Derivate des Ionentransporters Valinomycin

In der vorliegenden Arbeit wurden Derivate des Ionentransporters Valinomycin synthetisiert und als Sensorelemente in Modellmembransysteme inkorporiert. Als Modellmembranen wurden festkörpergestützte Lipiddoppelschichten (tBLMs, tethered bilayer lipid membranes) verwendet. rnValinomycin transportiert selektiv Kalium-Ionen durch Membranen, was durch einen Rückgang des Widerstandes über elektrochemische Messmethoden nachgewiesen werden kann. Es ist ein zyklisches Dodecadepsipeptid, das aus zwei verschiedenen Aminosäuren (L- und D-Valin) und  Hydroxysäuren (L Milchsäure und D Hydroxyisovaleriansäure) besteht. In dieser Arbeit wurde ein L Valin durch ein L-Lysin ausgetauscht, um eine freie Aminogruppe zum Anbinden verschiedenster Liganden zu erhalten. rnDie Synthese erfolgte in Lösung über einen linearen Decadepsipeptid-Precursor, hierbei wurde hauptsächlich mit Benzyl- und Boc-Schutzgruppen gearbeitet. An den Precursor wurden dann unterschiedlich modifizierte Lysin-Didepside gebunden und das daraus erhaltene lineare Dodecadepsipeptid zyklisiert.rnInsgesamt wurden sechs verschiedene Derivate synthetisiert, deren Ionentransportfähigkeit mit Hilfe eines angebundenen Liganden blockiert wurde. Diese Blockade kann entweder mechanisch durch Festhalten des Ionencarriers an der Oberfläche der Membran oder chemisch durch Einbringen einer Ladung erfolgen, da geladene Moleküle eine Membran nicht überwinden können. rnAcetyl-Lysin-Valinomycin wurde als Testsystem hergestellt, um zu zeigen, dass die Synthese einen funktionsfähigen Ionencarrier ergeben hatte. Im nächsten Schritt wurde Lysin-Valinomycin mit freier Aminogruppe synthetisiert, um es als pH-Sensor zu nutzen und damit zu überprüfen, ob das chemische Einbringen einer Ladung möglich ist. Es konnte ein pH abhängiger Kalium-Transport nachgewiesen werden, die Blockade der Ionentransportfähigkeit über eine eingebrachte Ladung ist somit möglich. rnAuf dem gleichen Konzept beruht Ferrocen-Valinomycin. Wird der Ferrocen-Ligand oxidiert, liegt eine positive Ladung vor und der Ionencarrier kann die Membran nicht mehr überwinden. Eine Reduktion macht diesen Prozess reversibel. Ferrocen-Valinomycin konnte innerhalb einer tBLM chemisch oxidiert und reduziert werden, dieses System kann somit als chemischer Redox-Sensor eingesetzt werden.rnEine mechanische Blockade liegt dem Biotin- und dem Sulfonamid-Valinomycin zugrunde. Dabei soll die Zugabe von Streptavidin bzw. BCA II (bovine Carboanhydrase) den Ionentransport durch die Membran stoppen. Beide Valinomycin-Derivate zeigten aber keine Ionentransportfähigkeit, eine Inkorporation in tBLMs konnte jedoch über SPR gezeigt werden. rnDie Synthese eines fluoreszenz-markierten (FITC) Valinomycins ergab zwar auch keinen transportfähigen Ionencarrier, aber mit diesem Derivat konnte der Diffusionskoeffizient von Valinomycin in sBLMs mit Hilfe von Fluorescence Recovery after photobleaching (FRAP) bestimmt werden.rn

Biomimese biologischer Membranen: Konzeptionierung, Synthese und biophysikalische Charakterisierung einer Hierarchie festkörpergestützter Mimikry biologischer Membranen

