A neutral loss activation method for improved phosphopeptide sequence analysis by quadrupole ion trap mass spectrometry

Recent advances in phosphopeptide enrichment prior to mass spectrometric analysis show genuine promise for characterization of phosphoproteomes. Tandem mass spectrometry of phosphopeptide ions, using collision-activated dissociation (CAD), often produces product ions dominated by the neutral loss of phosphoric acid. Here we describe a novel method, termed Pseudo MS(n), for phosphopeptide ion dissociation in quadrupole ion trap mass spectrometers. The method induces collisional activation of product ions, those resulting from neutral loss(es) of phosphoric acid, following activation of the precursor ion. Thus, the principal neutral loss product ions are converted into a variety of structurally informative species. Since product ions from both the original precursor activation and all subsequent neutral loss product activations are simultaneously stored, the method generates a "composite" spectrum containing fragments derived from multiple precursors. In comparison to analysis by conventional MS/MS (CAD), Pseudo MS(n) shows improved phosphopeptide ion dissociation for 7 out of 10 synthetic phosphopeptides, as judged by an automated search algorithm (TurboSEQUEST). A similar overall improvement was observed upon application of Pseudo MS(n) to peptides generated by enzymatic digestion of a single phosphoprotein. Finally, when applied to a complex phosphopeptide mixture, several phosphopeptides mis-assigned by TurboSEQUEST under the conventional CAD approach were successfully identified after analysis by Pseudo MS(n).     

Accuracy of continuous ice-core trace-element analysis by inductively coupled plasma sector field mass spectrometry

Trace elements trapped in glaciers are important indicators for the characterization of past biogeochemical cycles, the identification of numerous sources and their varying strength, and thus indirectly provide insight into past climate variations. However, this necessitates highly resolved and continuous records of trace elements in ice. To obtain records corresponding to these requirements, a continuous ice-core melting (CIM) device was coupled to an inductively coupled plasma sector field mass spectrometer (ICP-SFMS). Accuracy of this newly developed method was tested by replicate analysis of longitudinally cut ice-core sections (reproducibility) and by comparing results of the continuous method with the conventional decontamination and analysis procedure. The new, fast method is suited to accurately determine concentrations of a number of elements, such as Li, Na, Mg, Ca, Mn, Co, Br, Sr, Mo, and Tl. However, for 18 elements (including Al and lanthanides) observed concentrations were underestimated when analyzed using the continuous method. Possible explanations of these low concentrations are (i) incomplete dissolution of mineral dust particles contained in the ice resulting from a delayed acidification step and/or (ii) adsorption of dissolved trace elements or mineral dust particles on the surface of the ice melting device.     

Detection of the gasoline components methyl tert-butyl ether,benzene, toluene,and m-xylene using ion mobility spectrometers with a radioactive and UV ionization source

For the first time, ion mobility spectrometers (IMS) with radioactive and UV ionization sources in combination with multicapillary columns (MCCs) have been used to determine methyl tert-butyl ether (MTBE), a gasoline additive, in water and nitrogen as well as the monoaromatic compounds benzene, toluene, and m-xylene (BTX). A membrane extraction unit was set up to extract the substances from water, which is simple, effective, and easy to automate for further applications. Thus, the detection of MTBE and BTX of gasoline vapors was accomplished after a preliminary silicone membrane extraction. Two-dimensional data analyses of IMS-chromatograms allow us to separate these substances clearly according to their different retention and drift times. Method detection limits for MTBE were 2 microg/L (UV) and 30 pg/L (63Ni) in nitrogen and 20 mg/L (UV) and 1 microg/L (63Ni) in water. Rather a good reproducibility was achieved with relative standard deviations of between 2.9 and 9%. The method presented in this article has been proven to be suitable for nearly real-time monitoring as the total analysis time is less than 90 s. As an example of application, the detection of MTBE and BTX in a mixture of volatile organic compounds of pure gasoline using the 2-D IMS-chromatogram is presented.     

