ACS Macro Letters最新文献

The creation of well-defined surface nanostructures is important for a diverse set of applications such as cell adhesion, superhydrophobic coating, and lithography. In this study, we describe a robust bottom-up method for surface functionalization that involves surface-initiated reversible deactivation radical polymerization (RDRP) and the grafting of block copolymer nanoparticles to material surfaces via aqueous photoinduced polymerization-induced self-assembly (photo-PISA) at room temperature. Using silica nanoparticles as a model substrate, colloidal mesoscale hybrid assemblies with various morphologies were successfully prepared. The morphologies can be easily tuned by changing the lengths of macromolecular chain transfer agents and parameters of the silica nanoparticles. The surface-initiated photo-PISA approach can also be employed for other large-scale substrates such as silicon wafer. Taking advantage of mild reaction conditions of this method (room temperature, aqueous medium, and visible light), enzymatic deoxygenation was introduced to develop oxygen-tolerant surface-initiated photo-PISA that can fabricate well-defined nanostructures on large-scale substrates under open-to-air conditions.

Self-catalyzed hydrolysis upon storage of the common RAFT chain-transfer agent (CTA) 4-cyano-4-[(thiothiopropyl)sulfanyl] pentanoic acid (CTPPA) is confirmed, where the nitrile group is transformed into an amide by catalysis from the adjacent carboxylic acid moiety. The amide-CTA (APP) is found to poorly control molecular weight evolution during polymerization of two methacrylates, methyl methacrylate (MMA) and N,N-(dimethylamino)ethyl methacrylate (DMAEMA), likely due to poor reinitiation speed in the pre-equilibrium. However, when attached to a macromolecule, the impact of this amide moiety becomes insignificant and chain extension proceeds as expected with CTPPA. In light of CTPPA and similarly hydrolyzable CTAs being extensively employed for aqueous polymerizations of methacrylates, these findings highlight the importance of CTA purity when performing RAFT polymerizations.

Highly ordered, network-nanostructured polymers offer compelling geometric features and application potential. However, their practical utilization is hampered by the restricted accessibility. Here, we address this challenge using commercial Pluronic surfactants with a straightforward modification of tethering polymerizable groups. By leveraging lyotropic self-assembly, we achieve facile production of double-gyroid mesophases, which are subsequently solidified via photoinduced cross-linking. The exceptionally ordered periodicities of Ia3d symmetry in the photocured polymers are unambiguously confirmed by synchrotron small-angle X-ray scattering (SAXS), which can capture single-crystal-like diffraction patterns. Electron density maps reconstructed from SAXS data complemented by transmission electron microscopy analysis further elucidate the real-space gyroid assemblies. Intriguingly, by tuning the cross-linking through thiol–acrylate chemistry, the mechanical properties of the polymer are modulated without compromising the integrity of Ia3d assemblies. The 3-D percolating gyroid nanochannels demonstrate an ionic conductivity that surpasses that of disordered structures, offering promising prospects for scalable fabrication.

In this study, porous poly(butylene terephthalate) (PBT) fibers were produced by melt blowing cocontinuous blends of PBT and polystyrene (PS) and selectively extracting the interconnected PS domains. Small amounts of hydroxyl terminated PS additives that can undergo transesterification with the ester units in PBT were added to stabilize the cocontinuous structure during melt processing. The resulting fibers are highly ductile and display fine porous structural features, which persist at temperatures over 150 °C. Single fiber tensile testing and electron microscopy are presented to demonstrate the role of rapid quenching and drawing of the melt blowing process in defining the fiber properties. The templated highly aligned pore structure, which is not easily produced in solvent-based fiber spinning methods, leads to remarkable mechanical properties of the porous fibers and overcomes the notoriously poor tensile properties common to other cellular materials like foams.

We report the complexation of poly(ethylene glycol) conjugated double-stranded oligoDNA (PEG-(ds)oligoDNA) with imidazolium-based ionic liquids (ILs) to form polyelectrolyte complex aggregates (PCAs). The PEG-(ds)oligoDNA conjugates are prepared following a solution-phase coupling reaction. The binding of PEG-(ds)oligoDNA with either 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF₄]) or 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM][BF₄]) is confirmed by a fluorescence displacement assay. Both ILs show stronger binding affinity to PEG-(ds)oligoDNA than bare (ds)oligoDNA due to the PEG-assisted increase in IL cation concentration in the vicinity of (ds)oligoDNA. The complex morphology formed at various amine (N) to phosphate (P) ratios is also examined. At high N/P ratios above 4, nanosized PCAs are formed, driven by a counterion-mediated attraction among the IL-bound (ds)oligoDNA segments and stabilized by the conjugated PEG segments. The PCAs exhibit near-neutral surface charges and resistance to DNase degradation, suggesting their potential use in gene delivery applications.

