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All sources NASA NTRS DOE OSTI

DOE OSTI2021

Heterogeneity and Hysteresis in the Polymer Collapse of Single Core–Shell Stimuli-Responsive Plasmonic Nanohybrids

Broad application of polymeric stimuli-responsive smart nanohybrids requires understanding the mechanisms governing active control. Ensemble techniques have identified inhomogeneous polymer collapse in microgels that potentially arise from heterogeneous interchain interactions and differences in core size. A single-particle examination would establish the influence of core size and internal polymer network heterogeneity on local interactions that contribute to the observed inhomogeneous polymer collapse dynamics of nanohybrids. Using single-particle dark-field spectroscopy, we investigated the complex polymer collapse profiles of core–shell plasmonic nanohybrids comprising thermoresponsive poly(N-isopropylacrylamide) (pNIPAM)-encapsulated gold nanorods (AuNRs). We report that the polymer collapse behavior was independent of the core size. For thinner polymer shells, we observed hysteresis in the collapse of AuNR@pNIPAMs, likely related to local pNIPAM aggregation due to interchain hydrogen bonding. For thicker polymer shells, we observed a broad polymer collapse distribution that we attributed to a two-step phase transition that arises from a polymer network density gradient. Furthermore, our single-particle approach relates the internal heterogeneity of the polymer network of nanohybrids to the mechanisms underlying heterogeneous phase transitions that traditional, ensemble-averaged approaches are unable to discern.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Combining Chemistry, Material Science, Inspiration from nature, and Serendipity to Develop Stimuli-responsive Polymeric Materials

Neither of us can remember people talking about stimuli-responsive polymers when we were students. Even though this was still in the last century, it was almost 70 years after Staudinger's seminal paper "uber Polymerisation"![1] By the time we entered graduate school in the early 1990 s, the first papers on polymer light emitting diodes appeared, while research on electrically conducting, nonlinear optical, and other "functional" polymers was already in full swing. Looking back, there were some stimuli-responsive materials that were around at the time, but it took the better part of the last 30 years until the field had developed into what we think is one of the most vibrant areas of polymer science. Before the potential usefulness of this class of materials was recognized, researchers were focused on developing polymeric materials that would not respond to external influences, and in fact maintain (in particular) their mechanical properties in a wide range of environments. This has led to the development of many environmentally robust polymers, which have come to impact basically every aspect of our daily life. Ironically, this long-sought stability now comes back to haunt us in the form of plastic pollution, but this is another story. The concept of materials that adapt their properties in response to changing environmental conditions might appear like a complete reversal with respect to the original goals of creating stable materials. However, eventually a) it was recognized that materials that respond to a specific stimulus in a predictable and useful manner would significantly broaden the potential usefulness of polymers, and b) the field of polymer science had developed to the point where the rational design, preparation, and characterization of such materials became possible. The expression 'stimuli-responsive polymer' had been first used in the 1980's, however its use really only gained popularity a few decades later. In the early days, terms such as environmentally-sensitive or environmentally-responsive polymers, stimuli-reversible or stimuli-sensitive polymers, or polymers with phase transitions have also been used.

Rowan, Stuart J.↗

DOE OSTI2019

Patterning non-equilibrium morphologies in stimuli-responsive gels through topographical confinement

Stimuli-responsive “smart” polymers have generated significant interest for introducing dynamic control into the properties of antifouling coatings, smart membranes, switchable adhesives and cell manipulation substrates. Switchable surface morphologies formed by confining stimuli-responsive gels to topographically structured substrates have shown potential for a variety of interfacial applications. Beyond patterning the equilibrium swelling behavior of gels, subjecting stimuli-responsive gels to topographical confinement could also introduce spatial gradients in the various timescales associated with gel deformation, giving rise to novel non-equilibrium morphologies. In this work, we show how by curing poly(N-isopropylacrylamide) (pNIPAAm)-based gel under confinement to a rigid, bumpy substrate, we can not only induce the surface curvature to invert with temperature, but also program the transient, non-equilibrium morphologies that emerge during the inversion process through changing the heating path. Finite element simulations show that the emergence of these transient morphologies is correlated with confinement-induced gradients in polymer concentration and position-dependent hydrostatic pressure within the gel. To illustrate the relevance of such morphologies in interfacial applications, we show how they enable us to control the gravity-induced assembly of colloidal particles and microalgae. Finally, we show how more complex arrangements in particle assembly can be created through controlling the thickness of the temperature-responsive gel over the bumps. Patterning stimuli-responsive gels on topographically-structured surfaces not only enables switching between two invertible topographies, but could also create opportunities for stimuli ramp-dependent control over the local curvature of the surface and emergence of unique transient morphologies. Harnessing these features could have potential in the design of multifunctional, actuatable materials for switchable adhesion, antifouling, cell manipulation, and liquid and particle transport surfaces.

