Refine
Has Fulltext
- no (167) (remove)
Year of publication
- 2018 (167) (remove)
Document Type
- Article (140)
- Doctoral Thesis (13)
- Other (8)
- Review (5)
- Monograph/Edited Volume (1)
Keywords
- SERS (3)
- Through-space NMR shieldings (TSNMRS) (3)
- Conformational analysis (2)
- DBD dyes (2)
- DFT (2)
- DNA origami (2)
- Gas phase electron diffraction (2)
- Metabolomics (2)
- Molecular dynamics (2)
- biomarker (2)
Institute
- Institut für Chemie (167) (remove)
Hepcidin-25 was identified as themain iron regulator in the human body, and it by binds to the sole iron-exporter ferroportin. Studies showed that the N-terminus of hepcidin is responsible for this interaction, the same N-terminus that encompasses a small copper(II) binding site known as the ATCUN (amino-terminal Cu(II)- and Ni(II)-binding) motif. Interestingly, this copper-binding property is largely ignored in most papers dealing with hepcidin-25. In this context, detailed investigations of the complex formed between hepcidin-25 and copper could reveal insight into its biological role. The present work focuses on metal-bound hepcidin-25 that can be considered the biologically active form. The first part is devoted to the reversed-phase chromatographic separation of copper-bound and copper-free hepcidin-25 achieved by applying basic mobile phases containing 0.1% ammonia. Further, mass spectrometry (tandemmass spectrometry (MS/MS), high-resolutionmass spectrometry (HRMS)) and nuclear magnetic resonance (NMR) spectroscopy were employed to characterize the copper-peptide. Lastly, a three-dimensional (3D)model of hepcidin-25with bound copper(II) is presented. The identification of metal complexes and potential isoforms and isomers, from which the latter usually are left undetected by mass spectrometry, led to the conclusion that complementary analytical methods are needed to characterize a peptide calibrant or referencematerial comprehensively. Quantitative nuclear magnetic resonance (qNMR), inductively-coupled plasma mass spectrometry (ICP-MS), ion-mobility spectrometry (IMS) and chiral amino acid analysis (AAA) should be considered among others.
The thermoresponsive behavior of two diblock copolymers PS-b-PNIPAM and PS-b-PMDEGA, which both comprise a hydrophobic polystyrene (PS) block but different thermoresponsive blocks, also differing in length, poly(N-isopropylacrylamide) (PNIPAM) and poly(methoxy diethylene glycol acrylate) (PMDEGA), respectively, was comparatively investigated in a wide temperature range. Concentrated aqueous solutions containing 25 wt % polymer were studied by small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), and broadband dielectric spectroscopy (BDS). DSC measurements show that, during the demixing phase transition, the hydration number per oligo(ethylene glycol) side chain in the PS-b-PMDEGA solution decreases rather gradually, even up to 20 °C above the onset of the transition, i.e., the cloud point (CP). In contrast, the PS-b-PNIPAM solution exhibits an abrupt, stepwise dehydration behavior at its CP, indicated by the sharp, narrow endothermic peak. BDS measurements suggest that the organization of the expelled water during the phase transition and the subsequent evolution of the micellar aggregates are different for the two copolymers. In the PS-b-PMDEGA solution, the long-range charge transport process changes significantly at its CP and strong interfacial polarization processes appear, probably due to charge accumulation at the interfaces between the micellar aggregates and the aqueous medium. On the contrary, in the PS-b-PNIPAM solution, the phase transition has only a marginal effect on the long-range conduction process and is accompanied by a reduction in the high-frequency (1 MHz) dielectric permittivity, ε′. The latter effect is attributed to the reduced polarization strength of local chain modes due to an enhancement of intra- and interchain hydrogen bonds (HBs) in the polymer-rich phase during the water detaching process. Surprisingly, our BDS measurements indicate that prior to both the demixing and remixing processes the local chain mobility increases temporally. Our dielectric studies suggest that for PS-b-PNIPAM the water detaching process initiates a few degrees below CP and that the local chain mobility and intra- and/or interchain HBs of the PNIPAM blocks may control its thermoresponsive behavior. Dielectric “jump” experiments show that the kinetics of micellar aggregation in the PS-b-PMDEGA solution is slower than that in the PS-b-PNIPAM solution and is independent of the target temperature within the two-phase region. From the experimental point of view, it is shown that the dielectric susceptibility, especially, the dielectric permittivity, ε′, is a well-suited probe for monitoring both the reversible changes in the molecular dipolar bond polarizability and the long-range interfacial polarization at the phase transition.
