Zero-Bias Anti-Ohmic Behaviour in Diradicaloid Molecular Wires.

Open-shell materials bearing multiple spin centres provide a key route to efficient charge transport in single-molecule electronic devices. They have narrow energy gaps, and their molecular orbitals align closely to the Fermi level of the metallic electrodes, thus allowing efficient electronic transport and higher conductance. Maintaining and stabilising multiple open-shell states - especially in contact with metallic electrodes - is however very challenging, generally requiring a continuous chemical or electrochemical potential to avoid self-immolation of the open-shell character. To overcome this issue, we designed, synthesised, and measured the conductance of a series of bis(indeno) fused acenes, where stability is imparted by a close-shell quinoidal conformation in resonance with the diradical electronic configuration. We show here that these compounds have anti-ohmic behaviour, with conductance increasing with increasing molecular length, at an unprecedented rate and across the entire bias window ([[EQUATION]]). Density Functional Theory (DFT) calculations support our findings, showing the rapidly narrowing HOMO-LUMO gap, unique to these diradicaloid structures, is responsible for the observed behaviour. Our results provide a framework for achieving efficient transport in neutral compounds and demonstrate the promise that diradicaloid materials have in single-molecule electronics, owing to their great stability and unique electronic structure.

Radical 6-Endo Addition Enables Pyridine Synthesis under Metal-Free Conditions.

Metal-free synthesis of heterocycles is highly sought after in the pharmaceutical industry and has garnered widespread attention due to its environmental sustainability and cost-effectiveness. We report a radical 6-endo addition method for pyridine synthesis from cyclopropylamides and alkynes under metal-free conditions. Various terminal and substituted alkynes are inserted as C2 units into cyclopropylamides to synthesize versatile pyridines with more than 51 examples. Mechanistic investigations and computational studies indicate the unprecedented 6-endo-trig addition of vinyl radicals to the imine nitrogen atom rather than the conventional 5-exo-trig addition to the imine carbon atom, in which the hypervalent iodine(III) plays a critical role. This reaction easily scales up with excellent functional group compatibility and suits the late-stage pyridine installation on complex molecules.

Activation of peracetic acid by electrodes using biogenic electrons: A novel energy- and catalyst-free process to eliminate pharmaceuticals.

Peracetic acid (PAA) has received increasing attention as an alternative oxidant for wastewater treatment. However, existing processes for PAA activation to generate reactive species typically require external energy input (e.g., electrically and UV-mediated activation) or catalysts (e.g., Co2+), inevitably increasing treatment costs or introducing potential new contaminants that necessitate additional removal. In this work, we developed a catalyst-free, self-sustaining bioelectrochemical approach within a two-chamber bioelectrochemical system (BES), where a cathode electrode in-situ activates PAA using renewable biogenic electrons generated by anodic exoelectrogens (e.g., Geobacter) degrading biodegradable organic matter (e.g., acetic acid) in wastewater at the anode. This innovative BES-PAA technique achieved 98 % and 81 % removal of 2 µM sulfamethoxazole (SMX) in two hours at pH 2 (cation exchange membrane) and pH 6 (bipolar membrane) using 100 µM PAA without external voltage. Mechanistic studies, including radical quenching, molecular probe validation, electron spin resonance (ESR) experiments, and density functional theory (DFT) calculations, revealed that SMX degradation was driven by reactive species generated via biogenic electron-mediated OO cleavage of PAA, with CH3C(O)OO• contributing 68.1 %, •OH of 18.4 %, and CH3C(O)O• of 9.4 %, where initial formation of •OH and CH3C(O)O• rapidly reacts with PAA to produce CH3C(O)OO•. The presence of common water constituents such as anions (e.g., Cl-, NO3-, and H2PO4-) and humic acid (HA) significantly hinders SMX removal via the BES-PAA technique, whereas CO32- and HCO3- ions have a comparatively minor impact. Additionally, the study investigated the removal of various pharmaceuticals present in secondary treated municipal wastewater, attributing differences in removal efficiency to the selective action of CH3C(O)OO•. This research demonstrates a novel PAA activation method that is ecologically benign, inexpensive, and capable of overcoming catalyst deactivation and secondary pollution issues.

