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At least 505 records · Page 28

Long-term ultrasonic monitoring of concrete affected by alkali-silica reaction

This article presents continuous monitoring results of alkali-silica reaction (ASR) development in concrete specimens for over 400 days using ultrasonic testing and expansion measurements. Eight concrete specimens with nonreactive aggregate (Control), reactive coarse aggregate, and reactive fine aggregates were cast with two reinforced confinement conditions. The specimens were conditioned in an environmental chamber with high temperature and humidity (38°C and 90% relative humidity) to accelerate the ASR development. A multichannel ultrasonic monitoring system was developed to collect ultrasonic signals automatically, and the expansions in three directions were measured periodically. Results showed that the relative velocity change could detect the ASR initiation in all reactive specimens and show a correlation with expansion in the early stage. However, these correlations are inconsistent for different ASR specimens, and the velocity change becomes less sensitive to ASR damage in the late stage (after 300 days). Irrecoverable velocity drop was observed during every chamber shutdown period, especially in specimens with higher levels of ASR damage. This phenomenon suggests that the nonlinear ultrasonic response caused by the ambient temperature variation may indicate the ASR damage.

Engineering↗

Investigating the Evolution of Ice Particle Distributions in Mixed-Phase Clouds

The goal of this project is to conduct modeling studies that focus on the processes that control the macrophysical and microphysical properties of mixed phase clouds, such as the partitioning of water phase and the processes that promote precipitation and govern cloud evolution. The process specific to this project is the collection of vapor-grown non-spherical ice crystals and snow hydrometeors through aggregation, as uncertainty remains in the evolution of particle properties as they aggregate. To aid in the understanding of ice particle evolution from pristine monomers to aggregates, the aggregation process is depicted using an offline simulator for ice crystal collection, namely the Ice Particle and Aggregate Simulator (IPAS). Of particular interest in the context of this work is the influence of monomer habit on aggregation and subsequently on cloud microphysical structure. This overarching goal has been completed by conducting modeling studies using the Adaptive Habit Model (AHM) in mixed-phase cloud systems, which predicts and evolves ice shape. While the AHM is designed with physical detail in mind, those details may be lost on larger spatial or temporal scales. Hence, how the contributions of particle growth and collection control the evolution of ice particle size distributions (PSDs) and redistribute mass within the cloud and at the surface has been investigated. Analyses include microphysical sensitivity investigations that inform on future improvement capabilities of microphysical parameterizations in larger scale models. Further, improvements of processes within ice clouds have resulted from this work as the environmental processes controlling ice crystal growth, microphysical processes, and precipitation are inherently integrated within this investigation.

54 ENVIRONMENTAL SCIENCES↗

Hierarchical Model-Free Transactive Control of Building Loads to Support Grid Services

