Synthesis and characterization of a Bio-MOF based on mixed adeninate/tricarboxylate ligands and zinc ions

Rare earth elements (REEs) are critical to numerous technologies; however, a combination of increasing demand, environmental concerns, and monopolistic marketplace conditions has spurred interest in boosting the domestic REE production from sources such as coal utilization byproducts. The economic viability of this approach requires rapid, inexpensive, and sensitive analytical techniques capable of characterizing the REE content during resource exploration and downstream REE processing (e.g., analyzing REE separation, concentration, and purification production steps). Luminescence-based sensors are attractive because many REEs may be sensitized to produce element-specific emission. Hence, a single material may simultaneously detect and distinguish multiple REEs. Metal–organic frameworks (MOFs) can sensitize multiple REEs, but their viability has been hindered by sensitivity and selectivity challenges. Understanding how the MOF structure impacts the REE sensing efficacy is critical to the rational design of new sensors. Here, we evaluate the sensing performance of seven different anionic zinc-adeninate MOFs with different organic linkers and/or structures for the visible-emitting REEs Tb, Dy, Sm, and Eu. The choice of a linker determines which REEs are sensitized and significantly influences their sensitivity and selectivity against competing species (here, Fe(II) and HCl). For a given linker, structural changes to the MOF can further fine-tune the performance. The MOFs produce some of the lowest detection limits (sub-10 ppb for Tb) reported for the aqueous sensitization-based REE detection. Importantly, the most selective MOFs demonstrated the ability to sensitize the REE signal at sub-ppm levels in a REE-spiked acid mine drainage matrix, highlighting their potential for use in real-world sensing applications.

show abstract

“…BTC-2 was synthesized following an existing literature protocol . Briefly, 82.8 mg of adenine was dissolved in 8 mL of DMF.…”

Section: Experimental Sectionmentioning

confidence: 99%

“…BTC-2 was synthesized following an existing literature protocol. 49 Briefly, 82.8 mg of adenine was dissolved in 8 mL of DMF. In a separate vial, 83.7 mg of zinc chloride and 41.7 mg of sodium formate were dissolved in 4 mL of DMF, stirring at 1200 rpm.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Influence of the Anionic Zinc-Adeninate Metal–Organic Framework Structure on the Luminescent Detection of Rare Earth Ions in Aqueous Streams

Crawford

Ellis

Ohodnicki

et al. 2021

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

show abstract

“…54,55 These results were consistent with those in previous experiments, providing sufficient evidence that all bio-MOF-1 crystals could generally maintain their structures until a temperature of 400 °C. 43,56…”

Section: Resultsmentioning

confidence: 99%

Surface modification of the Ti surface with nanoscale bio-MOF-1 for improving biocompatibility and osteointegration in vitro and in vivo

Jiang

Xie

et al. 2022

J. Mater. Chem. B

View full text Add to dashboard Cite

show abstract

“…Whilst increasing linker length via isoreticular expansion has been thoroughly studied as a means of synthesising HPMOFs, the use of larger SBUs has received less attention [ 121 , 122 , 123 , 124 ]. Larger SBUs result in MOFs with higher connectivity, and thus larger pore size.…”

Section: Synthesismentioning

confidence: 99%

“…Biomolecules have also been used as ligands in the synthesis of MOFs, ranging from amino acids [ 223 , 224 ], peptides [ 187 , 188 ], oligosaccharides [ 225 , 226 , 227 ], nucleobases [ 51 , 123 , 172 ] as well as secondary metabolites [ 222 ]. There is a significant synthetic challenge in the synthesis due the requirement for strong metal coordinating groups in the biomolecules as well as their high flexibility making it challenging to construct rigid, crystalline and permanently porous materials.…”

Section: Large Biomoleculesmentioning

confidence: 99%

Synthesis and Biomedical Applications of Highly Porous Metal–Organic Frameworks

Ahmed

McHugh

Papatriantafyllopoulou

2022

Molecules

View full text Add to dashboard Cite

In this review, aspects of the synthesis, framework topologies, and biomedical applications of highly porous metal–organic frameworks are discussed. The term “highly porous metal–organic frameworks” (HPMOFs) is used to denote MOFs with a surface area larger than 4000 m2 g−1. Such compounds are suitable for the encapsulation of a variety of large guest molecules, ranging from organic dyes to drugs and proteins, and hence they can address major contemporary challenges in the environmental and biomedical field. Numerous synthetic approaches towards HPMOFs have been developed and discussed herein. Attempts are made to categorise the most successful synthetic strategies; however, these are often not independent from each other, and a combination of different parameters is required to be thoroughly considered for the synthesis of stable HPMOFs. The majority of the HPMOFs in this review are of special interest not only because of their high porosity and fascinating structures, but also due to their capability to encapsulate and deliver drugs, proteins, enzymes, genes, or cells; hence, they are excellent candidates in biomedical applications that involve drug delivery, enzyme immobilisation, gene targeting, etc. The encapsulation strategies are described, and the MOFs are categorised according to the type of biomolecule they are able to encapsulate. The research field of HPMOFs has witnessed tremendous development recently. Their intriguing features and potential applications attract researchers’ interest and promise an auspicious future for this class of highly porous materials.

show abstract

Synthesis and characterization of a Bio-MOF based on mixed adeninate/tricarboxylate ligands and zinc ions

Cited by 16 publications

References 37 publications

Influence of the Anionic Zinc-Adeninate Metal–Organic Framework Structure on the Luminescent Detection of Rare Earth Ions in Aqueous Streams

Influence of the Anionic Zinc-Adeninate Metal–Organic Framework Structure on the Luminescent Detection of Rare Earth Ions in Aqueous Streams

Surface modification of the Ti surface with nanoscale bio-MOF-1 for improving biocompatibility and osteointegration in vitro and in vivo

Synthesis and Biomedical Applications of Highly Porous Metal–Organic Frameworks

Contact Info

Product

Resources

About