<scp>H<sub>2</sub>S</scp>and Bioinorganic Metal Complexes

Tonzetich, Zachary J.

doi:10.1002/9781119799900.ch5

Cited by 6 publications

(5 citation statements)

References 105 publications

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“…25,41 Its inherent reactivity and incompatibility with many materials makes constructing a porous material capable of storing and releasing H2S a major challenge. 42,43 Recently, we have shown that the biocompatible Zr-based MOF, Zr-fum (fum = fumarate) or MOF-801, is capable of reversibly binding H2S via hydrogen-bonding interactions between the gas and nodes of the framework. 25 Through triggered release upon exposure to aqueous solution, Zr-fum was able to deliver H2S to injured cells in an in vitro hypoxiareoxygenation model that simulates ischemia-reperfusion injury.…”

Section: Introductionmentioning

confidence: 99%

Transdermal hydrogen sulfide delivery enabled by open metal site metal-organic frameworks

Mandel,

Lotlikar,

Runcevski

et al. 2024

Preprint

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Hydrogen sulfide (H2S) is an endogenously produced gasotransmitter involved in many physiological processes that are integral to proper cellular functioning, including chemical signaling, redox balancing, and modification of vital proteins. Due to its profound anti-inflammatory and antioxidant properties, H2S plays important roles in preventing inflammatory skin disorders and improving wound healing. Transdermal H2S delivery is a therapeutically viable option for the man-agement of such disorders. However, current small-molecule H2S donors are not optimally suited for transdermal deliv-ery and typically generate electrophilic byproducts that may lead to undesired toxicity. Here, we demonstrate that H2S release from metal-organic frameworks (MOFs) bearing coordinatively unsaturated metal centers is a promising alterna-tive for controlled transdermal delivery of gaseous H2S without the release of unwanted byproducts. In particular, exten-sive gas sorption measurements and powder X-ray diffraction (PXRD) studies of eleven MOFs support that the Mg-based framework Mg2(dobdc) (dobdc4− = 2,5-dioxidobenzene-1,4-dicarboxylate) is uniquely well-suited for transdermal H2S delivery due to its strong yet completely reversible binding of H2S, high capacity (14.7 mmol/g or 33.3 wt% at 1 bar and 25 °C), and lack of toxicity. In addition, Rietveld refinement of high-quality synchrotron PXRD data from a H2S-dosed mi-crocrystalline sample of Mg2(dobdc) supports that the high H2S capacity of this framework arises due to the presence of three distinct binding sites: at the Mg centers through a Mg⋅⋅⋅S interaction (primary site), through a short S⋅⋅⋅S interaction to the polarized H2S molecules at the primary sites (secondary site), and in the center of the pores (tertiary site). Last, we demonstrate that transdermal delivery of H2S from this framework is sustained over a 24 h period through porcine skin. Not only is this significantly longer than sodium sulfide (Na2S), but this represents the first example of controlled trans-dermal delivery of pure H2S gas. Overall, H2S-loaded Mg2(dobdc) is an easily accessible, solid-state source of H2S, ena-bling safe storage and transdermal delivery of this therapeutically relevant gas.

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Section: Introductionmentioning

confidence: 99%

Transdermal hydrogen sulfide delivery enabled by open metal site metal-organic frameworks

Mandel,

Lotlikar,

Runcevski

et al. 2024

Preprint

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show abstract

“…30,48 Its inherent reactivity and incompatibility with many materials makes constructing a porous material capable of delivering H 2 S a major challenge. 49,50 Recently, we have shown that the biocompatible Zr-based MOF, Zr-fum (fum = fumarate) or MOF-801, is capable of reversibly binding H 2 S via hydrogen-bonding interactions between the gas and nodes of the framework. 30 Through triggered release upon exposure to aqueous solution, Zr-fum was able to deliver H 2 S to injured cells in an in vitro hypoxiareoxygenation model that simulates ischemia-reperfusion injury.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In addition, the potential side effects of the framework on epidermal and dermal cells have not been thoroughly addressed, though one study reported good biocompatibility between the MOF and dermal fibroblasts . Likewise, although MOF-based DDS have been designed for NO − and CO, − there have been comparatively few such systems tailored for H 2 S delivery. , Its inherent reactivity and incompatibility with many materials makes constructing a porous material capable of delivering H 2 S a major challenge. , …”

Section: Introductionmentioning

confidence: 99%

Transdermal Hydrogen Sulfide Delivery Enabled by Open-Metal-Site Metal–Organic Frameworks