42 ENGINEERING↗

DOE OSTI2022

Maximizing Strength: The Stimuli and Mediators of Strength Gains and Their Application to Training and Rehabilitation

Abstract Spiering, BA, Clark, BC, Schoenfeld, BJ, Foulis, SA, and Pasiakos, SM. Maximizing strength: the stimuli and mediators of strength gains and their application to training and rehabilitation. J Strength Cond Res 37(4): 919–929, 2023—Traditional heavy resistance exercise (RE) training increases maximal strength, a valuable adaptation in many situations. That stated, some populations seek new opportunities for pushing the upper limits of strength gains (e.g., athletes and military personnel). Alternatively, other populations strive to increase or maintain strength but cannot perform heavy RE (e.g., during at-home exercise, during deployment, or after injury or illness). Therefore, the purpose of this narrative review is to (a) identify the known stimuli that trigger gains in strength; (b) identify the known factors that mediate the long-term effectiveness of these stimuli; (c) discuss (and in some cases, speculate on) potential opportunities for maximizing strength gains beyond current limits; and (d) discuss practical applications for increasing or maintaining strength when traditional heavy RE cannot be performed. First, by conceptually deconstructing traditional heavy RE, we identify that strength gains are stimulated through a sequence of events, namely: giving maximal mental effort, leading to maximal neural activation of muscle to produce forceful contractions, involving lifting and lowering movements, training through a full range of motion, and (potentially) inducing muscular metabolic stress. Second, we identify factors that mediate the long-term effectiveness of these RE stimuli, namely: optimizing the dose of RE within a session, beginning each set of RE in a minimally fatigued state, optimizing recovery between training sessions, and (potentially) periodizing the training stimulus over time. Equipped with these insights, we identify potential opportunities for further maximizing strength gains. Finally, we identify opportunities for increasing or maintaining strength when traditional heavy RE cannot be performed.

Sport Sciences↗

DOE OSTI2024

Functional stimuli-responsive polymers on micro- and nano-patterned interfaces

Micro- and nano-patterned surfaces offer precise control over morphology and chemical composition, enhancing the stability, durability, and functionality of coating materials. When combined with stimuli-responsive polymers, these surfaces gain dynamic adaptability, enabling reversible binding, reusable sensing, and selective molecular capture. Furthermore, while recent review articles have explored various aspects of stimuli-responsive materials, from hydrogel patterns for bioanalytical applications to shape-morphing hydrogels for soft robotics and sensors, a comprehensive review focused on the integration of smart polymers with micro- or nano-patterned interfaces remains absent. This review addresses key surface patterning techniques, including soft lithography, colloidal lithography, and polymer brush photolithography, as well as advances in surface-initiated polymerization methods, such as surface-initiated controlled radical polymerization (SI-CRP). In addition, we discuss recent progress in integrating stimuli-responsive polymers with patterned surfaces to create advanced, functional materials.

Colloidal lithography↗

DOE OSTI2020

Advances in Polymerizations Modulated by External Stimuli

Synthetic polymer chemistry endeavors to imitate the spatial and temporal control exhibited within biological systems to obtain well-defined polymeric materials with unique structures, properties, and applications. This is often approached through the development of dynamic catalyst (or initiator) systems that use external stimuli to elicit discrete, site specific transformations that impact the polymerization. In this work, we highlight developments in polymerizations that are modulated by external stimuli, with particular focus on those systems that enable notable changes in kinetics, monomer selectivity, polymer architecture, or tacticity. Examples of external stimuli include chemical oxidants or reductants, light, applied voltage, and mechanical force.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Development of a mnemonic discrimination task using naturalistic stimuli with applications to aging and preclinical Alzheimer's disease

Most tasks test memory within the same day, however, most forgetting occurs after 24 h. Further, testing memory for simple words or objects does not mimic real-world memory experiences. We designed a memory task showing participants video clips of everyday kinds of experiences, including positive, negative, and neutral stimuli, and tested memory immediately and 24 h later. During the memory test, we included repeated and similar stimuli to tax both target recognition and lure discrimination ability. Participants’ memory was worse after 24 h, especially the ability to discriminate similar stimuli. Emotional videos were better remembered when tested immediately, however, after 24 h we find gist versus detail trade-offs in emotional forgetting. We also applied this paradigm to a sample of cognitively normal older adults that also underwent amyloid and tau PET imaging. We found that older adults performed worse on the task compared to young adults. While both young and older adults showed similar patterns of forgetting of repeated emotional and neutral clips, older adults showed preserved neutral compared to emotional discrimination after 24 h. Further, lure discrimination performance correlated with medial temporal lobe tau in older adults with preclinical Alzheimer’s disease. These results suggest factors such as time between encoding and retrieval, emotion, and similarity influence memory performance and should be considered when examining memory performance for an accurate picture of memory function and dysfunction.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Stimuli‐Responsive Emission from Hybrid Metal Halides

