Arnulf Materny

Scope and limitations of principal component analysis of high resolution LC-TOF-MS data: the analysis of the chlorogenic acid fraction in green coffee beans as a case study

Within this contribution we have analysed aqueous methanolic extracts by LC-ESI-TOF-MS of a total of 38 green bean coffee samples, which vary in terms of coffee variety and processing conditions. The LC-MS data have been analysed by principal component analysis (PCA) using different PCA processing parameters using an unsupervised non-targeted approach as well as a knowledge-based targeted approach. Furthermore, different normalisation and scaling algorithms have been applied to the PCA dataset. The scope and limitation of the various PCA parameters are discussed with respect to the ability to differentiate between samples of different groups, including different coffee varieties (Arabica or Robusta coffee) or different processing parameters and with respect to the information content of the PCA analysis on a molecular level. We could show that while distinction between different groups of samples can be successfully carried out independent of PCA parameters employed, identifying molecular markers rationalising differentiation between sample groups varies significantly between PCA parameters and requires careful choice as well as critical evaluation.

Combined Labelled and Label-free SERS Probes for Triplex Three-dimensional Cellular Imaging

Cells are complex chemical systems, where the molecular composition at different cellular locations and specific intracellular chemical interactions determine the biological function. An in-situ nondestructive characterization of the complicated chemical processes (like e.g. apoptosis) is the goal of our study. Here, we present the results of simultaneous and three-dimensional imaging of double organelles (nucleus and membrane) in single HeLa cells by means of either labelled or label-free surface-enhanced Raman spectroscopy (SERS). This combination of imaging with and without labels is not possible when using fluorescence microscopy. The SERS technique is used for a stereoscopic description of the intrinsic chemical nature of nuclei and the precise localization of folate (FA) and luteinizing hormone-releasing hormone (LHRH) on the membrane under highly confocal conditions. We also report on the time-dependent changes of cell nuclei as well as membrane receptor proteins during apoptosis analyzed by statistical multivariate methods. The multiplex three-dimensional SERS imaging technique allows for both temporal (real time) and spatial (multiple organelles and molecules in three-dimensional space) live-cell imaging and therefore provides a new and attractive 2D/3D tracing method in biomedicine on subcellular level.

Facile and controlled synthesis of aligned WO3 nanorods and nanosheets as an efficient photocatalyst material

In this work, we have performed a facile and controlled synthesis of WO3 nanorods and sheets in different crystal phases (triclinic, orthorhombic and monoclinic) of WO3 using the sol-gel method. The detailed structures of the synthesized materials were examined by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and Raman spectroscopy measurements. The shapes and crystal phases of the WO3 nanostructures were found to be highly dependent on the calcination temperature. The variation in crystalline phases and shapes is modified the electronic structure of the samples, which causes a variation in the value of optical band gap. The value of the Raman line intensity ratio I264/I320 has been successfully used to identify the structural transition from the triclinic to the orthorhombic phase of WO3. The PL spectra of the synthesized products excited at wavelengths 380, 400, and 420nm exhibit intense emission peaks that cover the complete visible range (blue-green-red). The emission peaks at ~460 and ~486nm were caused by the near band-edge and band to band transition, respectively. The peaks in spectral range 500-600nm might be originated from the presence of oxygen vacancies lying within the energy band gap. The synthesized WO3 nanostructures showed improved photocatalytic activity for the photodegradation of MB dye. The enhanced photocatalytic activity of WO3 nanosheets compared to WO3 nanorods for photodegradation of methylene blue (MB) dye could be due to the shape of the nanostructured WO3. The sheet type of structure provides more active surface for the interaction of dye molecules compared to the rods, which results in a more efficient degradation of the dye molecules.

