Materials Science and Engineering

The transferability of force field parameters is a crucial aspect of high-quality force fields. Previous investigations have affirmed the transferability of electrostatic parameters derived from polarizable Gaussian multipole models (pGMs) when applied to water oligomer clusters, polypeptides across various conformations, and different sequences. In this study, we introduce PCMRESP, a novel method for electrostatic parametrization in solution, intended for the development of polarizable force fields. We utilized this method to assess the transferability of three models: a fixed charge model and two variants of pGM models. Our analysis involved testing these models on 377 small molecules and 100 tetra-peptides in five representative dielectric environments: gas, diethyl ether, dichloroethane, acetone, and water. Our findings reveal that the inclusion of atomic polarization significantly enhances transferability and the incorporation of permanent atomic dipoles, in the form of covalent bond dipoles, leads to further improvements. Moreover, our tests on dual-solvent strategies demonstrate consistent transferability for all three models, underscoring the robustness of the dual-solvent approach. In contrast, an evaluation of the traditional HF/6-31G* method indicates poor transferability for the pGM-ind and pGM-perm models, suggesting the limitations of this conventional approach.

In vat polymerization (VP) 3D printing, there is an urgent need to expand characterization efforts for resins derived from natural resources to counter the increasing consumption of fossil fuels required to synthesize conventional monomers. Here, we apply multiscale mechanical characterization techniques to interrogate a 3D printed biobased copolymer along a controlled range of monomer ratios. We varied the concentration of two dissimilar monomers to derive structural information about the polymer networks. Current research primarily considers the macroscale, but recent understanding of the process-induced anisotropy in 3D printed layers suggests a multiscale approach is critical. By combining typical macroscopic techniques with micro- and nanoscale analogues, clear correlations in the processing-structure-property relationships appeared. We observed that measured moduli were always greater via surface-localized methods, but property differences between formulations were easier to identify. As researchers continue to develop novel sustainable biopolymers that match or exceed the performance of commercial resins, it is vital to understand the multiscale relationships between the VP process, the structure of the formed polymer networks, and the resultant properties.

Inspired by the adaptability of biological materials, a variety of synthetic, chemically driven self-assembly processes have been developed that result in the transient formation of supramolecular structures. These structures form through two simultaneous reactions, forward and backward, which generate and consume a molecule that undergoes self-assembly. The dynamics of these assembly processes have been shown to differ from conventional thermodynamically stable molecular assemblies. However, the evolution of nanoscale morphologies in chemically driven self-assembly and how they compare to conventional assemblies has not been resolved. Here, we use a chemically driven redox system to separately carry out the forward and backward reactions. We analyze the forward and backward reactions both sequentially and synchronously with time-resolved cryogenic transmission electron microscopy (cryoEM). Quantitative image analysis shows that the synchronous process is more complex and heterogeneous than the sequential process. Our key finding is that a thermodynamically unstable stacked nanorod phase, briefly observed in the backward reaction, is sustained for ∼6 hours in the synchronous process. Kinetic Monte Carlo modeling show that the synchronous process is driven by multiple cycles of assembly and disassembly. The collective data suggest that chemically driven self-assembly can create sustained morphologies not seen in thermodynamically stable assemblies by kinetically stabilizing transient intermediates. This finding provides plausible design principles to develop and optimize supramolecular materials with novel properties.

Silver cations can mediate base pairing of guanine (G) DNA oligomers, yielding linear parallel G-Ag⁺-G duplexes with enhanced stabilities compared to those of canonical DNA duplexes. To enable their use in programmable DNA nanotechnologies, it is critical to understand solution-state formation and the nanomechanical stiffness of G-Ag⁺-G duplexes. Using temperature-controlled circular dichroism (CD) spectroscopy, we find that heating mixtures of G oligomers and silver salt above 50 °C fully destabilizes G-quadruplex structures and converts oligomers to G-Ag⁺-G duplexes. Electrospray ionization mass spectrometry supports that G-Ag⁺-G duplexes form at stoichiometries of 1 Ag⁺ per base pair, and CD spectroscopy suggests that as the Ag⁺/base stoichiometry increases further, G-Ag⁺-G duplexes undergo additional morphological changes. Using liquid-phase atomic force microscopy, we find that this excess Ag⁺ enables assembly of long fiberlike structures with ∼2.5 nm heights equivalent to a single DNA duplex but with lengths that far exceed a single duplex. Finally, using the conditions established to form single G-Ag⁺-G duplexes, we use a surface forces apparatus (SFA) to compare the solution-phase stiffness of single G-Ag⁺-G duplexes with dG-dC Watson-Crick-Franklin duplexes. SFA shows that G-Ag⁺-G duplexes are 1.3 times stiffer than dG-dC duplexes, confirming gas-phase ion mobility spectrometry measurements and computational predictions. These findings may guide the development of structural DNA nanotechnologies that rely on silver-mediated base pairing.

