Radical Depolymerization Research Articles

From health supplement to versatile monomer: Radical ring-opening polymerization and depolymerization of α-lipoic acid

The radical ring-opening polymerization (rROP) of α-lipoic acid (LA) and its derivatives represents a synthetically accessible, efficient, and scalable strategy to impart degradability into functional copolymers. This review highlights recent advances in the design of sustainable materials containing LA through rROP driven by heat and/or light.

The thermodynamics and kinetics of depolymerization: what makes vinyl monomer regeneration feasible?

Depolymerization is potentially a highly advantageous method of recycling plastic waste which could move the world closer towards a truly circular polymer economy. However, depolymerization remains challenging for many polymers with all-carbon backbones. Fundamental understanding and consideration of both the kinetics and thermodynamics are essential in order to develop effective new depolymerization systems that could overcome this problem, as the feasibility of monomer generation can be drastically altered by tuning the reaction conditions. This perspective explores the underlying thermodynamics and kinetics governing radical depolymerization of addition polymers by revisiting pioneering work started in the mid-20th century and demonstrates its connection to exciting recent advances which report depolymerization reaching near-quantitative monomer regeneration at much lower temperatures than seen previously. Recent catalytic approaches to monomer regeneration are also explored, highlighting that this nascent chemistry could potentially revolutionize depolymerization-based polymer recycling in the future.

Controlled radical depolymerization: Structural differentiation and molecular weight control

Controlled radical depolymerization: Structural differentiation and molecular weight control

Depolymerization of lignin model compounds by reactive oxygen species generated from peroxymonosulfate under mild conditions

Directional cleavage the linkages bonds between the lignin units is of great scientific interest although technically challenging. In this work, free radical depolymerization of lignin was investigated by using three model compounds. Peroxymonosulfate (PMS) was activated by N-doped carbon and thermal method, and could generate reactive oxygen species (ROS), including hydroxyl radical (OH∙), sulfate radical anion (SO4∙−), superoxide anion (O2∙−) and singlet oxygen(O12). pH of solution was used to regulate the types of ROS. The results showed that 1) pH value can tune the reaction pathway by regulating the type of ROS; 2) There should be an optimal temperature for maximum selectivity of monomer products in the depolymerization proces of lignin model compounds by ROS; 3) Hydroxyl group and Methoxy group can activate the reactivity of lignin model compounds, which is conductive to the directional generation of monomer products. In addition, the depolymerization mechanism of lignin model compound by PMS was proposed.This work illustrated the reaction characters and the influence factors of the lignin depolymerization by PMS, the results would facilitate the optimization of the lignin valorization process.

Radical chemistry in polymer science: an overview and recent advances.

Radical chemistry is one of the most important methods used in modern polymer science and industry. Over the past century, new knowledge on radical chemistry has both promoted and been generated from the emergence of polymer synthesis and modification techniques. In this review, we discuss radical chemistry in polymer science from four interconnected aspects. We begin with radical polymerization, the most employed technique for industrial production of polymeric materials, and other polymer synthesis involving a radical process. Post-polymerization modification, including polymer crosslinking and polymer surface modification, is the key process that introduces functionality and practicality to polymeric materials. Radical depolymerization, an efficient approach to destroy polymers, finds applications in two distinct fields, semiconductor industry and environmental protection. Polymer chemistry has largely diverged from organic chemistry with the fine division of modern science but polymer chemists constantly acquire new inspirations from organic chemists. Dialogues on radical chemistry between the two communities will deepen the understanding of the two fields and benefit the humanity.

Temporal Regulation of PET‐RAFT Controlled Radical Depolymerization

AbstractA photocatalytic RAFT‐controlled radical depolymerization method is introduced for precisely conferring temporal control under visible light irradiation. By regulating the deactivation of the depropagating chains and suppressing thermal initiation, an excellent temporal control was enabled, exemplified by several consecutive “on” and “off” cycles. Minimal, if any, depolymerization could be observed during the dark periods while the polymer chain‐ends could be efficiently re‐activated and continue to depropagate upon re‐exposure to light. Notably, favoring deactivation resulted in the gradual unzipping of polymer chains and a stepwise decrease in molecular weight over time. This synthetic approach constitutes a simple methodology to modulate temporal control during the chemical recycling of RAFT‐synthesized polymers while offering invaluable mechanistic insights.

