Poly(ethylene glycol) (PEG)-based materials, like PEG-diacrylate (PEGDA), are prized for their hydrophilic, inert properties, and leveraged in hydrogels and as membrane mimics. While network chemistry is often tuned for selective transport and antifouling, fundamental understanding of water dynamics at the network surface and the impact on bulk transport is limited. We utilize Overhauser dynamic nuclear polarization (ODNP) to measure nanoscale water diffusivity near a tethered spin label at the water-polymer surface and compare it to bulk water diffusivity from pulsed field gradient (PFG) NMR. Via active ester chemistry, spin labels and varied sidechain chemistries are introduced, modulating network hydrophilicity. Tuning network hydration through crosslinker content and functional groups further impacts water diffusivity. Results show rapid nanoscale water transport at the polymer surface, reflecting network volumetric water content, with further modulation by sidechain functionality. These findings demonstrate PEGDA's utility as a membrane mimic and the critical impact of network chemistry on water transport.

PEO restructures water near the polymer, reducing free volume and slowing local water.

Hydration water dynamics, structure, and thermodynamics are crucially important to understand and predict water-mediated properties at molecular interfaces.

Cryoprotectants play a crucial role in preserving biological material, ensuring their viability during storage and facilitating crucial applications such as the conservation of medical compounds, tissues, and organs for transplantation. However, the precise mechanism by which cryoprotectants modulate the thermodynamic properties of water to impede the formation and growth of ice crystals, thus preventing long-term damage, remains elusive. This is evident in the use of empirically optimized recipes for mixtures that typically contain DMSO, glycerol, and various sugar constituents. Here, we use terahertz calorimetry, Overhauser nuclear polarization, and molecular dynamics simulations to show that DMSO exhibits a robust structuring effect on water around its methyl groups, reaching a maximum at a DMSO mole fraction of XDMSO = 0.33. In contrast, glycerol exerts a smaller water-structuring effect, even at higher concentrations (Scheme 1). These results potentially suggest that the wrapped water around DMSO's methyl group, which can be evicted upon ligand binding, may render DMSO a more surface-active cryoprotectant than glycerol, while glycerol may participate more as a viscogen that acts on the entire sample. These findings shed light on the molecular intricacies of cryoprotectant solvation behavior and have potentially significant implications for optimizing cryopreservation protocols.

The superior antifouling performance of zwitterionic materials is commonly linked to their hydration structure, in which tight surface binding of water molecules inhibits solute adsorption. However, there is comparatively little direct experimental data on the hydration water structure and dynamics around zwitterionic moieties, including the longer-range behavior of the hydration shell that modulates the approach of solutes to the polymer surface. This work experimentally probes the dynamics of the diffusing hydration water molecules around a series of zwitterion chemistries using Overhauser dynamic nuclear polarization relaxometry. Surprisingly, water dynamics measured within ∼1 nm of the zwitterions were minimally inhibited compared to those near uncharged hydrophilic or cationic side chains. Specific dissolved ions further enhance the water diffusivity near the zwitterions, rendering the hydration shell bulk water-like. These results that the hydration of a zwitterion surface is nearly indistinguishable from bulk water suggest that these surfaces are "invisible" to biological constituents in a manner tunable by the ionic environment and the chemical design of the zwitterionic surface.

Water's unique thermophysical properties and how it mediates aqueous interactions between solutes have long been interpreted in terms of its collective molecular structure. The seminal work of Errington and Debenedetti [Nature 2001, 409, 318-321] revealed a striking hierarchy of relationships among the thermodynamic, dynamic, and structural properties of water, motivating many efforts to understand (1) what measures of water structure are connected to different experimentally accessible macroscopic responses and (2) how many such structural metrics are adequate to describe the collective structural behavior of water. Diffusivity constitutes a particularly interesting experimentally accessible equilibrium property to investigate such relationships because advanced NMR techniques allow the measurement of bulk and local water dynamics in nanometer proximity to molecules and interfaces, suggesting the enticing possibility of measuring local diffusivities that report on water structure. Here, we apply statistical learning methods to discover persistent structure-dynamic correlations across a variety of simulated aqueous mixtures, from alcohol-water to polypeptoid-water systems. We investigate a variety of molecular water structure metrics and find that an unsupervised statistical learning algorithm (namely, sequential feature selection) identifies only two or three independent structural metrics that are sufficient to predict water self-diffusivity accurately. Surprisingly, the translational diffusivity of water across all mixed systems studied here is strongly correlated with a measure of tetrahedral order given by water's triplet angle distribution. We also identify a separate small number of structural metrics that well predict an important thermodynamic property, the excess chemical potential of an idealized methane-sized hydrophobe in water. Ultimately, we offer a Bayesian method of inferring water structure by using only structure-dynamics linear regression models with experimental Overhauser dynamic nuclear polarization (ODNP) measurements of water self-diffusivity. This study thus quantifies the relationships among several distinct structural order parameters in water and, through statistical learning, reveals the potential to leverage molecular structure to predict fundamental thermophysical properties. In turn, these findings suggest a framework for solving the inverse problem of inferring water's molecular structure using experimental measurements such as ODNP studies that probe local water properties.

