Contextualizing engineering leadership development in Science, Technology, Engineering and Mathematics.

Science, Technology, Engineering and Mathematics (STEM) disciplines recognize the need for leadership development, but the lack of a professionally endorsed model has led to a patchwork of programmes across the nation, each with its unique brand of skills development. Leadership programmes in six diverse STEM fields are included.

Using fourier transform infrared spectroscopy to examine structure in bisurea organogels.

The structure of two bisurea organogels was examined by Fourier-transform infrared (FT-IR) spectroscopy. Organogels were prepared in benzene at different concentrations of gelator in order to determine the effect of concentration on the assembly of organogelator molecules. This work examined two types of bisurea organogelators, both with dodecyl alkyl tail groups. The two molecules differ only in the length of an alkyl chain separating their two urea groups: 6 carbons in the C6C12 organogelator (1,6-bis(3(3,5-didodecoxybinzyl)-urea-hexane) and 12 carbons in the C12C12 organogelator (1,12-bis(3(3,5-didodecoxybinzyl)-urea-dodecane). The degree of urea hydrogen bonding was determined from the position of the amide II band, and the conformational order of the alkyl chains in the organogelator was determined in the methylene bending region. Both gels showed a general trend of less hydrogen bonding and greater conformational disorder in the alkyl chains as the concentration of organogelator increased; however, the changes were smaller in the C12C12 gels. This decrease in structural order with increasing organogelator concentration is explained by the kinetics of gel formation; more concentrated gels solidify too quickly to assemble perfectly. The observed differences between the two organogelators are caused by the different structures into which these two similar molecules assemble. The C6C12 organogelator only assembles linearly, while the C12C12 organogelator can form sheets through brick-like packing, and these packing motifs were confirmed by scanning electron microscopy.

Modifying the adsorption behavior of polyamidoamine dendrimers at silica surfaces investigated by total internal reflection fluorescence correlation spectroscopy.

Polyamidoamine (PAMAM) dendrimers were modified and tested for use as solution-phase diffusion probes in silica nanostructures. In order for the successful application of dendrimers as solution-phase probes, their interactions with silica surfaces must be understood and controlled, so that the motion of the probe is not influenced by adsorption. Adsorption/desorption kinetics of PAMAM dendrimers and their diffusion in solution near silica surfaces were investigated with total internal reflection fluorescence correlation spectroscopy (TIR-FCS). Dendrimers of generations 3, 5, and 7 were dye-labeled with carboxyrhodamine 6G. Because PAMAM dendrimers are positively charged in solution (having primary amines as end groups), significant adsorption of these molecules to the negatively charged silica surface was observed. Adsorption/desorption rates and the equilibrium constant for adsorption were determined by fitting the autocorrelation functions to a kinetic model. The desorption rate decreases and the absorption equilibrium constant increases with higher dendrimer generation. To reduce the adsorption of these probes to silica surfaces, the labeled dendrimers were reacted with succinic anhydride, converting the primary amine end groups to negatively charged carboxylic acid groups. These carboxylated dendrimers did not detectably adsorb to silica from aqueous solution. TIR-FCS was used to determine their free-solution diffusion constants near silica surfaces, and the corresponding hydrodynamic radii compare favorably with values reported from forced Rayleigh scattering measurements.

Poly(amidoamine) dendrimers as nanoscale diffusion probes in sol-gel films investigated by total internal reflection fluorescence spectroscopy.

Three generations of poly(amidoamine) dendrimers were dye-labeled and chemically modified to have terminal carboxyl groups and used as variably sized probes to study diffusion in thin sol-gel films. Total internal reflection fluorescence spectroscopy experiments, both correlation and concentration-jump measurements, were employed to measure the relative populations and effective diffusion coefficients of dendrimers in the films. For films prepared from small (27-nm) silica particles, larger dendrimers could be completely excluded from penetrating the sol-gel structure. In films made of larger (150-nm) particles with correspondingly larger pores, concentration-jump experiments showed that larger dendrimers are excluded from more of the intraparticle pore space than small dendrimers. Similarly, fluorescence-correlation measurements showed that the diffusion of smaller dendrimers exhibited greater tortuosity than larger dendrimers in the interparticle pores of the film. The smaller dendrimers explore a greater volume of smaller, more convoluted pores, whereas larger dendrimers penetrate a smaller volume of larger, more open pores.

Single-molecule fluorescence trajectories for investigating molecular transport in thin silica sol-gel films.

Single-molecule fluorescence tracking has been used to examine diffusion of small molecules in sol-gel films in order to identify spatial heterogeneity in the structure and molecular diffusivities for different regions of the film. Fluorescence intensity profiles from single molecules are fit to a two-dimensional Gaussian function to determine their x,y positions with subpixel resolution. Scatter plots and histograms of molecular step sizes indicate that the trajectories conform to the predictions of a two-dimensional random walk. The mean-square step size is shown to be an unbiased estimate of the variance of the step-size probability distribution and a valid statistic for determining the diffusion coefficient from a molecular trajectory. The diffusion coefficients measured for different molecules are subjected to an F test, which showed that the sol-gel film exhibits spatial variation in the diffusion coefficient on a micrometer-length scale. The spatial variation in diffusivities is a measure of structural heterogeneity of these films.

Total internal reflection fluorescence-correlation spectroscopy study of molecular transport in thin sol-gel films.

Total internal reflection fluorescence correlation spectroscopy is used to measure mass transport rates through thin sol-gel films. Fluctuations in the fluorescence signal derive from molecular statistics due to the small number (approximately 1000) of rhodamine 6G dye molecules in the observation region. Autocorrelation of the fluctuating signal is fit to a model describing diffusion in the evanescent wave excitation. Silica sol-gel films were prepared by dip-coating 27-nm porous silica particles, which were synthesized by a base-catalyzed sol-gel method, onto microscope slides. The measured diffusivities ranged from 1 to 2 orders of magnitude slower than free diffusion and decreased with increasing number of dips used to prepare the film. Scanning electron microscopy (SEM) was used to examine the film structure and showed that increasing the number of dips produced more uniform and well-ordered films. To determine what role the dip-coating process plays in inducing order, deposited films were further dipped into ethanol containing no particles. These films were annealed by this process and become more ordered, as determined by SEM, and show a corresponding reduction in the molecular diffusivity.