A dual grafted fluorinated hydrocarbon amine weak anion exchange resin polymer for adsorption of perfluorooctanoic acid from water.

Perfluorooctanoic acid (PFOA) is a persistent and recalcitrant organic contaminant of exceptional environmental concern, and its removal from water has increasingly attracted global attention due to its wide distribution and strong bioaccumulation. Adsorption is considered an effective technique for PFOA removal and more efficient PFOA sorbents are still of interest. This study developed a dual grafted fluorinated hydrocarbon amine weak anion exchange (WAX) polymeric resin (Sepra-WAX-KelF-PEI) for PFOA removal from water. This polymer was synthesized by a two-step amine grafting reaction procedure involving first the reaction of the Sepra-WAX hydrocarbon polymer with poly(vinylidinefluoride-chlorotrifluoroethylene) (Kel-F 800) and then a second reaction with polyethyleneimine (PEI). Characterization of the synthesized polymers was performed using scanning electron microscopy and elemental analysis (F and Cl) by energy dispersive X-ray spectroscopy. The PFOA adsorption performance evaluations were conducted by packed column flow analyses with on-line detection. The results show the breakthrough of the Sepra-WAX-KelF-PEI synthesized with optimum stoichiometry was two times better than the starting anion exchange polymer Sepra-WAX, and six times better than powdered activated carbon, when using the same column size. The adsorption mechanisms of this novel adsorbent including hydrophobic interaction and electrostatic interaction were also clarified in this study. The adsorption kinetic parameters of the two optimum synthesized sorbents were determined using the Thomas model, the Yoon-Nelson model, and batch isotherm studies, and compared with those found with activated carbon and the starting WAX resin. Good agreement of the batch isotherm and column studies with respect to adsorption capacities trends between all three polymers (Sepra-WAX, Sepra-WAX-KelF, and Sepra-WAX-KelF-PEI) were noted.

Thiol-Disulfide Exchange in Human Growth Hormone.

PURPOSE: Thiol-disulfide exchange was monitored in recombinant human growth hormone (hGH) and in model tryptic peptides derived from hGH to investigate the effects of higher-order structure on the reaction. METHODS: Different free thiol-containing peptides, varying in length and amino acid sequence, were used to initiate the reaction at pH 7.0 and 37°C in hGH. Protein samples were digested with trypsin and analyzed for native disulfides, scrambled disulfides and free thiols using LC/MS. The loss of native disulfide and disulfide exchange was compared with model peptides derived from hGH. RESULTS: Loss of native disulfide in cyclic (cT20-T21) and linear peptides (T20-T21pep) derived from the C-terminal hGH disulfide during the first 60 min of reaction was greater than loss of the C-terminal disulfide in hGH itself. Of the thiols tested, glutathione (GSH) was the most reactive, forming the highest percentage of mixed disulfides in intact hGH and in the model peptides. At longer reaction times (>240 min), native disulfides in both hGH and cT20-T21 were regenerated. The fastest rates of regeneration were observed for Cys and the di- or tripeptide containing an Arg residue adjacent to Cys, suggesting that they may be useful in refolding. CONCLUSIONS: Thiol-disulfide exchange reactions in hGH and related model peptides were influenced by higher order structure, by the size of the thiol reactant and by an Arg residue adjacent to Cys in the thiol reactant. Reduction of disulfide bonds in hGH did not affect higher order structure as measured by CD and HDX-MS.