A metabolomic protocol for plant systematics by matrix-assisted laser-desorption/ionization time-of flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of flight mass spectrometry (MALDI-TOF MS) has been widely used for the identification and classification of microorganisms based on their proteomic fingerprints. However, the use of MALDI-TOF MS in plant research has been very limited. In the present study, a first protocol is proposed for metabolic fingerprinting by MALDI-TOF MS using three different MALDI matrices with subsequent multivariate data analysis by in-house algorithms implemented in the R environment for the taxonomic classification of plants from different genera, families and orders. By merging the data acquired with different matrices, different ionization modes and using careful algorithms and parameter selection, we demonstrate that a close taxonomic classification can be achieved based on plant metabolic fingerprints, with 92% similarity to the taxonomic classifications found in literature. The present work therefore highlights the great potential of applying MALDI-TOF MS for the taxonomic classification of plants and, furthermore, provides a preliminary foundation for future research.     

Multiresponse problems: desirability and other optimization approaches

A diversity of multiresponse optimization methods has been introduced in the literature; however, their performance has not been thoroughly explored, and only a classical desirability‐based criterion has been commonly used. With the aim of contributing to help practitioners in selecting an effective criterion for solving multiresponse optimization problems developed under the response surface methodology framework, and thus to find compromise solutions that are technically and economically more favorable, the working ability of several easy‐to‐use criteria is evaluated and compared with that of a theoretically sound method. Four case studies with different numbers and types of responses are considered. Less‐sophisticated criteria were able to generate solutions similar to those generated by sophisticated methods, even when the objective is to depict the Pareto frontier in problems with conflicting responses. Two easy‐to‐use criteria that require less‐subjective information from the user yielded solutions similar to those of a classical desirability‐based criterion. Preference parameters range and increment impact on optimal solutions were also evaluated.     

On‐Site Determination of Carbendazim,Cathecol and Hydroquinone in Tap Water Using a Homemade Batch Injection Analysis Cell for Screen Printed Electrodes

In this work, we present a simple homemade batch‐injection analysis cell for screen‐printed electrodes (BIA‐SPE). The potential of the proposed system for on‐site analysis was demonstrated by the determination of carbendazim, catechol, and hydroquinone in tap water. The system provided reduced injection volume (30 µL), high analytical frequency (≈200 h^?1) and low detection limits (nanomolar level). Moreover, the BIA‐SPE cell presented better stability (RSD≈0.4 %) than a conventional flow injection cell for SPE (RSD≈5.0 %) in organic media. The proposed homemade BIA‐SPE cell is very simple, inexpensive and can be easily constructed in any laboratory.     

Separation of glycosidic catiomers by TWIM‐MS using CO2 as a drift gas

Traveling wave ion mobility mass spectrometry (TWIM‐MS) is shown to be able to separate and characterize several isomeric forms of diterpene glycosides stevioside (Stv) and rebaudioside A (RebA) that are cationized by Na⁺ and K⁺ at different sites. Determination and characterization of these coexisting isomeric species, herein termed catiomers, arising from cationization at different and highly competitive coordinating sites, is particularly challenging for glycosides. To achieve this goal, the advantage of using CO₂ as a more massive and polarizable drift gas, over N₂, was demonstrated. Post‐TWIM‐MS/MS experiments were used to confirm the separation. Optimization of the possible geometries and cross‐sectional calculations for mobility peak assignments were also performed. Copyright © 2015 John Wiley & Sons, Ltd.     

Controlling chaotic oscillators by altering their energy

We developed the control technique for nonlinear oscillators when simple feedback alters the oscillation energy. The control does not require any computation nor knowledge of the system equations. Depending on the control perturbation parameters, two scenarios take place: (i) changing (linearly or nonlinearly) the oscillator damping, and (ii) suppressing (enhancing) the driving force. In the case of large deviations between phases of the chaotic oscillator and the driving force, only first scenario holds. Generalization of the technique to the case of oscillator networks is considered.     

Direct numerical simulation of the flow around a wall-mounted square cylinder under various inflow conditions