Residential buildings consume 4.4 quads of electricity annually, approximately 37% of the total electricity consumption in the United States. This represents a vast resource that can be used for demand management and other ancillary services. This project aims to develop a robust, scalable hierarchical transactional control mechanism incorporating elements of model-free control (MFC) and game theory to harness buildings to provide ancillary services to the grid. This approach is being taken to address the challenges of incorporating traditional transactional control schemes into existing buildings. The challenges include small individual building sizes requiring aggregation of many buildings, unpredictable energy usage that makes model identification difficult, and satisfying the sensitive occupant comfort constraints. In the proposed approach, by separating the control mechanism into two layers above and below the load aggregator, MFC can be used below the aggregator to modulate flexible building loads in response to pricing signals with guaranteed performance. This allows the burden of identifying an accurate model of the system to be shifted to the above-aggregator layer, where fluctuations in individual building usage have less impact on predicted building system behavior. Game theory concepts can then be used to determine pricing curves and control signals among regional aggregators. Managing this control in a game-theoretic approach will allow us to build in financial incentives that increase customer engagement. Additionally, the usage of MFC necessitates less burdensome computational and communication requirements, thus, it is easily deployable on small, embedded devices. In a broader sense, developing a strategy capable of effectively incorporating residential and small commercial buildings will allow greater throughput of existing and emerging grid services in addition to future transactive energy grid management methods. Using MFC within a hierarchical control architecture will allow the shifting of existing forecasting challenges to an aggregate level, where dynamics are slower and more predictable. This will enable a smooth interface between the grid services requests of utilities and the reliable control required by participating buildings. MFC, which supports distributed control architecture, permits a scalable solution that can be deployed to neighborhood-size systems as well as individual buildings. This project focuses on three objectives: (1) developing the mathematical framework, algorithm toolkit, and software toolset of the two-layer transactive control testbed; (2) developing a scalable solution for application over many residential and small-size commercial buildings with sparse distributed communication; and (3) field testing and implementation on hardware of the control strategies developed in the previous two objectives. The research and development activities are focused and designed to be impactful within the relevant 2025 targets timeframe. An open-source control framework for exploiting variability and dispatchability of building loads will be delivered as the outcome of the project. This capability enables greater participation of loads in electricity markets and ancillary services that are both useful for the utility and financially beneficial for building owners.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Methods for Computing Physically Realistic Estimates of Electric Water Heater Demand Response Resource Suitable for Bulk Power System Planning Models

Demand response is commonly called on to reduce load during system peak times or to respond to contingency events. In future power systems with higher shares of wind and solar generation (which we describe together as variable generation [VG]), demand response could have more opportunities to provide energy shifting or operating reserve services. This report evaluates the ability of residential electric water heaters, both electric resistance water heaters (ERWHs) and heat pump water heaters (HPWHs), to provide such services starting from detailed whole-building energy models that realistically represent New England single family home stock. We use a parsimonious surrogate model to represent operational flexibility in a form suitable for linear and mixed integer programming. This enables relatively fast determination of aggregate contingency reserve resource, price-taking energy shifting outcomes, and in some cases the determination of aggregate models at the megawatt (MW) scale that can be directly included in large-scale grid models. After selecting modeling methods and parameters through various computational experiments, we find interquartile ranges of contingency reserve resource in ISO-NE for about 603,400 ERWHs of 45 MW - 69 MW for Claim10 (50 minute responses provided with 10 minutes of advanced notification) and 65 MW - 102 MW for Claim30 (30 minute responses provided with 30 minutes of advanced notification), and for about 619,000 HPWHs of 48 MW - 88 MW for Claim10 and 52 MW - 90 MW for Claim30. The overall reserve resource is up to 32% of total load for ERWHs providing Claim10 service, 47% for ERWHs providing Claim30 service, 93% for HPWHs providing Claim10 service, and 97% for HPWHs providing Claim30 service. More work is required to determine if HPWHs are inherently more suitable than ERWHs for providing contingency reserve or if these results reflect idiosyncrasies of the single family home stock model used in this study. The value of this contingency resource in a Near-term VG model of ISO-NE is $\$ 0.40$ to $\$1.20$ per water heater-year, and significantly larger, $\$ 3.80$ to $\$ 5.30$ per water heater-year in a Mid-term VG model of ISONE. Aggregating surrogate models to the MW-scale for energy shifting service is more challenging than for contingency service and we only present such results for ERWHs, because we were unable to determine satisfactory ways to deal with HPWHs' time-varying and path dependent operational characteristics. Individual surrogate models suitable for evaluating the energy shifting resource from both ERWHs and HPWHs are created, however, and dispatched against day-ahead prices from the Near-Term VG and Mid-Term VG models of ISO-NE. The individual surrogate models are able to access and potentially shift all 640 GWh of HPWH load and 1,547 GWh of ERWH load we modeled in two different single family home stock models. In contrast, the most effective model of aggregate ERWH shifting resource we created only captured 34.7% of the total ERWH load. Energy shifting affected by price-taking dispatch against modeled day-ahead energy prices produces per water heater year profits of $\$19.44$ - $\$22.93$ for individual HPWHs, $\$39.11$ - $\$40.54$ for individual ERWHs, and up to $\$4.00$ - $\$4.24$ for aggregated ERWHs, with the variations mainly due to grid conditions (more or less VG). When the supply-side response to these changes is accounted for, the per water heater year production cost savings for ISO-NE are $\$7.50$ to $\$17.70$ for the most effective set of endogenously dispatched aggregate ERWHs, $\$15.60$ to $\$15.70$ for individual ERWHs dispatched against the DA prices, and $\$10.70$ to $\$11.20$ for individual HPWHs dispatched against DA prices. Those ranges primarily represent the difference between Near-Term VG and Mid-Term VG grid conditions.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Structural Reorganization of Noncellulosic Polymers Observed In Situ during Dilute Acid Pretreatment by Small-Angle Neutron Scattering

