Data-driven simulations for training AI-based segmentation of neutron images.

Neutron interferometry uniquely combines neutron imaging and scattering methods to enable characterization of multiple length scales from 1 nm to 10 µm. However, building, operating, and using such neutron imaging instruments poses constraints on the acquisition time and on the number of measured images per sample. Experiment time-constraints yield small quantities of measured images that are insufficient for automating image analyses using supervised artificial intelligence (AI) models. One approach alleviates this problem by supplementing annotated measured images with synthetic images. To this end, we create a data-driven simulation framework that supplements training data beyond typical data-driven augmentations by leveraging statistical intensity models, such as the Johnson family of probability density functions (PDFs). We follow the simulation framework steps for an image segmentation task including Estimate PDFs → Validate PDFs → Design Image Masks → Generate Intensities → Train AI Model for Segmentation. Our goal is to minimize the manual labor needed to execute the steps and maximize our confidence in simulations and segmentation accuracy. We report results for a set of nine known materials (calibration phantoms) that were imaged using a neutron interferometer acquiring four-dimensional images and segmented by AI models trained with synthetic and measured images and their masks.

Thermoreversible gels of hollow silica nanorod dispersions.

Colloidal suspensions of anisotropic particles are ubiquitous in particle-based industries. Consequently, there is a need to quantify the effects of particle shape on equilibrium phases and kinetic state transitions, particularly at lower aspect ratios (L/D ≈ 1-10). We present a new, colloidal system comprised of hollow, octadecyl-coated silica rods with 40 nm diameter with controlled aspect ratio and thermoreversible short-range attractions. Rheology and dynamic light scattering measurements on suspensions of these hollow adhesive hard rods with nominal aspect ratio ≈3 suspended in tetradecane exhibit thermoreversible gelation without complicating effects of gravitational settling. Small angle neutron scattering measurements of the microstructure are analyzed to determine the effective strength of attraction in the form of Baxter sticky parameter. Quantitative agreement is found with simulation predictions of the thermoreversible gel transition as a function of volume fraction, further validating a universal state diagram and providing guidance for the effects of aspect ratio on gelation.

Extracting microscopic insight from transient dielectric measurements during large amplitude oscillatory shear.

Probing the transient microstructure of soft matter far from equilibrium is an ongoing challenge to understanding material processing. In this work, we investigate inverse worm-like micelles undergoing large amplitude oscillatory shear using time-resolved dielectric spectroscopy. By controlling the Weissenburg number, we compare the non-linear microstructure response of branched and unbranched worm-like micelles and isolate distinct elastic effects that manifest near flow reversal. We validate our dielectric measurements with small angle neutron scattering and employ sequence of physical processes to disentangle the elastic and viscous contributions of the stress.

Rheology and dynamics of a solvent segregation driven gel (SeedGel).

Bicontinuous structures promise applications in a broad range of research fields, such as energy storage, membrane science, and biomaterials. Kinetically arrested spinodal decomposition is found responsible for stabilizing such structures in different types of materials. A recently developed solvent segregation driven gel (SeedGel) is demonstrated to realize bicontinuous channels thermoreversibly with tunable domain sizes by trapping nanoparticles in a particle domain. As the mechanical properties of SeedGel are very important for its future applications, a model system is characterized by temperature-dependent rheology. The storage modulus shows excellent thermo-reproducibility and interesting temperature dependence with the maximum storage modulus observed at an intermediate temperature range (around 28 °C). SANS measurements are conducted at different temperatures to identify the macroscopic solvent phase separation during the gelation transition, and solvent exchange between solvent and particle domains that is responsible for this behavior. The long-time dynamics of the gel is further studied by X-ray Photon Correlation Spectroscopy (XPCS). The results indicate that particles in the particle domain are in a glassy state and their long-time dynamics are strongly correlated with the temperature dependence of the storage modulus.

C-C σ-Bond Oxidative Addition and Hydrofunctionalization by a Macrocycle-Supported Diiron Complex.

This report describes the first examples of unassisted C(sp)-C(sp2) and C(sp)-C(sp3) bond oxidative addition reactions to give thermodynamically favorable products. Treatment of a diiron complex supported by a geometrically and electronically flexible macrocyclic ligand, (3PDI2)Fe2(µ-N2)(PPh3)2 ([Fe2N2]0), with stoichiometric amounts of various 4,4'-disubstituted diphenylacetylenes (ArX-C≡C-ArX; X = OMe, H, F, CF3) yielded C(sp)-C(sp2) bond oxidative addition products. When Ph-C≡C-R substrates were used as substrates (R = Me, Et, iPr, tBu), products of either C(sp)-C(sp2) or C(sp)-C(sp3) bond activation were obtained, with the less sterically encumbering alkynes exclusively undergoing C(sp)-C(sp3) bond activation. Treatment of the C-C activation species with either H2 or HBpin was found to form products of C-C σ-bond hydrofunctionalization. In both the hydrogenation and hydroboration schemes, the diiron species was observed to return to [Fe2N2]0, thereby completing synthetic cycles for C-C σ-bond functionalization.