Im Rahmen dieser Arbeit wurden drei neue Modelle zur funktionellen Mimiese biologischer Membranen im Bereich der Bionanotechnologie entwickelt. Um den Rahmen der notwendigen Faktoren und Komponenten für biomimetische Membranmodelle abzustecken, wurde das biologische Vorbild im Bezug auf Zusammensetzung, Organisation und Funktion analysiert. Die daraus abgeleiteten Erkenntnisse erlauben das Erreichen von biologisch relevanten Membranwiderständen im Bereich von mehreren MOhm cm2 und eine gute lokale Fluidität. Ein weiteres Ziel dieser Arbeit war die Entwicklung einer Hierachie unterschiedlich stark von der Festkörperoberfläche entkoppelter Membranen zur Vergrößerung des submembranen Raumes. Diese Ziele konnten realisiert werden. Das auf archaealen Etherlipiden basierende DPTL-System wurde analog dem biologischen Vorbild stereoselektiv synthetisiert und ist in der Lage die Membran bei maximaler Elongation des TEG-Spacers mit mehr als 2 nm von der Oberfläche zu entkoppeln. Die erzielten Wiederstände liegen im hohen ein- bis zweistelligen MOhm-Bereich, die Kapazität entspricht mit 0,5 µF cm-2 ebenfalls dem Wert biologischer Membranen. Die Membraneigenschaften wurden mit Hilfe von SPS, EIS, IR-Spektroskopie, QCM, AFM und Kontaktwinkelmessungen charakterisiert. Die Funktionalität und lokale Fluidität der DPTL-Membran konnte anhand des Valinomycin vermittelten K+-Transports über die Membran gezeigt werden. Fluide Elektroden oder laterale Verdünnung mit TEGL erlauben den Einbau größerer Ionenkanäle. Lipo-Glycopolymere (LGP) mit unterschiedlichen Kettenlängen wurden mit Hilfe der kontrollierten radikalischen Polymerisation mit einer PD < 1.2 synthetisiert. Es zeigte sich, daß die Vororientierung der LGPs auf dem LB-Trog, gefolgt von einem LB-Übertrag auf einen funktionalisierten Träger mit photoreaktivem SAM, nach Belichten des Systems zu einer verlässlichen kovalenten Anbindung der supramolekularen LGP-Architektur führt. Da die Lipo-Glycopolymerketten am Glycopolymerterminus nur mit oberflächennahen Repetiereinheiten an die photoaktivierte Oberfläche binden, sind sie in der Lage Oberflächenrauhigkeiten des Festkörpersubstrates auszugleichen. Die photochemische Immobilisierung von funktionell orientierten supramolekularen LGP-Architekturen auf Goldoberflächen resultiert in tBLMs mit großen vertikalen Enkopplungen der Membran von der Festkörperoberfläche (>8 nm). Der funktionelle Ionentransport von Kaliumionen durch Valinomycin zeigt eine ausreichende lokale Fluidität der Membran die mit einem guten Membranwiderstand (mehrere MOhm) kombiniert ist. Große Membran-Oberflächenentkopplungen konnten mit Hilfe plasmapolymerisierter elektrophiler Polymere erreicht werden. Filmdicken von 50 nm sind mit homogener Oberfläche und Rauhigkeiten im Bereich von Nanometern möglich. Das System zeigt interessante fluide Eigenschaften mit guten Erholungsraten bei FRAP-Experimenten (Diffusionskonstanten von etwa 17 mikro m2 s-1). Die elektrischen Eigenschaften liegen mit Widerständen von wenigen kOhm unterhalb der für gute Membranmimikrie notwendigen Werte. Erstmalig konnte gezeigt werden, daß mit Hilfe dieser Methode inerte Polymere/Plastikträger (zum Beispiel Polypropylen und TOPAS) in effizienter Weise kovalent mit reaktiven Polymeroberflächen modifiziert werden können (Anwendung als DNA-Chip ist beschrieben).

Ihwg-μnir: A Miniaturised Near-infrared Gas Sensor Based On Substrate-integrated Hollow Waveguides Coupled To A Micro-nir-spectrophotometer.

A miniaturised gas analyser is described and evaluated based on the use of a substrate-integrated hollow waveguide (iHWG) coupled to a microsized near-infrared spectrophotometer comprising a linear variable filter and an array of InGaAs detectors. This gas sensing system was applied to analyse surrogate samples of natural fuel gas containing methane, ethane, propane and butane, quantified by using multivariate regression models based on partial least square (PLS) algorithms and Savitzky-Golay 1(st) derivative data preprocessing. The external validation of the obtained models reveals root mean square errors of prediction of 0.37, 0.36, 0.67 and 0.37% (v/v), for methane, ethane, propane and butane, respectively. The developed sensing system provides particularly rapid response times upon composition changes of the gaseous sample (approximately 2 s) due the minute volume of the iHWG-based measurement cell. The sensing system developed in this study is fully portable with a hand-held sized analyser footprint, and thus ideally suited for field analysis. Last but not least, the obtained results corroborate the potential of NIR-iHWG analysers for monitoring the quality of natural gas and petrochemical gaseous products.

Measuring air pressure with a polymeric gas sensor

In this communication we describe the application of a conductive polymer gas sensor as an air pressure sensor. The device consists of a thin doped poly(4'-hexyloxy-2,5-biphenylene ethylene) (PHBPE) film deposited on an interdigitated metallic electrode. The sensor is cheap, easy to fabricate, lasts for several months, and is suitable for measuring air pressures in the range between 100 and 700 mmHg.