Production of second-generation bioethanol from lignocellulosic biomass requires pretreatment to open the plant cell wall structure and improve enzyme access. Many different thermochemical pretreatments have been extensively developed and employed, but the exact nature of plant cell wall recalcitrance and the most efficient and economical approach to alter plant cell wall structure via pretreatment still remain elusive. In order to understand the role of noncellulosic switchgrass polymers on the overall efficiency of pretreatment, the structural evolution of the noncellulosic polymers of the plant cell wall were investigated during dilute acid pretreatment (DAP) by employing in-situ small-angle neutron scattering (in-situ SANS). In this study, we observed real-time structural changes not possible to observe by any other technique. To deconvolute the structural evolution of lignin and hemicellulose polymers during DAP, native switchgrass (NATV), and isolated holocellulose (HOLO) and cellulose (CELL) fractions from NATV were studied. Our results show that aggregate particles first appear around 80 °C for NATV and HOLO samples. Further, due to the low temperature and pretreatment severity condition, these particles are likely derived from hemicellulose. The formations of much larger aggregate particles, only observed in the NATV sample, were attributed to lignin. For the HOLO sample, as the temperature and pretreatment severity condition increased, hemicellulose-derived aggregate particle sizes increased, suggesting this process was the nucleation and early stage formation of pseudolignin particles. Consistent with our interpretation of structural evolutions in NATV and HOLO samples, no formation of aggregate particles was observed in CELL samples for the entire duration of the pretreatment. These results suggest that not only lignin but also hemicellulose can form aggregate particles within plant cell walls during pretreatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coarse-grained molecular dynamics simulation of solvent-dependent cellulose nanofiber interactions

Associations between cellulose are important both in biofuel production and in the use of cellulose for biomaterials. Cellulose nanofibers (CNFs) are sustainable, strong, light-weight alternatives to traditional materials in manufacturing, but are challenging to obtain due to irreversible aggregation in solution during preparative fibrillation. Therefore, it is imperative to understand the underlying factors driving aggregation with a view to designing solvents that can effectively compete with interfiber interactions, hence reducing aggregation. Molecular dynamics (MD) simulation at atomic detail can provide useful information on local interactions. However, the length and timescales accessible are too short to fully capture association processes. Here, we provide a method for accessing the longer length and timescales required using coarse-grained (CG) MD simulations with a MARTINI force field to calculate the interaction behavior of CNFs in three selected solvents: NaOH-urea-water, acetone, and neat water. The CG results are consistent with our prior all-atom MD and with previous experimental results. While acetone is found not to be an effective solvent, urea and ionic moieties in NaOH-urea-water not only solvate the fibrils but also improve the confinement of water molecules around them as shown by the solvent residence times and mean-square displacements. Overall, the presence of urea and ions reduces the likelihood of aggregation in multi-CNF systems relative to neat water irrespective of whether the hydrophobic or hydrophilic CNF surfaces are interacting. In conclusion, the CG method shows clear promise for selecting potential high-performance solvents for experimental prioritization in bioenergy and biomaterials research in a relatively fast manner as well as for understanding the aggregation and rheological behavior of CNF-solvent systems.

