Transistor elettrochimici organici per biosensoristica

I transistor elettrochimici a base organica (OECT) hanno attratto sempre maggior interesse e sono oggetto di molti studi dagli anni '70 no ai nostri giorni. Questo lavoro di tesi ha come oggetto la realizzazione e la caratterizzazione di OECT a base di poli(3,4-etilen-diossi-tiofene) complessato con l'acido stirensolfonico (PSS). Questi dispositivi sono stati costruiti utilizzando solamente semiconduttori organici come materiali conduttivi ovvero senza l'uso di metalli, quindi risultano essere biocompatibili, economici e di semplice realizzazione. Questo tipo di sensori presenta un elevata sensibilità agli analiti e necessita di un'elettronica di controllo molto più semplice rispetto a metodi elettrochimici tradizionali che utilizzano un potenziostato ed un elettrodo di riferimento. Sono state studiate diverse geometrie e spessori di polimero depositato per ottimizzare le condizioni di lavoro per avere alta sensibilità e guadagno in corrente attraverso l'uso di misure di corrente di drain in funzione del tempo con aggiunte successive di analita. Questi dispositivi sono stati utilizzati come sensori di analiti quali la dopamina, l'acido ascorbico e l'acido urico. Attraverso scansioni in transcaratteristica, si è studiata la risposta dei transistor relativa agli analiti ed attraverso lo studio della transconduttanza si è ottenuta una nuova metodologia di lavoro in grado di separare i contributi relativi ai vari composti. Inoltre, in questa modalità, è stato possibile ottenere una selettività dei sensori ai vari analiti, problema principale dell'utilizzo di transistor elettrochimici, ed attraverso la modulazione della velocità di scansione dello strumento, è stata ottenuta una risposta alla sola dopamina, analita di maggior interesse per applicazioni biosensoristiche. In conclusione si può affermare che questo tipo di dispositivo possiede ottime proprietà e caratteristiche per ulteriori studi e sviluppi in applicazioni reali.

PEDOT:PSS: un polimero conduttivo organico per lo studio dell'integrità del tessuto cellulare

Questa tesi si inserisce nel campo della Bioelettronica Organica con lo scopo di utilizzare dei transistor elettrochimici (OECT) organici basati sul polimero conduttivo PEDOT:PSS per rilevare l’integrità di un tessuto cellulare e come biosensori di analiti in soluzione. Nella prima parte dell’elaborato, si spiegano le proprietà ed il trasporto di carica dei polimeri coniugati concentrandosi sulle caratteristiche fisico chimiche del PEDOT:PSS, seguito da una trattazione analitica del principio di funzionamento di un OECT. La seconda parte, si concentra sul lavoro sperimentale partendo da una descrizione dei processi di fabbricazione degli OECT, dei metodi di caratterizzazione utilizzati e della progettazione del set-up sperimentale per permettere le misure elettriche nell’incubatore cellulare. In seguito, viene dimostrato l’uso di un OECT completamente a base di PEDOT:PSS come sensore di un neurotrasmettitore (dopamina). In parallelo, il lavoro si è concentrato sull’ottimizzazione dei transistor in termini di formulazione di PEDOT:PSS e di geometria del dispositivo per ottenere tempi di spegnimento veloci compatibili con le risposte cellulari (<300ms). In fase di preparazione alle misure con le cellule si è valutato la funzionalità dell’OECT nelle condizioni di coltura cellulare dimostrando una buona stabilità dei dispositivi. Inoltre, sono stati progettati degli studi di simulazione tramite una membrana porosa per prevedere le risposte dei transistor in presenza di un tessuto cellulare. Partendo dall’esito positivo dei test preliminari, il lavoro si è concluso con il primo esperimento con le cellule tumorali HeLa, in cui si è monitorata la crescita cellulare con immagini ottiche correlate alle misure elettriche. I primi risultati confermano la biocompatibilità dei dispositivi e una risposta elettrica degli OECTs alla presenza delle cellule, aprendo la possibilità di utilizzare questi dispositivi per futuri esperimenti anche con diversi tipi di cellule.

The PSS : From Flat Maps to Layered Perspectives - the contribution of the Airport Metropolis Planning Support System (PSS) to sub-regional planning in the Brisbane Airport case environment

Conventional planning and decision making, with its sectoral and territorial emphasis and flat-map based processes are no longer adequate or appropriate for the increased complexity confronting airport/city interfaces. These crowed and often contested governance spaces demand a more iterative and relational planning and decision-making approach. Emergent GIS based planning and decision-making tools provide a mechanism which integrate and visually display an array of complex data, frameworks and scenarios/expectations, often in ‘real time’ computations. In so doing, these mechanisms provide a common ground for decision making and facilitate a more ‘joined-up’ approach to airport/city planning. This paper analyses the contribution of the Airport Metropolis Planning Support System (PSS) to sub-regional planning in the Brisbane Airport case environment.

