Toughening a Self-Healable Supramolecular Polymer by Ionic Cluster-Enhanced Iron-Carboxylate Complexes

Supramolecular polymers that can heal themselves automatically usually exhibit weakness in mechanical toughness and stretchability. Here we exploit a toughening strategy for a dynamic dry supramolecular network by introducing ionic cluster-enhanced iron-carboxylate complexes. The resulting dry supramolecular network simultaneous exhibits tough mechanical strength, high stretchability, self-healing ability, and processability at room temperature. The excellent performance of these distinct supramolecular polymers is attributed to the hierarchical existence of four types of dynamic combinations in the high-density dry network, including dynamic covalent disulfide bonds, noncovalent H-bonds, iron-carboxylate complexes and ionic clustering interactions. The extremely facile preparation method of this self-healing polymer offers prospects for high-performance low-cost material among others for coatings and wearable devices

Dual closed-loop chemical recycling of synthetic polymers by intrinsically reconfigurable poly(disulfides)

The excessive use of plastics has led to severe global problems involving environmental, energy, and health issues and demands for sustainable and recyclable alternatives. Toward circular plastics, the development of efficient chemical recycling methods without loss of properties or allowing reprocessing into new materials offer tremendous opportunities. Here, we report an intrinsically recyclable and reconfigurable poly(disulfide) polymer using a natural small molecule, thioctic acid (TA), as the feedstock. Taking advantage of its dynamic covalent ring-opening polymerization, this material enables a dual closed-loop chemical recycling network among TA monomers and two kinds of polymer products, including self-healing elastomers and mechanically robust ionic films. Mild and complete depolymerization into monomers in diluted alkaline aqueous solution is achieved with yields of recovered monomers up to 86%. The polymer materials can be repeatedly recycled and reused with reconfigurable polymer composition and tunable mechanical properties offering prospects for sustainable functional plastics

Acylhydrazine-based reticular hydrogen bonds enable robust, tough, and dynamic supramolecular materials

Supramolecular materials are widely recognized among the most promising candidates for future generations of sustainable plastics because of their dynamic functions. However, the weak noncovalent cross-links that endow dynamic properties usually trade off materials’ mechanical robustness. Here, we present the discovery of a simple and robust supramolecular cross-linking strategy based on acylhydrazine units, which can hierarchically cross-link the solvent-free network of poly(disulfides) by forming unique reticular hydrogen bonds, enabling the conversion of soft into stiff dynamic material. The resulting supramolecular materials exhibit increase in stiffness exceeding two to three orders of magnitude compared to those based on the hydrogen-bonding network of analogous carboxylic acids, simultaneously preserving the repairability, malleability, and recyclability of the materials. The materials also show high adhesion strength on various surfaces while allowing multiple surface attachment cycles without fatigue, illustrating a viable approach how robustness and dynamics can be merged in future material design

Light-Driven Spiral Deformation of Supramolecular Helical Microfibers by Localized Photoisomerization

Stimuli-responsive mechanical deformations widely occur in biological systems but the design of biomimetic shape-changing materials, especially those based on noncovalent interactions, remains highly challenging. Here, hydrogen-bonded supramolecular microfibers are reported, which can perform light-driven spiral deformation by switching an intrinsic azobenzene unit without monomer dissociation. The key design feature rests on rationally spaced multiple hydrogen bonds, which inhibits the disassembly pathway upon irradiation, allowing partial photomechanical actuation of the azobenzene cores in the confined environment of the assemblies. The light-controlled deformation process of the supramolecular microfibers can be switched in a fully reversible manner. This combination of confinement-inhibited disassembly and photoswitching to induce assembly deformation and actuation along length scales supports a distinctive strategy to design supramolecular materials with photomechanical motion

Identifying the programmed cell death index of hepatocellular carcinoma for prognosis and therapy response improvement by machine learning: a bioinformatics analysis and experimental validation