Tailoring of enhanced interfacial polarization in WO3 nanorods grown over reduced graphene oxide synthesized by a one-step hydrothermal method

In the present report, well-defined WO3 nanorods (NRs) and a rGO–WO3 composite were successfully synthesized using a one-pot hydrothermal method. The crystal phase, structural morphology, shape, and size of the as-synthesized samples were studied using X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements. The optical properties of the synthesized samples were investigated by Raman, ultraviolet-visible (UV-Vis) and photoluminescence (PL) spectroscopy. Raman spectroscopy and TEM results validate the formation of WO3 (NRs) on the rGO sheet. The value of the dielectric constant (e′) of WO3 NRs and rGO–WO3 composite is decreased with an increase in frequency. At low frequency (2.5 to 3.5 Hz), the value of e′ for the rGO–WO3 composite is greater than that of pure WO3 NRs. This could be due to the fact that the induced charges follow the ac signal. However, at higher frequency (3.4 to 6.0), the value of e′ for the rGO–WO3 composite is less compared to that of the pure WO3 NRs. The overall decrease in the value of e′ could be due to the occurrence of a polarization process at the interface of the rGO sheet and WO3 NRs. Enhanced interfacial polarization in the rGO–WO3 composite is observed, which may be attributed to the presence of polar functional groups on the rGO sheet. These functional groups trap charge carriers at the interface, resulting in an enhancement of the interfacial polarization. The value of the dielectric modulus is also calculated to further confirm this enhancement. The values of the ac conductivity of the WO3 NRs and rGO–WO3 composite were calculated as a function of the frequency. The greater value of the ac conductivity in the rGO–WO3 composite compared to that of the WO3 NRs confirms the restoration of the sp2 network during the in situ synthesis of the rGO–WO3 composite, which is well supported by the results obtained by Raman spectroscopy.

Controlled synthesis and magnetic properties of monodispersed ceria nanoparticles

In the present study, monodispersed CeO2 nanoparticles (NPs) of size 8.5 ± 1.0, 11.4 ± 1.0 and 15.4 ± 1.0 nm were synthesized using the sol-gel method. Size-dependent structural, optical and magnetic properties of as-prepared samples were investigated by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), high resolution transmission electron microscopy (HR-TEM), ultra-violet visible (UV-VIS) spectroscopy, Raman spectroscopy and vibrating sample magnetometer (VSM) measurements. The value of optical band gap is calculated for each particle size. The decrease in the value of optical band gap with increase of particle size may be attributed to the quantum confinement, which causes to produce localized states created by the oxygen vacancies due to the conversion of Ce4+ into Ce3+ at higher calcination temperature. The Raman spectra showed a peak at ∼461 cm-1 for the particle size 8.5 nm, which is attributed to the 1LO phonon mode. The shift in the Raman peak could be due to lattice ...

Raman Spectroscopic Characterization of the Interlayer Structure of Na+-Montmorillonite Clay Modified by Ditetradecyl Dimethyl Ammonium Bromide

Raman spectroscopy has been applied for the rapid and nondestructive monitoring of the interlayer structure of sodium montmorillonite (MMT) clay modified by ditetradecyl dimethyl ammonium (DDA+) bromide. This work demonstrates that a detailed analysis of Raman spectra in the fingerprint region (600-1600 cm(-1)), in combination with model simulation, allows one to distinguish different conformational states of DDA+ in the interlayer space of the modified clay, namely, a liquidlike state but rich in trans conformers, disordered conformational states, and a crystallike conformation appearing at increasing modifier content. These conformations differ in the angle between their alkyl chains, the relative content of trans and gauche conformers and the relative length of trans segments. The shape and width of the Raman band at 1300 cm(-1) and the peak intensity ratio I1088/I1064 can be used for a qualitative analysis of the ratio of gauche/trans conformers. The integral intensity ratios I*1064/I*1300 and I*1300/I*705 help to determine the proportion of trans conformers and the content of the modifier in the clay, respectively, thereof providing quantitative characterization of the modified clay (conformational reorganization and modifier content). Noteworthy, the transition from a liquidlike to crystal-like conformation is further supported by the splitting of the symmetric C-C stretching Raman band of the trans segments within the alkyl chains at 1133 cm(-1) (liquidlike conformation) into two modes at 1124 and 1135 cm(-1) corresponding to two parallel trans chains of nonequivalent lengths (crystal-like conformation).

