Spherical Nucleic Acids: Integrating Nanotechnology Concepts into General Chemistry Curricula.

Nanoscience and technology research offer exciting avenues to modernize undergraduate-level General Chemistry curricula. In particular, spherical nucleic acid (SNA) nanoconjugates, which behave as "programmable atom equivalents" (PAEs) in the context of colloidal crystals, are one system that one can use to reinforce foundational concepts in chemistry including matter and atoms, the Periodic Table, Lewis dot structures and the octet rule, valency and valence-shell electron-pair repulsion (VSEPR) theory, and Pauling's rules, ultimately leading to enriching discussions centered on materials chemistry and biochemistry with key implications in medicine, optics, catalysis, and other areas. These lessons connect historical and modern concepts in chemistry, relate course content to current professional and popular science topics, inspire critical and creative thinking, and spur some students to continue their science, technology, engineering, and mathematics (STEM) education and attain careers in STEM fields.

Stabilization of an enzyme cytochrome in a metal-organic framework against denaturing organic solvents.

Enzymes are promising catalysts with high selectivity and activity under mild reaction conditions. However, their practical application has largely been hindered by their high cost and poor stability. Metal-organic frameworks (MOFs) as host materials show potential in protecting proteins against denaturing conditions, but a systematic study investigating the stabilizing mechanism is still lacking.

Thermochemical Investigation of Oxyanion Coordination in a Zirconium-Based Metal-Organic Framework.

Porous materials possess high internal surface areas and void fractions that make them valuable in several applications, including gas storage, heterogeneous catalysis, and water purification. Despite the plentiful effort allocated to porous materials research annually, few methods exist to directly monitor and characterize chemical events occurring within a pore's confines. The crystalline nature of zeolites, covalent organic frameworks (COFs), and metal-organic frameworks (MOFs) permit structural characterization by X-ray diffraction; yet, quantifying the thermodynamics of chemical processes and transformations remains tedious and error ridden.

Insights into the Structure-Activity Relationship in Aerobic Alcohol Oxidation over a Metal-Organic-Framework-Supported Molybdenum(VI) Catalyst.

The understanding of structure-activity relationships at the atomic level has played a profound role in heterogeneous catalysis, providing valuable insights into designing suitable heterogeneous catalysts. However, uncovering the detailed roles of how such active species' structures affect their catalytic performance remains a challenge owing to the lack of direct structural information on a specific active species. Herein, we deposited molybdenum(VI), an active species in oxidation reactions, on the Zr node of a mesoporous zirconium-based metal-organic framework (MOF) NU-1200, using solvothermal deposition in MOFs (SIM).

Proton Conductivity via Trapped Water in Phosphonate-Based Metal-Organic Frameworks Synthesized in Aqueous Media.

Metal-organic frameworks (MOFs) are promising candidates for proton-conducting applications. Herein, we report the aqueous synthesis of two new phosphonate-based MOFs comprising glyphosate linkers, [Mg(dpmp)]·2HO (Mg-NU-225) and [Fe(dpmp)]·2HO (Fe-NU-225), (dpmp = ,'-diphosphonomethyl-2,5-piperazinedione), and explore their proton conductivities. Single crystal X-ray diffraction measurements revealed that both frameworks display a two-dimensional layered structure with a cyclic ring ligand which forms from the condensation of two glyphosate molecules.

The state of the field: from inception to commercialization of metal-organic frameworks.

As chemists and materials scientists, it is our duty to synthesize and utilize materials for a multitude of applications that promote the development of society and the well-being of its citizens. Since the inception of metal-organic frameworks (MOFs), researchers have proposed a variety of design strategies to rationally synthesize new MOF materials, studied their porosity and gas sorption performances, and integrated MOFs onto supports and into devices. Efforts have explored the relevance of MOFs for applications including, but not limited to, heterogeneous catalysis, guest delivery, water capture, destruction of nerve agents, gas storage, and separation.

Tuning the Atrazine Binding Sites in an Indium-Based Flexible Metal-Organic Framework.

Constructing flexible metal-organic frameworks (MOFs) with targeted properties is of high interest given their demonstrated potential as smart materials that undergo structural transformations in response to external stimuli. Herein, we report a flexible and interpenetrated indium-based MOF, , comprising four-connected [In(CO)] nodes and tetracarboxylate pyrene-based ligands assembled in the topology. The flexible framework of exhibits intricate structural transformations upon exposure to external stimuli, namely, guest solvent molecules and elevated temperatures.

