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This study provided the first attempt of grafting hydrophobic polyvinylidene fluoride (PVDF) membrane with hydrophilic hydroxyethyl acrylate (HEA) monomer via a radiation grafting method. This grafted membrane showed an enhanced hydrophilicity (10° decrease of water contact angle), water content ratio, settling ability and wettability compared to the control membrane. Interestingly, filtration tests showed an improved dependence of water flux of the grafted membrane on the solution pH in the acidic stage. Atomic force microscopy (AFM) analysis provided in-situ evidence that the reduced surface pore size of the grafted membrane with the solution pH governed such a dependence. It was proposed that, the reduced surface pore size was caused by the swelling of the grafted chain matrix, with the pH increase due to the chemical potential change. It was found that the grafted membrane showed a lower relative flux decreasing rate than the control membrane. Moreover, flux of the bovine serum albumin (BSA) solution was noticeably larger than that of pure water for the grafted membrane. Higher BSA flux than water flux can be explained by the effects of electric double layer compression on the polymeric swelling. This study not only provided a pH-sensitive PVDF membrane potentially useful for various applications, but also proposed novel mechanisms underlying the enhanced performance of the grafted membrane.

Prior studies in hairless mice have demonstrated that acute barrier disruption by acetone treatment increases the molecular weight (MW) cutoff of polyethylene glycol (PEG) penetration through the skin. The objective of the present study was to further investigate the dependence of permeability on MW with different forms of barrier disruption. A series of PEGs ranging in MW from near 300 to over 1000 Da were used to study the effects of tape stripping and sodium dodecyl sulfate (SDS) treatment on the MW permeability profiles of mouse skin in vitro. The 12-h percutaneous penetration of all the PEG 300, 600, and 1000 oligomers generally increased as a function of transepidermal water loss (TEWL) of the skin, either tape-stripped or SDS-treated. In addition, the total penetration of PEG oligomers across control skin, and skin tape-stripped and SDS-treated to different degrees of barrier disruption progressively decreased with increasing MW. There were no significant differences in the percutaneous penetration of the PEG oligomers between skin tape-stripped and SDS-treated to the same degree of barrier disruption. The penetration enhancement relative to control skin was more prominent with larger molecules. The MW cutoff for skin penetration increased with the degree of barrier disruption irrespective of the treatment applied, and was 986 Da (tape stripping) and 766 Da (SDS treatment) at TEWL levels in the range 10-20 g/m(2) per h in comparison with 414 Da for control skin. In accordance with previous findings in acetone-treated mouse skin, the results strongly suggest that, irrespective of the form of barrier disruption applied, not only higher amounts but also more varieties of chemicals (larger molecules) may penetrate skin with a compromised barrier than normal skin.

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