Tailoring Interfacial Interactions via Polymer-Grafted Nanoparticles Improves Performance of Parts Created by 3D Printing
Abstract not provided
Street, Dayton P.↗
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Selective CO 2 electrocatalysis at the pseudocapacitive nanoparticle/ordered-ligand interlayer
Enzymes feature the concerted operation of multiple components around an active site, leading to exquisite catalytic specificity. Realizing such configurations on synthetic catalyst surfaces remains elusive. In this article, we report a nanoparticle/ordered-ligand interlayer that contains a multi-component catalytic pocket for high-specificity CO 2 electrocatalysis. The nanoparticle/ordered-ligand interlayer comprises a metal nanoparticle surface and a detached layer of ligands in its vicinity. This interlayer possesses unique pseudocapacitive characteristics where desolvated cations are intercalated, creating an active-site configuration that enhances catalytic turnover by two orders and one order of magnitude against a pristine metal surface and nanoparticle with tethered ligands, respectively. The nanoparticle/ordered-ligand interlayer is demonstrated across several metals with up to 99% CO selectivity at marginal overpotentials and onset overpotentials of as low as 27 mV, in aqueous conditions. Furthermore, in a gas-diffusion environment with neutral media, the nanoparticle/ordered-ligand interlayer achieves nearly unit CO selectivity at high current densities (98.1% at 400 mA cm -2 ).
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Assessing turbulence and mixing parameterizations in the gray-zone of multiscale simulations over mountainous terrain during the METEX21 field experiment
Multiscale numerical weather prediction models transition from mesoscale, where turbulence is fully parameterized, to microscale, where the majority of highly energetic scales of turbulence are resolved. The turbulence gray-zone is situated between these two regimes and multiscale models must downscale through these resolutions. Here, we compare three multiscale simulations which vary by the parameterization used for turbulence and mixing within the gray-zone. The three parameterizations analyzed are the Mellor-Yamada Nakanishi and Niino (MYNN) Level 2.5 planetary boundary layer scheme, the TKE-1.5 large eddy simulation (LES) closure scheme, and a recently developed three-dimensional planetary boundary layer scheme based on the Mellor-Yamada model. The simulation domain includes complex (i.e., mountainous) terrain in Nevada that was instrumented with meteorological towers, profiling and scanning lidars, a tethered balloon, and a surface flux tower. Simulations are compared to each other and to observations, with assessment of model skill at predicting wind speed, wind direction and TKE, and qualitative evaluations of transport and dispersion of smoke from controlled releases. This analysis demonstrates that microscale predictions of transport and dispersion can be significantly influenced by the choice of turbulence and mixing parameterization in the terra incognita , particularly over regions of complex terrain and with strong local forcing. This influence may not be apparent in the analysis of model skill, and motivates future field campaigns involving controlled tracer releases and corresponding modeling studies of the turbulence gray-zone.
54 ENVIRONMENTAL SCIENCES↗
Interfacial dynamics mediate surface binding events on supramolecular nanostructures
The dynamic behavior of biological materials is central to their functionality, suggesting that interfacial dynamics could also mediate the activity of chemical events at the surfaces of synthetic materials. Here, we investigate the influence of surface flexibility and hydration on heavy metal remediation by nanostructures self-assembled from small molecules that are decorated with surface-bound chelators in water. We find that incorporating short oligo(ethylene glycol) spacers between the surface and interior domain of self-assembled nanostructures can drastically increase the conformational mobility of surface-bound lead-chelating moieties and promote interaction with surrounding water. In turn, we find the binding affinities of chelators tethered to the most flexible surfaces are more than ten times greater than the least flexible surfaces. Accordingly, nanostructures composed of amphiphiles that give rise to the most dynamic surfaces are capable of remediating thousands of liters of 50 ppb Pb 2+ -contaminated water with single grams of material. These findings establish interfacial dynamics as a critical design parameter for functional self-assembled nanostructures.
