Inside polyMOFs: layered structures in polymer-based metal-organic frameworks.

In this report, we explore the internal structural features of polyMOFs consisting of equal mass ratios of metal-coordinating poly(benzenedicarboxylic acid) blocks and non-coordinating poly(ethylene glycol) (PEG) blocks. The studies reveal alternating lamellae of metal-rich, crystalline regions and metal-deficient non-crystalline polymer, which span the length of hundreds of nanometers. Polymers consisting of random PEG blocks, PEG end-blocks, or non-coordinating poly(cyclooctadiene) (COD) show similar alternation of metal-rich and metal-deficient regions, indicating a universal self-assembly mechanism.

Remote Detection of HCN, HF, and Nerve Agent Vapors Based on Self-Referencing, Dye-Impregnated Porous Silicon Photonic Crystals.

A one-dimensional photonic crystal is prepared from porous silicon (pSi) and impregnated with a chemically specific colorimetric indicator dye to provide a self-referenced vapor sensor for the selective detection of hydrogen fluoride (HF), hydrogen cyanide (HCN), and the chemical nerve agent diisopropyl fluorophosphate (DFP). The photonic crystal is prepared with two stop bands: one that coincides with the optical absorbance of the relevant activated indicator dye and the other in a spectrally "clear" region, to provide a reference. The inner pore walls of the pSi sample are then modified with octadecylsilane to provide a hydrophobic interior, and the indicator dye of interest is then loaded into the mesoporous matrix.

Darunavir-Resistant HIV-1 Protease Constructs Uphold a Conformational Selection Hypothesis for Drug Resistance.

Multidrug resistance continues to be a barrier to the effectiveness of highly active antiretroviral therapy in the treatment of human immunodeficiency virus 1 (HIV-1) infection. Darunavir (DRV) is a highly potent protease inhibitor (PI) that is oftentimes effective when drug resistance has emerged against first-generation inhibitors. Resistance to darunavir does evolve and requires 10-20 amino acid substitutions.

Insights into the Structure and Dynamics of Metal-Organic Frameworks via Transmission Electron Microscopy.

Metal-organic frameworks (MOFs) are hybrid materials composed of metal ions and organic linkers featuring high porosity, crystallinity, and chemical tunability at multiple length scales. A recent advancement in transmission electron microscopy (TEM) and its direct application to MOF structure-property relationships have changed how we consider rational MOF design and development. Herein, we provide a perspective on TEM studies of MOFs and highlight the utilization of state-of-the-art TEM technologies to explore dynamic MOF processes and host-guest interactions.

MOF-Polymer Hybrid Materials: From Simple Composites to Tailored Architectures.

Metal-organic frameworks (MOFs) are inherently crystalline, brittle porous solids. Conversely, polymers are flexible, malleable, and processable solids that are used for a broad range of commonly used technologies. The stark differences between the nature of MOFs and polymers has motivated efforts to hybridize crystalline MOFs and flexible polymers to produce composites that retain the desired properties of these disparate materials.

Hierarchical Fractal Assemblies from Poly(ethylene oxide- b-lysine- b-leucine).

Poly(ethylene oxide- b-lysine- b-leucine) (wherein subscripts denote the degree of polymerization) was synthesized via ring-opening polymerization of N-carboxyanhydrides using an amine-terminated poly(ethylene oxide) macroinitiator, with polypeptide blocks produced by sequential monomer addition. Infrared and circular dichroism spectroscopy indicated that the peptide blocks in this polymer formed α-helices in the solid and solution states, respectively. In the aqueous solution, this polymer self-assembled into spherical micelles with a hydrodynamic radius of approximately 90 nm at concentrations between 0.

Multiple functional groups in UiO-66 improve chemical warfare agent simulant degradation.

A library of 26 mixed ligand UiO-66 analogs was synthesized, characterized, and screened for catalytic degradation of the chemical warfare agent (CWA) simulant dimethyl 4-nitrophenylphosphate (DMNP). The MOFs were screened and compared to physical mixtures of the same single component MOFs. Several of the MOFs display higher catalytic activity than the parent UiO-66 and other single ligand UiO-66 analogues.

Defect-Free MOF-Based Mixed-Matrix Membranes Obtained by Corona Cross-Linking.

