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At least 91 records · Page 5

High Resolution, Single-Step Patterning of Silica Aerogels

Three-dimensional metallic structures are fabricated with high spatial resolution in silica aerogels. In our method, silica hydrogels are prepared with a standard base-catalyzed route, and exchanged with an aqueous solution typically containing Ag' ions (1 M) and 2-propanol (0.2 M). The metal ions are reduced photolytically with a table-top ultraviolet lamp, or radiolytically, with a focused X-ray beam. We fabricated dots and lines as small as 30 x 70 km, protruding for several mm into the bulk of the materials. The hydrogels are eventually supercritically dried to yield aerogels, without any measurable change in the shape and spatial resolution of the lithographed structures. Transmission electron microscopy shows that illuminated regions are composed of Ag clusters with a size of several pm, separated by thin layers of silica.

Bertino, M. F.↗

Liquid crystalline order in mucus

Mucus plays an exceptionally wide range of important biological roles. It operates as a protective, exchange, and transport medium in the digestive, respiratory, and reproductive systems of humans and other vertebrates. Mucus is a polymer hydrogel. It is secreted as discrete packages (secretory granules) by specialized secretory cells. Mucus hydrogel is stored in a condensed state inside the secretory granules. Depending upon the architecture of their constituent macromolecules and on the composition of the solvent, polymer gels can form liquid crystalline microstructures, with orientational order being exhibited over optically resolvable distances. Individual mucin molecules consist of alternating rigid segments (heavily glycosylated; hydrophilic) and flexible segments (nonglycosylated; hydrophobic). Polymer molecules consisting of rigid units linked by flexible spacers are frequently associated with liquid crystalline behavior, which again raises the possibility that mucus could form anisotropic fluid phases. Suggestions that mucins may be self-associating in dilute solution have previously been challenged on the basis of sedimentation-equilibrium studies performed on mucus in which potential sites of association were competitively blocked with inhibitors. However, the formation of stable liquid crystalline phases does not depend on the existence of inter- or intramolecular associations; these phases can form on the basis of steric considerations alone.

NASA Discipline Number 40-20↗

Wipes, Coatings, and Patches for Detecting Hydrazines

Three color-indicating devices have been conceived as simple, rapid, inexpensive means of detecting hazardous liquid and gaseous substances in settings in which safety is of paramount concern and it would be too time-consuming or otherwise impractical to perform detection by use of such instruments as mass spectrometers. More specifically, these devices are designed for detecting hypergolic fuels (in particular, hydrazines) and hypergolic oxidizers in spacecraft settings, where occasional leakage of these substances in liquid or vapor form occurs and it is imperative to take early corrective action to minimize adverse health effects. With suitable redesign, including reformulation of their color indicator chemicals, these devices could be adapted to detection of other hazardous substances in terrestrial settings (e.g., industrial and military ones). One of the devices is a pad of a commercially available absorbent material doped with a color indicator. The absorbent material is made from 70 percent polyester and 30 percent nylon and can absorb about eight times its own weight of liquid. The color indicator is a mixture of conventional pH color indicator chemicals. Hydrazine and monomethyl hydrazine, which are basic, cause the color indicator to turn green. In the original intended application, the pad is wiped on a space suit that is suspected of having been exposed to leaking monomethyl hydrazine during a space walk, before the wearer returns to the interior of the spacecraft. If the wiped surface is contaminated with hydrazine, the pad turns green. In addition, the pad absorbs hydrazine from the wiped surface, thereby reducing or eliminating the hazard. Used pads, including ones that show contamination by hydrazine, can be stored in a sealed plastic bag for subsequent disposal. The second device, which has been proposed but not yet developed, would comprise a color indicator material in the form of either a coating on a space suit (or other protective garment) or a coating on a sheet that could be easily attached to and detached from the protective garment. The coating material would be a hydrogel doped with a suitable pH indicator. The hydrogel would also serve to maintain a level of moisture needed to support the chemical reaction mentioned in the next sentence. In addition to changing color to indicate the presence of any hypergolic fuel (which is basic) or hypergolic oxidizer (which is acidic) that might splash on the space suit, the pH indicator would also react with the hypergolic fuel or oxidizer and thereby bind it. The third device is a color dosimeter for detecting hydrazine liquid or vapor coming from microscopic leaks. This device is designed to satisfy several requirements specific to its original intended use in the auxiliary power unit of the space shuttle. These requirements include stability under vacuum, stability at moderate temperature, fast and irreversible change in color upon exposure to hydrazine, and visibility of the color change through polyimide tape.

