In Situ Grafting of Silica Nanoparticle Precursors with Covalently Attached Bioactive Agents to Form PVA-Based Materials for Sustainable Active Packaging

Sustainable antibacterial–antioxidant films were prepared using in situ graftings of silica nanoparticle (SNP) precursors with covalently attached bioactive agents benzoic acid (ba) or curcumin (cur) on polyvinyl alcohol (PVA). The modified PVA-SNP, PVA-SNP-ba and PVA-SNP-cur films were characterized using spectroscopic, physicochemical and microscopic methods. The prepared films showed excellent antibacterial and antioxidant activity, and increased hydrophobicity providing protection from undesired moisture. The PVA-SNP-ba films completely prevented the growth of the foodborne human pathogen Listeria innocua, whereas PVA-SNP-cur resulted in a 2.5 log reduction of this bacteria. The PVA-SNP-cur and PVA-SNP-ba films showed high antioxidant activity of 15.9 and 14.7 Mm/g TEAC, respectively. The described approach can serve as a generic platform for the formation of PVA-based packaging materials with tailor-made activity tuned by active substituents on silica precursors. Application of such biodegradable films bearing safe bioactive agents can be particularly valuable for advanced sustainable packaging materials in food and medicine

Transparent Gold as a Platform for Adsorbed Protein Spectroelectrochemistry: Investigation of Cytochrome <i>c</i> and Azurin

The majority of protein spectroelectrochemical methods utilize a diffusing, chemical mediator to exchange electrons between the electrode and the protein. In such methods, electrochemical potential control is limited by mediator choice and its ability to interact with the protein of interest. We report an approach for unmediated, protein spectroelectrochemistry that overcomes this limitation by adsorbing protein directly to thiol self-assembled monolayer (SAM) modified, thin (10 nm), semitransparent gold. The viability of the method is demonstrated with two diverse and important redox proteins: cytochrome <i>c</i> and azurin. Fast, reversible electrochemical signals comparable to those previously reported for these proteins on ordinary disk gold electrodes were observed. Although the quantity of protein in a submonolayer adsorbed at an electrode is expected to be insufficient for detection of UV–vis absorption bands based on bulk extinction coefficients, excellent spectra were detected for each of the proteins in the adsorbed state. Furthermore, AFM imaging confirmed that only a single layer of protein was adsorbed to the electrode. We hypothesize that interaction of the relatively broad gold surface plasmon with the proteins’ electronic transitions results in surface signal enhancement of the molecular transitions of between 8 and 112 times, allowing detection of the proteins at much lower than expected concentrations. Since many other proteins are known to interact with gold SAMs and the technical requirements for implementation of these experiments are simple, this approach is expected to be very generally applicable to exploring mechanisms of redox proteins and enzymes as well as development of sensors and other redox protein based applications

Submolecular Gates Self-Assemble for Hot-Electron Transfer in Proteins

Redox reactions play key roles in fundamental biological processes. The related spatial organization of donors and acceptors is assumed to undergo evolutionary optimization facilitating charge mobilization within the relevant biological context. Experimental information from submolecular functional sites is needed to understand the organization strategies and driving forces involved in the self-development of structure–function relationships. Here we exploit chemically resolved electrical measurements (CREM) to probe the atom-specific electrostatic potentials (ESPs) in artificial arrays of bacteriochlorophyll (BChl) derivatives that provide model systems for photoexcited (hot) electron donation and withdrawal. On the basis of computations we show that native BChl’s in the photosynthetic reaction center (RC) self-assemble at their ground-state as aligned gates for functional charge transfer. The combined computational and experimental results further reveal how site-specific polarizability perpendicular to the molecular plane enhances the hot-electron transport. Maximal transport efficiency is predicted for a specific, ∼5 Å, distance above the center of the metalized BChl, which is in remarkably close agreement with the distance and mutual orientation of corresponding native cofactors. These findings provide new metrics and guidelines for analysis of biological redox centers and for designing charge mobilizing machines such as artificial photosynthesis