Search NASA⌕ Search
Home/Archive/DOE OSTI

DOE OSTI · 3362665

Self‐Limiting Polymerization‐Induced Crystallization‐Driven Self‐Assembly (SL‐PI‐CDSA) Enables Templated Synthesis of Chiral Plasmonic, Hybrid 2D Hexagonal Assemblies

Scanga, Randall A. [Univ. of Massachusetts, Lowell, MA (United States)]·Sarault, Sean H. [Univ. of Massachusetts, Lowell, MA (United States)]·Kiani, Amin [Univ. of Massachusetts, Lowell, MA (United States)]·Wąsik, Patryk [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)] (ORCID:0000000274477472)·Branco, Anthony J. [Univ. of Massachusetts, Lowell, MA (United States)]·Harris, Sophie A. [Univ. of Massachusetts, Lowell, MA (United States)]·Jeong, Sangmin [Univ. of Massachusetts, Lowell, MA (United States)]·Shahrokhinia, Ali [Univ. of Massachusetts, Lowell, MA (United States); BASF Corporation, Wyandotte, MI (United States)]·Borges, Jake [Univ. of Massachusetts, Lowell, MA (United States); Auburn Univ., AL (United States)]·Anunciacao, Cassidy M. [Univ. of Massachusetts, Lowell, MA (United States)]·Kumar, Jayant [Univ. of Massachusetts, Lowell, MA (United States)]·Wolf, Lawrence M. [Univ. of Massachusetts, Lowell, MA (United States)]·Ross, Michael B. [Univ. of Massachusetts, Lowell, MA (United States)] (ORCID:0000000225110594)·Reuther, James F. [Univ. of Massachusetts, Lowell, MA (United States)] (ORCID:0000000156110290)
View original source ↗Read source document ↗Export metadata ↓

Abstract

Examples of self-regulating synthetic self-assembly are relatively few, with most known chemical systems relying on kinetic rather than thermodynamic control. Herein, we demonstrate the rapid generation (t ≤ 5 min) of size-tunable ultralow dispersity (Ð ≤ 1.01) 2D hexagonal nanosheets governed by self-limiting self-assembly (SLSA). Self-assembly in natural systems occurs with exquisite control of structure, function, and dimension. We demonstrate that key aspects of biological assembly can be rationally applied toward the development of bottom-up approaches for the construction of chiral nanomaterials. To this end, self-limiting polymerization-induced crystallization-driven self-assembly (SL-PI-CDSA) of modular and templating aryl isocyanide (AIC) monomers yields functional 2D assemblies permitting post-polymerization/assembly modifications. Detailed study of the internal and external structure of the hexagonal nanosheets reveals topological defects which offer mechanistic insights into both their assembly and subsequent utilization. Specifically, these features enable fabrication of chiral hybrid organic–inorganic nanomaterials incorporating chiral plasmonic metal nanoparticles (MNPs). Our results suggest that the synergistic interplay of template-driven confinement and hierarchical chirality induce symmetry breaking of in situ-generated gold MNPs. We anticipate that the platform presented will facilitate fabrication of new hybrid, chiral organic–inorganic nanostructures.

Explore related subjects

36 MATERIALS SCIENCE

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Scanga, Randall A. [Univ. of Massachusetts, Lowell, MA (United States)], Sarault, Sean H. [Univ. of Massachusetts, Lowell, MA (United States)], Kiani, Amin [Univ. of Massachusetts, Lowell, MA (United States)], Wąsik, Patryk [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)] (ORCID:0000000274477472), Branco, Anthony J. [Univ. of Massachusetts, Lowell, MA (United States)], Harris, Sophie A. [Univ. of Massachusetts, Lowell, MA (United States)], Jeong, Sangmin [Univ. of Massachusetts, Lowell, MA (United States)], Shahrokhinia, Ali [Univ. of Massachusetts, Lowell, MA (United States); BASF Corporation, Wyandotte, MI (United States)], Borges, Jake [Univ. of Massachusetts, Lowell, MA (United States); Auburn Univ., AL (United States)], Anunciacao, Cassidy M. [Univ. of Massachusetts, Lowell, MA (United States)], Kumar, Jayant [Univ. of Massachusetts, Lowell, MA (United States)], Wolf, Lawrence M. [Univ. of Massachusetts, Lowell, MA (United States)], Ross, Michael B. [Univ. of Massachusetts, Lowell, MA (United States)] (ORCID:0000000225110594), Reuther, James F. [Univ. of Massachusetts, Lowell, MA (United States)] (ORCID:0000000156110290). 2026-04-16. Self‐Limiting Polymerization‐Induced Crystallization‐Driven Self‐Assembly (SL‐PI‐CDSA) Enables Templated Synthesis of Chiral Plasmonic, Hybrid 2D Hexagonal Assemblies. https://doi.org/10.1002/anie.7896560

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related reports

DOE OSTI2026

Cyclic moisture reactivation of calcium sorbents for long duration thermochemical energy storage

The transition to a flexible and reliable energy infrastructure, using electro-thermal energy generation technologies such as geothermal, concentrated solar power, and nuclear, usually demands simultaneous advancement of thermal energy storage (TES) to support on-demand electricity generation and industrial applications while mitigating the inherent intermittency of renewable energy sources and power outages from direct energy generation. Among TES technologies, thermochemical energy storage (TCES) based on calcium looping emerges as a compelling high-power energy storage candidate due to its high reaction enthalpy, compatibility with elevated operating temperatures, and abundance of low-cost materials. However, the long-term durability of calcium-based sorbents for TCES is hindered by surface sintering and particle aggregation, leading to performance degradation over repeated thermal cycles. This study explores a moisture hydration-based strategy to regenerate a degraded calcium sorbent and mitigate performance degradation for long duration TCES. The addition of moisture transforms calcium oxide into calcium hydroxide and produces intercalation water layers, associated with a regenerated surface area and reduced calcium oxide crystallite size. Both these effects are beneficial in restoring the sorbents' reactivity for carbonization. Additionally, an optimized hydration-assisted reactivation protocol balances the recovered energy storage capacity with heating penalty required for moisture removal from hydrated samples, resulting in an enhanced energy storage capacity up to 176% compared to benchmark sorbents that undergo cycling without reactivation after 60 cycles. In conclusion, these results highlight the potential of hydration-assisted reactivation to enhance the long-term performance of TCES, providing an effective pathway to advancing electro-thermal storage technologies.

36 MATERIALS SCIENCE↗