aggregation↗

Radiolysis and Radiation-Driven Dynamics of Boehmite Dissolution Observed by In Situ Liquid-Phase TEM

We report over the last several decades, there have been several studies examining the radiation stability of boehmite and other aluminum oxyhydroxides, yet less is known about the impact of radiation on boehmite dissolution. Here, we investigate radiation effects on the dissolution behavior of boehmite by employing liquid-phase transmission electron microscopy (LPTEM) and varying the electron flux on the samples consisting of either single nanoplatelets or aggregated stacks. We show that boehmite nanoplatelets projected along the [010] direction exhibit uniform dissolution with a strong dependence on the electron dose rate. For nanoplatelets that have undergone oriented aggregation, we show that the dissolution occurs preferentially at the particles at the ends of the stacks that are more accessible to bulk solution than at the others inside the aggregate. In addition, at higher dose rates, electrostatic repulsion and knock-on damage from the electron beam causes delamination of the stacks and dissolution at the interfaces between particles in the aggregate, indicating that there is a threshold dose rate for electron-beam enhancement of dissolution of boehmite aggregates.

54 ENVIRONMENTAL SCIENCES↗

Copper Reductase Activity and Free Radical Chemistry by Cataract-Associated Human Lens γ-Crystallins

Cataracts are caused by high-molecular weight aggregates of human eye lens proteins that scatter light, causing lens opacity. Metal ions have emerged as important potential players in the etiology of cataract disease, as human lens γ-crystallins are susceptible to metal-induced aggregation. Here, the interaction of Cu 2+ ions with γD-, γC-, and γS- crystallins, the three most abundant γ-crystallins in the lens, has been evaluated. Cu 2+ ions induced non-amyloid aggregation in all three proteins. Solution turbidimetry, SDS-PAGE, circular dichroism and differential scanning calorimetry showed that the mechanism for Cu-induced aggregation involves: i) loss of beta-sheet structure in the N-terminal domain; ii) decreased thermal and kinetic stability; iii) formation of metal-bridged species; and iv) formation of disulfide-bridged dimers. Electron paramagnetic resonance (EPR) revealed two distinct Cu 2+ binding sites in each protein. Spin quantitation demonstrated reduction of γ-crystallin-bound Cu 2+ ions to Cu + under aerobic conditions, while X-ray absorption spectroscopy (XAS) confirmed the presence of linear or trigonal Cu + binding sites in γ-crystallins. Our EPR and XAS studies revealed that γ-crystallins’ Cu 2+ reductase activity yields a protein-based free radical that is likely a Tyr-based species in human γD-crystallin. This unique free radical chemistry carried out by distinct redox-active Cu sites in human lens γ-crystallins likely contributes to the mechanism of copper-induced aggregation. Finally, in the context of an aging human lens, γ-crystallins could be acting, not only as structural proteins, but also as key players for metal and redox homeostasis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Amyloidogenesis: What Do We Know So Far?

The study of protein aggregation, and amyloidosis in particular, has gained considerable interest in recent times. Several neurodegenerative diseases, such as Alzheimer’s (AD) and Parkinson’s (PD) show a characteristic buildup of proteinaceous aggregates in several organs, especially the brain. Despite the enormous upsurge in research articles in this arena, it would not be incorrect to say that we still lack a crystal-clear idea surrounding these notorious aggregates. In this review, we attempt to present a holistic picture on protein aggregation and amyloids in particular. Using a chronological order of discoveries, we present the case of amyloids right from the onset of their discovery, various biophysical techniques, including analysis of the structure, the mechanisms and kinetics of the formation of amyloids. We have discussed important questions on whether aggregation and amyloidosis are restricted to a subset of specific proteins or more broadly influenced by the biophysiochemical and cellular environment. The therapeutic strategies and the significant failure rate of drugs in clinical trials pertaining to these neurodegenerative diseases have been also discussed at length. At a time when the COVID-19 pandemic has hit the globe hard, the review also discusses the plausibility of the far-reaching consequences posed by the virus, such as triggering early onset of amyloidosis. Finally, the application(s) of amyloids as useful biomaterials has also been discussed briefly in this review.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heterogeneity of soil structure and fertility during desertification of alpine grassland in northwest Sichuan

