Hydration behaviors of nonfouling zwitterionic materials.

Zwitterionic materials have emerged as highly effective ultralow fouling materials for many applications, however the underlying mechanism of fouling resistance remains unclear. Using ab initio molecular dynamics simulations and surface-sensitive sum frequency generation vibrational spectroscopy, we studied the hydration behaviors of zwitterionic materials, including trimethylamine-N-oxide (TMAO) and carboxybetaines of different charge-separation distances, to understand their fouling-resistant mechanism and provide a design principle for improved performance. Our study reveals that the interplay among hydrogen bonding, net charge, and dipole moment is crucial to the fouling-resistant capabilities of zwitterionic materials. Shortening of the zwitterionic spacing strengthens hydrogen bonding with water against biomolecule attachment due to the increased electrostatic and induction interactions, charge transfer, and improved structural stability. Moreover, the shortened charge separation reduces the dipole moment of zwitterionic materials with an intrinsic near-neutral net charge, decreasing their electrostatic and dipole-dipole interactions with biofoulers, and increasing their resistance to fouling. Compared to carboxybetaine compounds, TMAO has the shortest zwitterionic spacing and exhibits the strongest hydrogen bonding, the smallest net charge, and the minimum dipole moment, making it an excellent nonfouling material.

Hidden hydrophobicity impacts polymer immunogenicity.

Antibodies against poly(ethylene glycol) (PEG) have been found to be the culprit of side reactions and efficacy loss of a number of PEGylated drugs. Fundamental mechanisms of PEG immunogenicity and design principles for PEG alternatives still have not been fully explored. By using hydrophobic interaction chromatography (HIC) under varied salt conditions, we reveal the "hidden" hydrophobicity of those polymers which are generally considered as hydrophilic. A correlation between the hidden hydrophobicity of a polymer and its polymer immunogenicity is observed when this polymer is conjugated with an immunogenic protein. Such a correlation of hidden hydrophobicity vs. immunogenicity for a polymer also applies to corresponding polymer-protein conjugates. Atomistic molecular dynamics (MD) simulation results show a similar trend. Based on polyzwitterion modification and with this HIC technique, we are able to produce extremely low-immunogenic protein conjugates as their hydrophilicity is pushed to the limit and their hydrophobicity is eliminated, breaking the current barriers of eliminating anti-drug and anti-polymer antibodies.

Multiscale Simulation of Protein Corona Formation on Silver Nanoparticles: Study of Ovispirin-1 Peptide Adsorption.

The exposure of nanoparticles (NPs) to biofluids leads to the rapid coverage of proteins, named protein corona, which alters the NPs' chemicophysical and biological properties. Fundamental studies of the protein corona are thus critical to the increasing applications of NPs in nanotechnology and nanomedicines. The present work utilizes multiscale simulations of a model biological system, small ovispirin-1 peptides, and bare silver nanoparticles (AgNPs) to examine the NPs' size and surface hydrophilicity effects on formation dynamics and the structure of the peptide corona. Our simulations revealed the different adsorption dynamics of ovispirin-1 peptides on the NPs, including the direct adsorption of a single peptide and peptide aggregates and multistep adsorption, as well as an intermediate cycle of desorption and readsorption. Notably, the whole process of peptide adsorption on hydrophilic AgNP surfaces can be generalized as three stages: diffusion to the surface, initial landing via hydrophilic residues, and the final attachment. The decrease in AgNP's size leads to faster adsorption with more heterogeneous peptide interfacial dynamics, a denser and inhomogeneous peptide packing structure, and a wider distribution of adsorption orientations. Subsequent atomistic molecular dynamics simulations demonstrated that on the hydrophilic AgNP surfaces, adsorbed peptides display moderate changes in their secondary structure, resulting in further changes of corona composition, i.e., amino acid residue distribution on the surface.

Strong Surface Hydration and Salt Resistant Mechanism of a New Nonfouling Zwitterionic Polymer Based on Protein Stabilizer TMAO.

Zwitterionic polymers exhibit excellent nonfouling performance due to their strong surface hydrations. However, salt molecules may severely reduce the surface hydrations of typical zwitterionic polymers, making the application of these polymers in real biological and marine environments challenging. Recently, a new zwitterionic polymer brush based on the protein stabilizer trimethylamine N-oxide (TMAO) was developed as an outstanding nonfouling material. Using surface-sensitive sum frequency generation (SFG) vibrational spectroscopy, we investigated the surface hydration of TMAO polymer brushes (pTMAO) and the effects of salts and proteins on such surface hydration. It was discovered that exposure to highly concentrated salt solutions such as seawater only moderately reduced surface hydration. This superior resistance to salt effects compared to other zwitterionic polymers is due to the shorter distance between the positively and negatively charged groups, thus a smaller dipole in pTMAO and strong hydration around TMAO zwitterion. This results in strong bonding interactions between the O- in pTMAO and water, and weaker interaction between O- and metal cations due to the strong repulsion from the N+ and hydration water. Computer simulations at quantum and atomistic scales were performed to support SFG analyses. In addition to the salt effect, it was discovered that exposure to proteins in seawater exerted minimal influence on the pTMAO surface hydration, indicating complete exclusion of protein attachment. The excellent nonfouling performance of pTMAO originates from its extremely strong surface hydration that exhibits effective resistance to disruptions induced by salts and proteins.

