Persistent Radicals Research Articles

How do zeolite-templated carbons grow?

Major insights into the formation mechanism of zeolite-templated carbons (ZTCs) were achieved via a thorough ex situ kinetic study of the hybrid (carbon/zeolite) and carbon materials. In depth characterization of the chemical, electrical, textural, and morphological properties of the materials allowed us to draw a precise picture of the key steps of the ZTC formation. An in situ time resolved GC study enabled us to achieve complementary insights into the ethylene consumption and hydrogen production during ZTC synthesis. Three stages could be disclosed: nucleation, growth and condensation. During nucleation, individual polyaromatic hydrocarbons (PAHs) develop through the aromatization of ethylene. These PAHs present high spin concentration and react upon zeolite dissolution, leading to unstructured carbon particles of undefined morphology. These carbons feature persistent radicals. During growth, the PAHs evolve to form more complex rylene-type molecules. Typical structural, textural, and morphological features of ZTCs start to emerge during this second stage. The evolution of electrical conductivity of hybrid materials indicates partial condensation of PAHs throughout the zeolite crystals leading to their connection. The carbon materials achieved during the second stage can be described as composites of ZTCs and randomly reacted PAHs. Condensation, which is importantly induced by heat treatment, triggers full connection of the ZTC network. Textural, morphological, structural, and electrical features develop, which result directly from zeolite templating. Final ZTCs feature carbonyl functionalization, which is inherent to the zeolite dissolution step and probably results from radical quenching with water.

π-Pimer, π-Dimer, π-Trimer, and 1D π-Stacks in a Series of Benzene Triimide Radical Anions: Substituent-Modulated π Interactions and Physical Properties in Crystalline State

π-Pimer, π-Dimer, π-Trimer, and 1D π-Stacks in a Series of Benzene Triimide Radical Anions: Substituent-Modulated π Interactions and Physical Properties in Crystalline State

Synthesis of Genuine Germenyl Lithiums and the First Persistent Germenyl Radicals.

The first isolated genuine germenyl lithiums (R3Si)(1‐Ad)C=Ge(SiMetBu2)(Li⋅2 L) (R3Si=tBu2MeSi, L=THF (1 a), or L=12‐crown‐4 (1 b) and R3Si=tBuMe2Si, L=THF (2 a), or L=12‐crown‐4 (2 b)), were synthesized by reaction of the corresponding acyl germanes 3 and 4, respectively, with tBu2MeSiLi in THF at 70 °C. The novel 1 a and 2 b were characterized by NMR and UV/Vis spectroscopy, and also by X‐ray crystallography (r(C=Ge)=1.865 Å for 1 a and 1.877 Å for 2 b). Nucleophilic addition reaction of 1 a with MeI and a C−H insertion reactions to the C=Ge bond of 1 a, 2 a and 2 b, are reported. Oxidation of 1 a and 2 b (toluene, 230 K) produces the first persistent germenyl radicals (R3Si)(1‐Ad)C=Ge⋅‐(SiMetBu2) (R3Si=tBu2MeSi (13 a), R3Si=tBuMe2Si (13 b)), which were characterized by EPR spectroscopy (t 1/2≈30 min at 230 K, g=2.029, a av(73Ge) is 55.0G for 13 a and 60.2G for 13 b). The experimental EPR parameters and DFT calculations indicate that 13 a and 13 b have a strongly bent structure at Ge (calc. ∡(C=Ge−Si)=136.7° (13 a), 135.9° (13 b)), and that the unpaired electron has a substantial s‐character.

Synthesis of Genuine Germenyl Lithiums and the First Persistent Germenyl Radicals

AbstractThe first isolated genuine germenyl lithiums (R3Si)(1‐Ad)C=Ge(SiMetBu2)(Li⋅2 L) (R3Si=tBu2MeSi, L=THF (1 a), or L=12‐crown‐4 (1 b) and R3Si=tBuMe2Si, L=THF (2 a), or L=12‐crown‐4 (2 b)), were synthesized by reaction of the corresponding acyl germanes 3 and 4, respectively, with tBu2MeSiLi in THF at 70 °C. The novel 1 a and 2 b were characterized by NMR and UV/Vis spectroscopy, and also by X‐ray crystallography (r(C=Ge)=1.865 Å for 1 a and 1.877 Å for 2 b). Nucleophilic addition reaction of 1 a with MeI and a C−H insertion reactions to the C=Ge bond of 1 a, 2 a and 2 b, are reported. Oxidation of 1 a and 2 b (toluene, 230 K) produces the first persistent germenyl radicals (R3Si)(1‐Ad)C=Ge⋅‐(SiMetBu2) (R3Si=tBu2MeSi (13 a), R3Si=tBuMe2Si (13 b)), which were characterized by EPR spectroscopy (t1/2≈30 min at 230 K, g=2.029, aav(73Ge) is 55.0G for 13 a and 60.2G for 13 b). The experimental EPR parameters and DFT calculations indicate that 13 a and 13 b have a strongly bent structure at Ge (calc. ∡(C=Ge−Si)=136.7° (13 a), 135.9° (13 b)), and that the unpaired electron has a substantial s‐character.

