Radical Chemistry Research Articles

Photocatalytic systems: reactions, mechanism, and applications.

The photocatalytic field revolves around the utilization of photon energy to initiate various chemical reactions using non-adsorbing substrates, through processes such as single electron transfer, energy transfer, or atom transfer. The efficiency of this field depends on the capacity of a light-absorbing metal complex, organic molecule, or substance (commonly referred to as photocatalysts or PCs) to execute these processes. Photoredox techniques utilize photocatalysts, which possess the essential characteristic of functioning as both an oxidizing and a reducing agent upon activation. In addition, it is commonly observed that photocatalysts exhibit optimal performance when irradiated with low-energy light sources, while still retaining their catalytic activity under ambient temperatures. The implementation of photoredox catalysis has resuscitated an array of synthesis realms, including but not limited to radical chemistry and photochemistry, ultimately affording prospects for the development of the reactions. Also, photoredox catalysis is utilized to resolve numerous challenges encountered in medicinal chemistry, as well as natural product synthesis. Moreover, its applications extend across diverse domains encompassing organic chemistry and catalysis. The significance of photoredox catalysts is rooted in their utilization across various fields, including biomedicine, environmental pollution management, and water purification. Of course, recently, research has evaluated photocatalysts in terms of cost, recyclability, and pollution of some photocatalysts and dyes from an environmental point of view. According to these new studies, there is a need for critical studies and reviews on photocatalysts and photocatalytic processes to provide a solution to reduce these limitations. As a future perspective for research on photocatalysts, it is necessary to put the goals of researchers on studies to overcome the limitations of the application and efficiency of photocatalysts to promote their use on a large scale for the development of industrial activities. Given the significant implications of the subject matter, this review seeks to delve into the fundamental tenets of the photocatalyst domain and its associated practical use cases. This review endeavors to demonstrate the prospective of a powerful tool known as photochemical catalysis and elucidate its underlying tenets. Additionally, another goal of this review is to expound upon the various applications of photocatalysts.

Muon spectrometers on China Spallation Neutron Source and its application prospects

<sec>The China Spallation Neutron Source Phase-II Project (CSNS-II) includes the construction of a muon source, namely “Muon station for sciEnce technoLOgy and inDustrY” (MELODY). A muon target station and a surface muon beam line will be completed as scheduled in 2029, making MELODY the first Chinese muon facility. This beam line mainly focuses on the application of muon spin relaxation/rotation/resonance (μSR) spectroscopy. The MELODY also reserves the tunnels for building a negative muon beam line and a decay muon beam line in the future, thereby further expanding the research field to muon-induced X-ray emission (MIXE) elemental analysis and μSR measurements in thick cells, respectively. The two types of material characterization technologies keep their uniqueness in multi-disciplinary researches, and also provide complementary insights for other techniques, such as neutron scattering, nuclear magnetic resonance, and X-ray fluorescence analysis.</sec><sec>The μSR spectroscopy is a mature technology for injecting highly spin polarized muon beams into various types of materials. The subsequent precession and relaxation of muon spin in its surrounding atomic environment reflect the static and dynamical properties of the material of interest, which are then measured by detecting the asymmetric emission of positrons from the decay of those muons, with an average lifetime of approximately 2.2 μs. This enables μSR to develop into a powerful quantum magnetic probe for investigating materials related to magnetism, superconductivity, and molecular dynamics. The combination of a positive muon and an electron is known as muonium, which is a unique and sensitive probe in studying semiconductors, new energy materials, free radical chemistry, etc. As the production of muon beams strongly relies on proton accelerator, only five muon facilities in the world are available for μSR experiments. This limits the large-scale application of muon related sciences. Especially, Chinese researchers face fierce competition and can only apply for precious and limited muon beam time from international muon sources to characterize the key properties of their materials.</sec><sec>The construction of the MELODY muon facility at CSNS-II aims to provide intense and pulsed muon beams for Chinese and international users to conduct their μSR measurements with high quality data in a low repetition rate operation mode. To achieve this goal, as shown in <xref ref-type="fig" rid="Figure1">Fig. 1</xref>, the μSR spectrometer is designed with 1) over 3000 detector units to obtain a sufficient counting rate of 80 Million/h to significantly suppress statistical fluctuations in a short measuring time, 2) a high asymmetry of 0.3 to greatly amplify μSR signals so as to further reduce statistical fluctuations, and 3) extendable low temperature devices to cover most μSR applications and also fulfill experiments with extreme condition requirements.</sec><sec>The MIXE elemental analysis is a type of particle induced X-ray emission (PIXE) technology. Due to the heavier mass of negative muon, the energy of muonic X-ray is around 207 higher than that of X-ray or electron induced fluorescence X-ray. Thus, the MIXE technology is more sensitive to materials with low atomic numbers, and thick samples can be effectively studied without scratching their surfaces. Due to these advantages, the MIXE has been successfully applied to the elemental analysis of cultural heritages, meteorites, Li-ion batteries, etc. MELODY reserves tunnels for negative muon extractions and transport to a MIXE terminal. The MELODY research team is developing a new detection technology with high energy resolution and high counting capability to shorten the measuring time to an acceptable amount based on the 1-Hz repetition rate of muon pulses.</sec><sec>The μSR spectroscopy and MIXE are the two most important application fields of accelerator muon beams. The MELODY muon facility aims to develop and promote these technologies in China by constructing dedicated muon beam lines in CSNS-II and in the future. In this overview, we introduce the principles and advantages of the μSR and MIXE technologies, as well as the physical design and application prospects of the μSR and MIXE spectrometers based on the CSNS-II muon source. Finally, discussions and expectations are made regarding the future upgrade of the CSNS-II muon source’s muon beamline and its broader applications.</sec>

