SEARCH · Search NASA

Results for “Hierarchical Materials”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 289 records · Page 16

All sources NASA NTRS DOE OSTI

DOE OSTI2026

Direct Air Capture Using Trapped Small Amines in Hierarchical Nanoporous Capsules on Porous Electrospun Fibers (Final Technical Report)

This report summarizes the carbon capture research and development conducted by The State University of New York at Buffalo (UB) and GTI Energy (GTI) for award “DE-FE0031969: Direct Air Capture Using Trapped Small Amines in Hierarchical Nanoporous Capsules on Porous Electrospun Fibers” sponsored by the U.S. Department of Energy (DOE). The objective of this project is to develop an innovative sorbent structure of trapped small amines in HNC embedded in PEF for DAC. This involves tailoring both sorbent and PEF materials to achieve a compact system for DAC with high capacity for CO 2 at concentrations typically available in air and at near ambient conditions. An innovative sorbent structure of trapped small amines in hierarchical nanoporous capsules (HNC) embedded in porous electrospun fibers (PEF) was developed for direct air capture (DAC). This involves tailoring both sorbent and PEF materials to achieve a compact system for DAC with high capacity for CO 2 at concentrations typically available in air and at near ambient conditions. An interfacial polymerization process was developed, which utilized loaded amines inside mesoporous silica and trimesoyl chloride (TMC) dissolved in organic solvents as the precursors, to generate a polyamide (PA) coating layer on mesoporous silica and thus trap amines. Reaction conditions, including TMC concentration, organic solvents, reaction time, etc., for interfacial polymerization were optimized to effectively trap loaded amines, and cyclic heating-cooling operation was conducted to evaluate the coating quality. Larger pore volume mesoporous silica was also synthesized to increase amine loading and thus increase CO 2 capacity. The optimized sorbent material exhibited CO 2 capacity as high as 4.88 mmol/g under humid DAC conditions and negligible loss (<1%) during 10 cyclic heating-cooling operations. The optimized PA-coated sorbent also showed fast adsorption and desorption kinetics, with <20% t1/2 increase compared to uncoated sorbent. PEF fabrication conditions, including organic solvents for dissolving core and shell polymers, voltage, distance from the nozzle to the collection panel, etc. were adjusted to better incorporate HNC. After incorporating the optimized sorbent material into PEF, the structured sorbent had a CO 2 capacity of approximately 4.0 mmol/g under humid DAC conditions, with capacity loss of 0.17% per cycle and t1/2 increase less than 10%. A techno-economic analysis (TEA) for the process design for a DAC system based on our developed sorbent structure of trapped small amines in HNC embedded in PEF was conducted. The process design included process description and major equipment sizing and energy and mass balances in addition to scale-up research results and estimated capture cost. Aspen Adsorption Simulator was used to fit the experimentally measured breakthrough curves and extract equilibrium and kinetic data of the optimized sorbent. Our results indicated that for a DAC plant with CO 2 productivity of 3,000 tonne/year, the levelized cost of CO 2 capture was $\$$612/tonne, with the largest contribution of 44.33% from the fixed operation cost. Increasing CO 2 productivity, while maintaining similar fixed operation cost, is expected to significantly reduce the CO 2 capture cost. A sensitivity study was also conducted to understand the influence of total plant cost, sorbent cost, CO 2 concentration in the feed, sorbent mat lifetime, sorbent regeneration electricity, and adsorption blower pressure drop on the levelized cost of CO 2 capture, revealing a capture cost range of $\$$520-870/tonne.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Efficient Hierarchical State Vector Simulation of Quantum Circuits via Acyclic Graph Partitioning

Early but promising results in quantum computing have been enabled by the concurrent development of quantum algorithms, devices, and materials. Classical simulation of quantum programs has enabled the design and analysis of algorithms and implementation strategies targeting current and anticipated quantum device architectures. In this paper, we present a graph-based approach to achieve efficient quantum circuit simulation. Our approach involves partitioning the graph representation of a given quantum circuit into sub-graphs/circuits that exhibit better data locality. Simulation of each sub-circuit is organized hierarchically, with the iterative construction and simulation of smaller state vectors, improving overall performance. Also, this partitioning reduces the number of passes through data, improving the total computation time. We present three partitioning strategies and observe that acyclic graph partitioning typically results in the best time-to-solution. In contrast, other strategies reduce the partitioning time at the expense of potentially increased simulation times. Experimental evaluation demonstrates the effectiveness of our approach.

