Small-Molecule Storage and Activation with Porous Molecules

Porous materials have played an important role in society for centuries. They have become more prevalent over the past two decades given the advent of designer materials. Novel porous solids have gained considerable recent attention for applications related to small molecules, such as storage, separation, and activation. The Bloch Group is working on developing tunable molecular adsorbents based on coordination cages for small molecule storage. We design, synthesize, and characterize novel porous coordination cages for their use as both solid and liquid adsorbents with tailorable functionalities. The materials proposed here will address long-standing shortfalls for adsorptive gas storage and significantly advance the field of network solids by serving as soluble, characterizable metal-organic framework analogs.

Project 1Porous Liquids

Metal-organic frameworks are currently among the most widely studied porous materials with potential applications in catalysis, gas storage, gas separation, and conductivity. This project seeks to develop porous liquids based on this promising new class of materials. Room temperature ionic liquids based on porous ionic clusters and neat liquids composed of surface functionalized particles are under investigation. Ultimately, these materials will be advantageous over current porous materials in terms of volumetric capacity, tunability, processability, and thermal, electrical, and ionic conductivity.
Metal-Organic Materials for Aerosol Pulmonary Theranostics
Respiratory infections impact millions of people worldwide and novel advances are needed to improve antimicrobial treatment options. To address this, we are working with the Fromen Lab at the University of Delaware to develop a library of metal-organic framework and coordination cage nanoparticles with controlled molecular-level porosity, particle size, and surface chemistry as a platform for improved antimicrobial lung delivery. Use of these highly tunable materials will give a level of synthetic control not accessible with typical heterogeneous materials. We are focused on evaluating the aerodynamic and biological-fate of nanoparticle structures in the lung, including diffusion, lung cellular biodistribution, and long-term metabolic studies to evaluate particle dissolution and toxicity in vivo. Our central hypothesis is that molecularly-defined metal-organic nanoparticle constructs can be optimized for pulmonary drug delivery of antimicrobial agents and specifically provide enhanced intracellular antimicrobial activity.
Biomass Conversion with Metal-Organic Materials
Although the Lewis acidity of metal-organic frameworks is easily tunable either by the choice of metal cation that serves as the structural building unit in the material or via simple post-synthetic metallation of chelating ligand groups, examples of systematic tuning of metal-organic framework Br√łnsted acidity are limited. Indeed, these have nearly exclusively consisted of sulfonic acid and carboxylic acid functional group-based MOFs. Further, structural effects are nearly unknown as one framework type has been studied nearly exclusively. This project focuses on the design and synthesis of a novel family of dicarboxylate-based bridging ligands that will allow us to probe the effects of acid strength, pore size, and framework topology on acid-catalyzed reactivity with a particular focus on biomass conversion.


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