Trapping the substrate radical of heme synthase AhbD.

The heme synthase AhbD catalyzes the last step of the siroheme-dependent heme biosynthesis pathway, which is operative in archaea and sulfate-reducing bacteria. The AhbD-catalyzed reaction consists of the oxidative decarboxylation of two propionate side chains of iron-coproporphyrin III to the corresponding vinyl groups of heme b. AhbD is a Radical SAM enzyme employing radical chemistry to achieve the decarboxylation reaction. Previously, it was proposed that the central iron ion of the substrate iron-coproporphyrin III participates in the reaction by enabling electron transfer from the initially formed substrate radical to an iron-sulfur cluster in AhbD. In this study, we investigated the substrate radical that is formed during AhbD catalysis. While the iron-coproporphyrinyl radical was not detected by electron paramagnetic resonance (EPR) spectroscopy, trapping and visualization of the substrate radical was successful by employing substrate analogs such as coproporphyrin III and zinc-coproporphyrin III. The radical signals detected by EPR were analyzed by simulations based on density functional theory (DFT) calculations. The observed radical species on the substrate analogs indicate that hydrogen atom abstraction takes place at the β-position of the propionate side chain and that an electron donating ligand is located in proximity to the central metal ion of the porphyrin.

Radical reactions enabled by polyfluoroaryl fragments: photocatalysis and beyond.

Polyfluoroarenes have been known for a long time, but they are most often used as fluorinated building blocks for the synthesis of aromatic compounds. At the same time, due to peculiar fluorine effect, they have unique properties that provide applications in various fields ranging from synthesis to materials science. This review summarizes advances in the radical chemistry of polyfluoroarenes, which have become possible mainly with the advent of photocatalysis. Transformations of the fluorinated ring via the C-F bond activation, as well as use of fluoroaryl fragments as activating groups and hydrogen atom transfer agents are discussed. The ability of fluoroarenes to serve as catalysts is also considred.

Bismuth in Radical Chemistry and Catalysis.