Planar silver nanowire, carbon nanotube and PEDOT:PSS nanocomposite transparent electrodes

Highly conductive, transparent and flexible planar electrodes were fabricated using interwoven silver nanowires and single-walled carbon nanotubes (AgNW:SWCNT) in a PEDOT:PSS matrix via an epoxy transfer method from a silicon template. The planar electrodes achieved a sheet resistance of 6.6 ± 0.0 Ω/squ and an average transmission of 86% between 400 and 800 nm. A high figure of merit of 367 Ω−1 is reported for the electrodes, which is much higher than that measured for indium tin oxide and reported for other AgNW composites. The AgNW:SWCNT:PEDOT:PSS electrode was used to fabricate low temperature (annealing free) devices demonstrating their potential to function with a range of organic semiconducting polymer:fullerene bulk heterojunction blend systems.

Viemärin päässä Kotkan kaupunki : Vesiensuojelun kehitys Kymijoen itäisen päähaaran suulla 1945-1970

The focus of this thesis is the marine environmental history of the eastern part and the estuary of the Kymi river from 1945 to 1970. There is no previous research on this area from an environmentally historical perspective, nor have many of the sources here discussed been previously used. Therefore the thesis expands academic understanding of local environmental processes and protection in and around the city of Kotka and the Kymi river. The thesis falls within the methodological field of socio-political history, as the research focus is centered on the local process of establishing the nature of environmental problems and solving them. The principal assumption has been that the city of Kotka, due to its ongoing expansion, was slow to respond to environmental hazards. The Kymi river was among the most degraded bodies of water during this period. Kotka on the other hand was a major center of wood processing industry and one of Finlands major industrial ports. In the past the river and its estuary had provided ample resources for fishers. It is this contradictory use of the environment that allows one to discuss the local struggle for the correct use of the environment. Primary sources include local and city archives, environmental studies, and legal documents linked with the above. The archives of the city of Kotka and of various private associations form the core sources. Environmental studies from the research period have been dealt with as sources to the local political power struggle. Alongside with current environmental research they also provide insight into the state of the environment. Another goals has been to accumulate environmental research for a future multidisciplinary study in this area. As a final conclusion it can be said that environmental degradation was widely understood as a problem only in the 1960s. The influential role of the city of Kotka however determined the pace with which these problems were then solved.

Hydrothermal synthesis of CdTe QDs: Their luminescence quenching in the presence of bio-molecules and observation of bistable memory effect in CdTe QD/PEDOT:PSS heterostructure

We report one-pot hydrothermal synthesis of nearly mono-disperse 3-mercaptopropionic acid capped water-soluble cadmium telluride (CdTe) quantum dots (QDs) using an air stable Te source. The optical and electrical characteristics were also studied here. It was shown that the hydrothermal synthesis could be tuned to synthesize nano structures of uniform size close to nanometers. The emissions of the CdTe QDs thus synthesized were in the range of 500-700 nm by varying the duration of synthesis. The full width at half maximum (FWHM) of the emission peaks is relatively narrow (40-90 nm), which indicates a nearly uniform distribution of QD size. The structural and optical properties of the QDs were characterized by transmission electron microscopy (TEM), photoluminescence (PL) and Ultraviolet-visible (UV-Vis) spectroscopy. The photoluminescence quenching of CdTe QDs in the presence of L-cysteine and DNA confirms its biocompatibility and its utility for biosensing applications. The room temperature current-voltage characteristics of QD film on ITO coated glass substrate show an electrically induced switching between states with high and low conductivities. The phenomenon is explained on the basis of charge confinement in quantum dots. (C) 2011 Elsevier B.V. All rights reserved.

A novel approach for Tuning of minimum performance robust PSS using Genetic algorithm

This paper presents a novel approach for designing a fixed gain robust power system stabilizer (PSS) with particu lar emphasis on achieving a minimum closed loop perfor mance, over a wide range of operating and system condi tion. The minimum performance requirements of the con troller has been decided apriori and obtained by using a genetic algorithm (GA) based power system stabilizer. The proposed PSS is robust to changes in the plant parameters brought about due to changes in system and operating con dition, guaranteeing a minimum performance. The efficacy of the proposed method has been tested on a multimachine system. The proposed method of tuning the PSS is an at tractive alternative to conventional fixed gain stabilizer de sign, as it retains the simplicity of the conventional PSS and still guarantees a robust acceptable performance over a wider range of operating and system condition.

