Another typical cationic polymer is the guanidinium-based polymer. Polyhexamethylene diamine guanidine (PHMG) is widely used in the water treatment, wound healing, and textile coating industries because of its efficient bactericidal activity [
80,
81]. Villanueva
et al. prepared an antibacterial PVC material by grafting PHMG [
82]. The obtained PVC maintained efficient bactericidal activity (99.9%, 24 h) and durable antibacterial stability (99.9%, 60 d) against
P. aeruginosa, S. aureus, Acinetobacter baumannii (A. baumannii), and
Bacillus subtilis (B. subtilis). In another study, Cao
et al. prepared PHMG-
grafted PP (PP-
g-PHMG) and mixed pure
polyethylene terephthalate (PET) and PP-
g-PHMG in different ratios to prepare antibacterial PET materials [
83]. The bactericidal efficiency of the modified PET gradually increased with increasing the PP-
g-PHMG ratio. PET containing 3.5% PP-
g-PHMG achieved 99.9% bactericidal activity against both
E. coli and
S. aureus within 24 h. Further experiments showed that the antibacterial components of this PET material were mainly enriched on the surface of the material and had nonleaching properties. The biosafety of a material is important if it is to be used as a medical device or an implantable material. Therefore, assessment of the biosafety of antibacterial polymers containing guanidine may require more in-depth studies. The degradation of guanidine-containing polymers to reduce their cytotoxicity after bactericidal effects may be feasible. In addition,
N-halamine polymers have attracted considerable attention because of their renewable antibacterial properties and diverse molecular structures [
84]. Chien
et al. explored the effectiveness of co-deposited coatings comprising chlorinated polydopamine (PDA) and polyethyleneimine (PEI) in eradicating
S. aureus and
E. coli. Their findings revealed that the chlorinated co-deposition coatings exhibited significantly superior antibacterial properties in comparison to their non-chlorinated counterparts (Fig. S1B in Supporting information) [
85]. Jing
et al. first prepared amine-containing polymers (PTMPM) by polymerizing 2,2,6,6-tetramethyl-4-piperidinyl methacrylate (TMPM) and the quaternary ammonium monomer trimethyl-2-methacryloyloxyethylammonium chloride (TMAC), followed by sodium hypochlorite treatment to prepare chlorinated poly(2,2,6,6-tetramethyl-4-piperidinyl methacrylate) (Cl-PTMPM) (Fig. S1C in Supporting information) [
86]. These results indicate that the antibacterial activity of Cl-PTMPM is not positively correlated with the amount of active chlorine in the polymer. The copolymer with 30% active chlorine killed > 99.9% of the bacteria within 10 h, which was greater than the antimicrobial activity of the copolymers with 50% and 70% active chlorine. This is because the hydrophilic side chains of TMAC were wrapped around the hydrophobic Cl-TMPM units. When the content of Cl-TMPM increased, the hydrophobic enhancement of Cl-TMPM made contact with bacteria more difficult, and thus, the contact bactericidal effect of active chlorine could not be achieved, leading to a decrease in antibacterial activity. This work illustrates that when designing
N-halamine polymers, the wettability of the copolymer units should be fully considered to determine the right hydrophilic-hydrophobic balance to achieve the best antibacterial activity.
N-Halamine polymers have shown potential as bioprotective agents. Wang
et al. fabricated a novel polysulfonamide (PSA)
N-halamine electrospun nanofiber membrane using Lewis acid-assisted chlorination [
87]. This fibrous membrane exhibited rechargeable and fast bactericidal properties and inactivated 6 log (99.9999%) of
E. coli and
S. aureus in 3 min.
N-Halamine polymers have rechargeable and rapid bacterial inactivation properties and can be considered for applications such as protective masks, protective clothing, and filter membranes. Considering the requirements of these applications, their biosafety must be further evaluated.