Young, Rebecca↗

Plant Growth Research for Food Production: Development and Testing of Expandable Tuber Growth Module

Controlled and reliable growth of a variety of vegetable crops is an important capability for manned deep space exploration systems for providing nutritional supplementation and psychological benefits to crew members. Because current systems have been limited to leafy vegetables that require minimal root space, a major goal for these systems is to increase their ability to grow new types of crops, including tuber plants and root vegetables that require a large root space. An expandable root zone module and housing was developed to integrate this capability into the Vegetable Production System (Veggie). The expandable module uses a waterproof, gas-permeable bag with a structure that allows for root space to increase vertically throughout the growth cycle to accommodate for expanding tuber growth, while minimizing the required media mass. Daikon radishes were chosen as an ideal tuber crop for their subterraneous tuber size and rapid growth cycle, and investigations were done to study expanding superabsorbent hydrogels as a potential growth media. These studies showed improved water retention, but restricted oxygen availability to roots with pure gel media. It was determined that these hydrogels could be integrated in lower proportions into standard soil to achieve media expansion and water retention desired. Using the constructed module prototype and ideal gel and soil media mixture, daikon radishes are being grown in the system to test the capability and success of the system through a full growth cycle.

food production↗

Plant Growth Research for Food Production: Development and Testing of Expandable Tuber Growth Module

Controlled and reliable growth of a variety of vegetable crops is an important capability for manned deep space exploration systems for providing nutritional supplementation and psychological benefits to crew members. Because current systems have been limited to leafy vegetables that require minimal root space, a major goal for these systems is to increase their ability to grow new types of crops, including tuber plants and root vegetables that require a large root space. An expandable root zone module and housing was developed to integrate this capability into the Veggie growth system. The expandable module uses a waterproof, gas-permeable bag with a structure that allows for root space to increase vertically throughout the growth cycle to accommodate for expanding tuber growth, while minimizing the required media mass. Daikon radishes were chosen as an ideal tuber crop for their subterraneous tuber size and rapid growth cycle, and investigations were done to study expanding superabsorbent hydrogels as a potential growth media. These studies showed improved water retention, but restricted oxygen availability to roots with pure gel media. It was determined that these hydrogels could be integrated in lower proportions into standard soil to achieve media expansion and water retention desired. Using the constructed module prototype and ideal gel and soil media mixture, Daikon radishes were grown in the system to test the capability and success of the system through a full growth cycle.

space↗

Virus Infection of Phytoplankton Increases Average Molar Mass and Reduces Hygroscopicity of Aerosolized Organic Matter

Viral infection of phytoplankton is a pervasive mechanism of cell death and bloom termination, which leads to the production of dissolved and colloidal organic matter that can be aerosolized into the atmosphere. Earth-observing satellites can track the growth and death of phytoplankton blooms on weekly time scales but the impact of viral infection on the cloud forming potential of associated aerosols is largely unknown. Here, we determine the influence of viral-derived organic matter, purified viruses, and marine hydrogels on the cloud condensation nuclei activity of their aerosolized solutions, compared to organic exudates from healthy phytoplankton. Dissolved organic material derived from exponentially growing and infected cells of well-characterized eukaryotic phytoplankton host-virus systems, including viruses from diatoms, coccolithophores and chlorophytes, was concentrated, desalted, and nebulized to form aerosol particles composed of primarily of organic matter. Aerosols from infected phytoplankton cultures resulted in an increase in critical activation diameter and average molar mass in three out of five combinations evaluated, along with a decrease in organic kappa (hygroscopicity) compared to healthy cultures and seawater controls. The infected samples also displayed evidence of increased surface tension depression at realistic cloud water vapor supersaturations. Amending the samples with xanthan gum to simulate marine hydrogels increased variability in organic kappa and surface tension in aerosols with high organic to salt ratios. Our findings suggest that the pulses of increased dissolved organic matter associated with viral infection in surface waters may increase the molar mass of dissolved organic compounds relative to surface waters occupied by healthy phytoplankton or low phytoplankton biomass.

