The influence of elongation-induced concentration fluctuations on segmental friction in polymer blends.

Recent experimental studies have revealed a lack of universality in the extensional behavior of linear polymers, which is not envisioned by classical molecular theories. These surprising findings, particularly the sharp contrast between polymer melts and solutions, have catalyzed the development of new theoretical ideas, including the concept of friction reduction in highly stretched polymer melts. By presenting evidence from rheology and small-angle neutron scattering, this work shows that deformation-induced demixing, which is due to the viscoelastic asymmetry in binary mixtures, contributes to the observed nonuniversality. In the case of polystyrene/oligostyrene blends, demixing increases the effective glass transition temperature of the long chain, leading to an apparent friction enhancement. On the other hand, the opposite case is found for the polystyrene/poly(α-methylstyrene) blend. These results highlight the important influence of deformation-induced concentration fluctuations on polymer segmental friction.

Viscoelastic relaxation and topological fluctuations in glass-forming liquids.

A method for characterizing the topological fluctuations in liquids is proposed. This approach exploits the concept of the weighted gyration tensor of a collection of particles and permits the definition of a local configurational unit (LCU). The first principal axis of the gyration tensor serves as the director of the LCU, which can be tracked and analyzed by molecular dynamics simulations. Analysis of moderately supercooled Kob-Andersen mixtures suggests that orientational relaxation of the LCU closely follows viscoelastic relaxation and exhibits a two-stage behavior. The slow relaxing component of the LCU corresponds to the structural, Maxwellian mechanical relaxation. Additionally, it is found that the mean curvature of the LCUs is approximately zero at the Maxwell relaxation time with the Gaussian curvature being negative. This observation implies that structural relaxation occurs when the configurationally stable and destabilized regions interpenetrate each other in a bicontinuous manner. Finally, the mean and Gaussian curvatures of the LCUs can serve as reduced variables for the shear stress correlation, providing a compelling proof of the close connection between viscoelastic relaxation and topological fluctuations in glass-forming liquids.

Solvation Structure of Methanol-in-Salt Electrolyte Revealed by Small-Angle X-ray Scattering and Simulations.

The solvation structure of water-in-salt electrolytes was thoroughly studied, and two competing structures─anion solvated structure and anion network─were well-defined in recent publications. To further reveal the solvation structure in those highly concentrated electrolytes, particularly the influence of solvent, methanol was chosen as the solvent for this proposed study. In this work, small-angle X-ray scattering, small-angle neutron scattering, Fourier-transform infrared spectroscopy, and Raman spectroscopy were utilized to obtain the global and local structural information. With the concentration increment, the anion network formed by TFSI- became the dominant structure. Meanwhile, the hydrogen bonds among methanol were interrupted by the TFSI- anion and formed a new connection with them. Molecular dynamic simulations with two different force fields (GAFF and OPLS-AA) are tested, and GAFF agreed with synchrotron small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) results well and provided insightful information about molecular/ion scale solvation structure. This article not only deepens the understanding of the solvation structure in highly concentrated solutions, but more importantly, it provides additional strong evidence for utilizing SAXS/WAXS to validate molecular dynamics simulations.

Multiscale embedded printing of engineered human tissue and organ equivalents.

Creating tissue and organ equivalents with intricate architectures and multiscale functional feature sizes is the first step toward the reconstruction of transplantable human tissues and organs. Existing embedded ink writing approaches are limited by achievable feature sizes ranging from hundreds of microns to tens of millimeters, which hinders their ability to accurately duplicate structures found in various human tissues and organs. In this study, a multiscale embedded printing (MSEP) strategy is developed, in which a stimuli-responsive yield-stress fluid is applied to facilitate the printing process. A dynamic layer height control method is developed to print the cornea with a smooth surface on the order of microns, which can effectively overcome the layered morphology in conventional extrusion-based three-dimensional bioprinting methods. Since the support bath is sensitive to temperature change, it can be easily removed after printing by tuning the ambient temperature, which facilitates the fabrication of human eyeballs with optic nerves and aortic heart valves with overhanging leaflets on the order of a few millimeters. The thermosensitivity of the support bath also enables the reconstruction of the full-scale human heart on the order of tens of centimeters by on-demand adding support bath materials during printing. The proposed MSEP demonstrates broader printable functional feature sizes ranging from microns to centimeters, providing a viable and reliable technical solution for tissue and organ printing in the future.

