Author: Isabel Abánades Lázaro

Controlled Transdermal Release of Antioxidant Ferulate by a Porous Sc(III) MOF

Summary The Sc(III) MOF-type MFM-300(Sc) is demonstrated in this study to be stable under physiological conditions (PBS), biocompatible (to human skin cells), and an efficient drug carrier for the long-term controlled release (through human skin) of antioxidant ferulate. MFM-300(Sc) also preserves the antioxidant pharmacological effects of ferulate while enhancing the bio-preservation of dermal skin fibroblasts, during the delivery process. These discoveries pave the way toward the extended use of Sc(III)-based MOFs as drug delivery systems (DDSs).

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Linker depletion for missing cluster defects in non-UiO Metal-Organic Frameworks

Defect engineering is a valuable tool to tune the properties of metal–organic frameworks. However, defect chemistry remains still predominantly limited to UiO-type MOFs. We describe the preferential formation of missing cluster defects in heterometallic titanium–organic frameworks of the MUV-10 family when synthesised in sub-stoichiometric linker conditions. Our results show the value of integrating experimental work, computational modelling and thorough characterization in rationalizing the impact of defects over the porosity and structure of this family of materials. Correlation of experiment with computational models reveals the dominance of missing cluster vacancies in the pore size dis…

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Effect of modulator connectivity on promoting defectivity in titanium–organic frameworks

The recognition of defect chemistry as a true synthetic tool for targeted creation of defects and controllable performance remains limited by the pool of frameworks explored. The value of defect engineering in controlling the properties of defective frameworks has been beautifully exemplified and largely demonstrated with UiO-type materials based on Zr(iv) nodes. However, titanium–organic frameworks remain largely unexplored in this context arguably due to the complex chemistry in solution of Ti(iv) and the difficulties in growing crystalline solids. We report a systematic study on the ability of mono- and dicarboxylic modulators (benzoic and isophthalic acid) to promote defect creation in …

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Controlling the molecular diffusion in MOFs with the acidity of monocarboxylate modulators.

The catalytic performance of metal-organic frameworks (MOFs) is related to their physicochemical properties, such as particle size, defect-chemistry and porosity, which synthetic control can be potentially achieved by coordination modulation. By combining PXRD, 1HNMR, FT-IR, N2 uptake measurements we have found insights that the different types of defects (missing linker or missing clusters consequence of the spatial distribution of missing linkers, and the combination of both) could be controlled by the type of modulator employed. We show that the molar percent of defects, either as missing linkers or as part of missing cluster defects, is related to the modulator’s acidity and subse…

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The excellent biocompatibility and negligible immune response of the titanium heterometallic MOF MUV-10

The Ti-Ca heterometallic MOF MUV-10 exhibits good dispersibility in phosphate buffer and low phosphate-induced degradation in comparison to other MOF systems. It induces no cytotoxicity towards cells of the immune system and no inmune response, making it an attractive candidate for biomedical applications and demonstrating its safe use for other applications.

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Ultramicroporous iron-isonicotinate MOFs combining size-exclusion kinetics and thermodynamics for efficient CO2/N2 gas separation

Two ultramicroporous 2D and 3D iron-based Metal-Organic Frameworks (MOFs) have been obtained by solvothermal synthesis using different ratios and concentrations of precursors. Their reduced pore space decorated with pendant pyridine from tangling isonicotinic ligands enables the combination of size-exclusion kinetic gas separation, due to their small pores, with thermodynamic separation, resulting from the interaction of the linker with CO2 molecules. This combined separation results in efficient materials for dynamic breakthrough gas separation with virtually infinite CO2/N2 selectivity in a wide operando range and with complete renewability at room temperature and ambient pressure.

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Rationalising the Multivariate Modulation of MUV-10 for the Defect-Introduction of Multiple Functionalised Modulators

Among multivariate Metal-Organic Frameworks, multivariate modulated (MTVM) MOFs offer the possibility of introducing multiple functionalised units into the MOFs as defect-compensating ligands promoting porosity among other defect-related properties. However, there are no studies that rationalise the incorporation of multiple functionalised modulators and their resultant properties, hindering their molecular design and multi-applicability. In this manuscript, we introduce up to five functionalised modulators bearing NO2, F, tBu, OH and NH2 units in significant quantities (up to ca. 31 mol%) into the Ti heterometallic MOF MUV-10 in one-pot synthesis, increasing the porosity up to ca. 1.3-fold…

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A Comprehensive Thermogravimetric Analysis Multifaceted Method for the Exact Determination of the Composition of Multifunctional Metal‐Organic Framework Materials

Thermogravimetric analysis (TGA) has been widely used as a tool to characterise the composition of materials such as Metal-Organic Frameworks (MOFs). However, given their multifunctionality and structural complexity, examples of detailed methodologies for the exact calculation of the composition of complex MOF structures and MOF composites are lacking in the literature. Herein, we introduce a new straightforward methodology – based on the experimental ratio between the mass of a structure and its residue – for the exact calculation of the composition of almost any MOF material. We provide a detailed guide for the application of our methodology to different MOF materials, including MOFs in w…

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Tuning the Photocatalytic Activity of Ti-Based Metal-Organic Frameworks through Modulator Defect-Engineered Functionalization.

Defect engineering is a valuable tool to tune the photocatalytic activity of metal–organic frameworks (MOFs). Inducing defects through the attachment of functionalized modulators can introduce cooperative units that can tune the bandgap of the material and enhance their chemical, thermal, and photostabilities among other properties. However, the majority of defect engineering studies for photocatalytic applications are limited to Zr-based MOFs, and there is still a lack of interrelation between synthetic variables, the resultant MOF properties, and their effect on their photocatalytic performance. We report a comprehensive study on the defect engineering of the titanium heterometallic MOF M…

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