Atmospheric science↗

Solution‐Like Water Transport Across Molecular to Macroscopic Length Scales in Crosslinked Poly(Ethylene Glycol Diacrylate) Networks With Tailored Sidechains

Poly(ethylene glycol) (PEG)‐based materials, like PEG‐diacrylate (PEGDA), are prized for their hydrophilic, inert properties, and leveraged in hydrogels and as membrane mimics. While network chemistry is often tuned for selective transport and antifouling, fundamental understanding of water dynamics at the network surface and the impact on bulk transport is limited. We utilize Overhauser dynamic nuclear polarization (ODNP) to measure nanoscale water diffusivity near a tethered spin label at the water‐polymer surface and compare it to bulk water diffusivity from pulsed field gradient (PFG) NMR. Via active ester chemistry, spin labels and varied sidechain chemistries are introduced, modulating network hydrophilicity. Tuning network hydration through crosslinker content and functional groups further impacts water diffusivity. Results show rapid nanoscale water transport at the polymer surface, reflecting network volumetric water content, with further modulation by sidechain functionality. These findings demonstrate PEGDA's utility as a membrane mimic and the critical impact of network chemistry on water transport.

hydrogels↗

RNA–Polymer Conjugates via Direct Incorporation of the Chain Transfer Agent and PET–RAFT Polymerization

Covalent conjugation of RNA with synthetic polymers has emerged as a powerful approach for creating bioconjugates with synergistically enhanced properties. However, conventional methods require solid-phase synthesis to preinstall functional groups in RNA, significantly limiting practical applications. Here, we present a novel approach for synthesizing RNA–polymer conjugates via direct incorporation of chain transfer agent (CTA) into RNA through acylation chemistry and reversible addition–fragmentation chain transfer (RAFT) polymerization. A CTA-functionalized acyl imidazole reagent was synthesized to facilitate direct and covalent modification of various RNAs by reacting with their 2′-hydroxyl groups. Subsequent RAFT polymerization using RNA–CTA as a macro-CTA enabled direct grafting-from RNA, yielding RNA conjugates with controlled molecular weight and low dispersity. Notably, this postsynthetic modification strategy was successfully extended to modify biomass RNA, yielding thermoresponsive conjugates and biodegradable hydrogels. Overall, this advance allowed for the direct modification of synthetic and biomass RNAs, significantly enhancing the accessibility of functional RNA–polymer materials.

biomass↗

Bioproduction, bioprotection, and biocontainment in multi-kingdom microbial systems with 3D spatial control

Engineered living materials (ELMs) are a class of hybrid materials that include engineered microbes encapsulated by a polymer matrix. The biotic and abiotic components define the ELMs design space and can be altered to improve performance and function. While current synthetic materials in the field display robust biocompatibility with both native and engineered living systems, we have a limited understanding of how to leverage three-dimensional (3D) form factors to spatially organize and control microbial dynamics within the material. Motivated by this knowledge gap, we employed extrusion-based 3D printing to fabricate multi-kingdom hydrogel constructs for the encapsulation of both single and multi-kingdom microbial systems. Core–shell cubic constructs enabled the spatial organization of a constitutive multi-kingdom system of levodopa (L-DOPA)-producing E. coli and betaxanthins (BXN)-producing S. cerevisiae. This spatial organization in 3D materials can introduce precise control over bioproduction, bioprotection, and biocontainment features that are critical to the efficacy of current ELMs. The relative spatial organization of the organisms, as well as the surface area-to-volume ratio were investigated to determine how these design elements impact microbial behavior (metabolite production, growth, expression, and cell distribution) over time. We demonstrated that F127-bis-urethane methacrylate (F127-BUM) core–shell geometries enable the hierarchical 3D printing of multi-kingdom constructs, offering customizable control over bioproduction, bioprotection, and biocontainment. With the optimization of these core–shell structures for continuous bioproduction, these ELMs could be deployed as compact and sustainable bioreactors in remote environments.

