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Institute
- Institut für Chemie (212) (remove)
Langmuir polymers films (LPFs) frequently form non-equilibrium states which are manifested in a decay of the surface pressure with time when the system is allowed to relax. Monitoring and manipulating the temporal evolution of these relaxations experimentally helps to shed light on the associated molecular reorganization processes. We present a systematic study based on different compression protocols and show how these reorganization processes impact the morphology of LPFs of poly(gamma-benzyl-L-glutamate) (PBLG); visualized by means of atomic force microscopy. Upon continuous compression, a fibrillar morphology was formed with a surface decorated by squeezed-out islands. By contrast, stepwise compression promoted the formation of a fibrillar network with a bimodal distribution of fibril diameters, caused by merging of fibrils. Finally, isobaric compression induced in-plane compaction of the monolayer. We correlate these morphological observations with the kinetics of the corresponding relaxations, described best by a sum of two exponential functions with different time scales representing two molecular processes. We discuss the observed kinetics and the resulting morphologies in the context of nucleation and growth, characteristic for first-order phase transitions. Our results demonstrate that the preparation conditions of LPFs have tremendous impact on ordering of the molecules and hence various macroscopic properties of such films.
The reaction mechanism for the rapid formation of a triplet oxygen atom, O(P-3), from a pair of triplet-state hydroxyl radicals in liquid water is explored utilizing extensive Car-Parrinello MD simulations and advanced visualization techniques. The local solvation structures, the evolution of atomic charges, atomic separations, spin densities, electron localization functions, and frontier molecular orbitals, as well as free energy profiles, evidence that the reaction proceeds through a hybrid (hydrogen atom transfer and electron proton transfer) and hemibond-assisted reaction mechanism. A benchmarking study utilizing high-level ab initio calculations to examine the interactions of a hydroxyl radical pair in the gas phase and the influence of a hemibonded water is also provided. The results presented here should serve as a foundation for further experimental and theoretical studies aimed at better understanding the role and potential applications of the triplet oxygen atom as a potent reactive oxygen species.
Dual responsive inverse opal hydrogels were designed as autonomous sensor systems for (bio)macromolecules, exploiting the analyte-induced modulation of the opal's structural color. The systems that are based on oligo(ethylene glycol) macromonomers additionally incorporate comonomers with various recognition units. They combine a coil-to-globule collapse transition of the LCST type with sensitivity of the transition temperature toward molecular recognition processes. This enables the specific detection of macromolecular analytes, such as glycopolymers and proteins, by simple optical methods. While the inverse opal structure assists the effective diffusion even of large analytes into the photonic crystal, the stimulus responsiveness gives rise to strong shifts of the optical Bragg peak of more than 100nm upon analyte binding at a given temperature. The systems' design provides a versatile platform for the development of easy-to-use, fast, and low-cost sensors for pathogens.
A synthetic pathway is described to construct thermoresponsive freestanding nanomembranes at the aqueous-air interface of a pendant drop. Dynamic control of the reaction kinetics allows formation of viscoelastic interfaces supporting anisotropic stresses and mechanical stability, which can be tuned by external stimuli.
cis-Diamminedichloroplatinum(II) (Cisplatin) is one of the most important and frequently used cytostatic drugs for the treatment of various solid tumors. Herein, a laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method incorporating a fast and simple sample preparation protocol was developed for the elemental mapping of Cisplatin in the model organism Caenorhabditis elegans (C. elegans). The method allows imaging of the spatially-resolved elemental distribution of platinum in the whole organism with respect to the anatomic structure in L4 stage worms at a lateral resolution of 5 μm. In addition, a dose- and time-dependent Cisplatin uptake was corroborated quantitatively by a total reflection X-ray fluorescence spectroscopy (TXRF) method, and the elemental mapping indicated that Cisplatin is located in the intestine and in the head of the worms. Better understanding of the distribution of Cisplatin in this well-established model organism will be instrumental in deciphering Cisplatin toxicity and pharmacokinetics. Since the cytostatic effect of Cisplatin is based on binding the DNA by forming intra- and interstrand crosslinks, the response of poly(ADP-ribose)metabolism enzyme 1 (pme-1) deletion mutants to Cisplatin was also examined. Loss of pme-1, which is the C. elegans ortholog of human poly(ADP-ribose) polymerase 1 (PARP-1) led to disturbed DNA damage response. With respect to survival and brood size, pme-1 deletion mutants were more sensitive to Cisplatin as compared to wildtype worms, while Cisplatin uptake was indistinguishable.
