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1.
Received: 21 May 1997/Accepted: 4 July 1997  相似文献   
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Ultrafast infrared heterodyne detected vibrational stimulated echoes with full phase information are used to obtain the vibrational correlation spectrum from a mixture of metal-carbonyl compounds. The linear absorption spectrum displays four peaks in the carbonyl stretching region. In the absence of knowledge of the molecules that make up the mixture, the absorption spectrum could arise from four molecules that each produces a single peak to one molecule with four peaks. In contrast, the correlation spectrum displays four peaks on the diagonal and off-diagonal peaks that make it straightforward to determine which peaks belong to a particular molecule.  相似文献   
3.
The attenuation due to the E2 nuclear resonance effect has been measured in hadronic atoms using pions with 111Cd and 112Cd, and for kaons with 122Sn. Energies of the relevant X-ray and γ-ray transitions and of the X-ray cascade intensities have also been measured so as to give a self-consistent set of information. The results are found to be in very good agreement with theoretical calculations.  相似文献   
4.
Hydrogen bond dynamics are explicated with exceptional detail using multidimensional infrared vibrational echo correlation spectroscopy with full phase information. Probing the hydroxyl stretch of methanol-OD oligomers in CCl4, the dynamics of the evolving hydrogen bonded network are measured with ultrashort (<50 fs) pulses. The data along with detailed model calculations demonstrate that vibrational relaxation leads to selective hydrogen bond breaking on the red side of the spectrum (strongest hydrogen bonds) and the production of singly hydrogen bonded photoproducts.  相似文献   
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We consider diffraction by a semi-infinite crack located alonga fusion interface between two differing elastic media. Twotypes of crack, namely open and partially closed cracks, areinvestigated. An open crack is modelled by a stress-free contactboundary condition and a partially closed crack is modelledby a spring contact boundary condition. For the latter, thejump in the stress across the crack is assumed to be proportionalto the jump in the displacement across the crack. This situationarises in, for example, a K-weld where the fine grain of theparent material (for example, ferritic or forged austeniticsteel) is in stark contrast with the coarse-grained weld metal(for example, austenitic weld metal). In the metal weld thedirection of the grain axis varies through the metal. However,diffraction is a local phenomenon and so the austenitic steelis assumed to have a zonal axis so that it may be modelled bya transversely isotropic composite. The ferritic or forged austeniticsteel will be modelled as an isotropic material.  相似文献   
7.
The Doppler broadened 26Mg* decay gamma peak hasma peak has been observed in coincidence with stopped kaons in an Al target. The results are compared with predictions based on single-nucleon absorption of the kaon.  相似文献   
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Since the introduction of matrix-assisted laser desorption/ionization (MALDI) mass spectrometry the majority of research has focused on developing analytical methods for the qualitative determination of water soluble biomolecules such as proteins, peptides, carbohydrates, and oligonucleotides. This paper, however, reports the use of MALDI for the analysis of triacylglycerols and develops a new sample preparation method for nonpolar analytes. MALDI enables the rapid analyses of triacylglycerol (TAG) standards and mixtures of whole oils. The new method provides excellent shot to shot reproducibility, making quantification possible. Detection limits were in the mid femtomole range and the resolution was around 2000 which easily separated TAGs differing by one double bond. Sensitivity decreased with increasing molecular weight, causing biased results when analyzing complex mixtures with a significant range of molecular weight. In all cases only sodiated molecules and prompt losses of a fatty acid sodium salt were observed in the spectra. From this information it was possible to identify the three fatty acids on the glycerol backbone. Collision-induced dissociation was carried out on a triacylglycerol which proved to be useful for additional structural information, including the corroboration of the fatty acid components. With MALDI the percent compositions of TAGs in a standard olive oil was accurately determined. Finally, MALDI was used to examine the differences in lipid components between aged and fresh onion seeds, showing the potential of the technique for observing changes in lipid components in seeds.  相似文献   
10.
While organic donor-acceptor (D-A) molecules are widely employed in multiple areas, the application of more D-A molecules could be limited because of an inherent polarity sensitivity that inhibits photochemical processes. Presented here is a facile chemical modification to attenuate solvent-dependent mechanisms of excited-state quenching through addition of a β-carbonyl-based polar substituent. The results reveal a mechanism wherein the β-carbonyl substituent creates a structural buffer between the donor and the surrounding solvent. Through computational and experimental analyses, it is demonstrated that the β-carbonyl simultaneously attenuates two distinct solvent-dependent quenching mechanisms. Using the β-carbonyl substituent, improvements in the photophysical properties of commonly used D-A fluorophores and their enhanced performance in biological imaging are shown.  相似文献   
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