Oliver M. D. Lutz

Reproducible quantification of ethanol in gasoline via a customized mobile near-infrared spectrometer.

This work describes the modification of an InGaAs diode array detector equipped miniaturized near-infrared (NIR) spectrometer enabling the reliable quantification of ethanol blended gasoline. A transflectance measurement cell is presented, utilizing a thermoelectric cooling (TEC) appliance ensuring thermostatic measurement conditions and a gold-coated spherical mirror as a reflector superior to conventional Spectralon(®). In total, four measurement modes (Spectralon(®) reflector, gold reflector and either reflectors with employed TEC) are discussed, enabling a straightforward comparison of the results. The test-set validated multivariate partial least squares regression (PLSR) model of the measurement mode involving both gold mirror and TEC yielded an Rval(2) value of 0.997, a limit of detection (LOD) of 0.68% w/w, a limit of quantification (LOQ) of 2.04% w/w, a standard error of prediction (SEP) of 0.21% w/w and a ratio performance deviation (RPD) of 15.2 while utilizing a single latent variable (LV). The NIR band assignment in this work has been established by employing the vibrational self-consistent field second order perturbative treatment (PT2-VSCF) and the computationally derived absorption maxima are compared to the experimentally observed data.

Selective enrichment of phosphopeptides by a metal–organic framework

A metal–organic framework, consisting of Er(III) linked together by 1,4-phenylenediacetate, was synthesised by a one-pot reaction and successfully used as an affinity material for the selective capturing of phosphopeptides. An optimised protocol for loading, washing and elution was developed and the eluents were analysed via matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry. A standard protein digest (α-casein, β-casein and ovalbumin) as well as digested egg white proteins were used to test the efficiency and selectivity of the presented approach. 14 phosphopeptides could be recovered from the peptide mixture and in the case of digested egg-white, four phosphorylated peptides which could be assigned to ovalbumin were isolated. Ab initio calculations based on the affinities of various ligands to the material have provided reasonable explanations of the observed experimental properties.

A QMCF-MD investigation of the structure and dynamics of Ce4+ in aqueous solution.

A quantum-mechanical charge-field molecular dynamics simulation has been performed for a tetravalent Ce ion in aqueous solution. In this framework, the complete first and second hydration spheres are treated by ab initio quantum mechanics supplemented by an electrostatic embedding technique, making the construction of non-Coulombic solute-solvent potentials unnecessary. During the 10 ps of simulation time, the structural aspects of the solution were analyzed by various methods. Experimental results such as the mean Ce-O bond distance and the predicted first-shell coordination number were compared to the results obtained from the simulation resolving some ambiguities in the literature. The dynamics of the system were characterized by mean ligand residence times and frequency/force constant calculations. Furthermore, Ce-O and Ce-H angular radial distribution plots were employed, yielding deeper insight into the structural and dynamical aspects of the system.

Combined Ab Initio Computational and Infrared Spectroscopic Study of the cis- and trans-Bis(glycinato)copper(II) Complexes in Aqueous Environment

The cis- and trans-bis(glycinato)copper(II) complexes in aqueous solution have been investigated by means of a combined theoretical and experimental approach. The conducted quantum mechanical charge field molecular dynamics (QMCF-MD) studies, being the first quantum mechanical simulations of organometallic complexes by this method, yielded accurate structural details of the investigated isomers as well as novel dynamic data, which has successfully been confirmed and extended by subsequent mid-infrared measurements. The spectroscopic results, critically assessed by adjacent multivariate data analysis, indicate an isomeric stability at ambient conditions, vanishing at elevated temperatures.

Largely Reduced Grid Densities in a Vibrational Self-Consistent Field Treatment Do Not Significantly Impact the ResultingWavenumbers

Especially for larger molecules relevant to life sciences, vibrational self-consistent field (VSCF) calculations can become unmanageably demanding even when only first and second order potential coupling terms are considered. This paper investigates to what extent the grid density of the VSCF’s underlying potential energy surface can be reduced without sacrificing accuracy of the resulting wavenumbers. Including single-mode and pair contributions, a reduction to eight points per mode did not introduce a significant deviation but improved the computational efficiency by a factor of four. A mean unsigned deviation of 1.3% from the experiment could be maintained for the fifteen molecules under investigation and the approach was found to be applicable to rigid, semi-rigid and soft vibrational problems likewise. Deprotonated phosphoserine, stabilized by two intramolecular hydrogen bonds, was investigated as an exemplary application.

Erbium(III) in aqueous solution: an ab initio molecular dynamics study.