42 ENGINEERING↗
The Role of Ligand–Ligand Interactions in Multimodal Ligand Conformational Equilibria and Surface Pattern Formation
Multimodal chromatography uses multiple modes of interaction such as charge, hydrophobic, or hydrogen bonding to separate proteins. Recently, we used molecular dynamics (MD) simulations to show that ligands immobilized on surfaces can interact and associate with neighboring ligands to form hydrophobic and charge patches, which may have important implications for the nature of protein–surface interactions. Here, we study interfacial systems of increasing complexity—from a single immobilized multimodal ligand to high density surfaces—to better understand how ligand behavior is affected by the presence of a surface and the presence of other ligands in the vicinity, and how this behavior scales to larger systems. Furthermore, we find that tethering a ligand to a surface restricts its conformations to a subset of those observed in free solution, yet the ligand maintains flexibility in the plane of the surface and can form contacts with neighboring ligands. We find that although the formation of a contact between two neighboring ligands is slightly unfavorable, three neighboring ligands exhibit a preference for the formation of a fully connected cluster. To explore how these trends in ligand association extend to a larger surface with high density of ligands, we performed coarse-grained Monte Carlo (MC) simulations of a 132-ligand surface using ligand interactions parametrized based on free energies obtained from the three-ligand MD simulations. Despite their simplicity, the coarse-grained simulations qualitatively capture the cluster size distribution of ligands observed in detailed MD simulations. Quantitative differences between the two suggest opportunities for improvements in the coarse-grained energy function for efficient predictions of cluster and pattern formations. Our approach presents a promising route to the engineering of multimodal patterns for future chromatographic resin design.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Colloidal Three-Dimensional Covalent Organic Frameworks and Their Application as Porous Liquids
Developing solid porous materials into free-flowing liquids with permanent porosity is a promising strategy for overcoming certain limitations of conventional sorbent materials employed in gas storage and separation applications. The ability to control the pore size and chemical functionalities of organic frameworks gives these particular nanoporous materials distinct advantages over other small cage-like molecules or hollow particles that have been developed into porous liquids. Here, we describe the synthesis of a 3D imine-linked colloidal covalent organic framework (COF)-based porous liquid, designed for efficient size-exclusion of solvent, as well as for long-term stability. By tethering ionic liquids to the colloid surface, the colloids can be dried, purified, and resuspended in a variety of solvents without irreversible aggregation typically observed of COF colloids. Colloid size could be controlled between 50 and 400 nm, with surface areas as high as 800 m2/g. The 3D intertwining morphology of the colloids had pore sizes ranging from 5 to 14 Å, allowing them to efficiently sizeexclude bulky ionic liquids. The COF colloids were stable towards flocculation in an ionic liquid for > 1 year. Permanent porosity was confirmed with a combination of 19F NMR measurements and gas sorption techniques. CO2 and CH4 uptake in these porous liquids increased more than 10 and 20-fold, respectively, over non-porous, neat ionic liquid control samples. The work not only advances the state of COF-based colloid science but also represents a practical advance towards developing more robust, tunable framework-based porous liquid materials for a host of gas storage and separation applications.
Mow, Rachel E.↗
Mixed lipid bilayers enable enhanced stability and activity retention of Lipase A in low-pH environments
Lipase A (LipA) from Bacillus subtilis is a versatile and industrially relevant enzyme, but its activity is compromised under acidic conditions due to aggregation and deactivation. In this study, we investigated the use of mixed lipid bilayers to stabilize and improve activity retention of LipA at low pH. Attachment to lipid bilayers, particularly those containing cationic lipids, greatly enhanced the long-term stability of LipA in acidic conditions while also leading to improvements in activity. Tethering to cationic bilayers not only shifted the apparent pH activity profile toward more acidic conditions, but also significantly enhanced activity retention upon incubation at pH 6. Notably, this protective effect persisted even without direct tethering, indicating that reversible, non-covalent interactions with the bilayer surface are sufficient for long-term stability. Circular dichroism further revealed that the secondary structure of LipA was retained, while dynamic light scattering suggested that activity loss in solution was primarily due to aggregation of the native state. Together, these findings support a model in which lipid bilayers mitigate aggregation and stabilize LipA through transient interactions and electrostatic modulation of the local surface environment. Furthermore, this approach exemplifies a simple, tether-free strategy for enhancing enzyme performance in acidic or destabilizing conditions, with implications for biocatalysis, biosensing, and therapeutic delivery.