NU-1000 is a stable, zirconium-based metal-organic framework (MOF) that has been used extensively as a scaffold for the installation of catalytic species, among other applications. The synthesis of NU-1000 follows a two-step modulated procedure, whereby the MOF grows as modulator molecules bound to the node are replaced with organic linker molecules. Manipulating the competition between the modulator and linker molecules for the binding sites on the node leads to control of reaction rate and the resulting NU-1000 particle size. By modifying the linker, modulator, and base concentrations and zirconium precursor, we can synthesize high-purity and mono-disperse NU-1000 from 300 nm to almost 10 mu m in length. Despite a wide range of particle sizes and synthetic conditions, the uptake of a dicobalt complex remained consistent per node. Further control over particle size can lead to more facile high-resolution characterization using methods like electron microscopy and spectroscopy as well as open a wider range of potential applications, including nanoscale applications like biological imaging.

The properties of water on both molecular and macroscopic surfaces critically influence a wide range of physical behaviors, with applications spanning from membrane science to catalysis to protein engineering. Yet, our current understanding of water interfacing molecular and material surfaces is incomplete, in part because measurement of water structure and molecular-scale properties challenges even the most advanced experimental characterization techniques and computational approaches. This review highlights progress in the ongoing development of tools working to answer fundamental questions on the principles that govern the interactions between water and surfaces. One outstanding and critical question is what universal molecular signatures capture the hydrophobicity of different surfaces in an operationally meaningful way, since traditional macroscopic hydrophobicity measures like contact angles fail to capture even basic properties of molecular or extended surfaces with any heterogeneity at the nanometer length scale. Resolving this grand challenge will require close interactions between state-of-the-art experiments, simulations, and theory, spanning research groups and using agreed-upon model systems, to synthesize an integrated knowledge of solvation water structure, dynamics, and thermodynamics.

We introduce a powerful, widely applicable approach to characterizing polymer conformational distributions, specifically the end-to-end distance distributions, P(Ree), accessed through double electron-electron resonance (DEER) spectroscopy in conjunction with molecular dynamics (MD) simulations. The technique is demonstrated on one of the most widely used synthetic, disordered, water-soluble polymers: poly(ethylene oxide) (PEO). Despite its widespread importance, no systematic experimental characterization of PEO's Ree conformational landscape exists. The evaluation of P(Ree) is particularly important for short polymers or (bio)polymers with sequence complexities that deviate from simple polymer physics scaling laws valid for long chains. In this study, we characterize the Ree landscape by measuring P(Ree) for low molecular weight (MW: 0.22-2.6 kDa) dilute PEO chains. We use DEER with end-conjugated spin probes to resolve Ree populations from ∼2-9 nm and compare them with full distributions from MD. The P( Ree)'s from DEER and MD show remarkably good agreement, particularly at longer chain lengths where populations in the DEER-unresolvable range (<1.5 nm) are low. Both the P(Ree) and the root-mean-square R̃ee indicate that aqueous PEO is a semiflexible polymer in a good solvent, with the latter scaling linearly with molecular weight up to its persistence length (lp ∼ 0.48 nm), and rapidly transitioning to excluded volume scaling above lp. The R̃ee scaling is quantitatively consistent with that from experimental scattering data on high MW (>10 kDa) PEO and the P(Ree)'s crossover to the theoretical distribution for an excluded volume chain.

Orthorhombic tin monosulfide (SnS) consists of layers of covalently bound Sn and S atoms held together by weak van der Waals forces and is a stable two-dimensional material with potentially useful properties in emerging applications such as valleytronics. Large-scale sustainable synthesis of few-layer (e.g., 1-10 layers) SnS is a challenge, which also slows progress in understanding their properties as a function of number of layers. Herein we describe solvothermal synthesis of SnS in water or ethylene glycol. The latter yields a flower-like morphology where the petals are SnS nanoplates and sonication and separation of these flowers via differential centrifugation yields 1-10 layer SnS nanoplates. The direct optical absorption edges of these SnS nanoplates blue-shift due to quantum confinement from 1.33 to 1.88 eV as the thickness (number of layers) is decreased from ∼5 nm (10 layers) to ∼2 nm (4 layers).