Abstract The variations of soil structure and soil physical–chemical properties in the process of alpine grassland desertification were revealed, and the indicators of grassland desertification were put forward in order to deepen the understanding of the law of degradation succession and development of alpine grassland. It was used to provide scientific basis for ecological restoration and improvement of ecological service function of alpine grassland. With severe desertification alpine grassland as the core in the Hongyuan County, Tibetan Qiang Autonomous Prefecture of Ngawa, Sichuan Province, China, along both the directions of wetland and arid grassland, the heterogeneity of soil structure and soil fertility in both directions was studied by the analysis of the mean weight diameter (MWD), geometric mean diameter (GMD), >0.25 mm aggregate content ( R 0.25 ), fractal dimension ( D ), soil bulk density, soil moisture content, and soil nutrients. Our results showed that MWD, GMD, and R 0.25 all gradually increased, but the D decreased with the reduction in the degree of desertification in the arid grassland and wetland, resulting in the strong stability of soil structure. The decreasing rate of the D in the direction of arid grassland was faster than that of wetland. Therefore, soil structure stability and erosion resistance in the direction of arid grassland were stronger than that of wetland soil; the D had different response to aggregates with different particle sizes. The aggregate less than 0.25 mm ( r = 0.981, P < 0.01) and 1–2 mm ( r = −0.79, P < 0.01) had the largest responses in the direction of the arid grassland and wetland, respectively; the aggregate more than 1 mm and 1–2 mm can be used as indicators to evaluate desertification of the soil in the direction of the arid grassland and wetland, respectively. The higher the content of the indicating aggregates, the weaker the degree of the desertification.

Ma, Li↗

Cover crops and poultry litter impact on soil structural stability in dryland soybean production in southeastern United States

Abstract This study explored the efficacy of soil aggregate indices in quantifying soil structural development, utilizing 5‐year field experiment data from the Southeastern United States. The experiment utilized a split‐plot design with cover crops (native vegetation as control, cereal rye (Secale cerealeL.), winter wheat (Triticum aestivum), hairy vetch (Vicia villosa), and mustard (Brassica rapa) plus cereal rye as the main factor and fertilizer source (no fertilizer as control, inorganic fertilizer with phosphorus, potassium, and elemental sulfur, and poultry litter) as the secondary factor. Aggregate size fractions were determined using the wet‐sieving method, and aggregate stability index (ASI), mean weight diameter (MWD), geometric mean diameter (GMD), and fractal dimension (FD) were calculated to assess soil structural stability. Main effects results indicated that cereal rye (55.11%) and poultry litter (50.97%) exhibited the highest ASI values. The highest MWD, GMD, and FD were observed under mustard plus cereal rye (1.187 mm), cereal rye (0.462 mm), and hairy vetch (2.573), respectively. Principal component analysis revealed that cover crops significantly improved soil aggregate structure and stability, overcoming limitations of sole fertilization practices. Regression analysis suggested that ASI, MWD, and GWD positively correlated with soil organic carbon, whereas FD negatively correlated with MWD, GMD, and ASI. Principal component analysis exhibited that FD decreased with increasing soil organic carbon, ASI, MWD, and GMD, demonstrating that lower FD values indicate enhanced soil aggregation and structure. Assessed indices, FD included, effectively gauged soil structural stability. These metrics should be prioritized in managerial decisions to support soil productivity and health in agricultural systems.

