Towards the development of adaptive nanostructured platforms

Since their discovery in 1977, intrinsically conducting polymers have been studies for applications such as electronic devices, sensors and actuators[1-3]. Polyaniline (PAni) is an example of a stable conducting polymer and can be classified as an ‘adaptive material’ in that it can be switched between two or more forms (each with their own distinct characteristics) using an external stimulus. In contrast to a classical metallic conductor or a polymeric insulator, PAni can be switched reversibly between an insulating emeraldine base form and a conducting emeraldine salt. More recently, interest has developed in the area of nanostructured polyaniline[4-6]. These one-dimensional objects combine the advantages of an organic conductor and a high surface area material, thus making them suitable for a diverse range of applications such as chemical sensors, flash memory and electro-optic devices[7-9]. Here we present how polyaniline nanofibres can be successfully functionalised with both amine and carboxylate groups. The modified nanofibres maintain their ability to switch between diffferent forms displaying distinctly different optical properties (as shown by Raman and UV-vis spectroscopy), thus making them suitable for adaptive sensing applications. The attachment of functional groups to polyaniline nanofibres provides a route for manipulating the surface chemistry of nanofibres. While interesting materials in themselves, these functionalised nanofibres are also attractive as molecular scaffolds for building yet more innovative derivatives that nonetheless retain the basic underlying nanostructure and intrinsic characteristics of PAni. That we have demonstrated the ability to regulate the extent of side-chain attachment to one-dimensional objects, in a safe and simple manner, represents a step forward in the area of adaptive nano-structured materials. Functionalisation can be controlled using a simple, scalable and inexpensive technique[10-11]. [1] C. O. Baker, B. Shedd, P. C. Innis, P. G. Whitten, G. M. Spinks, G. G. Wallace, R. B. Kaner, Adv Mater 20 (2008) 155-+. [2] W. R. Small, F. Masdarolomoor, G. G. Wallace, M. Panhuis, J Mater Chem 17 (2007) 4359-4361. [3] J. G. Roh, H. R. Hwang, J. B. Yu, J. O. Lim, J. S. Huh, Journal of Macromolecular Science-Pure and Applied Chemistry A39 (2002) 1095-1105. [4] J. X. Huang, R. B. Kaner, Chemical Communications (2006) 367-376. [5] N. R. Chiou, C. M. Lui, J. J. Guan, L. J. Lee, A. J. Epstein, Nat. Nanotechnol. 2 (2007) 354-357. [6] F. Masdarolomoor, P. C. Innis, S. Ashraf, R. B. Kaner, G. G. Wallace, Macromol. Rapid Commun. 27 (2006) 1995-2000. [7] S. Virji, J. X. Huang, R. B. Kaner, B. H. Weiller, Nano Lett. 4 (2004) 491-496. [8] S. Virji, R. B. Kaner, B. H. Weiller, J. Phys. Chem. B 110 (2006) 22266-22270. [9] S. Virji, R. B. Kaner, B. H. Weiller, Chemistry of Materials 17 (2005) 1256-1260. [10] E. Lahiff, T. Woods, W. Blau, G.G. Wallace, D. Diamond, Synth. Metals, accepted. [11] E. Lahiff, S. Bell, D. Diamond, Mat. Res. Soc. Symp. Proc., Vol. 1054, FF-05-05, 200

Development of new adaptive materials based on spiropyran molecular photoswitches

Spiropyrans are a family of photochromic compounds that can be reversibly switched between two states: a colourless, non-polar, uncharged spiro form (SP) and a highly coloured, polar, conjugated, zwitterionic merocyanine form (MC), i.e. SP → MC (UV light), MC → SP (green, white light). Furthermore, the MC form possesses a phenolate group that can reversibly bind metal ions and this ion binding is also photo-reversible, as when the MC-ion complex reverts to the passive SP form (upon green/white light exposure), it releases the bound ions. Using molecular-switches based on spiropyran-like molecules, new materials were produced whose properties such as metal-ion uptake/release and polarity can be controlled under external photonic stimulation. Spiropyran derivatives were immobilised on polystyrene and silica microbeads and evaluated for their reversible photoswitchable metal ion binding behaviour. When in the MC form, in the presence of metal ions such as Cu2+ and Zn2+, further spectral and colour changes occurred that were found to vary according which metal ion was bound. Subsequent irradiation with white light caused reformation of the SP form and release of the metal ion. This process was shown to be repeatable at least several times. The spiropyran functionalised silica microbeads were packed into a capillary column and the new stationary phase demonstrated to form the basis of a photodynamic system for retention, detection and release of metal ions pumped into the capillary. In parallel other spiropyran derivatives were incorporated into monolithic stationary phases. The spiropyran-functionalised polymer was switched between a protonated MC form and a neutral SP form upon white light irradiation. The monoliths were encased on a microfluidic chip and the system filled with an acid electrolyte. When a voltage was applied at the two ends of the encased monolith, electro-osmotic flow was generated and the flow rate shown to be variable upon white light exposure as a consequence of the formation of the SP form and the formation/disruption of the surface charge necessary for efficient electro-osmotic pumping. In this thesis the synthesis and the characterisation of these new materials is described and the switchable optical properties evaluated