Temporal Regulation of PET-RAFT Controlled Radical Depolymerization.

A photocatalytic RAFT-controlled radical depolymerization method is introduced for precisely conferring temporal control under visible light irradiation. By regulating the deactivation of the depropagating chains and suppressing thermal initiation, an excellent temporal control was enabled, exemplified by several consecutive "on" and "off" cycles. Minimal, if any, depolymerization could be observed during the dark periods while the polymer chain-ends could be efficiently re-activated and continue to depropagate upon re-exposure to light. Notably, favoring deactivation resulted in the gradual unzipping of polymer chains and a stepwise decrease in molecular weight over time. This synthetic approach constitutes a simple methodology to modulate temporal control during the chemical recycling of RAFT-synthesized polymers while offering invaluable mechanistic insights.

ИССЛЕДОВАНИЕ ЛЕТУЧИХ ОРГАНИЧЕСКИХ СОЕДИНЕНИЙ ПОЛИМЕРНЫХ КОМПОЗИЦИОННЫХ МАТЕРИАЛОВ ПРИ МОДЕЛИРОВАНИИ ТЕРМОДЕСТРУКЦИИ

Chromatography-mass spectrometry was used to investigate dynamics of volatile organic compounds released by 6 coal plastics of a carbon fiber and epoxy binder proposed for internal structures of manned spacecrafts. It was established that temperature growth higher than 90 °С increases migration and enlarges the spectrum of volatile organics, hygienically important aldehydes primarily, which is characteristic of autocatalytic radical depolymerization with production of volatile low-molecular-weight compounds. Kinetics of their off-gassing can be used to characterize destruction of the epoxy base of composite materials (CMs). Primary products of the thermo-oxidative destruction of these CMs are aldehydes and ketones; at 150 °С and 180 °С, concentrations of these compounds reached maximum levels and made up 98 % of off-gassed compounds.

Polysaccharides from Moroccan Green and Brown Seaweed and Their Derivatives Stimulate Natural Defenses in Olive Tree Leaves

This study aims to assess for the first time the ability of marine polysaccharides and their derivatives to stimulate natural defenses in olive tree leaves. Alginates, ALSM, and ALCM were isolated from the brown algae Sargassum muticum and Cystoseira myriophylloides, respectively. The OASM and OACM fractions were obtained after radical depolymerization of ALSM and ALCM, respectively. Three sulfated polysaccharides, arabinogalactans (AGB and AGP) and fucoidans (FUCCM) were extracted from the green alga Codium decorticatum and the brown seaweed C. myriophylloides, respectively. The extraction yield of different extracts was in the range of 0.82–32% and the average molecular weight (Mw) varied from 3000 Da to 2173 kDa. The M/G ratios of ALSM and ALCM were 0.87 and 1.12, respectively. FUCCM contained 53% of fucose and 12.83% of sulfates. The AGB and AGP fractions were characterized by the presence of a high degree of sulfation and protein (12–23% (w/w)) and were composed mainly of galactose, glucose, and arabinose. The aqueous saccharide solutions were applied to the leaf discs of the olive tree at 0.5 g/L, 1 g/L, and 2 g/L, for 24 h. These molecules triggered defense responses, by showing a differential capacity to induce the activity of the phenylalanine and tyrosine ammonia-lyase (TAL and PAL), polyphenols, and lignin contents in the leaves of the olive tree. Alginates and their derivatives as well as arabinogalactans exhibited an important induction of TAL activity compared to the PAL. The sulfated polysaccharides were more effective compared to the unsulfated polysaccharides (alginates) which were active at a low concentration. The optimum concentration for most of the studied elicitors was 2 g/L. These results suggest the valorization of these molecules derived from marine biomass as inducers of natural defenses of the olive tree to protect against phytopathogens in the context of sustainable development.