Abstract Stimuli‐responsive photoluminescent (PL) materials have attracted considerable attention in recent years owing to their potential applications in anti‐counterfeiting, information encryption, and sensing. Further investigations of the transformation mechanism and potential applications of stimulus‐responsive PL materials are considerably important. In the current study, an organic–inorganic metal halide, C 9 H 15 N 3 SbCl 5 ([C 9 H 13 N 3 ] 2+ is a 1‐(2‐pyridyl) piperazine cation) is obtained, which exhibits a 0D structure withP‐1 space group. At room temperature, when excited by UV light, the C 9 H 15 N 3 SbCl 5 single crystals exhibit unimodal blue light emission at 405 nm, and grinding or hydrostatic pressure induces double‐peak emissions at 405 and 650 nm. Interestingly, double‐emission samples can be restored to single‐emission samples by short annealing or storage in air for 2 weeks, and this process is reversible. Luminescence response to mechanical stimuli can also be achieved in the presence of hydrochloric acid and water. Spectral analysis and the analysis of the microstructural changes revealed that the structural modifications of the inorganic group play a pivotal role in the response to the stimulus. Finally, a composite film device based on C 9 H 15 N 3 SbCl 5 is prepared to demonstrate the potential of these smart materials in anti‐counterfeiting and sensing applications.

Chemistry↗

DOE OSTI2025

Secretory stimuli distinctly regulate insulin secretory granule maturation through structural remodeling

Insulin secretory granule (ISG) maturation is a crucial aspect of insulin secretion and glucose homeostasis. The regulation of this maturation remains poorly understood, especially how secretory stimuli affect ISG maturity and subcellular localization. In this study, we used soft X-ray tomography (SXT) to quantitatively map ISG morphology, density, and location in single INS-1E and mouse pancreatic β cells under the effect of various secretory stimuli. We found that the activation of glucokinase (GK), gastric inhibitory polypeptide receptor (GIPR), glucagon-like peptide-1 receptor (GLP-1R), and G protein-coupled receptor 40 (GPR40) promotes ISG maturation. Each stimulus induces unique structural remodeling in ISGs, by altering size and density, depending on the specific signaling cascades activated. These distinct ISG subpopulations mobilize and redistribute in the cell, altering the overall cellular structural organization. Our results provide insight into how current diabetes and obesity therapies impact ISG maturation and may inform the development of future treatments that target maturation specifically.

insulin granule maturation↗

DOE OSTI2022

Sequence-Controlled Secondary Structures and Stimuli Responsiveness of Bioinspired Polyampholytes

In this work, a comprehensive study focusing on the influence of the sequence charge pattern on the secondary structure preferences of annealed polyampholytes and their responsiveness to external stimuli is presented. Two sequences are designed composed entirely of ionizable amino acids (charge fraction f=1), and an equal number of positive and negative charges (f + =f - =0.5) with distinct charge-patterns consisting of lysine and glutamic acid monomers. The study reveals that the sequence charge pattern has a significant influence on the secondary structure preferences of polyampholytes at physiological pH. Furthermore, it shows that external stimuli such as pH, ionic strength and solvent dielectric constant can be used to modulate the secondary structure of the two designed sequences. The observed secondary structure transformations for the two sequences are also substantially different from those determined for uniformly charged polypeptides-homo-polypeptides under matching conditions.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Transmission Electron Microscopy Study on the Effect of Thermal and Electrical Stimuli on Ge2Te3 Based Memristor Devices

Memristor devices fabricated using the chalcogenide Ge 2 Te 3 phase change thin films in a metal-insulator-metal structure are characterized using thermal and electrical stimuli in this study. Once the thermal and electrical stimuli are applied, cross-sectional transmission electron microscopy (TEM) and X-ray energy-dispersive spectroscopy (XEDS) analyses are performed to determine structural and compositional changes in the devices. Electrical measurements on these devices showed a need for increasing compliance current between cycles to initiate switching from low resistance state (LRS) to high resistance state (HRS). The measured resistance in HRS also exhibited a steady decrease with increase in the compliance current. High resolution TEM studies on devices in HRS showed the presence of residual crystalline phase at the top-electrode/dielectric interface, which may explain the observed dependence on compliance current. XEDS study revealed diffusion related processes at dielectric-electrode interface characterized, by the separation of Ge 2 Te 3 into Ge- and Te- enriched interfacial layers. This was also accompanied by spikes in O level at these regions. Furthermore, in-situ heating experiments on as-grown thin films revealed a deleterious effect of Ti adhesive layer, wherein the in-diffusion of Ti leads to further degradation of the dielectric layer. This experimental physics-based study shows that the large HRS/LRS ratio below the current compliance limit of 1 mA and the ability to control the HRS and LRS by varying the compliance current are attractive for memristor and neuromorphic computing applications.