Fang, Bo↗

DOE OSTI2021

Liquid-free covalent reinforcement of carbon nanotube dry-spun yarns and free-standing sheets

Carbon nanotubes (CNTs) possess exceptional mechanical properties, surpassing stiffness and strength metrics of common materials such as steel alloys by 100× at the nanoscale. However, when myriads of individual CNTs are bundled together into macroscopic ensembles like fibers or sheets, the result is a 100-fold drop in strength compared to its individual components. Here we present a general strategy aimed to close this gap in property scaling. By using vapor-phase polymerization of a crosslinkable polymer, we reinforced the weak interlinkages among individual CNTs within both yarns and sheets to promote a better transference of mechanical load across the structure. Furthermore, after the treatment, dry-spun, low-density 2.3 μm thin yarns increased their elastic moduli by at least 300%, and free-standing CNT sheets exhibited a 10× boost. In-situ synchrotron small-angle X-ray scattering revealed that polymer-reinforced yarns undergo limited CNT bundle rearrangement when subjected to tensile loads compared to pristine yarns. This evidence supports the hypothesis that the polymer hinders CNTs slippage, the root cause of the poor scaling of mechanical properties in these materials. While we demonstrated this reinforcement method for CNT structures, it is not specific to CNTs and could be used in a wide variety of other hierarchical nanostructured ensembles.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Ultrathin Microporous Transport Layers: Implications for Low Catalyst Loadings, Thin Membranes, and High Current Density Operation for Proton Exchange Membrane Electrolysis

Porous transport layers (PTL) and their surface properties have the potential to improve the performance of proton exchange membrane water electrolyzers (PEMWE), which is imperative to reduce feedstock costs and lead to their widespread implementation. This work introduces a novel generation of titanium microporous layers (MPLs) with ultra-low thicknesses of approx. 20 um which reduces raw material costs. They also feature advanced interfacial properties tailored to maximize catalyst utilization at low Ir-loadings. The bulk morphology and surface properties of the hierarchically structured PTLs are assessed by X-ray tomographic microscopy. The low surface roughness of the MPL allows the use of thinner membranes since it minimizes possible deformations in the membrane. Cells containing the MPLs outperformed those containing state-of-the-art commercially available PTL materials by up to 100 mV at 7 A cm-2 in combination with low-loaded catalyst-coated membranes of 0.4 mgIr cm-2. Hydrogen crossover is also reduced, especially at low current densities, leading to a larger turndown ratio which can enable more cost-effective operating strategies. Finally, these rationally designed MPLs also lead to high catalyst utilization by overcoming the naturally occurring high in-plane resistance of low-loaded catalyst layers.

hydrogen crossover↗

DOE OSTI2025

Dry electrodes with a printed cellulose–graphene ink for low-profile strain sensors in electromyography