additive manufacturing↗

Additive Manufacturing with Cellulose-Based Composites: Materials, Modeling, and Applications

Recent advances in large-scale additive manufacturing (AM) with polymer-based composites have enabled efficient production of high-performance materials. Cellulose nanomaterials (CNMs) have emerged as bio-based feedstocks due to their exceptional strength and sustainability. However, challenges such as hornification and poor dispersion in polymer matrices still limit large-scale CNM–polymer composite manufacturing, requiring novel strategies. Here, this review outlines an approach starting with atomic-level simulations to link molecular composition to key parameters like bulk density, viscosity, and modulus. These simulations provide data for finite element analysis (FEA), which informs large-scale experiments and reduces the need for extensive trials. The strategy explores how atomic interactions impact the morphology, adhesion, and mechanical properties of CNM-based composites in AM processes. The review also discusses current developments in AM, along with predictions of mechanical and thermal properties for structural applications, packaging, flexible electronics, and hydrogel scaffolds. By integrating experimental findings with molecular dynamics (MD) simulations and finite element modeling (FEM), valuable insights for material design, process optimization, and performance enhancement in CNM-based AM are provided to address ongoing challenges.

36 MATERIALS SCIENCE↗

A magnetic‐directed micro‐particle with near‐ IR light triggered guest‐release property

Abstract In this study, guest carriers, composed of magnetic‐directed hydrogel particles with near‐infrared (NIR)‐light‐triggered guest‐release properties, are prepared via the one‐pot method. The gel particles contain photostable NIR‐responsive polypyrrole nanoparticles with temperature‐sensitive poly(N‐isopropyl acrylamide), the combination of which can induce the accelerated release of encapsulated drugs by 337% upon 5 minutes of NIR light irradiation based on the release profile of NRMG‐1 at 10–15 min. Additionally, with magnetic iron oxide particles crosslinking the polyvinyl alcohol frames, these gel particles can form a physical barrier that decreases the release rate by 20% under an external magnetic field over 24 h. The magnetic iron oxide particles also enable the gel particles to reach their target destination without extra drug losses.

60 APPLIED LIFE SCIENCES↗

Selective Recovery of Critical Minerals from Simulated Electronic Wastes Via Reaction‐Diffusion Coupling

Abstract Atom‐ and energy‐efficient chemical separations are urgently needed to meet the surging demand for critical materials that has strained supply chains and threatened environmental damage. In this study, we used reaction‐diffusion coupling to separate iron, neodymium, and dysprosium ions from model feedstocks of permanent magnets, which are typically found in electronic wastes. Feedstock solutions were placed in contact with a hydrogel loaded with potassium hydroxide and/or dibutyl phosphate, resulting in complex precipitation patterns as the various metal ions diffused into the reaction medium. Specifically, we observed the precipitation of up to 40 mM of iron from the feedstock, followed by the enrichment of 73 % dysprosium, and the extraction of >95 % neodymium product at a further distance from the solution‐gel interface. We designed a series of experiments and simulations to determine the relevant ion diffusivities, D Nd =5.4×10 −10 and D Dy =5.1×10 −10 m 2 /s, and precipitation rates, k Nd =1.0×10 −5 and k Dy =5.0×10 −3 m 9 mol −3 s −1 , which enabled a numerical model to be established for predicting the distribution of products in the reaction medium. Our proof‐of‐concept study validates reaction‐diffusion coupling as an effective and versatile approach for critical materials separations, without relying on ligands, membranes, resins, or other specialty chemicals.

