Mary Jane Saunders

One‐Step Multicomponent Self‐Assembly of a First‐Generation Sierpiński Triangle: From Fractal Design to Chemical Reality

A novel terpyridine-based architecture that mimics a first-generation Sierpiński triangle has been synthesized by multicomponent assembly and features tpy-Cd(II)-tpy connectivity (tpy=terpyridine). The key terpyridine ligands were synthesized by the Suzuki cross-coupling reaction. Mixing two different terpyridine-based ligands and Cd(II) in a precise stoichiometric ratio (1:1:3) produced the desired fractal architecture in near-quantitative yield. Characterization was accomplished by NMR spectroscopy, mass spectrometry, and transmission electron microscopy.

Precise Molecular Fission and Fusion: Quantitative Self-Assembly and Chemistry of a Metallo-Cuboctahedron†

Inspiration for molecular design and construction can be derived from mathematically based structures. In the quest for new materials, the adaptation of new building blocks can lead to unexpected results. Towards these ends, the quantitative single-step self-assembly of a shape-persistent, Archimedean-based building block, which generates the largest molecular sphere (a cuboctahedron) that has been unequivocally characterized by synchrotron X-ray analysis, is described. The unique properties of this new construct give rise to a dilution-based transformation into two identical spheres (octahedra) each possessing one half of the molecular weight of the parent structure; concentration of this octahedron reconstitutes the original cuboctahedron. These chemical phenomena are reminiscent of biological fission and fusion processes. The large 6 nm cage structure was further analyzed by 1D and 2D NMR spectroscopy, mass spectrometry, and collision cross-section analysis. New routes to molecular encapsulation can be envisioned.

Two-directional cascade molecules: synthesis and characterization of [9]-n-[9] arborols

A series of two-directional cascade molecules (arborols) has been synthesized by a two-step nucleophilic substitution–amidation procedure; the [9]-10-[9] arborol forms a thermally reversible aqueous gel, which has been investigated via microscopy and light scattering techniques.

Controlled Interconversion of Superposed-Bistriangle, Octahedron, and Cuboctahedron Cages Constructed Using a Single, Terpyridinyl-based Polyligand and Zn2.

Metallomacromolecular architectural conversion is expanded by the characterization of three different structures. A quantitative, single-step, self-assembly of a shape-persistent monomer, containing a flexible crown ether moiety, gives an initial Archimedean-based cuboctahedron that has been unequivocally characterized by 1D and 2D NMR spectroscopy, mass spectrometry, and collision cross section analysis. Both dilution and exchange of counterions, transforms this cuboctahedron into two identical octahedrons, which upon further dilution convert into four, superposed, bistrianglar complexes; increasing the concentration reverses the process. Ion binding studies using the cuboctahedral cage were undertaken.

Supercharged, Precise, Megametallodendrimers via a Single-Step, Quantitative, Assembly Process

Synthesis of giant unimolecular dendrimers is challenging due, in part, to difficulties encountered at higher generations, in both convergent and divergent protocols because of the multistep construction/purification process. Herein, we report a hybrid synthetic procedure in which the core is constructed last. This quantitative assembly generated a metallodendrimer that is supercharged (120+), large (11.3 nm diameter), and its core was previously established. The series of complexes has been unequivocally characterized by NMR, ESI-IM-MS, and TEM techniques.

Citizen Science: The Small World Initiative Improved Lecture Grades and California Critical Thinking Skills Test Scores of Nonscience Major Students at Florida Atlantic University

Course-based undergraduate research is known to improve science, technology, engineering, and mathematics student achievement. We tested “The Small World Initiative, a Citizen-Science Project to Crowdsource Novel Antibiotic Discovery” to see if it also improved student performance and the critical thinking of non-science majors in Introductory Biology at Florida Atlantic University (a large, public, minority-dominant institution) in academic year 2014–15. California Critical Thinking Skills Test pre- and posttests were offered to both Small World Initiative (SWI) and control lab students for formative amounts of extra credit. SWI lab students earned significantly higher lecture grades than control lab students, had significantly fewer lecture grades of D+ or lower, and had significantly higher critical thinking posttest total scores than control students. Lastly, more SWI students were engaged while taking critical thinking tests. These results support the hypothesis that utilizing independent course-based undergraduate science research improves student achievement even in nonscience students.

Amphiphilic [tpy-MII-tpy] metallotriangles: synthesis, characterisation and hierarchical ordering

Abstract Long chain (C16) alkylated metallocycles are synthesised and characterised. Their ordered aggregation was studied via TEM to gauge to the effects of molecular topology, solvent, counterion and metal centre(s) on morphology and nanoscale structure. The results indicate that their amphiphilicity significantly enhanced their self-ordering characteristics relative to controls and enabled the formation of nanoscale structures. Similar ordering was observed for both labile and non-labile analogues with SAXD showing comparable d-spacing values, suggesting the presence of intramolecular π–π stacking. Effect of counterion and solvent was studied with the non-labile system. Nanotubular, ribbon, or sheet-like structures were afforded depending upon conditions.

Coordination-Driven, Self-Assembly of a Polycyclic, Terpyridine-Based Nanobelt

A novel, tetrakisterpyridinyl-substituted porphyrin underwent self-assembly to form a three-dimensional, belt-shaped metallomacrocycle, which was characterized by 1D and 2D NMR and electrospray ionization traveling wave ion mobility mass spectrometry.