Biocatalysis↗
Ultrastable Gold Nanostars via Bottlebrush-like Block Copolymers
Gold (Au) nanostars are plasmonic nanostructures possessing potentials for small molecule detection, photocatalytic activities, and photothermal therapy. However, Au nanostars synthesized in the traditional way are often plagued by poor photo, thermal, and chemical stabilities. Here, we report an unconventional route to the synthesis of ultrastable colloidal Au nanostars enabled by bottlebrush-like block copolymers (BBCPs), dispensing with the need for Au seeds. Crafting of Au nanostars using BBCPs is rendered by bridging the latter with Au 3+ ions as cross-linkers that have multiple coordination sites. Notably, the presence of a covalently tethered polymer shell on the surface of Au nanostars (i.e., polymer-ligated Au nanostars) imparts remarkably high stability under high temperature and laser excitation over conventional cetyltrimethylammonium bromide (CTAB)-mediated Au nanostars. Due to enhanced laser stability, plasmonic fields near Au nanostars can be visualized under high laser fluence by ultrafast electron microscopy (UEM) without morphological degradation. Notably, the presence of insulating polystyrene chains does not compromise the plasmonic field distribution, with the highest field intensity observed along the star arms. In conclusion, the greatly improved long-term photo, thermal, and chemical stabilities make Au nanostars a prospective noble metal nanomaterial for a range of sensing applications.
Cellulose↗
Fluorescent Particle Vertical Profiles (Counts and Fractions) at SAIL
This dataset contains vertically resolved fluorescent aerosol number concentrations and fluorescent fractions of total aerosol number concentrations measured with the ARM Tethered Balloon System during the Surface Atmosphere Integrated Field Laboratory campaign near Gothic, Colorado. Measurements were collected during April and June 2023 as part of the ARM–EMSL FICUS project “Characterization of the Aerobiome during the ARM Surface-Atmosphere Integrated Laboratory Campaign,” which was designed to characterize the vertical distribution of bioaerosol-relevant particles in the Colorado River Basin. The dataset includes profiles of fluorescent particle concentrations measured with a Fluorescent Portable Optical Particle Sizer (FPOPS) in the approximately 0.5–3 µm diameter range. For fluorescent fractions of total aerosol number concentrations, we compare FPOPS measurements to POPS on the same TBS flight.
Fluorescent particle concentration↗
A Lunar Farside Low Radio Frequency Array for Dark Ages 21-cm Cosmology
An array of low-frequency dipole antennas on the lunar farside surface will probe a unique, unexplored epoch in the early Universe called the Dark Ages. It begins at Recombination when neutral hydrogen atoms formed, first revealed by the cosmic microwave background. This epoch is free of stars and astrophysics, so it is ideal to investigate high energy particle processes including dark matter, early Dark Energy, neutrinos, and cosmic strings. A NASA-funded study investigated the design of the instrument and the deployment strategy from a lander of 128 pairs of antenna dipoles across a 10 kmx10 km area on the lunar surface. The antenna nodes are tethered to the lander for central data processing, power, and data transmission to a relay satellite. The array, named FARSIDE, would provide the capability to image the entire sky in 1400 channels spanning frequencies from 100 kHz to 40 MHz, extending down two orders of magnitude below bands accessible to ground-based radio astronomy. The lunar farside can simultaneously provide isolation from terrestrial radio frequency interference, the Earth's auroral kilometric radiation, and plasma noise from the solar wind. It is thus the only location within the inner solar system from which sky noise limited observations can be carried out at sub-MHz frequencies. Through precision calibration via an orbiting beacon and exquisite foreground characterization, the farside array would measure the Dark Ages global 21-cm signal at redshifts z~35-200. It will also be a pathfinder for a larger 21-cm power spectrum instrument by carefully measuring the foreground with high dynamic range.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Solution‐Like Water Transport Across Molecular to Macroscopic Length Scales in Crosslinked Poly(Ethylene Glycol Diacrylate) Networks With Tailored Sidechains
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.
