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71.
Multi-way partial least-squares (N-PLS) is combined to the residual bi-linearization procedure (RBL) for the direct analysis of metabolites of polycyclic aromatic hydrocarbons in urine samples. Metabolite analysis is carried out via a two-step experimental procedure based on solid-phase extraction and room temperature fluorescence spectroscopy. Excitation-emission matrices are recorded from octadecyl (C18) membranes that serve as solid substrates for sample extraction and spectroscopic measurements. Excellent metabolite recoveries were obtained in all cases, which varied from 96.2 ± 1.35% (9-hydroxyphenanthrene) to 99.7 ± 0.49% (3-hydroxybenzo[a]pyrene). Background correction of extraction membranes is carried out with a new alternating least-squares (ALS) procedure adapted to second order data. The performance of N-PLS/RBL is compared to the well-established multivariate curve resolution-alternating least-squares (MCR-ALS) algorithm. Both algorithms provided similar analytical figures of merit, including their ability to handle unknown interference in urine samples. With only 10 mL of sample, the limits of detection varied between 0.06–0.08 ng mL−1 (1-hydroxypyrene) and 0.016–0.018 ng mL−1 (2-hydroxyfluorene). When compared to previously reported univariate calibration data, the limits of detection via N-PLS/RBL and MCR-ALS are approximately one order of magnitude higher. This was somehow expected due to the effect of unexpected components in multivariate figures of merit, i.e. a more realistic approach to the analysis of metabolites in human urine samples. 相似文献
72.
An holistic extension for classical propositional logic is introduced in the framework of quantum computation with mixed states. The mentioned extension is obtained by applying the quantum Fredkin gate to non-factorizable bipartite states. In particular, an extended notion of classical contradiction is studied in this holistic framework. 相似文献
73.
74.
Inverse Jacobi multipliers are a natural generalization of inverse integrating factors ton-dimensional dynamical systems. In this paper, the corresponding theory is developed from its beginning in the formal methods
of integration of ordinary differential equations and the “last multiplier” of K. G. Jacobi. We explore to what extent the
nice properties of the vanishing set of inverse integrating factors are preserved in then -dimensional case. In particular, vanishing on limit cycles (in restricted sense) of an inverse Jacobi multiplier is proved
by resorting to integral invariants. Extensions of known constructions of inverse integrating factors by means of power series,
local Lie Groups and algebraic solutions are provided for inverse Jacobi multipliers as well as a suitable generalization
of the concept to systems with discontinuous right-hand side. 相似文献
75.
David L. Olmsted Louis G. Hector Jr. 《Journal of the mechanics and physics of solids》2006,54(8):1763-1788
The strengthening of Al by Mg solute atoms is investigated using molecular dynamics (MD) studies of single dislocations moving through a field of randomly placed solutes. The MD method permits explicit treatment of “core” effects, dislocation pinning and deceleration, and dislocation unpinning by thermal activation, all under an applied load. Choice of an appropriate MD simulation cell size is assessed using analytic concepts developed by Labusch. The interaction energy of a single Mg atom with straight edge and screw dislocations is computed and compared with continuum models. Using the single Mg energies, a one-dimensional energy landscape for the motion of a straight edge dislocation through a random field of Mg solutes is computed. The minima in this landscape match well with those found in the MD simulations at zero temperature. The stress to unpin a straight edge dislocation trapped in a local energy minimum generated by the solutes is then predicted semi-analytically using the energy landscape, and good agreement is obtained with the MD results. At temperatures of 300 and 500 K, the thermally activated rate of unpinning vs. stress and temperature is calculated semi-analytically, and agreement with the full MD results is again obtained with the fitting of a single attempt frequency in a transition state model. The agreement of the semi-analytical models provides a basis for calculating yield stress vs. strain rate and temperature, resulting from statistical pinning, for the case of non-interacting dislocations on a single slip system, and for extending the analysis to study dynamic strain aging effects resulting from diffusion of Mg atoms around a pinned dislocation. 相似文献
76.
PRIMARY PHOTOCHEMISTRY OF BACTERIORHODOPSIN: COMPARISON OF FOURIER TRANSFORM INFRARED DIFFERENCE SPECTRA WITH RESONANCE RAMAN SPECTRA 总被引:2,自引:0,他引:2
Kenneth J. Rothschild Hector Marrero Mark Braiman † Richard Mathies 《Photochemistry and photobiology》1984,40(5):675-679
Abstract —Fourier transform infrared (FTIR) difference spectra of the BR→rK transition in bacteriorhodopsin at 77→K are compared with analogous resonance Raman difference spectra obtained using a spinning sample cell at 77→K. The vibrational frequencies observed in the FTIR spectra of native purple membrane and of purple membrane regenerated with 15-deuterioretinal are in good agreement with the frequencies observed in the Raman spectra, indicating that the lines in the FTIR difference spectra arise predominantly from retinal chromophore vibrations. This agreement confirms that the spinning cell method for obtaining resonance Raman spectra of K minimizes potential contributions from unwanted photoproducts. The unexpected similarity between the resonance Raman scattering intensities and the FTIR absorption intensities for BR and K is discussed in terms of the delocalized electronic structure of the chromophore. Finally, comparison of the Schiff base regions of the K Raman and FTIR spectra provide additional information on the assignment of its Schiff base vibration. 相似文献
77.
