Electron Acceptor Research Articles

Near-infrared polarity fluorescent probe for wash-free imaging lipid droplets and the application in the diagnosis of non-alcoholic fatty liver tissue

Lipid droplets (LDs), as primary cellular energy storage organelles, play essential roles not only in energy conservation but also in inflammatory responses, apoptosis, and the progression of diseases such as non-alcoholic fatty liver disease (NAFLD). Studies indicate that alterations in the polarity of LDs are closely linked to pathological factors like oxidative stress, ferroptosis, and lipophagy. Therefore, developing biological probes for precisely monitoring LDs polarity is crucial for understanding these biological phenomena and devising new therapeutic strategies. In this context, we synthesized four fluorescent probes (CNL1-CNL4) to precisely monitor the polarity of LDs using triphenylamine and carbazole derivatives as electron donors and isophorone and benzopyranonitrile units as electron acceptors, employing intramolecular charge transfer (ICT) mechanism. Our findings demonstrated that all four probes exhibited high sensitivity and specificity for polarity changes. Probes CNL2 and CNL4 were sensitive to polarity, and their maximum fluorescence intensity and maximum emission wavelength demonstrated a good linear relationship with polarity parameters within a certain range. Biological experiments demonstrated that both CNL2 and CNL4 possess excellent wash-free imaging capabilities and superior LDs targeting abilities but also enable dynamic monitoring of LDs and respond well to changes in LDs polarity under varying concentrations of oleic acid stimulation. Due to its longer emission wavelength (>650 nm), boasting excellent photostability, and featuring a larger Stokes shift (≈168 nm in acetonitrile), probe CNL4 was selected for further studies. Furthermore, probe CNL4 effectively monitors changes in LDs polarity under conditions of ferroptosis and oxidative stress. It has shown potential in the diagnosis of NAFLD tissue and during the process of lipophagy, highlighting its value in disease diagnostics and biological research. These findings not only deepen our understanding of the mechanisms underlying NAFLD progression but also provide new tools for diagnosing and treating related diseases.

Synthesis and Properties of Fused Polycyclic Donor–Acceptor Compounds Containing Carbazole and Diazapyrene Skeletons

Fused polycyclic aromatic compounds containing carbazole and diazapyrene skeletons as electron donors and acceptors, respectively, were synthesized in a few steps from readily accessible starting materials. The incorporation of diazapyrene units into the polycyclic compounds resulted in significant bathochromic shifts in their absorption and emission bands compared to those of the corresponding carbazole derivatives. Electrochemical measurements and density functional theory calculations were performed to gain further insight into their electronic properties. Our findings demonstrate that the incorporation of nitrogen atoms and substituents, as well as the different topologies of the fused‐ring system, exert a profound effect on the electronic properties of the polycyclic compounds.

Self-coupling of electron acceptor units in conjugated microporous polymers strengthening local donor-acceptor interaction for improving photocatalytic activity

The partial self-coupling of donor or acceptor unit during donor-acceptor (D-A) type CMPs synthesis is often overlooked for the effect on photocatalytic activity. Herein, we developed three D-A type CMPs, named SATE-CMP-n (n=1–3), which were constructed from triazine (TEPT) unit (A) and three salen units (D). With the rigidity of salen units increasing (the rigidity: salen-1 <salen-2 <salen-3), the self-coupling proportion of TEPT decreases. The experiments and DFT calculations reveal that salen-1 has the stronger electron-donating ability compared to salen-2 and salen-3, and that the self-coupling of TEPT units also enhances the electron-accepting ability. Therefore, SATE-CMP-1 exhibits the strongest D-A interaction and the highest separation and transfer efficiency of charge carriers, and has been used a photocatalyst for S−S and S−N coupling reactions. This work proves that the self-coupling of monomers in the construction of CMPs is not overlooked for adjusting the photocatalytic activity of catalyst.

Precisely Regulating Intermolecular Interactions and Molecular Packing of Nonfused-Ring Electron Acceptors via Halogen Transposition for High-Performance Organic Solar Cells.