Dihydrolevoglucosenone, commonly known as Cyrene, is a renewable and fully biodegradable cellulose-waste derived, environmentally friendly solvent, presenting a non-toxic alternative to N-methyl-2-pyrrolidone (NMP). Currently, solution-based processing of graphene and other similar van der Waals solids favor toxic solvents such as NMP, limiting their use for biosensing. However, with the use of Cyrene, bio-compatible printable devices are possible, and studies have already demonstrated its use in temperature and other biosensing methods through screen-printing. Screen-printing unfortunately often requires masks that constrain the minimum acquirable feature size to be above hundreds of centimeters and wastes material, adding to process complexity and cost. Conversely, inkjet-printing is an attractive alternative for the maskless patterning of hierarchically assembled structures, with micron length scales attainable. Graphene's high conductivity positions it ideally for long-wear sensors such as dry electrodes or respiration monitors. Here, we demonstrate the potential of Cyrene-based graphene inks through few-layer inkjet printing on flexible substrates for the first time, to produce non-toxic conductors toward a strain-mediated mechanism for biosensing, used to detect bodily motion for wearable electronics. The challenges overcome in this study include engineering ink chemistry and printing parameters such that Cyrene's relatively high viscosity compared to typical inkjet solvents, still allows for droplet ejection in a conventional material printer, yielding well-resolved clean line-edges in contrast to other solvents that exhibit diffuse line-edges possibly from stray droplets and ink-splashing. Temperature-dependent transport measurements on the inkjet-printed Cyrene-based graphene films showed the conductivity to be largely temperature-invariant but at lower temperatures below 100 K, conductivity decreased, likely as a result of increased inter-membrane separation arising from thermal contraction. Additionally, temperature-dependent Raman spectroscopy showed the red-shift in the G-band, 2D-band and D-band peaks, as temperature increased. As a result, by validating flexion motion detection of the proximal interphalangeal joint demonstrated in this study, our work is the first of its kind to successfully additively manufacture inkjet-printed Cyrene-based graphene strain sensors on flexible substrates for bio-sensing and wearables.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2004

Predicting the Influence of Nano-Scale Material Structure on the In-Plane Buckling of Orthotropic Plates

A multi-scale analysis of the structural stability of a carbon nanotube-polymer composite material is developed. The influence of intrinsic molecular structure, such as nanotube length, volume fraction, orientation and chemical functionalization, is investigated by assessing the relative change in critical, in-plane buckling loads. The analysis method relies on elastic properties predicted using the hierarchical, constitutive equations developed from the equivalent-continuum modeling technique applied to the buckling analysis of an orthotropic plate. The results indicate that for the specific composite materials considered in this study, a composite with randomly orientated carbon nanotubes consistently provides the highest values of critical buckling load and that for low volume fraction composites, the non-functionalized nanotube material provides an increase in critical buckling stability with respect to the functionalized system.

Gates, Thomas S.↗

NASA NTRS2012

The Pursuit of K: Reflections on the Current State-of-the-Art in Stress Intensity Factor Solutions for Practical Aerospace Applications