Agriculture↗

IntraShuffler: A Privacy Preserving Framework for Heterogeneous DP Federated Learning

Heterogeneous Differential Privacy (HDP) in Federated Learning (FL) allows clients to select individual privacy budgets () according to institutional policies and data sensitivity. In practice, many HDP-FL systems employ -aware server aggregation to improve model utility by re-weighting client updates according to their declared privacy budgets. However, gradient updates in FL retain structural patterns induced by non-independent and identically-distributed (non-IID) data, and these additional signals exposed by -aware aggregation create new opportunities for inference by an honest-but-curious server. In this work, we first show that a server equipped with gradient denoising and surrogate modeling can mount a Privacy Inference Attack that infers distributional attributes of clients and links updates from the same client across training rounds, measured via surrogate inference accuracy and linkage success, under realistic knowledge constraints. The Shuffle-Model has been widely studied as a defense against such inference risks by anonymizing update sources, but it is fundamentally incompatible with HDP-FL -aware aggregation. To address this challenge, we propose IntraShuffler, a middleware defense framework designed for HDP-FL systems. IntraShuffler introduces a privacy-aware shuffling mechanism that groups clients into privacy-compatible buckets and performs parameter-level shuffling within each bucket to disrupt persistent gradient structure while preserving -aware aggregation. Experiments across four different datasets show that IntraShuffler reduces gradient recoverability by over 60% and decreases surrogate inference accuracy from 0.78 to 0.33 while maintaining comparable model utility across multiple FL aggregation rules.

Riya, Farhin Farhad [ORNL]↗

Fracturing process of micro-concrete under uniaxial and triaxial compression: Insights from in-situ X-ray mechanical tests

This paper presents an experimental study of concrete at meso-scale (aggregates, macro-pores and mortar matrix) in order to get a better understanding of the local failure mechanisms known to drive the macroscopic mechanical behaviour of the material. The main originality comes from conducting in-situ X-ray mechanical tests on micro-concrete samples of realistic composition (including cement, sand, aggregates and water), under uniaxial compression and, for the first time, under triaxial compression at 5 MPa, 10 MPa and 15 MPa confining pressures. A timeseries analysis of the set of 3D images coming from each test allows for the measurement of the 3D kinematic fields (displacement and strain fields) throughout the experiments. The different failure patterns observed for each loading path are discussed, along with a quantification of the 3D fracturing processes at the scale of the largest heterogeneities (aggregates and macro-pores). With an increasing level of confinement, the transition from brittle to ductile response is observed, as well as an increase of the strength of the material. The pronounced impact of the meso-scale heterogeneities of concrete on their local failure mechanisms is highlighted. It is shown that strain localisation mainly originates between aggregates and mortar matrix, with the shape and location of the largest aggregates and macro-pores essentially driving the propagation of the cracking network.

36 MATERIALS SCIENCE↗

Shifting modes of iron sulfidization at the onset of OAE-2 drive regional shifts in pyrite δ 34 S records