Jose Portillo-Portillo Gabriel Sanchez-Perez Linda K. Toscano-Medina Aldo Hernandez-Suarez Jesus Olivares-Mercado Hector Perez-Meana Pablo Velarde-Alvarado Ana Lucila Sandoval Orozco Luis Javier García Villalba 《Entropy (Basel, Switzerland)》2022,24(7)
Most of the methods for real-time semantic segmentation do not take into account temporal information when working with video sequences. This is counter-intuitive in real-world scenarios where the main application of such methods is, precisely, being able to process frame sequences as quickly and accurately as possible. In this paper, we address this problem by exploiting the temporal information provided by previous frames of the video stream. Our method leverages a previous input frame as well as the previous output of the network to enhance the prediction accuracy of the current input frame. We develop a module that obtains feature maps rich in change information. Additionally, we incorporate the previous output of the network into all the decoder stages as a way of increasing the attention given to relevant features. Finally, to properly train and evaluate our methods, we introduce CityscapesVid, a dataset specifically designed to benchmark semantic video segmentation networks. Our proposed network, entitled FASSVid improves the mIoU accuracy performance over a standard non-sequential baseline model. Moreover, FASSVid obtains state-of-the-art inference speed and competitive mIoU results compared to other state-of-the-art lightweight networks, with significantly lower number of computations. Specifically, we obtain 71% of mIoU in our CityscapesVid dataset, running at 114.9 FPS on a single NVIDIA GTX 1080Ti and 31 FPS on the NVIDIA Jetson Nano embedded board with images of size and , respectively. 相似文献
78.
Stepwise Strategy to Cyclometallated PtII Complexes with N‐Heterocyclic Carbene Ligands: A Luminescence Study on New β‐Diketonate Complexes 下载免费PDF全文
Dr. Sara Fuertes Dr. Hector García Dr. Mariano Perálvarez Wim Hertog Dr. Josep Carreras Dr. Violeta Sicilia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1620-1631
The imidazolium salt 3‐methyl‐1‐(naphthalen‐2‐yl)‐1H‐imidazolium iodide ( 2 ) has been treated with silver(I) oxide and [{Pt(μ‐Cl)(η3‐2‐Me‐C3H4)}2] (η3‐2‐Me‐C3H4=η3‐2‐methylallyl) to give the intermediate N‐heterocyclic carbene complex [PtCl(η3‐2‐Me‐C3H4)(H$\widehat{CC}$ *‐κC*)] ( 3 ) (H$\widehat{CC}$ *‐κC*=3‐methyl‐1‐(naphthalen‐2‐yl)‐1H‐imidazol‐2‐ylidene). Compound 3 undergoes regiospecific cyclometallation at the naphthyl ring of the NHC ligand to give the five‐membered platinacycle compound [{Pt(μ‐Cl)($\widehat{CC}$ *)}2] ( 4 ). Chlorine abstraction from 4 with β‐diketonate Tl derivatives rendered the corresponding neutral compounds [Pt($\widehat{CC}$ *)(L‐O,O′)] {L=acac (HL=acetylacetone) 5 , phacac (HL=1,3‐diphenyl‐1,3‐propanedione) 6 , hfacac (HL=hexafluoroacetylacetone) 7 }. All of the compounds ( 3 – 7 ) were fully characterized by standard spectroscopic and analytical methods. X‐ray diffraction studies were performed on 5 – 7 , revealing short Pt?Pt and π–π interactions in the solid‐state structure. The influence of the R‐substituents of the β‐diketonate ligand on the photophysical properties and the use of the most efficient emitter, 5 , as phosphor converter has also been studied. 相似文献
79.
80.
Soltzberg LJ Slinker JD Flores-Torres S Bernards DA Malliaras GG Abruña HD Kim JS Friend RH Kaplan MD Goldberg V 《Journal of the American Chemical Society》2006,128(24):7761-7764
We have used matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry and micro-Raman spectroscopy to identify a quenching species that is formed during operation of [Ru(bpy)3]2+ electroluminescent devices. We identify this performance-degrading product to be the oxo-bridged dimer [(bpy)2(H2O)RuORu(OH2)(bpy)2]4+ and show this dimer to be an effective quencher of device luminescence. This work is the first to detect a specific chemical degradation product formed during iTMC OLED operation. 相似文献