TY - JOUR A1 - Villatoro, José Andrés A1 - Weber, M. A1 - Zühlke, Martin A1 - Lehmann, A. A1 - Zenichowski, Karl A1 - Riebe, Daniel A1 - Beitz, Toralf A1 - Löhmannsröben, Hans-Gerd A1 - Kreuzer, O. T1 - Structural characterization of synthetic peptides using electrospray ion mobility spectrometry and molecular dynamics simulations JF - International Journal of Mass Spectrometry N2 - Electrospray ionization-ion mobility spectrometry was employed for the determination of collision cross sections (CCS) of 25 synthetically produced peptides in the mass range between 540-3310 Da. The experimental measurement of the CCS is complemented by their calculation applying two different methods. One prediction method is the intrinsic size parameter (ISP) method developed by the Clemmer group. The second new method is based on the evaluation of molecular dynamics (MD) simulation trajectories as a whole, resulting in a single, averaged collision cross-section value for a given peptide in the gas phase. A high temperature MD simulation is run in order to scan through the whole conformational space. The lower temperature conformational distribution is obtained through thermodynamic reweighting. In the first part, various correlations, e.g. CCS vs. mass and inverse mobility vs. m/z correlations, are presented. Differences in CCS between peptides are also discussed in terms of their respective mass and m/z differences, as well as their respective structures. In the second part, measured and calculated CCS are compared. The agreement between the prediction results and the experimental values is in the same range for both calculation methods. While the calculation effort of the ISP method is much lower, the MD method comprises several tools providing deeper insights into the conformations of peptides. Advantages and limitations of both methods are discussed. Based on the separation of two pairs of linear and cyclic peptides of virtually the same mass, the influence of the structure on the cross sections is discussed. The shift in cross section differences and peak shape after transition from the linear to the cyclic peptide can be well understood by applying different MD tools, e.g. the root-mean-square deviation (RMSD) and the root mean square fluctuation (RMSF). (C) 2018 Elsevier B.V. All rights reserved. KW - Ion mobility spectrometry KW - Electrospray ionization KW - Peptides KW - Collision cross-section KW - Molecular dynamics Y1 - 2019 U6 - https://doi.org/10.1016/j.ijms.2018.10.036 SN - 1387-3806 SN - 1873-2798 VL - 436 SP - 108 EP - 117 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Riebe, Daniel A1 - Erler, Alexander A1 - Brinkmann, Pia A1 - Beitz, Toralf A1 - Löhmannsröben, Hans-Gerd A1 - Gebbers, Robin T1 - Comparison of Calibration Approaches in Laser-Induced Breakdown Spectroscopy for Proximal Soil Sensing in Precision Agriculture JF - Sensors N2 - The lack of soil data, which are relevant, reliable, affordable, immediately available, and sufficiently detailed, is still a significant challenge in precision agriculture. A promising technology for the spatial assessment of the distribution of chemical elements within fields, without sample preparation is laser-induced breakdown spectroscopy (LIBS). Its advantages are contrasted by a strong matrix dependence of the LIBS signal which necessitates careful data evaluation. In this work, different calibration approaches for soil LIBS data are presented. The data were obtained from 139 soil samples collected on two neighboring agricultural fields in a quaternary landscape of northeast Germany with very variable soils. Reference analysis was carried out by inductively coupled plasma optical emission spectroscopy after wet digestion. The major nutrients Ca and Mg and the minor nutrient Fe were investigated. Three calibration strategies were compared. The first method was based on univariate calibration by standard addition using just one soil sample and applying the derived calibration model to the LIBS data of both fields. The second univariate model derived the calibration from the reference analytics of all samples from one field. The prediction is validated by LIBS data of the second field. The third method is a multivariate calibration approach based on partial least squares regression (PLSR). The LIBS spectra of the first field are used for training. Validation was carried out by 20-fold cross-validation using the LIBS data of the first field and independently on the second field data. The second univariate method yielded better calibration and prediction results compared to the first method, since matrix effects were better accounted for. PLSR did not strongly improve the prediction in comparison to the second univariate method. KW - laser-induced breakdown spectroscopy KW - LIBS KW - proximal soil sensing KW - soil nutrients KW - elemental composition Y1 - 2019 U6 - https://doi.org/10.3390/s19235244 SN - 1424-8220 VL - 19 IS - 23 PB - MDPI CY - Basel ER -