The elastic stress intensity factor (SIF, commonly denoted as K) is the foundation of practical fracture mechanics (FM) analysis for aircraft structures. This single parameter describes the first-order effects of stress magnitude and distribution as well as the geometry of both structure/component and crack. Hence, the calculation of K is often the most significant step in fatigue analysis based on FM. This presentation will provide several reflections on the current state-of-the-art in SIF solution methods used for practical aerospace applications, including a brief historical perspective, descriptions of some recent and ongoing advances, and comments on some remaining challenges. Newman and Raju made significant early contributions to practical structural analysis by developing closed-form SIF equations for surface and corner cracks in simplified geometries, often based on empirical fits of finite element (FE) solutions. Those solutions (and others like them) were sometimes revised as new analyses were conducted or limitations discovered. The foundational solutions have exhibited striking longevity, despite the relatively "coarse" FE models employed many decades ago. However, in recent years, the accumulation of different generations of solutions for the same nominal geometry has led to some confusion (which solution is correct?), and steady increases in computational capabilities have facilitated the discovery of inaccuracies in some (not all!) of the legacy solutions. Some examples of problems and solutions are presented and discussed, including the challenge of maintaining consistency with legacy design applications. As computational power has increased, the prospect of calculating large numbers of SIF solutions for specific complex geometries with advanced numerical methods has grown more attractive. Fawaz and Andersson, for example, have been generating literally millions of new SIF solutions for different combinations of multiple cracks under simplified loading schemes using p-version FE methods. These data are invaluable, but questions remain about their practical use, because the tabular databases of key results needed to support practical life analysis can occupy gigabytes of storage for only a few classes of geometries. The prospect of using such advanced numerical methods to calculate in real time only those K solutions actually needed to support a specific crack growth analysis is also tempting, but the stark reality is that the computational cost is still so high that the approach is not practical except for specific, critical application problems. Some thoughts are offered about alternative paradigms. Compounding approaches are some of the earliest building blocks of SIF development for more complex geometries. These approaches are especially attractive because of their very low computational cost and their conceptual robustness; they are, in some ways, an intriguing contrast and complement to the brute-force numerical methods. In recent years, researchers at NRC-Canada have published remarkable results showing how compounding approaches can be used to generate accurate solutions for very difficult problems. Examples are provided of some successes--and some limitations--using this approach. These closed-form, tabulated numerical, and compounding approaches have typically been used for simple remote loading with simple load paths to the crack. However, many significant cracks occur in complex stress gradient fields. This is a job for weight function (WF) methods, where the arbitrary stress distribution on the crack plane in the corresponding uncracked body (typically determined using FE methods) is used to determine K. Several significant recent advances in WF methods and solutions are highlighted here. Fueled by advanced 3D numerical methods, many new solutions have been generated for classic geometries such as surface and corner cracks with wide ranges of geometrical validity. A new WF formulation has also be developed for part-through cracks considering the arbitrary stress gradients in all directions in the crack plane (so-called bivariant solutions). Basic WF methods have recently been combined with analytical expressions for crack plane stresses to develop a large family of accurate SIF solutions for corner, surface, and through cracks at internal or external notches with very wide ranges of shapes, sizes, acuities, and offsets. Finally, WF solutions are much faster than FE or boundary element solutions, but can still be much slower than simple closed-form solutions, especially for bivariant solutions that can require 2D numerical integration. Novel pre-integration and dynamic tabular methods have been developed that substantially increase the speed of these advanced WF solutions. The practical utility of advanced SIF methods, including both WF and direct numerical methods, is greatly enhanced if the FM life analysis can be directly and efficiently linked with digital models of the actual structure or component (e.g., FE models for stress analysis). Two recent advances of this type will be described. One approach directly interfaces the FM life analysis with the FE model of the uncracked component (including stress results). Through a powerful graphical user interface, simplified FM life models can be constructed (and visualized) directly on the component model, with the computer collecting the geometry and stress gradient information needed for the life calculation. An even more powerful paradigm uses expert logic to automatically build an optimum simple fracture model at any and every desired location in the component model, perform the life calculation, and even generate fatigue crack growth life contour maps, all with minimal user intervention. This paradigm has also been extended to the automatic calculation of fracture risk, considering uncertainty or variability in key input parameters such as initial crack size or location. Another new integrated approach links the engineering life analysis, the component model, and a 3D numerical fracture analysis built with the same component model to generate a table of SIF values at a specific location that can then be employed efficiently to perform the life calculation. Some attention must be given to verification and validation (V&V) issues and challenges: how good are these SIF solutions, how good is good enough, and does anyone believe the life answer? It is important to think critically about the different sources of error or uncertainty and to perform V&V in a hierarchal, building-block manner. Some accuracy issues for SIF solutions, for example, may actually involve independent material behavior issues, such as constraint loss effects for crack fronts near component surfaces, and can be a source of confusion. Recommendations are proposed for improved V&V approaches. This presentation will briefly but critically survey the range of issues and advances mentioned above, with a particular view towards assembling an integrated approach that combines different methods to create practical tools for real-world design and analysis problems. Examples will be selectively drawn from the recent literature, from recent enhancements in the NASGRO and DARWIN computer codes, and from previously unpublished research

CraigMcClung, R.↗

DOE OSTI2020

Perspectives on three-dimensional printing of self-assembling materials and structures

Spiders, silks, and webs are marvels of nature that have inspired high-performance material design, resilient structural design, and innovative manufacturing in the materials science and engineering fields. In this article, we review the roles and mechanisms of self-assembly and spinning processes for making hierarchical structures of synthetic and natural fibers with multifunctionality. We discuss the ability of spider webs to maintain their functionality under construction while withstanding predator, human, and environmental threats, which comes from their self-assembled structures from nanoscales to macroscales. We conclude by exploring the future of novel mobile, autonomous, time- and cost-effective spider-inspired three-dimensional printing technology for making resilient biomaterials, structures, and synthetic silk materials.

