An essential amino acid, histidine, has a vital role in the secondary structure and catalytic activity of proteins because of the diverse interactions its side chain imidazole (Im) ring can take part in. Among these interactions, hydrogen donating and accepting bonding are often found to operate at the charged interfaces. However, despite the great biological significance, hydrogen-bond interactions are difficult to investigate at electrochemical interfaces due to the lack of appropriate experimental methods. Here, we present a surface-enhanced infrared absorption spectroscopy (SEIRAS) and density functional theory (DFT) study addressing this issue. To probe the hydrogen-bond interactions of the Im at the electrified organic layer/water interface, we constructed Au-adsorbed self-assembled monolayers (SAMs) that are functionalized with the Im group. As the prerequisite for spectroelectrochemical investigations, we first analyzed the formation of the monolayer and the relationship between the chemical composition of SAM and its structure. Infrared absorption markers that are sensitive to hydrogen-bonding interactions were identified. We found that negative electrode polarization effectively reduced hydrogen-bonding strength at the Im ring at the organic layer–water interface. The possible mechanism governing such a decrease in hydrogen-bonding interaction strength is discussed.
Tethered bilayer lipid membranes (tBLMs) are versatile platforms for the analysis of biochemical and biophysical processes at biological membranes. To control the stability and functional properties of these artificial constructions, molecular-level knowledge on the organization and structure is required. We used surface-enhanced infrared absorption spectroscopy (SEIRAS) to elucidate the in situ formation of tBLMs on a gold substrate. The alkyl chains of long-chain anchoring thiol in a mixed self-assembled monolayer after 60 min of incubation in an adsorption methanol-d4 solution was found to be in a disordered state. Spectroscopic data revealed the complete formation of a bilayer after 60 min of incubation of a mixed anchoring monolayer in a phosphate buffer solution containing vesicles formed from partially deuterated lipid DPPC-d62 and cholesterol-d7. The temporal evolution of absorption bands from the lipid, anchoring mixed monolayer thiol, and water with increasing the bilayer formation time in the phosphate buffer solution containing vesicles revealed a two-stage process. Firstly, the adsorption of lipid molecules with a simultaneous withdrawal of water takes place at the interface. Secondly, the transformation of alkyl chains of the anchoring monolayer due to the insertion and interaction of lipids with the monolayer proceeds.
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