Undergo Electron Transfer Research Articles

Photoinduced Radical Borylation of Robust Carbon–Heteroatom Bonds

AbstractPhotoinduced borylation has emerged as a valuable strategy for synthesizing arylboronic esters. However, photochemical transformations involving inert bonds such as C(sp2)−F bonds are still challenging. Herein, we report a straightforward and operationally simple method for the activation of various inert carbon–heteroatom bonds, enabling the synthesis of diverse arylboronic esters without the need for transition metals or catalysts. Mechanistic investigations reveal that the deprotonation of DMSO plays a pivotal role in the reaction, and the excited DMSO anion can undergo electron transfer to the aryl substrates activated by anionic sp2–sp3 diboron compounds, i. e., [FB2pin2]−, thereby facilitating the cleavage of carbon–heteroatom bonds. The reaction allows the conversion of diverse Caryl–hetero bonds in batch and flow reactors into the corresponding arylboronic esters. The products can be used in a subsequent Suzuki‐Miyaura cross‐coupling without isolation.

Redox factors in the antioxidant activity of nitroxides toward DNA guanyl and 2-deoxyribose-peroxyl radicals

A series of eight nitroxide compounds (four substituted piperidines, three pyrrolidines and one oxo-piperidine) are found to undergo electron transfer to 2’-deoxyribose-peroxyl and the guanyl radical. One-electron oxidation potentials of the nitroxides to oxoammonium cations (oxoammonium reduction potential), E 0’, have been measured against a common redox indicator, chlorpromazine, and found to span the range 751 ± 15 mV to 973 ± 15 mV. Fast chemical reduction of the 2’-deoxyribose-peroxyl radical to the hydroperoxide, generated by • OH radical attack on 2-deoxyribose, dR, in oxygenated aqueous solution, is a redox-dependent reaction, with rate constants of 0.8–3.5 x 107 M−1 s−1.The guanyl radicals, produced upon one-electron oxidation of 2’-deoxyguanosine monophosphate, dG, by the selenite radical, SeO3 • -, react with the nitroxides in a redox-independent reaction with diffusion rate constants of 1–2 x 108 M−1 s−1. These findings represent a possible antioxidant role for nitroxides in the fast chemical repair of DNA radicals, which is supported by an in vitro strand break study using a plasmid.

Polydopamine‐Mediated Contact‐Electro‐Catalysis for Efficient Partial Oxidation of Methane

The direct conversion and efficient utilization of methane pose a critical scientific challenge. Indirect activation via reactive oxygen species (ROS) offers a high probability of contact with methane and conversion efficiency under mild conditions. However, reported product yields are suboptimal due to challenges in activating oxygen and facilitating mass transfer in suspension systems. We propose the use of contact‐electro‐catalysis (CEC), employing polydopamine (PDA) as a catalyst that undergoes electron transfer with oxygen under ultrasound, generating ROS that drives the partial oxidation of methane (POM). Corresponding experimental results indicate that CH3OH and most HCHO are produced directly from CH4. Furthermore, through in situ characterizations, we have shown that light pretreatment of the catalysts in an oxygenated atmosphere facilitates the forming of more C=O functional groups with strong electron‐withdrawing properties, thereby significantly enhancing overall product yields, particularly for CH3OH. Within two hours, product yields reach 1.5 mmol·gcat−1 for HCHO and 0.9 mmol·gcat−1 for CH3OH. This work introduces a novel approach for efficient POM, while highlighting the distinctive catalytic properties of PDA.

Polydopamine-Mediated Contact-Electro-Catalysis for Efficient Partial Oxidation of Methane.