We report total reduced inorganic S isotope ratios (δ 34 S CRS ) shift toward more negative values across much of the southern North Atlantic just before the onset of the Cenomanian-Turonian Ocean Anoxic Event (OAE-2). At the same time, there is no parallel isotopic change in the significantly larger pool of kerogen (organic) S, which indicates that the distribution and S-isotope composition of sulfide in the environment likely did not drive the change in δ 34 S CRS . Here, we investigate possible explanations for the negative shift in δ 34 S CRS values and their divergence from organic S by isolating iron sulfides for morphological identification and grain-specific isotopic analysis using secondary ion mass spectrometry (SIMS). In pre- and syn-OAE-2 sedimentary rocks from Demerara Rise, we find four distinct morphologies of iron sulfides: pyrite framboids (1–20 μm diameter), irregular pyrite aggregates (1–38 μm diameter), large cemented pyrite aggregates (~60 μm diameter), and irregular and cemented aggregates of the pyrite polymorph marcasite (1–45 μm diameter). These different textural groups have distinct S-isotopic compositions that are largely consistent through the onset of OAE-2. As such, the secular change in bulk δ 34 S CRS values likely reflects the changing proportions of these phases stratigraphically across OAE-2. All textural groups feature resolvable intra-grain δ 34 S variability, suggesting that the environments in which they formed were characterized by dynamic sulfide δ 34 S values and/or by partial closed-system distillation. We use grain-specific δ 34 S distributions to rule out shoaling of the chemocline within the sediments as a mechanism for the observed decrease in δ 34 S CRS . Instead, we propose that changes in the reactivity of the iron species delivered to Demerara Rise over the ~200 kyr leading up to the onset of OAE-2 impacted the relative contributions of pyrite with S-isotope signatures reflecting the water column, shallow sediments, and deeper sediments to the bulk sedimentary δ 34 S CRS value. Specifically, the change in iron reactivity at the onset of OAE-2 favored the production of 34 S-depleted large, cemented aggregates and framboids at the expense of more 34 S-enriched irregular aggregates. Our results underscore that bulk δ 34 S CRS measurements integrate multiple reduced phases that form via distinct reaction mechanisms and potentially in different parts of the depositional environment. Grain-specific SIMS analyses dramatically enrich our ability to interpret pyrite isotopic patterns in the geologic record.

58 GEOSCIENCES↗

Structural evolution during gelation of pea and whey proteins envisaged by time-resolved ultra-small-angle x-ray scattering (USAXS)

Hydrogels from plant proteins commonly exhibit inferior gel strength compared to those from dairy proteins partially due to their distinct gel networks. How protein aggregates to form such networks in response to heat remains largely unknown. In this work, pea (PPI) and whey (WPI) protein isolate gels were produced at the same protein content and similar heating/cooling rate. The process was monitored using rheology, microscopy and in situ ultra-small-angle x-ray scattering (USAXS). Rheology showed an initial decrease in G' and G'' in PPI followed by a steady increase when the temperature surpassed ~60 °C whereas a much higher temperature (~80 °C) was required for WPI, both using 2 °C/min heating rate. Microscopy showed a coarse and heterogenous network in PPI, whereas for WPI, the network was finer and more continuous. In both gels, nano-sized spherical or ellipsoidal particles were present as the basic constituents. USAXS found individual protein was dominant in PPI or WPI solution at temperature below 57 °C. Their proportions decreased together with appearance of aggregates with an average R g of 9–10 nm in PPI and 6–7 nm in WPI at higher temperature. The size of the aggregates changed slightly during further heating and cooling, but their proportions increased. Power law exponents revealed the aggregates were mass fractals for WPI and PPI gels, and they became more compact during heating. Our findings suggested formation of primary aggregates in protein gel networks is a more organized process and provided theoretical guidance for production of high protein food gels with desirable texture.

59 BASIC BIOLOGICAL SCIENCES↗

Enhanced Photo-Cross-Linking of Thymines in DNA Holliday Junction-Templated Squaraine Dimers

