2015, Alebrahim, M.A., Krafft, C., Popp, J., El-Khateeb, Mohammad Y.

The structure and chemical features of the human dentin enamel junction (DEJ) were characterized using Raman spectroscopic imaging. Slices were prepared from 10 German, and 10 Turkish teeth. Raman images were collected at 785 nm excitation and the average Raman spectra were calculated for analysis. Univariate and multivariate spectral analysis were applied for investigation. Raman images were obtained based on the intensity ratios of CH at 1450 cm-1 (matrix) to phosphate at 960 cm-1 (mineral), and carbonate to phosphate (1070/960) ratios. Different algorithms (HCA, K-means cluster and VCA) also used to study the DEJ. The obtained results showed that the width of DEJ is about 5 pm related to univariate method while it varies from 6 to 12 μm based on multivariate spectral technique. Both spectral analyses showed increasing in carbonate content inside the DEJ compared to the dentin, and the amide I (collagen) peak in dentin spectra is higher than DEJ spectra peak.

2014, Bohlender, C., Gläser, S., Klein, M., Weisser, J., Thein, S., Neugebauer, U., Popp, J., Wyrwa, R., Schiller, A.

The water insoluble and photoactive CO releasing molecule dimanganese decacarbonyl (CORM-1) has been non-covalently embedded into poly(l-lactide-co-d/ l-lactide) fibers via electrospinning to enable bioavailability and water accessibility of CORM-1. SEM images of the resulting hybrid non-wovens reveal a nanoporous fiber morphology. Slight CO release from the CORM-1 in the electrospinning process induces nanoporosity. IR spectra show the same set of carbonyl bands for the CORM-1 precursor and the non-woven. When the material was exposed to light (365-480 nm), CO release from the incorporated CORM-1 was measured via heterogeneous myoglobin assay, a portable CO electrode and an IR gas cuvette. The CO release rate was wavelength dependent. Irradiation at 365 nm resulted in four times faster release than at 480 nm. 3.4 μmol of CO per mg non-woven can be generated. Mouse fibroblast 3T3 cells were used to show that the hybrid material is non-toxic in the darkness and strongly photocytotoxic when light is applied.

2015, Stanca, S.E., Fritzsche, W., Dellith, J., Froehlich, F., Undisz, A., Deckert, V., Krafft, C., Popp, J.

Since ancient times, noble gold has continuously contributed to several aspects of life from medicine to electronics. It perpetually reveals its new features. We report the finding of a unique form of gold, reticular nanostructured gold (RNG), as an aqueous black colloid, for which we present a one-step synthesis. The reticules consist of gold crystals that interconnect to form compact strands. RNG exhibits high conductivity and low reflection and these features, coupled with the high specific surface area of the material, could prove valuable for applications in electronics and catalysis. Due to high absorption throughout the visible and infrared domain, RNG has the potential to be applied in the construction of sensitive solar cells or as a substrate for Raman spectroscopy.

2014, Meyer-Ilse, J., Bauroth, S., Bräutigam, M., Schmitt, M., Popp, J., Beckert, R., Rockstroh, N., Pilz, T.D., Monczak, K., Heinemann, F.W., Rau, S., Dietzek, B.

The photophysical properties of Ruthenium-bipyridine complexes bearing a bibenzimidazole ligand were investigated. The nitrogens on the bibenzimidazole-ligand were protected, by adding either a phenylene group or a 1,2-ethandiyl group, to remove the photophysical dependence of the complex on the protonation state of the bibenzimidazole ligand. This protection results in the bibenzimidazole ligand contributing to the MLCT transition, which is experimentally evidenced by (resonance) Raman scattering in concert with DFT calculations for a detailed mode assignment in the (resonance) Raman spectra.

2014, Zedler, L., Hager, M.D., Schubert, U.S., Harrington, M.J., Schmitt, M., Popp, J., Dietzek, B.

Self-healing materials are designed to heal damage caused by, for example, mechanical stress or aging such that the original functionality of the material is at least partially restored. Thus, self-healing materials hold great promise for prolonging the lifetime of machines, particularly those in remote locations, as well as in increasing the reliability and safety associated with functional materials in, for example, aeronautics applications. Recent material science applications of self-healing have led to an increased interest in the field and, consequently, the spectroscopic characterization of a wide range of self-healing materials with respect to their mechanical properties such as stress and strain resistance and elasticity was in the focus. However, the characterization of the chemical mechanisms underlying various self-healing processes locally within the damaged region of materials still presents a major challenge. This requires experimental techniques that work non-destructively in situ and are capable of revealing the chemical composition of a sample with sufficient spatial and temporal resolution without disturbing the healing process. Along these lines, vibrational spectroscopy and, in particular Raman spectroscopy, holds great promise, largely due to the high spatial resolution in the order of several hundreds of nanometers that can be obtained. This article aims to summarize the state of the art and prospective of Raman spectroscopy to contribute significant insights to the research on self-healing materials - in particular focusing on polymer and biopolymer materials.