A Redox-active Phenothiazine-based Pd2L4-type Coordination Cage and Its Isolable Crystalline Polyradical Cations.

Polyradical cages are of great interest because they show very fascinating physical and chemical properties, but many challenges remain, especially for their synthesis and characterization. Herein, we present the synthesis of a polyradical cation cage 14•+ through post-synthetic oxidation of a redox-active phenothiazine-based Pd2L4-type coordination cage 1. It's worth noting that 1 exhibits excellent reversible electrochemical and chemical redox activity due to the introduction of a bulky 3,5-di-tert-butyl-4-methoxyphenyl substituent. The generation of 14•+ through reversible electrochemical oxidation is investigated by in situ UV-vis-NIR and EPR spectroelectrochemistry. Meanwhile, chemical oxidation of 1 can also produce 14•+ which can be reversibly reduced back to the original cage 1, and the process is monitored by EPR and NMR spectroscopies. Eventually, we succeed in the isolation and single crystal X-ray diffraction analysis of 14•+, whose electronic structure and conformation are distinct to original 1. The magnetic susceptibility measurements indicate the predominantly antiferromagnetic interactions between the four phenothiazine radical cations in 14•+. We believe that our study including the facile synthesis methodology and in situ spectroelectrochemistry will shed some light on the synthesis and characterization of novel polyradical systems, opening more perspectives for developing functional supramolecular cages.

Observation of SOMO-HOMO Inversion in a Neutral Polycyclic Conjugated Hydrocarbon.

We report the generation of a nonbenzenoid polycyclic conjugated hydrocarbon, which consists of a biphenyl moiety substituted by indenyl units at the 4,4' positions, on ultrathin sodium chloride films by tip-induced chemistry. Single-molecule characterization by scanning tunneling and atomic force microscopy reveals an open-shell biradical ground state with a peculiar electronic configuration wherein the singly occupied molecular orbitals (SOMOs) are lower in energy than the highest occupied molecular orbital (HOMO).

Organic radicals driving polycyclic aromatic hydrocarbon polymerization with peracetic acid activation in soil.

The use of peracetic acid (PAA) in advanced oxidation processes has gained significant attention recently, but the knowledge of activating PAA to degrade polycyclic aromatic hydrocarbons (PAHs) is limited due to the variety and selectivity of reactive substances in PAA oxidation system. This paper presented the first systemically study on the degradation of PAHs by PAA activation in soil. It was found that heat-activated peracetic acid (heat/PAA) was capable of degrading phenanthrene (PHE) efficiently with degradation efficiency > 90 % within 30 min. Experimental results demonstrated that a series of reactive oxygen species (ROS) including organic radicals (RO•), hydroxyl radicals (HO•) and singlet oxygen (1O2) were generated, while acetylperoxyl (CH3C(O)OO•) and acetyloxyl (CH3C(O)O•) radicals were primarily responsible for PHE degradation in soil. Further analysis shows that polymerization products such as diphenic acid, 2'-formyl-2-biphenylcarboxylic acid and other macromolecules were dominant products of PHE degradation, suggesting polymerization driving PHE degradation instead of the conventional mineralization process. Toxicity analysis shows that most of the polymerization products had less toxicity than that of PHE. These results indicate that PAA activation was a highly effective remediation method for PAHs contaminated soil, which also provided a novel mechanism for pollutant degradation with the PAA activation process for environmental remediation.

Tailoring the selective generation of oxidative organic radicals for toxic-by-product-free water decontamination.

Peracetic acid (PAA) is emerging as a versatile agent for generating long-lived and selectively oxidative organic radicals (R-O•). Currently, the conventional transition metal-based activation strategies still suffer from metal ion leaching, undesirable by-products formation, and uncontrolled reactive species production. To address these challenges, we present a method employing BiOI with a unique electron structure as a PAA activator, thereby predominantly generating CH3C(O)O• radicals. The specificity of CH3C(O)O• generation ensured the superior performance of the BiOI/PAA system across a wide pH range (2.0 to 11.0), even in the presence of complex interfering substances such as humic acids, chloride ions, bicarbonate ions, and real-world water matrices. Unlike conventional catalytic oxidative methods, the BiOI/PAA system degrades sulfonamides without producing any toxic by-products. Our findings demonstrate the advantages of CH3C(O)O• in water decontamination and pave the way for the development of eco-friendly water decontaminations based on organic peroxides.

