A Dual‐Kinetic Control Strategy for Designing Nano‐Metamaterials: Novel Class of Metamaterials with Both Characteristic and Whole Sizes of Nanoscale

Abstract

Increasingly intricate in their multilevel multiscale microarchitecture, metamaterials with unique physical properties are challenging the inherent constraints of natural materials. Their applicability in the nanomedicine field still suffers because nanomedicine requires a maximum size of tens to hundreds of nanometers; however, this size scale has not been achieved in metamaterials. Therefore, “nano‐metamaterials,” a novel class of metamaterials, are introduced, which are rationally designed materials with multilevel microarchitectures and both characteristic sizes and whole sizes at the nanoscale, investing in themselves remarkably unique and significantly enhanced material properties as compared with conventional nanomaterials. Microarchitectural regulation through conventional thermodynamic strategy is limited since the thermodynamic process relies on the frequency‐dependent effective temperature, Teff(ω), which limits the architectural regulation freedom degree. Here, a novel dual‐kinetic control strategy is designed to fabricate nano‐metamaterials by freezing a high‐free energy state in a Teff(ω)‐constant system, where two independent dynamic processes, non‐solvent induced block copolymer (BCP) self‐assembly and osmotically driven self‐emulsification, are regulated simultaneously. Fe3+‐“onion‐like core@porous corona” (Fe3+‐OCPCs) nanoparticles (the products) have not only architectural complexity, porous corona and an onion‐like core but also compositional complexity, Fe3+ chelating BCP assemblies. Furthermore, by using Fe3+‐OCPCs as a model material, a microstructure‐biological performance relationship is manifested in nano‐metamaterials.

Nano‐Metamaterial: A State‐of‐the‐Art Material for Magnetic Resonance Imaging

“…[ 51 ] However, the thermodynamic process only depends on the T eff ( ω ), which limits the freedom degrees of architectural regulation. [ 52 ] In contrast, the time‐dependent dynamic pathway owns multiple variable parameters, providing opportunities for creating various nonequilibrium structures under a T eff ( ω )‐constant system. [ 53 ] Accordingly, Ling, Wang, and co‐workers [ 52 ] proposed a pioneering dual‐kinetic control strategy to fabricate multilevel multiscale nano‐metamaterials by manipulating dynamic processes in a thermodynamically constant system, where the two independent kinetic pathways, nonsolvent‐induced block copolymer (BCP) self‐assembly and osmotically driven self‐emulsification could be simultaneously regulated ( Figure a).…”

“…[ 52 ] In contrast, the time‐dependent dynamic pathway owns multiple variable parameters, providing opportunities for creating various nonequilibrium structures under a T eff ( ω )‐constant system. [ 53 ] Accordingly, Ling, Wang, and co‐workers [ 52 ] proposed a pioneering dual‐kinetic control strategy to fabricate multilevel multiscale nano‐metamaterials by manipulating dynamic processes in a thermodynamically constant system, where the two independent kinetic pathways, nonsolvent‐induced block copolymer (BCP) self‐assembly and osmotically driven self‐emulsification could be simultaneously regulated ( Figure a). Utilizing this strategy, multilevel multiscale Fe 3+ –“onion‐like core porous crown” nanoparticles (Fe 3+ –OCPCs), which consist of two substructures: 1) an onion‐like core; and 2) a hierarchical porous corona, were successfully prepared (Figure 4b,c).…”

“…a–g) Reproduced under the terms of the CC‐BY Creative Commons Attribution 4.0 International license (https://creativecommons.org/licenses/by/4.0). [ 52 ] Copyright 2023, The Authors, Wiley‐VCH.…”

“…g) In vivo T 1 contrast enhancement of Fe 3þ 0.06 -P2VP, Fe 3þ0.02 -OCPCs, and Fe 3þ 0.06 -OCPCs in mice with subcutaneous axillary tumors after 30 min intratumor injection. a-g) Reproduced under the terms of the CC-BY Creative Commons Attribution 4.0 International license (https://creativecommons.org/licenses/by/4.0) [52]. Copyright 2023, The Authors, Wiley-VCH.…”

Hydrogen-Bonded Organic Frameworks Chelated Manganese for Precise Magnetic Resonance Imaging Diagnosis of Cancers

“…According to the Solomon–Bloembergen–Morgan (SBM) theory, one of the main causes of the low relaxation of chelates is their fast tumbling (τ R ) in water, which is a result of their low molecular weights. , Although larger magnetic metal oxide nanoparticles have longer τ R values, the transverse relaxation ( T 2 ) decaying effect may partially attenuate the longitudinal relaxivity ( r 1 ), making them more prone to T 2 CAs. − T 1 CAs that provide positive signals are preferred in the clinic over T 2 CAs with negative (dark) signals . Another is the interaction of water molecules with magnetic ions as a stronger interaction can result in a higher relaxation rate.…”