cis-Diamminedichloroplatinum(II) (Cisplatin) is one of the most important and frequently used cytostatic drugs for the treatment of various solid tumors. Herein, a laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method incorporating a fast and simple sample preparation protocol was developed for the elemental mapping of Cisplatin in the model organism Caenorhabditis elegans (C. elegans). The method allows imaging of the spatially-resolved elemental distribution of platinum in the whole organism with respect to the anatomic structure in L4 stage worms at a lateral resolution of 5 μm. In addition, a dose- and time-dependent Cisplatin uptake was corroborated quantitatively by a total reflection X-ray fluorescence spectroscopy (TXRF) method, and the elemental mapping indicated that Cisplatin is located in the intestine and in the head of the worms. Better understanding of the distribution of Cisplatin in this well-established model organism will be instrumental in deciphering Cisplatin toxicity and pharmacokinetics. Since the cytostatic effect of Cisplatin is based on binding the DNA by forming intra- and interstrand crosslinks, the response of poly(ADP-ribose)metabolism enzyme 1 (pme-1) deletion mutants to Cisplatin was also examined. Loss of pme-1, which is the C. elegans ortholog of human poly(ADP-ribose) polymerase 1 (PARP-1) led to disturbed DNA damage response. With respect to survival and brood size, pme-1 deletion mutants were more sensitive to Cisplatin as compared to wildtype worms, while Cisplatin uptake was indistinguishable.
In this work, gold nanostars (AuNSs) with size around 90 nm were prepared through an easy one-step method. They show excellent catalytic activity and large surface-enhanced Raman scattering (SERS) activity at the same time. Surprisingly, they exhibited different catalytic performance on the reduction of aromatic nitro compounds with different substituents on the para position. To understand such a difference, the SERS spectra were recorded, showing that the molecular orientation of reactants on the gold surface were different. We anticipate that this research will help to understand the relationship of the molecular orientation with the catalytic activity of gold nanoparticles.
L-selectin is a protein with potential importance for numerous diseases and clinical disorders. In this paper, we present a new aptamer-based luminescent assay developed to detect L-selectin. The sensing system working principle is based on Forster Resonance Energy Transfer (FRET) from a donor terbium complex (TbC) to an acceptor cyanine dye (Cy5). In the present approach, the biotinylated aptamer is combined with Cy5-labelled streptavidin (Cy5-Strep) to yield an aptamer-based acceptor construct (Apta-Cy5-Strep), while L-selectin is conjugated using luminescent TbC. Upon aptamer binding to the TbC-labelled L-selectin (L-selectin-TbC), permanent donor-acceptor proximity is established which allows for radiationless energy transfer to occur. However, when unlabelled L-selectin is added, it competes with the L-selectin-TbC and the FRET signal decreases as the L-selectin concentration increases. FRET from the TbC to Cy5 was observed with time-gated time-resolved luminescence spectroscopy. A significant change in the corrected luminescence signal was observed in the dynamic range of 10 -500 ng/mL L-selectin, the concentration range relevant for accelerated cognitive decline of Alzheimer's disease, with a limit of detection (LOD) equal to 10 ng/mL. The aptasensor-based assay is homogeneous and can be realized within one hour. Therefore, this method has the potential to become an alternative to tedious heterogeneous analytical methods, e.g. based on enzyme-linked immunosorbent assay (ELISA). (C) 2015 Elsevier B.V. All rights reserved.
What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer–surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density sc—defining the adsorption–desorption transition—are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of sc for the concave interfaces versus the Debye screening length 1/k and the extent of confinement a for these three interfaces for small ka values. For large ka the critical adsorption condition approaches the known planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness a is of the order of 1/k. We also rationalize how sc(k) dependence gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length for critical adsorption—the effect often hard to tackle theoretically—putting an emphasis on polymers inside attractive spherical cavities. The applications of our findings to some biological systems are discussed, for instance the adsorption of nucleic acids onto the inner surfaces of cylindrical and spherical viral capsids.