Efficient activation of peracetic acid by cobalt modified nitrogen-doped carbon nanotubes for drugs degradation: Performance and mechanism insight.

Peracetic acid (PAA) has garnered significant attention as a novel disinfectant owing to its remarkable oxidative capacity and minimal potential to generate byproducts. In this study, we prepared a novel catalyst, denoted as cobalt modified nitrogen-doped carbon nanotubes (Co@N-CNTs), and evaluated it for PAA activation. Modification with cobalt nanoparticles (∼4.8 nm) changed the morphology and structure of the carbon nanotubes, and greatly improved their ability to activate PAA. Co@N-CNTs/PAA catalytic system shows outstanding catalytic degradation ability of antiviral drugs. Under neutral conditions, with a dosage of 0.05 g/L Co@N-CNT-9.8 and 0.25 mM PAA, the removal efficiency of acyclovir (ACV) reached 98.3% within a mere 10 min. The primary reactive species responsible for effective pollutant degradation were identified as acetylperoxyl radicals (CH3C(O)OO•) and acetyloxyl radicals (CH3C(O)O•). In addition, density functional theory (DFT) proved that Co nanoparticles, as the main catalytic sites, were more likely to adsorb PAA and transfer more electrons than N-doped graphene. This study explored the feasibility of PAA degradation of antiviral drugs in sewage, and provided new insights for the application of heterogeneous catalytic PAA in environmental remediation.

Regulating charge transfer for enhanced PAA activation over sulfur-doped magnetic CoFe2O4: A novel strategy for simultaneous micropollutants degradation and bacteria inactivation.

Micropollutants and bacteria are prevalent pollutants in wastewater, posing significant risks to ecosystems and human health. As peracetic acid (PAA) is being increasingly used as a disinfectant, activation of PAA by low-cost and high-performance activators is a promising strategy for wastewater treatment. In this study, the sulfur-doped magnetic CoFe2O4 (SCFO) is successfully developed for efficient PAA activation to simultaneously decontaminate and disinfect wastewater. PAA/SCFO-0.3 exhibits exceptional performance, degrading 100 % of 8 µM sulfamethoxazole (SMX) with a first-pseudo reaction rate of 1.275 min-1, and achieving 5.3-log inactivation of Escherichia coli (E. coli) within 3 min at a PAA dosage of 0.2 mM and catalyst dosage of 0.025 g/L (initial pH 6.5). Scavenging experiments and electron paramagnetic resonance (EPR) analysis identify CH3C(O)O• and CH3C(O)OO• as the dominant reactive species for SMX degradation. The sulfur species in SCFO-0.3 facilitate Co2+ regeneration and regulate charge transfer, promoting PAA activation for SMX degradation. Moreover, the PAA/SCFO-0.3 system demonstrates operational feasibility over a broad range of water matrices and has excellent stability and reusability (maintaining 93 % removal of SMX after 5 cycles), demonstrating its potential for industrial applications. This study provides insights into enhancing PAA activation through sulfur doping in transition metal catalysts and highlights the practical applicability of the PAA/SCFO-0.3 system as an advanced alternative to conventional disinfection for simultaneous decontamination and disinfection in wastewater.

Bimetallic metal-organic framework as a high-performance peracetic acid activator for sulfamethoxazole degradation.

A novel 3D bimetallic metal-organic framework (MOF(Fe-Co)) was successfully prepared and its performance on sulfamethoxazole (SMX) removal in advanced oxidation process (AOP) based on peracetic acid (PAA) was evaluated. MOF(Fe-Co) exhibited an efficient catalytic performance on PAA activation for SMX degradation under neutral condition. Increasing PAA concentration could enhance SMX removal, while the variation of MOF(Fe-Co) dosage from 0.05 to 0.2 g/L had an inappreciable effect on SMX removal. According to the results of inductively coupled plasma mass spectrometry analyses and X-ray photoelectron spectroscopy, catalytic reactions mainly occurred on the surface of MOF(Fe-Co). Organic radicals (i.e., CH3C(O)OO• and CH3C(O)O•) were demonstrated to be the predominant reactive radicals for SMX degradation by MOF(Fe-Co)/PAA through radical quenching experiments. The presence of Cl- could enhance the degradation of SMX by MOF(Fe-Co)/PAA, while HCO3- and natural organic matter inhibited SMX degradation severely. Five identified degradation products were detected in this system and four possible SMX transformation pathways were proposed, including amino oxidation, S-N bond cleavage, coupling reaction and hydroxylation.

