Comparison of Polypentenamer and Polynorbornene Bottlebrushes in Dilute Solution.

Bottlebrush (BB) polymers were synthesized via grafting-from-atom transfer radical polymerization (ATRP) of styrene on polypentenamer and polynorbornene macroinitiators with matched grafting density (n g = 4) and backbone degrees of polymerization (122 ≥ N bb ≥ 61) to produce a comparative study on their respective dilute solution properties as a function of increasing side chain degree of polymerization (116 ≥ N sc ≥ 5). The grafting-from technique produced near quantitative grafting efficiency and narrow dispersity N sc as evidenced by spectroscopic analysis and ring closing metathesis depolymerization of the polypentenamer BBs. The versatility of this synthetic approach permitted a comprehensive survey of power law expressions that arise from monitoring intrinsic viscosity, hydrodynamic radius, and radius of gyration as a function of increasing the molar mass of the BBs by increasing N sc. These values were compared to a series of linear (nongrafted, N sc = 0) macroinitiators in addition to linear grafts. This unique study allowed elucidation of the onset of bottlebrush behavior for two different types of bottlebrush backbones with identical grafting density but inherently different flexibility. In addition, grafting-from ATRP of methyl acrylate on a polypentenamer macroinitiator allowed the observation of the effects of graft chemistry in comparison to polystyrene. Differences in the observed scaling relationships in dilute solution as a function of each of these synthetic variants are discussed.

A Thermally Stable SO2-Releasing Mechanophore: Facile Activation, Single-Event Spectroscopy, and Molecular Dynamic Simulations.

Polymers that release small molecules in response to mechanical force are promising candidates as next-generation on-demand delivery systems. Despite advancements in the development of mechanophores for releasing diverse payloads through careful molecular design, the availability of scaffolds capable of discharging biomedically significant cargos in substantial quantities remains scarce. In this report, we detail a nonscissile mechanophore built from an 8-thiabicyclo[3.2.1]octane 8,8-dioxide (TBO) motif that releases one equivalent of sulfur dioxide (SO2) from each repeat unit. The TBO mechanophore exhibits high thermal stability but is activated mechanochemically using solution ultrasonication in either organic solvent or aqueous media with up to 63% efficiency, equating to 206 molecules of SO2 released per 143.3 kDa chain. We quantified the mechanochemical reactivity of TBO by single-molecule force spectroscopy and resolved its single-event activation. The force-coupled rate constant for TBO opening reaches ∼9.0 s-1 at ∼1520 pN, and each reaction of a single TBO domain releases a stored length of ∼0.68 nm. We investigated the mechanism of TBO activation using ab initio steered molecular dynamic simulations and rationalized the observed stereoselectivity. These comprehensive studies of the TBO mechanophore provide a mechanically coupled mechanism of multi-SO2 release from one polymer chain, facilitating the translation of polymer mechanochemistry to potential biomedical applications.

Mechanically Triggered Carbon Monoxide Release with Turn-On Aggregation-Induced Emission.

Polymers that release functional small molecules under mechanical stress potentially serve as next-generation materials for catalysis, sensing, and mechanochemical dynamic therapy. To further expand the function of mechanoresponsive materials, the discovery of chemistries capable of small molecule release are highly desirable. In this report, we detail a nonscissile bifunctional mechanophore (i.e., dual mechano-activated properties) based on a unique mechanochemical reaction involving norborn-2-en-7-one (NEO). One property is the release of carbon monoxide (CO) upon pulsed solution ultrasonication. A release efficiency of 58% is observed at high molecular weights (Mn = 158.8 kDa), equating to ∼154 molecules of CO released per chain. The second property is the bright cyan emission from the macromolecular product in its aggregated state, resulting in a turn-on fluorescence readout coincident with CO release. This report not only demonstrates a unique strategy for the release of small molecules in a nonscissile way but also guides future designs of force-responsive aggregation-induced emission (AIE) luminogens.

Selective Ring-Opening Allene Metathesis: Polymerization or Ruthenium Vinylidene Formation.

Selective ring-opening allene metathesis polymerization (ROAlMP) and ruthenium vinylidene formation from 1,2-cyclononadiene (1) by simple catalyst selection are discussed. Grubbs second-generation catalyst (G2) favors the formation of an alkylidene leading to the ROAlMP of (1). Grubbs first-generation catalyst (G1) favors vinylidene formation and prevents the homopolymerization of (1) even at elevated temperatures. Isolation and characterization of poly(1) by NMR analysis and MALDI-TOF confirms the generation of a well-defined polyallene that exhibits good thermal stability (TD ca. 390 °C) and fluorescent properties. Ring-opening metathesis polymerization (ROMP) of a highly strained norbornene derivative (NBE-iPr) at 80 °C using the ruthenium vinylidene generated from (1) is also investigated. The discovery of ROAlMP allows for the simple access of well-defined polyallenes from commercially available catalysts and will ultimately guide structure-property determinations of polyallenes.

Depolymerization of Bottlebrush Polypentenamers and Their Macromolecular Metamorphosis.

