We use vibrational sum-frequency generation (VSFG) spectroscopy to study the structure of hen egg-white lysozyme (HEWL) aggregates adsorbed to DOPG/D2O and air/D2O interfaces. We find that aggregates with a parallel and anti-parallel β-sheet structure together with smaller unordered aggregates and a denaturated protein are adsorbed to both interfaces. We demonstrate that to retrieve this information, fitting of the VSFG spectra is essential. The number of bands contributing to the VSFG spectrum might be misinterpreted, due to interference between peaks with opposite orientation and a non-resonant background. Our study identified hydrophobicity as the main driving force for adsorption to the air/D2O interface. Adsorption to the DOPG/D2O interface is also influenced by hydrophobic interaction; however, electrostatic interaction between charged protein's groups and lipid's head-groups has the most significant effect on the adsorption. We find that the intensity of the VSFG spectrum at the DOPG/D2O interface is strongly enhanced by varying the pH of the solution. We show that this change is not due to a change of lysozyme's and its aggregates' charge, but due to dipole reorientation at the DOPG/D2O interface. This finding suggest that extra care must be taken when interpreting the VSFG spectrum of proteins adsorbed at the lipid/water interface.
Multifunctional amide-containing self-assembled monolayers (SAMs) provide prospects for the construction of interfaces with required physicochemical properties and distinctive stability. In this study, we report the synthesis of amide-containing thiols with terminal phenylalanine (Phe) ring functionality (HS(CH2)7CONH(CH2)2C6H5) and the characterization of the formation of SAMs from these thiols on gold by reflection absorption infrared spectroscopy (RAIRS). For reliable assignments of vibrational bands, ring deuterated analogs were synthesized and studied as well. Adsorption time induced changes in Amide-II band frequency and relative intensity of Amide-II/Amide-I bands revealed two-state sigmoidal form dependence with a transition inflection points at 2.2 ± 0.5 and 4.7 ± 0.5 min, respectively. The transition from initial (disordered) to final (hydrogen-bonded, ordered) structure resulted in increased Amide-II frequency from 1548 to 1557 cm−1, which is diagnostic for a strongly hydrogen-bonded amide network in trans conformation. However, the lateral interactions between the alkyl chains were found to be somewhat reduced when compared with well-ordered alkane thiol monolayers.
Carbonization of biomass residues followed by activation has great potential to become a safe process for the production of various carbon materials for various applications. Demand for commercial use of biomass-based carbon materials is growing rapidly in advanced technologies, including in the energy sector, as catalysts, batteries and capacitor electrodes. In this study, carbon materials were synthesized from hardwood using two carbonization methods, followed by activation with H3PO4, KOH and NaOH and doping with nitrogen. Their chemical composition, porous structure, thermal stability and structural order of samples were studied. It was shown that, despite the differences, the synthesized carbon materials are active catalysts for oxygen reduction reactions. Among the investigated carbon materials, NaOH-activated samples exhibited the lowest Tafel slope values, of −90.6 and −88.0 mV dec–1, which are very close to the values of commercial Pt/C at −86.6 mV dec–1.
Noble metal nanoparticles, specifically gold and silver, are extensively utilized in sensors, catalysts, surface-enhanced Raman scattering (SERS), and optical-electronic components due to their unique localized surface plasmon resonance (LSPR) properties. The production of these nanoparticles involves various methods, but among the environmentally friendly approaches, laser ablation stands out as it eliminates the need for toxic chemicals during purification. However, nanoparticle aggregation poses a challenge in laser ablation, necessitating the addition of extra materials that contaminate the otherwise clean process. In this study, we investigate the effectiveness of a biocompatible material, potassium chloride (KCl), in preventing particle aggregation. Although salt is known to trigger aggregation, we observed that certain concentrations of KCl can slow down this process. Over an eight-week period, we examined the aggregation rate, extinction behavior, and stability of gold, silver, and hybrid nanoparticles generated in different KCl concentrations. Extinction spectra, SEM images, SERS signal strength, and zeta potential were analyzed. Our results demonstrate that laser ablation in water and salt solutions yields nanoparticles with a spherical shape and a negative zeta potential. Importantly, we identified the optimal concentration of potassium chloride salt that maintains solution stability and SERS signal strength. Adsorbed chloride ions on silver nanoparticles were evidenced by low-frequency SERS band near 242 cm-1. A better understanding of the effect of KCl concentration on the properties of noble metal nanoparticles can lead to improved generation protocols and the development of tailored nanoparticle systems with enhanced stability and SERS activity.