Unveiling mesoscopic structures in distorted lamellar phases through deep learning-based small angle neutron scattering analysis.

HYPOTHESIS: The formation of distorted lamellar phases, distinguished by their arrangement of crumpled, stacked layers, is frequently accompanied by the disruption of long-range order, leading to the formation of interconnected network structures commonly observed in the sponge phase. Nevertheless, traditional scattering functions grounded in deterministic modeling fall short of fully representing these intricate structural characteristics. Our hypothesis posits that a deep learning method, in conjunction with the generalized leveled wave approach used for describing structural features of distorted lamellar phases, can quantitatively unveil the inherent spatial correlations within these phases. EXPERIMENTS AND SIMULATIONS: This report outlines a novel strategy that integrates convolutional neural networks and variational autoencoders, supported by stochastically generated density fluctuations, into a regression analysis framework for extracting structural features of distorted lamellar phases from small angle neutron scattering data. To evaluate the efficacy of our proposed approach, we conducted computational accuracy assessments and applied it to the analysis of experimentally measured small angle neutron scattering spectra of AOT surfactant solutions, a frequently studied lamellar system. FINDINGS: The findings unambiguously demonstrate that deep learning provides a dependable and quantitative approach for investigating the morphology of wide variations of distorted lamellar phases. It is adaptable for deciphering structures from the lamellar to sponge phase including intermediate structures exhibiting fused topological features. This research highlights the effectiveness of deep learning methods in tackling complex issues in the field of soft matter structural analysis and beyond.

Temperature-responsive binary superlattices prepared by the selective solvent evaporation of O/W microemulsion composed of gold nanoparticles and surfactants.

Binary nanoparticle superlattices (BNSLs) are one of the important classes of nanomaterial architectures for a wide range of potential applications because they can provide synergistically enhanced properties depending on the morphology and spatial arrangement of nanoparticles (NPs). However, although many studies have been conducted on the fabrication of BNSLs, there are still several challenges in achieving BNSLs with a three-dimensional lattice due to their complicated synthesis, hindering their practical applications. Herein, we report the fabrication of temperature-sensitive BNSLs in complexes of gold nanoparticles (AuNPs), Brij 58 surfactant, and water via a two-step evaporation method. The surfactant was utilized for two different purposes, i.e., surface modification of the AuNPs to control their interfacial energy and as a template material for the formation of the superlattice. Depending on the size and concentration of the AuNPs, the mixture of AuNPs and surfactant self-assembled into three types of BNSLs, including CaF2, AlB2, and NaZn13, which were sensitive to temperature. This study is the first demonstration of the temperature- and particle size-dependent control of BNSLs in the bulk state without the covalent functionalization of NPs via a simple two-step solvent evaporation method.

Selective deconstruction of mixed plastics by a tailored organocatalyst.

Plastic represents an essential material in our society; however, a major imbalance between their high production and end-of-life management is leading to unrecovered energy, economic hardship, and a high carbon footprint. The adoption of plastic recycling has been limited, mainly due to the difficulty of recycling mixed plastics. Here, we report a versatile organocatalyst for selective glycolysis of diverse consumer plastics and their mixed waste streams into valuable chemicals. The developed organocatalyst selectively deconstructs condensation polymers at a specific temperature, and additives or other polymers such as polyolefin or cellulose can be readily separated from the mixed plastics, providing a chemical recycling path for many existing mixed plastics today. The Life Cycle Assessment indicates that the production of various condensation polymers from the deconstructed monomers will result in a significant reduction in greenhouse gas emissions and energy input, opening a new paradigm of plastic circularity toward a net-zero carbon society.

