Functionally Active Membrane Proteins Incorporated in Mesostructured Silica Films.

A versatile synthetic protocol is reported that allows high concentrations of functionally active membrane proteins to be incorporated in mesostructured silica materials. Judicious selections of solvent, surfactant, silica precursor species, and synthesis conditions enable membrane proteins to be stabilized in solution and during subsequent coassembly into silica-surfactant composites with nano- and mesoscale order. This was demonstrated by using a combination of nonionic ( n-dodecyl-ß-d-maltoside or Pluronic P123), lipid-like (1,2-diheptanoyl- s n-glycero-3-phosphocholine), and perfluoro-octanoate surfactants under mild acidic conditions to coassemble the light-responsive transmembrane protein proteorhodopsin at concentrations up to 15 wt % into the hydrophobic regions of worm-like mesostructured silica materials in films. Small-angle X-ray scattering, electron paramagnetic resonance spectroscopy, and transient UV-visible spectroscopy analyses established that proteorhodopsin molecules in mesostructured silica films exhibited native-like function, as well as enhanced thermal stability compared to surfactant or lipid environments. The light absorbance properties and light-activated conformational changes of proteorhodopsin guests in mesostructured silica films are consistent with those associated with the native H+-pumping mechanism of these biomolecules. The synthetic protocol is expected to be general, as demonstrated also for the incorporation of functionally active cytochrome c, a peripheral membrane protein enzyme involved in electron transport, into mesostructured silica-cationic surfactant films.

Chalcogenide Hybrid Inorganic/Organic Polymers: Ultrahigh Refractive Index Polymers for Infrared Imaging.

We report on the preparation of ultrahigh refractive index polymers via the inverse vulcanization of elemental sulfur, selenium, and 1,3-diisopropenylbenzene for use as novel transmissive materials for mid-infrared (IR) imaging applications. Poly(sulfur-random-selenium-random-(1,3-diisopropenylbenzene)) (poly(S-r-Se-r-DIB) terpolymer materials from this process exhibit the highest refractive index of any synthetic polymer (n > 2.0) and excellent IR transparency, which can be directly tuned by terpolymer composition. Sulfur or selenium containing (co)polymers prepared via inverse vulcanization can be described as Chalcogenide Hybrid Inorganic/Organic Polymers (CHIPs) and are polymeric analogues to wholly inorganic Chalcogenide Glasses (ChGs), which are commonly used as transmissive materials in mid-IR imaging. Finally, we demonstrate that CHIPs composed of (poly(S-r-Se-r-DIB) can be melt processed into windows that enabled high quality mid-IR thermal imaging of human subjects and highly resolved imaging of human vasculature.