Hemin Covalently Functionalized Carbon Nanobranch with Enzyme‐Like and Photocatalytic Activities for Synergistic Dye Degradation and Antibacterial Therapy

Abstract

The development of artificial enzymes with excellent enzyme‐like activities and unique features is highly desirable for their practical applications. Herein, a one‐pot facile method to synthesize hemin covalently functionalized carbon nanobranch (CN‐hemin) via direct pyrolysis of citric acid and covalent coupling of hemin to the formed carbon skeleton, is reported. This strategy is reasonably straightforward, cheap, and environmentally friendly, without any extraneous oxidant, reductant, and harmful additives during the preparation process. Furthermore, the obtained dendritic hybrids possess good water‐solubility, intrinsic peroxidase‐like activity, and satisfactory photocatalytic performance in visible light. These extraordinary properties are mainly due to the structure of CN‐hemin which contains iron porphyrin, aromatic carbon, and citric acid residues. Most importantly, under visible light irradiation, the as‐prepared hemin‐incorporated nanohybrid can act as robust agents for synergistic dye degradation and antibacterial therapy toward Staphylococcus aureus and methicillin‐resistant S. aureus. It is expected that this study can shed valuable light on developing advanced multifunctional nanozymes with combined favorable properties for highly efficient elimination of environmental pollutants and antibacterial treatment.

Porphyrin‐Based Nanozymes for Biomedical Applications

“…In summary, we have provided a comprehensive overview of the growing field of porphyrin-based nanozymes (Table 2). Mn-PC nanocage [ 6a ] TPyP(2) Mn (III) POD Detection of H 2 O 2 , sarcosine, and glucose AG73@Zn-TCPP(Fe) [ 32] TCPP(Fe) AG73 POD Detection of heparin Fe@PCN-224 [ 54b] H 2 TCPP Zr6, Fe 3+ POD Detection of H 2 O 2 and glucose CN-hemin [ 52] Hemin Citric acid POD Dye degradation and antibacterial therapy FH/hemin assemblies [ 40] Hemin Fmoc-histidine POD Detection of glucose SWNT-NH 2 @hemin [ 51] Hemin SWNTs POD Detection of glucose FePor-TFPA-COP [ 69] Hemin TFPA POD Detection of 𝛼-fetoprotein…”

“…Hemin can also be loaded onto a carrier by covalent interaction, as shown by covalent coupling of hemin to carbon nanobranches via esterification reaction during the pyrolysis of citric acid. [ 52 ] The resulting nanozyme retains iron porphyrins, citric acid residues, and aromatic carbon. This simple and environmentally friendly one‐pot method effectively avoids the addition of toxic reagents and achieves environmental sustainability.…”

“…[ 71 ] For instance, covalent conjugation of hemin on carbon nanobranches (CN) generated CN‐hemin nanozyme that possesses both POD activity and photocatalytic activity. [ 52 ] In the presence of CN‐hemin, increased hydrogen peroxide concentrations were observed, leading to reduced S. aureus and methicillin‐resistant S. aureus (MRSA) counts. Especially, increased singlet oxygen production and antibacterial capacity were realized under light conditions.…”

Electrospinning of n-hemin/PAN Nanocomposite Membranes and Its Photo-Enhanced Enzyme-like Catalysis

“…Moreover, the composite displayed high loading content and sustainable releasing behavior of the anticancer drug doxorubicin hydrochloride, resulting in promising biomedical application. Xu and co-workers [ 17 ] coupled hemin to the carbon skeleton via a covalent bond to synthesize a kind of functionalized carbon nanobranch (CN-hemin), which showed intrinsic peroxidase-like activity and satisfactory photocatalytic performance. Importantly, the hybrids showed effective performance for synergistic dye degradation and antibacterial therapy toward S. aureus and methicillin-resistant S. aureus .…”