Alkylaminopyridine-Modified Aluminum Aminoterephthalate Metal-Organic Frameworks As Components of Reactive Self-Detoxifying Materials

Abstract

Aluminum aminoterephthalate MOF particulate materials (NH(2)-MIL-101(Al) and NH(2)-MIL-53(Al)), studied here as components of self-detoxifying surfaces, retained their reactivity following their covalent attachment to protective surfaces utilizing a newly developed strategy in which the MOF particles were deposited on a reactive adhesive composed of polyisobutylene/toluene diisocyanate (PIB/TDI) blends. Following MOF attachment and curing, the MOF primary amino groups were functionalized with highly nucleophilic 4-methylaminopyridine (4-MAP) by disuccinimidyl suberate-activated conjugation. The resulting MOF-4-MAP modified PIB/TDI elastomeric films were mechanically flexible and capable of degrading diisopropyl fluorophosphate (DFP), a chemical threat simulant.

Toxic gas removal – metal–organic frameworks for the capture and degradation of toxic gases and vapours

“…Thus, Su, Liu and colleagues have taken advantage of the improved hydrolytic activity of the sodalite type H 3 [(Cu 4 Cl) 3 (btc) 8 ] 2 [PW 12 O 40 ] 3 (C 4 H 12 N) 6 (NENU-11) system for the capture and posterior hydrolytic degradation of the model nerve agent dimethylmethylphosphonate (DMMP). 49 Hatton and colleagues 50 have reported the incorporation of highly nucleophilic 4-methylaminopyridine residues by means of covalent coupling of the amino residues of aluminium aminoterephthalate MOF systems to give rise to [Al 3 OF(4-MAP-NH-bdc) 2 ] (NH 2 -MIL-101(Al)) and [AlOH(4-MAP-NH-bdc)] (4-MAP-NH-MIL-53(Al)) active materials (Fig. 10).…”

Textile/Metal–Organic‐Framework Composites as Self‐Detoxifying Filters for Chemical‐Warfare Agents

“…[1,2] Indeed, the suitability of the established [Cu 3 (btc) 2 ]( btc = benzene-1,3,5-tricarboxylate) system has been studied in the capture and degradation of CWAs, [4][5][6][7] however, the results show ap oor performance related to its limited stability to hydrolysis. [9] In the search for more efficient MOF materials for this application, [Zr 6 O 4 (OH) 4 (bdc) 6 ]( bdc = benzene-1,4-dicarboxylate) system, named UiO-66 ( Figure 1), is receiving attention because of its robustness [10] and the Lewis acidic nature of the Zr 4+ centers [11] which combined with the basic hydroxide residues gives rise to biomimetic phosphotriesterase activity useful for the hydrolysis of simulants of nerve agents. [9] In the search for more efficient MOF materials for this application, [Zr 6 O 4 (OH) 4 (bdc) 6 ]( bdc = benzene-1,4-dicarboxylate) system, named UiO-66 ( Figure 1), is receiving attention because of its robustness [10] and the Lewis acidic nature of the Zr 4+ centers [11] which combined with the basic hydroxide residues gives rise to biomimetic phosphotriesterase activity useful for the hydrolysis of simulants of nerve agents.…”

“…[8] Themore robust [Al 3 (OH)F-(bdc_NH 2 ) 2 ]( NH 2 -MIL-101(Al)) and [AlOH(bdc_NH 2 )] (NH 2 -MIL-53(Al)) systems,w here bdc_NH 2 = 2-aminobenzene-1,4-dicarboxylate,h ave been assayed for the hydrolysis of the nerve-agent simulant diisopropylfluorophosphate (DIFP) after the covalent attachment of 4-methylaminopyridine nucleophile,tothe bdc_NH 2 linkers. [9] In the search for more efficient MOF materials for this application, [Zr 6 O 4 (OH) 4 (bdc) 6 ]( bdc = benzene-1,4-dicarboxylate) system, named UiO-66 ( Figure 1), is receiving attention because of its robustness [10] and the Lewis acidic nature of the Zr 4+ centers [11] which combined with the basic hydroxide residues gives rise to biomimetic phosphotriesterase activity useful for the hydrolysis of simulants of nerve agents. [12] Herein, we show different post-synthetic approaches (introduction of acidic and basic sites and/or missing linker defects) to further improve the phosphotriesterase activity of UiO-66 for the capture and hydrolytic degradation of CWA simulants ( Figure 1a nd Scheme 1).…”

Simple and Compelling Biomimetic Metal–Organic Framework Catalyst for the Degradation of Nerve Agent Simulants

“…[29] Herein, we report the use of the MOF UiO-66 (Figure 1 c) [30] as a compelling biomimetic catalyst for the methanolysis and hydrolysis of two organophosphate nerve agent simulants. [31] The node of UiO-66 is a [Zr 6 O 4 (OH) 4 ] cluster that contains several Zr À OH À Zr bonds, reminiscent of the bimetallic ZnÀOHÀZn active site found in phosphotriesterase enzymes (Figure 1 a,b). UiO-66 is also particularly attractive as a solid catalyst because: 1) it is readily synthesized in high yield, and 2) it is among the most chemically, hydrothermally, and mechanically stable MOFs known.…”