Functionalised polyanaline nanofibers

Polyaniline (PAni) is a conducting polymer which switches between distinct states exhibiting dramatically different properties. The colour, conductivity and redox state of PAni all depend on the local chemical environment of the material. Consequently PAni has great potential for sensing applications. The nanostructured form of PAni is particularly interesting as it provides a very large surface-to-volume ratio that can lead to dramatic enhancement of sensor sensitivity and response time. In this work, we focus on derivatising polyaniline nanofibres. Using the technique described, carboxylate terminated side-chains can be covalently bound to solution based fibres

Schizophrenic molecules and materials with multiple personalities - how materials science could revolutionise how we do chemical sensing

Molecular photoswitches like spiropyrans derivatives offer exciting possibilities for the development of analytical platforms incorporating photo-responsive materials for functions such as light-activated guest uptake and release and optical reporting on status (passive form, free active form, guest bound to active form). In particular, these switchable materials hold tremendous promise for microflow-systems, in view of the fact that their behaviour can be controlled and interrogated remotely using light from LEDs, without the need for direct physical contact. We demonstrate the immobilisation of these materials on microbeads which can be incorporated into a microflow system to facilitate photoswitchable guest uptake and release. We also introduce novel hybrid materials based on spiropyrans derivatives grafted onto a polymer backbone which, in the presence of an ionic liquid, produces a gel-like material capable of significant photoactuation behaviour. We demonstrate how this material can be incorporated into microfluidic platforms to produce valve-like structures capable of controlling liquid movement using light

Beads, boats and switches: making things happen with molecular photoswitches

In this paper we present recent results obtained with a stimulus-responsive materials based on the photo-switchable behaviour exhibited by spiro-cyclic derivatives. Our results suggest that these highly novel materials offer unique capabilities hitherto inaccessible using conventional materials. In particular, we will focus on photocontrolled guest binding and release, inherent signalling of status, photo-actuation and solvent driven motion of small structures as examples of the fascinating behaviour of these exceptional materials

Spiropyran modified microfluidic chip channels for photonically controlled sensor array detection of metal ions

Microfluidic chips are particularly attractive for analytical purposes because they provide a convenient small platform for rapid analysis and detection.1 Furthermore, spiropyrans dyes can be used as photonically controlled, self-indicating molecular recognition agents for the fabrication of sensors.2 Here, we show how through integrating the beneficial characteristics of microfluidic devices and spiropyrans dyes, a simple and very innovative chip for on-line metal ion sensor array can be realised. The chip (4x3cm) consists of four independent 180m depth, polydimethylsiloxane (PDMS) channels. 1’-(3-Carboxypropyl)-3,3’-dimethyl-6-nitrospiro-[2H-1]-benzopyran-2,2’-indoline is covalently immobilised on the ozone plasma activated PDMS microchannel surfaces. Upon exposure to UV light, the transparent PDMS channels change to light purple colour because the spiropyran molecules of the surface undergo a heterocyclic ring cleavage that result in the formation of the highly conjugated merocyanine form. When stock solutions of several ion metals (Ca2+,Zn2+,Hg2+,Cu2+) are pumped independently through the four channels, different optical responses were observed for each metal. 1-L.Basabe-Desmonts et al. Anal.Bioanal.Chem.(2008)390:307–315. 2-R.J.Byrne et al. J.Mat.Chem.(2006)16:1332-1337

Análise das propriedades mecânicas de um solo da formação palermo estabilizado mecanicamente

Artigo submetido ao Curso de Engenharia Civil da UNESC - como requisito parcial para obtenção do Título de Engenheiro Civil.O presente trabalho tem por objetivo estabilizar mecanicamente, através da aplicação de diferentes energias de compactação (Proctor Normal, Intermediária e Modificada), um solo da Formação Palermo, a fim de utiliza-lo como subleito de uma rodovia. Para isto foram coletadas amostras às margens da Rod. Antônio Just, que foram submetidas a ensaios de caracterização química, mineralógica, física (granulometria por peneiramento, Limite de Liquidez - LL e Limite de Plasticidade - LP) e mecânica (compactação, Índice de Suporte Califórnia - ISC e expansão) nos Laboratórios de Mecânica dos Solos (LMS) e de Materiais, do Instituto de Engenharia e Tecnologia (IDT), da Universidade do Extremo Sul Catarinense (UNESC) e, no Laboratório de Desenvolvimento e Caracterização de Materiais (LDCM), do Serviço Nacional de Aprendizagem Industrial (SENAI). Na análise mineralógica realizada através do ensaio de difratometria de raios-X detectou-se a presença de ilita (22%), argilomineral este, responsável pelo comportamento expansivo do solo estudado. Os resultados dos ensaios demonstraram que o aumento na energia de compactação elevou o ISCinundado médio em 20,0%, para as energias Proctor Intermediária, e Modificada, enquanto que a expansão reduziu 6,95%, na energia Intermediária e elevou 9,35% na Modificada, quando comparadas à energia Proctor Normal. A explicação para tal fato está com certeza num percentual maior de ilita presente nas amostras, utilizadas para determinação do ISCinundado na energia Modificada. Constatou-se, que dentre as propriedades mecânicas analisadas, a expansão não atendeu aos parâmetros do Departamento Nacional de Infraestrutura de Transportes (DNIT)

