In collision-induced dissociation mass spectrometry experiments, the collision energy required for dissociation linearly depends on the degrees of freedom in the precursor ion. The magnitude of the slope of this relationship previously has been shown to qualitatively correlate to the relative binding strength of a noncovalently bound, monovalent complex. The goal of the work presented here is to determine if a similar methodology can be applied for assessing relative binding strengths in multivalent species. We have tested the method on complexes formed from 18-crown-6 and a variety of protonated, primary alkylamines, [C(n)H(2n+1)NH(3)](+) (n=9, 12, 14, 16 and 18) and alkyldiamines, [H(3)NC(n)H(2n)NH(3)](2+) (n=3, 5, 6, 9 and 12), and compared our results with dissociation energies calculated using density functional theory at the B3LYP/6-31G* level. We found that the method correctly assessed the stronger crown ether/headgroup interaction in the two divalent species (1:1 and 2:1 complexes formed from the diaminoalkanes) compared with the weaker interaction in the monovalent species (1:1 complexes formed from mono-aminoalkanes). However, the experimental method could not distinguish between the binding strengths of the two divalent complexes, perhaps because their calculated dissociation energies were quite similar. Our preliminary results suggest that this method could potentially be used for a quick and simple analysis of binding strengths in multivalent species if the binding strengths of the species are significantly different from one another.
DegreePlus is a recently developed program at Western Carolina University (WCU) that aims to develop transferable skills, including professionalism, cultural responsiveness, leadership and teamwork, in students via their participation in extracurricular activities. A mixed-methods study that included focus groups and a survey was used to identify the preliminary impacts of the program. Researchers found that students view the program as a supportive initiative to help them prepare for their future and meet their career goals. Students also perceive that they are learning the targeted skills and are able to apply them to a limited extent. Finally, students view the program as a means of connecting to their university community. We anticipate that student participation in this program may assist with other institutional goals, such as retention and student success, as many of the impacts from the program align with principles that support these objectives.
Big Harris Creek, North Carolina, possesses a geomorphic history and alluvial stratigraphic record similar to many drainages in southern Appalachian Piedmont. An approximately 1 km reach of Upper Stick Elliott Creek, a tributary to Big Harris Creek, was used herein to (1) explore the use of chemostratigraphic methods to define and correlate late Holocene alluvial deposits along this relatively uncontaminated rural stream containing legacy sediments (historic, anthropogenically derived deposits), and (2) interpret depositional floodplain processes within small (<10 km2), headwater drainages. The lithofacies within four floodplain sections were described in channel banks and sampled at about 5 cm intervals. The 128 collected samples were then analyzed for grain size and the concentration of 22 elements using X-ray fluorescence. Well-defined chemostratigraphic units (facies) were defined on the basis of a multi-elemental fingerprint using a principal component analysis (PCA) and verified using discriminant analysis (DA). Chemostratigraphic units did not reflect grain size at a site (by design) but marginally correlated to lithofacies defined by field descriptions. Of significant importance, chemostratigraphic units could be quantitatively correlated between the four stratigraphic sections at a much higher spatial resolution (~5 cm) than could be performed using other sedimentologic parameters alone. In combination, the lithostratigraphic and chemostratigraphic architecture of the floodplain is consistent with a previously proposed sequence of deposition for the legacy deposits in which extensive land-use change associated with the onset of cotton farming in the 1860s led to upstream incision and gully formation and downstream deposition on the floodplain surface. Deposition appears to have progressed downvalley as incision deepened, probably in the form of crevasse splay deposits or proximal sandsheets that were occasionally interbedded with vertically accreted sediments. The results indicate that chemostratigraphy represents a highly useful approach to the assessment of floodplain depositional processes over (at least) relatively small temporal and spatial scales, even in areas with minimal sediment contamination.
The DegreePlus program at Western Carolina University is a newly developed initiative to help students develop transferable skills, including professionalism, cultural responsiveness, leadership and teamwork, by attendance at specific extracurricular events. The program was first implemented in the 2017-2018 academic year as a pilot with Honors College students, conditionally admitted students and students in specific living-learning communities. Participation by these student groups was encouraged through targeted marketing, transition courses, required attendance at DegreePlus events, and gamification. This research addresses how these methods impacted student participation. We concluded that requiring early participation influenced some students to continue their involvement in DegreePlus, and gamification helped students get interested in the program, but students also recognized the intrinsic value of the program and planned to continue their involvement. Targeted marketing helped to increase awareness and understanding of the program and how it works.
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