Structural and dynamical properties of the erbium(III) ion in water have been obtained by means of ab initio quantum mechanical charge field molecular dynamics (QMCF-MD) simulations for the ground state and an excited state. The quality of the simulations has been monitored by recording UV/vis and Raman spectra of dilute solutions of ErCl3 and Er(NO3)3 in water and by comparison with EXAFS data from literature. Slight deviations between these data can be mainly attributed to relativistic effects, which are not sufficiently considered by the methodological framework. In both simulations, a mixture of coordination numbers eight and nine and a ligand exchange on the picosecond range are observed. The strength of the Er-ligand bond is considerably lower than that of trivalent transition metal ions but higher than that for La(III) and Ce(III) in aqueous solution. The main difference between ground state and excited state is the ligand exchange rate of the first shell. The second hydration shell is stable in both cases but with significantly different properties.

A dissociative quantum mechanical/molecular mechanical molecular dynamics simulation and infrared experiments reveal characteristics of the strongly hydrolytic arsenic(III).

This work presents a hybrid ab initio quantum mechanical/molecular mechanical simulation at the RI-MP2 level of theory investigating the hydrolysis process of arsenic(III), ultimately leading to arsenous acid (H3AsO3). A newly implemented dissociative water model has been applied to treat the interactions in the classical region, which is capable of describing non-neutral water species such as hydroxide and oxonium ions. Three stages of hydrolysis have been observed during the simulation and besides profound dynamical considerations, detailed insights into structural changes and atomic partial charge shifts are presented. In particular, the geometrical properties of H-bonds involved in each of the three proton transfer events and subsequent proton hopping reactions are discussed. A Laguerre tessellation analysis has been employed to estimate the molecular volume of H3AsO3. Estimations of pKa values of the arsenic(III)-aquo-complexes have been obtained at the G4 and CBS-Q//B3 levels of theory using a thermodynamic cycle, whereas rate constants for the final hydrolysis step have been determined via reaction path optimization and transition state theory. Newly recorded Fourier transform infrared (FT-IR) spectroscopy measurements have been compared to power spectra obtained from the simulation data, confirming its quality. The simulation findings, as well as results from computational spectroscopic calculations utilizing the PT2-VSCF methodology, proved valuable for the interpretation of the experimental FT-IR data, elucidating the particularities of the strongly observed IR Raman noncoincidence effect.

Structure and dynamics of chromatographically relevant Fe(III)-chelates.

Immobilized metal ion affinity chromatography (IMAC) is an important chromatographic technique for biomolecules. In order to get a detailed understanding of the hydration of immobilized Fe(III), complexes of Fe(III) with methyl substituted iminodiacetate ([Fe(MSIDA)(H2O)3](+)) as well as with methyl substituted nitrilotriacetate ([Fe(MSNTA)(H2O)2]) were simulated in aqueous solutions with the quantum mechanical charge field molecular dynamics (QMCF MD) approach. The simulations were carried out at the Hartree-Fock (HF) level of theory, since cluster calculations at the HF, MP2, and B3LYP levels of theory showed that this method results in a good compromise between computational effort and accuracy. None of the coordinating water molecules were exchanged during the simulation period of 15 ps. The Fe-OH2O bond distances as well as the Fe-OH2O stretching motions differed among the coordinating water molecules, indicating different bond strengths. For the water molecules in the second hydration layer, mean residence times of 2.7 and 1.9 ps were obtained for [Fe(MSIDA)(H2O)3](+) and [Fe(MSNTA)(H2O)2], respectively. Furthermore, infrared measurements were carried out to characterize the most prominent bond features of aqueous Fe(III)-NTA and to discuss these results in conjunction with the computationally derived frequencies.

Vibrational spectroscopic methods for the overall quality analysis of washing powders

The aim of this study was to compare and evaluate the ability of near infrared- (NIR), Raman- and attenuated-total-reflection infrared (ATR-IR) spectroscopy as tools for the identification of washing powder brands as well as for an overall quantitative analysis of all ingredients of the analyzed laundry detergents. The laundry detergents used in this work were composed of 22 different ingredients. For this purpose, principal component analysis (PCA) cluster models and partial least-squares (PLS) regression models were developed and different data pre-processing algorithms such as standard-normal-variate (SNV), multiplicative scatter correction (MSC), first derivative BCAP (db1), second derivative smoothing (ds2), smoothing Savitzky Golay 9 points (sg9) as well as different normalization procedures such as normalization between 0 and 1 (n01), normalization unit length (nle) or normalization by closure (ncl) were applied to reduce the influence of systematic disturbances. The performance of the methods was evaluated by comparison of the number of principal components (PCs), regression coefficient (r), Bias, Standard error of prediction (SEP), ratio performance deviation (RPD) and range error ratio (RER) for each calibration model. For each of the 22 ingredients separate calibration models were developed. Raman spectroscopy was suitable for the analysis of only two ingredients (dye transfer inhibitor 1 and surfactant 6) and it was not possible to record all Raman spectra due to high fluorescence. NIR and ATR-IR are powerful methods to analyze washing detergents with low numbers of PCs being necessary, regression coefficients of only little below 1, small Biases and SEPs compared to the range and high RPDs and RERs.