Encapsulation of β-alanine model amino-acid in zirconium(IV) metal organic frameworks: Defect engineering to improve host guest interactions

Asier R Muguruza; Roberto Fernandez de Luis; Naroa Iglesias; Begoña Bazán; Miren-Karmele Urtiaga; Edurne S Larrea; Arkaitz Fidalgo-Marijuan; Gotzone Barandika

doi:10.1016/j.jinorgbio.2019.110977

Encapsulation of β-alanine model amino-acid in zirconium(IV) metal organic frameworks: Defect engineering to improve host guest interactions

J Inorg Biochem. 2020 Apr:205:110977. doi: 10.1016/j.jinorgbio.2019.110977. Epub 2019 Dec 28.

Authors

Asier R Muguruza¹, Roberto Fernandez de Luis², Naroa Iglesias², Begoña Bazán³, Miren-Karmele Urtiaga⁴, Edurne S Larrea⁴, Arkaitz Fidalgo-Marijuan², Gotzone Barandika⁵

Affiliations

¹ Dept. of Inorganic Chemistry, Universidad del País Vasco (UPV/EHU), Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain; BCMaterials, Ed. Martiana Casiano, Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain.
² BCMaterials, Ed. Martiana Casiano, Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain.
³ BCMaterials, Ed. Martiana Casiano, Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain; Dept. of Mineralogy and Petrology, Universidad del País Vasco (UPV/EHU), Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain.
⁴ Dept. of Mineralogy and Petrology, Universidad del País Vasco (UPV/EHU), Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain.
⁵ Dept. of Inorganic Chemistry, Universidad del País Vasco (UPV/EHU), Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain; BCMaterials, Ed. Martiana Casiano, Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain. Electronic address: gotzone.barandika@ehu.eus.

PMID: 31926376
DOI: 10.1016/j.jinorgbio.2019.110977

Abstract

Metal-Organic Frameworks (MOFs) are porous coordination networks assembled through metal complexes with organic linkers. Due to their chemical versatility, these materials are being investigated for various applications including gas storage and separation, biomedicine and catalysis. The aim of this work is the encapsulation of the model β-alanine amino-acid in the nanostructured zirconium-based MOF (UiO-66) which contains the ligand H₂BDC (1,4-benzenedicaboxylic acid). Additionally, ligand functionalization (by using H₂doBDC (2,5-dihydroxy-1,4-benzenedicarboxylic acid) and defect engineering have been carried out to produce UiO-66 derivatives, in order to modify the host-guest interactions, and hence study their influence on the β-alanine loading capacity and release kinetics. The as-obtained materials have been characterized by X-ray diffraction (XRD), X-ray thermo diffraction (TDX), infrared (IR) spectroscopy, thermogravimetric analysis-differential scanning calorimetry (TG-DSC) and elemental analysis (EA). Morphology of nanoscale MOFs has been explored by transition electron microscopy (TEM). Adsorption isotherms have been constructed, and the concentration of β-alanine in the post-adsorption solution (supernatant) has been quantified by high performance liquid chromatography coupled with mass spectroscopy (HPLC-MS) and EA. Adsorption capacity values indicate that the presence of hydroxyl groups at the organic linker H₂doBDC enhances the host-guess affinity between the framework and the adsorbate β-alanine. The influence of defect engineering, on the adsorption however, is not that obvious. On the other hand, desorption experiments show similar behaviour for H₂doBDC-based derivatives. An adsorption mechanism has been proposed consisting of a combination of host-guest interaction at low concentrations, and covalent anchoring/ligand displacement by β-alanine at the inorganic clusters.

Keywords: Defect engineering; Drug delivery systems; Encapsulation; Host-guest interactions; Zirconium(IV)-based metal organic frameworks; β-Alanine.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Catalysis
Metal-Organic Frameworks / chemical synthesis*
Metal-Organic Frameworks / chemistry*
Zirconium / chemistry*
beta-Alanine / chemistry*

Substances

Metal-Organic Frameworks
beta-Alanine
Zirconium