Whereas indications of radical reactivity in bismuth compounds can be traced back to the 19th century, the preparation and characterization of both transient and persistent bismuth-radical species has only been established in recent decades. These advancements led to the emergence of the field of bismuth radical chemistry, mirroring the progress seen for other main-group elements. The seminal and fundamental studies in this area have ultimately paved the way for the development of catalytic methodologies involving bismuth-radical intermediates, a promising approach that remains largely untapped in the broad landscape of synthetic organic chemistry. In this review, we delve into the milestones that eventually led to the present state-of-the-art in the field of radical bismuth chemistry. Our focus aims at outlining the intrinsic discoveries in fundamental inorganic/organometallic chemistry and contextualizing their practical applications in organic synthesis and catalysis.

Bismuth in Radical Chemistry and Catalysis

AbstractWhereas indications of radical reactivity in bismuth compounds can be traced back to the 19th century, the preparation and characterization of both transient and persistent bismuth‐radical species has only been established in recent decades. These advancements led to the emergence of the field of bismuth radical chemistry, mirroring the progress seen for other main‐group elements. The seminal and fundamental studies in this area have ultimately paved the way for the development of catalytic methodologies involving bismuth‐radical intermediates, a promising approach that remains largely untapped in the broad landscape of synthetic organic chemistry. In this review, we delve into the milestones that eventually led to the present state‐of‐the‐art in the field of radical bismuth chemistry. Our focus aims at outlining the intrinsic discoveries in fundamental inorganic/organometallic chemistry and contextualizing their practical applications in organic synthesis and catalysis.

The diverse roles of halide ions in the degradation of bisphenol A via UV/peracetic acid process at different pH values: Radical chemistry, and transformation pathways

UV/Peracetic Acid (UV/PAA), as an innovative advanced oxidation process (AOP), is employed to treat bisphenol A (BPA) in water through the generation of hydroxyl radicals (•OH) and carbon-centered radicals (R−C•). The impact of halide ions (Cl−; Br−; I−) on the efficiency of UV/PAA was investigated for the first time under varying pH levels. The presence of halide ions exerted an influence on the reactivity of •OH and R−C•, exhibiting varying degrees of impact across different pH conditions. It was discovered that pH exerts a significant influence on its efficiency, with optimal removal performance observed at a pH 9. The degradation of BPA was inhibited by Cl− through the generation of reactive chlorine species (RCS), which triggers the interconversion between •OH and R−C•. Reactive bromine species (RBS) were produced in the presence of Br−, facilitating BPA degradation and generating HOBr as a supplementary source of •OH radicals. I− primarily generate reactive iodine species (RIS) through photolysis, which facilitates the degradation of BPA. The transformation of BPA involves hydroxylation, demethylation, halogenation, and cleavage reactions to form various products and pathways. The toxicity test demonstrates that the UV/PAA treatment of BPA exhibits lower toxicity, thereby indicating its environmentally friendly.

Mechanochromic polymers based on radical-type dynamic covalent chemistry

Abstract Polymer mechanochemistry has emerged as a field of considerable interest from both an academic and an industrial perspective. Mechanochromic polymers that show optical change in response to mechanical stimuli can be used to visualize the mechanical force applied to the materials, which provides a wide range of information from the nano- to the macroscale, and also enables damage detection to prevent critical failure of the materials. We have explored a wide variety of radical-type dynamic covalent chemistry in the field of polymer reactions and revealed its great potential in developing mechanochromic materials. This account describes our recent efforts in the precise design of mechanochromic polymers based on radical-type dynamic covalent chemistry to impart polymeric materials with bespoke chromic properties, and discusses their characteristics derived from the radical chemistry as well as potential applications.

Nickel-Catalyzed Radical Mechanisms: Informing Cross-Coupling for Synthesizing Non-Canonical Biomolecules.