Mandel,

Lotlikar,

Runčevski

et al. 2024

J. Am. Chem. Soc.

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Hydrogen sulfide (H 2 S) is an endogenously produced gasotransmitter involved in many physiological processes that are integral to proper cellular functioning. Due to its profound anti-inflammatory and antioxidant properties, H 2 S plays important roles in preventing inflammatory skin disorders and improving wound healing. Transdermal H 2 S delivery is a therapeutically viable option for the management of such disorders. However, current small-molecule H 2 S donors are not optimally suited for transdermal delivery and typically generate electrophilic byproducts that may lead to undesired toxicity. Here, we demonstrate that H 2 S release from metal−organic frameworks (MOFs) bearing coordinatively unsaturated metal centers is a promising alternative for controlled transdermal delivery of H 2 S. Gas sorption measurements and powder X-ray diffraction (PXRD) studies of 11 MOFs support that the Mg-based framework Mg 2 (dobdc) (dobdc 4− = 2,5-dioxidobenzene-1,4-dicarboxylate) is uniquely well-suited for transdermal H 2 S delivery due to its strong yet reversible binding of H 2 S, high capacity (14.7 mmol/g at 1 bar and 25 °C), and lack of toxicity. In addition, Rietveld refinement of synchrotron PXRD data from H 2 S-dosed Mg 2 (dobdc) supports that the high H 2 S capacity of this framework arises due to the presence of three distinct binding sites. Last, we demonstrate that transdermal delivery of H 2 S from Mg 2 (dobdc) is sustained over a 24 h period through porcine skin. Not only is this significantly longer than sodium sulfide but this represents the first example of controlled transdermal delivery of pure H 2 S gas. Overall, H 2 S-loaded Mg 2 (dobdc) is an easily accessible, solid-state source of H 2 S, enabling safe storage and transdermal delivery of this therapeutically relevant gas.

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“…With nitric oxide (NO) and carbon monoxide (CO) it belongs to the family of the "gasotransmitters". [1][2][3] Whereas the chemical biology of NO and CO has been well studied, this is much less so for H 2 S. Among the cellular targets of H 2 S, the transition metals constitute the more common sites of attack as they easily react with the Lewis-base sulfur of H 2 S. [4][5][6][7][8][9][10][11] More recent studies revealed signaling pathways involving metalloproteins. [12][13][14][15][16] In this context, motivated by our aim of clarifying the reactions H 2 S is involved in, our studies on the coordination of H 2 S to transition metals started a few years ago and focused both on properly tailored low molecular weight metal complexes and on natural metalloproteins.…”

Section: Introductionmentioning

confidence: 99%

Effect of Metal Coordination Environment on the Stability of Zinc Complexes and Their Reactivity with NaSH

Lamberti,

Galotto,

Vasca

et al. 2024

ChemistrySelect

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Metal complexes with multidentate ligands are frequently used as model compounds to shed light on the (bio)‐inorganic chemistry of H2S. Zinc complexes bearing salen‐type ONNO ligands with different bridging groups are particularly relevant in this respect. Here, we describe the use of zinc complexes with the sulfur‐analogues of the ONNO ligands with the S‐donors replacing either the neutral nitrogen donors or the anionic oxygen atoms of the classical salen ligands. In addition, we studied a hexadentate cyclic ligand, with four neutral sulfur atoms and two anionic oxygens. Having two coordinative pockets this ligand is able to form a bimetallic zinc complex. We report how the different coordinative environments of the explored ligands influence the stability of the zinc complexes and their abilities to form the related hydrosulfide species.

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H₂Sand Bioinorganic Metal Complexes

Cited by 6 publications

References 105 publications

Transdermal hydrogen sulfide delivery enabled by open metal site metal-organic frameworks

Transdermal hydrogen sulfide delivery enabled by open metal site metal-organic frameworks

Transdermal Hydrogen Sulfide Delivery Enabled by Open-Metal-Site Metal–Organic Frameworks

Effect of Metal Coordination Environment on the Stability of Zinc Complexes and Their Reactivity with NaSH

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H2Sand Bioinorganic Metal Complexes

Cited by 6 publications

References 105 publications

Transdermal hydrogen sulfide delivery enabled by open metal site metal-organic frameworks

Transdermal hydrogen sulfide delivery enabled by open metal site metal-organic frameworks

Transdermal Hydrogen Sulfide Delivery Enabled by Open-Metal-Site Metal–Organic Frameworks

Effect of Metal Coordination Environment on the Stability of Zinc Complexes and Their Reactivity with NaSH

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H₂Sand Bioinorganic Metal Complexes