Thianthrenium-enabled sulfonylation via electron donor-acceptor complex photoactivation

Sulfone-containing compounds are prevalent building blocks in pharmaceuticals and other biomolecules, and they serve as key intermediates in the synthesis of complex scaffolds. During the past decade, several methods have been developed to access sulfones. These strategies, however, require the use of strong reaction conditions, limiting their substrate scope. Recently, visible light-mediated transformations have emerged as novel platforms to access unprecedented structural motifs. This report demonstrates a thianthrenium-enabled sulfonylation via intra-complex charge transfer to generate transient aryl- and persistent sulfonyl radicals that undergo selective coupling to generate alkyl- and (hetero)aryl sulfones under ambient conditions. Importantly, this strategy allows retention of halide handles, presenting a complementary approach to transition metal-mediated photoredox couplings. Furthermore, this sulfonylation allows high functional group tolerance and is amenable to late-stage functionalization of complex biomolecules. Mechanistic investigations support the intermediacy of electron donor-acceptor (EDA) complexes.

Невыносимость подполья. Коллективное самоубийство староверов-странников в межвоенной Вятке

Abstract In the first half of the 1930s in the Vyatka region about 60 Old Believers-Wanderers, mostly women, committed suicide, no longer wanting to live in a world overrun by the Antichrist. The initiator of the wave of voluntary deaths was the local preacher, Khristofor Ivanovich. It is easy to write off these episodes as an actualization of traditional Old Believers’ religiously-motivated suicides or as a reaction to the excesses of Stalinist religious policies. However, as will be shown in the article, the Vyatka Wanderers were neither persistent escapist radicals nor uncompromising dissidents in their dealings with the Soviet authorities. My hypothesis is that this grim practice became possible not because the Wanderers were consistent underground millenarians, but because, squeezed into the catacombs by Stalin’s social and religious policies, they found themselves unable to maintain this unprecedented (for them) regime of existence.

Persistent Radicals in Irradiated Imidazolium Ionic Liquids Probed by EPR Spectroscopy

Persistent Radicals in Irradiated Imidazolium Ionic Liquids Probed by EPR Spectroscopy

Frontier orbital stability of nitroxyl organic radicals probed by means of inner shell resonantly enhanced valence band photoelectron spectroscopy.

We have investigated the frontier orbitals of persistent organic radicals known as nitroxyls by resonant photoelectron spectroscopy (ResPES) under inner shell excitation. By means of this site-specific technique, we were able to disentangle the different atomic contributions to the outer valence molecular orbitals and examine several core-hole relaxation pathways involving the singly occupied molecular orbital (SOMO) localized on the nitroxyl group. To interpret the ResPES intensity trends, especially the strong enhancement of the SOMO ionized state at the N K-edge, we computed the Dyson spin orbitals (DSOs) pertaining to the transitions between the core-excited initial states and several of the singly ionized valence final states. We found that the computed vertical valence ionization potentials and norms of the DSOs are reasonably reliable when based on the long-range corrected CAM-B3LYP density functional. Thanks to their unpaired electrons, nitroxyls have recently found application in technological fields implying a spin control, such as spintronics and quantum computing. The present findings on the electronic structure of nitroxyl persistent radicals furnish important hints for their implementation in technological devices and, more in general, for the synthesis of new and stable organic radicals with tailored properties.

α-Branched amines through radical coupling with 2-azaallyl anions, redox active esters and alkenes.

α-Branched amines are fundamental building blocks in a variety of natural products and pharmaceuticals. Herein is reported a unique cascade reaction that enables the preparation of α-branched amines bearing aryl or alkyl groups at the β- or γ-positions. The cascade is initiated by reduction of redox active esters to alkyl radicals. The resulting alkyl radicals are trapped by styrene derivatives, leading to benzylic radicals. The persistent 2-azaallyl radicals and benzylic radicals are proposed to undergo a radical–radical coupling leading to functionalized amine products. Evidence is provided that the role of the nickel catalyst is to promote formation of the alkyl radical from the redox active ester and not promote the C–C bond formation. The synthetic method introduced herein tolerates a variety of imines and redox active esters, allowing for efficient construction of amine building blocks.