Oriented internal electrostatic fields: an emerging design element in coordination chemistry and catalysis.

The power of oriented electrostatic fields (ESFs) to influence chemical bonding and reactivity is a phenomenon of rapidly growing interest. The presence of strong ESFs has recently been implicated as one of the most significant contributors to the activity of select enzymes, wherein alignment of a substrate's changing dipole moment with a strong, local electrostatic field has been shown to be responsible for the majority of the enzymatic rate enhancement. Outside of enzymology, researchers have studied the impacts of "internal" electrostatic fields via the addition of ionic salts to reactions and the incorporation of charged functional groups into organic molecules (both experimentally and computationally), and "externally" via the implementation of bulk fields between electrode plates. Incorporation of charged moieties into homogeneous inorganic complexes to generate internal ESFs represents an area of high potential for novel catalyst design. This field has only begun to materialize within the past 10 years but could be an area of significant impact moving forward, since it provides a means for tuning the properties of molecular complexes via a method that is orthogonal to traditional strategies, thereby providing possibilities for improved catalytic conditions and novel reactivity. In this perspective, we highlight recent developments in this area and offer insights, obtained from our own research, on the challenges and future directions of this emerging field of research.

Measuring the Time-evolution of Nanoscale Materials with Stopped-flow and Small-angle Neutron Scattering.

This paper presents the use of a stopped-flow small-angle neutron-scattering (SANS) sample environment to quickly mix liquid samples and study nanoscale kinetic processes on time scales of seconds to minutes. The stopped-flow sample environment uses commercially available syringe pumps to mix the desired volumes of liquid samples that are then injected through a dynamic mixer into a quartz glass cell in approximately 1 s. Time-resolved SANS data acquisition is synced with the sample mixing to follow the evolution of the nanostructure in solution after mixing. To make the most efficient use of neutron beam time, we use a series of flow selector valves to automatically load, rinse, and dry the cell between measurements, allowing for repeated data collection throughout multiple sample injections. Sample injections are repeated until sufficient neutron scattering statistics are collected. The mixing setup can be programmed to systematically vary conditions to measure the kinetics at different mixing ratios, sample concentrations, additive concentrations, and temperatures. The minimum sample volume required per injection is approximately 150 µL depending on the path length of the quartz cell. Representative results using this stopped-flow sample environment are presented for rapid lipid exchange kinetics in the presence of an additive, cyclodextrin. The vesicles exchange outer-leaflet (exterior) lipids on the order of seconds and fully exchange both interior and exterior lipids within hours. Measuring lipid exchange kinetics requires in situ mixing to capture the faster (seconds) and slower (minutes) processes and extract the kinetic rate constants. The same sample environment can also be used to probe molecular exchange in other types of liquid samples such as lipid nanoparticles, proteins, surfactants, polymers, emulsions, or inorganic nanoparticles. Measuring the nanoscale structural transformations and kinetics of exchanging or reacting systems will provide new insights into processes that evolve at the nanoscale.

Role of Low Molecular Weight Polymers on the Dynamics of Silicon Anodes During Casting.

This work probes the slurry architecture of a high silicon content electrode slurry with and without low molecular weight polymeric dispersants as a function of shear rate to mimic electrode casting conditions for poly(acrylic acid) (PAA) and lithium neutralized poly(acrylic acid) (LiPAA) based electrodes. Rheology coupled ultra-small angle neutron scattering (rheo-USANS) was used to examine the aggregation and agglomeration behavior of each slurry as well as the overall shape of the aggregates. The addition of dispersant has opposing effects on slurries made with PAA or LiPAA binder. With a dispersant, there are fewer aggregates and agglomerates in the PAA based silicon slurries, while LiPAA based silicon slurries become orders of magnitude more aggregated and agglomerated at all shear rates. The reorganization of the PAA and LiPAA binder in the presence of dispersant leads to a more homogeneous slurry and a more heterogeneous slurry, respectively. This reorganization ripples through to the cast electrode architecture and is reflected in the electrochemical cycling of these electrodes.

Probing clustering dynamics between silicon and PAA or LiPAA slurries under processing conditions.