hydrogels↗
ESnet Watershed Field Science Data Backhaul Campaign Report
ESnet’s Watershed Field Science Data Backhaul Campaign is intended to improve the ability to gather data from sensors deployed across the East River and Trail Creek watersheds, with a special focus on the Snodgrass distributed sensor area, the Pumphouse instruments with co-located U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) User Facility Surface Atmosphere Integrated Field Laboratory (SAIL) tethered balloon setup, and the former ARM SAIL campaign’s second ARM Mobile Facility (AMF2) site by the Watershed Function Science Focus Area (WFSFA) program. This program is not funded by ARM, but collaborates with ARM as part of the SAIL campaign, collocated with the WFSFA field sites in Colorado’s East River Watershed.
54 ENVIRONMENTAL SCIENCES↗
Tethering Effects in Oligomer-Based Metal–Organic Frameworks
Metal–organic frameworks (MOFs) can be con- structed using conventional molecular linkers or polymeric linkers (polyMOFs), but the relationship and relative properties of these related materials remain understudied. As an intermediate between these two extremes, a library of oligomeric ligand precursors (dimers, trimers) was used to prepare a series of oligomeric-linker MOFs (oligoMOFs) based on the prototypical IRMOF-1 system. IRMOF-1 was found to be remarkably tolerant to a wide variety of oligomeric linkers, the use of which greatly enhanced the MOF yield and prevented framework interpenetration. Tether length-dependent ordering of ligand and metal cluster orientations was also observed in these oligoMOFs. Improved low-humidity stability was found in oligoIRMOF-1 samples, with surface area preservation varying as a function of tether length and a complete suppression of crystalline hydrolysis products for all oligoIRMOF-1 materials. Furthermore, these findings pave the way toward a better understanding of the structure–function relationships between monomeric, oligomeric, and polymeric MOFs and highlight an underutilized strategy for tuning MOF properties.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Assembly of small silica nanoparticles using lipid-tethered DNA ‘bonds’
Single-stranded DNA molecules modified with cholesterol functional groups are physically tethered to silica nanoparticles (diameter 25 nm) that are encapsulated in a lipid bilayer. Such tethering increases the azimuthal mobility of the DNA molecules across the nanoparticle surface and enables nonspecific bonding, eliminating the need for specialized surface chemistries (such as silane or thiol ligands). To induce assembly, double-stranded DNA ‘bridge’ molecules are then added with complementary nucleotides to the DNA ‘anchor’ molecules that are physically tethered to the lipids on the surface of the particles. Assembly is observed to occur at room temperature and without the need for temperature annealing. Using automated liquid handling tools, assemblies are created in high throughput and rapidly characterized using SAXS. It is determined that the relative concentration of DNA-to-silica and the ionic strength of the solution are important parameters that affect the resulting assembly. Analysis of SAXS data is performed using coarse-grained particle dynamics simulations. The results support the spontaneous formation of semi-crystalline particle assemblies by particle condensation, where the interparticle distance is tuned by the sequence of the DNA ‘bridge’ used to link the particles. Crystallinity analysis performed on the resulting simulations, optimized to match SAXS observations, suggest that particle clusters display increased crystallinity in the center of the clusters, but their maximum size remains relatively small (sub-micron) before settling occurs, which limits the extent of crystallization.
Chiang, Huat Thart [Univ. of Washington, Seattle, ↗
Contextualizing Ancestral Pueblo Turkey (Meleagris gallopavo spp.) Management
Abstract Penning turkeys ( Meleagris gallopavo spp.) in the Ancestral Pueblo American Southwest/Mexican Northwest (SW/NW) involved the creation or use of a variety of spaces and contexts throughout AD 1–1600 and into the post-contact era. Turkey pens, or captivity, occur through simple tethering, reuse of abandoned pit houses or surface rooms, or creation of pens within villages, plazas, and elsewhere. Turkey dung, droppings, and eggshells are fundamental for determining the presence or absence of pens at archaeological sites. In this paper, I review the archaeological record for turkey pens and focus on three main questions: (1) how are turkey pens identified in the SW/NW, (2) if turkey pen construction or evidence for turkey captivity shifts through time, and (3) what the record of turkey penning informs us regarding the long-term human management of these birds and global perspectives on human–bird/human–animal management. Ancestral Pueblo peoples created an adaptive and flexible strategy for turkey penning, which successfully integrated these birds into ceremonial and socioeconomic processes for approximately 1600 years.