Mechanistic and Kinetic Consideration of the Photochemically Generated Oxidative Organic Radicals in Dissolved Black Carbon Solutions under Simulated Solar Irradiation.

The photochemically generated oxidative organic radicals (POORs) in dissolved black carbon (DBC) was investigated and compared with that in dissolved organic matter (DOM). POORs generated in DBC solutions exhibited higher one-electron reduction potential values (1.38-1.56 V) than those in DOM solutions (1.22-1.38 V). We found that the photogeneration of POORs from DBC is enhanced with dissolved oxygen (DO) increasing, while the inhibition of POORs is observed in reference to DOM solution. The behavior of the one-electron reducing species (DBC•-/DOM•-) was employed to explain this phenomenon. The experimental results revealed that the DO concentration had a greater effect on DBC•- than on DOM•-. Low DO levels led to a substantial increase in the steady-state concentration of DBC•-, which quenched the POORs via back-electron reactions. Moreover, the contribution of POORs to the degradation of 19 emerging organic contaminants (EOCs) in sunlight-exposed DBC and DOM solutions was estimated. The findings indicate that POORs play an important role in the photodegradation of EOCs previously known to react with triplets, especially in DBC solutions. Compared to DOM solutions, POOR exhibits a lower but considerable contribution to EOC attenuation. This study enhances the understanding of pollutant fate in aquatic environments by highlighting the role of DBC in photochemical pollutant degradation and providing insights into pollutant transformation mechanisms involving POORs.

Activation of Peracetic Acid by CoFe2O4 for Efficient Degradation of Ofloxacin: Reactive Species and Mechanism.

Peroxyacetic acid (PAA)-based advanced oxidation processes (AOPs) have attracted much attention in wastewater treatment by reason of high selectivity, long half-life reactive oxygen species (ROS), and wider applicability. In this study, cobalt ferrite (CoFe2O4) was applied to activate PAA for the removal of ofloxacin (OFX). The degradation of OFX could reach 83.0% via the CoFe2O4/PAA system under neutral conditions. The low concentration of co-existing anions and organic matter displayed negligible influence on OFX removal. The contributions of hydroxyl radicals (·OH), organic radicals (R-O·), and other reactive species to OFX degradation in CoFe2O4/PAA were systematically evaluated. Organic radicals (especially CH3C(O)OO·) and singlet oxygen (1O2) were verified to be the main reactive species leading to OFX destruction. The Co(II)/Co(III) redox cycle occurring on the surface of CoFe2O4 played a significant role in PAA activation. The catalytic performance of CoFe2O4 remained above 80% after five cycles. Furthermore, the ecotoxicity of OFX was reduced after treatment with the CoFe2O4/PAA system. This study will facilitate further research and development of the CoFe2O4/PAA system as a new strategy for wastewater treatment.

Large Mechanosensitive Thermoelectric Enhancement in Metallo-Organic Magnetic Molecules.

Organic materials are promising candidates for thermoelectric cooling and energy harvesting at room temperature. However, their electrical conductance (G) and Seebeck coefficient (S) need to be improved to make them technologically competitive. Therefore, radically new strategies need to be developed to tune their thermoelectric properties. Here, we demonstrate that G and S can be tuned mechanically in paramagnetic metallocenes, and their thermoelectric properties can be significantly enhanced by the application of mechanical forces. With a 2% junction compression, the full thermoelectric figure of merit is enhanced by more than 200 times. We demonstrate that this is because spin transport resonances in paramagnetic metallocenes are strongly sensitive to the interaction between organic ligands and the metal center, which is not the case in their diamagnetic analogue. These results open a new avenue for the development of organic thermoelectric materials for cooling future quantum computers and generating electricity from low-grade energy sources.

Phytochemical cocktail of Asanadi ganaextract in the management of diabetes.