Nickel excels at facilitating selective radical chemistry, playing a pivotal role in metalloenzyme catalysis and modern cross-coupling reactions. Radicals, being nonpolar and neutral, exhibit orthogonal reactivity to nucleophilic and basic functional groups commonly present in biomolecules. Harnessing this compatibility, we delve into the application of nickel-catalyzed radical pathways in the synthesis of noncanonical peptides and carbohydrates, critical for chemical biology studies and drug discovery.We previously characterized a sequential reduction mechanism that accounts for chemoselectivity in cross-electrophile coupling reactions. This catalytic cycle begins with nickel(I)-mediated radical generation from alkyl halides, followed by carbon radical capture by nickel(II) complexes, and concludes with reductive elimination. These steps resonate with mechanistic proposals in nickel-catalyzed cross-coupling, photoredox, and electrocatalytic reactions. Herein, we present our insights into each step involving radicals, including initiation, propagation, termination, and the nuances of kinetics, origins of selectivity, and ligand effects.Radical generation from C(sp3) electrophiles via one-electron oxidative addition with low-valent nickel radical intermediates provides the basis for stereoconvergent and cross-electrophile couplings. Our electroanalytical studies elucidate a concerted halogen atom abstraction mechanism, where electron transfer is coupled with halide dissociation. Using this pathway, we have developed a nickel-catalyzed stereoselective radical addition to dehydroalanine, facilitating the synthesis of noncanonical peptides. In this application, chiral ligands modulate the stereochemical outcome through the asymmetric protonation of a nickel-enolate intermediate.The capture of the alkyl radical by nickel(II) expands the scope of cross-coupling, promotes reductive elimination through the formation of high-valent nickel(III) species, and governs chemo- and stereoselectivity. We discovered that nickel(II)-aryl efficiently traps radicals with a barrier ranging from 7 to 9 kcal/mol, followed by fast reductive elimination. In contrast, nickel(II)-alkyl captures radicals to form a nickel(III) species, which was characterized by EPR spectroscopy. However, the subsequent slow reductive elimination resulted in minimal product formation. The observed high diastereoselectivity of radical capture inspired investigations into C-aryl and C-acyl glycosylation reactions. We developed a redox auxiliary that readily couples with natural carbohydrates and produces glycosyl radicals upon photoredox activation. Nickel-catalyzed cross-coupling of the glycosyl radical with bromoarenes and carboxylic acids leads to diverse non-natural glycosides that can facilitate drug discovery.Stoichiometric studies on well-defined d8-nickel complexes have showcased means to promote reductive elimination, including ligand association, oxidation, and oxidative addition.In the final section, we address the influence of auxiliary ligands on the electronic structure and redox activity of organonickel intermediates. Synthesis of a series of low-valent nickel radical complexes and characterization of their electronic structures led us to a postulate that ligand redox activity correlates with coordination geometry. Our data reveal that a change in ligand redox activity can shift the redox potentials of reaction intermediates, potentially altering the mechanism of catalytic reactions. Moreover, coordinating additives and solvents may stabilize nickel radicals during catalysis by adjusting ligand redox activity, which is consistent with known catalytic conditions.

Unraveling the Unimolecular Ion Chemistry of Protonated Isoprene and Prenol.

The atmospheric chemistries of isoprene and prenol have been studied extensively; however, much of that research has focused on neutral or radical chemistry. Recent studies have demonstrated that under acidic conditions, isoprene and prenol can become protonated in the atmosphere, and we have explored the unimolecular chemistry of protonated isoprene and prenol with tandem mass spectrometry (using a triple-quadrupole mass spectrometer) and density functional theory. The collision-induced dissociation of protonated isoprene revealed two product ion channels: the neutral losses of C2H4 and H2, the former dominating over the latter. Protonated prenol dissociates by four product ion channels: the neutral losses of water, formaldehyde, methanol, and propene, with the former two being minor channels and the latter two being major channels. Density functional theory supplemented with CBS-QB3 single-point calculations revealed the underlying mechanisms to explain the breakdown behavior. The two competing channels from protonated isoprene could easily be rationalized due to the relative energy difference between key transition states along the reaction coordinates. However, in the case of protonated prenol, it was revealed that the minor products observed in the breakdown of protonated prenol had significantly lower reaction barriers when compared to the major products, an apparent contradiction. This could be rationalized if the initial ion population entering the collision cell is comproed of several isomeric species on the minimum energy reaction pathway, species populated by collisional excitation in the ion source region.