The drimane sesquiterpenoids drimenin, cinnamolide, dendocarbin A, and polygodial were purified from the Canelo tree (Drimys winteri) and chemically characterized by spectroscopic methods. The pharmacological activity of these natural compounds were determined on hα4β2, hα3β4, and hα7 nicotinic acetylcholine receptors (AChRs) by Ca2+ influx measurements. The results established that drimane sesquiterpenoids inhibit AChRs with the following selectivity: hα4β2 > hα3β4 > hα7. In the case of hα4β2 AChRs, the following potency rank order was determined (IC50’s in μM): drimenin (0.97 ± 0.35) > cinnamolide (1.57 ± 0.36) > polygodial (62.5 ± 19.9) ≫ dendocarbin A (no activity). To determine putative structural features underlying the differences in inhibitory potency at hα4β2 AChRs, additional structure–activity relationship and molecular docking experiments were performed. The Ca2+ influx and structural results supported a noncompetitive mechanism of inhibition, where drimenin interacted with luminal and nonluminal (TMD-β2 intrasubunit) sites. The structure–activity relationship results, i.e., the lower the ligand polarity, the higher the inhibitory potency, supported the nonluminal interaction. Ligand binding to both sites might inhibit the hα4β2 AChR by a cooperative mechanism, as shown experimentally (nH > 1). Drimenin could be used as a molecular scaffold for the development of more potent inhibitors with higher selectivity for the hα4β2 AChR.
Fabrication of well-ordered porous silicon tubular structures using colloidal lithography and metal assisted chemical etching is reported. A continuous hexagonal hole/particle gold pattern was designed over monocrystalline silicon through deposition of polyNIPAM microspheres, followed by the surface decoration with gold nanoparticles and thermal treatment. An etching reaction with HF, ethanol and H2O2 dissolved the silicon in contact with the metal nanoparticles (NP), creating a porous tubular array in the "off-metal area". The morphological characterization revealed the formation of a cylindrical hollow porous tubular shape with external and internal diameter of approx. 900 nm and 400 nm respectively, though it can be tuned to other desired sizes by choosing an appropriate dimension for the microspheres. The porous morphology and optical properties were studied as a function of resistivity of silicon substrates. Compared to two different gold templates on cSi and nontubular porous pillar structures, porous silicon tubular framework revealed a maximum surface enhanced Raman scattering enhancement factor of 10(6) for the detection of 6-mercaptopurine (6-MP). Due to the large surface area available for any surface modification, open nanostructured platforms such as those studied here have potential applications in the field of reflection/photoluminescene and SERS based optical bio-/chemical sensors.
Mit einer ausgewogenen Stoffauswahl aus den Teilgebieten Chemische Thermodynamik, Reaktionskinetik und Elektrochemie wird der Leser an das Studium der Physikalischen Chemie herangeführt. Das Verständnis der Theorie wird durch zahlreiche Aufgabenstellungen und die Angabe ihrer Lösungswege erleichtert. Das Buch gibt dem Studenten darüber hinaus Anregungen für ausgewählte Experimente zu den behandelten Teilgebieten, mit denen sich ein Grundverständnis physikalisch-chemischer Zusammenhänge entwickeln lässt.
Metal-free entropy-driven disulfide metathesis polymerization of unsaturated L-cystine based macrocycles produces high-molar-mass heterofunctional poly(disulfide)s, i.e., poly(ester-disulfide-alkene) and poly(amide-disulfide-alkene); M-w(app) = 44-60 kDa, (sic) > 1.7. The polymerization is fast and reaches equilibrium within 1-5 minutes (monomer conversion 70-90%) in polar aprotic solvents such as N,N-dimethylacetamide, dimethylsulfoxide, or y-valerolactone. Thiol-terminated polymers are stable in bulk or when dissolved in weakly polar solvents, but rapidly depolymerize in dilute polar solution.
Nowadays, the role of trace elements (TE) is of growing interest because dyshomeostasis of selenium (Se), manganese (Mn), zinc (Zn), and copper (Cu) is supposed to be a risk factor for several diseases. Thereby, research focuses on identifying new biomarkers for the TE status to allow for a more reliable description of the individual TE and health status. This review mirrors a lack of well-defined, sensitive, and selective biomarkers and summarizes technical limitations to measure them. Thus, the capacity to assess the relationship between dietary TE intake, homeostasis, and health is restricted, which would otherwise provide the basis to define adequate intake levels of single TE in both healthy and diseased humans. Besides that, our knowledge is even more limited with respect to the real life situation of combined TE intake and putative interactions between single TE.
