A PLL-based frequency shift measurement system for chemical and biological sensing was developed and implemented in the form of two discrete electronic assemblies. One of the assemblies consists of a VCO which contains a microwave resonator sensor while the other assembly contains commercially available PLL and MCU devices, as well as various other discrete components. When mated together, a PLL-based frequency synthesizer is realized, the output frequency of which is ~4.5 GHz. The system is used to measure the frequency shift exhibited by the frequency synthesizer when several commonly-known chemical substances are applied to the microwave resonator sensor test fixture. Because the amount of measured frequency shift is proportional to the dielectric constant of a given material under test (MUT), this system can potentially be used as part of a chemical identification system. This measurement system is also attractive in that it represents a stand-alone or 'self-contained' system which does not require usage of any additional expensive and bulky electronic diagnostic equipment such as a network analyzer or signal generator, making it a relatively inexpensive and portable solution. Attempts to use the system to measure frequency shift resulting from application of various common chemical substances to the sensor fixture results in derivation of dielectric constant values which hold very close agreement (+/-2%) to the published/theoretical dielectric constant values for each respective chemical substance.

This work attempted to detect chemical warfare agent (CWA) simulants via electrochemistry utilizing two approaches. The first approach consisted of a ferrocene (Fc) amino acid derivative film on Au surfaces. The molecule [(BocHN)Fc(CO)CSA]2 was electrodeposited onto Au microelectrodes through a SAu bond. Once immobilized, the Fc amino acid derivative was Boc deprotected allowing for the amino group to react with the target molecule. Detection of the target simulant was monitored by cyclic voltammetry (CV) while following the formal potential of the Fc molecule, which is influenced by its immediate electronic microenvironment. Reaction with either 1 mM diethyl cyanophosphonate (DECP) or 2 chloroethyl ethyl sulfide (2 CEES), both effectively simulants for the CWAs Tabun nerve agent and blistering sulfur mustard respectively, was not observed. However, detection of 1 mM acetyl chloride was achieved by observing a potential anodic shift from 217 ± 6 mV, for the Boc deprotected form, to 388 ± 7 mV for the reacted state of the molecule. The lack of reactivity with the Fc amino acid system was hypothesized as a kinetic issue.<p> In the second approach, the electrochemistry of gas generated naked Ag nanoparticles (NPs) deposited on indium tin oxide covered glass plates is compared to bulk polycrystalline Ag. The nano specific electrochemistry of Ag NPs has been identified and includes the preferential formation of â oxides. In 100 mM KOH supporting electrolyte, disruption of â oxide formation is exploited to test for the presence of 1 mM DECP resulting in the dissolution of Ag via cyanide complexes leading to a CV signal decrease. While in 8.0 M KOH, â oxide formation is enhanced leading to testing capabilities for 1 mM 2 CEES resulting in the disappearance of the â oxide peak and the appearance of surface oxide peak during CV. Analogous electrochemistry is not observed on polycrystalline bulk Ag.

This work attempted to detect chemical warfare agent (CWA) simulants via electrochemistry utilizing two approaches. The first approach consisted of a ferrocene (Fc) amino acid derivative film on Au surfaces. The molecule [(BocHN)Fc(CO)CSA]2 was electrodeposited onto Au microelectrodes through a SAu bond. Once immobilized, the Fc amino acid derivative was Boc deprotected allowing for the amino group to react with the target molecule. Detection of the target simulant was monitored by cyclic voltammetry (CV) while following the formal potential of the Fc molecule, which is influenced by its immediate electronic microenvironment. Reaction with either 1 mM diethyl cyanophosphonate (DECP) or 2 chloroethyl ethyl sulfide (2 CEES), both effectively simulants for the CWAs Tabun nerve agent and blistering sulfur mustard respectively, was not observed. However, detection of 1 mM acetyl chloride was achieved by observing a potential anodic shift from 217 ± 6 mV, for the Boc deprotected form, to 388 ± 7 mV for the reacted state of the molecule. The lack of reactivity with the Fc amino acid system was hypothesized as a kinetic issue.<p> In the second approach, the electrochemistry of gas generated naked Ag nanoparticles (NPs) deposited on indium tin oxide covered glass plates is compared to bulk polycrystalline Ag. The nano specific electrochemistry of Ag NPs has been identified and includes the preferential formation of â oxides. In 100 mM KOH supporting electrolyte, disruption of â oxide formation is exploited to test for the presence of 1 mM DECP resulting in the dissolution of Ag via cyanide complexes leading to a CV signal decrease. While in 8.0 M KOH, â oxide formation is enhanced leading to testing capabilities for 1 mM 2 CEES resulting in the disappearance of the â oxide peak and the appearance of surface oxide peak during CV. Analogous electrochemistry is not observed on polycrystalline bulk Ag.

Microcantilever sensor has gained much popularity because of its high sensitivity and selectivity. It consists of a micro-sized cantilever that is usually coated on one side with chemical/biological probe agents to generate strong attraction to target molecules. The interactions between the probe and target molecules induce surface stress that bends the microcantilever. This current work applied the molecular dynamics simulation to study the microcantilever system. Lennard-Jones potentials were used to model the target-target and target-probe interactions and bond bending potentials to model the solid cantilever beam. In addition, this work studied the effect of probe locations on the microcantilever deflection. The simulation results suggest that both target-target and target-probe interactions as well as the probe locations affect the arrangement of the bonds; in term of the bonding number, the area containing the bonded molecules, and the distances between them. All these factors influence the microcantilever deflection.

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Ce mémoire présente l'étude d'un capteur chimique à fibre optique à gradient d'indice inversé basé sur la résonance de plasmons de surface. Des dispositifs optiques à prisme ou mettant en jeu des fibres optiques classiques en silice utilisant cette technique de mesure sont déjà commercialisés. L'objectif de notre travail a été de caractériser théoriquement et expérimentalement un nouveau type de fibre optique permettant d'accroître les performances de ce capteur et d'en simplifier l'instrumentation. Un état de l'art des capteurs à plasmons de surface est présenté. Les structures basées sur une fibre optique (unimodale, multimodale) font l'objet d'une présentation détaillée mettant en évidence les caractéristiques des montages employés ainsi que leurs performances respectives. Nous avons cherché à déterminer le profil d'indice de réfraction du cœur de la fibre rendant les angles d'incidence à l'interface cœur-gaine quasiment égaux quels que soient les rayons se propageant dans la fibre. Ceci a été réalisé en utilisant une source lumineuse ponctuelle monochromatique positionnée dans l'axe et à une distance définie de l'entrée de la fibre. Le profil idéal présente un gradient d'indice inversé très proche d'un profil parabolique inversé pour lequel l'indice est minimal au centre du cœur de la fibre. Une description des caractéristiques de cette fibre comprenant l'étude de la propagation des rayons a été réalisée. Le phénomène de plasmon de surface est ensuite décrit, de manière générale puis ses conditions d'excitation dans la fibre employée sont étudiées. Une étude expérimentale et théorique a été menée sur les paramètres les plus influents du capteur (nature et épaisseur du métal, position de la source ...). La présentation de deux applications pratiques (détection de traces de toluène dans un milieu aqueux et étude en temps réel du mécanisme de formation d'une monocouche auto-assemblée) montre les champs d'applications du dispositif optique simple développé.