Programmable self-assembly of dyes using DNA templates to promote exciton delocalization in dye aggregates is gaining considerable interest. New methods to improve the rigidity of the DNA scaffold and thus the stability of the molecular dye aggregates to encourage exciton delocalization are desired. In these dye–DNA constructs, one potential way to increase the stability of the aggregates is to create an additional covalent bond via photo-cross-linking reactions between thymines in the DNA scaffold. Specifically, we report an approach to increase the yield of photo-cross-linking reaction between thymines in the core of a DNA Holliday junction while limiting the damage from UV irradiation to DNA. We investigated the effect of the distance between thymines on the photo-cross-linking reaction yields by using linkers with different lengths to tether the dyes to the DNA templates. By comprehensively evaluating the photo-cross-linking reaction yields of dye–DNA aggregates using linkers with different lengths, we conclude that interstrand thymines tend to photo-cross-link more efficiently with short linkers. A higher cross-linking yield was achieved due to the shorter intermolecular distance between thymines influenced by strong dye–dye interactions. Furthermore, our method establishes the possibility of improving the stability of DNA-scaffolded dye aggregates, thereby expanding their use in exciton-based applications such as light harvesting, nanoscale computing, quantum computing, and optoelectronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrastructure of Critical-Gel-like Polyzwitterion–Polyoxometalate Complex Coacervates: Effects of Temperature, Salt Concentration, and Shear

The structure of unconventional complex coacervates, such as polymer-nonpolymer complex coacervates, remains less investigated than that of the conventional coacervates formed between oppositely charged polyelectrolytes with symmetric charge species. Yet, their microscopic structural organization is important to further elucidate the mechanism of liquid-liquid-phase separation processes upon complexation. In this work, we characterize the microstructural organization of complex coacervates formed between inorganic polyoxometalate (POM) and polyzwitterion by small-angle X-ray scattering (SAXS) with in situ temperature and shear control. Furthermore, despite the apparent transparent and homogeneous morphology of dense coacervates as observed by optical microscopy, our previous results (Macromolecules 2018, 51, 22, 9405-9411) suggest that dense polyzwitterion-POM coacervates exhibit critical-gel-like networks containing both complex-poor region (mesh pore) and complex-rich region (connective network). SAXS results as reported in this work support that the complex-rich region is actually in the form of loosely packed POM aggregates linked by polyzwitterion, designated as complex particles. The structure of aggregating complex particles is further examined against varied composition and salt concentrations, temperature, and shear, thanks to the high X-ray scattering contrast of POMs from that of other components in the coacervates. The complex particles in the dense coacervates appear to grow with more tightly packed POM aggregates with increasing POM-to-polyzwitterion concentration ratio, in contrast to more loosely packed POM aggregates with decreasing salt concentration. Conversely, increasing temperature could result in smaller complex particles containing more loosely packed POM aggregates, consistent with temperature-dependent viscoelasticity of dense coacervates. Furthermore, such POM-based hybrid dense coacervates exhibit intriguing strain-hardening behavior, resulting from shear-enhanced POM packing inside the complex particles. Distinct from the shear-thinning behavior of most conventional crosslinked polymeric networks, the strain-hardening property combined with thermal- and salt-responsive characteristics of polyzwitterion-POM coacervates could broaden the applications of hybrid organic-inorganic macroion coacervates as smart functional materials working under extreme environmental conditions.

36 MATERIALS SCIENCE↗

Recursive Gaussian Process over graphs for Integrating Multi-timescale Measurements in Low-Observable Distribution Systems

The transition to a smarter grid is empowered by enhanced sensor deployments and smart metering infrastructure in the distribution system. Measurements from these sensors and meters can be used for many applications, including distribution system state estimation (DSSE). However, these measurements are typically sampled at different rates and could be intermittent due to losses during the aggregation process. These multi timescale measurements should be reconciled in real-time to perform accurate grid monitoring. This paper tackles this problem by formulating a recursive multi-task Gaussian process (RGP-G) approach that sequentially aggregates sensor measurements. Specifically, we formulate a recursive multi-task GP with and without network connectivity information to reconcile the multi time-scale measurements in distribution systems. Here, the proposed framework is capable of aggregating the multi-time scale measurements batch-wise or in real-time. Following the aggregation of the multi time-scale measurements, the spatial states of the consistent time-series are estimated using matrix completion based DSSE approach. Simulation results on IEEE 37 and IEEE 123 bus test systems illustrate the efficiency of the proposed methods from the standpoint of both multi time-scale data aggregation and DSSE.

42 ENGINEERING↗