Structural characterization of oligosaccharides from free radical depolymerized fucosylated glycosaminoglycan and suggested mechanism of depolymerization

Free radical depolymerization is a common method in structural analysis of polysaccharides, the major challenge is the analysis of the cleavage site and characterization of newly formed ends in this reaction. Here, a fucosylated glycosaminoglycan from H. fuscopunctata (HfFG) was depolymerized by H2O2 and a series of oligosaccharides were purified and their structures were elucidated. For non-reducing ends of the trisaccharides were intact GalNAc4S6S, the cleavage site should mainly be the β(1,3) linkages between GlcA and GalNAc in the backbone of FG. Meanwhile, the reducing ends of the disaccharides and trisaccharides were almost dicarboxylic acid derivatives of GlcA, possibly arising from oxidative breaking of the CC bond of GlcA at the reducing ends. In addition, glycosidic linkages in D-GalNAc-β(1,4)-D-GlcA and L-FucS-α(1,3)-D-GlcA located at the reducing end could be cleaved, and the released GalNAc4S6S were oxidized to N-acetylgalactosaminic acid.

Marine Exopolysaccharide Complexed With Scandium Aimed as Theranostic Agents.

(1) Background: Exopolysaccharide (EPS) derivatives, produced by Alteromonas infernus bacterium, showed anti-metastatic properties. They may represent a new class of ligands to be combined with theranostic radionuclides, such as 47Sc/44Sc. The goal of this work was to investigate the feasibility of such coupling. (2) Methods: EPSs, as well as heparin used as a drug reference, were characterized in terms of molar mass and dispersity using Asymmetrical Flow Field-Flow Fractionation coupled to Multi-Angle Light Scattering (AF4-MALS). The intrinsic viscosity of EPSs at different ionic strengths were measured in order to establish the conformation. To determine the stability constants of Sc with EPS and heparin, a Free-ion selective radiotracer extraction (FISRE) method has been used. (3) Results: AF4-MALS showed that radical depolymerization produces monodisperse EPSs, suitable for therapeutic use. EPS conformation exhibited a lower hydrodynamic volume for the highest ionic strengths. The resulting random-coiled conformation could affect the complexation with metal for high concentration. The LogK of Sc-EPS complexes have been determined and showing that they are comparable to the Sc-Hep. (4) Conclusions: EPSs are very promising to be coupled with the theranostic pair of scandium for Nuclear Medicine.

Radical Depolymerization of Alginate Extracted from Moroccan Brown Seaweed Bifurcaria bifurcata

The degradation of alginate extracted from Moroccan Bifurcaria bifurcata has not been fully established to date. In this work, we report the extraction and the characterization of alginate (ASBB) from the brown algae B. bifurcata, as well as the production of oligo-alginates (OGABs) by using a green chemistry process. The depolymerization of ASBB was carried out by controlled radical hydrolysis through our green chemistry process using a hydrogen peroxide (H2O2) catalyst. The molecular weight (Mw) and degree of polymerization (DP) distribution of oligo-alginates (OGABs) obtained were then characterized by HPLC size exclusion chromatography (SEC) and high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD). Structural characterization revealed that after 6 h of depolymerization of ASBB, we obtained OGABs with Mw ≤ 5.5 kDa and 2 ≤ DP ≤ 24. These results highlight the effectiveness of the controlled radical hydrolysis of alginate to produce good yields of alginate fractions with controlled Mw with a known polymerization degree (DP) and without altering properties of oligo-alginates. Bifurcaria bifurcata can be a potential source of alginate and oligo-alginates given its abundance on the northwest Atlantic coast. The production and characterization of oligo-alginates promote their exploitation in the cosmetic, pharmaceutic, and agriculture fields.

Immunoenhancing glucuronoxylomannan from Tremella aurantialba Bandoni et Zang and its low-molecular-weight fractions by radical depolymerization: Properties, structures and effects on macrophages

In this study, a glucuronoxylomannan named TAP-3 was obtained from high-value Tremella aurantialba Bandoni et Zang. Physicochemical analysis revealed that TAP-3, which had a molecular weight of ∼624 kDa, mainly consisted of d-mannose (Man), d-xylose (Xyl), and d-glucuronic acid (GlcA) in a molar ratio of 3.0:1.0: 1.0. Structural analyses of its depolymerized fragments clarified that TAP-3 contained a (1 → 3) and (1 → 2)-linked α-Manp backbone, side chains formed by β-Xylp and β-GlcpA linked to the C-2 position of α-Manp, and acetyl groups connected to the sixth hydroxyl positions of Manp. TAP-3 showed marked immune enhancement activity, promoting NO, IL-1β and TNF-α secretion from macrophages. The critical membrane receptor of TAP-3 was identified to be TLR4, and the chain length was essential for its immunoregulatory activity. These findings expand knowledge of the structural types of glucuronoxylomannan and illustrate its biological activity as an immunopotentiator.