All-optical tunability of semiconductor metasurfaces offers unique opportunities for novel time-varying effects, including frequency conversion and light trapping. However, the all-optical processes often induce optical absorption that fundamentally limits the possible dynamic increase of their quality factor (Q-boosting). Here, we propose and numerically demonstrate the concept of large Q-boosting in a single-material metasurface by dynamically reducing its structural anisotropy on a femtosecond timescale. This balance is achieved by excitation with a structured pump and takes advantage of the band-filling effect in a GaAs direct-bandgap semiconductor to eliminate the free-carrier-induced loss. We show that this approach allows a dynamic boosting of the resonance quality factor over orders of magnitude, only limited by the free-carrier relaxation processes. The proposed approach offers complete dynamic control over the resonance bandwidth and opens applications in frequency conversion and light trapping.

The creation of metal-metal oxide interfaces is an important approach to fine-tuning catalyst properties through strong interfacial interactions. This article presents the work on developing interfaces between Pt and CeOx that improve Pt surface energetics for the hydrogen evolution reaction (HER) within an alkaline electrolyte. The Pt-CeOx interfaces are formed by depositing size-controlled Pt nanoparticles onto a carbon support already coated with ultrathin CeOx nanosheets. This interface structure facilitates substantial electron transfer from Pt to CeOx, resulting in decreased hydrogen binding energies on Pt surfaces, and water dissociation for the HER, as predicted by the density functional theory (DFT) calculations. Electrochemical testing indicates that both Pt specific activity and mass activity are improved by a factor of 2 to 3 following the formation of Pt-CeOx interfaces. This study underscores the significance and potential of harnessing robust interfacial effects to enhance electrocatalytic reactions.

A unique prospect of using halides as charge carriers is the possibility of the halides undergoing anodic redox behaviors when serving as charge carriers for the charge-neutrality compensation of electrodes. However, the anodic conversion of halides to neutral halogen species has often been irreversible at room temperature due to the emergence of diatomic halogen gaseous products. Here, we report that chloride ions can be reversibly converted to near-neutral atomic chlorine species in the Mn3O4 electrode at room temperature in a highly concentrated chloride-based aqueous electrolyte. Notably, the Zn2+ cations inserted in the first discharge and trapped in the Mn3O4 structure create an environment to stabilize the converted chlorine atoms within the structure. Characterization results suggest that the Cl/Cl- redox is responsible for the observed large capacity, as the oxidation state of Mn barely changes upon charging. Computation results corroborate that the converted chlorine species exist as polychloride monoanions, e.g., [Cl3]- and [Cl5]-, inside the Zn2+-trapped Mn3O4, and the presence of polychloride species is confirmed experimentally. Our results point to the halogen plating inside electrode lattices as a new charge-storage mechanism.

Photocatalytic plastic waste upcycling into value-added feedstock is a promising way to mitigate the environmental issues caused by the nondegradable nature of plastic waste. Here, we developed a MoS₂/g-C₃N₄ photocatalyst that can efficiently upcycle poly(ethylene terephthalate) (PET) into valuable organic chemicals. Interestingly, the conversion mechanism is concentration-dependent. For instance, at a low ethylene glycol (EG) concentration (7.96 mM), acetate is the main product. Unexpectedly, the conversion of PET water bottle hydrolysate with only 7.96 mM ethylene glycol (EG) can produce a 4 times higher amount of acetate (704.59 nmol) than the conversion of 300 mM EG (174.50 nmol), while at a higher EG concentration (300 mM), formate is the dominant product. Herein, a 40 times higher EG concentration (300 mM compared to 7.96 mM) would produce only ∼3 times more formate (179 nmol compared to 51.86 nmol). In addition, under natural sunlight conditions, comparable amounts of liquid and gaseous products are produced when commercial PET plastics are employed. Overall, the photocatalytic PET conversion process is quite efficient under a low concentration of EG in PET hydrolysate, indicating the enormous potential of this photocatalysis strategy for real plastics upcycling.

In this work, the CuAgZr metallic glasses (MGs) are investigated, a promising material for biomedical applications due to their high strength, corrosion resistance, and antibacterial activity. Using an integrated approach of combinatorial synthesis, high-throughput characterization, and machine learning (ML), the mechanical properties of CuAgZr MGs are efficiently explored. The investigation find that post-deposition oxidation in inter-columnar regions with looser packing causes high oxygen content in Cu-rich regions, significantly affecting the alloys mechanical behavior. The study also reveals that nanoscale structural features greatly impact plastic yielding and flow in the alloys. ML algorithms are tested, and the multi-layer perceptron algorithm produced satisfactory predictions for the alloys hardness of untested alloys, providing valuable clues for future research. The work demonstrates the potential of using combinatorial synthesis, high-throughput characterization, and ML  techniques to facilitate the development of new MGs with improved strength and economic feasibility.