Shallcross, Austin↗

DOE OSTI2021

Structural Manipulation of a Zirconocene-Based Porous Coordination Cage Using External and Host–Guest Stimuli

Porous coordination cages (PCCs) constructed from a zirconocene-based cluster have drawn great attention for their high stability and structural tunability. These features have enabled these cages to be utilized for a wide array of applications. Here this work demonstrates the structural flexibility and stimulus-responsive features of two interconvertible zirconocene-based PCCs. The subjects, PCC-20c (capsular) and PCC-20t (tetrahedral), are constructed from the same cluster and ligand but exhibit different shapes and properties. In the synthetic study of the cages, it is found that higher temperatures of synthesis yield PCC-20c in several different crystalline phases while lower temperatures of synthesis yield pure phase PCC-20t. Thermodynamic studies on the interconversion of the two cages show that the conversion from PCC-20t into PCC-20c is an entropically driven process and can be largely affected by the solvent environment. Additionally, the process of PCC-20t/c conversion can be mediated by the counter anions and light irradiation as evidenced by the change in equilibrium constants under these influences. The current studies are conducted to decipher how the PCC-20t/c phase can be controllably synthesized, interconverted, and their properties can be modified under the use of external stimuli: heat, light, and guest molecules.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Polyoxometalate‐Surfactant Assemblies: Responsiveness to Orthogonal Stimuli

Abstract Integrating different types of supramolecular interactions opens the possibility to generate nanoparticle surfactants (NPSs) at the liquid–liquid interface that are responsive to multiple stimuli. Here we develop a covalently modified polyoxometalate/β‐cyclodextrin (POM/β‐CD) organic–inorganic hybrid, consisting of a negatively charged POM cluster with β‐CD host groups. The POM/β‐CD hybrid can be dispersed in water and interacts at a water/oil interface with ligands dissolved in an oil phase through electrostatic or host–guest interactions, thereby generating POM‐surfactants (POMSs) having pH, redox, and guest‐competitive responsiveness, respectively. By taking advantage of the jamming of POMSs at the interface, a reconfigurable all‐liquid system could be produced that is responsive to orthogonal changes in the external environment.

Xia, Zhiqin↗

DOE OSTI2022

Polyoxometalate‐Surfactant Assemblies: Responsiveness to Orthogonal Stimuli

Xia, Zhiqin↗

DOE OSTI2025

Evaluating the Structural Response of Amphiphilic Monolayers to Environmental Stimuli

Amphiphilic monolayers composed of end groups with distinct polar and nonpolar functional groups offer rapid and reversible interfacial adaptation in response to environmental stimuli such as a change in interfacial medium polarity. We have synthesized and characterized a suite of monolayers with functional groups of competing polarity designed to reconfigure their interfacial chemical composition in response to solvent polarity. In these films, the end group is designed to be able to reorient and expose the functional groups that minimize the interfacial free energy between the film and the environment. Using a combination of spectroscopic, computational, and wettability studies, we have investigated the responsive interfacial behavior of different end groups upon exposure to environments with varying polarities. Contact angle measurements across a series of polar and dispersive probe liquids reveal trends that reflect the underlying molecular flexibility and composition. Vibrational sum frequency generation (SFG) spectroscopy and atomistic molecular dynamics (MD) simulations confirm solvent-driven reorientation of the end groups, with restructuring observed at the interface. To quantify these effects, we have developed a surface energy calculation model that incorporates solvent-induced surface rearrangements into the estimations. Our findings reveal a strong dependence of surface energy and switching behavior on the length and flexibility of the functionalities in the end group, which affects the exposure of certain interfacial compositions under different solvents. These results offer new insights into the design of adaptive monolayers and provide a framework for evaluating solvent-responsive surfaces.

functional groups↗

DOE OSTI2025

Intracellular Biomacromolecule Delivery by Stimuli-Responsive Protein Vesicles Loaded by Hydrophobic Ion Pairing