The structure of molecular aggregates is crucial for charge transport and photovoltaic performance in organic solar cells (OSCs). Herein, the intermolecular interactions and aggregated structures of nonfused-ring electron acceptors (NFREAs) are precisely regulated through a halogen transposition strategy, resulting in a noteworthy transformation from a 2D-layered structure to a 3D-interconnected packing network. Based on the 3D electron transport pathway, the binary and ternary devices deliver outstanding power conversion efficiencies (PCEs) of 17.46 % and 18.24 %, respectively, marking the highest value for NFREA-based OSCs.

The impact of a ZnO space layer on enhancing the efficiency of P3HT: PCBM blend-based organic solar cells

The performance of Organic Solar Cells (OSCs) based on a composite photoactive of poly(3-hexylthiophene) (P3HT) and 6,6-phenylC61-butyric acid methyl ester (PCBM) as the donor and acceptor electrons, respectively, is examined in this paper through a simulation study. Optical Zinc oxide (ZnO) spacers between the active layer and the Aluminum (Al) cathode contact layer, serving as a hole transport layer (HTL), are compared to the usual configuration without a ZnO spacer in the second device construction. With and without the ZnO optical spacer, we calculate the electric field intensities and generation rates (G) for a range of incident wavelengths. Under AM 1.5 G at 100 mW cm−2 illumination and in the dark, the short-circuit current density (Jsc) is improved by up to 9.47% after adding the ZnO layer as an optical spacer. In addition, there is a gain of up to 11.42% in external quantum efficiency (EQE). Furthermore, the ZnO spacer layer device has a markedly higher incident photon-to-electron conversion efficiency (IPCE), going from 77% in the control device (without ZnO) to 90% with ZnO spacer layer. The numerical simulation results based on the finite element method (FEM) are consistent with the published experimental data.

Glycyrrhetinic acid interaction with solvated and free electrons studied by the CIDNP and dissociative electron attachment techniques.

Electron transfer plays a crucial role in living systems, including the generation of reactive oxygen species (ROS). Oxygen acts as the terminal electron acceptor in the respiratory chains of aerobic organisms as well as in some photoinduced processes followed by the formation of ROS. This is why the participation of exogenous antioxidants in electron transfer processes in living systems is of particular interest. In the present study, using chemically induced dynamic nuclear polarization (CIDNP) and dissociative electron attachment (DEA) techniques, we have elucidated the affinity of solvated and free electrons to glycyrrhetinic acid (GA)-the aglicon of glycyrrhizin (the main active component of Licorice root). CIDNP is a powerful instrument to study the mechanisms of electron transfer reactions in solution, but the DEA technique shows its effectiveness in gas phase processes. For CIDNP experiments, the photoionization of the dianion of 5-sulfosalicylic acid (HSSA2-) was used as a model reaction of solvated electron generation. DEA experiments testify that GA molecules are even better electron acceptors than molecular oxygen, at least under gas-phase conditions. In addition, the effect of the solvent on the energetics of the reactants is discussed.

Calculation of the geometry, absorption spectrum, and first hyperpolarizability of 4,5-dicyanoimidazole derivatives in solution. A multiscale ASEC-FEG study.

We investigate the effects of solvents on the geometry, absorption spectrum, and first hyperpolarizability of six push-pull molecules, each containing a 4,5-dicyanoimidazole group as an electron acceptor and a N,N-dimethylamino group as an electron donor, with systematically extended π-conjugated systems. Geometry optimizations in dichloromethane, methanol, water, and formamide under normal thermodynamic conditions were performed using the average solvent electrostatic configuration-free energy gradient method, which employs a discrete solvent model. The conformational structure of molecules is moderately affected by the environment, with the π-conjugated system becoming more planar in protic solvents. Solvent effects on the first hyperpolarizability result in marked increases that are in line with the red shifts of the absorption spectrum. The hyperpolarizability of smaller molecules within the set may be significantly influenced by the effects of geometry relaxation in highly polar protic solvents. The results illustrate the role of hydrogen bonds in the structure and electronic properties of push-pull molecules in protic environments. For smaller molecules, hydrogen bonds significantly contribute to enhancing the hyperpolarizability, but the effect of these specific interactions becomes less significant with the length of the π-conjugated system.

