High-pressure pulse radiolysis as a tool in the study of transition metal reaction mechanisms

The unique combination of high-pressure and pulse radiolysis kinetic techniques enables detailed mechanistic insight for a large variety of chemical processes to be gained. Typical examples for transition metal reactions are presented. These include ligand substitution, electron transfer, reactions of complexes with uncommon oxidation states, and reactions with radicals, including the formation and decomposition reactions of complexes with metal-carbon sigma bonds. The volumes of activation and volume profiles obtained form the basis of a critical analysis of different plausible reaction mechanisms.     

PSpice simulation of ultrasonic systems

The usage of electrical analogies for the simulation of wave generation and propagation in ultrasound transducers is well established. In this paper a PSpice approach that includes the temperature and frequency dependency of the transducer performance is proposed. The analogy between acoustic wave propagation and wave propagation in an electric transmission line is given. Further ways to deduce temperature and frequency dependencies are discussed. The simulation approach is applied to a pulse-echo setup for the determination of speed of sound and attenuation in liquids and solids. Experiments and simulations are made for three temperatures and in the frequency range 1-12 MHz using water, glycerine, and polymers (PMMA and PEEK) as test samples. Comparison shows a good agreement between simulation and experiments. Results for glycerine indicates that the available attenuation models for high viscosity liquids is inappropriate.     

Asthmatic airways obstruction assessment based on detailed analysis of respiratory sound spectra

This paper concerns the analysis of adventitious sounds produced by individual asthmatic patients, and relates the sounds to the degree of airways obstruction at the moment of sound recording. In this study, airways obstruction is represented by a parameter commonly used in clinical tests, the forced expiratory volume in one second. A nonrestrictive approach using spectral information in detail is followed, resulting in a fairly high resolution of respiration sounds with respect to airways obstruction. The beneficial effect of a power raising transformation is presented, together with an illumination of the background of this effect.     

A liquid chromatography-mass spectrometry method for the quantification of bioavailability and bioconversion of beta-carotene to retinol in humans

A method based on high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (APCI LC-MS) was developed for the quantification of the bioavailability of retinyl palmitate and beta-carotene and the bioconversion of beta-carotene to retinol in humans. Following oral administration of [8,9,10,11,12,13,14,15,19,20-13C10]-retinyl palmitate and [12,13,14,15,20,12',13',14',15',20'-13C10]-beta-carotene at physiological doses to children between 8 and 11 years of age, blood samples were drawn and serum was prepared. Retinol and beta-carotene were extracted from 0.2- and 1.0-mL serum samples, respectively, and analyzed using reversed-phase HPLC with a C30 column interfaced to an APCI mass spectrometer. Unlike other LC-MS assays for carotenoids, no additional purification steps were necessary, nor was any derivatization of retinol or beta-carotene required. APCI LC-MS showed a linear detector response for beta-carotene over 4 orders of magnitude. Using selected ion monitoring to record the elution profile of protonated circulating beta-carotene at m/z 537 and [13C10]-beta-carotene at m/z 547, the limit of detection was determined to be 0.5 pmol injected on-column. To assess the ratio of labeled to unlabeled retinol, selected ion monitoring was carried out at m/z 269, 274, and 279. These abundant fragment ions corresponded to the loss of water from the protonated molecule of circulating retinol, [13C5]-retinol (metabolically formed from orally administered [13C10]-beta-carotene), and [13C10]-retinol (formed by hydrolysis of [13C10]-retinyl palmitate). The ratios of labeled to unlabeled retinol and the ratio of labeled to unlabeled beta-carotene were calculated. Combined with standard HPLC measurement of beta-carotene and retinol concentration and a mathematical model, these results showed that this simple LC-MS method can be used to quantify beta-carotene bioavailability and its bioconversion to retinol at physiologically relevant doses.     

Use of high-performance liquid chromatography-tandem mass spectrometry to distinguish Panax ginseng C. A. Meyer (Asian ginseng) and Panax quinquefolius L. (North American ginseng)

A liquid chromatography-tandem mass spectrometry (LC-MS-MS) method was developed to distinguish Asian ginseng (Panax ginseng C. A. Meyer) and North American ginseng (Panax quinquefolius L.). The method is based on the baseline chromatographic separation of ginsenoside Rf and 24(R)-pseudoginsenoside F11, two potential chemical markers present in ginseng root methanolic extracts, and their unambiguous on-line identification using tandem mass spectrometry. Consistent with the literature, 24(R)-pseudoginsenoside F11 was detected in abundance in North American ginseng roots in excess of 0.1% (w/w) of the dried root. In contrast to some reports, 24(R)-pseudoginsenoside F11 was also identified in Asian ginseng roots at trace levels using LC-MS-MS but at less than 0.0001% (w/w). Besides showing identical tandem mass spectra to authentic 24(R)-pseudoginsenoside F11, the corresponding compound in Asian ginseng root coeluted with standard under different HPLC conditions, thus confirming this compound as 24(R)-pseudoginsenoside F11. Another ginsenoside often used to distinguish Asian and North American ginseng, ginsenoside Rf, was found in abundance in Asian ginseng roots at more than 0.021% (w/w). In Asian ginseng roots, the ratio of ginsenoside Rf to 24(R)-pseudoginsenoside F11 exceeded 700:1. The limit of detection of ginsenoside Rf or 24(R)-pseudoginsenoside F11 was 120 pg injected on-column, and the limit of quantification was 240 pg on-column. In summary, LC-MS-MS analysis of ginseng products for the presence and ratio of ginsenoside Rf and 24(R)-pseudoginsenoside F11 may be used for the unambiguous identification of Asian and North American ginsengs.     

Cognitive task analysis and innovation of training: the case of structured troubleshooting

Troubleshooting is often a time-consuming and difficult activity. The question of how the training of novice technicians can be improved was the starting point of the research described in this article. A cognitive task analysis was carried out consisting of two preliminary observational studies on troubleshooting in naturalistic settings, combined with an interpretation of the data obtained in the context of the existing literature. On the basis of this cognitive task analysis, a new method for the training of troubleshooting was developed (structured troubleshooting), which combines a domain-independent strategy for troubleshooting with a context-dependent, multiple-level, functional decomposition of systems. This method has been systematically evaluated for its use in training. The results show that technicians trained in structured troubleshooting solve twice as many malfunctions, in less time, than those trained in the traditional way. Moreover, structured troubleshooting can be taught in less time than can traditional troubleshooting. Finally, technicians learn to troubleshoot in an explicit and uniform way. These advantages of structured troubleshooting ultimately lead to a reduction in training and troubleshooting costs.     

Synergy in a neural code

We show that the information carried by compound events in neural spike trains-patterns of spikes across time or across a population of cells-can be measured, independent of assumptions about what these patterns might represent. By comparing the information carried by a compound pattern with the information carried independently by its parts, we directly measure the synergy among these parts. We illustrate the use of these methods by applying them to experiments on the motion-sensitive neuron H1 of the fly's visual system, where we confirm that two spikes close together in time carry far more than twice the information carried by a single spike. We analyze the sources of this synergy and provide evidence that pairs of spikes close together in time may be especially important patterns in the code of H1.     

Medical image matching-a review with classification

A classification scheme for multimodal image matching is considered. The scope of the classification is restricted to methods that register data after acquisitions. The classification scheme may be used for any modality; not only for (2-D) projection images and (3-D) tomographic images, but also for other signal modalities that provide spatial insight into function or anatomy, e.g., EEG (electroencephalography) or MEG (magnetoencephalography) and for the real physical patient. The available literature on image matching is discussed and classified