We report strong evidence of Berry phase effects in intense laser dissociation of D-2(+) molecules, manifested as Aharonov-Bohm-like oscillations in the photofragment angular distribution (PAD). Our calculations show that this interference pattern strongly depends on the parity of the diatom initial rotational state, (-1)(j). Indeed, the PAD local maxima (minima) observed in one case (j odd) correspond to local minima (maxima) in the other case (j even). Using simple topological arguments, we clearly show that such interference conversion is a direct signature of the Berry phase. The sole effect of the latter on the rovibrational wave function is a sign change of the relative phase between two interfering components, which wind in opposite senses around a light-induced conical intersection (LICI). Therefore, encirclement of the LICI leads to constructive (j odd) or destructive (j even) self-interference of the initial nuclear wavepacket in the dissociative limit. To corroborate our theoretical findings, we suggest an experiment of strong-field indirect dissociation of D-2(+) molecules, comparing the PAD of the ortho and para molecular species in directions nearly perpendicular to the laser polarization axis.
In this study, the apparent relationship between the transport process and the surface chemistry of the Calcium-Silicate Hydrate (CSH) phases was investigated. For this purpose, a method was developed to synthesize ultrathin CSH phases to be used as a model substrate with the specific modification of their structure by introducing europium (Eu(III)). The structural and chemical changes during this Eu(III)-doping were observed by means of infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and time-resolved laser fluorescence spectroscopy (TRLFS). These alterations of the CSH phases led to significant changes in the surface chemistry and consequently to considerable variations in the interaction with water, as evidenced by measurements of the contact angles on the modified model substrates. Our results provide the basis for a more profound molecular understanding of reactive transport processes in cement-based systems. Furthermore, these results broaden the perspective of improving the stability of cement-based materials, which are subjected to the impact of aggressive aqueous environments through targeted modifications of the CSH phases.
DBD fluorescent dyes have proven to be useful in numerous applications. To widen the range of biological applications, we propose three different types of DBD molecules that have been modified in such a way that DNA interaction becomes probable. After the successful synthesis of all three compounds, we tested their fluorescent properties and their DNA binding abilities. Two of the three probes exhibit an interaction with dsDNA with subsequent fluorescence enhancement. The determined binding constants of the two new DNA dyes are comparable to other minorgroove-binding dyes. Their large Stokes shifts and their long fluorescent lifetimes are outstanding features of these dyes.
Nanoparticles (NPs) are particles between 1 and 100 nanometers in size. They have attracted enormous research interests owing to their remarkable physicochemical properties and potential applications in the optics, catalysis, sensing, electronics, or optical devices. The thesis investigates systems of NPs attached to planar substrates.
In the first part of the results section of the thesis a new method is presented to immobilize NPs. In many NP applications a strong, persistent adhesion to substrates is a key requirement. Up to now this has been achieved with various methods, which are not always the optimum regarding adhesion strength or applicability. We propose a new method which uses capillarity to enhance the binding agents in the contact area between NP and substrate. The adhesion strength resulting from the new approach is investigated in detail and it is shown that the new approach is superior to older methods in several ways.
The following section presents the optical visualization of nano-sized objects through a combination of thin film surface distortion and interference enhanced optical reflection microscopy. It is a new, fast and non-destructive technique. It not only reveals the location of NPs as small as 20nm attached to planar surfaces and embedded in a molecularly thin liquid film. It also allows the measurement of the geometry of the surface distortion of the liquid film. Even for small NPs the meniscus reaches out for micrometers, which is the reason why the NPs produce such a pronounced optical footprint.
The nucleation and growth of individual bubbles is presented in chapter 5. Nucleation is a ubiquitous natural phenomenon and of great importance in numerous industrial processes. Typically it occurs on very small scales (nanometers) and it is of a random nature (thermodynamics of small systems). Up to now most experimental nucleation studies deal with a large number of individual nucleation processes to cope with its inherently statistical, spatio-temporal character. In contrast, in this thesis the individual O2-bubble formation from single localized platinum NP active site is studied experimentally. The bubble formation is initiated by the catalytic reaction of H2O2 on the Pt surface. It is studied how the bubble nucleation and growth depends on the NP size, the H2O2 concentration and the substrate surface properties. It is observed that in some cases the bubbles move laterally over the substrate surface, driven by the O2-production and the film ablation.