What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer–surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density sc—defining the adsorption–desorption transition—are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of sc for the concave interfaces versus the Debye screening length 1/k and the extent of confinement a for these three interfaces for small ka values. For large ka the critical adsorption condition approaches the known planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness a is of the order of 1/k. We also rationalize how sc(k) dependence gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length for critical adsorption—the effect often hard to tackle theoretically—putting an emphasis on polymers inside attractive spherical cavities. The applications of our findings to some biological systems are discussed, for instance the adsorption of nucleic acids onto the inner surfaces of cylindrical and spherical viral capsids.
The polymer architecture of telechelic or associative polymers has a large impact on the bridging of self-assembled structures. This Work presents: the phase behavior, small angle neutron scattering (SANS), dynamic light scattering (DLS), and fluorescence correlation spectroscopy (FCS) of a nonionic oil-in-water (O/W) microemulsion with hydrophobically end-capped multiarm polymers With functionalities f = 2, 3, and 4. For high polymer concentrations and large average interdroplet distance relative to the end-to-end distance of the polymer, d/R-ee; the system phase separates into a dense, highly connected droplet network phase, in equilibrium with a dilute phase. The extent of the two-phase region is larger for polymers With similar length but higher f. The Interaction potential between the droplets in the presence of polymer has both a repulsive and an attractive contribution as a result of the counterbalancing effects of the exclusion by polymer chains and bridging between droplets. This study experimentally demonstrates that higher polymer functionalities induce a stronger attractive force between droplets, which is responsible for a more extended phase separation region., and correlate with lower Collective droplet diffusivities and higher amplitude of the second relaxation time in DLS. The viscosity and the droplet self-diffusion obtained from FCS, however, are dominated by the end-capped chain concentration.
Organosilanes are used routinely to functionalize various support materials for further modifications. Nevertheless, reliable quantitative information about surface functional group densities after layer formation is rarely available. Here, we present the analysis of thin organic nanolayers made from nitrogen containing silane molecules on naturally oxidized silicon wafers with reference-free total reflection X-ray fluorescence (TXR.F) and X-ray photoelectron spectroscopy (XPS). An areic density of 2-4 silane molecules per nm(2) was calculated from the layer's nitrogen mass deposition per area unit obtained by reference-free TXRF. Complementary energy and angle-resolved XPS (ER/AR-XPS) in the Si 2p core-level region was used to analyze the outermost surface region of the organic (silane layer)-inorganic (silicon wafer) interface. Different coexisting silicon species as silicon, native silicon oxide, and silane were identified and quantified. As a result of the presented proof-of-concept, absolute and traceable values for the areic density of silanes containing nitrogen as intrinsic marker are obtained by calibration of the XPS methods with reference-free TXRF. Furthermore, ER/AR-XPS is shown to facilitate the determination of areic densities in (mono)layers made from silanes having no heteroatomic marker other than silicon. After calibration with reference-free TXRF, these areic densities of silane molecules can be determined when using the XPS component intensity of the silane's silicon atom.
X-ray photoelectron spectroscopy (XPS) is a powerful tool for probing the local chemical environment of atoms near surfaces. When applied to soft matter, such as polymers, XPS spectra are frequently shifted and broadened due to thermal atom motion and by interchain interactions. We present a combined quantum mechanical QM/molecular dynamics (MD) simulation of X-ray photoelectron spectra of polyvinyl alcohol (PVA) using oligomer models in order to account for and quantify these effects on the XPS (C1s) signal. In our study, molecular dynamics at finite temperature were performed with a classical forcefield and by ab initio MD (AIMD) using the Car-Parrinello method. Snapshots along, the trajectories represent possible conformers and/or neighbouring environments, with different C1s ionization potentials for individual C atoms leading to broadened XPS peaks. The latter are determined by Delta-Kohn Sham calculations. We also examine the experimental practice of gauging XPS (C1s) signals of alkylic C-atoms in C-containing polymers to the C1s signal of polyethylene.
