CARS laboratory experiments were done in the 2905–2925 cm−1 range, in the vicinity of the ν1 band of the methane molecule, for pressures ranging from 1 to 50 bar, and temperatures up to 1100 K. These experiments were carried out in order to retrieve the pressure evolution of the CH4 spectrum, as well as to confirm its temperature dependance. After a brief recall on the theory used to compute pressure broadening coefficients and relaxation rates, we consider the ν3 and ν4 infrared bands of methane for benchmark calculations purposes. Next, we present recent experimental CARS spectra and calculated ones. Lastly, we discuss flame experiments as well as comparisons of temperature retrieval using N2 and CH4 as probe molecules. 相似文献
Unraveling of all of the information contained in proteomes poses a tremendous chemical challenge, which is balanced by the promise of potentially transformational knowledge. Mass spectrometry offers an unprecedented arsenal of tools for diverse proteomic investigations. Recently, it was demonstrated that ultraviolet light can be utilized to initiate unique and potentially useful fragmentations in peptides and proteins. Either nonspecific dissociation or highly specific dissociation at engineered chromophoric sites is possible following photon absorption. The level of specificity and control over fragmentation in these experiments is greater than with other fragmentation methods. Novel techniques made possible by this technology are poised to make substantial contributions to the field of proteomics. 相似文献
Novel regioisomers of 2′-methyl-branched nucleosides were designed and synthesized to mimic potent anti-viral drugs like Valopicitabine. The short and efficient synthesis of the targets involves a one-pot tosylation/cyclization step that leads to an activated furan scaffold on which the isonucleosides were built. 相似文献
Here we discuss the types of waves which can be supported on compact regions of vorticity. This is a subject first studied by Lord Kelvin for waves propagating along the vortex lines of the Rankine and hollow-core vorticity distributions. Kelvin's major interest was in the stability of vortex rings and the numerous resurgencies in interest have usually been driven by practically important phenomena, e.g., the observations of vortex breakdown and waves on tornado and aircraft vortices in the early 1960's and more recently in technologically and geophysically significant flows and on the quantised vortices of super fluid HeII.
The major wave-types of interest are of varicose, helicoidal and fluted form and represent a periodic swelling and contraction, a bending and a “krinkling” of the core, respectively. The first two propagate along and the third around the vortex lines. All have been studied theoretically, experimentally and numerically in the limit of small wave amplitude and their major characteristics are now clear. Of particular interest is the extension of these results to the non-linear regime in which case the two first types are known to exhibit solitary wave or soliton characteristics in certain parameter ranges. It is these non-linear waves which often dominate observations of vortex flows both in nature and in technological applications and which have caused much controversy in the interpretation of results found under complex circumstances of flow and apparatus geometry. 相似文献
o-(N,N-Dialkylaminomethyl)arylboronate systems are an important class of compounds in diol-sensor development. We report results from a computational investigation of fourteen o-(N,N-dialkylaminomethyl)arylboronates using second-order M?ller-Plesset (MP2) perturbation theory. Geometry optimizations were performed at the MP2/cc-pVDZ level and followed by single-point calculations at the MP2/aug-cc-pVDZ(cc-pVTZ) levels. These results are compared to those from density functional theory (DFT) at the PBE1PBE(PBE1PBE-D)/6-311++G(d,p)(aug-cc-pVDZ) levels, as well as to experiment. Results from continuum PCM and CPCM solvation models were employed to assess the effects of a bulk aqueous environment. Although the behavior of o-(N,N-dialkylaminomethyl) free acid and ester proved to be complicated, we were able to extract some important trends from our calculations: (1) for the free acids the intramolecular hydrogen-bonded B-O-H···N seven-membered ring conformers 12 and 16 are found to be slightly lower in energy than the dative-bonded N→B five-membered ring conformers 10 and 14 while conformers 13 and 17, with no direct boron-nitrogen interaction, are significantly higher in energy than 12 and 16; (2) for the esters where no intramolecular B-O-H···N bonded form is possible, the N→B conformers 18 and 21 are significantly lower in energy than the no-interaction forms 20 and 23; (3) H(2)O insertion reactions into the N→B structures 10, 14, 18, and 21 leading to the seven-membered intermolecular hydrogen-bonded B···OH(2)···N ring structures 11, 15, 19, and 22 are all energetically favorable. 相似文献