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.

The effects of audio cueing and an instructions, feedback and praise package on the distribution of teacher praise to students of differing on-task levels

In an audio cueing system, a teacher is presented with randomly spaced auditory signals via tape recorder or intercom. The teacher is instructed to praise a child who is on-task each time the cue is presented. In this study, a baseline was obtained on the teacher's praise rate and the children's on-task behaviour in a Grade 5 class of 37 students. Children were then divided into high, medium and low on-task groups. Followinq baseline, the teacher's praise rate and the children's on-task behaviour were observed under the following successively implemented conditions: (l) Audio Cueing 1: Audio cueing at a rate of 30 cues per hour was introduced into the classroom and remained in effect during subsequent conditions. A group of consistently low on-task children were delineated. (2) Audio Cueing Plus 'focus praise package': Instructions to direct two-thirds o£ the praise to children identified by the experimenter (consistently low on-task children), feedback and experimenter praise for meeting or surpassing the criterion distribution of praise ('focus praise package') were introduced. (3) Audio Cueing 2: The 'focus praise package' was removed. (4) Audio Cueing Plus 'increase praise package': Instructions to increase the rate of praise, feedback and experimenter praise for improved praise rates ('increase praise package') were introduced. The primary aims of the study were to determine the distribution of praise among hi~h, medium and low on-task children when audio cueinq was first introduced and to investigate the effect of the 'focus praise package' on the distribution of teacher praise. The teacher distributed her praise evenly among the hiqh, medium and low on-task groups during audio cueing 1. The effect of the 'focus praise package' was to increase the percentage of praise received by the consistently low on-task children. Other findings tended to suggest that audio cueing increased the teacher's praise rate. However, the teacher's praise rate unexpectedly decreased to a level considerably below the cued rate during audio cueing 2. The 'increase praise package' appeared to increase the teacher's praise rate above the audio cueing 2 level. The effect of an increased praise rate and two distributions of praise on on-task behaviour were considered. Significant increases in on-task behaviour were found in audio cueing 1 for the low on-task group, in the audio cueing plus 'focus praise package' condition for the entire class and the consistently low on-task group and in audio cueing 2 for the medium on-task group. Except for the high on-task children who did not change, the effects of the experimental manipulations on on-task behaviour were e quivocal. However, there were some indications that directing 67% of the praise to the consistently low on-task children was more effective for increasing this group's on-task behaviour than distributing praise equally among on-task groups.