Single-Crystal 2D Covalent Organic Frameworks for Plant Biotechnology.

Molecules chemically synthesized as periodic two-dimensional (2D) frameworks via covalent bonds can form some of the highest-surface area and -charge density particles possible. There is significant potential for applications such as nanocarriers in life sciences if biocompatibility can be achieved; however, significant synthetic challenges remain in avoiding kinetic traps from disordered linking during 2D polymerization of compatible monomers, resulting in isotropic polycrystals without a long-range order. Here, we establish thermodynamic control over dynamic control on the 2D polymerization process of biocompatible imine monomers by minimizing the surface energy of nuclei. As a result, polycrystal, mesocrystal, and single-crystal 2D covalent organic frameworks (COFs) are obtained. We achieve COF single crystals by exfoliation and minification methods, forming high-surface area nanoflakes that can be dispersed in aqueous medium with biocompatible cationic polymers. We find that these 2D COF nanoflakes with high surface area are excellent plant cell nanocarriers that can load bioactive cargos, such as the plant hormone abscisic acid (ABA) via electrostatic attraction, and deliver them into the cytoplasm of intact living plants, traversing through the cell wall and cell membrane due to their 2D geometry. This synthetic route to high-surface area COF nanoflakes has promise for life science applications including plant biotechnology.

Homologated amino acids with three vicinal fluorines positioned along the backbone: development of a stereoselective synthesis.

Backbone-extended amino acids have a variety of potential applications in peptide and protein science, particularly if the geometry of the amino acid is controllable. Here we describe the synthesis of δ-amino acids that contain three vicinal C-F bonds positioned along the backbone. The ultimately successful synthetic approach emerged through the investigation of several methods based on both electrophilic and nucleophilic fluorination chemistry. We show that different diastereoisomers of this fluorinated δ-amino acid adopt distinct conformations in solution, suggesting that these molecules might have value as shape-controlled building blocks for future applications in peptide science.

Design of Biodegradable, Climate-Specific Packaging Materials That Sense Food Spoilage and Extend Shelf Life.

The AgriFood systems in tropical climates are under strain due to a rapid increase in human population and extreme environmental conditions that limit the efficacy of packaging technologies to extend food shelf life and guarantee food safety. To address these challenges, we rationally designed biodegradable packaging materials that sense spoilage and prevent molding. We nanofabricated the interface of 2D covalent organic frameworks (COFs) to reinforce silk fibroin (SF) and obtain biodegradable membranes with augmented mechanical properties and that displayed an immediate colorimetric response (within 1 s) to food spoilage, using packaged poultry as an example. Loading COF with antimicrobial hexanal also mitigated biotic spoilage in high-temperature and -humidity conditions, resulting in a four-order of magnitude decrease in the total amount of mold growth in soybeans packaged in silk-COF, when compared to cling film (i.e., polyethylene). Together, the integration of sensing, structural reinforcement, and antimicrobial agent delivery within a biodegradable nanocomposite framework defines climate-specific packaging materials that can decrease food waste and enhance food safety.

Sequential deoxyfluorination approach for the synthesis of protected α,ß,γ-trifluoro-δ-amino acids.

Backbone-homologated amino acids have been synthesized, containing three vicinal fluorine atoms placed stereospecifically along the carbon chain. Different trifluoro stereoisomers are found to have contrasting conformations, consistent with known stereoelectronic effects associated with C-F bonds.