Trajectory-based change detection for automated characterization of forest disturbance dynamics

Satellite sensors are well suited to monitoring changes on the Earth's surface through provision of consistent and repeatable measurements at a spatial scale appropriate for many processes causing change on the land surface. Here, we describe and test a new conceptual approach to change detection of forests using a dense temporal stack of Landsat Thematic Mapper (TM) imagery. The central premise of the method is the recognition that many phenomena associated with changes in land cover have distinctive temporal progressions both before and after the change event, and that these lead to characteristic temporal signatures in spectral space. Rather than search for single change events between two dates of imagery, we instead search for these idealized signatures in the entire temporal trajectory of spectral values. This trajectory-based change detection is automated, requires no screening of non-forest area, and requires no metric-specific threshold development. Moreover, the method simultaneously provides estimates of discontinuous phenomena (disturbance date and intensity) as well as continuous phenomena (post-disturbance regeneration). We applied the method to a stack of 18 Landsat TM images for the 20-year period from 1984 to 2004. When compared with direct interpreter delineation of disturbance events, the automated method accurately labeled year of disturbance with 90% overall accuracy in clear-cuts and with 77% accuracy in partial-cuts (thinnings). The primary source of error in the method was misregistration of images in the stack, suggesting that higher accuracies are possible with better registration.     

Business owners' action planning and its relationship to business success in three African countries.

A model of business success was developed with motivational resources (locus of control, self-efficacy, achievement motivation, and self-reported personal initiative) and cognitive resources (cognitive ability and human capital) as independent variables, business owners' elaborate and proactive planning as a mediator, and business size and growth as dependent variables. Three studies with a total of 408 African micro and small-scale business owners were conducted in South Africa, Zimbabwe, and Namibia. Structural equation analyses partially supported the hypotheses on the importance of psychological planning by the business owners. Elaborate and proactive planning was substantially related to business size and to an external evaluation of business success and was a (partial) mediator for the relationship between cognitive resources and business success. The model carries important implications for selection, training, and coaching of business owners. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Volume Preservation of Multiresolution Meshes

Geometric constraints have proved to be efficient for enhancing the realism of shape animation. The present paper addresses the computation and the preservation of the volume enclosed by multiresolution meshes. A wavelet based representation allows the mesh to be handled at any level of resolution. The key contribution is the calculation of the volume as a trilinear form with respect to the multiresolution coefficients. Efficiency is reached thanks to the pre-processing of a sparse 3D data structure involving the transposition of the filters while represented as a lifting scheme. A versatile and interactive method for preserving the volume during a deformation process is then proposed. It is based on a quadratic minimization subject to a linearization of the volume constraint. A closed form of the solution is derived.     

A large deformation solid‐shell concept based on reduced integration with hourglass stabilization

In this paper a new eight‐node (brick) solid‐shell finite element formulation based on the concept of reduced integration with hourglass stabilization is presented. The work focuses on static problems. The starting point of the derivation is the three‐field variational functional upon which meanwhile established 3D enhanced strain concepts are based. Important additional assumptions are made to transfer the approach into a powerful solid‐shell. First of all, a Taylor expansion of the first Piola–Kirchhoff stress tensor with respect to the normal through the centre of the element is carried out. In this way the stress becomes a linear function of the shell surface co‐ordinates whereas the dependence on the thickness co‐ordinate remains non‐linear. Secondly, the Jacobian matrix is replaced by its value in the centre of the element. These two assumptions lead to a computationally efficient shell element which requires only two Gauss points in the thickness direction (and one Gauss point in the plane of the shell element). Additionally three internal element degrees‐of‐freedom have to be determined to avoid thickness locking. One important advantage of the element is the fact that a fully three‐dimensional stress state can be modelled without any modification of the constitutive law. The formulation has only displacement degrees‐of‐freedom and the geometry in the thickness direction is correctly displayed. Copyright © 2006 John Wiley & Sons, Ltd.