ß-Triketones as Reactive Handles for Polymer Diversification via Dynamic Catalyst-Free Diketoenamine Click Chemistry.

The spontaneous condensation of amines with ß-triketones (TK), forming ß,ß'-diketoenamines (DKE) and releasing water as the sole byproduct, exhibits many of the hallmarks of "click" reactions. Such characteristics render TKs as a highly advantageous platform for efficient polymer diversification, even in biological contexts. Leveraging reversible addition-fragmentation chain transfer (RAFT) and photoiniferter polymerization of novel TK-containing vinylic monomers, we synthesized polymers containing pendent TKs with excellent control of molecular weights, even in excess of 106 g mol-1. Under mild, catalyst-free conditions, poly(ß-triketone methacrylate) could be modified with a diverse scope of amines containing a plethora of functional groups. The high efficiency of this functionalization approach was further emphasized when grafting-to with poly(ethylene glycol)-amine resulting in bottlebrushes with molecular weights reaching 2.0 × 107 g mol-1. Critically, while the formed DKE linkages are stable under ambient conditions, they undergo catalyst-free, dynamic transamination at elevated temperatures, paving the way for associative covalent adaptable networks. Overall, we introduce pendent triketone moieties into methacrylate and acrylamide polymers, establishing a novel postpolymerization modification technique that facilitates catalyst-free ligation of amines under highly permissible conditions.

Hybrid Photoiniferter and Ring-Opening Polymerization Yields One-Pot Anisotropic Nanorods.

Polymerization-induced self-assembly (PISA) has emerged as a scalable one-pot technique to prepare block copolymer (BCP) nanoparticles. Recently, a PISA process, that results in poly(l-lactide)-b-poly(ethylene glycol) BCP nanoparticles coined ring-opening polymerization (ROP)-induced crystallization-driven self-assembly (ROPI-CDSA), was developed. The resulting nanorods demonstrate a strong propensity for aggregation, resulting in the formation of 2D sheets and 3D networks. This article reports the synthesis of poly(N,N-dimethyl acrylamide)-b-poly(l)-lactide BCP nanoparticles by ROPI-CDSA, utilizing a two-step, one-pot approach. A dual-functionalized photoiniferter is first used for controlled radical polymerization of the acrylamido-based monomer, and the resulting polymer serves as a macroinitiator for organocatalyzed ROP to form the solvophobic polyester block. The resulting nanorods are highly stable and display anisotropy at higher molecular weights (>12k Da) and concentrations (>20% solids) than the previous report. This development expands the chemical scope of ROPI-CDSA BCPs and provides readily accessible nanorods made with biocompatible materials.

Optomechanical Quantum Control of a Nitrogen-Vacancy Center in Diamond.

We demonstrate optomechanical quantum control of the internal electronic states of a diamond nitrogen-vacancy (NV) center in the resolved-sideband regime by coupling the NV to both optical fields and surface acoustic waves via a phonon-assisted optical transition and by taking advantage of the strong excited-state electron-phonon coupling of a NV center. Optomechanically driven Rabi oscillations as well as quantum interferences between the optomechanical sideband and the direct dipole-optical transitions are realized. These studies open the door to using resolved-sideband optomechanical coupling for quantum control of both the atomlike internal states and the motional states of a coupled NV-nanomechanical system, leading to the development of a solid-state analog of trapped ions.

Dynamic Ablative Networks: Shapeable Heat-Shielding Materials.

Thermoset materials sacrifice recyclability and reshapeability for increased chemical and mechanical robustness because of an immobilized, cross-linked polymeric matrix. The robust material properties of thermosets make them well-suited for applications such as heat-shielding materials (HSMs) or ablatives where excellent thermal stability, good mechanical strength, and high charring ability are paramount. Many of these material properties are characteristic of covalent adaptable networks (CANs), where the static connectivity of thermosets has been replaced with dynamic cross-links. This dynamic connectivity allows network mobility while retaining cross-link connectivity to permit damage repair and reshaping that are traditionally inaccessible for thermoset materials. Herein, we report the synthesis of hybrid inorganic-organic enaminone vitrimers that contain an exceptionally high weight percent of polyhedral oligomeric silsesquioxane (POSS)-derivatives. Polycondensation of ß-ketoester-containing POSS with various diamine cross-linkers led to materials with facile tunability, shapeability, predictable glass transition temperatures, good thermal stability, and high residual char mass following thermal degradation. Furthermore, the char materials show notable retention of their preordained shape following decomposition, suggesting their future utility in the design of HSMs with complex detailing.

High-performance polyimine vitrimers from an aromatic bio-based scaffold.

Bio-based vitrimers represent a promising class of thermosetting polymer materials, pairing the recyclability of dynamic covalent networks with the renewability of non-fossil fuel feedstocks. Vanillin, a low-cost lignin derivative, enables facile construction of polyimine networks marked by rapid exchange and sensitivity to acid-catalyzed hydrolysis. Furthermore, the aromatic structure makes it a promising candidate for the design of highly aromatic networks capable of high-performance thermal and dimensional stability. Such properties are paramount in polymeric thermal protection systems. Here, we report on the fabrication of polyimine networks with particularly high aromatic content from a novel trifunctional vanillin monomer prepared from the nucleophilic aromatic substitution of perfluoropyridine (PFP) on a multi-gram scale (>20 g) in high yield (86%). The trifunctional aromatic scaffold was then crosslinked with various diamines to demonstrate tunable viscoelastic behavior and thermal properties, with glass transition temperatures (Tg) ranging from 9 to 147 °C, degradation temperatures (5% mass loss) up to approximately 370 °C, and excellent char yields up to 68% at 650 °C under nitrogen. Moreover, the vitrimers displayed mechanical reprocessability over five destruction/healing cycles and rapid chemical recyclability following acidic hydrolysis at mild temperatures. Our findings indicate that vitrimers possessing tunable properties and high-performance thermomechanical behavior can be easily constructed from vanillin and electrophilic aromatic scaffolds for applications in heat-shielding materials and ablative coatings.