Design and facile synthesis of a photothermally active metal–organic framework bearing persistent radicalsviapost-synthetic thermal annealing

Through simple thermal annealing, post-synthetically modified MOFs with biradical properties were obtained. These MOFs bear persistent radicals, even stable in boiling water, and exhibit high conversion efficiency in solar-driven water evaporation.

The First Observation of the Formation of Persistent Aminoxyl Radicals and Reactive Nitrogen Species on Photoirradiated Nitrogen-Containing Microplastics.

Nitrogen-containing microplastics (N-MPs) are widely present in the atmosphere, but their potential health risks have been overlooked. In this study, the formation of persistent aminoxyl radicals (PAORs) and reactive nitrogen species (RNSs) on the N-MPs under light irradiation was investigated. After photoaging, an anisotropic triplet with the g-factor of ∼2.0044, corresponding to PAORs, was detected on the nonaromatic polyamide (PA) rather than amino resin (AmR) by electron paramagnetic resonance and confirmed by density functional theory calculations. The generated amine oxide portions on the photoaged PA were identified using X-ray photoelectron spectroscopy and Raman spectroscopy, which were considered to be the main structural basis/precursors of a PAOR. Surprisingly, RNSs were also observed on the irradiated PA. The generated ·NO due to the aphotolysis of nitrone groups simultaneously reacted with peroxide radicals and O2·- to yield ·NO2 and peroxynitrite, respectively, which were responsible for peroxyacyl nitrates (PAN) and CO3·- formation. Besides, a significantly higher oxidative potential and reductive potential were observed for the aged PA than AmR, which is assigned to the abundant RNSs, organic hydroperoxides and PANs, and a strong ability to transfer electrons from PAOR, respectively. This work provides important information for the potential risks of airborne N-MPs and may serve as a guide for future toxicological assessments.

The sorption of Tebuconazole and Linuron from an Aqueous Environment with a Modified Sludge-Based Biochar: Effect, Mechanisms, and Its Persistent Free Radicals Study

In this study, the sludge-based biochar was prepared and utilized as an adsorbent for the removal of two commonly used pesticides in agriculture, namely tebuconazole (Teb) and linuron (Lin) in an aqueous solution. The main contributing factors such as biochar preparation conditions, persistent free radicals as well as contact time, agitation speed, biochar dose, temperature, and pH were investigated. The physicochemical properties were characterized by SEM + EDS, FTIR, BET, EPR, etc. The results showed that the maximum adsorption capacities based on the Langmuir model was 7.8650 mg g−1 for tebuconazole and that based on Freundlich model was 9.0645 mg·g-1 for linuron at 25°C. The pseudo-second-order kinetic equations were all fitted well to the kinetic process of the adsorption of the two pesticides with all R2 ≥ 0.915. The maximum values of tebuconazole adsorption capacity occur at pH = 3. Meanwhile, linuron was not affected by pH. Both Cr6+ (r = −0.793∗∗/ −0.943∗∗) and humic acid (r = −0.798∗∗/ −0.947∗∗) significantly inhibited the adsorption amount of tebuconazole and linuron onto the biochar. Electron spin resonance signals (ESR) indicated that environmentally persistent radicals (EPFRs) are preferentially formed at lower pyrolysis temperatures and lower transition metal concentrations. The g-factors for BC400, BC600, BCF400, and BCF600 were 2.0036, 2.0035, 2.0034, and 2.0033, respectively, indicating that the EPFRs mainly have a carbon-centered structure with adjacent oxygen atoms. In addition, to close to the actual situation, natural water (from YanTai) was collected to simulate pesticide contamination. This study demonstrates that sludge-based biochar can achieve efficient removal of tebuconazole and linuron in aqueous environment in a short period of time with no secondary environmental risk especially on the waste activated sludge.

Labile Photo-Induced Free Radical in α-Ketoglutaric Acid: a Universal Endogenous Polarizing Agent for In Vivo Hyperpolarized 13 C Magnetic Resonance.

