Two-Dimensional Supramolecular Polymerization of DNA Amphiphiles is Driven by Sequence-Dependent DNA-Chromophore Interactions

Two-dimensional (2D) assemblies of water-soluble block copolymers have been limited by a dearth of systematic studies that relate polymer structure to pathway mechanism and supramolecular morphology. Here, we employ sequence-defined triblock DNA amphiphiles for the supramolecular polymerization of free-standing DNA nanosheets in water. Our systematic modulation of amphiphile sequence shows the alkyl chain core forming a cell membrane-like structure and the distal π-stacking chromophore block folding back to interact with the hydrophilic DNA block on the nanosheet surface. This interaction is crucial to sheet formation, marked by a chiral “signature”, and sensitive to DNA sequence, where nanosheets form with a mixed sequence, but not with a homogeneous poly(thymine) sequence. This work opens the possibility of forming well-ordered, bilayer-like assemblies using a single DNA amphiphile for applications in cell sensing, nucleic acid therapeutic delivery and enzyme arrays.     

An Antitumor Dual-Responsive Host-Guest Supramolecular Polymer Based on Hypoxia-Cleavable Azocalix[4]arene

The exploitation of specific guests which can respond to external stimuli is the main approach for the construction of stimuli-responsive supramolecular polymers (SPs) based on host–guest interactions. Most functional guests, however, fail to manifest stimuli-responses. Herein, a hypoxia-responsive dimeric azocalixarene (D-SAC4A) with outstanding hosting properties was used as the macrocyclic building block for the preparation of host stimuli-responsive SPs. Since azocalixarenes can also be compatible with stimuli-responsive guests, an antitumor drug, camptothecin (CPT), was chosen and linked via a disulfide-containing linker to afford a glutathione (GSH)-responsive ditropic guest (D-CPT). A unique dual-responsive SP was obtained by 1 : 1 mixing of D-SAC4A and D-CPT in water, which further assembled into SP nanoparticles (DSPNs). DSPNs displayed outstanding stability against dilution and biological interferants, as well as precise CPT-release under GSH and hypoxia conditions. In vitro and in vivo experiments demonstrated the good biosafety and tumor-suppressive effects of DSPNs.     

Modulating Ligand-Exchange Dynamics on Metal-Organic Polyhedra for Reversible Sorting and Hybridization of Miktoarm Star Polymers

The precise synthesis of miktoarm star polymers (MSPs) remains one of the great challenges in synthetic chemistry due to the difficulty in locating appropriate structural templates and polymer grafting/growing strategies with high selectivity and efficiency. Herein, ≈2 nm metal-organic polyhedra (MOPs), constructed from the coordination of isophthalic acid (IPA) and Cu²⁺, are applied as templates for the precise synthesis of 24-arm MSPs for their unique logarithmic ligand-exchange dynamics. Six different polymers are prepared with IPA as an end group and they further coordinated with Cu²⁺ to afford the corresponding 24-arm star homo-polymers. MSPs can be obtained by mixing targeted homo-arm star polymers in solutions upon thermal annealing. The compositions of MSPs can be facilely and precisely tuned by the recipe of the star polymer mixtures used. Interestingly, the obtained MSPs can be sorted into homo-arm star polymers through a typical solvent extraction procedure. The hybridization and sorting process can be reversibly conducted through the cycle of thermal annealing and solvent treatment. The complex coordination framework not only opens new avenues for the facile and precise synthesis of MSPs and MOPs with hybrid functionalities, but also provides the capability to design sustainable polymer systems.     

Light-Responsive Polyblend Films with Reconfigurable Surface Micropatterns as Rewritable Information Storage Media

Stimulus-sensitive surfaces with tunable morphologies exhibit a wide range of applications in the fields of surface science and engineering. Herein, a cost-effective yet practical strategy is proposed to fabricate photo-sensitive patterning surface on film/substrate wrinkle system based on an azo-containing polyblend. By manipulating the stress field of the bilayer system globally and/or locally upon the stress relaxation triggered by the reversible cis-trans isomerization of the azobenzene, heating/cooling triggered surface wrinkles on the polyblend films could be tailor-made with visible-light-irradiation. Notably, upon selective photo-irradiation, bespoke surface patterns may be cyclically generated or eliminated, allowing these reconfigurable patterned polyblend surfaces to be used as rewritable information storage media for non-ink printing. The as-prepared photo-printed information patterns with high-resolution are shown to be rewritable for multiple cycles and legible for over 90 d in dark ambient conditions. This study not only provides a versatile strategy for flourishing the stimulus-sensitive systems, but also sheds light on the stress relaxation-triggered morphological evolution of the wrinkling polyblend films.      

Closed-Loop Recycling of Vinylogous Urethane Vitrimers

Devising energy-efficient strategies for the depolymerization of plastics and the recovery of their structural components in high yield and purity is key to a circular plastics economy. Here, we report a case study in which we demonstrate that vinylogous urethane ( VU ) vitrimers synthesized from bis-polyethylene glycol acetoacetates ( aPEG ) and tris(2-aminoethyl)amine can be degraded by water at moderate temperature with almost quantitative recovery (≈98 %) of aPEG . The rate of depolymerization can be controlled by the temperature, amount of water, molecular weight of aPEG , and composition of the starting material. These last two parameters also allow one to tailor the mechanical properties of the final materials, and this was used to access soft, tough, and brittle vitrimers, respectively. The straightforward preparation and depolymerization of the aPEG -based VU vitrimers are interesting elements for the design of polymer materials with enhanced closed-loop recycling characteristics.     

