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- Creators: Barrett, The Honors College
- Creators: Schumann, Robert, 1810-1856
Amidinates and guanidinates are promising supporting ligands in organometallic and coordination chemistry, highly valued for their accessibility, tunability, and comparability with other popular anionic N-chelating hard donor ligands like β-diketiminates. By far the most powerful way to access these ligands involves direct metal-nucleophile insertion into N,N’- substituted carbodiimides. However, the majority of reported examples require the use of commercially accessible carbodiimide peptide coupling reagents with simple alkyl substituents leading to low variation in potential substituents. Presented here is the design, synthesis, and isolation of a novel N,N’-bis[3-(diphenylphosphino)propyl]carbodiimide via an Aza-Wittig reaction between two previously described air stable substrates. At room temperature, 3-(diphenylphosphanyl-borane)-propylisocyanate was added to N-(3-(diphenylphospino)propyl)-triphenylphosphinimine, leading to product formation in minutes. One-pot phosphine-borane deprotection, followed by simple filtration of the crude mixture through a small, basic silica plug using pentane and diethyl ether granted the corresponding carbodiimide in high purity and yield (over 70%), confirmed by 1H, 13C, and 31P NMR spectroscopy. In addition to accessing different central carbon substituents, modification of phosphine substituents should be easily accessible through minor variations in the synthesis. With these precursors, anionic amidinates and guanidinates capable of κ4 -N,N,P,P-coordination may be accessed. The ability of the labile phosphine arms to associate and dissociate may facilitate catalysis. Thus, this carbodiimide provides a tunable, reliable one step precursor to novel substituted amidinates and guanidinates for homogeneous transition metal catalysis.
Traumatic brain injury (TBI) is defined as an injury to the head that disrupts normal brain function. TBI has been described as a disease process that can lead to an increased risk for developing chronic neurodegenerative diseases, like frontotemporal lobar degeneration (FTLD) and amyotrophic lateral sclerosis (ALS). A pathological hallmark of FTLD and a hallmark of ALS is the nuclear mislocalization of TAR DNA Binding Protein 43 (TDP-43). This project aims to explore neurodegenerative effects of TBI on cortical lesion area using immunohistochemical markers of TDP-43 proteinopathies. We analyzed the total percent of NEUN positive cells displaying TDP-43 nuclear mislocalization. We found that the percent of NEUN positive cells displaying TDP-43 nuclear mislocalization was significantly higher in cortical tissue following TBI when compared to the age-matched control brains. The cortical lesion area was analyzed for each injured brain sample, with respect to days post-injury (DPI), and it was found that there were no statistically significant differences between cortical lesion areas across time points. The percent of NEUN positive cells displaying TDP-43 nuclear mislocalization was analyzed for each cortical tissue sample, with respect to cortical lesion area, and it was found that there were no statistically significant differences between the percent of NEUN positive cells displaying TDP-43 nuclear mislocalization, with respect to cortical lesion area. In conclusion, we found no correlation between the percent of cortical NEUN positive cells displaying TDP-43 nuclear mislocalization with respect to the size of the cortical lesion area.
This novel study on children investigates separate constructs of child development: adjunctive behavior, curiosity, and creativity. The hypotheses were that there would be 1) a positive correlation between overall levels of adjunctive behavior and curiosity; (2) a positive correlation between appropriate adjunctive behavior, creativity, and curiosity; and (3) a negative correlation between inappropriate adjunctive behavior, creativity, and curiosity. The study took place over two visits via Zoom, split into two testing sessions. Eighteen children, ages 3.5-6.5, with ranging demographics (race, bilingualism, and exposure to another language) participated in the study. The children played an online aquarium game in the first session (50-85 minutes). They explored five different fish tanks to search for sea creatures. In the second visit (65-100 minutes), children completed thinking and drawing tasks, the Peabody Picture Vocabulary Test, and the Lifespan Self-Esteem Scale. Caregivers received a $10 online gift card for their child’s participation. The data showed no significant correlations but trends between adjunctive behavior, curiosity, and creativity. The study lacked a greater sample size, which may have caused lower correlations. For future studies, adjunctive behavior could be studied within the school setting and focus on how children can use their adjunctive behavior to maintain their creativity and curiosity.
The purpose of this research is to address the inequality and lack of accessibility within the dance community. This thesis will support the argument that students with disabilities should not be limited in what they can do within recreational activities.