The direct conversion and efficient utilization of methane pose a critical scientific challenge. Indirect activation via reactive oxygen species (ROS) offers a high probability of contact with methane and conversion efficiency under mild conditions. However, reported product yields are suboptimal due to challenges in activating oxygen and facilitating mass transfer in suspension systems. We propose the use of contact-electro-catalysis (CEC), employing polydopamine (PDA) as a catalyst that undergoes electron transfer with oxygen under ultrasound, generating ROS that drives the partial oxidation of methane (POM). Corresponding experimental results indicate that CH3OH and most HCHO are produced directly from CH4. Furthermore, through in situ characterizations, we have shown that light pretreatment of the catalysts in an oxygenated atmosphere facilitates the forming of more C=O functional groups with strong electron-withdrawing properties, thereby significantly enhancing overall product yields, particularly for CH3OH. Within two hours, product yields reach 1.5 mmol·gcat-1 for HCHO and 0.9 mmol·gcat-1 for CH3OH. This work introduces a novel approach for efficient POM, while highlighting the distinctive catalytic properties of PDA.

Therapeutic Applications of Azo Dye Reduction: Insights From Methyl Orange Degradation for Biomedical Innovations.

This paper emphasizes the possible application of methyl orange reduction as a therapeutic technique, highlighting the potential of azo dye reduction in biomedical fields. The generally used azo dyes are toxic and carcinogenic; hence, they implicitly threaten the environment and health. The degradation of methyl orange, a famous example of azo dyes, is used to describe the degradation process for other azo dyes. This work discusses the ability of different methyl orange degradation methods, focusing on biocatalysts and nanomaterials, among the methods that identified enzymatic degradation with azoreductase enzymes as the method that quickly breaks down azo dyes under mild conditions as the most appropriate method, as well as its specificity as environmentally friendly. Moreover, metal nanoparticles such as silver and gold impellers increase the reducing efficiency because they offer a pivotal surface for the reduction reactions that undergo electron transfer. The complete breakdown of methyl orange is essential in biomedical usage. The strategies for treating azo dye reduction can be extended to next-generation drug delivery systems (DDS), biosensors, and therapeutic agents. Organisms involved in degradation can be functionalized to selectively degrade specific cells or tissues, thus presenting a new targeted therapy. Knowledge of degradation pathways and non-toxic products is essential in creating programs that build better and more efficient therapeutic agents. This work endeavors to illustrate the development of enzymatic and nanomaterials-based approaches to achieve sustainable azo dye decolorisation to open the gateway to developing other biomedical applications that tend to promote environmental and health-friendly solutions.

Visible Light-Induced Oxy-perfluoroalkylation of Olefins via Ternary Electron Donor-Acceptor Complexes.

Perfluoroalkyl iodides generally formed electron donor-acceptor (EDA) complexes by halogen bonding with a nitrogen atom containing Lewis bases. Since the electronegativity of the oxygen atom is stronger than that of the nitrogen atom, the resulting Rf-I···O-type halogen bonding EDA complex is less inclined to undergo electron transfer. Here, we reported rare ternary EDA complexes among perfluoroalkyl iodide, oxygen atom, and base. Mechanism experiments and density functional theory theoretical (DFT) calculations indicated that a base-promoted proton-coupled electron transfer (PCET) process was involved in this photochemical reaction. The intracomplex electron transfer event generated two radical species, perfluoroalkyl radical and TEMPO radical, enabling the subsequent oxy-perfluoroalkylation of olefins.

Viologen‐based host–guest supramolecule with tunable intramolecular/intermolecular electron transfer chromism and dynamic fluorescence

AbstractViologen, as a type of strong electron acceptor, is prone to undergo electron transfer (ET) and change color under external stimuli. However, due to the easy aggregation of viologen molecules, they usually suffer from poor fluorescence emission in the condensed phase. Herein, a new viologen derivative of VioCl2·2Cl (12+·2Cl) was designed and synthesized, in which the fluorescence was enhanced by introducing Me‐β‐CD to weaken the interactions between viologen molecules. Then a viologen‐based host–guest supramolecule of 12+@Me‐β‐CD was obtained by electrostatic interactions. Photo‐/chemo‐responded guest 12+ supplies 12+@Me‐β‐CD, a green and dark purple caused by intramolecular and intermolecular ET. Furthermore, 12+@Me‐β‐CD displays an additional thermal responsive purple color. The triple chromic behaviors all exhibit excellent reversibility and cycling stability. As expected, 12+@Me‐β‐CD exhibits strong photoluminescence (PL) in solid–liquid dual states, presenting an improved quantum yield (Φ) from 12+ (Φs = 0.37%, Φl = 16.74%) to 12+@Me‐β‐CD (Φs = 10.45%, Φl = 25.86%), and the fluorescence intensity can be dynamically modulated by light, heat, and acid/base vapors. The multi‐responsive chromism and tunable fluorescence of 12+@Me‐β‐CD allow for potential applications in information security and smart windows.