This work explores the complex interplay between slurry aggregation, agglomeration, and conformation (i.e. shape) of poly(acrylic acid) (PAA) and lithiated poly(acrylic acid) (LiPAA) based silicon slurries as a function of shear rate, and the resulting slurry homogeneity. These values were measured by small angle neutron scattering (SANS) and rheology coupled ultra-small angle neutron scattering (rheo-USANS) at conditions relevant to battery electrode casting. Different binder solution preparation methods, either a ball mill (BM) process or a planetary centrifugal mixing (PCM) process, dramatically modify the resulting polymer dynamics and organization around a silicon material. This is due to the different energy profiles of mixing where the more violent and higher energy PCM causes extensive breakdown and reformation of the binder, which is now likely in a branched conformation, while the lower energy BM results in simply lower molecular weight linear polymers. The break down and reorganization of the polymer structure affects silicon slurry homogeneity, which affects subsequent electrode architecture.

Multiscale Microstructure, Composition, and Stability of Surfactant/Polymer Foams.

Inclusion of polymer additives is a known strategy to improve foam stability, but questions persist about the amount of polymer incorporated in the foam and the resulting structural changes that impact material performance. Here, we study these questions in sodium dodecyl sulfate (SDS)/hydroxypropyl methylcellulose (HPMC) foams using a combination of flow injection QTOF mass spectrometry and small-angle neutron scattering (SANS) measurements leveraging contrast matching. Mass spectrometry results demonstrate polymer incorporation and retention in the foam during drainage by measuring the HPMC-to-SDS ratio. The results confirm a ratio matching the parent solution and stability over the time of our measurements. The SANS measurements leverage precise contrast matching to reveal detailed descriptions of the micellar structure (size, shape, and aggregation number) along with the foam film thickness. The presence of HPMC leads to thicker films, correlating with increased foam stability over the first 15-20 min after foam production. Taken together, mass spectrometry and SANS present a structural and compositional picture of SDS/HPMC foams and an approach amenable to systematic study for foams, gathering mechanistic insights and providing formulation guidance for rational foam design.

Comparison of radiofrequency and microwave ablation and identification of risk factors for primary treatment failure and local progression.

PURPOSE: To compare percutaneous radiofrequency ablation (RFA) and microwave ablation (MWA) for treatment of Hepatocellular carcinoma (HCC) and to identify risk factors for treatment failure and local progression. METHODS: 145 unique HCC [87 (60%) RFA, 58 (40%) MWA] were retrospectively reviewed from a single tertiary medical center. Adverse events were classified as severe, moderate, or mild according to the Society of Interventional Radiology Adverse Event Classification system. Primary and secondary efficacy, as well as local progression, were determined using mRECIST. Predictors of treatment failure and time to local progression were analyzed using generalized estimating equations and Cox regression, respectively. RESULTS: Technical success was achieved in 143/145 (99%) HCC. There were 1 (0.7%) severe and 2 (1.4%) moderate adverse events. Of the 143 technically successful initial treatments, 136 (95%) completed at least one follow-up exam. Primary efficacy was achieved in 114/136 (84%). 9/22 (41%) primary failures underwent successful repeat ablation, so secondary efficacy was achieved in 128/136 (90%) HCC. Local progression occurred in 24 (19%) HCC at a median of 25 months (95% CI = 19-32 months). There was no difference in technical success, primary efficacy, or time to local progression between RFA and MWA. In HCC treated with MWA, same-day biopsy was associated with primary failure (RR = 9.0, 95% CI: 1.7-47, P = 0.015), and proximity to the diaphragm or gastrointestinal tract was associated with local progression (HR = 2.40, 95% CI:1.5-80, P = 0.017). CONCLUSION: There was no significant difference in primary efficacy or time to local progression between percutaneous RFA and MWA.

Capillary RheoSANS: measuring the rheology and nanostructure of complex fluids at high shear rates.

Complex fluids containing micelles, proteins, polymers and inorganic nanoparticles are often processed and used in high shear environments that can lead to structural changes at the nanoscale. Here, capillary rheometry is combined with small-angle neutron scattering (SANS) to simultaneously measure the viscosity and nanostructure of model complex fluids at industrially-relevant high shear rates. Capillary RheoSANS (CRSANS) uses pressure-driven flow through a long, flexible, silica capillary to generate wall shear rates up to 106 s-1 and measure pressure drops up to 500 bar. Sample volumes as small as 2 mL are required, which allow for measurement of supply-limited biological and deuterated materials. The device design, rheology and scattering methodologies, and broad sample capabilities are demonstrated by measuring a variety of model systems including silica nanoparticles, NIST monoclonal antibodies, and surfactant worm-like micelles. For a shear-thinning suspension of worm-like micelles, CRSANS measurements are in good agreement with traditional RheoSANS measurements. Collectively, these techniques provide insight into relationships between nanostructure and steady-shear viscosity over eight orders of magnitude in shear rate. Overall, CRSANS expands the capabilities of traditional RheoSANS instruments toward higher shear rates, enabling in situ structural measurements of soft materials at shear rates relevant to extrusion, coating, lubrication, and spraying applications.