Enhancement of polymer thermoresponsiveness and drug delivery across biological barriers by addition of small molecules.

Thermoresponsive polymers that undergo sol-gel transitions in the physiological temperature range have been widely used in biomedical applications. However, some commercially and clinically available thermoresponsive materials, particularly poloxamer 407 (P407), have the significant drawback of insufficient gel strength, which limit their performance. Furthermore, co-delivery with some small molecules, including chemical permeation enhancers (CPEs) can further impair the physical properties of P407. Here, we have developed a thermoresponsive platform by combination of CPEs with the poloxamer P188 to enable gelation at physiological temperatures and enhance gel strength. P188 gels at 60 °C, which is far above the physiological range. In combination with limonene (LIM) and sodium dodecyl sulfate (SDS), P188 gels at ∼25 °C, a temperature that in useful for biomedical applications. Gelation behavior was studied by small angle neutron scattering (SANS) experiments, which identified micelle-to-cubic mesophase transitions with increasing temperature. Analysis of the SANS intensities revealed that P188 micelles became larger as LIM or SDS molecules were incorporated, making it easier to form a micellar gel structure. P188-3CPE (i.e., 2% LIM, 1% SDS and 0.5% bupivacaine (BUP)) had low viscosity at room temperature, facilitating administration, but rapidly gelled at body temperature. P188-3CPE enabled the flux of the antibiotic ciprofloxacin across the TM and completely eradicated otitis media from nontypable Haemophilus influenzae (NTHi) in chinchillas after a single administration.

Molecular Structure and Conformational Design of Donor-Acceptor Conjugated Polymers to Enable Predictable Optoelectronic Property.

Tuning the optoelectronic properties of donor-acceptor conjugated polymers (D-A CPs) is of great importance in designing various organic optoelectronic devices. However, there remains a critical challenge in precise control of bandgap through synthetic approach, since the chain conformation also affects molecular orbital energy levels. Here, D-A CPs with different acceptor units are explored that show an opposite trend in energy band gaps with the increasing length of oligothiophene donor units. By investigating their chain conformation and molecular orbital energy, it is found that the molecular orbital energy alignment between donor and acceptor units plays a crucial role in dictating the final optical bandgap of D-A CPs. For polymers with staggered orbital energy alignment, the higher HOMO with increasing oligothiophene length leads to a narrowing of the optical bandgap despite decreased chain rigidity. On the other hand, for polymers with sandwiched orbital energy alignment, the increased band gap with increasing oligothiophene length originates from the reduction of bandwidth due to more localized charge density distribution. Thus, this work provides a molecular understanding of the role of backbone building blocks on the chain conformation and bandgaps of D-A CPs for organic optoelectronic devices through the conformation design and segment orbital energy alignment.

Enabling quantitative analysis of complex polymer blends by infrared nanospectroscopy and isotopic deuteration.

Atomic-force microscopy coupled with infrared spectroscopy (AFM-IR) deciphers surface morphology of thin-film polymer blends and composites by simultaneously mapping physical topography and chemical composition. However, acquiring quantitative phase and composition information from multi-component blends can be challenging using AFM-IR due to the possible overlapping infrared absorption bands between different species. Isotope labeling one of the blend components introduces a new type of bond (carbon-deuterium vibration) that can be targeted using AFM-IR and responds at wavelengths sufficiently shifted toward unoccupied regions (around 2200 cm-1). In this project, AFM-IR was used to probe the surface morphology and chemical composition of three polymer blends containing deuterated polystyrene; each blend is expected to exhibit various degrees of miscibility. AFM-IR results successfully demonstrated that deuterium labeling prevents infrared spectral overlap and enables the visualization of blend phases that could not normally be distinguished by other scanning probe techniques. The nanoscale domain composition was resolved by fast infrared spectrum analysis. Overall, we presented isotope labeling as a robust approach for circumventing obstacles preventing the quantitative analysis of multiphase systems by AFM-IR.

Insight into the assembly of lipid-hyaluronan complexes in osteoarthritic conditions.