Wang, Qingpu [Physical and Computational Sciences ↗

Rheology of lignin and lignin-based solutions, dispersions, gels, polymer blends, and melts

Lignin is an abundant resource that finds application in energy and sustainable materials development. In addition to the utilization of lignin in three-dimensional (3D) printing and hydrogel production, recent studies have reported the use of lignin as a liquid fuel additive. The characterization of the rheological properties of lignin and its derivatives is a dynamic and evolving field, underpinned by advances in experimental, analytical, and modeling techniques. Here, this review provides a comprehensive overview of the recent progress in the study of lignin rheology, highlighting the interplay between structure, modification, and flow behavior in lignin-based solutions, dispersions, gels, polymer blends, and melts. A specific highlight of this review is how lignin concentration affects the rheological properties of lignin-based solutions and dispersions. Furthermore, the effect of lignin type on the properties of 3D-printed lignin-based composites is discussed. For polymer systems, this review discussed lignin-in-polymer solutions separately from lignin-filled polymer systems. Finally, challenges and perspectives on lignin rheology are presented.

Dispersions↗

Conducting polymer-based electrochemical sensors: Progress, challenges, and future perspectives

Conducting polymers are promising due to their unique properties, such as excellent electrical and optical properties, physical and chemical stability, high conductivity, and effective redox properties with high-temperature stability and biocompatibility. Due to these properties, conducting polymers are useful in diverse applications like sensors, batteries, oil industries, biosensors, biomedicines, catalysis, cancer treatment, etc. This review article aims to discuss the recent trends and analysis of conducting polymer-based electrochemical sensors in diverse areas with all required sensor characteristics, such as the derived limit of detection, utilized techniques for the sensing analysis and derived linear dynamic range with the stability of the sensors. Conducting polymers and their nanocomposites-based electrochemical sensors have demonstrated exceptional capabilities towards detecting various biomolecules, heavy metals, pesticides, and viruses like SARS-COV-2. Incorporation of redox mediators, use of conducting hydrogels, and molecular imprinting are promising strategies for better performance of the derived sensor. The article has demonstrated the existing challenges and limitations and provided solutions in the field. In the future, conducting polymers-based electrochemical sensors can be utilized in wearable sensors and integrated with IoT devices for better reach in real-time applications. They can also be made more accessible with precise control and data output by following specific methodologies. Utilizing green and sustainable conducting polymers can be crucial in advancing eco-friendly practices in the future. Conducting polymer-based electrochemical sensors has affectivity in neurochemical and pathogen sensing, which is essential for brain function and mental health.

42 ENGINEERING↗

Dynamical Ion Correlations in Polymer and Membrane Electrolytes: Recent Advances and Open Questions

Ion transport in polymer and membrane electrolytes is often described using uncorrelated models like the Nernst–Einstein (NE) approximation, which link conductivity, transference number, and salt diffusivity to individual ion mobilities. However, growing evidence shows that dynamical ion correlations─arising from ion pairing, polymer-mediated coupling, confinement, and electrostatic interactions─can substantially alter macroscopic transport properties. The Onsager transport formalism offers a rigorous framework to quantify these effects via cross-correlated ionic displacements. This Perspective highlights how such correlations manifest across dry and hydrated systems, including salt-doped polymers, block copolymers, hydrogels, and ion-exchange membranes. Here, we examine key physical origins, the influence of salt chemistry and polymer structure, and open questions in measuring and controlling correlated motion. Embracing correlation-aware design enables new pathways to optimize conductivity, transference number, and selectivity─shifting the focus from individual ion mobility to engineered collective dynamics for next-generation electrolytes in energy storage and separations.

