Molecular Segments Reorganization Strategy Coupled With Retrosynthetic Analysis for Designing Sustainable Alternatives to Alkylphenol Ethoxylates.

Catalyst-controlled sustainable crosslinking reaction for green itaconate polyester coatings

In the context of a bio-based circular economy, replacing fossil raw materials with renewable alternatives has become a major trend. Platform chemicals such as itaconic acid and 2.5-furandicarboxylic acid can now be produced from sugars or lignocellulose and used to synthesize fully bio-based polyesters e.g. poly(ethylene 2.5-furandicarboxylate) with thermomechanical and barrier properties comparable to conventional polyesters. Life cycle assessments indicate that these bio-based polymers emit significantly less greenhouse gas than their fossil-derived counterparts, and thermomechanical testing and degradation studies confirm their practical suitability. Current crosslinking methods typically rely on melamine and isocyanates, which pose toxicological and ecological disadvantages. We propose using itaconic acid as a renewable crosslinking component to address these issues, with the crosslinking reaction tailored through catalyst selection. In our work, the incorporation of itaconic units into the polyester was confirmed by SEC (size-exclusion chromatography), 1 H-NMR (nuclear magnetic resonance spectroscopy), ATR-FTIR (attenuated total reflectance-Fourier-transform infrared spectroscopy) analysis. Thermal/mechanical properties were characterized by DSC (differential scanning calorimetry) and DMTA (dynamic mechanical analysis). In situ ATR-FTIR and rheology reveal that network formation proceeds via two competing mechanisms: radical C–C crosslinking and oxa-Michael (C–O–C) addition. Catalyst choice dictates the dominant pathway. Brønsted acids (DBSA, MSA) reduce the apparent reaction order to ~ 0.6, whereas a radical initiator (di-tert-butyl peroxide, DTBP) enhances radical crosslinking (apparent order ~ 1.7). In contrast, Lewis acids and metal salts (e.g. AlCl 3 , Zn(OAc) 2 ) suppress covalent gelation, favouring coordinative and supramolecular interactions over permanent covalent crosslinks. In coating tests, selected itaconate-containing formulations achieved an optimal balance of hardness, adhesion (crosscut = 0), and solvent resistance, with pendulum hardness values reaching 94–105 when catalyzed by MSA (methanesulfonic acid)/DBSA (dodecylbenzene sulfonate)/DTBP. These results demonstrate that the network architecture and thus the functional properties of itaconic acid–based renewable polyester coatings can be precisely controlled through targeted selection of catalysts and matrices. This approach offers a promising strategy for developing sustainable, high-performance bio-based coating materials.

A Comprehensive Review of Recent Advances in Sustainable Synthesis of Bio-Based Furanic Compounds Via Chemical, Biological, Chemobiological and Other Combination Approach in Benign Systems.

Critical Assessment of Sustainable Synthetic Methodologies for the Construction of Oxazole and Benzoxazole Derivatives

Oxazole and benzoxazole motifs are privileged heterocyclic frameworks with broad relevance in pharmaceuticals due to their exceptional biological activity. In response to increasing demands for sustainable chemical protocols, significant strides have been taken toward the development of greener strategies for their construction. This review critically examines existing green protocols for oxazole‐based compound synthesis, with an emphasis on non‐conventional techniques and recyclable catalytic systems. Microwave and ultrasound‐assisted approaches are demonstrated as technologies that enhance reaction efficiency, reduce energy input, and facilitate transformations under milder conditions. Meanwhile, the role of ionic liquids is evaluated in terms of their multifunctionality as solvents and catalysts. Advances in nanoparticle catalysis are discussed for their high activity, ease of recovery, and reuse. In this review, we comparatively analyze each methodology through a green chemistry lens, while also providing a structured framework for selecting sustainable strategies. Furthermore, we have also identified emerging opportunities for the future development of environmentally benign oxazole synthesis.

Topology-Directed Synthesis of Macroscopic Perylene-Silsesquioxane Polymeric Aerogels: Overcoming Aggregation-Caused Quenching for Dual-Action Water Remediation.

The persistent toxicity of phenolic contaminants necessitates the development of integrated water remediation technologies. While the synergistic "trap-and-destroy" pathway-combining rapid adsorption with in-situ photocatalytic degradation-is highly promising, its practical deployment is often hindered by the aggregation-caused quenching (ACQ) of organic chromophores and the recovery challenges associated with suspended powder catalysts. This work proposes a topology-directed engineering strategy to fabricate a macroscopic, metal-free material (PCSOA) by crosslinking perylene diimides with rigid polyhedral oligomeric silsesquioxane (POSS or SQs) cages. DFT calculations suggest that the rigid POSS nodes provide strong structural constraint to restrict the molecular motion of the photoactive perylene units, thereby suppressing non-radiative decay pathways while largely preserving the intrinsic frontier molecular orbitals. Driven by strong electrostatic and π-π affinities, the highly polarized network captures trinitrophenol with an uptake reaching 929 mg g-1. By gathering target molecules directly around the active sites, this localized accumulation significantly enhances visible-light photoactivity. Consequently, the system delivers a phenol mineralization rate constant of 1.79 h- 1 and removes over 98% of the total organic carbon (TOC). From a practical standpoint, formatting the material into a macroscopic aerogel bypasses the cumbersome separation steps inherent to powders, allowing for stable and high-throughput water treatment in continuous-flow setups.

Recent Advancements in Nickel-catalyzed Olefin Polymerization: Molecular Design, Mechanistic Insights, and Sustainable Polyolefin Materials

Modified halloysite for heterogeneous conversion of saccharides to 5-hydroxymethylfurfural: recent advances and future trends