Interactions between molecules in the synovial fluid and the cartilage surface may play a vital role in the formation of adsorbed films that contribute to the low friction of cartilage boundary lubrication. Osteoarthritis (OA) is the most common degenerative joint disease. Previous studies have shown that in OA-diseased joints, hyaluronan (HA) not only breaks down resulting in a much lower molecular weight (MW), but also its concentration is reduced ten times. Here, we have investigated the structural changes of lipid-HA complexes as a function of HA concentration and MW to simulate the physiologically relevant conditions that exist in healthy and diseased joints. Small angle neutron scattering and dynamic light scattering were used to determine the structure of HA-lipid vesicles in bulk solution, while a combination of atomic force microscopy and quartz crystal microbalance was applied to study their assembly on a gold surface. We infer a significant influence of both MW and HA concentrations on the structure of HA-lipid complexes in bulk and assembled on a gold surface. Our results suggest that low MW HA cannot form an amorphous layer on the gold surface, which is expected to negatively impact the mechanical integrity and longevity of the boundary layer and could contribute to the increased wear of the cartilage that has been reported in joints diseased with OA.

Sequence-Enhanced Self-Healing in "Lock-and-Key" Copolymers.

Van der Waals-driven self-healing in copolymers with "lock-and-key" architecture has emerged as a concept to endow engineering-type polymers with the capacity to recover from structural damage. Complicating the realization of "lock-and-key"-enabled self-healing is the tendency of copolymers to form nonuniform sequence distributions during polymerization reactions. This limits favorable site interactions and renders the evaluation of van der Waals-driven healing difficult. Here, methods for the synthesis of lock-and-key copolymers with prescribed sequence were used to overcome this limitation and enable the deliberate synthesis of "lock-and-key" architectures most conducive to self-healing. The effect of molecular sequence on the material's recovery behavior was evaluated for the particular case of three poly(n-butyl acrylate/methyl methacrylate) [P(BA/MMA)] copolymers with similar molecular weights, dispersity, and overall composition but with different sequences: alternating (alt), statistical (stat), and gradient (grad). They were synthesized using atom transfer radical polymerization (ATRP). Copolymers with alt and stat sequence displayed a 10-fold increase of recovery rate compared to the grad copolymer variant despite a similar overall glass transition temperature. Investigation with small-angle neutron scattering (SANS) revealed that rapid property recovery is contingent on a uniform microstructure of copolymers in the solid state, thus avoiding the pinning of chains in glassy MMA-rich cluster regions. The results delineate strategies for the deliberate design and synthesis of engineering polymers that combine structural and thermal stability with the ability to recover from structural damage.

Improved chemical and isotopic labeling of biomembranes in Bacillus subtilis by leveraging CRISPRi inhibition of beta-ketoacyl-ACP synthase (fabF).

Assessing the structure of living microbial cell membranes is a challenging analytical goal. The cell membrane is defined by its transverse structure, an approximately 5 nm-thick selectively permeable bilayer that serves many important cellular functions. Compositionally complex, dynamic, and organized in both the transverse and lateral dimensions, understanding the cell membrane structure-and the role that structure plays in cellular function, communication, and environmental sensing is an active scientific effort. Previously, we have devised a novel isotopic labeling approach for membrane lipids to enable direct in vivo structural studies of the cell membrane in the Gram-positive bacterium, Bacillus subtilis, using small-angle neutron scattering. This was accomplished through a genetic inhibition of fatty acid (FA) degradation (ΔfadN) and a chemical inhibition of FA biosynthesis using cerulenin, an irreversible inhibitor of type II fatty acid synthases. Here, we improve upon the previous system by introducing a dCas9/sgRNA-fabF complex that blocks transcription of the essential fabF gene when under xylose induction. This leads to greater sensitivity to cerulenin in the mutant strain (JEBS102) and more robust cell growth when supplementary FAs are introduced to the culture medium. A subtle change in FA uptake is noted when compared to the prior labeling strategy. This is seen in the gas chromatography/mass spectrometry (GC/MS) data as a higher ratio of n16:0 to a15:0, and manifests in an apparent increase in the membrane thickness determined via neutron scattering. This represents an improved method of isotopic labeling for the cell membrane of Bacillus subtilis; enabling improved investigations of cellular uptake and utilization of FAs, cell membrane structure and organization as a phenotypic response to metabolic and environmental changes.