Experimental and Theoretical Investigation of the Inhibitor Efficiency of Eucalyptus globulus Leaf Essential Oil (EuEO) on Mild Steel Corrosion in a Molar Hydrochloric Acid Medium.

As a corrosion inhibitor for mild steel in a molar hydrochloric acid medium, we investigated the potential of Eucalyptus globulus essential oil (EuEO). Through electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves, and theoretical methods, including DFT/B3LYP 6-31G (d, p) and Monte Carlo simulations, the interactions between the EuEO components and the steel surface were analyzed. D-Allose, Betulinaldehyde, and Uvaol were identified as the major active compounds in the GC-MS analysis. The experimental results showed that EuEO reached an inhibitory efficiency as high as 97% at a 1 g/L concentration. The findings suggest that EuEO operates as a mixed-type inhibitor, reducing both cathodic and anodic reactions, as well as building up a protective coating on the steel surface. Simulations also confirmed that EuEO molecules function as electron donors and acceptors, enhancing corrosion resistance.

Ultrasensitive self-powered biosensor with facile chemical signal amplification strategy using hydrogen peroxide-triggered silver oxidation reaction

The amplification strategies used for self-powered biosensor based on biofuel cell (BFC-SPB) need to be further developed. Because the currently developed strategies utilized the complicated hybridization of DNA or poorly readable current signal of capacitors for amplification, which limits the practical application in public health emergencies. Here, we present a facile chemical amplification strategy for BFC-SPB. The 5-min amplification was triggered by simply adding H2O2 solution dropwise to the sensing cathode after the formation of the immune sandwich. The Ag NP of immunoprobe were oxidized to Ag(I), which can be served as the electron acceptor of the cathode. The amount of immunoprobe was positively correlated with that of the antigen, resulting in corresponding and high concentration of Ag(I) after the amplification, which enhanced the ability of the cathode as the electron acceptor. Meanwhile the glucose oxidation reaction (GOR) was performed on the bioanode modified with glucose oxidase (GOx). After assembling the bioanode and sensing cathode, the open circuit voltage of the BFC-SPB, measured by digital multimeter, distinctly rised with the elevated concentration of the antigen. To demonstrate the proof of concept, immunoglobulin G (IgG), selecting as a model analyte, was sensitively detected using this method. Result indicated that the limit of detection was 4.4 fg mL−1 (0.03 amol mL−1) in the linear range of 1 pg mL−1-10 μg mL−1. This work initiates a brand-new way of chemical amplification strategy for BFC-SPB, and offers a promising platform for practical applications.

Tailored synthesis of CoFe2O4 nanorods to prevent clogging in the microstructured biochar-supported MFC anode for sustained performance

Biochar with highly porous structures and organic functional moieties can act as an efficient micro-substrate for bacterial interaction. This study explores the potential of biochar combined with a CoFe2O4 catalyst as an anode material in Microbial Fuel Cells (MFCs). To prevent bacterial clogging of the biochar pores, we strategically synthesized rod-shaped CoFe2O4 nano substrates. When decorated on the biochar surface, these nanorods served as pillars for bacterial growth, preventing pore clogging and enhancing the electron transfer mechanism. SEM and TEM images confirmed the presence of nanorods on the biochar surface. S. putrefaciens utilizes Co+2 and Fe+2 ions released from CoFe2O4 as electron acceptors, promoting their growth and colonization on the anode surface. The contact angle measurements of the fabricated anode showed it to be hydrophilic, with a water contact angle (θw) of 37.4°. OSP analyses revealed that the anode has a textured surface, further favoring bacterial adhesion and biofilm formation. The double-chambered MFC exhibited the highest current density of 32.225 A/m3. This study underscores the importance of biochar and the strategic enhancement of electrode performance through the surface tuning of nanocatalysts for application in microbial fuel cells.