Salinity measurements and use of the Practical Salinity Scale (PSS)

Salinity, temperature and pressure are parameters which govern the oceanographic state of a marine water body and together they make up density of seawater. In this contribution we will focus our interest on one of these parameters, the salinity: accuracy in relation to different purposes as well as observation technique and instrumentation. We will also discuss the definition of salinity. For example most of the Indian Ocean waters are within the salinity range from 34.60-34.80, which emphasize the importance of careful observations and clear definitions of salinity, in such a way that it is possible to define water masses and predict their movements. In coastal waters the salinity usually features much larger variation in time and space and thus less accuracy is sometimes needed. Salinity has been measured and defined in several ways over the past century. While early measurements were based on the amount of salt in a sea water sample, today the salinity of seawater is most often determined from its conductivity. As conductivity is a function of salinity and temperature, determination involves also measurement of the density of seawater is now more precisely estimated and thus the temperature. As a result of this method the Practical Salinity Scale (PSS) was developed. The best determination of salinity from conductivity and the temperature measurements gives salinity with resolution of 0.001 psu, while the accuracy of titration method was about ± 0.02‰. Because of that, even calculation of movements in the ocean is also improved.

How PEDOT:PSS solutions produce satellite-free inkjets

Satellite droplets are unwanted in inkjet printing and various approaches have been suggested for their reduction. Low jetting speeds limit applications of the process. Added surfactants for wetting and conductivity enhancement may help but dynamic surface tension effects may counteract improvements. A higher fluid viscosity delays ligament break-up, but also leads to slower jets, while viscoelasticity reduces satellite formation only in certain cases. We show here that aqueous solutions of PEDOT:PSS (1:2.5 by weight) are strongly shear-thinning. They exhibit low viscosity within the printing nozzle over a wide range of jet speeds, yet rapidly (<100 μs) recover a higher viscosity at the low shear rates applicable once the jet has formed, which give the benefit of delayed satellite formation. The delay over a 0.8 mm stand-off distance can be sufficient to completely suppress satellites, which is significant for many printing applications. © 2012 Elsevier B.V. All rights reserved.

Substrate treatment and drying conditions effect on the properties of roll-to-roll gravure printed PEDOT:PSS thin films

The optical, structural and electrical properties of poly(3,4- ethylenedioxythiophene):poly(4-styrenesulfonic acid) (PEDOT:PSS) thin films printed by roll-to-roll gravure have been investigated. Corona treatment has been applied to enhance the adhesion of PEDOT:PSS on PolyEthylene Terephthalate (PET) web. It has been found that there was a stronger in-depth surface modification of PET with the increase of corona efficiency; however, the adhesion of PEDOT:PSS was not actually affected. Also, Spectroscopic Ellipsometry and Atomic Force Microscopy have been used to extract information on the mechanisms that define PEDOT:PSS properties. The increase of the drying temperature of the PEDOT:PSS films has been found to reduce the remaining water inside the films and lead to the decrease of the PEDOT:PSS particles size. © 2011 Elsevier B.V. All rights reserved.

Picosecond laser patterning of PEDOT:PSS thin films

Picosecond pulsed laser (10.4 ps, 1064 nm, 5 and 50 kHz) patterning studies were performed, of PEDOT:PSS thin films of varying thickness deposited by spin coating on glass substrates, by ablating the films or by changing locally by laser irradiation the optical and electrical properties of the polymer. From a detailed observation of the morphology of single pulse ablated holes on the surfaces of the films, in combination with simple calculations, it is concluded that photomechanical ablation is the likely ablation mechanism of the films. The single pulse ablation thresholds were measured equal to 0.13-0.18 J/cm 2 for films with thicknesses in the region of ∼100-600 nm. The implications on ablation line patterning of the films using different fluences, scanning speeds and pulse repetition rates, were investigated systematically. Laser irradiation of the films before ablation induces a metal-insulator transition of the polymer because of the formation of charge localization due to a possible creation of molecular disorder in the polymer and shortening of its conjugation length. © 2010 Elsevier B.V. All rights reserved.

Electropolymerized poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) film on ITO glass and its application in photovoltaic device

Poly(3,4-ethylenedioxythiopliene):poly(styrene sulfonate) (PEDOT:PSS) films have been electrochemically polymerized in situ on ITO glass substrate in boron trifluoride diethyl etherate electrolyte (BFEE). Cyclic voltammograms show good redox activity and stability of the PEDOT films. These films had been directly used to fabricate organic-inorganic hybrid solar cells with the structure of ITO/PEDOT/ZnO:MDMC-PPV/Al. The solar cells made of electrochemically polymerized films exhibit higher energy conversion efficiencies compared with that prepared by the spin-coating method, and the highest value is 0.33%. This in-situ electropolymerized method effectively simplifies fabricating procedures and may blaze a facile and economical route for producing high-efficiency solar cells.