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61.
R.Gary Lee Robert H. Hunt Earle K. Plyler David M. Dennison 《Journal of Molecular Spectroscopy》1975,57(1):138-154
The OH-stretch fundamental of CH3OH has been observed with 0.025 cm?1 resolution between 3430 and 3940 cm?1 and the resulting spectrum deconvoluted using the procedure of P. A. Jansson. Approximately 600 lines have been assigned to a total of 67 P- or R-branch series and some 30 excited state levels have been determined. Of these, 14 belong to the lowest torsional state with n = 0, 13 to n = 1 and 3 to n = 2. A nonlinear least-squares fit to these levels varying the major parameters used by Y. Y. Kwan and D. M. Dennison in their analysis of the normal state produces an rms deviation between observed and calculated levels of 0.51 cm?1. Variation of all the parameters including those of the smaller Kirtman perturbation terms produces only a slight improvement in the fit. Both analyses yield a barrier height of 411 cm?1 in the excited vibrational state as compared to the normal state value of 373 cm?1. A number of unexplained anomalies appear in the spectra including large and irregular changes in the coefficient of J2 + J for different torsion-rotation states. 相似文献
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Mutually immiscible ionic liquids 总被引:1,自引:0,他引:1
Arce A Earle MJ Katdare SP Rodríguez H Seddon KR 《Chemical communications (Cambridge, England)》2006,(24):2548-2550
This work presents the novel discovery of room-temperature ionic liquids that are mutually immiscible, some of which are also immiscible with solvents as diverse as water and alkanes; an archetypal biphasic system is trihexyltetradecylphosphonium chloride with 1-alkyl-3-methylimidazolium chloride (where the alkyl group is shorter than hexyl). 相似文献
65.
The free solution mobilities of curved and normal 199-bp DNA fragments have been measured in buffer solutions containing various quantities of the organic cosolvents methanol, ethanol, 2-propanol, 2-methyl-2,4-pentanediol (MPD), ethylene glycol, and ACN, using CE. The curved fragment, taken from the VP1 gene of SV40, contains five unevenly spaced A- and T-tracts in a centrally located "curvature module"; the A- and T-tracts have been mutated to other sequences in the normal 199-bp fragment. The free solution mobility of the curved 199-bp fragment is significantly lower than that of its normal counterpart in aqueous solutions [Stellwagen, E., Lu, Y. J., Stellwagen, N. C., Nucleic Acids Res. 2005, 33, 4425-4432]. The mobilities of both the curved and normal fragments decrease with increasing cosolvent concentration, due to the effect of the cosolvent on the viscosity and dielectric constant of the solution. The mobility differences between the curved and normal 199-bp fragments and the mobility ratios decrease approximately linearly with the increasing mole fraction of cosolvent in the solution. Hence, MPD and other organic cosolvents affect DNA electrophoretic mobility by a common mechanism, most likely the preferential hydration of the DNA surface that occurs in aqueous cosolvents. The gradual loss of the anomalously slow mobility of the curved 199-bp fragment with increasing cosolvent concentration, combined with other data in the literature, suggests that preferential hydration gradually widens the narrow A-tract minor groove, releasing site-bound counterions in the minor groove and shifting the conformation toward that of normal DNA. 相似文献
66.
The sensitivity of a high-frequency electron spin resonance (ESR) spectrometer depends strongly on the structure used to couple the incident millimeter wave to the sample that generates the ESR signal. Subsequent coupling of the ESR signal to the detection arm of the spectrometer is also a crucial consideration for achieving high spectrometer sensitivity. In previous work, we found that a means for continuously varying the coupling was necessary for attaining high sensitivity reliably and reproducibly. We report here on a novel asymmetric mesh structure that achieves continuously variable coupling by rotating the mesh in its own plane about the millimeter-wave transmission-line optical axis. We quantify the performance of this device with nitroxide spin label spectra in both a lossy aqueous solution and a low-loss solid-state system. These two systems have very different coupling requirements and are representative of the range of coupling achievable with this technique. Lossy systems, in particular, are a demanding test of the achievable sensitivity and allow us to assess the suitability of this approach for applying high-frequency ESR, e.g., to the study of biological systems at physiological conditions. The variable coupling technique reported on here allows us to readily achieve a factor of ca. 7 improvement in the signal-to-noise ratio at 170 GHz and a factor of ca. 5 at 95 GHz over what has previously been reported for lossy samples. 相似文献
67.
S. K. Misra S. I. Andronenko K. A. Earle J. H. Freed 《Applied magnetic resonance》2001,21(3-4):549-561
Electron paramagnetic resonance (EPR) single-crystal rotation studies at very high frequency (249.9 GHz) of transition metal ions with electron spins greater than one-half are reported. At 249.9 GHz, the spectra are in the high-field limit despite large zero-field splittings. This leads to a considerable simplification of the spectra, and aids in their interpretation. Single-crystal 249.9 GHz EPR spectra of Ni2+ in Ni2CdCl6· 12H2O, Mn2+ (0.2%) in ZnV2O7, and Fe3+ (2%) in CaYA104 were recorded at 253 K in an external magnetic field of up to 9.2 T, along with those at X-band and Q-band frequencies at 295 K and lower temperatures. The goniometer used at 249.9 GHz for single-crystal rotation is based on a quasi-optical design and is an integral part of a special Fabry-Pérot resonator. The values of the spin-Hamiltonian parameters were estimated from a simultaneous fitting of all of the observed line positions at several microwave frequencies recorded at various orientations of each crystal with respect to the external magnetic field with least-squares fitting in conjunction with matrix diagonalization. Estimates of zero-field splitting parameterD at room temperature are: for Ni2+, about ?31 GHz (site I) and about ?7 GHz (site II); for Mn2+, about 6 GHz; and for Fe3+, about 29 GHz. 相似文献
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Colin W. Earle Mark E. Baker M.Bonner Denton Robert S. Pomeroy 《Trends in analytical chemistry : TRAC》1993,12(10):395-403
Scientific charge transfer devices (CTDs) are rapidly becoming the detector of choice for optical chemical analysis. The high sensitivity and resolution of these detectors make them ideal for a wide range of chemical imaging applications. In this article we highlight some of the current trends and future research directions of CTDs as imaging detectors for chemical analysis. 相似文献