Probing solution conformations of l-DOPA: Integration of experiment and simulation via vibrational optical activity.

l-DOPA plays a critical role as a precursor to dopamine and is a standard treatment for Parkinson's disease. Recent research has highlighted the potential therapeutic advantages of deuterated l-DOPA analogs having a longer biological half-life. For their spectroscopic characterization, the in-detail characterization of l-DOPA itself is necessary. This article presents a thorough examination of the vibrational spectra of l-DOPA, with a particular emphasis on chirally sensitive VOA techniques. We successfully obtained high-quality Raman and ROA spectra of l-DOPA in its cationic form, under low pH conditions, and at a high concentration of 100 mg/ml. These spectra cover a broad spectral range, allowing for precise comparisons with theoretical simulations. We also obtained IR and VCD spectra, but they faced limitations due to the narrow accessible spectral region. Exploration of l-DOPA's conformational landscape revealed its intrinsic flexibility, with multiple coexisting conformations. To characterize these conformations, we employed two methods: one involved potential energy surface scans with implicit solvation, and the other utilized molecular dynamics simulations with explicit solvation. Comparing ROA spectra from different conformer groups and applying spectral decomposition proved crucial in determining the correct conformer ratios. The use of explicit solvation significantly improved the quality of the final simulated spectral profiles. The accurate determination of conformer ratios, rather than solely relying on the number of averaged spectra, played a crucial role in simulation accuracy. In conclusion, our study offers valuable insights into the structure and conformational behavior of l-DOPA and represents a valuable resource for subsequent spectroscopic studies of its deuterated analogs.

Probing charge transfer through antifouling polymer brushes by electrochemical methods: The impact of supporting self-assembled monolayer chain length.

Ultrathin surface-tethered polymer brushes represent attractive platforms for a wide range of sensing applications in strategically vital areas such as medicine, forensics, or security. The recent trends in such developments towards "real world conditions" highlighted the role of zwitterionic poly(carboxybetaine) (pCB) brushes which provide excellent antifouling properties combined with bio-functionalization capacity. Highly dense pCB brushes are usually prepared by the "grafting from" polymerization triggered by initiators on self-assembled monolayers (SAMs). Here, multi-methodological experimental studies are pursued to elucidate the impact of the alkanethiolate SAM chain length (C6, C8 and C11) on structural and functional properties of antifouling poly(carboxybetaine methacrylamide) (pCBMAA) brush. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in a custom-made 3D printed cell employing [Ru(NH3)6]3+/2+ redox probe were used to investigate penetrability of SAM/pCBMAA bilayers for small molecules and interfacial charge transfer characteristics. The biofouling resistance of pCBMAA brushes was characterized by surface plasmon resonance; ellipsometry and FT-IRRAS spectroscopy were used to determine swelling and relative density of the brushes synthesized from initiator-bearing SAMs with varied carbon chain length. The SAM length was found to have a substantial impact on all studied characteristics; the highest value of charge transfer resistance (Rct) was observed for denser pCBMAA on longer-chain (C11) SAM when compared to shorter (C8/C6) SAMs. The observed high value of Rct for C11 implies a limitation for the analytical performance of electrochemical sensing methods. At the same time, the pCBMAA brushes on C11 SAM exhibited the best bio-fouling resistance among inspected systems. This demonstrates that proper selection of supporting structures for brushes is critical in the design of these assemblies for biosensing applications.

Negligible risk of surface transmission of SARS-CoV-2 in public transportation.

BACKGROUND: Exposure to pathogens in public transport systems is a common means of spreading infection, mainly by inhaling aerosol or droplets from infected individuals. Such particles also contaminate surfaces, creating a potential surface-transmission pathway. METHODS: A fast acoustic biosensor with an antifouling nano-coating was introduced to detect severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) on exposed surfaces in the Prague Public Transport System. Samples were measured directly without pre-treatment. Results with the sensor gave excellent agreement with parallel quantitative reverse-transcription polymerase chain reaction (qRT-PCR) measurements on 482 surface samples taken from actively used trams, buses, metro trains and platforms between 7 and 9 April 2021, in the middle of the lineage Alpha SARS-CoV-2 epidemic wave when 1 in 240 people were COVID-19 positive in Prague. RESULTS: Only ten of the 482 surface swabs produced positive results and none of them contained virus particles capable of replication, indicating that positive samples contained inactive virus particles and/or fragments. Measurements of the rate of decay of SARS-CoV-2 on frequently touched surface materials showed that the virus did not remain viable longer than 1-4 h. The rate of inactivation was the fastest on rubber handrails in metro escalators and the slowest on hard-plastic seats, window glasses and stainless-steel grab rails. As a result of this study, Prague Public Transport Systems revised their cleaning protocols and the lengths of parking times during the pandemic. CONCLUSIONS: Our findings suggest that surface transmission played no or negligible role in spreading SARS-CoV-2 in Prague. The results also demonstrate the potential of the new biosensor to serve as a complementary screening tool in epidemic monitoring and prognosis.