Regenerable Antimicrobial Polymeric Resin with N-halamine and Quaternary Ammonium Salt Groups

  • 格式:pdf
  • 大小:816.51 KB
  • 文档页数:7

a
The Education Ministry Key Lab of Resource Chemistry, Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University, Shanghai 200234, P. R. China. E-mail: liangjie@; Fax: +86-21-64322511; Tel: +86-21-64321045 Department of Chemistry & Biochemistry, Auburn University, Auburn, AL 36849, USA information (ESI) available. See DOI: † Electronic supplementary 10.1039/c3ra47147k
Received 4th December 2013 Accepted 17th December 2013 DOI: 10.1039/c3ra47147k /advances
Cite this: RSC Adv., 2014, 4, 6048
spectroscopy, and zeta-potential measurement. The antimicrobial tests showed that the as-synthesized antimicrobial polymeric resin was capable of 7-log inactivation of S. aureus and 8-log inactivation of E. coli within 1 minute contact time. Moreover, the N-halamine moieties in Cl-PSHTMA exhibited excellent regenerability.
6048 | RSC Adv., 2014, 4, 6048–6054
This journal is © The Royal Society of Chemistry 2014
Paper
RSC Advances
Scheme 1
Synthesis of Cl-PSHTMA.
Cl-PSHTMA is shown in Scheme 1. Macroporous crosslinked CMPS resin can react easily with the salt of DMH and TMA in water to produce PSHTMA resin containing hydantoinyl and quaternary ammonium salt moieties. Upon chlorination with sodium hypochlorite solution, PSHTMA was transformed into Cl-PSHTMA. Very interestingly, only water was used as solvent in the whole synthetic process. Also, the mild reaction temperature and short reaction time can save energy and enhance productivity. Apparently, this two-step synthetic reaction could be easily enlarged for industrial application. It is well known that the surfaces of bacterial cells are usually negatively charged. So, antibacterial polymers with positive charges in their surfaces can easily hold the bacteria and then effectively kill them. Moreover, the presence of quaternary ammonium salt moieties in the surface of the resin can enhance its hydrophilicity and swelling capacity in water, which may increase its disinfection efficacy.
Introduction
Microbial contamination remains one of the most serious problems in several areas, particularly in water purication systems.1,2 Common disinfectants used in the treatment of water are free halogen, ozone, and chlorine dioxide. However, these soluble disinfectants suffer from some disadvantages such as instability in water and reactivity with organic impurities in water to form undesired byproducts.3–6 As a result, the development of insoluble polymeric antimicrobial materials as disinfectants is desirable. Recently, extensive research has been reported on antimicrobial polymers including polymeric quaternary ammonium salts (poly-quats),7,8 polymeric quaternary phosphonium salts,9–12 polymers containing halogenated sulphonamide groups,13–16 and N-halamine polymers.17–26 Among them, polymeric N-halamines are excellent disinfectants for several reasons including super antimicrobial efficacies, broad antimicrobial spectra, regenerabilities, lack of corrosion of surfaces, low toxicities, and relatively low expense. Worley and co-workers have focused on the development of novel polymeric N-halamines for use in water disinfection since the early 1990s. They rst developed water-insoluble N-
RSC Advances
PAPER Eco-friendly synthesis of regenerable antimicrobial polymeric resin with N-halamine and quaternary ammonium salt groups†
Zhiqiang Jie,a Xiufang Yan,a Lianhong Zhao,a Shelby Davis Worleyb and Jie Liang*a
b
halogenated polystyrenehydantoins, poly[1,3-dichloro-5-methyl5-(4-vinylphenyl)hydantoin] (poly1-Cl) and poly[1,3-dibromo-5methyl-5-(4-vinyl-phenyl)hydantoin] (poly1-Br) by Friedel–Cras acylation, cyclization, and halogenation.17–21 It was found that these polymeric N-halamine powders could inactivate numerous species of bacteria, fungi, and even rotavirus in only seconds of contact time in owing water. However, when these polymeric Nhalamine powders were lled in cartridge for disinfection of water, water could not easily pass through it without external pressure. To solve this issue, Worley group developed macroporous cross-linked poly1-Cl and poly1-Br beads which were suitable for the disinfection of drinking water in a cartridge lter.22,23 Encouragingly, poly1-Br beads have been commercially used for disinfection of drinking water in developing countries such as India, China, and Brazil. However, in its production, large quantities of waste organic solvent and waste water containing high concentrations of cyanide and aluminum ions were produced. Thus, new macroporous cross-linked halogenated methylated polystyrene hydantoin beads (PHY-Cl and PHY-Br) were synthesized by dehydrochlorination between the macroporous crosslinked CMPS resin and DMH and then halogenation of amide nitrogen in the hydantoinyl ring.24 However, this dehydrochlorination can only undergo in few organic solvents such as N,N-dimethylformamide (DMF) and under high temperature due to hydrophobic CMPS and hydrophilic DMH. In this study, we designed an eco-friendly and economical route to synthesize a macroporous cross-linked antimicrobial polymeric resin containing N-halamine and quaternary ammonium salt moieties, Cl-PSHTMA. The synthetic route for