2014, Schmälzlin, E., Moralejo, B., Rutowska, M., Monreal-Ibero, A., Sandin, C., Tarcea, N., Popp, J., Roth, M.M.

Until now, spatially resolved Raman Spectroscopy has required to scan a sample under investigation in a time-consuming step-by-step procedure. Here, we present a technique that allows the capture of an entire Raman image with only one single exposure. The Raman scattering arising from the sample was collected with a fiber-coupled high-performance astronomy spectrograph. The probe head consisting of an array of 20 × 20 multimode fibers was linked to the camera port of a microscope. To demonstrate the high potential of this new concept, Raman images of reference samples were recorded. Entire chemical maps were received without the need for a scanning procedure.

2014, Matthäus, C., Cicchi, R., Meyer, T., Lattermann, A., Schmitt, M., Romeike, B.F.M., Krafft, C., Dietzek, B., Brehm, B.R., Pavone, F.S., Popp, J.

Cardiovascular diseases in general and atherothrombosis as the most common of its individual disease entities is the leading cause of death in the developed countries. Therefore, visualization and characterization of inner arterial plaque composition is of vital diagnostic interest, especially for the early recognition of vulnerable plaques. Established clinical techniques provide valuable morphological information but cannot deliver information about the chemical composition of individual plaques. Therefore, spectroscopic imaging techniques have recently drawn considerable attention. Based on the spectroscopic properties of the individual plaque components, as for instance different types of lipids, the composition of atherosclerotic plaques can be analyzed qualitatively as well as quantitatively. Here, we compare the feasibility of multimodal nonlinear imaging combining two-photon fluorescence (TPF), coherent anti-Stokes Raman scattering (CARS) and second-harmonic generation (SHG) microscopy to contrast composition and morphology of lipid deposits against the surrounding matrix of connective tissue with diffraction limited spatial resolution. In this contribution, the spatial distribution of major constituents of the arterial wall and atherosclerotic plaques like elastin, collagen, triglycerides and cholesterol can be simultaneously visualized by a combination of nonlinear imaging methods, providing a powerful label-free complement to standard histopathological methods with great potential for in vivo application.

2014, Neugebauer, U., Kurz, C., Bocklitz, T., Berger, T., Velten, T., Clement, J.H., Krafft, C., Popp, J.

Circulating tumor cells (CTCs) from blood of cancer patients are valuable prognostic markers and enable monitoring responses to therapy. The extremely low number of CTCs makes their isolation and characterization a major technological challenge. For label-free cell identification a novel combination of Raman spectroscopy with a microhole array platform is described that is expected to support high-throughput and multiplex analyses. Raman spectra were registered from regularly arranged cells on the chip with low background noise from the silicon nitride chip membrane. A classification model was trained to distinguish leukocytes from myeloblasts (OCI-AML3) and breast cancer cells (MCF-7 and BT-20). The model was validated by Raman spectra of a mixed cell population. The high spectral quality, low destructivity and high classification accuracy suggests that this approach is promising for Raman activated cell sorting.

2015, Schröder, U.-Ch., Beleites, C., Assmann, C., Glaser, U., Hübner, U., Pfister, W., Fritzsche, W., Popp, J., Neugebauer, U.

Vancomycin resistant enterococci (VRE) constitute a challenging problem in health care institutions worldwide. Novel methods to rapidly identify resistances are highly required to ensure an early start of tailored therapy and to prevent further spread of the bacteria. Here, a spectroscopy-based rapid test is presented that reveals resistances of enterococci towards vancomycin within 3.5 hours. Without any specific knowledge on the strain, VRE can be recognized with high accuracy in two different enterococci species. By means of dielectrophoresis, bacteria are directly captured from dilute suspensions, making sample preparation very easy. Raman spectroscopic analysis of the trapped bacteria over a time span of two hours in absence and presence of antibiotics reveals characteristic differences in the molecular response of sensitive as well as resistant Enterococcus faecalis and Enterococcus faecium. Furthermore, the spectroscopic fingerprints provide an indication on the mechanisms of induced resistance in VRE.