Mononuclear and dinuclear copper species were synthesized at the nodes of an NU-1000 metal-organic framework (MOF) via cation exchange and subsequent oxidation at 200 °C in oxygen. Copper-exchanged MOFs are active for selectively converting methane to methanol at 150-200 °C. At 150 °C and 1 bar methane, approximately a third of the copper centers are involved in converting methane to methanol. Methanol productivity increased by 3-4-fold and selectivity increased from 70% to 90% by increasing the methane pressure from 1 to 40 bar. Density functional theory showed that reaction pathways on various copper sites are able to convert methane to methanol, the copper oxyl sites with much lower free energies of activation. Combining studies of the stoichiometric activity with characterization by in situ X-ray absorption spectroscopy and density functional theory, we conclude that dehydrated dinuclear copper oxyl sites formed after activation at 200 °C are responsible for the activity.

The postmodification of metal organic frameworks (MOFs) affords exceedingly high surface area materials with precisely installed chemical features, which provide new opportunities for detailed structure-function correlation in the field of catalysis. Here, we significantly expand upon the number of vapor-phase postmodification processes reported to date through screening a library of atomic layer deposition (ALD) precursors, which span metals across the periodic table and which include ligands from four distinct precursor classes. With a large library of precursors and synthesis conditions, we discern trends in the compatibility of precursor classes for well-behaved ALD in MOFs (AIM) and identify challenges and solutions to more precise postsynthetic modification.

The process of nanocasting in metal-organic frameworks (MOFs) is a versatile approach to modify these porous materials by introducing supporting scaffolds. The nanocast scaffolds can stabilize metal-oxo clusters in MOFs at high temperatures and modulate their chemical environments. Here we demonstrate a range of nanocasting approaches in the MOF NU-1000, which contains hexanuclear oxozirconium clusters (denoted as Zr-6 clusters) that are suitable for modification with other metals. We developed methods for introducing SiO2, TiO2, polymeric, and carbon scaffolds into the NU-1000 structure. The responses of NU-1000 toward different scaffold precursors were studied, including the effects on morphology, precursor distribution, and porosity after nano casting. Upon removal of organic linkers in the MOF by calcination/pyrolysis at 500 degrees C or above, the Zr-6 clusters remained accessible and maintained their Lewis acidity in SiO2 nanocast samples, whereas additional treatment was necessary for Zr-6 clusters to become accessible to pyridine probe molecules in carbon nanocast samples. Aggregation of Zr-6 clusters was largely prevented with SiO2 or carbon scaffolds even after thermal treatment at 500 degrees C or above. In the case of titania nanocasting, NU-1000 crystals underwent a pseudomorphic transformation, in which Zr-6 clusters reacted with titania to form small aggregates of a Zr/Ti mixed oxide with a local structure resembling that of ZrTi2O6. The ability to maintain high densities of discrete Lewis acidic Zr-6 clusters on SiO2 or carbon supports at high temperatures provides a starting point for designing new thermally stable catalysts.

Promoters are ubiquitous in industrial heterogeneous catalysts. The wider roles of promoters in accelerating catalysis and/or controlling selectivity are, however, not well understood. A model system has been developed where a heterobimetallic active site comprising an active metal (Rh) and a promoter ion (Ga) is preassembled and delivered onto a metal-organic framework (MOF) support, NU-1000. The Rh-Ga sites in NU-1000 selectively catalyze the hydrogenation of acyclic alkynes to E-alkenes. The overall stereoselectivity is complementary to the well-known Lindlar's catalyst, which generates Z-alkenes. The role of the Ga in promoting this unusual selectivity is evidenced by the lack of semihydrogenation selectivity when Ga is absent and only Rh is present in the active site.

Nanocasting can be a useful strategy to transfer the catalytic metal clusters in metal-organic frameworks (MOFs) to an all-inorganic support such as silica. The incorporation of silica in the MOF pores as a secondary support has the potential to extend the application of the highly tunable metal-based active sites in MOFs to high temperature catalysis. Here, we demonstrate the applicability of the nanocasting method to a range of MOFs that incorporate catalytically attractive hexazirconium, hexacerium, or pentanickel oxide-based clusters (UiO-66, (Ce)UiO-66, (Ce)UiO-67, (Ce)MOF-808, DUT-9, and In- and Ni-postmetalated NU-1000). We describe, in tutorial form, the challenges associated with nanocasting of MOFs that are related to their small pore size and to considerations of chemical and mechanical stability, and we provide approaches to overcome some of these challenges. Some of these nanocast materials feature the site-isolated clusters in a porous, thermally stable silica matrix, suitable for catalysis at high temperatures; in others, structural rearrangement of clusters or partial cluster aggregation occurs, but extensive aggregation can be mitigated by the silica skeleton introduced during nanocasting.