Fluorocarbon amphiphiles are anthropogenic substances widely used in diverse applications such as food packaging, clothing or cookware. Due to their widespread use and non-biodegradability, these chemicals are now ubiquitous in the natural world with high propensity to bioaccumulate in biological membranes, wherein they may affect microscopic properties. Here, we test the hypothesis that a typical fluorocarbon amphiphile can affect lipid membranes similarly to cholesterol by investigating the effect of 1H,1H,2H,2H-perfluoro-1-decanol (8:2 FTOH) on 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) membranes. Using solid-state nuclear magnetic resonance spectroscopy, differential scanning calorimetry and confocal microscopy, we present a consistent set of independent experimental evidences supporting this hypothesis, namely that upon incorporation of 8:2 FTOH, (i) a condensing effect on the acyl chains occurs in the fluid phase, (ii) coexistence of two membrane phases is observed below melting, and (iii) the melting temperature of DPPC varies no more than approximately ±1 °C up to a concentration of 40 mol% of 8:2 FTOH. The condensing effect is quantified by means of advanced dipolar recoupling solid-state NMR experiments and is found to be of approximately half the magnitude of the cholesterol effect at the same concentration.

A family of polyesters, poly(glycerol adipate) (PGA), poly(sorbitol adipate) and PGA-graft-poly( -caprolactone), bearing OH groups on their backbones were synthesized by enzymatic polycondensation. They were successfully converted into macroinitiators for atom transfer radical polymerization (ATRP) by esterification with α-bromoisobutyryl bromide. As a proof of concept, glycerol monomethacrylate was polymerized by ATRP from a PGA backbone yielding the amphiphilic graft copolymer PGA-graft-poly(glycerol monomethacrylate). Its self-assembly in aqueous solution was studied using dynamic light scattering.

Poly (glycerol adipate) is enzymatically prepared by reacting glycerol with divinyl adipate in the presence of a lipase as catalyst fromCandida Antarcticatype B (CAL-B). The reaction yields linear polyesters with free pendent hydroxyl groups. Poly (glycerol adipate) is hydrophobically modified by incomplete acylation of some of the pendent hydroxyl groups using stearoyl chloride. The resulting polymer is further functionalized with α-bromoisobutyryl groups. The final polymer is purified and well characterized to calculate the ratio of substitution in both cases. Furthermore, nanoparticles in water are prepared from the functionalized polymer using the interfacial precipitation method. Dynamic light scattering measurements depict nanoparticles with relatively narrow size distributions and with an average hydrodynamic radius of 70 nm. Additionally, transmission electron microscopy images reveal well dispersed spherical nanoparticles with nanophase separation. Finally, the interactions between the graft copolymers and lipid monolayers of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) are investigated on a Langmuir trough equipped with a fluorescence microscope.

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