Bioinspired polyoxometalates as light-driven water oxidation catalysts

The design of molecular systems with capabilities to carry out the water oxidation reaction and thereby overcome the bottleneck of artificial photosynthesis is one of the scientific fields of most significant interest and urgency due to its potential to address energy demand and climate change. Nevertheless, the search for efficient and robust catalysts has been limited by the degradation of carbon-based ligands under oxidative conditions, leading to the search for fully inorganic catalysts. Polyoxometalates (POMs), an emerging class of carbon-free ligands with oxygen-enriched surfaces, offer a unique alternative as inorganic scaffolds to self-assemble and stabilize transition-metal clusters with unique redox properties. Under catalytic working conditions, POMs can undergo electron transfer reactions coupled to O2 formation without modifying their parental structure. As a result, these materials have recently entered the scene as catalytic players in designing new artificial photosynthetic platforms for water oxidation. We focus on the methods used to create these compounds, their unique structural characteristics, and how effectively they function as catalysts. We also explore the proposed mechanisms behind their ability to produce O2 and their potential use in designing photosynthetic devices.

Thermal and protonation-induced electron transfer coupled spin transition in a discrete [Fe2Co3] Prussian blue analogue.

Multi-stimuli responsive switchable molecules have garnered interest for their potential applications in the field of magnetic materials. However, the persistent challenge lies in isolating these properties within the same material. Herein, we report a discrete [Fe2Co3] pentanuclear cyanide bridged complex, [Co(L)2]3[Fe(CN)6]2·20H2O, (1) (L = (Z)-N'-(4-(trifluoromethyl)phenyl)picolinimidamide) which undergoes electron transfer coupled spin transition (ETCST) from [FeII2CoIIHSCoIII2] to [FeIII2CoII3] configurations through thermal activation and upon protonation.

Nanoconfinement of polyoxometalates in cyclodextrin: computational inspections of the binding affinity and experimental demonstrations of reactivity modulation.

Chaotropic polyoxometalates (POMs) form robust host-guest complexes with γ-cyclodextrin (γ-CD), offering promising applications in catalysis, electrochemical energy storage, and nanotechnology. In this article, we provide the first computational insights on the supramolecular binding mechanisms using density-functional theory and classical molecular dynamics simulations. Focusing on the encapsulation of archetypal Keggin-type POMs (PW12O40 3-, SiW12O40 4- and BW12O40 5-), our findings reveal that the lowest-charged POM, namely PW12O40 3- spontaneously confines within the wider rim of γ-CD, but BW12O40 5- does not exhibit this behaviour. This striking affinity for the hydrophobic pocket of γ-CD originates from the structural characteristics of water molecules surrounding PW12O40 3-. Moreover, through validation using 31P NMR spectroscopy, we demonstrate that this nanoconfinement regulates drastically the POM reactivity, including its capability to undergo electron transfer and intermolecular metalate Mo/W exchanges. Finally, we exploit this nanoconfinement strategy to isolate the elusive mixed addenda POM PW11MoO40 3-.

Adsorption of As(V) and P(V) by magnetic iron-based alginate-chitosan beads: Competitive adsorption and reduction mechanism of As(V) induced by Fe(II)