Radical chemistry and ozone production at a UK coastal receptor site

Abstract. OH, HO2, total and partially speciated RO2, and OH reactivity (kOH′) were measured during the July 2015 ICOZA (Integrated Chemistry of OZone in the Atmosphere) project that took place at a coastal site in north Norfolk, UK. Maximum measured daily OH, HO2 and total RO2 radical concentrations were in the range 2.6–17 × 106, 0.75–4.2 × 108 and 2.3–8.0 × 108 molec. cm−3, respectively. kOH′ ranged from 1.7 to 17.6 s−1, with a median value of 4.7 s−1. ICOZA data were split by wind direction to assess differences in the radical chemistry between air that had passed over the North Sea (NW–SE sectors) and that over major urban conurbations such as London (SW sector). A box model using the Master Chemical Mechanism (MCMv3.3.1) was in reasonable agreement with the OH measurements, but it overpredicted HO2 observations in NW–SE air in the afternoon by a factor of ∼ 2–3, although slightly better agreement was found for HO2 in SW air (factor of ∼ 1.4–2.0 underprediction). The box model severely underpredicted total RO2 observations in both NW–SE and SW air by factors of ∼ 8–9 on average. Measured radical and kOH′ levels and measurement–model ratios displayed strong dependences on NO mixing ratios, with the results suggesting that peroxy radical chemistry is not well understood under high-NOx conditions. The simultaneous measurement of OH, HO2, total RO2 and kOH′ was used to derive experimental (i.e. observationally determined) budgets for all radical species as well as total ROx (i.e. OH + HO2 + RO2). In NW–SE air, the ROx budget could be closed during the daytime within experimental uncertainty, but the rate of OH destruction exceeded the rate of OH production, and the rate of HO2 production greatly exceeded the rate of HO2 destruction, while the opposite was true for RO2. In SW air, the ROx budget analysis indicated missing daytime ROx sources, but the OH budget was balanced, and the same imbalances were found with the HO2 and RO2 budgets as in NW–SE air. For HO2 and RO2, the budget imbalances were most severe at high-NO mixing ratios, and the best agreement between HO2 and RO2 rates of production and destruction rates was found when the RO2 + NO rate coefficient was reduced by a factor of 5. A photostationary-steady-state (PSS) calculation underpredicted daytime OH in NW–SE air by ∼ 35 %, whereas agreement (∼ 15 %) was found within instrumental uncertainty (∼ 26 % at 2σ) in SW air. The rate of in situ ozone production (P(Ox)) was calculated from observations of ROx, NO and NO2 and compared to that calculated from MCM-modelled radical concentrations. The MCM-calculated P(Ox) significantly underpredicted the measurement-calculated P(Ox) in the morning, and the degree of underprediction was found to scale with NO.

Local radical chemistry driven ozone pollution in a megacity: A case study

A comprehensive field campaign (STORM) was conducted from October to November 2018 at Peking University Shenzhen Graduate School (DXC, 22.60 °N, 113.97 °E) in Shenzhen, Guangdong Province, to investigate the influence of oxidation on secondary pollution formation under different environmental conditions. Precursor concentrations introduced typical urban characteristics on the modeled OH reactivity (kOH) levels with a broad range between 15.0 and 30.0 s−1. The daily maxima of the observed OH and HO2 radical concentrations were (2.3–12.8) × 106 cm−3 and (1.3–9.1) × 108 cm−3, respectively. Abundant photolysis sources (e.g., HONO, HCHO, and O3) intensified photochemistry in the polluted period, and the OH radical concentration peaked 6.0 × 106 cm−3 at noon (11:00–13:00). A low kOH of 12.0 s−1 in the clean atmosphere prolonged the OH lifetime by decreasing the termination efficiency while maintaining a sustained OH concentration comparable to the polluted period. In terms of meteorology, the dominating air mass was isolated from the east and northeast directions, which promoted the transition of ozone from mild pollution to severe pollution. The immense precursor emissions at urban sites first compensated for the negative effect of declined solar radiation, and then they amplified radical propagation. Simultaneously amplified radical propagation promoted oxidation capacity, and increased the chain length (ChL) from 3.6 to 4.1, and P(O3) has lifted effectively by approximately 13.3 %. Stable wind direction and velocity reduced the physical dilution loss, which supported the fast Ox rise around 16:00. Further detailed investigations are required on the environmental causes of ozone pollution to address the influence of the oxidation processes on secondary pollution formation under other environmental conditions.