Dynamic arrest of adhesive hard rod dispersions.

The phenomenon of dynamic arrest, more commonly referred to as gel and glass formation, originates as particle motion slows significantly. Current understanding of gels and glasses stems primarily from dispersions of spherical particles, but much less is known about how particle shape affects dynamic arrest transitions. To better understand the effects of particle shape anisotropy on gel and glass formation, we systematically measure the rheology, particle dynamics, and static microstructure of thermoreversible colloidal dispersions of adhesive hard rods (AHR). First, the dynamic arrest transitions are mapped as a function of temperature T, aspect ratio L/D≈ 3 to 7, and volume fraction φ≈ 0.1 to 0.5. The critical gel temperature Tgel and glass volume fraction φg are determined from the particle dynamics and rheology. Second, an effective orientation-averaged, short-range attraction between rods is quantified from small-angle scattering measurements and characterized by a reduced temperature τ. Similar τ is found at low rod concentrations, indicating that rod gelation occurs at similar effective attraction strength independent of L/D. Monte Carlo simulations reveal a similar convergence in τ when rods cluster and percolate with an average bond coordination number 〈nc〉≈ 2.4, supporting the link between physical gelation and rigidity percolation. Lastly, AHR results are mapped onto a dimensionless state diagram to compare with previous predictions of attraction-driven gels, repulsion-driven glasses, and liquid crystal phases.

Radiation exposure in adult and pediatric patients with osteogenesis imperfecta.

Diagnostic radiographs, computed tomography (CT), nuclear medicine studies, and intraoperative fluoroscopy durations were analyzed for radiation exposure. Cumulative and yearly effective ionizing radiation doses, cumulative background radiation, and total radiograph studies were compared between pediatric and adult populations. In 24 patients with 1,246 imaging studies (average 5.5 years longitudinal treatment duration), the mean estimated cumulative effective radiation dose per patient was 30.0 mSv (range 2.3-115.0), with an average yearly dose of 4.9 mSv (range 0.4-24.8). Pediatric patients had significantly more radiograph studies per year than adults and greater average yearly effective radiation doses.

Single Nanocrystal Spectroscopy of Shortwave Infrared Emitters.

Short-wave infrared (SWIR) emitters are at the center of ground-breaking applications in biomedical imaging, next-generation optoelectronic devices, and optical communications. Colloidal nanocrystals based on indium arsenide are some of the most promising SWIR emitters to date. However, the lack of single-particle spectroscopic methods accessible in the SWIR has prevented advances in both nanocrystal synthesis and fundamental characterization of emitters. Here, we demonstrate an implementation of a solution photon correlation Fourier spectroscopy (s-PCFS) experiment utilizing the SWIR sensitivity and time resolution of superconducting nanowire single-photon detectors to extract single-particle emission linewidths from colloidal indium arsenide/cadmium selenide (InAs/CdSe) core/shell nanocrystals emissive from 1.2 to 1.6 µm. We show that the average single InAs/CdSe nanocrystal fluorescence linewidth is, remarkably, as narrow as 52 meV, similar to what has been observed in some of the most narrowband nanostructured emitters in the visible region. Additionally, the single nanocrystal fluorescence linewidth increases with increasing shell thickness, suggesting exciton-phonon coupling as the dominant emission line-broadening mechanism in this system. The development of the SWIR s-PCFS technique has enabled measurements of spectral linewidths of colloidal SWIR-emissive NCs in solution and provides a platform to study the single NC spectral characteristics of SWIR emitters.

Monte Carlo simulation of cylinders with short-range attractions.

Cylindrical or rod-like particles are promising materials for the applications of fillers in nanocomposite materials and additives to control rheological properties of colloidal suspensions. Recent advances in particle synthesis allows for cylinders to be manufactured with short-ranged attractions to study the gelation as a function of packing fraction, aspect ratio and attraction strength. In order to aid in the analysis of small-angle scattering experiments of rod-like particles, computer simulation methods were used to model these particles with specialized Monte Carlo algorithms and tabular superquadric potentials. The attractive interaction between neighboring rods increases with the amount of locally-accessible surface area, thus leading to patchy-like interactions. We characterize the clustering and percolation of cylinders as the attractive interaction increases from the homogenous fluid at relatively low attraction strength, for a variety of aspect ratios and packing fractions. Comparisons with the experimental scattering results are also presented, which are in agreement.