Assessing the adsorption competition between arsenate (As(V)) and phosphate (P(V)) is crucial due to their coexistence in water. This paper studied the competitive adsorption processes of As(V) and P(V) on magnetic iron-based alginate-chitosan beads by beaker experiments, simultaneously using XRD and FTIR techniques for characterization. In the single system, both As(V) and P(V) adsorption on M-IACBs followed the Langmuir model, with maximum adsorption capacities of 14.2 ± 0.4 mg g−1 and 18.5 ± 0.4 mg g−1, respectively. In the binary system, the competitive adsorption of As(V) and P(V) is a multilevel heterogeneous process well evaluated by the extended Freundlich and pseudo-second-order models. When loaded simultaneously, the adsorption of As(V) was more significant than that of P(V) (2.72 mg g−1 vs. 1.71 mg g−1). The desorption of P(V) was favored over As(V) during sequential loading, and the adsorption of P(V) was more influenced by pH compared to As(V). The adsorption affinity of the composites follows the order: As(V) < P(V) (for the single system) and As(V) > P(V) (for the binary system). Finally, changes in arsenic species were studied under anoxic aqueous solutions and oxygen-enriched air. In aqueous solutions, As(V) is reduced to the more toxic and mobile As(III) by Fe(II), and As(III) exhibits desorption-readsorption behavior. In oxygen-enriched air, As(V) undergoes electron transfer with Fe(II) and O2, resulting in the appearance of As(III), which can also be oxidized back to As(V). This study provides an objective and critical evaluation of the data regarding the use of Fe-based adsorbents in removing As(V), offering novel insights for designing such adsorbents.

Sterically‐Hindered Molecular p‐Dopants Promote Integer Charge Transfer in Organic Semiconductors

AbstractMolecular p‐dopants designed to undergo electron transfer with organic semiconductors are typically planar molecules with high electron affinity. However, their planarity can promote the formation of ground‐state charge transfer complexes with the semiconductor host and results in fractional instead of integer charge transfer, which is highly detrimental to doping efficiency. Here, we show this process can be readily overcome by targeted dopant design exploiting steric hindrance. To this end, we synthesize and characterize the remarkably stable p‐dopant 2,2′,2′′‐(cyclopropane‐1,2,3‐triylidene)tris(2‐(perfluorophenyl)acetonitrile) comprising pendant functional groups that sterically shield its central core while retaining high electron affinity. Finally, we demonstrate it outperforms a planar dopant of identical electron affinity and increases the thin film conductivity by up to an order of magnitude. We believe exploiting steric hindrance represents a promising design strategy towards molecular dopants of enhanced doping efficiency.

Sterically-Hindered Molecular p-Dopants Promote Integer Charge Transfer in Organic Semiconductors.

Molecular p-dopants designed to undergo electron transfer with organic semiconductors are typically planar molecules with high electron affinity. However, their planarity can promote the formation of ground-state charge transfer complexes with the semiconductor host and results in fractional instead of integer charge transfer, which is highly detrimental to doping efficiency. Here, we show this process can be readily overcome by targeted dopant design exploiting steric hindrance. To this end, we synthesize and characterize the remarkably stable p-dopant 2,2',2''-(cyclopropane-1,2,3-triylidene)tris(2-(perfluorophenyl)acetonitrile) comprising pendant functional groups that sterically shield its central core while retaining high electron affinity. Finally, we demonstrate it outperforms a planar dopant of identical electron affinity and increases the thin film conductivity by up to an order of magnitude. We believe exploiting steric hindrance represents a promising design strategy towards molecular dopants of enhanced doping efficiency.

Electron Acceptor Molecule Doping Induced π–π Interaction to Promote Charge Transport Kinetics for Efficient and Stable 2D/3D Perovskite Solar Cells

AbstractAlthough the incorporation of 2D perovskite into 3D perovskite can greatly enhance intrinsic stability, power conversion efficiency (PCE) of 2D/3D perovskite is still inferior to its 3D counterpart due to poor carrier transport kinetics resulted from the quantum and dielectric confinement of 2D component. To overcome this issue, the electron acceptor molecule 1,2,4,5‐tetracyanobenzene (TCNB) was introduced to trigger intermolecular π–π interaction in 2D perovskite along with the electronic doping of 2D/3D perovskite to improve charge transfer efficiency. By virtue of high electron affinity, TCNB can undergo electron transfer reaction and subsequently establish π–π interaction with 1‐naphthalenemethylammonium (NMA) cations, greatly strengthening lattice rigidity and reducing exciton binding energy. Transmission electron microscopy results demonstrate that 2D phases are mainly distributed at grain boundaries, reducing defect density and weakening nonradiative recombination. Meanwhile, the p‐type doping of perovskite by TCNB optimizes energy level alignment at perovskite/hole transport layer interface. Consequently, PCE of champion device is significantly boosted to 24.01 %. The unencapsulated device retains an initial efficiency close to 94 % after exposure to ambient environment for over 1000 h. This work paves a novel path for designing new mixed‐dimensional perovskite solar cells with high PCE and superior stability.

