Adsorption in Pyrene-Based Metal-Organic Frameworks: The Role of Pore Structure and Topology.

Pore topology and chemistry play crucial roles in the adsorption characteristics of metal-organic frameworks (MOFs). To deepen our understanding of the interactions between MOFs and CO during this process, we systematically investigate the adsorption properties of a group of pyrene-based MOFs. These MOFs feature Zn(II) as the metal ion and employ a pyrene-based ligand, specifically 1,3,6,8-tetrakis(-benzoic acid)pyrene (TBAPy).

A Simple, Transition Metal Catalyst-Free Method for the Design of Complex Organic Building Blocks Used to Construct Porous Metal-Organic Frameworks.

The design of metal-organic frameworks (MOFs) having large pore sizes and volumes often requires the use of complex organic ligands, currently synthesized using costly and time-consuming palladium-catalyzed coupling chemistry. Thus, in the present work, a new strategy for ligand design is reported, where piperazine and dihydrophenazine units are used as substitutes for benzene rings, which are the basic building block of most MOF ligands. This chemistry, which is based on simple, nucleophilic aromatic substitution (S Ar) reactions, is used for the transition metal catalyst-free construction of 21 new, carboxylate-based ligands with varying sizes, shapes, and denticity and 15 linear di- and tetra-nitriles.

Hybridization of Synthetic Humins with a Metal-Organic Framework for Precious Metal Recovery and Reuse.

The number of synthetic strategies used to functionalize MOFs with polymers is rapidly growing; this stems from the knowledge that non-native polymeric guests can significantly boost MOF performance in a number of desirable applications. The current work presents a scalable and solid-state method for MOF/polymer composite production. This simple method constitutes mixing a MOF powder, namely, Fe-BTC (BTC = 1,3,5-benzenetricarboxylate), with a biomass-derived solid monomer, 5-hydroxymethylfurfural (HMF), and subsequently heating the solids; the latter promotes both solid-state diffusion of HMF into the MOF and the formation of polymeric humin species with a high density of accessible hydroxyl functionality within the MOF pore.

A Two Step Postsynthetic Modification Strategy: Appending Short Chain Polyamines to Zn-NH-BDC MOF for Enhanced CO Adsorption.

Functionalizing metal-organic frameworks (MOFs) with amines is a commonly used strategy to enhance their performance in CO capture applications. As such, in this work, a two-step strategy to covalently functionalize NH-containing MOFs with short chain polyamines was developed. In the first step, the parent MOF, ZnO(NH-BDC), was exposed to bromoacetyl bromide (BrAcBr), which readily reacts with pendant -NH groups on the 2-amino-1,4-benzenedicarboxylate (NH-BDC) ligand.

The photothermal effect in MOFs: covalent post-synthetic modification of MOFs mediated by UV-Vis light under solvent-free conditions.

Here, we report the covalent post-synthetic modification (CPSM) of MOFs using the photothermal effect. Specifically, we subjected mixtures of a photothermally active MOF and another reagent to irradiation with a UV-Vis lamp. This caused the MOF to heat up, which in turn caused the other reagent to melt and subsequently react with the functional groups on the walls of the MOF pores.

Photothermal Activation of Metal-Organic Frameworks Using a UV-Vis Light Source.

Metal-organic frameworks (MOFs) usually require meticulous removal of the solvent molecules to unlock their potential porosity. Herein, we report a novel one-step method for activating MOFs based on the photothermal effect induced by directly irradiating them with a UV-vis lamp. The localized light-to-heat conversion produced in the MOF crystals upon irradiation enables a very fast solvent removal, thereby significantly reducing the activation time to as low as 30 min and suppressing the need for time-consuming solvent-exchange procedures and vacuum conditions.

Narrowing the Zero-Field Tunneling Resonance by Decreasing the Crystal Symmetry of Mn12 Acetate.

We report the discovery of a less symmetric crystalline phase of Mn12 acetate, a triclinic phase, resulting from recrystallizing the original tetragonal phase reported by Lis in acetonitrile and toluene. This new phase exhibits the same structure of Mn12 acetate clusters and the same positions of tunneling resonances on the magnetic field as the conventional tetragonal phase. However, the width of the zero-field resonance is at least 1 order of magnitude smaller-can be as low as 50 Oe-indicating very small inhomogeneous broadening due to dipolar and nuclear fields.

Synthesis, culture medium stability, and in vitro and in vivo zebrafish embryo toxicity of metal-organic framework nanoparticles.

Metal-organic frameworks (MOFs) are among the most attractive porous materials available today. They have garnered much attention for their potential utility in many different areas such as gas storage, separation, catalysis, and biomedicine. However, very little is known about the possible health or environmental risks of these materials.

Full characterization of the Cu-, Zn-, and Cd-binding properties of CnMT1 and CnMT2, two metallothioneins of the pathogenic fungus Cryptococcus neoformans acting as virulence factors.

We report here the full characterization of the metal binding abilities of CnMT1 and CnMT2, two Cryptococcus neoformans proteins recently identified as metallothioneins (MTs), which have been shown to play a crucial role in the virulence and pathogenicity of this human-infecting fungus. In this work, we first performed a thorough in silico study of the CnMT1 and CnMT2 genes, cDNAs and corresponding encoded products. Subsequently, the Zn(II)-, Cd(II)- and Cu(I) binding abilities of both proteins were fully determined through the analysis of the metal-to-protein stoichiometries and the structural features (determined by ESI-MS, CD, ICP-AES and UV-vis spectroscopies) of the corresponding recombinant Zn-, Cd- and Cu-MT preparations synthesized in metal-enriched media.

Cryptococcus neoformans copper detoxification machinery is critical for fungal virulence.

Copper (Cu) is an essential metal that is toxic at high concentrations. Thus, pathogens often rely on host Cu for growth, but host cells can hyperaccumulate Cu to exert antimicrobial effects. The human fungal pathogen Cryptococcus neoformans encodes many Cu-responsive genes, but their role in infection is unclear.