Abstract
Thermal imprinting of the lipid-water interface of phospholipid vesicles is achieved by reversible non-covalent assembly of membrane embedded amphiphilic metal complexes. The complexes have affinity to phosphate and imidazole groups and are preorganized by a phosphorylated hexapeptide template above the phase transition temperature. The template induced patterning is transferred into the gel phase of the membrane by cooling below the transition temperature. This limits the lateral diffusion and stabilizes the metal complex receptor organization, as confirmed by FRET measurements with dye-labeled receptors. After template removal an enhanced rebinding affinity of one order of magnitude for the target peptide was observed for the imprinted membranes compared to identical non-imprinted interfaces.
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Note: Fluorescence intensity and therefore FRET emission is temperature dependent. Hence it is not possible to compare FRET signals monitored at different temperatures. Therefore we determine the FRET ratio (I580nm / I520nm) before and after analyte addition at different temperatures. The change of FRET ratio (ΔFRET ratio) is the difference between FRET ratio in the presence of a binding partner and the FRET ratio without analyte. This value is used to estimate the degree of analyte guided receptor arrangement below and above TM.
FRET emission intensities were not changing during 10 min after cooling V1 to 10 °C.
We previously reported the covalent molecular imprinting by photopolymerization using the same receptor – ligand pair (see ref. 27).
Rebinding of P1 with a value of log K = 8.0 for imprinted and a value of log K = 7.3 for non-imprinted DPPC vesicles (TM = 41 °C) was determined analogously.
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Balk, S., König, B. Thermally induced molecular imprinting of luminescent vesicles. J Incl Phenom Macrocycl Chem 81, 135–139 (2015). https://doi.org/10.1007/s10847-014-0442-2
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DOI: https://doi.org/10.1007/s10847-014-0442-2