We find that (i) the experimental XPS (C1s) spectra of PVA (position and width) can be roughly represented by single-strand models, (ii) interchain interactions lead to red-shifts of the XPS peaks by about 0.6 eV, and (iii) AIMD simulations match the findings from classical MD semi-quantitatively. Further, (iv) the gauging procedure of XPS (C1s) signals to the values of PE, introduces errors of about 0.5 eV. (C) 2014 Elsevier B.V. All rights reserved.
Bright or dark immune complexes of anti-TAMRA antibodies for adapted fluorescence-based bioanalysis
(2015)
Fluorescence labels, for example fluorescein or rhodamin derivatives, are widely used in bioanalysis applications including lateral-flow assays, PCR, and fluorescence microscopy. Depending on the layout of the particular application, fluorescence quenching or enhancement may be desired as the detection principle. Especially for multiplexed applications or high-brightness requirements, a tunable fluorescence probe can be beneficial. The alterations in the photophysics of rhodamine derivatives upon binding to two different anti-TAMRA antibodies were investigated by absorption and fluorescence-spectroscopy techniques, especially determining the fluorescence decay time and steady-state and time-resolved fluorescence anisotropy. Two monoclonal anti-TAMRA antibodies were generated by the hybridoma technique. Although surface-plasmon-resonance measurements clearly proved the high affinity of both antibodies towards 5-TAMRA, the observed effects on the fluorescence of rhodamine derivatives were very different. Depending on the anti-TAMRA antibody either a strong fluorescence quenching (G71-DC7) or a distinct fluorescence enhancement (G71-BE11) upon formation of the immune complex was observed. Additional rhodamine derivatives were used to gain further information on the binding interaction. The data reveal that such haptens as 5-TAMRA could generate different paratopes with equal binding affinities but different binding interactions, which provide the opportunity to adapt bioanalysis methods including immunoassays for optimized detection principles for the same hapten depending on the specific requirements.
Ziel dieser Arbeit war die Synthese und Charakterisierung von neuartigen fluoreszierenden Copolymeren zur Analytdetektion in wässrigen Systemen. Das Detektionssystem sollte ein einfaches Schalten der Fluoreszenz bei Analytbindung „Aus“ bzw. Verdrängung „An“ ermöglichen. Dafür wurde die Synthese eines funktionalisierten Monomers so geplant, dass sich Fluorophor und Analyt innerhalb derselben Monomereinheit in direkter Nachbarschaft zueinander befinden. So sollten bei Erkennung des Analyten durch eine mit einem Fluoreszenzlöscher funktionalisierte Erkennungsstruktur Fluorophor und Löscher in einen vorgegebenen Abstand zueinander gezwungen und die Fluoreszenz des Fluorophors effizient gelöscht werden. Bei anschließender Verdrängung der Erkennungseinheit durch einen stärker bindenden Analyten sollte die Fluoreszenz wieder „angeschaltet“ werden. Eine weitere Zielstellung für das Detektionssystem war eine hohe Löslichkeit und Fluoreszenzintensität in Wasser. Da die Anwendung solcher Sensoren besonders in der Medizin und Biologie, z.B. für Schnellerkennungstest von Pathogenen, von Interesse ist, ist die Kompatibilität mit wässrigen Medien essentiell. Die funktionalisierten Monomere wurden frei radikalisch mit N Vinyl-pyrrolidon bzw. N Vinyl¬caprolactam zu wasserlöslichen, fluoreszierenden Copolymeren umgesetzt. In den N-Vinyl¬pyrrolidon-Polymeren (PNVP) wurde RhodaminB, in den thermoresponsiven N Vinyl¬caprolactam-Polymeren (PNVCL) ein Naphthalsäureimid als Fluorophor verwendet. Während Rhodamine eine hohe Fluoreszenzintensität, gute Quantenausbeuten und hohen Extinktionskoeffizienten in Wasser zeigen, sind Naphthalsäure¬imide umgebungssensitive