Selective radical depolymerization of cellulose to glucose induced by high frequency ultrasound.

The depolymerization of cellulose to glucose is a challenging reaction and often constitutes a scientific obstacle in the synthesis of downstream bio-based products. Here, we show that cellulose can be selectively depolymerized to glucose by ultrasonic irradiation in water at a high frequency (525 kHz). The concept of this work is based on the generation of H˙ and ˙OH radicals, formed by homolytic dissociation of water inside the cavitation bubbles, which induce the cleavage of the glycosidic bonds. The transfer of radicals on the cellulose particle surfaces prevents the side degradation of released glucose into the bulk solution, allowing maintaining the selectivity to glucose close to 100%. This work is distinguished from previous technologies in that (i) no catalyst is needed, (ii) no external source of heating is required, and (iii) the complete depolymerization of cellulose is achieved in a selective fashion. The addition of specific radical scavengers coupled to different gaseous atmospheres and ˙OH radical dosimetry experiments suggested that H˙ radicals are more likely to be responsible for the depolymerisation of cellulose.

Characterization of New Oligosaccharides Obtained by An Enzymatic Cleavage of the Exopolysaccharide Produced by the Deep-Sea Bacterium Alteromonas infernus Using its Cell Extract.

Bacteria from deep-sea hydrothermal vents constitute an attractive source of bioactive molecules. In particular, exopolysaccharides (EPS) produced by these bacteria become a renewable source of both biocompatible and biodegradable molecules. The low molecular weight (LMW) derivatives of the GY785 EPS produced by the deep-sea hydrothermal vent strain Alteromonas infernus have previously displayed some biological properties, similar to those of glycosaminoglycans (GAG), explored in cancer and tissue engineering. These GAG-mimetic derivatives are obtained through a free radical depolymerization process, which could, however, affect their structural integrity. In a previous study, we have shown that A. infernus produces depolymerizing enzymes active on its own EPS. In the present study, an enzymatic reaction was optimized to generate LMW derivatives of the GY785 EPS, which could advantageously replace the present bioactive derivatives obtained by a chemical process. Analysis by mass spectrometry of the oligosaccharide fractions released after enzymatic treatment revealed that mainly a lyase activity was responsible for the polysaccharide depolymerization. The repeating unit of the GY785 EPS produced by enzyme cleavage was then fully characterized.

Production of Active Poly- and Oligosaccharidic Fractions from Ulva sp. by Combining Enzyme-Assisted Extraction (EAE) and Depolymerization.

Data on fractionation and depolymerization of the matrix ulvan polysaccharides, and studies on the biological activities on skin cells, are very scarce. In this work, crude ulvans were produced by using EAE (enzyme-assisted extraction) and compared to maceration (an established procedure). After different fractionation procedures—ethanolic precipitation, dialysis, or ammonium sulfate precipitation—the biochemical composition showed that EAE led to an increased content in ulvans. Coupling EAE to sulfate ammonium precipitation led to protein enrichment. Oligosaccharides were obtained by using radical depolymerization by H2O2 and ion-exchange resin depolymerization. Sulfate groups were partially cleaved during these chemical treatments. The potential bioactivity of the fractions was assessed using a lipoxygenase inhibition assay for anti-inflammatory activity and a WST-1 assay for human dermal fibroblast viability and proliferation. All ulvans extracts, poly- and oligosaccharidic fractions from EAE, expanded the fibroblast proliferation rate up to 62%. Our research emphasizes the potential use of poly- and oligosaccharidic fractions of Ulva sp. for further development in cosmetic applications.