59 BASIC BIOLOGICAL SCIENCES↗
High-Energy Hybridized States Enable Long-Lived Hot Electrons in Cobaloxime-Silicon Nanocrystal System
Strong electronic coupling is achieved between the molecular catalyst cobaloxime ([Co]) and silicon nanocrystals (Si NCs) bridged by an ethylenepyridine group derived from vinylpyridine (vpy) covalently bound to the Si NC surface (Si-vpy-[Co]). The ethylenepyridine tether in Si-vpy-[Co] is key to dramatic changes to the system’s physical properties which are not observed in the corresponding formylpyridine (fpy) system (Si-fpy-[Co]) consistent with strong electronic coupling previously observed only in dark electrochemical systems. UV−vis absorption spectroscopy reveals new [Co]-centered electronic states in Si-vpy-[Co], and transient absorption spectroscopy finds a strong absorption feature appearing within 250 fs and persisting for at least 5 ns. Astoundingly, spectroelectrochemical measurements reveal that this absorption feature is consistent with both the singly reduced [Co] − and doubly reduced [Co] 2− complexes, leading to the conclusion that these long-lived charges are derived from high-energy “hot” electrons residing in [Co]-centered states. Detailed analysis using cyclic voltammetry, spectroelectrochemistry, electron paramagnetic resonance spectroscopy, and density functional theory (DFT) calculations provides insight into the unique electronic structure created in Si-vpy-[Co]. DFT reveals that the new electronic states arise from hybridization between deep Si NC band states and high-energy molecular orbitals of the ethylenepyridine tether and the [Co] catalyst and are facilitated by σ-bonding character at the ethylenepyridine linkage. This study demonstrates that strong electronic coupling achieved through precise molecular chemistry can change the paradigm of otherwise fixed energy levels in hybrid photoelectrochemical systems for artificial photosynthesis and related applications.
14 SOLAR ENERGY↗
Organic nanoparticles with tunable size and rigidity by hyperbranching and cross-linking using microemulsion ATRP
Unlike inorganic nanoparticles, organic nanoparticles (oNPs) offer the advantage of “interior tailorability,” thereby enabling the controlled variation of physicochemical characteristics and functionalities, for example, by incorporation of diverse functional small molecules. In this study, a unique inimer-based microemulsion approach is presented to realize oNPs with enhanced control of chemical and mechanical properties by deliberate variation of the degree of hyperbranching or cross-linking. The use of anionic cosurfactants led to oNPs with superior uniformity. Benefitting from the high initiator concentration from inimer and preserved chain-end functionality during atom transfer radical polymerization (ATRP), the capability of oNPs as a multifunctional macroinitiator for the subsequent surface-initiated ATRP was demonstrated. This facilitated the synthesis of densely tethered poly(methyl methacrylate) brush oNPs. Detailed analysis revealed that exceptionally high grafting densities (~1 nm −2 ) were attributable to multilayer surface grafting from oNPs due to the hyperbranched macromolecular architecture. The ability to control functional attributes along with elastic properties renders this “bottom-up” synthetic strategy of macroinitiator-type oNPs a unique platform for realizing functional materials with a broad spectrum of applications.
ATRP↗
Tethered oxygen turns methane into methanol
Precise control of the oxidant — that is, preventing overoxidation — is the missing link in low-temperature methane upgrading. Now, the electro-splitting of carbonate on rutile IrO 2 is shown to cover the surface with on-top oxygen adatoms that act as tethered, single-step hydrogen abstractors. One subset can pull the hydrogen from methane to form a methoxy intermediate, while the neighbouring site can protonate this intermediate to form methanol. Together, this mechanism delivers a room-temperature conversion of methane to methanol with >90% selectivity.
climate-change mitigation↗