Electron Acceptor Molecule Doping Induced π-π Interaction to Promote Charge Transport Kinetics for Efficient and Stable 2D/3D Perovskite Solar Cells.

Although the incorporation of 2D perovskite into 3D perovskite can greatly enhance intrinsic stability, power conversion efficiency (PCE) of 2D/3D perovskite is still inferior to its 3D counterpart due to poor carrier transport kinetics resulted from the quantum and dielectric confinement of 2D component. To overcome this issue, the electron acceptor molecule 1,2,4,5-tetracyanobenzene (TCNB) was introduced to trigger intermolecular π-π interaction in 2D perovskite along with the electronic doping of 2D/3D perovskite to improve charge transfer efficiency. By virtue of high electron affinity, TCNB can undergo electron transfer reaction and subsequently establish π-π interaction with 1-naphthalenemethylammonium (NMA) cations, greatly strengthening lattice rigidity and reducing exciton binding energy. Transmission electron microscopy results demonstrate that 2D phases are mainly distributed at grain boundaries, reducing defect density and weakening nonradiative recombination. Meanwhile, the p-type doping of perovskite by TCNB optimizes energy level alignment at perovskite/hole transport layer interface. Consequently, PCE of champion device is significantly boosted to 24.01 %. The unencapsulated device retains an initial efficiency close to 94 % after exposure to ambient environment for over 1000 h. This work paves a novel path for designing new mixed-dimensional perovskite solar cells with high PCE and superior stability.

New strategy of drinking water sludge as conditioner to enhance waste activated sludge dewaterability: Collaborative disposal

Drinking water sludge (DWS) and waste activated sludge (WAS) are usually treated separately. With the continuous deepening understanding of the characteristics of two types sludge, the research and application of the collaborative disposal is worth considering. The heated modification DWS (HDWS) rich in inorganic matter and aluminum (Al2O3) can be used as a conditioner to enhance WAS dewaterability using its properties with physical skeleton and chemically catalyzed ozone (O3). The results showed that the minimum values of capillary water time (CST) and specific resistance filtration (SRF) for WAS were 20.9±2.40 s and 1.07±0.19×1013 m/kg at pH=4, O3 dosage=60 mg/g VS and HDWS dosage=700 mg/g VS, corresponding to the reduction of sludge cake water content (Wc) to 60.37±0.97 %. The mechanism of HDWS+O3 enhanced WAS dewaterability was systematically elucidated through pyridine-infrared analysis and density functional theory (DFT) calculations. The surface of Al2O3 in HDWS had more Lewis acidic sites, and the oxygen atoms of O3 combined with Al atoms to form Al-O bonds and undergo electron transfer, while O3 molecules dissociated to produce more hydroxyl radicals (·OH). With the oxidation of ·OH, the extra-microcolony/cellular polymers (EMPS/ECPS) structure were destroyed and became looser, promoting the conversion of internal moisture to free moisture. Zeta potential tended to zero, particle size increased, and the surface was more hydrophobic. Correlation analysis revealed that the component content, protein (PN) secondary structure and molecular weight (MW) in ECPS were positively and more strongly correlated with the sludge dewaterability compared to EMPS. The discovery of HDWS+O3 applied to effectively enhance WAS dewaterability provided an inspiring perspective on the emerging DWS and WAS co-processing disposition.

Two-electron transfer photoreduction of methyl viologen and perfluorooctanoic acid mediated by flavin mononucleotide at colloidal titanium dioxide interfaces

Environmentally friendly catalyst consisting of a flavin mononucleotide and titanium dioxide nanoparticles for MV2+ and poly-fluorinated octanoic acid reduction.