Hyperpolarized (HP) 13 C magnetic resonance enables non-invasive probing of metabolism in vivo. To date, only 13 C-molecules hyperpolarized with persistent trityl radicals have been injected in humans. We show here that the free radical photo-induced in alpha-ketoglutaric acid (α-KG) can be used to hyperpolarize photo-inactive 13 C-molecules such as [1-13 C]lactate. α-KG is an endogenous molecule with an exceptionally high radical yield under photo-irradiation, up to 50 %, and its breakdown product, succinic acid, is also endogenous. This radical precursor therefore exhibits an excellent safety profile for translation to human studies. The labile nature of the radical means that no filtration is required prior to injection while also offering the opportunity to extend the 13 C relaxation time in frozen HP 13 C-molecules for storage and transport. The potential for in vivo metabolic studies is demonstrated in the rat liver following the injection of a physiological dose of HP [1-13 C]lactate.

Labile Photo-Induced Free Radical in α-Ketoglutaric Acid: a Universal Endogenous Polarizing Agent for In Vivo Hyperpolarized 13C Magnetic Resonance.

Hyperpolarized (HP) 13C magnetic resonance enables non-invasive probing of metabolism in vivo. To date, only 13C-molecules hyperpolarized with persistent trityl radicals have been injected in humans. We show here that the free radical photo-induced in alpha-ketoglutaric acid (α-KG) can be used to hyperpolarize photo-inactive 13C-molecules such as [1-13C]lactate. α-KG is an endogenous molecule with an exceptionally high radical yield under photo-irradiation, up to 50 %, and its breakdown product, succinic acid, is also endogenous. This radical precursor therefore exhibits an excellent safety profile for translation to human studies. The labile nature of the radical means that no filtration is required prior to injection while also offering the opportunity to extend the 13C relaxation time in frozen HP 13C-molecules for storage and transport. The potential for in vivo metabolic studies is demonstrated in the rat liver following the injection of a physiological dose of HP [1-13C]lactate.

Protein Modification at Tyrosine with Iminoxyl Radicals.

Post-translational modifications (PTMs) of proteins are a biological mechanism for reversibly controlling protein function. Synthetic protein modifications (SPMs) at specific canonical amino acids can mimic PTMs. However, reversible SPMs at hydrophobic amino acid residues in proteins are especially limited. Here, we report a tyrosine (Tyr)-selective SPM utilizing persistent iminoxyl radicals, which are readily generated from sterically hindered oximes via single-electron oxidation. The reactivity of iminoxyl radicals with Tyr was dependent on the steric and electronic demands of oximes; isopropyl methyl piperidinium oxime 1f formed stable adducts, whereas the reaction of tert-butyl methyl piperidinium oxime 1o was reversible. The difference in reversibility between 1f and 1o, differentiated only by one methyl group, is due to the stability of iminoxyl radicals, which is partly dictated by the bond dissociation energy of oxime O-H groups. The Tyr-selective modifications with 1f and 1o proceeded under physiologically relevant, mild conditions. Specifically, the stable Tyr-modification with 1f introduced functional small molecules, including an azobenzene photoswitch, to proteins. Moreover, masking critical Tyr residues by SPM with 1o, and subsequent deconjugation triggered by the treatment with a thiol, enabled on-demand control of protein functions. We applied this reversible Tyr modification with 1o to alter an enzymatic activity and the binding affinity of a monoclonal antibody with an antigen upon modification/deconjugation. The on-demand ON/OFF switch of protein functions through Tyr-selective and reversible covalent-bond formation will provide unique opportunities in biological research and therapeutics.

Unrevealing the Mechanism of Aminoxyl Catalyzed Electrochemical Oxidation of Alcohols By Unpolished Glassy Carbon Electrode

2,2,6,6-tetramethyl-1-piperidine N-oxyl (TEMPO, 1) and related aminoxyl derivatives are important catalysts for alcohol oxidation. They are featured in the synthesis of pharmaceuticals and recently found considerable attention for the conversion of hydroxyl bearing biomass-derived feedstocks to value-added products. Aminoxyl compounds undergo facile redox reactions at electrode surfaces, enabling them to mediate electrochemical oxidation of alcohols.The well-known electron transfer reaction of these persistent radicals involves a reversible one electron oxidation to the corresponding oxoammonium species (TEMPO+ , 3), which are relatively strong oxidants. Aminoxyl radicals can also undergo a proton coupled reduction to hydroxylamines (2), which is quasireversible and less known. However, for many of their electrosynthetic reactions, the catalytic cycle involves not only aminoxyl/oxoammonium redox couple, but also formation of hydroxylamines and regeneration of the oxoammonium from the hydroxylamine. This two steps oxidation has been proposed to occur via two distinct pathways: the comproportionation reaction between the hydroxylamine and a second oxoammonium cation to form aminoxyloxyl radical (two) followed by oxidation of aminoxyl radicals to oxoammonium (pathway b), or the two-electron oxidation of the hydroxylamine to the oxoammonium (pathway a). The electron transfer of the hydroxylamine, at the electrode surface, is a quasireversible ill-defined reaction that strongly depends on the electrode material and conditionings, and its detailed understanding is still lacking. Herein, we investigated the electron transfer reaction of TEMPO and its hydroxylamine, is formed during catalytic alcohol oxidation, using the glassy carbon electrodes that treated under different conditions. Well-treated electrode facilitates the electron transfer of hydroxylamine and enables two-electrons oxidation to oxoammonium, whereas on the untreated electrode, two separated one-electron oxidations are observed that enables measuring the rate of generation and consumption of hydroxylamine. Understanding of how each regeneration pathway affects the catalytic behavior made it possible to comprehensively understand all the features of the current profiles obtained under various alcohol oxidation conditions. Figure 1. Possible mechanism for regeneration of oxoammonium during aminoxyl catalyzed alcohol oxidation. Figure 1