The depolymerization of bottlebrush (BB) polymers with varying lengths of polycyclopentene (PCP) backbone and polystyrene (PS) grafts is investigated. In all cases, ring closing metathesis (RCM) depolymerization of the PCP BB backbone appears to occur through an end-to-end depolymerization mechanism as evidenced by size exclusion chromatography. Investigation on the RCM depolymerization of linear PCP reveals a more random chain degradation process. Quantitative depolymerization occurs under thermodynamic conditions (higher temperature and dilution) that drives RCM into cyclopentenes (CPs), each bearing one of the original PS grafts from the BB. Catalyst screening reveals Grubbs' third (G3) and second (G2) generation catalyst depolymerize BBs significantly faster than Grubbs' first generation (G1) and Hoveyda-Grubbs' second generation (HG2) catalyst under identical conditions while solvent (toluene versus CHCl3) plays a less significant role. The length of the BB backbone and PS side chains also play a minor role in depolymerization kinetics, which is discussed. The ability to completely deconstruct these BB architectures into linear grafts provides definitive insights toward the ATRP "grafting-from" mechanism originally used to construct the BBs. Core-shell BB block copolymers (BBCPs) are shown to quantitatively depolymerize into linear diblock polymer grafts. Finally, the complete depolymerization of BBs into α-cyclopentenyl-PS allows further transformation to other architectures, such as 3-arm stars, through thiol-ene coupling onto the CP end group. These unique materials open the door to stimuli-responsive reassembly of BBs and BBCPs into new morphologies driven by macromolecular metamorphosis.

Polypentenamer Renaissance: Challenges and Opportunities.

This Viewpoint highlights the viability and increasing variety of functionalized polypentenamers as unique and valuable materials created through enthalpy-driven ring-opening metathesis polymerization (ROMP) of low ring strain cyclopentene monomers. The terms "low ring strain" and "enthalpy-driven" are typically conflicting ideologies for successful ROMP; however, these monomers possess a heightened sensitivity to reaction conditions, which may be leveraged in a number of ways to provide performance elastomers with good yield and precise functional topologies. Over the last several years, a rekindled interest in these systems has led to a renaissance of research aimed at improving their synthesis and exploring their potential. Their chemistry, applications, and future outlook are discussed.

Precision Polyelectrolytes with Phenylsulfonic Acid Branches at Every Five Carbons.

A precision polyethylene containing phenyl branches at every fifth carbon (p5Ph) is nearly quantitatively functionalized (≈95%) with sulfonic acid groups on the para-position of each phenyl branch (p5PhS-H). Unlike polystyrene sulfonate (PSS), p5PhS-H has a glass transition temperature (Tg = 109 °C) well below its thermal decomposition temperature (Td ≈ 200 °C), making this new material capable of thermal processing into molds and films at temperatures between these thermal limits. Neutralization of the sulfonic acid groups with varying counter cations (Li+ , Na+ , Cs+ ) produces a new class of precision polyelectrolytes. Neutralization and increasing size of the counter cation improves the thermal decomposition temperature (Td ) to over 400 °C for the Cs+ form. Neutralization causes Tg to increase above Td for the Li+ and Na+ form. The Cs+ form is found to have an accessible Tg = 294 °C. Further investigations of water absorption and the polyelectrolyte effect of these systems are discussed.

Well-Defined and Precision-Grafted Bottlebrush Polypentenamers from Variable Temperature ROMP and ATRP.

Polypentenamer macroinitiators are synthesized through variable temperature ring opening metathesis polymerization of 3-cyclopentenyl α-bromoisobutyrate, which has sufficient ring strain (ΔHp = -22.6 kJ mol-1) to produce targeted molar mass (<5% from theoretical), low dispersity (1.17 ≤ D ≤ 1.23), and high conversion (∼72%). An initiation site for atom-transfer radical polymerization at every fifth backbone carbon allows "grafting-from" of styrene with quantitative initiation and linear molar mass increase with time. These bottlebrushes retain a low dispersity (D ≤ 1.34) at varying graft degrees of polymerization (5 ≤ Nsc ≤ 49) and have a glass transition temperature highly sensitized to graft length. Extension of the grafts with methyl methacrylate produces a core-shell brush polymer with high molar mass (>1000 kg mol-1) and D = 1.33. This system exhibits high synthetic versatility and control with a unique flexible backbone to expand the suite of densely grafted polymers.

A Precision Ethylene-Styrene Copolymer with High Styrene Content from Ring-Opening Metathesis Polymerization of 4-Phenylcyclopentene.

Ring-opening metathesis polymerization of 4-phenylcyclopentene is investigated for the first time under various conditions. Thermodynamic analysis reveals a polymerization enthalpy and entropy sufficient for high molar mass and conversions at lower temperatures. In one example, neat polymerization using Hoveyda-Grubbs second generation catalyst at -15 °C yields 81% conversion to poly(4-phenylcyclopentene) (P4PCP) with a number average molar mass of 151 kg mol(-1) and dispersity of 1.77. Quantitative homogeneous hydrogenation of P4PCP results in a precision ethylene-styrene copolymer (H2 -P4PCP) with a phenyl branch at every fifth carbon along the backbone. This equates to a perfectly alternating trimethylene-styrene sequence with 71.2% w/w styrene content that is inaccessible through molecular catalyst copolymerization strategies. Differential scanning calorimetry confirms P4PCP and H2 -P4PCP are amorphous materials with similar glass transition temperatures (Tg ) of 17 ± 2 °C. Both materials present well-defined styrenic analogs for application in specialty materials or composites where lower softening temperatures may be desired.