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Kevin S. Peters 《Angewandte Chemie (International ed. in English)》1994,33(3):294-302
Why have molecules only been seen but not heard? For over a century chemists have probed reactions with various spectroscopic methods to learn about structures, dynamics, and reactivities of their molecules. What they have not done is to listen to their molecules react. Although the photoacoustic phenomenon has been known since 1880, it is only in the last twenty years that technology has developed to the point where sound waves produced by reacting molecules can be time resolved and the information contained within the waves deciphered. The information content within the photoacoustic wave is indeed rich, for one can learn about the dynamics and the magnitude of enthalpy changes associated with the reaction as well as the changes in molecular volume. This review article chronicles the development of time-resolved photoacoustic calorimetry and its application to a variety of reactions encountered in organic and organometallic chemistry and biochemistry. 相似文献
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Kevin Welford 《Optical and Quantum Electronics》1991,23(1):1-27
Surface plasmon-polaritons have been experimentally and theoretically studied for many years but in recent years interest has grown substantially due to their possible use in novel device applications. The aim of this review is to introduce the concept of surface plasmon-polaritons so that the reader will be able to appreciate the physics they can probe, and the device applications in which they may be utilized. 相似文献
16.
Utilizing forward recoil spectrometry (FRES), we have determined the segregation isotherm which describes the interfacial excess zi* of diblock copolymers of poly (d8-styrene-b-2-vinylpyridine) (dPS-PVP) at the interface between the homopolymers PS and PVP as a function of ?∞, the volume fraction of diblock copolymer remaining in the host homopolymer. All the samples were analyzed after annealing at temperatures and times sufficient to achieve equilibrium segregation. The effect of the degree of polymerization of both the diblock copolymers and the host homopolymers on the segregation isotherm is investigated. When the degree of polymerization of the homopolymer is much larger than that of the diblock copolymer, the normalized interfacial excess (zi*/Rg), where Rg is the radius of gyration of an isolated block copolymer chain, is a universal function of that portion of the block copolymer chemical potential due to chain stretching. The existence of such a universal function is predicted by theory and its form is in good agreement with self-consistent mean field calculations. Using these results, one can predict important aspects of the block copolymer segregation (e.g., the saturation interfacial excess) without recourse to the time-consuming numerical calculations. © 1994 John Wiley & Sons, Inc. 相似文献
17.
The kinetics of domain size equilibration were studied for asymmetric poly(ethylene‐alt‐propylene)‐b‐poly(dimethyl siloxane) (EPDMS) and polyisoprene‐b‐poly(dimethyl siloxane) (IDMS) block copolymers in the body‐centered cubic ordered phase. Small‐angle X‐ray scattering measurements of the principal peak position (q*) were made as a function of time after temperature jumps within the ordered state. The equilibration times were remarkably long, especially on cooling and for temperatures below 100 °C. For example, after a quench to 40 °C, q* for EPDMS had not fully equilibrated even after several weeks of annealing; IDMS required several days to equilibrate at the same temperature. In contrast, a lamella‐forming EPDMS sample was able to adjust q* within the timescale of the measurements (i.e., minutes) with both heating and cooling over the same temperature range. Measurements of tracer diffusion indicated that chain mobility was not the rate‐limiting step, although differences in mobility did account for the differences between EPDMS and IDMS. Rather, the limiting step was the required reduction in the number density of spheres on cooling; the disappearance of spheres, either by evaporation or by fusion, provided a large kinetic barrier. Lamellae, however, could adjust domain dimensions simply by local displacements of individual chains. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 715–724, 2003 相似文献
18.
Kevin W Kells 《Tetrahedron》2004,60(10):2247-2257
Transmetalation of urea derivatives of α-aminoorganostannanes with alkyllithiums provides α-aminoorganolithiums which undergo rapid N to C acyl migration to afford α-aminocarboxamides. The stereochemical course of the transmetalation/migration process depends on the substituents on the urea and varies from complete retention of configuration to complete racemization. 相似文献
19.
Rehan A. Kazi Vyas M.N. Prasad Jeeve Kanagalingam Christopher M. Nutting Peter Clarke Peter Rhys-Evans Kevin J. Harrington 《Journal of voice》2007,21(6):661-668
The objective of this study was to assess the difference in voice quality as defined by acoustical analysis using sustained vowel in laryngectomized patients in comparison with normal volunteers. This was designed as a retrospective single center cohort study. An adult tertiary referral unit formed the setting of this study. Fifty patients (40 males) who underwent total laryngectomy and 31 normal volunteers (18 male) participated. Group comparisons with the first three formant frequencies (F1, F2, and F3) using linear predictive coding (LPC) (Laryngograph Ltd, London, UK) was performed. The existence of any significant difference of F1, F2, and F3 between the two groups using the sustained vowel /i/ and the effects of other factors namely, tumor stage (T), chemoradiotherapy, pharyngectomy, cricothyroid myotomy, closure of pharyngoesophageal segment, and postoperative complication were analyzed. Formant frequencies F1, F2, and F3 were significantly different in male laryngectomees compared to controls: F1 (P<0.001, Mann-Whitney U test), F2 (P<0.001, Student's t test), and F3 (P=0.008, Student's t test). There was no significant difference between females in both groups for all three formant frequencies. Chemoradiotherapy and postoperative complications (pharyngocutaneous fistula) caused a significantly lower formant F1 in men, but showed little effect in F2 and F3. Laryngectomized males produced significantly higher formant frequencies, F1, F2, and F3, compared to normal volunteers, and this is consistent with literature. Chemoradiotherapy and postoperative complications significantly influenced the formant scores in the laryngectomee population. This study shows that robust and reliable data could be obtained using electroglottography and LPC in normal volunteers and laryngectomees using a sustained vowel. 相似文献
20.
In 1987 the Canadian Department of National Defence enunciated the Total Force concept. The Total Force is comprised of Regular and Reserve components. The intention is to make maximum use of the Reserve to reduce defence expenditures and at the same time to ensure that military capability remains adequate to support national policy objectives. This paper discusses some of the governing parameters that affect the modelling of the composition of the Total Force and analyses the mix of regular and reserve forces. The interplay between the key factors and their marginal costs will be stressed. The models are employed to study two units in the Canadian Forces, a maintenance support unit and a tactical unit with high operational activity cost. The lessons drawn from these studies are highlighted. 相似文献