Spontaneous Production of Ultrastable Reactive Oxygen Species on Titanium Oxide Surfaces Modified with Organic Ligands

AbstractThe spontaneous formation and long‐term surface stabilization of superoxide radicals are observed on specific TiO2 hybrid materials in which titanium is coordinated to an organic ligand. Here the rationale for this uncommon phenomenon is investigated by a synergistic theoretical and experimental approach involving density functional theory (DFT) calculations and spectroscopic techniques. Stoichiometric and reduced anatase (101) surfaces modified with acetylacetone, dibenzoylmethane, and catechol are comparatively examined. These results reveal that the interaction between organic ligands and adsorbed O2 molecules improves when O vacancies are present on the external layer of the surface, promoting O2 reduction. The electronic features of the ligand play a pivotal role for both an effective electronic interaction with the surface and the stabilization of the generated reactive oxygen species. These results agree with experimental data showing that sol–gel‐derived Ti‐diketonate hybrid oxides spontaneously produce very persistent superoxide radicals under ambient conditions, thus holding a high intrinsic oxidative activity.

Carborane Stabilized "19-Electron" Molybdenum Metalloradical.

Paramagnetic metal complexes gained a lot of attention due to their participation in a number of important chemical reactions. In most cases, these complexes are dominated by 17-e metalloradicals that are associatively activated with highly reactive paramagnetic 19-e species. Molybdenum paramagnetic complexes are among the most investigated ones. While some examples of persistent 17-e Mo-centered radicals have been reported, in contrast, 19-e Mo-centered radicals are illusive species and as such could rarely be detected. In this work, the photodissociation of the [Cp(CO)3Mo]2 dimer (1) in the presence of phosphines was revisited. As a result, the first persistent, formally 19-e Mo radical with significant electron density on the Mo center (22%), Cp(CO)3Mo•PPh2(o-C2B10H11) (5b), was generated and characterized by EPR spectroscopy and MS as well as studied by DFT calculations. The stabilization of 5b was likely achieved due to a unique electron-withdrawing effect of the o-carboranyl substituent at the phosphorus center.

Wavelength-Gated Photochemical Synthesis of Phenalene Diimides.

Herein, we pioneer a wavelength‐gated synthesis route to phenalene diimides. Consecutive Diels–Alder reactions of methylisophthalaldehydes and maleimides afford hexahydro‐phenalene‐1,6‐diol diimides via 5‐formyl‐hexahydro‐benzo[f]isoindoles as the intermediate. Both photoreactions are efficient (82–99 % yield) and exhibit excellent diastereoselectivity (62–98 % d.r.). The wavelength‐gated nature of the stepwise reaction enables the modular construction of phenalene diimide scaffolds by choice of substrate and wavelength. Importantly, this synthetic methodology opens a facile avenue to a new class of persistent phenalenyl diimide neutral radicals, constituting a versatile route to spin‐active molecules.

Synthesis of Fluorogenic Arylureas and Amides and Their Interaction with Amines: A Competition between Turn-on Fluorescence and Organic Radicals on the Way to a Smart Label for Fish Freshness

We describe the synthesis of fluorogenic arylureas and amides and their interaction with primary or secondary amines under air and light in organic-aqueous mixtures to give rise to a new class of persistent organic radicals, described on the basis of their electron paramagnetic resonance (EPR), as well as UV–vis, fluorescence, NMR, and quantum mechanics calculations, and their prospective use as multi-signal reporters in a smart label for fish freshness.