Functionalized UiO-66 metal-organic frameworks (MOF) particles were covalently grafted with hydride-terminated poly(dimethylsiloxane) (PDMS) via postsynthetic modification. These PDMS-coated MOF particles (termed here "corona-MOF") were used in the preparation of mixed-matrix membranes (MMMs). Defect-free MMMs with weight loadings of 50% were achieved with corona-MOF particles, attributed to the improved dispersibility of the corona-MOF particles and covalent linkages between the corona-MOF particles and the polymer matrix.

Block co-polyMOFs: morphology control of polymer-MOF hybrid materials.

The hybridization of block copolymers and metal-organic frameworks (MOFs) to create novel materials (block co-polyMOFs, BCPMOFs) with controlled morphologies is reported. In this study, block copolymers containing poly(1,4-benzenedicarboxylic acid, Hbdc) and morphology directing poly(ethylene glycol) (PEG) or poly(cyclooctadiene) (poly(COD)) blocks were synthesized for the preparation of BCPMOFs. Block copolymer architecture and weight fractions were found to have a significant impact on the resulting morphology, mediated through the assembly of polymer precursors prior to MOF formation, as determined through dynamic light scattering.

Halogen bonding in UiO-66 frameworks promotes superior chemical warfare agent simulant degradation.

Herein, a series of halogenated UiO-66 derivatives was synthesized and analyzed for the breakdown of the chemical warfare agent simulant dimethyl-4-nitrophenyl phosphate (DMNP) to analyze ligand effects. UiO-66-I degrades DMNP at a rate four times faster than the most active previously reported MOFs. MOF defects were quantified and ruled out as a cause for increased activity.

Multicomponent metal-organic framework membranes for advanced functional composites.

The diverse chemical and structural properties of metal-organic frameworks (MOFs) make them attractive for myriad applications, but their native powder form is limiting for industrial implementation. Composite materials of MOFs hold promise as a means of exploiting MOF properties in engineered forms for real-world applications. While interest in MOF composites is growing, research to date has largely focused on utilization of single MOF systems.

Nylon-MOF Composites through Postsynthetic Polymerization.

Hybridization of metal-organic frameworks (MOFs) and polymers into composites yields materials that display the exceptional properties of MOFs with the robustness of polymers. However, the realization of MOF-polymer composites requires efficient dispersion and interactions of MOF particles with polymer matrices, which remains a significant challenge. Herein, we report a simple, scalable, bench-top approach to covalently tethered nylon-MOF polymer composite materials through an interfacial polymerization technique.

Probing Membrane Hydration at the Interface of Self-Assembled Peptide Amphiphiles Using Electron Paramagnetic Resonance.

The relative hydrophilicity at the interface of a nanoparticle was measured utilizing electron paramagnetic resonance (EPR) spectroscopy. The supramolecular structure was assembled from spin-labeled peptide amphiphiles (PA) derived from carboxy anhydrides (NCA). Cyanuric chloride, or 2,4,6-trichloro-1,3,5-triazine (TCT), was used as a modular platform to synthesize the spin-labeled, lipid-mimetic macroinitiator used for the ring-opening polymerization of γ-benzyl-l-glutamic acid NCA to produce polyglutamate--dodecanethiol.

Quantitative relationship between cavitation and shear rheology.

Cavitation rheology is a powerful, simple, and inexpensive technique to study the moduli of polymer gels, however its use has not yet become widespread because few studies to date have directly compared this technique to traditional oscillatory shear rheology. Herein, we report a quantitative relationship between the gel modulus determined using cavitation and shear rheology for three series of model gels whose networks are composed of (1) permanently covalent, (2) dynamic-covalent, and (3) physical hydrogen-bond crosslinks. We determine a simple proportionality constant that allows for conversion of the moduli obtained from both types of experiments and is highly dependent on the bond energy responsible for gelation.

Supramolecular Metallopolymers: From Linear Materials to Infinite Networks.

The fields of coordination polymers (CPs) and supramolecular metallopolymers (SMPs) have been extensively studied for decades. Spectacular recent advances in both fields have created new compounds that lie at the interface between these two classes of organic-inorganic hybrid materials. At this interface, materials based on molecular weaving, supramolecular clusters, and metal-organic framework-polymer hybrids have emerged.