Controlled radical depolymerization of chlorine-capped PMMA via reversible activation of the terminal group by ruthenium catalyst

This paper deals with a preliminary study in controlled radical depolymerization, that is a unimodal polymer is converted into monomer while maintaining the narrow molecular weight distribution. Thus, our effort has been directed to unzipping-type depolymerization triggered by the reversible activation of the terminal group. An indenyl-based ruthenium catalyst afforded depolymerization of a chlorine-capped poly(methyl methacrylate) (PMMA-Cl) at relatively high temperature (>100 °C). Interestingly, the SEC curve shifted to lower molecular weight as the time proceeds, and the monomer, that is MMA, definitely generated and the amount almost corresponded to the decrease in molecular weight. The depolymerization was eventually saturated due to the equilibrium monomer concentration, but evaporation of the generating monomer followed by an addition of solvent and re-heating allowed further progress of depolymerization. We have thus demonstrated four consecutive depolymerizations via the evaporation methodology resulting in the unimodal SEC curve shift to lower molecular weight.

Electron Spin Resonance Analysis of γ-induced Free Radicals in Riceberry Rice Grain

Gamma irradiation has long been serving as one alternative preservation method for food and agriculture products. Initial physical interactions of gamma with biomaterials lead through radical formation, depolymerization, and molecular changes to eventual sterilization, decontamination and preservation. An effective penetration of gamma radiation homogenize the effects throughout the materials. Riceberry rice composes mainly of starch, which has α-D glucopyranose (C6H12O6 or glucose) as a building block in its polysaccharide network. Follow irradiating rice with Co-60 gammas of a few kilograys, the polysaccharide chains have undergone several changes in their molecular structure, which lead to generation of free radicals. Electron spin resonance (ESR) analysis has shown that quite a few free radicals were formed with different strengths. Their respective Landes g-values were in the range of 2.0020 to 2.0039. Mechanisms such as hydrogen abstraction on C1 and C6 position and formation of primary hydroxyalkyl between C1 and C6 are presumably accounted for the formation of these free radicals. However, the unknown species which is singlet shape was found in this study.

Structural characterization and in vitro antioxidant activities of chondroitin sulfate purified from Andrias davidianus cartilage

Origin and manufacturing process are key factors affecting the biological activities of chondroitin sulfate (CS), which can be utilized as a nutraceutical in dietary supplements. Herein, we extracted and purified CS from the cartilage of artificially breeding Andrias davidianus (ADCS), i.e., Chinese giant salamander (CGS), one of the prospective functional food source materials in China. Low molecular weight CS (LMWADCS) was then prepared by free radical depolymerization of ADCS. High-performance gel permeation chromatography (HPGPC) analysis showed that the average molecular weight (Mw) of ADCS was 49.2 kDa, while the Mw of LMWADCS was 6.4 kDa. After the eliminative degradation of ADCS by chondroitinase ABC, strong anion-exchange high-performance liquid chromatography (SAX-HPLC) analysis showed that the disaccharide composition of ADCS was 14.6% ΔDi0S, 60.9% ΔDi6S and 24.5% ΔDi4S. Then, in vitro antioxidant assays were performed with ADCS, LMWADCS and CS from a commercial source. Our results showed that LMWADCS exerted the highest total antioxidant activity out of the total antioxidant capacity, including the capacity of scavenging DPPH radicals, hydroxyl radicals and superoxide anion radicals. From the results of this study, we can conclude that the Mw and composition of ADCS are different from those reported for bovine and shark CS, and LMWADCS can be utilized as a valuable and potential nutraceutical for the functional food industry.

Cytokine-inducing and anti-inflammatory activity of chitosan and its low-molecular derivative

A low-molecular derivative of the polysaccharide (5 kDa) was obtained and its cytokine-inducing and anti-inflammatory activity was studied by free radical depolymerization of chitosan (110 kDa). It was shown that high-molecular chitosan in vitro inhibited the synthesis of anti-inflammatory cytokine, the tumor necrosis factor alpha induced by endotoxin. In the case of peroral introduction to experimental animals, high- and low-molecular chitosans stimulated synthesis of the anti-inflammatory cytokine IL-10 in the blood serum of mice; in this case, the activity of the high-molecular derivative was two times higher as compared with the initial polysaccharide. With peroral introduction, the initial polysaccharide (50 mg/kg) and its derivative inhibited the development of chemically induced inflammation of experimental animals’ large intestines, which was manifested as a decrease in the affected area and the degree of damage to the large intestine wall, as well as a two-fold reduction of myeloperoxidase activity. According to morphological and biochemical characteristics, the effect of chitosans was similar to that of a hormone anti-inflammatory drug, prednisolone.