Synthetic control of the size, shape, and polydispersity of anisotropic silica colloids.

The microstructure and rheological properties of colloidal suspensions depend on particle size and shape. This work aims to further control the size, shape, and polydispersity of anisotropic silica colloids, to reduce particle size, and to provide additional mechanistic insights on a prevalent, water-in-oil emulsion synthesis method. Key findings show that the dimensions of anisotropic silica particles can be systematically varied by approximately fivefold, with a limiting minimum particle size (D≈60nm, L≈300nm) obtained from emulsions with excess polyvinylpyrrolidone (PVP) and sodium citrate. The synthesis conditions are identified and discussed for which the emulsion composition, temperature, sonication, polymer entanglements, mixing, and other perturbations may induce or mitigate emulsion instabilities, citrate precipitation, a competing mechanism of templated growth, termination of anisotropic growth, irregular silica structures, and fiber formation. An improved mechanistic understanding will expand the roadmap for rational design and synthetic control of anisotropic colloids using sol-gel silica chemistry confined within water-in-oil emulsions.

Complications and Radiographic Outcomes of Posterior Spinal Fusion and Observation in Patients Who Have Undergone Distraction-Based Treatment for Early Onset Scoliosis.

STUDY DESIGN: Retrospective, multicenter. OBJECTIVES: To compare surgical and radiographic outcomes of early-onset scoliosis (EOS) patients who had stopped lengthening for ≥2 years without additional surgery to those who had posterior spinal fusion (PSF) at the end of lengthening. SUMMARY OF BACKGROUND DATA: Because of the risk of significant complications with PSF in patients with EOS, "watchful waiting" at the end of lengthening has been suggested as a viable alternative. METHODS: Retrospective review of the Children's Spine Study Group (CSSG) database identified all patients with the diagnosis of EOS who had distraction-based treatment, who were ≥2 years from their last distraction, and who had complete records. Radiographic measures were obtained by a single unbiased trained observer. Treatment outcomes including curve correction, height and length gain, as well as complications were recorded. RESULTS: The 37 patients (21 females and 16 males) had a mean age of 7.2 years; 12 were in the observation (OBS) and 25 in the PSF group. The PSF group had a slightly greater coronal Cobb angle and maximal kyphosis at the end of distraction. Although there was some correction of the coronal Cobb angle and maximal kyphosis following PSF, the differences between the two groups were not statistically significant at final follow-up. At final follow-up, the OBS group obtained 88% of T1-T12 height and 90% of T1-L1 length of that obtained by the PSF group. Twenty-six complications occurred in 15 patients, all in the PSF group. CONCLUSIONS: Observation may be a viable alternative to PSF after distraction-based treatment in a subset of patients with EOS. PSF was found to provide no significant curve correction or gains in spine height and length compared to observation and carries a significant risk of complications. LEVEL OF EVIDENCE: Level III, therapeutic.

Thermoreversible Gels Composed of Colloidal Silica Rods with Short-Range Attractions.

Dynamic arrest transitions of colloidal suspensions containing nonspherical particles are of interest for the design and processing of various particle technologies. To better understand the effects of particle shape anisotropy and attraction strength on gel and glass formation, we present a colloidal model system of octadecyl-coated silica rods, termed as adhesive hard rods (AHR), which enables control of rod aspect ratio and temperature-dependent interactions. The aspect ratios of silica rods were controlled by varying the initial TEOS concentration following the work of Kuijk et al. (J. Am. Chem. Soc., 2011, 133, 2346-2349) and temperature-dependent attractions were introduced by coating the calcined silica rods with an octadecyl-brush and suspending in tetradecane. The rod length and aspect ratio were found to increase with TEOS concentration as expected, while other properties such as the rod diameter, coating coverage, density, and surface roughness were nearly independent of the aspect ratio. Ultrasmall angle X-ray scattering measurements revealed temperature-dependent attractions between octadecyl-coated silica rods in tetradecane, as characterized by a low-q upturn in the scattered intensity upon thermal quenching. Lastly, the rheology of a concentrated AHR suspension in tetradecane demonstrated thermoreversible gelation behavior, displaying a nearly 5 orders of magnitude change in the dynamic moduli as the temperature was cycled between 15 and 40 °C. The adhesive hard rod model system serves as a tunable platform to explore the combined influence of particle shape anisotropy and attraction strength on the dynamic arrest transitions in colloidal suspensions with thermoreversible, short-range attractions.