The fate of biomolecules in the environment depends in part on understanding the surface chemistry occurring at the biological-geochemical (bio-geo) interface. Little is known about how environmental DNA (eDNA) or smaller components, like nucleotides and oligonucleotides, persist in aquatic environments and the role of surface interactions. This study aims to probe surface interactions and adsorption behavior of nucleotides on oxide surfaces. We have investigated the interactions of individual nucleotides (dGMP, dCMP, dAMP, and dTMP) on TiO₂ particle surfaces as a function of pH and in the presence of complementary and noncomplementary base pairs. Using attenuated total reflectance-Fourier transform infrared spectroscopy, there is an increased number of adsorbed nucleotides at lower pH with a preferential interaction of the phosphate group with the oxide surface. Additionally, differential adsorption behavior is seen where purine nucleotides are preferentially adsorbed, with higher surface saturation coverage, over their pyrimidine derivatives. These differences may be a result of intermolecular interactions between coadsorbed nucleotides. When the TiO₂ surface was exposed to two-component solutions of nucleotides, there was preferential adsorption of dGMP compared to dCMP and dTMP, and dAMP compared to dTMP and dCMP. Complementary nucleotide base pairs showed hydrogen-bond interactions between a strongly adsorbed purine nucleotide layer and a weaker interacting hydrogen-bonded pyrimidine second layer. Noncomplementary base pairs did not form a second layer. These results highlight several important findings: (i) there is differential adsorption of nucleotides; (ii) complementary coadsorbed nucleotides show base pairing with a second layer, and the stability depends on the strength of the hydrogen bonding interactions and; (iii) the first layer coverage strongly depends on pH. Overall, the importance of surface interactions in the adsorption of nucleotides and the templating of specific interactions between nucleotides are discussed.

Plasmonic gold nanorods (AuNRs) are often employed as photoacoustic (PA) contrast agents due to their ease of synthesis, functionalization, and biocompatibility. These materials can produce activatable signals in response to a change in optical absorbance intensity or absorbance wavelength. Here, we report a surprising finding: Ag₂S/Se-coated AuNRs have a ~40-fold PA enhancement upon addition of an oxidant but with no change in absorption spectra. We then study the mechanism underlying this enhancement. Electron micrographs and absorption spectra show good colloidal stability and retention of the core-shell structure after potassium hexacyanoferrate(III) (HCF) addition, ruling out aggregation and morphology-induced PA enhancement. X-ray diffraction data showed no changes, ruling out crystallographic phase changes upon HCF addition, thus leading to induced PA enhancement. Attenuated total reflectance-Fourier transform infrared spectroscopy and zeta potential analysis suggest that PA enhancement is driven by the irreversible displacement of hexadecyltrimethylammonium bromide with HCF. This is further confirmed using elemental mapping with energy-dispersive X-ray analysis. PA characterization after HCF addition showed a four-fold increase in the Grüneisen parameter (Γ), thus resulting in PA enhancement. The PA enhancement is not seen in uncoated AuNRs or spherical particles. Two possible mechanisms for PA enhancement are proposed: first, the photo-induced redox heating at the Ag₂S/Se shell-HCF interface, resulting in an increase in temperature-dependent Γ, and second, an enhanced electrostriction response due to HCF adsorption on a layered plasmonic nanoparticle surface, resulting in a high thermal expansion coefficient (β) that is directly proportional to Γ.

Vibrational sum frequency generation (VSFG) spectroscopy and surface pressure measurements are used to investigate the adsorption of a globular protein, bovine serum albumin (BSA), at the air/water interface with and without the presence of salts. We find at low (2 to 5 ppm) protein concentrations, which is relevant to environmental conditions, both VSFG and surface pressure measurements of BSA behave drastically different from at higher concentrations. Instead of emerging to the surface immediately, as observed at 1000 ppm, protein adsorption kinetics is on the order of tens of minutes at lower concentrations. Most importantly, salts strongly enhance the presence of BSA at the interface. This "salting up" effect differs from the well-known "salting out" effect as it occurs at protein concentrations well-below where "salting out" occurs. The dependence on salt concentration suggests this effect relates to a large extent electrostatic interactions and volume exclusion. Additionally, results from other proteins and the pH dependence of the kinetics indicate that salting up depends on the flexibility of proteins. This initial report demonstrates "salting up" as a new type of salt-driven interfacial phenomenon, which is worthy of continued investigation given the importance of salts in biological and environmental aqueous systems.

Organic acids are prevalent in the environment and their acidity and the corresponding dissociation constants can change under varying environmental conditions. The impact of nanoconfinement (when acids are confined within nanometer-scale domains) on physicochemical properties of chemical species is poorly understood and is an emerging field of study. By combining infrared and Raman spectroscopies with molecular dynamics (MD) simulations, we quantified the effect of nanoconfinement in silica nanopores on one of the fundamental chemical reactions-the dissociation of organic acids. The pKa of formic and acetic acids confined within cylindrical silica nanopores with 4 nm diameters were measured. MD models were constructed to calculate the shifts in the pKa values of acetic acid nanoconfined within 1, 2, 3, and 4 nm silica slit pores. Both experiments and MD models indicate a decrease in the apparent acid dissociation constants (i.e., increase in the pKa values) when organic acids are nanoconfined. Therefore, nanoconfinement stabilizes the protonated species. We attribute this observation to (1) a decrease in the average dielectric response of nanoconfined aqueous solutions where charge screening may be decreased; or (2) an increase in proton concentration inside nanopores, which would shift the equilibrium towards the protonated form. Overall, the results of this study provide the first quantification of the pKa values for nanoconfined formic and acetic acids and pave the way for a unifying theory predicting the impact of nanoconfinement on acid-base chemistry.