Three-Dimensional Printing in Stimuli-Responsive Yield-Stress Fluid with an Interactive Dual Microstructure.

Yield-stress support bath-enabled three-dimensional (3D) printing has been widely used in recent years for diverse applications. However, current yield-stress fluids usually possess single microstructures and still face the challenges of on-demand adding and/or removing support bath materials during printing, constraining their application scope. This study aims to propose a concept of stimuli-responsive yield-stress fluids with an interactive dual microstructure as support bath materials. The microstructure from a yield-stress additive allows the fluids to present switchable states at different stresses, facilitating an embedded 3D printing process. The microstructure from stimuli-responsive polymers enables the fluids to have regulable rheological properties upon external stimuli, making it feasible to perfuse additional yield-stress fluids during printing and easily remove residual fluids after printing. A nanoclay-Pluronic F127 nanocomposite is studied as a thermosensitive yield-stress fluid. The key material properties are characterized to unveil the interactions in the formed dual microstructure and microstructure evolutions at different stresses and temperatures. Core scientific issues, including the filament formation principle, surface roughness control, and thermal effects of the newly added nanocomposite, are comprehensively investigated. Finally, three representative 3D structures, the Hall of Prayer, capsule, and tube with changing diameter, are successfully printed to validate the printing capability of stimuli-responsive yield-stress fluids for fabricating arbitrary architectures.

EXPANSE: A time-of-flight EXPanded Angle Neutron Spin Echo spectrometer at the Second Target Station of the Spallation Neutron Source.

EXPANSE, an EXPanded Angle Neutron Spin Echo instrument, has been proposed and selected as one of the first suite of instruments to be built at the Second Target Station of the Spallation Neutron Source at the Oak Ridge National Laboratory. This instrument is designed to address scientific problems that involve high-energy resolution (neV-µeV) of dynamic processes in a wide range of materials. The wide-angle detector banks of EXPANSE provide coverage of nearly two orders of magnitude in scattering wavenumbers, and the wide wavelength band affords approximately four orders of magnitude in Fourier times. This instrument will offer unique capabilities that are not available in the currently existing neutron scattering instruments in the United States. Specifically, EXPANSE will enable direct measurements of slow dynamics in the time domain over wide Q-ranges simultaneously and will also enable time-resolved spectroscopic studies. The instrument is expected to contribute to a diverse range of science areas, including soft matter, polymers, biological materials, liquids and glasses, energy materials, unconventional magnets, and quantum materials.

CENTAUR-The small- and wide-angle neutron scattering diffractometer/spectrometer for the Second Target Station of the Spallation Neutron Source.

CENTAUR has been selected as one of the eight initial instruments to be built at the Second Target Station (STS) of the Spallation Neutron Source at Oak Ridge National Laboratory. It is a small-angle neutron scattering (SANS) and wide-angle neutron scattering (WANS) instrument with diffraction and spectroscopic capabilities. This instrument will maximally leverage the high brightness of the STS source, the state-of-the-art neutron optics, and a suite of detectors to deliver unprecedented capabilities that enable measurements over a wide range of length scales with excellent resolution, measurements on smaller samples, and time-resolved investigations of evolving structures. Notably, the simultaneous WANS and diffraction capability will be unique among neutron scattering instruments in the United States. This instrument will provide much needed capabilities for soft matter and polymer sciences, geology, biology, quantum condensed matter, and other materials sciences that need in situ and operando experiments for kinetic and/or out-of-equilibrium studies. Beam polarization and a high-resolution chopper will enable detailed structural and dynamical investigations of magnetic and quantum materials. CENTAUR's excellent resolution makes it ideal for low-angle diffraction studies of highly ordered large-scale structures, such as skyrmions, shear-induced ordering in colloids, and biomembranes. Additionally, the spectroscopic mode of this instrument extends to lower momentum transfers than are currently possible with existing spectrometers, thereby providing a unique capability for inelastic SANS studies.

