Pure component spectral recovery and constrained matrix factorizations: concepts and applications

Neymeyr, Klaus; Sawall, Mathias; Hess, Dieter

doi:10.1002/cem.1273

Cited by 46 publications

(47 citation statements)

References 14 publications

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“…27,28 In this regard, the data analysis combines classical MCR techniques with the relatively new complementarity theory. 31 The concentration proles are similar for all studied dyes. In all cases two of the three pure component spectra are available.…”

Section: Pure Contribution Of Species and Stoichiometric Analysismentioning

confidence: 76%

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Solute-induced perturbation of methanol–water association

et al. 2015

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This article addresses experimental evidence of changes in the equilibrium constant of methanol-water association induced by solutes. The behavior of four solutes (solvatochromic dyes) in methanol-water binary mixtures is probed using augmentation of infrared and UV-Vis spectroscopy methods followed by multivariate analysis. In order to get more reliable concentration and spectral profiles, with fewer ambiguities, complementarity and coupling theorems have been utilized. A ternary system was resolved using multivariate analysis on the noted augmented data for each chemical probe. Resultant concentration profiles showed the unique behavior of each solute in the binary-solvent system. Therefore, an individual association constant for the formation of the methanol-water association was achieved for each solvatochromic probe. Indeed, different solutes can change the solvent-solvent interaction based on their hydrogen binding affinity. Diverse hydrogen binding affinities for different solutes were investigated using charge distribution analysis via molecular electrostatic potential (MEP) calculations as well as the atomic charge on the oxygen atoms. In addition, obtained spectral profiles of standard solvatochromic probes were used to calculate solvatochromic parameters of dipolarity/ polarizability and hydrogen-bonding basicity of three resolved components (i.e. methanol, water and methanol-water complex surrounded probes).

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Section: Pure Contribution Of Species and Stoichiometric Analysismentioning

confidence: 76%

“…[31][32][33] Whenever additional information on the pure component factors is available, it should be used in order to reduce the rotational ambiguity; see e.g. The number of signicant singular values indicates the number of independent components.…”

Section: Data Analysis Methodsmentioning

confidence: 99%

Solute-induced perturbation of methanol–water association

et al. 2015

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“…The pure component spectra of these species and the associated concentration profiles were extracted with an algorithm based on factor analysis. [38] Their relative concentrations during the reaction are shown in Figure 11.…”

Section: A C H T U N G T R E N N U N G Ammonium Hydrogen Undecacarbonmentioning

confidence: 99%

Photocatalytic Hydrogen Generation from Water with Iron Carbonyl Phosphine Complexes: Improved Water Reduction Catalysts and Mechanistic Insights

Gärtner

Boddien

Barsch

et al. 2011

Chemistry A European J

105

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An extended study of a novel visible-light-driven water reduction system containing an iridium photosensitizer, an in situ iron(0) phosphine water reduction catalyst (WRC), and triethylamine as sacrificial reductant is described. The influences of solvent composition, ligand, ligand-to-metal ratio, and pH were studied. The use of monodentate phosphine ligands led to improved activity of the WRC. By applying a WRC generated in situ from Fe(3) (CO)(12) and tris[3,5-bis(trifluoromethyl)phenyl]phosphine (P[C(6)H(3)(CF(3))(2)](3), Fe(3)(CO)(12)/PR(3)=1:1.5), a catalyst turnover number of more than 1500 was obtained, which constitutes the highest activity reported for any Fe WRC. The maximum incident photon to hydrogen efficiency obtained was 13.4% (440 nm). It is demonstrated that the evolved H(2) flow (0.23 mmol H(2) h(-1) mg(-1) Fe(3)(CO)(12)) is sufficient to be used in polymer electrolyte membrane fuel cells, which generate electricity directly from water with visible light. Mechanistic studies by NMR spectroscopy, in situ IR spectroscopy, and DFT calculations allow for an improved understanding of the mechanism. With respect to the Fe WRC, the complex [HNEt(3)](+)[HFe(3)(CO)(11)](-) was identified as the key intermediate during the catalytic cycle, which led to light-driven hydrogen generation from water.

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“…(2) The rows of A are scaled so that the coefficients of the linear combinations of each row of A with respect to the first right singular vector of D equals 1. For the singular value decomposition [16] of the spectroscopic data matrix D see [18] and Section 2.2. Theorem 2.2 in [9] proves that this coefficient is nonzero under a certain weak assumption on D. In the following, we call this f irst right singular vector scaling the FSV-scaling.…”

Section: The Row Sum Scaling and The First Singular Vector Scalingmentioning

confidence: 99%

On generalized Borgen plots. I: From convex to affine combinations and applications to spectral dataSpectra

Jürß

Sawall

Neymeyr

2015

Journal of Chemometrics

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In this work, the concept of generalized Borgen plots is introduced for spectral data, which are polluted by small negative entries. The analysis is not restricted to three-component systems but can be applied to general s-component systems. Generalized Borgen plots are identical to the classical Borgen plots for nonnegative data. The analysis in this work also bridges the gap between the different scalings (Borgen norms) used for AFS computations.The algorithmic procedure of generalized Borgen plots for three-component systems and its implementation in the FAC-PACK software are described in the second part of this paper.

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Pure component spectral recovery and constrained matrix factorizations: concepts and applications

Cited by 46 publications

References 14 publications

Solute-induced perturbation of methanol–water association

Solute-induced perturbation of methanol–water association

Photocatalytic Hydrogen Generation from Water with Iron Carbonyl Phosphine Complexes: Improved Water Reduction Catalysts and Mechanistic Insights

On generalized Borgen plots. I: From convex to affine combinations and applications to spectral dataSpectra

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