Alkylperoxy radicals are responsible for the formation of oxygenated primary organic aerosol.

Organic aerosol (OA) is an air pollutant ubiquitous in urban atmospheres. Urban OA is usually apportioned into primary OA (POA), mostly emitted by mobile sources, and secondary OA (SOA), which forms in the atmosphere due to oxidation of gas-phase precursors from anthropogenic and biogenic sources. By performing coordinated measurements in the particle phase and the gas phase, we show that the alkylperoxy radical chemistry that is responsible for low-temperature ignition also leads to the formation of oxygenated POA (OxyPOA). OxyPOA is distinct from POA emitted during high-temperature ignition and is chemically similar to SOA. We present evidence for the prevalence of OxyPOA in emissions of a spark-ignition engine and a next-generation advanced compression-ignition engine, highlighting the importance of understanding OxyPOA for predicting urban air pollution patterns in current and future atmospheres.

Acetal Radicals: Synthetic Access and Applications

AbstractAldehydes and ketones are two of the most versatile functional groups in organic synthesis, and the development of new reagents and protocols to install them are always warranted. Recently, the reemergence of radical chemistry has provided new opportunities to introduce these important carbonyl motifs. As such, acetal radicals can be employed as synthetic radical equivalents for acyl radicals that can also circumvent known stability challenges. This review aims to summarize the advancements and known uses of acetal radicals, as well as explore acetal radical formation and synthetic applications.

Astrochemical Modeling of Propargyl Radical Chemistry in TMC-1

Recent detections of aromatic species in dark molecular clouds suggest that formation pathways may be efficient at very low temperatures and pressures, yet current astrochemical models are unable to account for their derived abundances, which can often deviate from model predictions by several orders of magnitude. The propargyl radical, a highly abundant species in the dark molecular cloud TMC-1, is an important aromatic precursor in combustion flames and possibly interstellar environments. We performed astrochemical modeling of TMC-1 using the three-phase gas-grain code NAUTILUS and an updated chemical network, focused on refining the chemistry of the propargyl radical and related species. The abundance of the propargyl radical has been increased by half an order of magnitude compared to the previous GOTHAM network. This brings it closer in line with observations, but it remains underestimated by 2 orders of magnitude compared to its observed value. Predicted abundances for the chemically related C4H3N isomers within an order of magnitude of observed values corroborate the high efficiency of CN addition to closed-shell hydrocarbons under dark molecular cloud conditions. The results of our modeling provide insight into the chemical processes of the propargyl radical in dark molecular clouds and highlight the importance of resonance-stabilized radicals in polycyclic aromatic hydrocarbon formation.

Controllable Regiodivergent Alkynylation of 1,3-Bis(Boronic) Esters Activated by Distinct Organometallic Reagents.

1,3-Bis(boronic) esters can be readily synthesized from alkylBpin precursors. Selective transformations of these compounds hold the potential for late-stage functionalization of the remaining C-B bond, leading to a diverse array of molecules. Currently, there are no strategies available to address the reactivity and, more importantly, the controllable regiodivergent functionalization of 1,3-bis(boronic) esters. In this study, we have achieved controllable regiodivergent alkynylation of these molecules. The regioselectivity has been clarified based on the unique chelation patterns observed with different organometallic reagents. Remarkably, this methodology effectively addresses the low reactivity of 1,3-bis(boronic) esters and bridges the gap in radical chemistry, which typically yields only the classical products formed via stable radical intermediates. Furthermore, the compounds synthesized through this approach serve as potent building blocks for creating molecular diversity.