Proteins can perform ideal therapeutic functions. However, their large size and significant surface hydrophilicity and charge prohibit them from reaching intracellular targets. These chemical features also render them poorly encapsulated by nanoparticles used for intracellular delivery. In this work, a novel combination of protein vesicles and hydrophobic ion pairing (HIP) was used to load protein cargo and achieve cytosolic delivery to overcome the limitations of previous protein vesicle properties. Protein vesicles are thermally self-assembling nanoparticles made from elastin-like polypeptide (ELP) fused to an arginine-rich leucine zipper and a globular protein fused to a glutamate-rich leucine zipper. To impart stimuli-responsive disassembly, physiological stability, and small size, the ELP sequence was modified to include histidine and tyrosine residues. HIP was used to load and release protein cargo requiring endosomal escape for cytosolic function. HIP vesicles enabled delivery of cytochrome c, a cytosolically active protein, and a significant reduction in viability in both a traditional two-dimensional (2D) human cancer cell line culture and a biomimetic three-dimensional (3D) organoid model of acute myeloid leukemia. By examining the uptake of positively and negatively charged fluorescent protein cargos loaded by HIP, this work revealed the necessity of HIP for cytosolic cargo delivery and how HIP loading influences protein vesicle self-assembly and disassembly using microscopy, small-angle X-ray scattering, and nanoparticle tracking analysis. HIP protein vesicles have the potential to broaden the use of intracellular proteins as therapeutics for various diseases and extend protein vesicles to deliver other biomacromolecules, as the strategy developed here resulted in the first cytosolic protein cargo delivery using protein vesicles.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2019

Insights into a Greener Stimuli-Responsive Fracturing Fluid for Geothermal Applications

StimuFracTM, is a non-toxic stimuli-responsive fracturing fluid consisting on a CO2-reactive polymer which has shown at the lab-scale to consistently fracture rock cores at significantly lower net pressures in a range of representative geothermal pressure/temperature conditions. In this work, we report on the two main mechanisms responsible for fracturing rock at lower net pressures with this novel fracturing fluid. The first mechanism is the additional work / overpressure generated by aqueous polymer solution during its CO2-triggered volume expansion. The second mechanism is associated to a reduction in pore invasion pressure as a result of the lower interfacial tension of StimuFrac. This reduction in pore invasion pressure results in a reduction in fracturing net pressure as previously reported. The results presented in this work illustrate the potential of StimuFrac as a greener and less-energy intensive fracturing fluid for geothermal and fossil energy production.

Fernandez, Carlos A.↗

DOE OSTI2019

Multi-stimuli responsive tetra-PPO 60 -PEO 20 ethylene diamine block copolymer enables pH, temperature, and solvent regulation of Au nanoparticle composite plasmonic response

In this work a gold nanoparticle (NP) hydrogel composite prepared by multi-step cascade synthesis undergoes temperature, pH, and solvent dependent nanoscale structural transformations promoting modulation of the plasmon resonance. The composite is spontaneously prepared from a non-covalent lamellar structured lyotropic mesophase (complex fluid) composed of amphiphiles (DMPC and Triton X-100) that support the reactive constituents, a mixture of hydroxyl and acrylate end-derivatized Tetronic (Poloxamine) polymer and [AuCl4] – . The reaction sequence begins with the reduction of [AuCl4] – by the ethylene diamine linkage and PEO blocks of the Tetronic, yielding Au NPs. The redox reaction generates free radicals initiating crosslinking of the acrylate end-derivatized polymer producing a chemical hydrogel. Optical spectroscopy and electron microscopy confirm Au NP formation. ATR/FT-IR spectroscopy and thermal analysis establish acrylate crosslinking and network formation. X-ray scattering reveals the composite reversibly converts between multilamellar and bicontinuous cubic structures as temperature is increased above 35 °C for composites containing protonated ethylene diamine linkages (un-buffered water or acidic buffer). The reversible changes in nanoarchitecture red shifts and broadens the collective plasmon (from 523 nm to 575 nm) of the composite, an observation attributed to re-organization of confined NPs from 2D sheets (lamellae) to 1D columns (bicontinuous cubic channels). Composites prepared in alkaline buffer do not undergo a structural conversion with temperature, retaining a multilamellar architecture. In addition to pH and thermo-responsivity, the composite swells reversibly in polar solvents, which acts to de-aggregate and aggregate the encapsulated NPs and varies the plasmon resonance by Δ52 nm. This work reports the first combined use of a polymer to achieve both the in situ synthesis of spatially confined plasmonic NPs and their reversible stimuli-triggered re-organization mediated by interconvertible changes in scaffold nanoarchitecture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