Nanostructured films of PM6 and Y6 and their assembly using Langmuir–Schaefer technique

This study investigates the molecular-level assembly and electronic properties of Langmuir and Langmuir–Schaefer (LS) films formed from Y6 (a non-fullerene electron acceptor) and PM6 (a wide bandgap electron donor polymer). We employ a variety of techniques including surface pressure-area isotherms, Brewster angle microscopy, ultraviolet-visible spectroscopy, Raman spectroscopy, and electrical characterizations to explore the behavior of these films. Our findings reveal that the films exhibit a tendency to aggregate and form non-homogeneous layers, which impacts their optical and electrical properties. The LS films show a significant sensitivity to solar radiation, which is evident from the changes in conductivity under illumination. This study highlights the potential of these materials in the development of photovoltaic applications, emphasizing the importance of molecular packing and film morphology in optimizing device performance.

Optimizing Light Dynamics: Designing ANi-MOF Functionalized g-C3N4Type II Heterostructure and a Ti3C2 MXene Schottky Junction for Efficient Photocatalytic H2 Production.

The photocatalytic production of hydrogen (H2) from water is a vital avenue towards sustainable energy and addressing global environmental challenges. To maximize efficiency, harnessing the synergistic effects of multiple co-catalysts is essential, as these interactions can significantly enhance performance. In this study, we introduce a ternary heterojunction composed of a nickel-imidazole framework (Ni-MOF), graphitic carbon nitride (CN), and Ti3C2 MXene (TC), employing solvothermal and wet impregnation methods, featuring a well-designed Type II heterojunction and a noble metal-free Schottky junction for efficient hydrogen evolution. The Type II heterojunction between Ni-MOF and CN minimizes charge carrier recombination and promotes photogenerated electron generation, while TC as an electron acceptor enhances electron capture, increases participation in surface reactions, and augments active sites. Consequently, the Ni-MOF/CN/TC hybrid catalyst achieves outstanding photocatalytic hydrogen evolution under visible light, with a peak production rate of 1044.46 μmol/g over 3 hours, surpassing CN by 13 fold and Ni-MOF/CN by 50%. This work provides insights into MXene-based ternary systems, emphasizing the potential for enhanced light absorption and efficient charge separation, making it a promising platform for photocatalytic applications.

Rational Design of a Flavoenzyme for Aerobic Nicotine Catabolism.

Enzymatic therapy with nicotine-degrading enzyme is a new strategy in treating nicotine addiction, which can reduce nicotine concentrations and weaken withdrawal in the rat model. However, when O2 is used as the electron acceptor, no satisfactory performance has been achieved with one of the most commonly studied and efficient nicotine-catabolizing enzymes, NicA2. To obtain more efficient nicotine-degrading enzyme, we rationally designed and engineered a flavoenzyme Pnao, which shares high structural similarity with NicA2 (RMSD = 1.143 Å) and efficiently catalyze pseudooxynicotine into 3-succinoyl-semialdehyde pyridine using O2. Through amino acid alterations with NicA2, five Pnao mutants were generated, which can degrade nicotine in Tris-HCl buffer and retained catabolic activity on its natural substrate. Nicotine-1'-N-oxide was identified as one of the reaction products. Four of the derivative mutants showed activity in rat serum and Trp220 and Asn224 were found critical for enzyme specificity. Our findings offer a novel avenue for research into aerobic nicotine catabolism and provides a promising method of generating additional nicotine-catalytic enzymes.

Thiophene structured additives toward enhanced structural order and reduced non-radiative loss for 19.9 % efficiency organic solar cells

Organic semiconductors usually exhibit low structural-order owing to their weak intermolecular interactions, which leads to inferior charge transport and strong carrier recombination in photovoltaics. In this work, three thiophene structured solid additives namely thieno[3,2-b]thiophene (TT), 3,6-dibromothieno[3,2-b]thiophene (TTBB) and 3-bromo-6-iodio-thieno[3,2-b]thiophene (TTBI) are utilized to enhance the molecular interactions in a range of electron donors and acceptors. X-ray technique and molecular dynamics simulations reveal that by adjusting their electrostatic potential and dipole moment, their interacting site and interaction energy with donor (PM6 and D18) or acceptor (L8-BO) can be finely tuned. We find the most electropositive TTBB shows the strongest interaction with PM6, leading to enhanced crystallization; whilst the asymmetric TTBI brings the strongest molecular packing of L8-BO, consequent to more compact π-π stacking and ordered alkyl chain packing. As the results, the bulk heterojunction PM6:L8-BO photovoltaics upon the assistance of TTBI or TTBB obtain improved charge transport and reduced non-radiative energy loss, translating to power conversion efficiency (PCE) values of 18.7 % and 19.1 %. When further taking the synergetic effect of TTBB and TTBI on PM6(D18) and L8-BO respectively, the layer-by-layer deposited PM6(TTBB)/L8-BO(TTBI) and D18(TTBB)/L8-BO(TTBI) allowed superior PCEs of 19.4 % and 19.9 %, which are among the highest values of single-junction organic solar cells.