42 ENGINEERING↗

DOE OSTI2022

Developing ductile and isotropic Ti alloy with tailored composition for laser powder bed fusion

Laser powder bed fusion (LPBF) is an advanced technology to create metallic components with complex geometry. Ti-6Al-4V (Ti64) is one of the most frequently used materials for LPBF. The intrinsic high cooling rates and ultra-high directional thermal gradient of melt, however, lead to a hierarchical structure composed of fine martensitic alpha' within columnar prior-beta grains in LPBF Ti64. This microstructure results in poor ductility and strong mechanical anisotropy in as-built Ti64 components, which largely limit their applications. Here, we report that the above shortcomings can be overcome by tailoring the alloy composition. Specifically, by reducing the aluminum content from 6 wt% to 4 wt%, the resultant LPBF Ti-4Al-4V (Ti44) alloy exhibits substantially improved ductility and mechanical isotropy. These improvements are attributed to grain refinement during solidification and the activation of multiple slip modes and twinning in the as-built material during deformation. This work offers a simple strategy to design new titanium alloys for LPBF with significantly improved ductility and isotropy.

36 MATERIALS SCIENCE↗

NASA NTRS2015

Mechanical Properties of Graphene Nanoplatelet/Carbon Fiber/Epoxy Hybrid Composites: Multiscale Modeling and Experiments

Because of the relatively high specific mechanical properties of carbon fiber/epoxy composite materials, they are often used as structural components in aerospace applications. Graphene nanoplatelets (GNPs) can be added to the epoxy matrix to improve the overall mechanical properties of the composite. The resulting GNP/carbon fiber/epoxy hybrid composites have been studied using multiscale modeling to determine the influence of GNP volume fraction, epoxy crosslink density, and GNP dispersion on the mechanical performance. The hierarchical multiscale modeling approach developed herein includes Molecular Dynamics (MD) and micromechanical modeling, and it is validated with experimental testing of the same hybrid composite material system. The results indicate that the multiscale modeling approach is accurate and provides physical insight into the composite mechanical behavior. Also, the results quantify the substantial impact of GNP volume fraction and dispersion on the transverse mechanical properties of the hybrid composite, while the effect on the axial properties is shown to be insignificant.

molecular dynamics↗

NASA NTRS2015

Mechanical Properties of Graphene Nanoplatelet Carbon Fiber Epoxy Hybrid Composites: Multiscale Modeling and Experiments

computational mechanics↗

NASA NTRS2015

Mechanical Properties of Graphene Nanoplatelet/Carbon Fiber/Epoxy Hybrid Composites: Multiscale Modeling and Experiments

Because of the relatively high specific mechanical properties of carbon fiber/epoxy composite materials, they are often used as structural components in aerospace applications. Graphene nanoplatelets (GNPs) can be added to the epoxy matrix to improve the overall mechanical properties of the composite. The resulting GNP/carbon fiber/epoxy hybrid composites have been studied using multiscale modeling to determine the influence of GNP volume fraction, epoxy crosslink density, and GNP dispersion on the mechanical performance. The hierarchical multiscale modeling approach developed herein includes Molecular Dynamics (MD) and micromechanical modeling, and it is validated with experimental testing of the same hybrid composite material system. The results indicate that the multiscale modeling approach is accurate and provides physical insight into the composite mechanical behavior. Also, the results quantify the substantial impact of GNP volume fraction and dispersion on the transverse mechanical properties of the hybrid composite while the effect on the axial properties is shown to be insignificant.