It is of interest to investigate that the phytochemical analysis, in-vitro antioxidant potential and glycosidase inhibitory potential of Asanadi ganaa polyherbal formulation. Asanadi ganais a classical Ayurvedic polyherbal formulation, markedly used for alleviation of Prameha and Medodosha, which correlates in many ways with obesity, metabolic syndrome, and diabetes mellitus (madhumeha). The phytochemical constituents, total phenolic, total flavonoids, total tannin content, total antioxidant capacity, total reducing power, and free radical scavenging activity of the polyherbal formulation extracts were determined. Comparing it to the common medication Acarbose, its inhibitory impact against the digestive enzymes α-amylase and α-glucosidase was also examined. The formulation showed the presence of major constituents such as terpenoids, triterpenoids, sterols, flavonoids, tannins, phenolic, saponins, alkaloids and Glycosides. The ethanol extract had high phenolic content and flavonoid content, whereas the aqueous extract had more tannin content (181 ± 5.5µg/mg), (132 ± 5.50 µg/mg), (22± 1.6 µg/mg respectively. we conclude that the extracts of ayurvedic polyherbal formulations, particularly ethanol extract are a potential source of natural antioxidants and remarkable glycosidase inhibitory activity. Hence, Asanadi ganahas the potential to be a safe and effective natural treatment for the delay or prevention of diabetic complications.

Efficient and Bright Organic Radical Light-Emitting Diodes with Low Efficiency Roll-Off.

Organic radicals have been of interest due to their potential to replace nonradical-based organic emitters, especially for deep-red/near-infrared (NIR) electroluminescence (EL), based on the spin-allowed doublet fluorescence. However, the performance of the radical-based EL devices is limited by low carrier mobility which causes a large efficiency roll-off at high current densities. Here, highly efficient and bright doublet EL devices are reported by combining a thermally activated delayed fluorescence (TADF) host that supports both electron and hole transport and a tris(2,4,6-trichlorophenyl)methyl-based radical emitter. Steady-state and transient photophysical studies reveal the optical signatures of doublet luminescence mechanisms arising from both host and guest photoexcitation. The host system presented here allows balanced hole and electron currents, and a high maximum external quantum efficiency (EQE) of 17.4% at 707 nm peak emission with substantially improved efficiency roll-off is reported: over 70% of the maximum EQE (12.2%) is recorded at 10 mA cm-2 , and even at 100 mA cm-2 , nearly 50% of the maximum EQE (8.4%) is maintained. This is an important step in the practical application of organic radicals to NIR light-emitting devices.

Cucurbit[7]uril Enhances Distance Measurements of Spin-Labeled Proteins.

We report complex formation between the chloroacetamide 2,6-diazaadamantane nitroxide radical (ClA-DZD) and cucurbit[7]uril (CB-7), for which the association constant in water, Ka = 1.9 × 106 M-1, is at least one order of magnitude higher than the previously studied organic radicals. The radical is highly immobilized by CB-7, as indicated by the increase of the rotational correlation time, τrot, by a factor of 36, relative to that in the buffer solution. The X-ray structure of ClA-DZD@CB-7 shows the encapsulated DZD guest inside the undistorted CB-7 host, with the pendant group protruding outside. Upon addition of CB-7 to T4 Lysozyme (T4L) doubly spin-labeled with the iodoacetamide derivative of DZD, we observe the increase in τrot and electron spin coherence time, Tm, along with the narrowing of inter-spin distance distributions. Sensitivity of the DEER measurements at 83 K increases by a factor 4 - 9, compared to the common spin label such as MTSL, which is not affected by CB-7. Inter-spin distances of 3-nm could be reliably measured in water/glycerol up to temperatures near the glass transition/melting temperature of the matrix at 200 K, thus bringing us closer to the goal of supramolecular recognition-enabled long-distance DEER measurements at near physiological temperatures. The X-ray structure of DZD-T4L 65 at 1.12 Å resolution allows for unambiguous modeling of the DZD label (0.88 occupancy), indicating undisturbed structure and conformation of the protein.

Modulation of Radical Intermediates in Rechargeable Organic Batteries.