Chromophore, die bei Änderung ihrer Lösungsmittelumgebung, wie z.B. beim Kollaps eines thermoresponsiven Polymers in Wasser, ihre Fluoreszenzintensität und Quantenausbeute drastisch ändern können. Der Vorteil der hier verwendeten Strategie der Monomersynthese liegt darin, dass bei jeder spezifischen Analytdetektion durch eine Erkennungseinheit die Fluoreszenz effizient gelöscht bzw. bei Verdrängung durch einen stärker bindenden Analyten wieder „angeschaltet“ wird. Dieses Prinzip wird bereits vielfach in der Biologie in sogenannten „Molecular Beacons“ ausgenutzt, wobei ein Fluorophor und ein Löscher durch spezifische DNA Basenpaarung in einen vorgegebenen Abstand zueinander gezwungen werden und so ein „Schalten“ der Fluoreszenz ermöglichen. Aufgrund der vorgegebenen Struktur der DNA Basensequenzen ist es jedoch nicht direkt auf andere Erkennungsreaktionen übertragbar. Daher wurde ein Modellsystem entwickelt, welches die Möglichkeit bietet Analyt, Erkennungseinheit und Signalgeber variabel, je nach Anforderungen des Systems, auszutauschen. So soll es möglich sein, den Sensor a priori für jede Erkennungs¬reaktion zu verwenden. Als Modell Bindungs¬paare wurden ß Cyclodextrin/Adamantan und Con¬cana¬valinA/Mannose ausgewählt. Adamantan bzw. Mannose wurde als Analyt zusammen mit dem Fluorophor in das Polymer eingebunden. ß Cyclo¬dextrin (ß CD) bzw. ConcanavalinA (ConA) wurde als Erkennungsstruktur an einem Fluoreszenzlöscher immobilisiert. Polymer-basierte Fluoreszenzsensoren sind in der Fachliteratur gut dokumentiert. In der Regel sind Signalgeber und Analyt jedoch statistisch im Polymer verteilt, da sie sich entweder in unterschiedlichen Monomereinheiten befinden oder die Funktionalisierung durch eine polymeranaloge Umsetzung erfolgt. Der gewählte Ansatz Fluorophor und Analyt innerhalb derselben Monomereinheit einzubinden, soll bei jeder Erkennungsreaktion des Analyten zu einer Änderung der Signalintensität des Fluorophors führen. Eine hohe Signalintensität bei Analytdetektion ist wünschenswert, insbesondere für Erkennungsreaktionen, die mit möglichst geringem apparativem Aufwand, am besten mit dem bloßen Auge zu verfolgen sein sollen. Des Weiteren ist es möglich den Fluorophorgehalt im Polymer genau einzustellen und so Selbstlöschung zu vermeiden. Die synthetisierten Polymere haben einen Fluorophorgehalt von 0,01 mol% bis 0,5 mol%. Für die RhodaminB haltigen Polymere zeigte sich, dass ein Fluorophorgehalt unterhalb 0,1 mol% im Polymer die höchsten Ausbeuten, Molmassen und Quantenausbeuten liefert. Für die Naphthalsäureimid haltigen Polymere hingegen wurden auch für einen Fluorophorgehalt von bis zu 1 mol% hohe Ausbeuten und Molmassen erreicht. Die Naphthalsäureimid haltigen Polymere haben jedoch in wässriger Lösungsmittelumgebung nur geringe Quantenausbeuten. Als Fluoreszenzlöscher wurden Goldnanopartikel synthetisiert, die mit den entsprechenden Erkennungsstrukturen (ß-CD oder ConA) für den verwendeten Analyten funktionalisiert wurden. Goldnanopartikel als Löscher bieten den Vorteil, dass ihre Dispergierbarkeit in einem Lösemittel durch Funktionalisierung ihrer Hülle gezielt gesteuert werden kann. Durch die hohe Affinität von Goldnanopartikeln zu Thiolen und Aminen konnten sie mit Hilfe einfacher Syntheseschritte mit Thio ß CD Derivaten bzw. ConA funktionalisiert werden. In der hier vorgelegten Arbeit sollte ein Modellsystem für einen solches fluoreszenz-basiertes Detektionssystem in Wasser entwickelt werden. Nachfolgend werden die zu erfüllenden strukturellen Voraussetzungen für die Synthese eines solchen Sensors nochmals zusammengefasst:
1. Verwendung eines Fluorophors, der eine hohe Signalintensität zeigt.
2. Analyt bzw. Erkennungseinheit soll sich im Abstand von wenigen Nanometern zum Signalgeber befinden, um bei jeder Detektionsreaktion die Signalintensität des Signalgebers beeinflussen zu können.