nanocomposites↗

DOE OSTI2025

Tailoring multi-dimensional hierarchical self-assembly of metallacages through balancing non-covalent interactions

Despite advances in non-covalent interactions and complex self-assembly, precise control of multi-dimensional hierarchical self-assembly (HSA) from the molecular level to larger scales remains challenging. Herein, we designed and synthesized two rigid tetratopic ligands with multiple preset driving forces, and assembled them with Zn(II) ions to obtain metallacages SC6 and SC12 . Through balancing multiple non-covalent interactions, including metal–organic coordination, hydrophobic, and π–π interactions, SC6 can hierarchically self-assemble driven by a poor solvent, from one-dimensional nanowires to super-helical nanostructures via non-equilibrium self-assembly, progressing continuously with time and the increasing proportion of the poor solvent. However, for SC12 with enhanced hydrophobic interactions, two-dimensional monolayer nanogrids were formed by hierarchical self-assembly. Notably, these structures can be recycled back to primary metallacages through simple dissolution, highlighting their potential for efficient recycling and reuse. These results demonstrate that multi-dimensional hierarchical structures enable precise construction by balancing non-covalent interactions through a bottom-up self-assembly approach. This study provides deeper insight into the mechanisms of HSA and a promising strategy for the tailored creation of complex structures and sustainable porous materials.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Hierarchical 3D Printed Porous Silicones with Porosity Derived from Printed Architecture and Silicone-Shell Microballoons

A method is reported to prepare siloxane microballoons that can be loaded into a direct ink write siloxane ink for 3D printing. The resulting structure is subjected to a solvent removal and supercritical drying process to provide a final printed siloxane having both macroscopic and microscopic porosity. Core-shell particles are generated by an emulsion template and phase separation process. Intra-strand closed-cell porosities can be achieved between 10 and 40 vol% thus facilitating additional compressive strain before lockup. Here short term compression set testing highlights the excellent shape retention properties of these elastomers, which have less than 8% relative compression set under load.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Design of materials with supramolecular polymers

One hundred years ago Hermann Staudinger was strongly criticized by his scientific peers for his macromolecular hypothesis, but today it is hard to imagine a world without polymers. His hypothesis described polymers as macromolecules composed of large numbers of structural units connected by covalent bonds. In the 1990s the concept of supramolecular polymers emerged in the scientific literature as discrete entities of large molar mass comparable to that of classical polymers but built through non-covalent bonds among monomers. Supramolecular polymers exist in biological systems, and potentially blend the physical properties of covalent polymers with unique features such as high degrees of internal order within the polymeric structure, defined shapes, and novel dynamics. This trend article provides a summary of seminal contributions in supramolecular polymerization and provides recent examples from the Stupp laboratory to demonstrate the potential applications of an exciting class of materials composed fully or partially of supramolecular polymers. Finally, in closing, we provide our perspective on future opportunities provided by this field at the onset of a second century of polymers. It is our objective here to demonstrate that this second century could be as prosperous, if not more so, than the preceding one.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Pushing and Pulling: A Dual pH Trigger Controlled by Varying the Alkyl Tail Length in Heme Coordinating Peptide Amphiphiles

Some organisms in nature that undergo anaerobic respiration utilize 1D nanoscale arrays of densely packed cytochromes containing the molecule heme. The assemblies can be mimicked with 1D nanoscale fibrils composed of peptide amphiphiles designed to coordinate heme in dense arrays. To create such materials and assemblies it is critical to understand the assembly process and what controls the various aspects of hierarchical assembly. MD simulations suggest that shorter alkyl chains on the peptide lead to more dynamic structures than the peptides with longer chains that yield kinetically trapped states. The hydration parameters manifest themselves experimentally through the observation of a dual pH trigger which controls the peptide assembly rate, the heme binding affinity, and heme organization kinetics. Great strides in understanding the relative complexity of the self-assembly process in relation to incorporating a functional moiety like heme opens up many possibilities in developing abiotic assemblies for bioelectronic devices and assemblies