Active waveguide effects from porous anodic alumina: An optical sensor proposition

We present in this paper an active waveguide effect observed in porous anodic alumina (PA), which can be applied in optical sensors. The spectral position, shape, and polarization effect of the narrow waveguide modes is described. An analytical test with a commercial pesticide was performed. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3447375]

Chromic materials for responsive surface-enhanced resonance Raman scattering systems: a nanometric pH sensor

The use of chromic materials for responsive surface-enhanced resonance Raman scattering (SERRS) based nanosensors is reported. The potential of nano-chromic SERRS is demonstrated with the use of the halochrome methyl yellow to fabricate an ultrasensitive pH optical sensor. Some of the challenges of the incorporation of chromic materials with metal nanostructures are addressed through the use of computational calculations and a comparison to measured SERRS and surface-enhanced Raman scattering (SERS) spectra is presented. A strong correlation between the measured SERRS and the medium's proton concentration is demonstrated for the pH range 2-6. The high sensitivity achieved by the use of resonance Raman conditions is shown through responsive SERRS measurements from only femtolitres of volume and with the concentration of the reporting molecules approaching the single molecule regime.

Flow injection analysis of paracetamol using a biomimetic sensor as a sensitive and selective amperometric detector

This work describes the coupling of a biomimetic sensor to a flow injection system for the sensitive determination of paracetamol. The sensor was prepared as previously described in the literature (M. D. P. T. Sotomayor, A. Sigoli, M. R. V. Lanza, A. A. Tanaka and L. T. Kubota, J. Braz. Chem. Soc., 2008, 19, 734) by modifying a glassy carbon electrode surface with a Nafion (R) membrane doped with iron tetrapyridinoporphyrazine (FeTPyPz), a biomimetic catalyst of the P450 enzyme. The performance of the sensor for paracetamol detection was investigated and optimized in a flow injection system (FIA) using a wall jet electrochemical cell. Under optimized conditions a wide linear response range (1.0 x 10(-5) to 5.0 x 10(-2) mol L(-1)) was obtained, with a sensitivity of 2579 (+/- 129) mu A L mu mol(-1). The detection and quantification limits of the sensor for paracetamol in the FIA system were 1.0 and 3.5 mu mol L(-1), respectively. The analytical frequency was 51 samples h(-1), and over a period of five days (320 determinations) the biosensor maintained practically the same response. The system was successfully applied to paracetamol quantification in seven pharmaceutical formulations and in water samples from six rivers in Sao Paulo State, Brazil.

Sensor arrays to detect humic substances and Cu(II) in waters

The interaction between poly(o-ethoxyaniline) (POEA) adsorbed onto solid substrates and humic substances (HS) and Cu(2+) ions has been investigated using UV-vis spectroscopy and atomic force microscopy (AFM). Both HS and Cu(2+) are able to dope POEA and change film morphology. This interaction was exploited in a sensor array made with nanostructured films of POEA, sulfonated lignin and HS, which could detect small concentrations of HS and Cu(2+) in water. (C) 2009 Elsevier B.V. All rights reserved.

Phase fraction distribution measurement of oil-water flow using a capacitance wire-mesh sensor

In this paper, a novel wire-mesh sensor based on permittivity (capacitance) measurements is applied to generate images of the phase fraction distribution and investigate the flow of viscous oil and water in a horizontal pipe. Phase fraction values were calculated from the raw data delivered by the wire-mesh sensor using different mixture permittivity models. Furthermore, these data were validated against quick-closing valve measurements. Investigated flow patterns were dispersion of oil in water (Do/w) and dispersion of oil in water and water in oil (Do/w&w/o). The Maxwell-Garnett mixing model is better suited for Dw/o and the logarithmic model for Do/w&w/o flow pattern. Images of the time-averaged cross-sectional oil fraction distribution along with axial slice images were used to visualize and disclose some details of the flow.

A survey on key management mechanisms for distributed Wireless Sensor Networks

Wireless Sensor Networks (WSNs) have a vast field of applications, including deployment in hostile environments. Thus, the adoption of security mechanisms is fundamental. However, the extremely constrained nature of sensors and the potentially dynamic behavior of WSNs hinder the use of key management mechanisms commonly applied in modern networks. For this reason, many lightweight key management solutions have been proposed to overcome these constraints. In this paper, we review the state of the art of these solutions and evaluate them based on metrics adequate for WSNs. We focus on pre-distribution schemes well-adapted for homogeneous networks (since this is a more general network organization), thus identifying generic features that can improve some of these metrics. We also discuss some challenges in the area and future research directions. (C) 2010 Elsevier B.V. All rights reserved.