A Golgi-targeted fluorescent probe for monitoring polarity dynamic during programmed cell death

Programmed cell death (PCD) is a controlled form of cell death and it plays an essential role in maintaining homeostasis. Golgi apparatus works as the hotspot during the early event of PCD and Golgi polarity, a vital microenvironment factor, can be regarded as an indicator of physiological status. Combined Golgi-targeted group phenylsulfonamide as electron acceptor group and triphenylamine as electron donor group, a novel Golgi-targeted fluorescent probe GTO had been developed. GTO showed good sensitivity and selectivity to polarity and its remarkable photostability makes it potentially useful for long-term cellular monitoring. In practice, GTO demonstrated good cell permeability and Golgi targeting capabilities. According to our results, GTO was applied to reveal the polarity increase during the early event of PCD and the encouraging results illustrated that GTO was an imaging tool for monitoring polarity in Golgi apparatus and the exploration in early diagnosis and drug discovery.

Extracellular electron transfer explained

Extracellular electron transfer explained Arpita Bose, PhD from Washington University in St. Louis, guides us through host-associated impacts and biotechnological applications of extracellular electron transfer in electrochemically active bacteria. Electron flow and oxidative and reductive reactions, referred to as “redox reactions,” collectively impact the outcomes of biochemical pathways essential for cell growth, energy conservation, and stress response throughout various organisms. An example of these organisms is electrochemically active bacteria (EAB), which can link internal redox reactions with external electron acceptors or donors via a process known as extracellular electron transfer (EET).

Ultra-efficient peroxymonosulfate utilization and trichloroethylene degradation in heterogeneous catalytic system guided by sheet-like Cu2MnO4 nanoparticles: The role of Cu(III)–O species and free radicals

Synthesizing cubic spinel Cu2MnO4 with nanosheet structure (SCMO) aimed to construct a “non-radical-mediated radical-oxidative reaction”, for increasing PMS utilization efficiency, and solving the defects of SO4•− and •OH through indirect PMS activation by electron transfer process. Compared with box-like Cu2MnO4 (11.1%, 0.0035 min−1) and ordinary Cu2MnO4 nanoparticles (21.3%, 0.0070 min−1), SCMO/PMS showed excellent trichloroethylene removal (98.8%, 0.1577 min−1). The pivotal role of Cu(III) was determined based on EPR analysis, quenching experiments, chemical probe experiments, hydrogen temperature-programmed reduction and Raman spectroscopy analysis, in-situ FTIR and Raman analyses. In brief, the interaction between PMS and SCMO could produce surface-bonded reactive complexes and the subsequent breaking of O–O bond in the sub-stable structure allowed the conversion of Cu(II) to Cu(III), which in turn facilitates the generation of •OH and SO4•−. The density functional theory (DFT) calculations provided supporting evidence for the electron donor role of SCMO and the increase of the electron acceptance capacity of PMS. SCMO/PMS system showed good resistance and degradation efficiency to complex composition and combined pollutants in actually contaminated groundwater, respectively. However, the coexistence of high concentrations of arsenic could significantly affect SCMO performance due to their adsorption on –OH groups, which still need in-depth study.

