Antifouling and antimicrobial cobaltocenium-containing metallopolymer double-network hydrogels

doi:10.12336/biomatertransl.2022.02.008

Biomaterials Translational ›› 2022, Vol. 3 ›› Issue (2): 162-171.doi: 10.12336/biomatertransl.2022.02.008

• RESEARCH ARTICLE • Previous Articles

Antifouling and antimicrobial cobaltocenium-containing metallopolymer double-network hydrogels

Hui Li¹^,², Peng Yang¹, JiHyeon Hwang¹, Parasmani Pageni¹, Alan W. Decho³, Chuanbing Tang¹^,^*()

1 Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC, USA
2 School of Chemistry and Chemical Engineering, University of Jinan, Jinan, Shandong Province, China
3 Department of Environmental Health Sciences, Arnold School of Public Health, University of South Carolina, Columbia, SC, USA

Received:2022-04-07 Revised:2022-05-19 Accepted:2022-06-13 Online:2022-06-28 Published:2022-06-28
Contact: Chuanbing Tang E-mail:tang4@mailbox.sc.edu
About author:Chuanbing Tang, tang4@mailbox.sc.edu.
First author contact:#Author Equally.

Abstract

Abstract:

Compared with single-network hydrogels, double-network hydrogels offer higher mechanical strength and toughness. Integrating useful functions into double-network hydrogels can expand the portfolios of the hydrogels. We report the preparation of double-network metallopolymer hydrogels with remarkable hydration, antifouling, and antimicrobial properties. These cationic hydrogels are composed of a first network of cationic cobaltocenium polyelectrolytes and a second network of polyacrylamide, all prepared via radical polymerization. Antibiotics were further installed into the hydrogels via ion-complexation with metal cations. These hydrogels exhibited significantly enhanced hydration, compared with polyacrylamide-based hydrogels, while featuring robust mechanical strength. Cationic metallopolymer hydrogels exhibited strong antifouling against oppositely charged proteins. These antibiotic-loaded hydrogels demonstrated a synergistic effect on the inhibition of bacterial growth and antifouling of bacteria, as a result of the unique ion complexation of cobaltocenium cations.

Key words: antimicrobial, cobaltocenium, double network hydrogel, metallopolymer

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Figures/Tables 12

Figure 1. (A) Synthesis and homo-polymerization of 2-cobaltocenium amidoethyl methacrylate chloride (CoAEMACl). (B) Preparation of penicillin-conjugated cobaltocenium metallopolymer double-network (PCoPeni-DN) hydrogel via free radical polymerization and ion exchange. AIBN: azobisisobutyronitrile; AM: acrylamide; CoAEMAPF6: 2-cobaltocenium amidoethyl methacrylate hexafluorophosphate; HEMA: hydroxyethyl methacrylate; MBA: N,N′-methylenebisacrylamide; PCoCl: chloride-paired cobaltocenium polymer; PEGDMA: poly(ethylene glycol) dimethacrylate.

Table 1. The network compositions of hydrogels, and their EWC and mechanical properties

Sample	First network	Second network	Penicillin-G content (mg/g)	EWC (wt %)	σ_max(MPa)	λ_max(%)
SN-1	PCoCl	-	-	97.5	0.014	37
SN-2	-	PAM	-	94.3	0.55	91
DN-0	PHEMA	PAM	-	72.4	0.64	53
DN-1	PCoCl	PAM	-	95.1	0.47	49
DN-2	PAM	PAM	-	93.2	3.74	85
DN-3	P(CoCl-AM)	PAM	-	94.3	3.22	74
DN-4	P(CoCl-HEMA)	PAM	-	87.9	1.86	66
DN-5	P(CoCl-AM)	PAM	7.41	91.7	5.81	79
DN-6	P(CoCl-HEMA)	PAM	6.85	83.5	2.45	68

Figure 2. Compression stress-strain plots of PCoCl-DN hydrogels (DN-3 and DN-4) and PCoPeni-DN hydrogels (DN-5 and DN-6) (upper). Photographs showing reversible compression of hydrogel (DN-5) (lower). A video of compression testing is included in the Additional Video 1. DN: double network; PCoCl-DN: chloride-paired cobaltocenium-containing double-network; PCoPeni-DN: penicillin-conjugated cobaltocenium metallopolymer double-network.

Figure 3. (A) DSC curves of different DN hydrogels and DI water. (B) Enthalpy change (∆Hf) associated with the melting of freezable water per weight of a hydrogel measured by DSC. The enthalpy change for the melting of bulk water is ∆Hw = 335.2 J/g. ∆Hf: the enthalpy associated with the melting of freezable water and free water in a hydrogel; ∆Hw: the enthalpy for the melting.

Figure 4. Average fluorescence intensities of cobaltocenium-containing DN hydrogel surfaces after immersing into 0.5 mg/mL of BSA-FITC solution; fluorescence microscopy images are attached. BSA-FITC: fluorescein isothiocyanate-conjugated bovine serum albumin; DN: double-network.

Figure 5. (A-G) Images of Escherichia coli (E. coli) colonies of viable adherent bacterial cells on the surfaces of glass slides (A), glass slides with penicillin-G sodium salts (B), DN-2 (C), DN-3 (D), DN-4 (E), DN-5 (F) and DN-6 (G). (H) Viable adherent fractions of E. coli on the surfaces of samples from the above spread plates. DN: double-network; Peni: penicillin-G.

Figure 6. (A) Optical density at 600 nm (OD 600) of Escherichia coli (E. coli) culture solution upon 24 hours incubation with different hydrogels. (B) OD600 values of the E. coli suspension washed from different hydrogels. OD 600 of DI water is about 0.03. DI: deionized; DN: double-network.

Additional Figure 1. 1H NMR spectrum of monomer CoAEMACl. 1H NMR: proton nuclear magnetic resonance; CoAEMACl: 2-cobaltocenium amidoethyl methacrylate chloride; D2O: deuterium oxide.

Additional Figure 2. Compression stress-strain plots of hydrogels SN-1, SN-2, DN-1 and DN-2. DN: double-network; SN: single-network.

Additional Figure 3. Release profile of excess penicillin-G from hydrogels as a function of time in deionized water.

Additional Figure 4. Tensile strength-strain plots of hydrogels DN-3, DN-4, DN-5 and DN-6. DN: double-network.

Additional Figure 5. Confocal laser scanning microscopy images of live and dead Escherichia coli cells washed from the surfaces of glass (control) and the surface of hydrogels DN-2, DN-3, DN-4, DN-5 and DN-6. For DN-2, most of bacterial cells were fluoresced green, indicating that these cells were viable. A majority of dead cells (stained red) appeared on the DN-3 surface. Significantly most cells were dead with very few live cells appearing on the DN-5 surface. For DN-4 and DN-6, few live and dead bacteria cells were observed on their surfaces because of their good antifouling and antibacterial properties. Green denotes live cells; red denotes dead cells. Scale bars: 100 μm.

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Antifouling and antimicrobial cobaltocenium-containing metallopolymer double-network hydrogels

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