Light-modulated ion binding: towards calibrationless sensors

Emerging technologies create new application fields but few of them require that we completely rethink our approach in preparation and characterization of sensors. The vision of internet scale wireless sensor networks (WSNs) requires the deployment of enormous numbers of sensors. This necessarily means that the cost of each sensor must be brought down significantly if this vision is to be realized. An ideal solution for this problem would be a sensor that does not interact with its environment in any way until there is a need for measurement. Upon the measurement, the sensor’s surface is completely regenerated and returned into the state as before the measurement. This step is critical as it ensures that the measurement did not any effect on the sensor hence no calibration is necessary. In our work, we use compounds that indeed can be switched between the active and passive state using light. Most commonly used compounds are so called spiropyrans (SP) and spirooxazines (SO). Here we show the recent advance in preparation of reversible, light-modulated sensors using surface immobilised SP/SO derivatives. A further attractive property of these materials is that they are inherently self-indicating through striking colour changes that enable the state to be easily determined (active vs. passive), and the presence of a bound guest to be detected. These spectral changes enable a range of self-diagnostic tests to be incorporated that enable binding events to be controlled at the surface interface, and for real binding events to be distinguished from artefacts arsing from changes in light intensity, or photobleaching of the active component. We have identified most notable problems for utilization of these compounds in “calibrationless” sensors such as relatively weak binding constants, photodegradation, and unfavourable kinetics of switching between the active and passive state and we demonstrate our approach in solving these problems

Spiropyran modified PDMS micro-fluidic chip device for photonically controlled sensor array detection of metal ions

Micro‐fluidic chips are particularly attractive in biological and life sciences for analytical purposes because they provide a convenient small platform for rapid analysis and detection [1]. Using micro‐fluidic devices for the determination of ions emerges as a potential solution to some of the challenges not overtaken by conventional techniques e.g. atomic absorption, inductively‐coupled plasma‐optical emission, mass spectrometry and ion‐selective electrodes [2]. For example, these devices can integrate complex sample handling processes, calibration, and detection steps into a compact, portable system. Moreover they require small sample volumes (low μl or nl), consume little power, and are easily constructed for multi‐analyte detection, either through multiple parallel fluidic architectures or by using arrays of detection elements. Organic photochromic compounds like spiropyrans are particularly interesting targets for the development of new approaches to sensing since they offer new routes to multi‐functional materials that take advantage of their photo‐reversible interconversion between two thermodynamically stable states (a spiropyran (SP) form, and a merocyanine (MC) form), which have dramatically different charge, polarity and molecular conformations. Furthermore, they can be easily incorporated into membranes for improved robustness and ease of handling [3], but from our perspective, most interesting of all, they have metal ion‐binding and molecular recognition properties which are only manifested by the MC form. Based on the coordinationinduced photochromism characteristic of the MC form, spiropyrans have been employed as molecular probes for metal ions and organic molecules [4]. In this abstract, we show how through integrating the beneficial characteristics of micro‐fluidic devices and spiropyrans photoswitches, a simple and very innovative chip configured as an on‐line metal ion sensor array can be realised (Figure 1). The micro‐fluidic device consists of five independent 94 μm depth, 150 μm width channels fabricated in polydimethylsiloxane. The spiropyran 1’‐(3‐carboxypropyl)‐3,3’‐dimethyl‐6‐nitrospiro‐1‐benzopyran‐2,2’‐indoline (SP‐COOH) is immobilised by physical adsorption directly on ozone plasma activated PDMS micro‐channel walls. When the colourless, inactive, spiropyran coating absorbs UV light it switches to the highly coloured merocyanine form (MC‐COOH), which also has an active binding site for certain metal ions. Therefore metal ion uptake can be triggered using UV light and subsequently reversed on demand by shining white light on the coloured complex, which regenerates the inactive spiropyran form, and releases the metal ion. When stock solutions of several metal ions (Ca2+, Zn2+, Hg2+, Cu2+, Co2+) are pumped independently through the five channels, different optical responses were observed for each metal (Figure 2), (i.e. complex formation with metal ions is associated with characteristic shifts in the visible spectrum), and the platform can therefore be regarded as a micro‐structured device for online multi‐component monitoring of metal cations