Biomimetic Photodegradation of Glyphosate in Carborane-Functionalized Nanoconfined Spaces

Биомиметическая фотодеградация глифосата в наноконфинированных пространствах, функционализированных карборанами
Lei Gan, Makenzie T. Nord, Jacob M. Lessard, Noah Q. Tufts, Arunraj Chidambaram, Mark E. Light, Hongliang Huang, Eduardo Solano, Julio Fraile, Fabián Suárez‐García, Clara Viñas, Francesç Teixidor, Kyriakos C. Stylianou, José Giner Planas
2023-06-20

biomimetic C–P lyase pathwaycarborane-functionalized MOFglyphosate photodegradationmCB-MOF-2organophosphorus herbicide removal
High Resolution Image Download MS PowerPoint Slide The removal of organophosphorus (OP) herbicides from water has been studied using adsorptive removal, chemical oxidation, electrooxidation, enzymatic degradation, and photodegradation. The OP herbicide glyphosate (GP) is one of the most used herbicides worldwide, leading to excess GP in wastewater and soil. GP is commonly broken down in environmental conditions to compounds such as aminomethylphosphonic acid (AMPA) or sarcosine, with AMPA having a longer half-life and similar toxicity to GP. Metal–organic frameworks (MOFs) are excellent materials for purifying OP herbicides from water due to their ability to combine adsorption and photoactivity within one material. Herein, we report the use of a robust Zr-based MOF with a meta -carborane carboxylate ligand ( m CB-MOF-2 ) to examine the adsorption and photodegradation of GP. The maximum adsorption capacity of m CB-MOF-2 for GP was determined to be 11.4 mmol/g. Non-covalent intermolecular forces between the carborane-based ligand and GP within the micropores of m CB-MOF-2 are thought to be responsible for strong binding affinity and capture of GP. After 24 h of irradiation with ultraviolet–visible (UV–vis) light, m CB-MOF-2 selectively converts 69% of GP to sarcosine and orthophosphate, following the C–P lyase enzymatic pathway and biomimetically photodegrading GP. Circumventing the production of AMPA is desirable, as it has a longer half-life and similar toxicity to GP. The exceptional adsorption capacity of GP by m CB-MOF-2 and its biomimetic photodegradation to non-toxic sarcosine make it a promising material for removing OP herbicides from water.
1
A robust zirconium-based MOF containing a meta-carborane carboxylate ligand was developed to combine glyphosate adsorption and photodegradation.
2
After 24 hours of UV–visible irradiation, mCB-MOF-2 selectively converts 69% of glyphosate into sarcosine and orthophosphate.
3
The material’s strong glyphosate capture and conversion to nontoxic sarcosine indicate promise for removing organophosphorus herbicides from water.
4
The photodegradation follows a biomimetic C–P lyase enzymatic pathway and avoids forming AMPA, which has similar toxicity and a longer half-life than glyphosate.
5
mCB-MOF-2 exhibits a maximum glyphosate adsorption capacity of 11.4 mmol/g, attributed to noncovalent interactions within its micropores.

Glyphosate in water treated with the carborane-functionalized Zr-based MOF mCB-MOF-2

Adsorption capacity, binding affinity, and biomimetic UV–vis photodegradation of glyphosate into sarcosine and orthophosphate while circumventing AMPA formation

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2023-06-20
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Authors
Lei Gan
Makenzie T. Nord
Jacob M. Lessard
Noah Q. Tufts
Arunraj Chidambaram
Mark E. Light
Hongliang Huang
Eduardo Solano
Julio Fraile
Fabián Suárez‐García
Clara Viñas
Francesç Teixidor
Kyriakos C. Stylianou
José Giner Planas
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