3. Die Detektionseinheit benötigt eine funktionelle Gruppe zur Immobilisierung. Immobilisierung kann z.B. durch Einbindung in ein Polymer erfolgen.
4. Der Fluorophor soll bei Änderung seiner lokalen Umgebung, durch Binden eines Löschers oder Änderung seiner Lösemittelumgebung seine Fluoreszenzeigenschaften drastisch ändern.
5. Die Reaktion sollte schnell und mit möglichst geringem apparativem Aufwand, am besten mit bloßem Auge zu verfolgen sein.
Für das ß-CD/Adamantan Modellsystem wurde ein Fluoreszenz Aus/An Sensor entwickelt, der bei Binden ß CD funktionalisierter Goldnanopartikel an das polymergebundene Adamantan die Fluoreszenz des RhodaminB Fluorophors effizient löscht und bei Verdrängung der Goldnanopartikel wieder zurück gewinnt. Dies konnte auch mit bloßem Auge verfolgt werden.
Für die Naphthalsäureimid Monomere, die mit NVCL copolymerisiert wurden, wurde abhängig von der lokalen Umgebung des Fluorophors eine unterschiedliche Verstärkung der Fluoreszenzintensität bei Überschreiten des Trübungspunktes des Polymers gefunden. Dabei zeigte sich, dass die Einführung eines Abstandshalters zwischen Polymerrückgrat und Fluorophor zu einer großen Fluoreszenz¬verstärkung führt, während sich ohne Abstandshalter die Fluoreszenzintensität bei Über¬schreiten des Trübungspunktes kaum ändert.
This study reports on the investigation of a thermoresponsive polymer as a thin film on electrodes and the influence of coupling a peptide and an antibody to the film. The utilized polymer from the class of poly(oligoethylene glycol)-methacrylate polymers (poly(OEGMA)) with carboxy functions containing side chains was synthesized and properly characterized in aqueous solutions. The dependence of the cloud point on the pH of the surrounding media is discussed. The responsive polymer was immobilized on gold electrodes as shown by electrochemical, quartz crystal microbalance (QCM), and atomic force microscopy (AFM) techniques. The temperature dependent behavior of the polymer covalently grafted to gold substrates is investigated using cyclic voltammetry (CV) in ferro-/ferricyanide solution. Significant changes in the slope of the temperature-dependence of the voltammetric peak current and the peak separation values clearly indicate the thermally induced conformational change on the surface. Finally, a biorecognition reaction between a short FLAG peptide (N-Asp-Tyr-Lys-Asp-Asp-Asp-Asp-Lys-C) covalently immobilized on the polymer interface and the corresponding IgG antibody was performed. The study shows that the responsiveness of the electrode is retained after peptide coupling and antibody binding, although the response is diminished.
Mimicking the binding epitopes of protein-protein interactions by using small peptides is important for generating modular biomimetic systems. A strategy is described for the design of such bioactive peptides without accessible structural data for the targeted interaction, and the effect of incorporating such adhesion peptides in complex biomaterial systems is demonstrated. The highly repetitive structure of decorin was analyzed to identify peptides that are representative of the inner and outer surface, and it was shown that only peptides based on the inner surface of decorin bind to collagen. The peptide with the highest binding affinity for collagenI, LHERHLNNN, served to slow down the diffusion of a conjugated dye in a collagen gel, while its dimer could physically crosslink collagen, thereby enhancing the elastic modulus of the gel by one order of magnitude. These results show the potential of the identified peptides for the design of biomaterials for applications in regenerative medicine.
