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. 2024 Jul 8:12:1430457.
doi: 10.3389/fchem.2024.1430457. eCollection 2024.

From 0D-complex to 3D-MOF: changing the antimicrobial activity of zinc(II) via reaction with aminocinnamic acids

Simone d'Agostino  1 , Laura Macchietti  1 , Raymond J Turner  2 , Fabrizia Grepioni  1
Affiliations

From 0D-complex to 3D-MOF: changing the antimicrobial activity of zinc(II) via reaction with aminocinnamic acids

Simone d'Agostino et al. Front Chem. .

Abstract

Combining zinc nitrate with 3- and/or 4- aminocinnamic acid (3-ACA and 4-ACA, respectively) leads to the formation of the 0D complex [Zn(4-AC)2(H2O)2], the 1D coordination polymer [Zn(3-AC)(4-AC)], and the 2D and 3D MOFs [Zn(3-AC)2]∙2H2O and [Zn(4-AC)2]∙H2O, respectively. These compounds result from the deprotonation of the acid molecules, with the resulting 3- and 4-aminocinnamate anions serving as bidentate terminal or bridging ligands. All solids were fully characterized via single crystal and powder X-ray diffraction and thermal techniques. Given the mild antimicrobial properties of cinnamic acid derivatives and the antibacterial nature of the metal cation, these compounds were assessed and demonstrated very good planktonic cell killing as well as inhibition of biofilm growth against Pseudomonas aeruginosa, Escherichia coli, and Staphylococcus aureus.

Keywords: MOFs; aminocinnamic acid; antimicrobial activity; mechanochemistry; solid state structure; zinc (II) complexes.

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Conflict of interest statement

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Figures

SCHEME 1
SCHEME 1
4- and 3- aminocinnamic acids (4-ACA and 3-ACA) and their deprotonated forms 4- and 3- aminocinnamate anions (4-AC- and 3-AC-).
FIGURE 1
FIGURE 1
Comparison between the experimental PXRD patterns for the starting materials 4-ACA, NaOH, and Zn(NO3)2∙6H2O and for the milling product [Zn(4-AC)2]∙H2O] as prepared and after washing with water. The asterisk indicates the presence of NaNO3 as a by-product.
FIGURE 2
FIGURE 2
Tetrahedral coordination geometry of the 3-cinnamate anions around the zinc(II) cation in crystalline [Zn(3-AC)2]∙2H2O (A). Stacking of 2D-layers (B) and a representation of the infinite channels (C), each filled with a water molecules chain (D). Coordination polyhedra around the zinc cation in purple, C atoms in orange, Owater atoms in blue. HCH atoms omitted for clarity.
FIGURE 3
FIGURE 3
Infinite channels, shown here either filled with water molecules (A) and empty (B), extend parallel to the a-axis direction in crystalline [Zn(4-AC)2]∙H2O. The water molecules inside the channel are largely spaced and they are at hydrogen bonding distance with the surrounding carboxylate and amino groups. Coordination polyhedra around the zinc cation in purple, empty channels evidenced in ochra, Owater atoms in blue. HCH atoms omitted for clarity.
FIGURE 4
FIGURE 4
Main packing motif in crystalline [Zn(3-AC)(4-AC)]. Each 3- and 4-cinnamate ligand is bridging two Zn2+ cations; the resulting motif is an infinite ribbon (A) in which pairs of different cinnamate anions are at π-π stacking distance (B). C atoms in orange and grey for the 3- and 4-cinnamate anions, respectively; zinc(II) in purple; HCH atoms omitted for clarity.
FIGURE 5
FIGURE 5
The 0D complex [Zn(4-AC)2(H2O)2] (top), and the 3D hydrogen bonding network (bottom) involving the water molecules bound to zinc and the carboxylate and amino groups belonging to adjacent 4-cynnamate ligands. [Zinc(II) in purple, Owater atoms in blue. HCH atoms omitted for clarity].
SCHEME 2
SCHEME 2
The solid-state products of mechanochemical and solution reactions of 4-ACA and 3-ACA with zinc nitrate.
FIGURE 6
FIGURE 6
The Antimicrobial and antibiofilm activity of the compound. Concentration exposure at 0.5 mg/mL Zn equivalent levels. (A) Planktonic cell kill reflecting the culture viable cell density reduction in log10. (B) Evaluation of total biofilm density of cultures compared to unchallenged (averages and standard deviations from 4 replicates).
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