scalar 5J(H1',F) couplings, where the J-couplings can be extracted from inspection of intraresidual (H1',H6) NOE cross-peaks. Quantum chemical calculations were exploited to investigate the relation between scalar couplings and conformations around the glycosidic bond in oligonucleotides. The theoretical dependence of the observed 5J(H1',F) couplings on the torsion angle chi can be described by a generalized Karplus relationship. The corresponding density functional theory (DFT) analysis is outlined. Additional NMR experiments facilitating the resonance assignments of 5-fluoropyrimidine-substituted RNAs are described, and chemical shift changes due to altered shielding in the presence of fluorine-19 (19F) are presented.  相似文献   
105.
The acoustic noise generated during an MRI sequence can be effectively reduced with the help of soft gradient pulses using sinusoidal ramps. The long slope duration, however, leads to long acquisition times. The use of interleaved spiral trajectories, calculated with long gradient slopes, is proposed to reduce the acquisition time while maintaining low acoustic noise levels. The practibility of this approach is demonstrated on phantom and volunteer images.  相似文献   
106.
It could be shown that the preparation of sodium A zeolite is possible by the reaction of quartz and γ-Al2O3 with NaOH-solution. The zeolite formation is dependent on the mechanical preliminary treatment of quartz. Only the partially crystalline part of quartz dissolves and reacts with Al2O3 to form zeolite. The grinding of quartz/γ-Al2O3 mixtures can in certain limits raise the zeolite formation but essentially only influences the kinetics of the zeolite formation.  相似文献   
107.
The fast Fourier flow technique offers a convenient way for extremely exact flow measurements. In combination with ECG gating, arterial flow can be studied. The total acquisition time for a single measurement is about 10 s, an ECG-gated cine sequence can be acquired in about 4 min. Fast Fourier flow can, therefore, be easily combined with a conventional imaging examination.  相似文献   
108.

It is well known that variable selection in multiple regression can be unstable and that the model uncertainty can be considerable. The model uncertainty can be quantified and explored by bootstrap resampling, see Sauerbrei et al. (Biom J 57:531–555, 2015). Here approaches are introduced that use the results of bootstrap replications of the variable selection process to obtain more detailed information about the data. Analyses will be based on dissimilarities between the results of the analyses of different bootstrap samples. Dissimilarities are computed between the vector of predictions, and between the sets of selected variables. The dissimilarities are used to map the models by multidimensional scaling, to cluster them, and to construct heatplots. Clusters can point to different interpretations of the data that could arise from different selections of variables supported by different bootstrap samples. A new measure of variable selection instability is also defined. The methodology can be applied to various regression models, estimators, and variable selection methods. It will be illustrated by three real data examples, using linear regression and a Cox proportional hazards model, and model selection by AIC and BIC.

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109.
110.
Some results on structural stability which are known to hold for flows of a compact manifold are extended to semiflows of a Banach space.  相似文献   
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