Organic materials have been considered as promising electrodes for next-generation rechargeable batteries in view of their sustainability, structural flexibility, and potential recyclability. The radical intermediates generated during the redox process of organic electrodes have profound effect on the reversible capacity, operation voltage, rate performance, and cycling stability. However, the radicals are highly reactive and have very short lifetime during the redox of organic materials. Great efforts have been devoted to capturing and investigating the radical intermediates in organic electrodes. Herein, this review summarizes the importance, history, structures, and working principles of organic radicals in rechargeable batteries. More importantly, challenges and strategies to track and regulate the radicals in organic batteries are highlighted. Finally, further perspectives of organic radicals are proposed for the development of next-generation high-performance rechargeable organic batteries.

Molecular Engineering of Corrole Radicals by Polycyclic Aromatic Fusion: Towards Open-Shell Near-Infrared Materials for Efficient Photothermal Therapy.

Open-shell radicals are promising near-infrared (NIR) photothermal agents (PTAs) owing to their easily accessible narrow band gaps, but their stabilization and functionalization remain challenging. Herein, highly stable π-extended nickel corrole radicals with [4n+1] π systems are synthesized and used to prepare NIR-absorbing PTAs for efficient phototheranostics. The light-harvesting ability of corrole radicals gradually improves as the number of fused benzene rings on ß-pyrrolic locations increases radially, with naphthalene- and anthracene-fused radicals and their one-electron oxidized [4n] π cations exhibiting panchromatic visible-to-NIR absorption. The extremely low doublet excited states of corrole radicals promote heat generation via nonradiative decay. By encapsulating naphthocorrole radicals with amphiphilic polymer, water-soluble nanoparticles Na-NPs are produced, which exhibit outstanding photostability and high photothermal conversion efficiency of 71.8 %. In vivo anti-tumor therapy results indicate that Na-NPs enable photoacoustic imaging of tumors and act as biocompatible PTAs for tumor ablation when triggered by 808 nm laser light. The "aromatic-ring fusion" strategy for energy-gap tuning of corrole radicals opens a new platform for developing robust NIR-absorbing photothermal materials.

Heat induced superfast diclofenac removal in Cu(II)-activated peracetic acid system: Mediation from non-radical to radical pathway.

A Cu(II)/heat coactivated peracetic acid (PAA) system for enhancing diclofenac (DCF) degradation was proposed in this work. The superiority of this synergetic activation strategy for PAA, working reactive species, catalytic mechanism and effects of reaction parameters on DCF elimination in this system were simultaneously investigated. Based on our results, the DCF loss rate in Cu(II)-heat/PAA process at pH 8.0 was about 49.3 and 4.2 times of that in Cu(II)/PAA and heat/PAA processes, respectively. Increasing the reaction temperature to 60 оC not only motivated the conversion of Cu(II) to Cu(I) but also facilitated the one-electron transfer between Cu(I) and PAA, boosting the generation of radicals. Organic radicals (mainly CH3C(O)O• and CH3C(O)OO•) were evidenced to be the core oxidizing substances dominating in the destruction of DCF while hydroxyl radical (•OH) made a minor contribution in this system by electron paramagnetic resonance (EPR) method together with scavenging experiments. This study broads the eyes into enhanced PAA activation initiated by homogenous Cu(II), providing a simple but efficient tool to degrade micropollutants.

Molecular One- and Two-Qubit Systems with Very Long Coherence Times.

General-purpose quantum computation and quantum simulation require multi-qubit architectures with precisely defined, robust interqubit interactions, coupled with local addressability. This is an unsolved challenge, primarily due to scalability issues. These issues often derive from poor control over interqubit interactions. Molecular systems are promising materials for the realization of large-scale quantum architectures, due to their high degree of positionability and the possibility to precisely tailor interqubit interactions. The simplest quantum architecture is the two-qubit system, with which quantum gate operations can be implemented. To be viable, a two-qubit system must possess long coherence times, the interqubit interaction must be well defined and the two qubits must also be addressable individually within the same quantum manipulation sequence. Here results are presented on the investigation of the spin dynamics of chlorinated triphenylmethyl organic radicals, in particular the perchlorotriphenylmethyl (PTM) radical, a mono-functionalized PTM, and a biradical PTM dimer. Extraordinarily long ensemble coherence times up to 148 µs are found at all temperatures below 100 K. Two-qubit and, importantly, individual qubit addressability in the biradical system are demonstrated. These results underline the potential of molecular materials for the development of quantum architectures.