Multiblock-like amphiphilic polyurethanes constituted by poly(ethylene oxide) and biosourced betulin are designed for antifouling and synthesized by a convenient organocatalytic route comprising tandem chain-growth and step-growth polymerizations. The doping density of betulin (D-B) in the polymer chain structure is readily varied by a mixed-initiator strategy. The spin-coated polymer films exhibit unique nanophase separation and protein resistance behaviors. Higher D-B leads to enhanced surface hydrophobicity and, unexpectedly, improved protein resistance. It is found that the surface holds molecular-level heterogeneity when D-B is substantially high due to restricted phase separation; therefore, broad-spectrum protein resistance is achieved despite considerable surface hydrophobicity. As D-B decreases, the distance between adjacent betulin units increases so that hydrophobic nanodomains are formed, which provide enough landing areas for relatively small-sized proteins to adsorb on the surface.
What is the underlying diffusion process governing the spreading dynamics and search strategies employed by amoeboid cells? Based on the statistical analysis of experimental single-cell tracking data of the two-dimensional motion of the Dictyostelium discoideum amoeboid cells, we quantify their diffusive behaviour based on a number of standard and complementary statistical indicators. We compute the ensemble- and time-averaged mean-squared displacements (MSDs) of the diffusing amoebae cells and observe a pronounced spread of short-time diffusion coefficients and anomalous MSD-scaling exponents for individual cells. The distribution functions of the cell displacements, the long-tailed distribution of instantaneous speeds, and the velocity autocorrelations are also computed. In particular, we observe a systematic superdiffusive short-time behaviour for the ensemble- and time-averaged MSDs of the amoeboid cells. Also, a clear anti-correlation of scaling exponents and generalised diffusivity values for different cells is detected. Most significantly, we demonstrate that the distribution function of the cell displacements has a strongly non-Gaussian shape andusing a rescaled spatio-temporal variablethe cell-displacement data collapse onto a universal master curve. The current analysis of single-cell motions can be implemented for quantifying diffusive behaviours in other living-matter systems, in particular, when effects of active transport, non-Gaussian displacements, and heterogeneity of the population are involved in the dynamics.
DNA origami nanostructures provide a platform where dye molecules can be arranged with nanoscale accuracy allowing to assemble multiple fluorophores without dye-dye aggregation. Aiming to develop a bright and sensitive ratiometric sensor system, we systematically studied the optical properties of nanoarrays of dyes built on DNA origami platforms using a DNA template that provides a high versatility of label choice at minimum cost. The dyes are arranged at distances, at which they efficiently interact by Forster resonance energy transfer (FRET). To optimize array brightness, the FRET efficiencies between the donor fluorescein (FAM) and the acceptor cyanine 3 were determined for different sizes of the array and for different arrangements of the dye molecules within the array. By utilizing nanoarrays providing optimum FRET efficiency and brightness, we subsequently designed a ratiometric pH nanosensor using coumarin 343 as a pH-inert FRET donor and FAM as a pH responsive acceptor. Our results indicate that the sensitivity of a ratiometric sensor can be improved simply by arranging the dyes into a well-defined array. The dyes used here can be easily replaced by other analyte-responsive dyes, demonstrating the huge potential of DNA nanotechnology for light harvesting, signal enhancement, and sensing schemes in life sciences.
Here we present a self-made annular continuous-flow reactor that can be used in the UV/vis range in an internal numbering-up manner. As a model reaction, we chose a powerful batch-scale-limited benzoannelation method, namely, an intramolecular photodehydro-Diels-Alder (IMPDDA) reaction. The scale-up potential of this particular photochemical benchmark reaction toward the preparation of macrocylic (1,7)naphthalenophanes by variation of selected flow parameters is presented.
Sortase A (SrtA) from Staphylococcus aureus has been often used for ligating a protein with other natural or synthetic compounds in recent years. Here we show that SrtA-mediated ligation (SML) is universally applicable for the linkage of two purely artificial building blocks. Silica nanoparticles (NPs), poly(ethylene glycol) and poly(N-isopropyl acrylamide) are chosen as synthetic building blocks. As a proof of concept, NP-polymer, NP-NP, and polymer-polymer structures are formed by SrtA catalysis. Therefore, the building blocks are equipped with the recognition sequence needed for SrtA reaction-the conserved peptide LPETG-and a pentaglycine motif. The successful formation of the reaction products is shown by means of transmission electron microscopy (TEM), matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-ToF MS), and dynamic light scattering (DLS). The sortase catalyzed linkage of artificial building blocks sets the stage for the development of a new approach to link synthetic structures in cases where their synthesis by established chemical methods is complicated.