Maximizing Magnetic Resonance Contrast in Gd(III) Nanoconjugates: Investigation of Proton Relaxation in Zirconium Metal-Organic Frameworks.

Gadolinium(III) nanoconjugate contrast agents (CAs) provide significant advantages over small-molecule complexes for magnetic resonance imaging (MRI), namely increased Gd(III) payload and enhanced proton relaxation efficiency (relaxivity, ). Previous research has demonstrated that both the structure and surface chemistry of the nanomaterial substantially influence contrast. We hypothesized that inserting Gd(III) complexes in the pores of a metal-organic framework (MOF) might offer a unique strategy to further explore the parameters of nanomaterial structure and composition, which influence relaxivity.

Isothermal Titration Calorimetry to Explore the Parameter Space of Organophosphorus Agrochemical Adsorption in MOFs.

The expansion of manufacturing and commercial agriculture alongside rapid globalization have resulted in the widespread contamination of freshwater supplies with chemical toxins including persistent organic pollutants. Effective mitigation of such pollution is paramount to the safeguarding of human health, animal and aquatic life, and the environment. Currently, adsorption is the most economically viable water purification strategy.

A Bismuth Metal-Organic Framework as a Contrast Agent for X-ray Computed Tomography.

A new bismuth metal-organic framework (MOF), bismuth-NU-901 (Bi-NU-901), featuring the topology and a pore with a diameter of ∼11 Å, was solvothermally synthesized, and its use as an X-ray computed tomography (CT) contrast agent was tested. X-ray CT is a common diagnostic method used in the medical field. Inside the body, contrast media enhance the distinction between tissues and organs of similar density.

Exploiting π-π Interactions to Design an Efficient Sorbent for Atrazine Removal from Water.

The United States Environmental Protection Agency (EPA) recognizes atrazine, a commonly used herbicide, as an endocrine disrupting compound. Excessive use of this agrochemical results in contamination of surface and ground water supplies via agricultural runoff. Efficient removal of atrazine from contaminated water supplies is paramount.

Direct Imaging of Isolated Single-Molecule Magnets in Metal-Organic Frameworks.

Practical applications involving the magnetic bistability of single-molecule magnets (SMMs) for next-generation computer technologies require nanostructuring, organization, and protection of nanoscale materials in two- or three-dimensional networks, to enable read-and-write processes. Owing to their porous nature and structural long-range order, metal-organic frameworks (MOFs) have been proposed as hosts to facilitate these efforts. Although probing the channels of MOF composites using indirect methods is well established, the use of direct methods to elucidate fundamental structural information is still lacking.

Inorganic "Conductive Glass" Approach to Rendering Mesoporous Metal-Organic Frameworks Electronically Conductive and Chemically Responsive.

A representative mesoporous metal-organic-framework (MOF) material, NU-1000, has been rendered electronically conductive via a robust inorganic approach that permits retention of MOF crystallinity and porosity. The approach is based on condensed-phase grafting of molecular tin species onto the MOF nodes via irreversible reaction with hydroxyl and aqua ligands presented at the node surface, a self-limiting process termed solvothermal installation (of metal ions) in MOFs (SIM, a solution-phase analog of atomic layer deposition in MOFs). Treatment of the modified MOF with aerated steam at 120 °C converts the grafted tin molecules to tetratin(IV)oxy clusters, with the clusters being sited between insulating pairs of zirconia-like nodes (the zirconium component being key to endowing the parent material with requisite chemical and thermal stability).

Acid-Resistant Mesoporous Metal-Organic Framework toward Oral Insulin Delivery: Protein Encapsulation, Protection, and Release.

Diabetes affects millions of people worldwide and the number of diagnoses continues to climb annually. Though several effective medications and therapeutic methods have been developed to treat type 1 (T1DM) and type 2 (T2DM) diabetes mellitus, direct insulin injection remains the only effective treatment for insulin resistant (IR) diabetes patients. Here, we immobilize insulin in a crystalline mesoporous metal-organic framework (MOF), NU-1000, and obtain a high loading of ∼40 wt % in only 30 min.