Piezoresistive sensor design using topology optimization

Piezoresistive materials, materials whose resistivity properties change when subjected to mechanical stresses, are widely utilized in many industries as sensors, including pressure sensors, accelerometers, inclinometers, and load cells. Basic piezoresistive sensors consist of piezoresistive devices bonded to a flexible structure, such as a cantilever or a membrane, where the flexible structure transmits pressure, force, or inertial force due to acceleration, thereby causing a stress that changes the resistivity of the piezoresistive devices. By applying a voltage to a piezoresistive device, its resistivity can be measured and correlated with the amplitude of an applied pressure or force. The performance of a piezoresistive sensor is closely related to the design of its flexible structure. In this research, we propose a generic topology optimization formulation for the design of piezoresistive sensors where the primary aim is high response. First, the concept of topology optimization is briefly discussed. Next, design requirements are clarified, and corresponding objective functions and the optimization problem are formulated. An optimization algorithm is constructed based on these formulations. Finally, several design examples of piezoresistive sensors are presented to confirm the usefulness of the proposed method.

A sensor array based on mass and capacitance transducers for the detection of adulterated gasolines

The simultaneous use of different sensors technologies is an efficient method to increase the performance of chemical sensors systems. Among the available technologies, mass and capacitance transducers are particularly interesting because they can take advantage also from non-conductive sensing layers, such as most of the more interesting molecular recognition systems. In this paper, an array of quartz microbalance sensors is complemented by an array of capacitors obtained from a commercial biometrics fingerprints detector. The two sets of transducers, properly functionalized by sensitive molecular and polymeric films, are utilized for the estimation of adulteration in gasolines, and in particular to quantify the content of ethanol in gasolines, an application of importance for Brazilian market. Results indicate that the hybrid system outperforms the individual sensor arrays even if the quantification of ethanol in gasoline, due to the variability of gasolines formulation, is affected by a barely acceptable error. (C) 2009 Elsevier B.V. All rights reserved.

Ultra-thin films of alternating semi-interpenetrating layers of a conducting polymer with thermosetting phenolic resins for sensor application

In this work a new method for crosslinking ultra-thin films with potential applications in sensor systems is proposed. The films were produced by layer-by-layer (LbL) assembly using a conducting polymer, poly(o-ethoxyaniline) (POEA), alternated with a thermosetting resin, novolac-type phenolformaldehyde (PF), crosslinked by a simple thermal treatment. The PF resin served as both alternating and crosslinking agents. The films were characterized by Fourier transform infrared (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy, thermogravimetry (TG), desorption, doping/dedoping cycling and electrical measurements. The results showed that film architecture and crosslinking degree can be controlled by the conditions used for film deposition (number of bilayers, polymer concentration, pH, and deposition time), and crosslinking time. Moreover, this approach offers several advantages such as fast curing time and low cost, indicating that these films can be used to produce sensors with improved stability.

Porous silicon optical cavity structure applied to high sensitivity organic solvent sensor

The present work reports the thermal annealing process, the number of layer and electrochemical process effect in the optical response quality of Bragg and microcavity devices that were applied as organic solvent sensors. These devices have been obtained by using porous silicon (PS) technology. The optical characterization of the Bragg reflector, before annealing, showed a broad photonic band-gap structure with blue shifted and narrowed after annealing process. The electrochemical process used to obtain the PS-based device imposes the limit in the number of layers because of the chemical dissolution effect. The interface roughness minimizations in the devices have been achieved by using the double electrochemical cell setup. The microcavity devices showed to have a good sensibility for organic solvent detection. The thermal annealed device showed better sensibility feature and this result was attributed to passivation of the surface devices. (c) 2007 Elsevier Ltd. All rights reserved.

Hardware/firmware implementation of a soft sensor using an improved version of a fuzzy identification algorithm

This paper presents the design and implementation of an embedded soft sensor, i. e., a generic and autonomous hardware module, which can be applied to many complex plants, wherein a certain variable cannot be directly measured. It is implemented based on a fuzzy identification algorithm called ""Limited Rules"", employed to model continuous nonlinear processes. The fuzzy model has a Takagi-Sugeno-Kang structure and the premise parameters are defined based on the Fuzzy C-Means (FCM) clustering algorithm. The firmware contains the soft sensor and it runs online, estimating the target variable from other available variables. Tests have been performed using a simulated pH neutralization plant. The results of the embedded soft sensor have been considered satisfactory. A complete embedded inferential control system is also presented, including a soft sensor and a PID controller. (c) 2007, ISA. Published by Elsevier Ltd. All rights reserved.