The flow around a wall-mounted square cylinder of side d is investigated by means of direct numerical simulation (DNS). The effect of inflow conditions is assessed by considering two different cases with matching momentum-thickness Reynolds numbers Re_θ ? 1000 at the obstacle: the first case is a fullyturbulent zero pressure gradient boundary layer, and the second one is a laminar boundary layer with prescribed Blasius inflow profile further upstream. An auxiliary simulation carried out with the pseudo-spectral Fourier–Chebyshev code SIMSON is used to obtain the turbulent time-dependent inflow conditions which are then fed into the main simulation where the actual flow around the cylinder is computed. This main simulation is performed, for both laminar and turbulent-inflows, with the spectral-element method code Nek5000. In both cases the wake is completely turbulent, and we find the same Strouhal number St ? 0.1, although the two wakes exhibit structural differences for x > 3d downstream of the cylinder. Transition to turbulence is observed in the laminar-inflow case, induced by the recirculation bubble produced upstream of the obstacle, and in the turbulent-inflow simulation the streamwise fluctuations modulate the horseshoe vortex. The wake obtained in our laminar-inflow case is in closer agreement with reference particle image velocimetry measurements of the same geometry, revealing that the experimental boundary layer was not fully turbulent in that dataset, and highlighting the usefulness of DNS to assess the quality of experimental inflow conditions.     

Aspect ratio effects in turbulent duct flows studied through direct numerical simulation

Three-dimensional effects in turbulent duct flows, i.e., sidewall boundary layers and secondary motions, are studied by means of direct numerical simulation (DNS). The spectral element code Nek5000 is used to compute turbulent duct flows with aspect ratios 1–7 (at Re_{b, c} = 2800, Re_{τ, c} ? 180) and aspect ratio 1 (at Re_{b, c} = 5600, Re_{τ, c} ? 330), in streamwise-periodic boxes of length 25h. The total number of grid points ranges from 28 to 145 million, and the pressure gradient is adjusted iteratively in order to keep the same bulk Reynolds number in the centreplane with changing aspect ratio. Turbulence is initiated via a trip forcing active during the initial stages of the simulation, and the statistical convergence of the data is discussed both in terms of transient approach and averaging period. Spanwise variations in wall shear, mean-flow profiles, and turbulence statistics are analysed as a function of aspect ratio, and also compared with the spanwise-periodic channel (as idealisation of an infinite aspect ratio duct). The computations show good agreement with experimental measurements carried out in parallel at the Illinois Institute of Technology (IIT) in Chicago, and highlight the relevance of sidewall boundary layers and secondary vortices in the physics of the duct flow. The rich array of secondary vortices extending throughout the upper and lower walls of the duct, and their dependence on Reynolds number and aspect ratio, had not been reported in the literature before.     

Quantum–chemical study of photo–excited states in tetragonal SrTiO3 lattice

The nature of photo-excited states in SrTiO₃ has been a topic of intense debate during the last few decades. Using a quantum-chemical method developed for crystals, we present a theoretical interpretation of the structural and electronic properties of triplet excitons in the tetragonal SrTiO₃ crystal. Our study demonstrates that the defect structure may correspond to the Mott–Wannier-type exciton having a considerable distance, 2.14Å, between the hole and the electron parts of the defect. The geometry optimization leads to an extensive defective region containing up to five atoms. However, the obtained magnitudes of atomic movements do not exceed 0.15Å. It is also observed that the self-trapped exciton polarizes the lattice around it. Using the so-called (ΔSCF method, the luminescence energy due to the exciton is found to be equal to 1.13 eV. As it corresponds to the infrared part of the spectrum, the experimentally detected green luminescence due to photo-excited states should be attributed to the singlet excitons.     

A discrete time method to the first variation of fractional order variational functionals

The fact that the first variation of a variational functional must vanish along an extremizer is the base of most effective solution schemes to solve problems of the calculus of variations. We generalize the method to variational problems involving fractional order derivatives. First order splines are used as variations, for which fractional derivatives are known. The Grünwald-Letnikov definition of fractional derivative is used, because of its intrinsic discrete nature that leads to straightforward approximations.     

Isotope hydrology and baseflow geochemistry in natural and human-altered watersheds in the Inland Pacific Northwest,USA

This study presents a stable isotope hydrology and geochemical analysis in the inland Pacific Northwest (PNW) of the USA. Isotope ratios were used to estimate mean transit times (MTTs) in natural and human-altered watersheds using the FLOWPC program. Isotope ratios in precipitation resulted in a regional meteoric water line of δ²H?=?7.42·δ¹⁸O?+?0.88 (n?=?316; r²?=?0.97). Isotope compositions exhibited a strong temperature-dependent seasonality. Despite this seasonal variation, the stream δ¹⁸O variation was small. A significant regression (τ?=?0.11D^?1.09; r²?=?0.83) between baseflow MTTs and the damping ratio was found. Baseflow MTTs ranged from 0.4 to 0.6 years (human-altered), 0.7 to 1.7 years (mining-altered), and 0.7 to 3.2 years (forested). Greater MTTs were represented by more homogenous aqueous chemistry whereas smaller MTTs resulted in more dynamic compositions. The isotope and geochemical data presented provide a baseline for future hydrological modelling in the inland PNW.