Seeded growth termed “living” crystallization-driven self-assembly (CDSA) has been identified as a powerful method to create one- or two-dimensional nanoparticles. Epitaxial crystallization is usually regarded as the growth mechanism for the formation of uniform micelles. From this perspective, the unimer depositing rate is largely related to the crystallization temperature, which is a key factor to determine the crystallization rate and regulate the core composition distribution among nanoparticles. In the present work, the coassembly of two distinct crystallizable polymers is explored in detail in a one-pot seeded growth protocol. Results have shown that polylactone containing a larger number of methylene groups (−CH₂−) in their repeating units such as poly(η-octalactone) (POL) has a faster crystallization rate compared to poly(ε-caprolactone) (PCL) with a smaller number of −CH₂– at ambient temperature (25 °C), thus a block or blocky platelet structure with heterogeneous composition distribution is formed. In contrast, when the crystallization temperature decreases to 4 °C, the difference of crystallization rate between both cores become negligible. Consequently, a completely random component distribution within 2D platelets is observed. Moreover, we also reveal that the core component of seed micelles is also paramount for the coassembly seeded growth, and a unique structure of flower-like platelet micelle is created from the coassembly of PCL/POL using POL core-forming seeds. This study on the formation of platelet micelles by one-pot seeded growth using two crystallizable components offers a considerable scope for the design of 2D polymer nanomaterials with a controlled core component distribution.

We report the preparation of chiral silica using a linear polysiloxane main chain with a preferred-handed helical structure as the template. Poly(methylvinyl siloxane) (PMVS) with a cysteine derivative side chain designated as PMVS-Cys was prepared using anionic polymerization and an ene-thiol reaction. PMVS-Cys forms a helical conformation in both solution and film via hydrogen bonding between amide groups at side chains. The helical structure remains during the calcination process, resulting in silica with helical structure. The silica with a helical structure shows optical activity.

The incorporation of cleavable comonomers as additives into polymers can imbue traditional polymers with controlled deconstructability and expanded end-of-life options. The efficiency with which cleavable comonomer additives (CCAs) can enable deconstruction is sensitive to their local distribution within a copolymer backbone, which is dictated by their copolymerization behavior. While qualitative heuristics exist that describe deconstructability, comprehensive quantitative connections between CCA loadings, reactivity ratios, polymerization mechanisms, and deconstruction reactions on the deconstruction efficiency of copolymers containing CCAs have not been established. Here, we broadly define these relationships using stochastic simulations characterizing various polymerization mechanisms (e.g., coltrolled/living, free-radical, and reversible ring-opening polymerizations), reactivity ratio pairs (spanning 2 orders of magnitude between 0.01 and 100), CCA loadings (2.5% to 20%), and deconstruction reactions (e.g., comonomer sequence-dependent deconstruction behavior). We show general agreement between simulated and experimentally observed deconstruction fragment sizes from the literature, demonstrating the predictive power of the methods used herein. These results will guide the development of more efficient CCAs and inform the formulation of deconstructable materials.

The classic Born model can be used to predict salt partitioning properties observed in hydrated polymers, but there are often significant quantitative discrepancies between these predictions and the experimental data. Here, we use an updated version of the Born model, reformulated to account for the local environment and mesh size of a hydrated polymer, to describe previously published NaCl, KCl, and LiCl partitioning properties of model cross-linked poly(ethylene glycol) diacrylate polymers. This reformulated Born model describes the influence of polymer structure (i.e., network mesh size and its relationship with water content) and external salt concentration on salt partitioning in the polymers with a significant improvement relative to the classic Born model. The updated model most effectively describes NaCl partitioning properties and provides an additional fundamental understanding of salt partitioning processes, for NaCl, KCl, and LiCl, in hydrated polymers that are of interest for a variety of environmental and biological applications.

Polymeric materials that undergo photoinduced degradation have wide application in fields such as controlled release. Most methods for photoinduced degradation rely on the UV or near-UV region of the electromagnetic spectrum; however, use of the deeply penetrating and benign wavelengths of visible light offers a multitude of advantages. Here we report a lactone monomer for ring-opening copolymerizations to introduce a sacrificial linker into a polymer backbone which can be cleaved by reactive oxygen species which are produced by a photocatalyst under visible light irradiation. We find that copolymers of this material readily degrade under visible light. We followed polymer degradation using a continuous flow size exclusion chromatography system, the components of which are described herein.