Diese Arbeit befasst sich mit der ganzheitlichen Betrachtung der Fluideigenschaften eines unterpermischen Reservoirs am Geothermie Forschungsstandort Groß Schönebeck (GrSk) bei Reservoirbedingungen und im Betrieb der Geothermieanlage. Die Untersuchungen zur Fluidherkunft ergeben, dass es sich um ein konnates Wasser meteorischen Ursprungs ohne den Einfluss der darüberliegenden Zechsteinwässer handelt. Die Ionen und Isotopenverhältnisse im Formationswasser gelöster Komponenten in GrSk belegen einen gemeinsamen Genesepfad mit Wässern anderer Rotliegend-Reservoire des Nordostdeutschen Beckens (NEGB). Die Isotopenverhältnisse von ⁸⁷Sr/⁸⁶Sr ≈ 0,7158 und von δ³⁴SV CDT ≈ 4,1 ‰ des Sulfats weisen auf die Anreicherung des Fluids mit schweren Isotopen durch die Fluid Gestein-Wechselwirkung mit Vulkaniten und Rotliegend Sandsteinen des Unteren Perms hin.
Das im Formationswasser bei Reservoirbedingungen gelöste Gas (Gas/Wasser ≤ 2 bei STP) enthält Stickstoff (δ¹⁵NAir ≈ 0,6 ‰) und thermogenes Methan (δ¹³CV-PDB ≈ - 18 ‰) aus organischen Karbonablagerungen (Kerogen Typ - III Kohlen) hoher Reife. Die Isotopenverhältnisse der Edelgase belegen eine krustale Herkunft des Gasgemisches. Die berechnete Verweilzeit τ (⁴He) der Gase im Reservoir liegt zwischen 275 und 317 Ma und überschreitet damit bei gegebener Konzentration von Mutternukliden im Reservoirgestein das allgemein angenommene Zeitalter der Sedimentgruppe. Das lässt sich durch eine Zuwanderung von Gasen aus älteren Sedimentfolgen erklären.
Die Veränderungen der physikochemischen Fluidparameter während des Anlagenbetriebs sind hauptsächlich temperaturbedingt. Bei stabilen Produktionsbedingungen und einer Temperatur von ca. 100 °C stabilisieren sich auch die Fluideigenschaften. Bei In situ Bedingungen übertage beträgt die Dichte ρ = 1,1325 ± 0,0002 g ∙ mL⁻¹, das Redoxpotential Eh = -105,5 ± 1,3 mV und der pH = 6,61 ± 0,002. Die relative Zusammensetzung der Gasphase bei stabilen Produktionsbedingungen zeigt dagegen eine geringe Erhöhung des Stickstoffanteils sowie des Anteils der Kohlenwasserstoffe (Ethan, Propan, usw.) und Abnahme des relativen Methananteils im Laufe des Betriebs.
Die quantitative Untersuchung der sekundären mineralischen Ausfällungen im Fluid mittels sequentieller Extraktion zeigte, dass Schwermetalle als eine Hauptkomponente der Fluidfestphase größtenteils in Verbindung mit organischen Molekülen vorliegen. Experimente zum Einfluss organischer Verbindungen unterschiedlicher Substanzklassen auf eine Mobilisierung der Schwermetalle aus dem Reservoirgestein ergaben, dass die Verbindungen wie Fettsäuren und PAK (polyzyklische aromatische Kohlenwasserstoffe) die Freisetzung von Kupfer, Nickel, Chrom und Blei verhindern bzw. zu derer Immobilisierung beitragen. Im Gegensatz dazu wird die Mobilität von Zink in Anwesenheit von diesen Verbindungen erhöht. Niedermolekulare Monocarbonsäuren und stickstoffhaltige Heteroaromaten tragen, mit Ausnahme von Blei, zur Freisetzung bzw. Mobilisierung von Schwermetallen aus dem Reservoirgestein bei.
Die gewonnenen Erkenntnisse dieser Arbeit bestätigen das Risiko massiver Ausfällungen auf der kalten Seite der Geothermieanlage bei Inbetriebnahme des Kraftwerks, wenn keine an den Fluidchemismus angepassten Präventionsmethoden eingesetzt werden. Die Isotopenzusammensetzung der Fluidkomponenten sowie geringfügige Schwankungen der Gaszusammensetzung im kontinuierlichen Anlagenbetrieb lässt eine Kommunikation des unterpermischen Reservoirs mit dem darunter liegenden Oberkarbon vermuten, was eine nachträgliche Veränderung der Fluidzusammensetzung beim Dauerbetrieb der Anlage bedeuten kann.