We use fluorescence microscopy to examine the dynamics of the crowding-induced mixing transition of liquid ordered (Lo)-liquid disordered (Ld) phase separated lipid bilayers when the following particles of increasing size bind to either the Lo or Ld phase: Ubiquitin, green fluorescent protein (GFP), and nanolipoprotein particles (NLPs) of two diameters. These proteinaceous particles contained histidine-tags, which were phase targeted by binding to iminodiacetic acid (IDA) head groups, via a Cu2+ chelating mechanism, of lipids that specifically partition into either the Lo phase or Ld phase. The degree of steric pressure was controlled by varying the size of the bound particle (10-240 kDa) and the amount of binding sites present (i.e. DPIDA concentrations of 9 and 12 mol%) in the supported lipid multibilayer platform used here. We develop a mass transfer-based diffusional model to analyze the observed Lo phase domain dissolution that, along with visual observations and activation energy calculations, provides insight into the sequence of events in crowding-induced mixing. Our results suggest that the degree of steric pressure and target phase influence not only the efficacy of steric-pressure induced mixing, but the rate and controlling mechanism for which it occurs.
Titanium dioxide gel monoliths were synthesized using an organic precursor and 0-30 vol % ethanol in water. The visible-light-activated proton pump, bacteriorhodopsin, in its native purple membrane form, was successfully encapsulated within the titanium dioxide gels. Absorption spectra showed that the folded functional state of the protein remained intact within gels made with 0 and 15 vol % ethanol and retained the ability to make reversible conformational changes associated with the photocycle within the gel made with 0 vol % ethanol. The photocatalytic activity of gels made with no ethanol was significantly detectable and gels made with 0-30 vol % ethanol were comparable to commercial crystalline nanoparticles in similar solution conditions when irradiated with UV light. Our results show that sol-gel-derived photocatalytic titanium dioxide can be made biocompatible for a membrane-associated protein by minimizing the amount of ethanol and maximizing the amount of water in the synthesis procedure. The entrapment of the membrane protein, bacteriorhodopsin, in sol-gel-derived titanium dioxide provides the first step in future explorations of this bionanocomposite for visible light photocatalysis, including hydrogen production.
This report describes the thermodynamic assessments for the ZrF 4 -BeF 2 , AlCl 3 -NaCl, AlCl 3 -KCl and the PuCl 3 -CsCl pseudo-binary subsystems. Calculation results are compared to the inputs used to optimize the adjustable model parameters. The data came from experimental studies reported in the open literature, from the MSR research community, and/or computational results generated within the NEAMS program and from collaborators. The models from the thermodynamic assessment of these salt systems are integrated into the MSTDB-TC (Molten Salt Thermal Properties Database-Thermochemical). A brief description of the companion MSTDB-TP (Molten Salt Thermal Properties Database-Thermophysical) is given along with an overview of the approach for predicting both thermodynamic and thermophysical property behavior of multicomponent systems.
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