Stable covalently photo-cross-linked porous poly(ionic liquid) membrane with gradient pore size
(2018)
Porous polyelectrolyte membranes stable in a highly ionic environment are obtained by covalent crosslinking of an imidazolium-based poly(ionic liquid). The crosslinking reaction involves the UV light-induced thiol-ene (click) chemistry, and the phase separation, occurring during the crosslinking step, generates a fully interconnected porous structure in the membrane. The porosity is on the order of the micrometer scale and the membrane shows a gradient of pore size across the membrane cross-section. The membrane can separate polystyrene latex particles of different size and undergoes actuation in contact with acetone due to the asymmetric porous structure.
Boric acid and sodium borates are currently classified in the EU-CLP regulation as "toxic to reproduction" under "Category 1B", with hazard statement of H360FD. However, so far field studies on male reproduction in China and in Turkey could not confirm such boron-associated toxic effects. As validation by another independent study is still required, the present study has investigated possible boron-associated effects on male reproduction in workers (n = 212) under different boron exposure conditions. The mean daily boron exposure (DBE) and blood boron concentration of workers in the extreme exposure group (n = 98) were 47.17 +/- 17.47 (7.95-106.8) mg B/day and 570.6 +/- 160.1 (402.6-1100) ng B/g blood, respectively. Nevertheless, boron-associated adverse effects on semen parameters, as well as on FSH, LH and total testosterone levels were not seen, even within the extreme exposure group. With this study, a total body of evidence has accumulated that allows to conclude that male reproductive effects are not relevant to humans, under any feasible and realistic conditions of exposure to inorganic boron compounds.
Pump-probe near edge X-ray absorption fine structure (PP-NEXAFS) spectra of molecules offer insight into valence-excited states, even if optically dark. In PP-NEXAFS spectroscopy, the molecule is "pumped" by UV or visible light enforcing a valence excitation, followed by an X-ray "probe" exciting core electrons into (now) partially empty valence orbitals. Calculations of PP-NEXAFS have so far been done by costly, correlated wavefunction methods which are not easily applicable to medium-sized or large molecules. Here we propose an efficient, first principles method based on density functional theory in combination with the transition potential and Delta SCF methodology (TP-DFT/Delta SCF) to compute molecular ground state and PP-NEXAFS spectra. We apply the method to n ->pi* pump/O-K-edge NEXAFS probe spectroscopy of thymine (for which both experimental and other theoretical data exist) and to n -> pi* or pi -> pi* pump/N-K-edge NEXAFS probe spectroscopies of trans-and cis-azobenzene. Published by AIP Publishing.
The problem of atmospheric emission from OH molecules is a long standing problem for near-infrared astronomy. PRAXIS is a unique spectrograph which is fed by fibres that remove the OH background and is optimised specifically to benefit from OH-Suppression. The OH suppression is achieved with fibre Bragg gratings, which were tested successfully on the GNOSIS instrument. PRAXIS uses the same fibre Bragg gratings as GNOSIS in its first implementation, and will exploit new, cheaper and more efficient, multicore fibre Bragg gratings in the second implementation. The OH lines are suppressed by a factor of similar to 1000, and the expected increase in the signal-to-noise in the interline regions compared to GNOSIS is a factor of similar to 9 with the GNOSIS gratings and a factor of similar to 17 with the new gratings. PRAXIS will enable the full exploitation of OH suppression for the first time, which was not achieved by GNOSIS (a retrofit to an existing instrument that was not OH-Suppression optimised) due to high thermal emission, low spectrograph transmission and detector noise. PRAXIS has extremely low thermal emission, through the cooling of all significantly emitting parts, including the fore-optics, the fibre Bragg gratings, a long length of fibre, and the fibre slit, and an optical design that minimises leaks of thermal emission from outside the spectrograph. PRAXIS has low detector noise through the use of a Hawaii-2RG detector, and a high throughput through a efficient VPH based spectrograph. PRAXIS will determine the absolute level of the interline continuum and enable observations of individual objects via an IFU. In this paper we give a status update and report on acceptance tests.