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Assembly of Building Blocks by Double-End-Anchored Polymers in the Dilute Regime Mediated by Hydrophobic Interactions at Controlled Distances

Hierarchical assembly of building blocks via competing, orthogonal interactions is a hallmark of many of nature’s composite materials that do not require highly specific ligand-receptor interactions. To mimic this assembly mechanism requires the development of building blocks capable of tunable interactions. In the present work, we explored the interplay between repulsive (steric and electrostatic) and attractive hydrophobic forces. The designed building blocks allow hydrophobic forces to effectively act at controlled, large distances, to create and tune the assembly of membrane-based building blocks under dilute conditions and affect their interactions with cellular membranes via physical cross-bridges. Specifically, we employed double-end-anchored poly(ethylene glycol)s (DEA-PEGs)—hydrophilic PEG tethers with hydrophobic tails on both ends. Using differential-interference-contrast optical microscopy, synchrotron small angle X-ray scattering (SAXS), and cryogenic electron microscopy, we investigated the ability of DEA-PEGs to mediate assembly in the dilute regime on multiple length scales and on practical time scales. The PEG length, anchor hydrophobicity, and molar fraction of DEA-PEG molecules within a membrane strongly affect the assembly properties. Additional tuning of the intermembrane interactions can be achieved by adding repulsive interactions via PEG-lipids (steric) or cationic lipids to the DEA-PEG-mediated attractions. Further, while the optical and electron microscope imaging methods provided qualitative evidence of the ability of DEA-PEGs to assemble liposomes, the SAXS measurements and quantitative line-shape analysis in dilute preparations demonstrated that the ensemble average of loosely organized liposomal assemblies maintains DEA-PEG concentration-dependent tethering on defined nanometer length scales. For cationic liposome–DNA nanoparticles (CL–DNA NPs), aggregation induced by DEA-PEGs decreased internalization of NPs by cells, but tuning the DEA-PEG-induced attractions by adding repulsive steric interactions via PEG-lipids limited aggregation and increased NP uptake. However, confocal microscopy imaging together with colocalization studies with Rab11 and LysoTracker as markers of intracellular pathways showed that modifying CL–DNA NPs with DEA-PEGs alters their interactions with the plasma and endosomal membranes.

- x-ray scattering↗

DOE OSTI2024

A bioactive supramolecular and covalent polymer scaffold for cartilage repair in a sheep model

Regeneration of hyaline cartilage in human-sized joints remains a clinical challenge, and it is a critical unmet need that would contribute to longer healthspans. Injectable scaffolds for cartilage repair that integrate both bioactivity and sufficiently robust physical properties to withstand joint stresses offer a promising strategy. We report here on a hybrid biomaterial that combines a bioactive peptide amphiphile supramolecular polymer that specifically binds the chondrogenic cytokine transforming growth factor β-1 (TGFβ-1) and crosslinked hyaluronic acid microgels that drive formation of filament bundles, a hierarchical motif common in natural musculoskeletal tissues. The scaffold is an injectable slurry that generates a porous rubbery material when exposed to calcium ions once placed in cartilage defects. The hybrid material was found to support in vitro chondrogenic differentiation of encapsulated stem cells in response to sustained delivery of TGFβ-1. Using a sheep model, we implanted the scaffold in shallow osteochondral defects and found it can remain localized in mechanically active joints. Evaluation of resected joints showed significantly improved repair of hyaline cartilage in osteochondral defects injected with the scaffold relative to defects injected with the growth factor alone, including implantation in the load-bearing femoral condyle. These results demonstrate the potential of the hybrid biomimetic scaffold as a niche to favor cartilage repair in mechanically active joints using a clinically relevant large-animal model.

Science & Technology - Other Topics↗