SANS characterization of time dependent, slow molecular exchange in an SDS micellar system.

We have investigated the molecular exchange of sodium dodecyl sulfate (SDS) micelles in aqueous solution by time-resolved small angle neutron scattering (TR-SANS) measurements as a function of the surfactant and salt concentration. Starting with deuterated (d-SDS) and protonated (h-SDS) SDS micelles, surfactant exchange across the micelles leads to a randomized distribution of d-SDS and h-SDS within each micelle. By employing the contrast matching technique, we have studied this randomization process which is a direct measure of the molecular exchange of this system. Our results show that the randomization of the pure h-SDS and d-SDS micelles occurs in two steps: first, an almost instantaneous drop in the scattering intensity is observed where ∼80% of the micelles are randomized (contrast matched). After this, micelle randomization progresses slowly spanning over ∼100 hours. Importantly, we show that the kinetics in the second step are dominated by the formation of domains rich in either h-SDS, d-SDS and randomized (50 : 50 h-SDS : d-SDS). The slow exchange step is modeled via a phenomenological approach by drawing analogy to the Langmuir adsorption theory. Finally, the effects of the surfactant and salt concentrations on the instantaneous, and the time dependent randomization of SDS micelles are discussed.

Impact of Two Water-Miscible Ionic Liquids on the Temperature-Dependent Self-Assembly of the (EO)6-(PO)34-(EO)6 Block Copolymer.

There are many studies on the self-assembly of triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymers in aqueous solution. These polymers display a rich phase diagram as a function of block length, concentration, temperature, and additives. Here, we present a small-angle neutron scattering study of the impact of two water-miscible ionic liquids, 1-butyl-3-methylimidazolium chloride ([C4C1mim][Cl]) and 1-butyl-3-methylpyrrolidinium chloride ([C4C1pyrr][Cl]), on the temperature-dependent self-assembly of (EO)6-(PO)34-(EO)6, also known as L62 Pluronic, in aqueous solution. Both ionic liquids depress the temperatures of the various structural transitions that take place, but ([C4C1pyrr][Cl]) has a stronger effect. The structures that the triblock copolymer self-assembles into do not dramatically change nor do they significantly change the series of structures that the system transitions through as a function of temperature relative to the various transition temperatures.

Ion Atmosphere of Wormlike Micelles Profiled by Contrast Variation Small-Angle Neutron Scattering.

Structural studies of wormlike micelles have so far mostly focused on the conformational properties of surfactant aggregates. The diffuse ionic atmosphere, which has a profound influence on various micellization phenomena such as thermodynamic stability and structural polymorphism, remains largely unexplored experimentally. In this report a strategy of contrast variation small-angle neutron scattering for this crucial structural study is outlined. Underlined by a general criterion established for unbiasedly identifying the length scale relevant to charge association from the spectral evolution, our analytical framework can provide a quantitative description of counterion distribution in a mathematically tractable manner. Our method can be conveniently extended to facilitate structural studies of complex multicomponent systems using contrast variation neutron scattering.

Small angle scattering of diblock copolymers profiled by machine learning.

We outline a machine learning strategy for quantitively determining the conformation of AB-type diblock copolymers with excluded volume effects using small angle scattering. Complemented by computer simulations, a correlation matrix connecting conformations of different copolymers according to their scattering features is established on the mathematical framework of a Gaussian process, a multivariate extension of the familiar univariate Gaussian distribution. We show that the relevant conformational characteristics of copolymers can be probabilistically inferred from their coherent scattering cross sections without any restriction imposed by model assumptions. This work not only facilitates the quantitative structural analysis of copolymer solutions but also provides the reliable benchmarking for the related theoretical development of scattering functions.