High Throughput Preparation of UV-Protective Polymers from Essential Oil Extracts via the Biginelli Reaction

Abstract

A high throughput (HTP) system has been developed to exploit new functional polymers. We synthesized 25 monomers in a mini-HTP manner through the tricomponent Biginelli reaction with high yields. The starting materials were five aldehydes extracted from essential oils. The 25 corresponding polymers were conveniently prepared via mini-HTP radical polymerization initially realizing the benefit of HTP methods to quickly fabricate sample libraries. The distinct radical scavenging ability of these Biginelli polymers was evaluated through a HTP measurement to choose the three best radical scavengers. This confirms the superiority of the HTP strategy to rapidly collect and analyze data. The selected polymers have been upgraded and screened according to different requirements for biomaterials and offer water-soluble and biocompatible copolymers that effectively protect cells from the fatal UV damage. This research is a straightforward way to establish new libraries of monomers with abundant diversity. It offers polymers with interesting functionalities. This suggests that a broader study of multicomponent reactions and HTP methods might be useful in many interdisciplinary fields. To the best of our knowledge, this is the first report of a HTP study of the Biginelli reaction to develop a promising polymeric biomaterial, which might have important implications for the organic chemistry and polymer communities.

Antioxidant Polymers via the Kabachnik‐Fields Reaction to Control Cellular Oxidative Stress

“…As a typical example, the KF reaction between benzaldehyde, N‐(3‐aminopropyl) methacrylamide (APMA), and diethylphosphite was performed during polymerization in acetonitrile/ethanol (1:1, v/v). Poly(ethylene glycol) (PEG) and its derivatives are well known biocompatible polymers; [ 21,46,47 ] thus, poly(ethylene glycol) methyl ether methacrylate (PEGMA) was used here as a comonomer to improve the water‐solubility and biocompatibility of resulting polymers. Mesitylene and azodiisobutyronitrile (AIBN, 1 mol% to monomers) were used as internal standard and initiator, respectively.…”

“…Examples of such MCRs include the Passerini, Ugi, Biginelli, Hantzsch, Kabachnik–Fields (KF), and Mannich reactions. [ 15–32 ] MCRs are suitable for the preparation of polymer antioxidants for several reasons. Some antioxidative groups such as phenol are compatible with many MCRs and can be easily introduced into polymer chains without losing their antioxidative ability.…”

Identifying Structural Determinants of Mesomorphism from Focused Libraries of Tripedal Mesogens Prepared via the Passerini Three‐Component Reaction

“…Complex molecular architectures can be accessed in a high throughput manner using multicomponent reactions to generate libraries of novel materials , . We have taken advantage of the modular and combinatorial attributes of the Passerini three‐component reaction to explore the structural basis of smectic mesomorphism in heterolithic ABC tripedal mesogens.…”

“…Multicomponent reactions have recently gained interest among polymer and supramolecular chemists as tools that enable combinatorial exploration of novel materials The strategic value of multicomponent reactions is well established for elaborating libraries of biologically active compounds . By combining three or more reactants into a single product, multicomponent reactions provide access to structural diversity while maintaining high step‐economy.…”

Theory Behind Biginelli Reaction Revisited

“…Entre os compostos bioativos sintetizados, destacam-se aqueles com atividades anti-inflamatórias, antibióticas, antitumorais, inibidoras do vírus HIV, para proteção contra radiação ultravioleta, entre outros. 1,7,[18][19][20][21][22][23] Ao longo dos anos as RMCs vêm sofrendo alterações como substituições de um ou mais reagentes por derivados funcionalizados, utilização de diferentes solventes e catalisadores, uso de micro-ondas, entre outras mudanças que fazem com que haja uma ampliação da diversidade estrutural dos produtos possíveis de serem obtidos por estes métodos, assim como uma otimização no processo.…”