Direct Determination of Unsaturation Level of Milk Fat Using Raman Spectroscopy

We have demonstrated the potential of visible Raman spectroscopy in combination with chemometric analysis as a fast and simple tool for the determination of the unsaturation level of milk fat. The Raman measurements have been performed directly on liquid milk and on fat extracted from liquid milk. The Raman spectra taken from the extracted fat showed a higher resolution. The spectra directly obtained from the milk samples had some fluorescence background but nevertheless yielded the desired information. For calibration purposes, the iodine value (IV) was determined in all cases in order to evaluate the unsaturation level of the investigated samples. Two separate calibration models have been constructed; one for the milk samples and the second one for the extracted fat. The accuracy of these calibration models was estimated using the root mean square error of calibration and validation (RMSE) and the coefficient of determination (R 2 ) between actual and predicted values.

Vibrational spectroscopy and density functional theory analysis of 3-O-caffeoylquinic acid.

Density functional theory (DFT) calculations are being performed to investigate the geometric, vibrational, and electronic properties of the chlorogenic acid isomer 3-CQA (1R,3R,4S,5R)-3-{[(2E)-3-(3,4-dihydroxyphenyl)prop-2-enoyl]oxy}-1,4,5-trihydroxycyclohexanecarboxylic acid), a major phenolic compound in coffee. DFT calculations with the 6-311G(d,p) basis set produce very good results. The electrostatic potential mapped onto an isodensity surface has been obtained. A natural bond orbital analysis (NBO) has been performed in order to study intramolecular bonding, interactions among bonds, and delocalization of unpaired electrons. HOMO-LUMO studies give insights into the interaction of the molecule with other species. The calculated HOMO and LUMO energies indicate that a charge transfer occurs within the molecule.

Investigation of molecular dynamics in β-carotene using femtosecond pump-FWM spectroscopy

We have carried out two different pump four-wave mixing experiments, combining an initial pump excitation and a subsequent four-wave mixing probe process, on the photosynthetic pigment β-carotene to reveal different aspects of its molecular dynamics after photoexcitation. Firstly, the pump degenerate four-wave mixing (pump -DFWM) technique, in which the DFWM is resonant with the S1- to Sn-transition of β-carotene, is used to monitor the events following excitation of the system. The transient shows a peculiar shape and is seen to depend on the energy of the initial pump pulse as well as on the concentration of the solute in the solvent. Secondly, pump coherent anti-Stokes Raman scattering (pump-CARS) is used to elucidate the excited state vibrational dynamics of β-carotene. This technique gives access to the dynamics of both ground and excited electronic states with vibrational selectivity.

Well-controlled in-situ growth of 2D WO 3 rectangular sheets on reduced graphene oxide with strong photocatalytic and antibacterial properties

Finding the materials, which help to control the water pollution caused by organic and bacterial pollutants is one of the challenging tasks for the scientific community. 2D sheets of WO3 and composite of WO3 and reduced graphene oxide (rGO) have been synthesized in a well-controlled way using a hydrothermal method. The as synthesized 2D sheet of WO3 and rGO-WO3 composite were characterized by various techniques. The 2D sheets of WO3 and rGO-WO3 composite are efficiently utilized for the photocatalytic degradation of methylene blue (MB) and Rhodamine B (RhB) dyes under sunlight. The rGO-WO3 composite reveals excellent photocatalytic degradation of RhB dye by degrading it upto 85% under sunlight. However, the MB dye was degraded by 32%. The greater degradation of RhB dye was explained in terms of the molecular electrostatic potential. We found that RhB has a more positive potential compared to MB dye where O2- and OH̊ radicals interact more strongly, resulting in a greater degradation of the RhB dye. The antibacterial activity of the 2D sheets of WO3 and rGO-WO3composite was also investigated on gram positive (B. subtilis) and gram negative (P. aeroginosa) microbes for the first time.