BackgroundDespite advancements in hepatocellular carcinoma (HCC) treatments, the prognosis for patients remains suboptimal. Cumulative evidence suggests that programmed cell death (PCD) exerts crucial functions in HCC. PCD-related genes are potential predictors for prognosis and therapeutic responses.MethodsA systematic analysis of 14 PCD modes was conducted to determine the correlation between PCD and HCC. A novel machine learning-based integrative framework was utilized to construct the PCD Index (PCDI) for prognosis and therapeutic response prediction. A comprehensive analysis of PCDI genes was performed, leveraging data including single-cell sequencing and proteomics. GBA was selected, and its functions were investigated in HCC cell lines by in vitro experiments.ResultsTwo PCD clusters with different clinical and biological characteristics were identified in HCC. With the computational framework, the PCDI was constructed, demonstrating superior prognostic predictive efficacy and surpassing previously published prognostic models. An efficient clinical nomogram based on PCDI and clinicopathological factors was then developed. PCDI was intimately associated with immunological attributes, and PCDI could efficaciously predict immunotherapy response. Additionally, the PCDI could predict the chemotherapy sensitivity of HCC patients. A multilevel panorama of PCDI genes confirmed its stability and credibility. Finally, the knockdown of GBA could suppress both the proliferative and invasive capacities of HCC cells.ConclusionThis study systematically elucidated the association between PCD and HCC. A robust PCDI was constructed for prognosis and therapy response prediction, which would facilitate clinical management and personalized therapy for HCC

Comparison of sequencing-based methods to profile DNA methylation and identification of monoallelic epigenetic modifications.

Analysis of DNA methylation patterns relies increasingly on sequencing-based profiling methods. The four most frequently used sequencing-based technologies are the bisulfite-based methods MethylC-seq and reduced representation bisulfite sequencing (RRBS), and the enrichment-based techniques methylated DNA immunoprecipitation sequencing (MeDIP-seq) and methylated DNA binding domain sequencing (MBD-seq). We applied all four methods to biological replicates of human embryonic stem cells to assess their genome-wide CpG coverage, resolution, cost, concordance and the influence of CpG density and genomic context. The methylation levels assessed by the two bisulfite methods were concordant (their difference did not exceed a given threshold) for 82% for CpGs and 99% of the non-CpG cytosines. Using binary methylation calls, the two enrichment methods were 99% concordant and regions assessed by all four methods were 97% concordant. We combined MeDIP-seq with methylation-sensitive restriction enzyme (MRE-seq) sequencing for comprehensive methylome coverage at lower cost. This, along with RNA-seq and ChIP-seq of the ES cells enabled us to detect regions with allele-specific epigenetic states, identifying most known imprinted regions and new loci with monoallelic epigenetic marks and monoallelic expression

Dynamic poly(disulfide)s for sustainable materials

The rise of supramolecular and dynamic covalent chemistry has provided many approaches for the construction of dynamic polymers and materials with complex dynamic functions such as adaptability, responsiveness, self-healing properties, and green recycling properties. Among them, 1,2-dithiolane-based building blocks have become an important scaffold, featuring their ability of dynamic covalent disulfide-mediated reversible polymerization. This advantage endows this class of dynamic materials with both advantages of supramolecular polymers and adaptable covalent networks. In this thesis, multi-functional dynamic materials are explored, focusing on the polymeric materials made from thioctic acid and its derivatives

Converting inorganic sulfur into degradable thermoplastics and adhesives by copolymerization with cyclic disulfides

Converting elementary sulfur into sulfur-rich polymers provides a sustainable strategy to replace fossil-fuel-based plastics. However, the low ring strain of eight-membered rings, i.e., S 8 monomers, compromises their ring-opening polymerization (ROP) due to lack of an enthalpic driving force and as a consequence, poly(sulfur) is inherently unstable. Here we report that copolymerization with cyclic disulfides, e.g., 1,2-dithiolanes, can enable a simple and energy-saving way to convert elementary sulfur into sulfur-rich thermoplastics. The key strategy is to combine two types of ROP-both mediated by disulfide bond exchange-to tackle the thermodynamic instability of poly(sulfur). Meanwhile, the readily modifiable sidechain of the cyclic disulfides provides chemical space to engineer the mechanical properties and dynamic functions over a large range, e.g., self-repairing ability and degradability. Thus, this simple and robust system is expected to be a starting point for the organic transformation of inorganic sulfur toward sulfur-rich functional and green plastics. </p