Facile Synthesis of Linear and Cyclic Poly(diphenylacetylene)s by Molybdenum and Tungsten Catalysis

Improved methods for the synthesis of linear and cyclic poly(diphenylacetylene)s by polymerization of the corresponding diphenylacetylenes using MoCl₅- and WCl₄-based catalytic systems have been developed. MoCl₅ induces migratory insertion polymerization of diphenylacetylenes in the presence of arylation reagents such as Ph₄Sn and ArSnⁿBu₃ to produce cis-stereoregular linear poly(diphenylacetyelene)s with high molecular weights (number-average molar mass (M_n)=30,000–3,200,000) in good yields (up to 98 %). On the other hand, WCl₄ induces ring expansion polymerization of diphenylacetylenes in the presence of Ph₄Sn or reducing reagents to produce cis-stereoregular cyclic poly(diphenylacetylene)s with high molecular weights (M_n=20,000–250,000) in moderate to good yields (up to 90 %). Both catalytic systems are applicable to the polymerization of various diphenylacetylenes having polar functional groups such as esters that are not efficiently polymerized by conventional methods using WCl₆-Ph₄Sn and TaCl₅-ⁿBu₄Sn systems.     

Insight into the Molecular Mechanism for Enhanced Longevity of Supramolecular Vesicular Photocatalysts

Supramolecular self-assembly is a promising strategy for stabilizing the photo-sensitive components in photocatalysis. However, the underlying correlation between the enhanced photostability and supramolecular structure at the molecular level has not yet been fully understood. Herein, we develop a biomimetic vesicular membrane-based polyporphyrin photocatalyst exhibiting excellent photocatalytic stability with at least activity time of 240 h in hydrogen generation. Time-domain ab initio modelling together with transient absorption spectroscopy, visual frontier orbitals and Gibbs free energy calculation disclose that the ordered aggregation of porphyrin units in the vesicle membrane facilitates “hot” electron relaxation and the rapid dissipation of photo-generated charges, thereby contributing to the longevity. This work deepens the molecular-level understanding on photostability and photocatalytic mechanism of supramolecular photocatalysts.     

Functional Polythioamides Derived from Thiocarbonyl Fluoride**

Polythioamide is a unique type of sulfur-containing polymer with advanced functionalities. Nonetheless, the elemental sulfur commonly used in their synthesis tends to react readily with unsaturated functional groups, thereby limiting the scope of eligible substrates. Inspired by the highly efficient sulfur-fluoride exchange ( SuFEx ) polymerization through discrete hubs, we present herein a pioneering and versatile approach to the synthesis of polythioamides from diboronic acids, secondary diamines, and thiocarbonyl fluoride as the central connective hub. Well-defined structures, including previously inaccessible unsaturated substrates, were realized. These newly devised polythioamides can efficiently and selectively bind to metal ions and were applied in precious-metal recovery. Further development resulted in Pd^II-crosslinked single-chain nanoparticles serving as recyclable homogeneous catalysts, thus demonstrating the vast potential of these unprecedented polythioamides. We anticipate that thiocarbonyl fluoride could emerge as a potent hub for facilitating the intricate synthesis of sulfur-containing polymers.     

Phase Transition-Promoted Rapid Photomechanical Motions of Single Crystals of a Triene Coordination Polymer

Molecular crystals with the ability to transform light energy into macroscopic mechanical motions are a promising class of materials with potential applications in actuating and photonic devices. In regard to such materials, coordination polymers that exhibit dynamic photomechanical motion, associated with a phase transition, are unknown. Herein, we report an intriguing photoactive, one-dimensional Zn^II coordination polymer, 1 , derived from 1,3,5-tri-4-pyridyl-1,2-ethenylbenzene and 3,5-difluorobenzoate. Single crystals of 1 under UV light irradiation exhibit rapid shrinking and bending, violent bursting-jumping, splitting, and cracking behavior. Single-crystal X-ray diffraction analysis and ¹H NMR spectroscopy reveal an unusual photoinduced phase transition involving a single-crystal-to-single-crystal [2+2] cycloaddition reaction that results in photomechanical responses. Interestingly, crystals of 1 , which are triclinic with space group , are transformed into a higher symmetry, monoclinic cell with space group C2/c. This process represents a rare example of symmetry enhancement upon photoirradiation. The photomechanical activity is likely due to the sudden release of stress associated with strained molecular geometries and significant solid-state molecular movement arising from cleavage and formation of chemical bonds. A composite membrane fabricated from 1 and polyvinyl alcohol (PVA) also displays interesting photomechanical behavior under UV light illumination, indicating the material's potential as a photoactuator.     

Biodegradable High-Density Polyethylene-like Material

We report a novel polyester material generated from readily available biobased 1,18-octadecanedicarboxylic acid and ethylene glycol possesses a polyethylene-like solid-state structure and also tensile properties similar to high density polyethylene (HDPE). Despite its crystallinity, high melting point (T_m=96 °C) and hydrophobic nature, polyester-2,18 is subject to rapid and complete hydrolytic degradation in in vitro assays with isolated naturally occurring enzymes. Under industrial composting conditions (ISO standard 14855-1) the material is biodegraded with mineralization above 95 % within two months. Reference studies with polyester-18,18 (T_m=99 °C) reveal a strong impact of the nature of the diol repeating unit on degradation rates, possibly related to the density of ester groups in the amorphous phase. Depolymerization by methanolysis indicates suitability for closed-loop recycling.