Photodissociation pathways of 1,1-dichloroacetone

We present a comprehensive investigation of the dissociation dynamics following photoexcitation of 1,1-dichloroacetone (CH(3)COCHCl(2)) at 193 nm. Two major dissociation channels are observed: cleavage of a C-Cl bond to form CH(3)C(O)CHCl + Cl and elimination of HCl. The branching between these reaction channels is roughly 9:1. The recoil kinetic energy distributions for both C-Cl fission and HCl elimination are bimodal. The former suggests that some of the radicals are formed in an excited electronic state. A portion of the CH(3)C(O)CHCl photoproducts undergo secondary dissociation to give CH(3) + C(O)CHCl. Photoelimination of Cl(2) is not a significant product channel. A primary C-C bond fission channel to give CH(3)CO + CHCl(2) may be present, but this signal may also be due to a secondary dissociation. Data from photofragment translational spectroscopy with electron impact and photoionization detection, velocity map ion imaging, and UV-visible absorption spectroscopy are presented, along with G3//B3LYP calculations of the bond dissociation energetics.     

Errors in crack closure measurements caused by flexure test fixture support effects

Flexural tests are sometimes used for the evaluation of fatigue and fracture properties, especially for thin cross sections such as plate material where compact tension speciments cannot be used, or where material thicness is limited in the direction required for data generation. The method is also useful for evaluation of crack closure provided the force transfer occurs correctly. This paper shows how the influence of incorrect test fixture supports, which are outside the standard testing arrangement for such test specimens, can affect the force-displacement curves as evidenced using the backface strain method. The results show that incorrect test fixture supports may cause deviations in the force-displacement trace as an artifact of the testing conditions. This effect can severely influence crack closure measurements. The effect was also modeled with finite element analysis.     

Detecting high-frequency hearing loss with click-evoked otoacoustic emissions

In contrast to clinical click-evoked otoacoustic emission (CEOAE) tests that are inaccurate above 4-5 kHz, a research procedure measured CEOAEs up to 16 kHz in 446 ears and predicted the presence/absence of a sensorineural hearing loss. The behavioral threshold test that served as a reference to evaluate CEOAE test accuracy used a yes-no task in a maximum-likelihood adaptive procedure. This test was highly efficient between 0.5 and 12.7 kHz: Thresholds measured in 2 min per frequency had a median standard deviation (SD) of 1.2-1.5 dB across subjects. CEOAE test performance was assessed by the area under the receiver operating characteristic curve (AUC). The mean AUC from 1 to 10 kHz was 0.90 (SD=0.016). AUC decreased to 0.86 at 12.7 kHz and to 0.7 at 0.5 and 16 kHz, possibly due in part to insufficient stimulus levels. Between 1 and 12.7 kHz, the medians of the magnitude difference in CEOAEs and in behavioral thresholds were <4 dB. The improved CEOAE test performance above 4-5 kHz was due to retaining the portion of the CEOAE response with latencies as short as 0.3 ms. Results have potential clinical significance in predicting hearing status from at least 1 to 10 kHz using a single CEOAE response.     

Measurement of an aeroacoustic dipole using a linear microphone array

It is shown that the standard beamformer technique is inadequate for both the source location and the measurement of a simple dipole and that this is due to the assumption of monopole propagation in the calculation of the phase weights used to steer the focus of the array. A numerical simulation is used to illustrate the problem and to develop a correction to the signal processing algorithm to account for the dipole propagation characteristic. This is then applied to array measurements for an aeroacoustic dipole produced by a cylinder in a cross flow. The resulting source map and the beamformed spectrum are shown to give a true representation of the source energy and frequency content. A secondary effect of this correction is that the array becomes insensitive to other source types so that in addition to acting as a spatial filter, the array can perform as a source filter. This work also demonstrates how an array measurement can be misinterpreted if applied without consideration of the source mechanism.     

Row depth effects on turbulence spectra and acoustic vibrations in tube banks

The effect of row depth on Strouhal numbers derived from peaks in the turbulence spectra measured in an in-line tube bank and on the excitation of acoustic standing waves in the duct containing the bank has been investigated. The results indicate significant variations with bank depth and location in the bank although common features are evident. A buffeting type frequency predicted by Owen [1] is clearly shown beyond the fifth row of deeper banks whilst peaks evident in the turbulence spectra at the front of these banks and for less deep banks are assumed to be generated by vortex action and interaction in the wakes of tube rows. For the geometrical configuration tested, acoustic resonance is generated by the coincidence of a vorticity peak frequency with the standing wave frequency for all cases but the two row deep bank in which the excitation source was most probably in the wake of the bank. Finally, a modification of Owen's theory yields an equation which predicts a Strouhal number of the correct order.     

不同岩蔷薇浸膏挥发性致香成分的SED-GC-MS分析研究

岩蔷薇(cistusladaniferusL.)又名赖百当(labdanum),属半日花科。利用其树脂分泌物及枝叶,通过蒸馏、浸提和萃取等方法,可制得岩蔷薇精油、浸膏、净油、油树脂等各种香原料品种。岩蔷薇的香原料制品是膏香类的极重要品种,主要应用于日化和食品行业,在烟草行业也多有应用。因香料烟香味的主要来源是类赖百当化合物的降解,故被归为烟草的五大类香味物质之一:赖百当类、双萜烯及其降解产物类。这类物质在香料烟中的含量较高,对形成香料烟的特殊香味风格具有重要意义,且在烟草中赖百当仅存在于香料烟中,烤烟、自肋烟中均不存在。赖百当类化合物是香料烟中特有的香气物质,主要成分是冷杉醇、赖百当烯二醇,经调制和醇化转化为多种降赖百当类化合物,其中降龙涎香醚、龙涎香内酯、脱氢龙涎香内酯等都具有强烈的龙涎香香气,对增进卷烟香气和吃味有很好作用。     

Flow Chemistry Meets Advanced Functional Materials

Flow chemistry and continuous processing techniques are beginning to have a profound impact on the production of functional materials ranging from quantum dots, nanoparticles and metal organic frameworks to polymers and dyes. These techniques provide robust procedures which not only enable accurate control of the product material’s properties but they are also ideally suited to conducting experiments on scale. The modular nature of flow and continuous processing equipment rapidly facilitates reaction optimisation and variation in function of the products.     

Determination of Arsenic in Drinking Water by Graphite Furnace Atomic Absorption Spectroscopy. An Undergraduate Instrumental Analysis Laboratory

A laboratory exercise, the analysis of arsenic in drinking water by graphite furnace atomic absorption spectroscopy (GFAA), is presented for use in an undergraduate instrumental methods course. The purpose of this GFAA exercise is to expose students to a practical and commonly used application, to provide students with hands-on experience with the instrument, and to reinforce concepts taught in the classroom. Students safely analyze a real-world sample containing an analyte in the parts-per-billion concentration range.