Designing A–D–A Type Fused‐Ring Electron Acceptors with a Bulky 3D Substituent at the Central Donor Core to Minimize Non‐Radiative Losses and Enhance Organic Solar Cell Efficiency

AbstractDesigning and synthesizing narrow band gap acceptors that exhibit high photoluminescence quantum yield (PLQY) and strong crystallinity is a highly effective, yet challenging, approach to reducing non‐radiative energy losses (▵Enr) and boosting the performance of organic solar cells (OSCs). We have successfully designed and synthesized an A–D–A type fused‐ring electron acceptor, named DM‐F, which features a planar molecular backbone adorned with bulky three‐dimensional camphane side groups at its central core. These bulky substituents effectively hinder the formation of H‐aggregates of the acceptors, promoting the formation of more J‐aggregates and notably elevating the PLQY of the acceptor in the film. As anticipated, DM‐F showcases pronounced near‐infrared absorption coupled with impressive crystallinity. Organic solar cells (OSCs) leveraging DM‐F exhibit a high EQEEL value and remarkably low ▵Enr of 0.14 eV‐currently the most minimal reported value for OSCs. Moreover, the power conversion efficiency (PCE) of binary and ternary OSCs utilizing DM‐F has reached 16.16 % and 20.09 %, respectively, marking a new apex in reported efficiency within the OSCs field. In conclusion, our study reveals that designing narrow band gap acceptors with high PLQY is an effective way to reduce ▵Enr and improve the PCE of OSCs.

Increased performance of A-DA’D-A type acceptor based organic solar cell using a thermally coevaporated cathode-modifying blend layer

The blend thin films of bathocuproine and fullerene (BCP:C60) have been thermally coevaporated to modify the active layer/cathode interfaces in organic solar cells. The BCP forms a much smaller-barrier contact with cathode than the C60. Because the surface zone of active layer is polymer donor-rich and small-molecular acceptor-deficient, C60 molecules make insufficiently large contact area with electron acceptor, leading to inefficient electron extraction. However, BCP molecules penetrate the surface of active layer, due to the smaller molecular size of BCP than that of C60, and likely form sufficiently large contact area with electron acceptor thereby to enable efficient electron extraction. Compared to conventional 10 nm BCP, 10 nm BCP:C60 (1:1 in mass ratio) enables higher efficiency based on the active layer using A-DA’D-A type acceptor, mostly because C60 constituent dissociates some excitons photogenerated in the polymer donor of surface zone and thereby increases short-circuit current density. The current research provides novel insights into the development of cathode-modifying layers for organic solar cells.

Genomic Insights into the Landfill Microbial Community: Denitrifying Activity Supporting One-Carbon Utilization.

In spite of the developments in understanding of denitrifying methylotrophy in the recent years, challenges still exist in unravelling the overall biochemistry of nitrate-dependent methane oxidation in novel or poorly characterized/not-yet-cultured bacteria. In the present study, landfill site was mined for novel C1-carbon-metabolizing bacteria which can use nitrate/nitrite as an electron acceptor. A high-throughput rapid plate assay identified three bacterial isolates with eminent ability for nitrate-dependent methane metabolism under anaerobic conditions. Taxonomic identification by whole-genome sequence-based overall genome relatedness indices accurately assigned the isolates AAK_M13, AAK_M29, and AAK_M39 at the species level to Enterobacter cloacae, Bacillus subtilis, and Bacillus halotolerans, respectively. Several genes encoding sub-components involved in alcohol utilization and denitrification pathways, such as adh, fdh, fdo, nar, nir, and nor, were identified in all the genomes. Though no gene clusters encoding MMO/AMO were annotated, sequencing of PCR amplicons revealed similarity with pMMO/AMO gene using translated nucleotide sequence of strains AAK_M29 and AAK_M39, while strain AAK_M13 showed similarity with XRE family transcriptional regulator. This suggests the horizontal gene transfer and/or presence of a truncated version of a housekeeping enzyme encoded by genes exhibiting partial sequence similarity with pMMO genes that mimicked its function at greenhouse gas emission sites. Owing to lack of conclusive evidence for presence of methane metabolism genes in the selected isolates, further experiment was performed to validate their nitrate-dependent methane oxidation capacities. Bacillus subtilis AAK_M29, Bacillus halotolerans AAK_M39, and Enterobacter cloacae AAK_M13 could oxidize 60%, 75%, and 85% of the added methane respectively accompanied by high nitrate reduction (56-62%) thus supporting the correlation between these two activities. The remarkable ability of these isolates for nitrate-dependent methane metabolism has highlighted their role in ecological contribution and biotechnological potential to serve as methane and nitrate sinks in the landfill sites.