Charge transport↗

Surfactant-like peptide gels are based on cross-β amyloid fibrils

Surfactant-like peptides, in which hydrophilic and hydrophobic residues are encoded within different domains in the peptide sequence, undergo facile self-assembly in aqueous solution to form supramolecular hydrogels. These peptides have been explored extensively as substrates for the creation of functional materials since a wide variety of amphipathic sequences can be prepared from commonly available amino acid precursors. The self-assembly behavior of surfactant-like peptides has been compared to that observed for small molecule amphiphiles in which nanoscale phase separation of the hydrophobic domains drives the self-assembly of supramolecular structures. Here, we investigate the relationship between sequence and supramolecular structure for a pair of bola-amphiphilic peptides, Ac-KLIIIK-NH 2 (L2) and Ac-KIIILK-NH 2 (L5). Despite similar length, composition, and polar sequence pattern, L2 and L5 form morphologically distinct assemblies, nanosheets and nanotubes, respectively. Cryo-EM helical reconstruction was employed to determine the structure of the L5 nanotube at near-atomic resolution. Rather than displaying self-assembly behavior analogous to conventional amphiphiles, the packing arrangement of peptides in the L5 nanotube displayed steric zipper interfaces that resembled those observed in the structures of β-amyloid fibrils. Like amyloids, the supramolecular structures of the L2 and L5 assemblies were sensitive to conservative amino acid substitutions within an otherwise identical amphipathic sequence pattern. This study highlights the need to better understand the relationship between sequence and supramolecular structure to facilitate the development of functional peptide-based materials for biomaterials applications.

Das, Abhinaba [Emory University, Atlanta, GA (Unit↗

Aluminosilicate colloidal gels: from the early age to the precipitation of zeolites

Aluminosilicate hydrogels are often considered to be precursors for the crystallisation of zeolites carried out under hydrothermal conditions. The preparation of mechanically homogeneous aluminosilicate gels enables the study of these materials through bulk rheology and observation of the aging dynamics until the precipitation of crystalline zeolites. The first part of this study deals with the establishment of ternary state diagrams, in order to identify the range of chemical formulations that enable preparation of single-phase homogeneous gels. Then, by studying the viscoelastic moduli during the gelation reaction, and by yielding the gel under large deformation, we propose an empirical law considering the partial order of reaction on each chemical element, to predict the gelation time according to the chemical formulation. The scaling behavior of the elastic properties of this colloidal gel shows a transition from a strong link behavior to a weak link regime. Long term aging results in the shrinkage of the gel, accompanied by syneresis of interstitial liquid at the surface. Zeolites precipitate through crystallisation by a particle attachment mechanism, when thermodynamic equilibrium is reached. The stoichiometry of the precipitated zeolites is not only consistent with the concentration of the remaining species in the supernatant but, surprisingly, it is also very close to the partial order of the reaction of the chemical elements involved in the determination of the critical gel point. This indicates a strong correlation between the morphology of the soft amorphous gel network that is formed at an early age and those of the final solid precipitated crystals.

36 MATERIALS SCIENCE↗

Strategies for fabricating aligned nano- and microfiber scaffolds: an overview for cell culture applications

The rapidly growing demand for cell manufacturing and in vitro tissue fabrication has led to the development of various technologies for biomimetic artificial extracellular matrix (ECM), including three major materials: hydrogels, fibrous scaffolds, and decellularized tissues. The latter two materials are closer to the biomimetic goal of replicating natural ECM. The scalability of the scaffolds made of decellularized tissues is limited. The development of 3D fibrous ECM is at the initial stage owing to the recent advantages of novel nanofiber spinning technologies. These novel technologies brought about simultaneous control over a range of critical characteristics, such as fiber diameter, length, material, draw ratio, spacing, and alignment into well-controlled 3D constructs. There is still a long way to go in designing 3D fibrous scaffolds based on cell response studies. The primary objective of this review is to provide an analysis of the recent progress in novel nano- and microfiber spinning methods and uncover their potential for precise fiber alignment into 3D structures.

Peranidze, Kristina [University of Georgia, Athens↗