Development of calix[4]arene-functionalized microcantilever array sensing system for the rapid, sensitive and simultaneous detection of metal ions in aqueous solutions

The work described in this thesis was conducted with the aim of: 1) investigating the binding capabilities of calix[4]arene-functionalized microcantilevers towards specific metal ions and 2) developing a new16-microcantilever array sensing system for the rapid, and simultaneous detection of metal ions in fresh water. Part I of this thesis reports on the use of three new bimodal calix[4]arenes (methoxy, ethoxy and crown) as potential host/guest sensing layers for detecting selected ions in dilute aqueous solutions using single microcantilever experimental system. In this work it was shown that modifying the upper rim of the calix[4]arenes with a thioacetate end group allow calix[4]arenes to self-assemble on Au(111) forming complete highly ordered monolayers. It was also found that incubating the microcantilevers coated with 5 nm of Inconel and 40 nm of Au for 1 h in a 1.0 M solution of calix[4]arene produced the highest sensitivity. Methoxy-functionalized microcantilevers showed a definite preference for Ca²⁺ ions over other cationic guests and were able to detect trace concentration as low as 10⁻¹² M in aqueous solutions. Microcantilevers modified with ethoxy calix[4]arene displayed their highest sensitivity towards Sr²⁺ and to a lesser extent Ca²⁺ ions. Crown calix[4]arene-modified microcantilevers were however found to bind selectively towards Cs⁺ ions. In addition, the counter anion was also found to contribute to the deflection. For example methoxy calix[4]arene-modified microcantilever was found to be more sensitive to CaCl₂ over other water-soluble calcium salts such as Ca(NO₃)₂ , CaBr₂ and CaI₂. These findings suggest that the response of calix[4]arene-modified microcantilevers should be attributed to the target ionic species as a whole instead of only considering the specific cation and/or anion. Part II presents the development of a 16-microcantilever sensor setup. The implementation of this system involved the creation of data analysis software that incorporates data from the motorized actuator and a two-axis photosensitive detector to obtain the deflection signal originating from each individual microcantilever in the array. The system was shown to be capable of simultaneous measurements of multiple microcantilevers with different coatings. A functionalization unit was also developed that allows four microcantilevers in the array to be coated with an individual sensing layer one at the time. Because of the variability of the spring constants of different cantilevers within the array, results presented were quoted in units of surface stress unit in order to compare values between the microcantilevers in the array.

Centrifuge modeling of oblique pipe-soil interaction in dense and loose sand

Due to relative ground movement, buried pipelines experience geotechnical loads. The imposed geotechnical loads may initiate pipeline deformations that affect system serviceability and integrity. Engineering guidelines (e.g., ALA, 2005; Honegger and Nyman, 2001) provide the technical framework to develop idealized structural models to analyze pipe‒soil interaction events and assess pipe mechanical response. The soil behavior is modeled using discrete springs that represent the geotechnical loads per unit pipe length developed during the interaction event. Soil forces are defined along three orthogonal directions (i.e., axial, lateral and vertical) to analyze the response of pipelines. Nonlinear load-displacement relationships of soil defined by a spring, is independent of neighboring spring elements. However, recent experimental and numerical studies demonstrate significant coupling effects during oblique (i.e., not along one of the orthogonal axes) pipe‒soil interaction events. In the present study, physical modeling using a geotechnical centrifuge was conducted to improve the current understanding of soil load coupling effects of buried pipes in loose and dense sand. A section of pipeline, at shallow burial depth, was translated through the soil at different oblique angles in the axial-lateral plane. The force exerted by the soil on pipe is critically examined to assess the significance of load coupling effects and establish a yield envelope. The displacements required to soil yield force are also examined to assess potential coupling in mobilization distance. A set of laboratory tests were conducted on the sand used for centrifuge modeling to find the stress-strain behavior of sand, which was used to examine the possible mechanisms of centrifuge model test. The yield envelope, deformation patterns, and interpreted failure mechanisms obtained from centrifuge modeling are compared with other physical modeling and numerical simulations available in the literature.