Abstract:Poly(glycidyl methacrylate) (PGMA) has been synthesised by cobalt catalysed chain transfer polymerisation (CCTP) yielding, in one step, polymers with two points for post polymerisation functionalisation; the activated terminal vinyl bond and in chain epoxide groups. Epoxide ring-opening and a combination of thiol-Michael addition and epoxide ring-opening has been used for the post-functionalisation with amines and thiols to prepare a range of functional materials.
“…Theoretically, the reaction of polyGMA and cysteamine (CYS) is a 1:1 reaction with the primary amine of the CYS attaching to the GMA epoxide group; however, it has been reported that the CYS-GMA reaction has an efficiency of 58% [32]. Therefore, 1 g (0.007 moles) of polyGMA and 0.935 g (0.012 moles) of CYS were needed for the reaction.…”
“…The amount of DMSO and DI water were based on previous studies [24,30]. This mixture was covered with Parafilm and stirred at 600 rpm, 60 • C for 6 h. The solvents and experimental conditions were based on literature [24,32]. The contents of the beaker were centrifuged for 3 min at 112× g (times gravity) to harvest the polyGMA-CYS from the solution.…”
Silver nanoparticles (AgNPs) have been widely studied for the control of biofouling on polymeric membranes due to their antimicrobial properties. However, nanoparticle leaching has posed a significant impediment against their widespread use. In this study, a one-step method of chemically embedding AgNPs on cellulose acetate (CA) membranes via their affinity to thiol group chemistry was investigated. The operational efficiency of the membranes was then determined via filtration and biofouling experiments. During filtration study, the average flux values of pure CA membranes was determined to be 11 ± 2 L/(m2·hr) (LMH), while membranes embedded with AgNPs showed significant increases in flux to 18 ± 2 LMH and 25 ± 9 LMH, with increasing amounts of AgNPs added, which is likely due to the NPs acting as pore formers. Leaching studies, performed both in dead-end and crossflow filtration, showed approximately 0.16 mg/L leaching of AgNPs after the first day of filtration, but afterwards the remaining chemically-attached AgNPs did not leach. Over 97% of AgNPs remained on the membranes after seven days of crossflow leaching filtration studies. Serratia marcescens were then used as target microorganisms in biofouling studies. It was observed that membranes embedded with AgNPs effectively suppressed the growth of Serratia marcescens, and specifically, membranes with AgNPs displayed a decrease in microbial growth by 59% and 99% as the amount of AgNP increased.
“…Theoretically, the reaction of polyGMA and cysteamine (CYS) is a 1:1 reaction with the primary amine of the CYS attaching to the GMA epoxide group; however, it has been reported that the CYS-GMA reaction has an efficiency of 58% [32]. Therefore, 1 g (0.007 moles) of polyGMA and 0.935 g (0.012 moles) of CYS were needed for the reaction.…”
“…The amount of DMSO and DI water were based on previous studies [24,30]. This mixture was covered with Parafilm and stirred at 600 rpm, 60 • C for 6 h. The solvents and experimental conditions were based on literature [24,32]. The contents of the beaker were centrifuged for 3 min at 112× g (times gravity) to harvest the polyGMA-CYS from the solution.…”
Silver nanoparticles (AgNPs) have been widely studied for the control of biofouling on polymeric membranes due to their antimicrobial properties. However, nanoparticle leaching has posed a significant impediment against their widespread use. In this study, a one-step method of chemically embedding AgNPs on cellulose acetate (CA) membranes via their affinity to thiol group chemistry was investigated. The operational efficiency of the membranes was then determined via filtration and biofouling experiments. During filtration study, the average flux values of pure CA membranes was determined to be 11 ± 2 L/(m2·hr) (LMH), while membranes embedded with AgNPs showed significant increases in flux to 18 ± 2 LMH and 25 ± 9 LMH, with increasing amounts of AgNPs added, which is likely due to the NPs acting as pore formers. Leaching studies, performed both in dead-end and crossflow filtration, showed approximately 0.16 mg/L leaching of AgNPs after the first day of filtration, but afterwards the remaining chemically-attached AgNPs did not leach. Over 97% of AgNPs remained on the membranes after seven days of crossflow leaching filtration studies. Serratia marcescens were then used as target microorganisms in biofouling studies. It was observed that membranes embedded with AgNPs effectively suppressed the growth of Serratia marcescens, and specifically, membranes with AgNPs displayed a decrease in microbial growth by 59% and 99% as the amount of AgNP increased.
“…Particularly, many studies have been attempting to develop new functionalization techniques, to allow the production of functionalized polymer materials that may interact more efficiently with specific enzymes. [ 5–15 ]…”
Section: Introductionmentioning
confidence: 99%
“…Thus, distinct polymer structures can be synthesized, new surfaces and interfaces can be produced and new materials with distinct properties can be obtained through functionalization reactions. [ 6–17 ]…”
New nanoparticles are synthesized through emulsion polymerization, using distinct comonomers (styrene, divinylbenzene, glycidyl methacrylate and pentafluorostyrene). Then, for the first time, two strategies are adopted to functionalize such nanoparticles using benzylamine and thiophenol: (i) after the manufacture of the nanoparticles; and (ii) in situ during the polymerization reaction. Afterwards, the functionalized nanoparticles are used as nanosupports for immobilization of lipase B from Candida antarctica and the performance of the novel nanobiocatalysts are evaluated. It is shown that the nanoparticles exhibit different properties (specific areas ranging from 34 m2 g−1 to 324 m2 g−1; and contact angles ranging from 29° to 126°), indicating that both procedures can be used to adjust the properties of the polymer supports. Moreover, the nanobiocatalysts are applied successfully in hydrolysis and esterification reactions, exhibiting higher activities than the non‐functionalized biocatalysts. It is also observed that more hydrophilic supports result in more active biocatalysts in hydrolysis (27 ± 1 U g−1) and intermediate hydrophobic matrices conduct to more active biocatalysts in esterification reactions (1564 ± 50 U g−1). It is shown that highly hydrophobic surfaces may cause a significant decrease in the activity of such biocatalysts, probably due to distortions on the enzyme active center and to more intense chemical partitioning effects.
“…Typically, low spin cobalt(II) complexes are used as catalytic chain transfer agents, and are only required in ppm amounts relative to the concentration of monomer due to extremely high chain transfer constants when compared with other chain transfer agents, such as thiols or halocarbons. [32][33][34][35] The generally accepted mechanism for the CCTP of methacrylates proceeds via a two-step reaction, Scheme 1. 36 The process is highly adaptable, and polymers produced by CCTP have found applications within hair care, 37 as toner for printing applications, 38 and have also been used for the synthesis of low-VOC (Volatile Organic Compound) high solid coatings.…”
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