Protein Corona on Gold Nanoparticles Studied with Coarse-Grained Simulations.

Understanding protein corona formation in an aqueous environment at the molecular and atomistic levels is critical to applications such as biomolecule-detection and drug delivery. In this work, we employed mesoscopic coarse-grained simulations to study ovispirin-1 and lysozyme protein coronas on bare gold nanoparticles. Our study showed that protein corona formation is governed by protein-surface and protein-protein interactions, as well as the surface hydrophobic effect. The corona structure was found to be dependent on protein types and the size of nanoparticles. Ovispirin proteins form homogeneous single-layered adsorption in comparison with the lysozyme's inhomogeneous multilayered aggregates on gold NP surfaces. The decrease in nanoparticle size leads to more angular degrees of freedom for protein adsorption orientation. Subsequent atomistic molecular dynamics simulations further demonstrate the loss of secondary structure of ovispirin upon adsorption and the heterogeneity of its local structure.

High-entropy high-hardness metal carbides discovered by entropy descriptors.

High-entropy materials have attracted considerable interest due to the combination of useful properties and promising applications. Predicting their formation remains the major hindrance to the discovery of new systems. Here we propose a descriptor-entropy forming ability-for addressing synthesizability from first principles. The formalism, based on the energy distribution spectrum of randomized calculations, captures the accessibility of equally-sampled states near the ground state and quantifies configurational disorder capable of stabilizing high-entropy homogeneous phases. The methodology is applied to disordered refractory 5-metal carbides-promising candidates for high-hardness applications. The descriptor correctly predicts the ease with which compositions can be experimentally synthesized as rock-salt high-entropy homogeneous phases, validating the ansatz, and in some cases, going beyond intuition. Several of these materials exhibit hardness up to 50% higher than rule of mixtures estimations. The entropy descriptor method has the potential to accelerate the search for high-entropy systems by rationally combining first principles with experimental synthesis and characterization.

Photoelectrochemical Properties and Behavior of α-SnWO4 Photoanodes Synthesized by Hydrothermal Conversion of WO3 Films.

Metal oxides with moderate band gaps are desired for efficient production of hydrogen from sunlight and water via photoelectrochemical (PEC) water splitting. Here, we report an α-SnWO4 photoanode synthesized by hydrothermal conversion of WO3 films that achieves photon to current conversion at wavelengths up to 700 nm (1.78 eV). This photoanode is promising for overall PEC water-splitting because the flat-band potential and voltage of photocurrent onset are more negative than the potential of hydrogen evolution. Furthermore, the photoanode utilizes a large portion of the solar spectrum. However, the photocurrent density reaches only a small fraction of that which is theoretically possible. Density functional theory based thermodynamic and electronic structure calculations were performed to elucidate the nature and impact of defects in α-SnWO4 prepared by this synthetic route, from which hole localization at Sn-at-W antisite defects was determined to be a likely cause for the poor photocurrent. Measurements further showed that the photocurrent decreases over time due to surface oxidation, which was suppressed by improving the kinetics of hole transfer at the semiconductor/electrolyte interface. Alternative synthetic methods and the addition of protective coatings and/or oxygen evolution catalysts are suggested to improve the PEC performance and stability of this promising α-SnWO4 material.

Time- and energy-efficient solution combustion synthesis of binary metal tungstate nanoparticles with enhanced photocatalytic activity.

In the search for stable and efficient photocatalysts beyond TiO2 , the tungsten-based oxide semiconductors silver tungstate (Ag2 WO4 ), copper tungstate (CuWO4 ), and zinc tungstate (ZnWO4 ) were prepared using solution combustion synthesis (SCS). The tungsten precursor's influence on the product was of particular relevance to this study, and the most significant effects are highlighted. Each sample's photocatalytic activity towards methyl orange degradation was studied and benchmarked against their respective commercial oxide sample obtained by solid-state ceramic synthesis. Based on the results herein, we conclude that SCS is a time- and energy-efficient method to synthesize crystalline binary tungstate nanomaterials even without additional excessive heat treatment. As many of these photocatalysts possess excellent photocatalytic activity, the discussed synthetic strategy may open sustainable materials chemistry avenues to solar energy conversion and environmental remediation.

Photocatalytic generation of syngas using combustion-synthesized silver bismuth tungstate.

Silver bismuth tungstate (AgBiW(2)O(8)) nanoparticles were prepared for the first time by solution combustion synthesis by using the corresponding metal nitrates as the precursor and urea as the fuel. These nanoparticles were subsequently modified with Pt catalyst islands using a photocatalytic procedure and used for the photogeneration of syngas (CO+H(2)). Formic acid was used for this purpose for the in situ generation of CO(2) and its subsequent reduction to CO. In the absence of Pt modification, H(2) was not obtained in the gas products evolved. These results were compared with those obtained with acetic acid in place of formic acid. The combustion process was simulated by thermogravimetry and the synthesized powder was characterized using transmission electron microscopy, diffuse reflectance UV/Vis spectroscopy, X-ray diffraction, surface area measurements, and X-ray photoelectron spectroscopy. Tauc plots derived from the diffuse reflectance data yielded an optical band gap of 2.74 eV. The photocatalytic activity of these nanoparticles was superior to a sample prepared by solid-state synthesis. Mechanistic aspects are finally presented, as are structural models and electronic calculations, using density functional theory (DFT).