Finite Element Modeling of the Combined Faradaic and Electrostatic Contributions to the Voltammetric Response of Monolayer Redox Films.

The voltammetric response of electrodes coated with a redox-active monolayer is computed by finite element simulations based on a generalized model that couples the Butler–Volmer, Nernst–Planck, and Poisson equations. This model represents the most complete treatment of the voltammetric response of a redox film to date and is made accessible to the experimentalist via the use of finite element modeling and a COMSOL-generated report. The model yields a full description of the electric potential and charge distributions across the monolayer and bulk solution, including the potential distribution associated with ohmic resistance. In this way, it is possible to properly account for electrostatic effects at the molecular film/electrolyte interface, which are present due to the changing charge states of the redox head groups as they undergo electron transfer, under both equilibrium and nonequilibrium conditions. Specifically, our numerical simulations significantly extend previous theoretical predictions by including the effects of finite electron-transfer rates (k0) and electrolyte conductivity. Distortion of the voltammetric wave due to ohmic potential drop is shown to be a function of electrolyte concentration and scan rate, in agreement with experimental observations. The commonly used Laviron analysis for the determination of k0 fails to account for ohmic drop effects, which may be non-negligible at high scan rates. This model provides a more accurate alternative for k0 determination at all scan rates. The electric potential and charge distributions across an electrochemically inactive monolayer and electrolyte solution are also simulated as a function of applied potential and are found to agree with the Gouy-Chapman-Stern theory.

Protic Ferrocenyl Acyclic Diamino Carbene Gold(I) Complexes

AbstractTwo mononuclear protic ferrocenyl acyclic diamino carbene gold(I) complexes AuCl[C(NHFc)(NR2)] were prepared by nucleophilic attack of diethylamine (R = Et) and diisopropylamine (R = iPr) at the ferrocenyl substituted isocyanide complex chlorido(isocyanoferrocene)gold(I) AuCl(CN−Fc). In the solid state, the multifunctional protic carbene gold(I) complexes display intermolecular aurophilic interactions or intermolecular NH⋅⋅⋅Cl hydrogen bonding in addition to intramolecular non‐classical NH⋅⋅⋅Fe hydrogen bonds. Oxidation of the AuCl[C(NHFc)(NR2)] complexes initially takes place at the iron centres giving highly coloured ferrocenium ions, which subsequently likely undergo electron transfer from gold(I) to iron(III) yielding putative EPR‐active gold(II) species.

Targeted photodynamic therapy using reconstituted high-density lipoproteins as rhodamine transporters

Reconstituted high-density lipoprotein (rHDL) nanoparticles are excellent transporters of molecules and very useful for targeted therapy as they specifically recognize the scavenger receptor, class B1 (SR-B1) that is present on the surface of a wide range of tumor cells. However, they have rarely been employed to transport photosensitizers (PS) for photodynamic therapy (PDT). Rhodamine (R) compounds have been dismissed as useful PSs for PDT due to their low 1O2 production, excitation wavelengths with little tissue penetration, and poor selectivity for tumor cells. It was recently demonstrated that when irradiating at 532 nm or with Cerenkov radiation (CR) from a β-emitting radionuclide, R123, R6G, and RB undergo electron transfer reactions (type I reaction) with folic acid. R6G also produces type I reactions with O2. In this work, the photodynamic effects of the rHDL-R system were evaluated in vitro. rHDL nanoparticles loaded with R123, R6G, and RB were synthesized, and the PS was internalized into T47D tumor cells. When cells were irradiated with a 532-nm laser in the presence of an rHDL-R systems, a cytotoxic photodynamic effect was obtained in the order R6G > R123 > RB. In the presence of CR from a 177Lu source, cytotoxicity showed the order R6G > RB > R123. The higher cytotoxicity induced by R6G in both cases corresponds to higher cellular internalization and larger production of type I and II reactions. Thus, in this work, it is proposed that rHDL-R/177Lu system can be applied in theragnostics as a multimodal radiotherapy-PDT-imaging system (imaging by SPECT or Cerenkov) and in hypoxic solid tumors in which external radiation is not effective and 177Lu-CR acts as light source.