Controllable Regiodivergent Alkynylation of 1,3‐Bis(Boronic) Esters Activated by Distinct Organometallic Reagents

Abstract1,3‐Bis(boronic) esters can be readily synthesized from alkylBpin precursors. Selective transformations of these compounds hold the potential for late‐stage functionalization of the remaining C−B bond, leading to a diverse array of molecules. Currently, there are no strategies available to address the reactivity and, more importantly, the controllable regiodivergent functionalization of 1,3‐bis(boronic) esters. In this study, we have achieved controllable regiodivergent alkynylation of these molecules. The regioselectivity has been clarified based on the unique chelation patterns observed with different organometallic reagents. Remarkably, this methodology effectively addresses the low reactivity of 1,3‐bis(boronic) esters and bridges the gap in radical chemistry, which typically yields only the classical products formed via stable radical intermediates. Furthermore, the compounds synthesized through this approach serve as potent building blocks for creating molecular diversity.

Light-Induced Polymeric Frustrated Radical Pairs as Building Blocks for Materials and Photocatalysts.

Polymeric frustrated Lewis pairs, or poly(FLP)s, have served to bridge the gap between functional polymer science and main group catalysis, pairing the uniqueness of sterically frustrated Lewis acids and bases with a polymer scaffold to create self-healing gels and recyclable catalysts. However, their utilization in radical chemistry is unprecedented. In this paper, we disclose the synthesis of polymeric frustrated radical pairs, or poly(FRP)s, by in situ photoinduction of FLP moieties, where their Lewis acidic and basic centers are tuned to promote single electron transfer (SET). Through systematic manipulation of the chemical structure, we demonstrate that inclusion of ortho-methyl groups on phosphine monomers is crucial to enable SET. The generation of radicals is evidenced by monitoring the stable polymeric phosphine radical cations via UV/vis and EPR spectroscopy. These new poly(FRP)s enable both catalytic hydrogenation and radical-mediated photocatalytic perfluoroalkylations. These polymeric radical systems open new avenues to design novel functional polymers for catalysis and photoelectrical chemistry.

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.

Theoretical Kinetics studies of isoprene peroxy radical chemistry: The fate of Z-δ-(4-OH, 1-OO)-ISOPOO radical

The OH radical recycling mechanism in isoprene oxidation is one of the most exciting topics in atmospheric chemistry, and the corresponding studies expand our understanding of oxidation mechanisms of volatile organic compounds in the troposphere and provide reliable evidence to improve and develop conventional atmospheric models. In this work, we performed a detailed theoretical kinetics study on the Z-δ-(4-OH, 1-OO)-ISOPOO radical chemistry, which is proposed as the heart of OH recycling in isoprene oxidation. With the full consideration of its accumulation and consumption channels, we studied and discussed the fate of Z-δ-(4-OH, 1-OO)-ISOPOO radical by solving the energy-resolved master equation over a broad range of conditions, including not only room temperatures but also high temperatures of a forest fire or low temperatures and pressures of the upper troposphere. We found non-negligible pressure dependence of its fate at combustion temperatures (up to two orders of magnitude) and demonstrated the significance of both the multi-structural torsional anharmonicity and tunneling for accurately calculating kinetics of the studied system. More interestingly, the tunneling effect on the phenomenological rate constants of the H-shift reaction channel is also found to be pressure-dependent due to the competition with the O2 loss reaction. In addition, our time evolution calculations revealed a two-stage behavior of critical species in this reaction system and estimated the shortest half-lives for the Z-δ-(4-OH, 1-OO)-ISOPOO radical at various temperatures, pressures and altitudes. This detailed kinetics study of Z-δ-(4-OH, 1-OO)-ISOPOO radical chemistry offers a typical example to deeply understand the core mechanism of OH recycling pathways in isoprene oxidation, and provides valuable insights for promoting the development of relevant atmospheric models.