Search Results (38)

Damage to mitochondrial DNA (mtDNA) results in defective electron transport system (ETS) complexes, initiating a cycle of impaired oxidative phosphorylation (OXPHOS), increased reactive oxygen species (ROS) production, and chronic low-grade inflammation (inflammaging). This culminates in energy failure, cellular senescence, and progressive tissue degeneration. Rapamycin and metformin are the most extensively studied longevity drugs. Rapamycin inhibits mTORC1, promoting mitophagy, enhancing mitochondrial biogenesis, and reducing inflammation. Metformin partially inhibits Complex I, lowering reverse electron transfer (RET)-induced ROS formation and activating AMPK to stimulate autophagy and mitochondrial turnover. Both compounds mimic caloric restriction, shift metabolism toward a catabolic state, and confer preclinical—and, in the case of metformin, clinical—longevity benefits. More recently, small molecules directly targeting mitochondrial membranes and ETS components have emerged. Compounds such as Elamipretide, Sonlicromanol, SUL-138, and others modulate metabolism and mitochondrial function while exhibiting similarities to metformin and rapamycin, highlighting their potential in promoting longevity. The key question moving forward is whether these interventions should be applied chronically to sustain mitochondrial health or intermittently during episodes of stress. A pragmatic strategy may combine chronic metformin use with targeted mitochondrial therapies during acute physiological stress. Full article

Copper(I) oxide (Cu₂O)-based photocathodes are promising materials for carbon dioxide (CO₂) reduction under visible light due to copper’s abundance and favorable energy band alignment. However, Cu₂O suffers from photocorrosion and chemical instability. Here, we present a novel approach utilizing a porous titanosilicate material (ETS-10) as a protective layer for Cu₂O, addressing these limitations. The Cu₂O was electrodeposited and coated with a thin ETS-10 layer, which prevents photocorrosion, enhances charge separation and transfer, and facilitates CO₂ capture through its highly porous structure. Comprehensive structural, compositional, and morphological analyses confirmed that ETS-10 effectively stabilized Cu₂O while maintaining its electronic properties (UV–Vis, XPS). The Cu₂O/ETS-10 photocathode exhibited a 25% enhancement in the photocurrent density at 0.0–0.1 V vs. RHE and significantly improved stability compared to bare Cu₂O. The thin ETS-10 layer acted as a passivation layer, improving charge transfer via tunneling mechanisms. This study introduces a multicomponent photocathode system, demonstrating a new application of ETS-10 in photoelectrochemical cells. The results highlight the potential of ETS-10 to enhance the efficiency and stability of photocathodes, offering a pathway for the design of advanced systems for solar-driven CO₂ reduction and artificial photosynthesis. Full article

Photooxidation imposes structural damage on proteins, and the amino acid tryptophan (Trp) is a key target for protein oxidation. The Trp radical cation (Trp^•⁺), as an oxidative product, can be reduced by plant phenols (φ-OH), a category of dietary phytochemicals essential for human health. This work is intended to investigate the efficacy of φ-OH regeneration of Trp from Trp^•⁺ as a function of φ-OH concentration and environmental pH. We have examined, by using laser flash photolysis, six different kinds of φ-OH in the aqueous system consisting of Trp and riboflavin as a photosensitizer. Taking syringic acid (Syr) as an example, upon systematically varying the pH from 2 to 10, the partition of Syr phenolate, Syr-O²⁻, increases from 0% to 70% and, accordingly, the rate of Trp regeneration increases from 4.8 × 10⁶ M⁻¹·s⁻¹ to 1.7 × 10⁸ M⁻¹·s⁻¹. It is found that the regeneration rate correlates with the driving force of the electron transfer (ET) reaction between φ-OH and Trp^•+, which can be well accounted for by Marcus’s ET theory (R² = 0.89). The λ = 0.43 ± 0.08 eV for the reorganization energy for ET from the plant phenols to the Trp^•⁺. The effects of φ-OH concentration, environmental pH, and ET driving force on the Trp regeneration reaction herein revealed are significant for enlightening further study of protein (anti)oxidation. Full article

Long-range electron transfer (ET) is an essential component of all biological systems. Reactions of metalloproteins are important in this context. Recent work on protein “charge ladders” has revealed how the redox state of embedded metal ions can influence the ionization of amino acid residues at protein surface sites. Inspired by these observations, we carried out a variable pH investigation of intramolecular ET reactions in a ruthenium-modified protein system built on azurin from Pseudomonas aeruginosa. We also generate a Pourbaix diagram that describes the variable pH redox behavior of a Ru model complex, Ru(2,2′-bipyridyl)₂(imidazole)₂(PF₆)₂. The intramolecular ET rate constants for the oxidation of azurin-Cu⁺ by flash-quench-generated Ru³⁺ oxidants do not follow the predictions of the semi-classical ET rate expression with fixed values of reorganization energy (λ) and electronic coupling (H_DA). Based on the pH dependence of the Ru^3+/2+ redox couple, we propose a model where pure ET is operative at acidic pH values (≤ 7) and the mechanism changes to proton-coupled electron transfer at pH ≥ 7.5. The implications of this mechanistic proposal are discussed in the context of biological redox reactions and with respect to other examples of intramolecular ET reactions in the literature. Full article

Photosystem I (PSI) serves as a model system for studying fundamental processes such as electron transfer (ET) and energy conversion, which are not only central to photosynthesis but also have broader implications for bioenergy production and biomimetic device design. In this study, we employed electron paramagnetic resonance (EPR) spectroscopy to investigate key light-induced charge separation steps in PSI isolated from several green algal and cyanobacterial species. Following photoexcitation, rapid sequential ET occurs through either of two quasi-symmetric branches of donor/acceptor cofactors embedded within the protein core, termed the A and B branches. Using high-frequency (130 GHz) time-resolved EPR (TR-EPR) and deuteration techniques to enhance spectral resolution, we observed that at low temperatures prokaryotic PSI exhibits reversible ET in the A branch and irreversible ET in the B branch, while PSI from eukaryotic counterparts displays either reversible ET in both branches or exclusively in the B branch. Furthermore, we observed a notable correlation between low-temperature charge separation to the terminal [4Fe-4S] clusters of PSI, termed F_A and F_B, as reflected in the measured F_A/F_B ratio. These findings enhance our understanding of the mechanistic diversity of PSI’s ET across different species and underscore the importance of experimental design in resolving these differences. Though further research is necessary to elucidate the underlying mechanisms and the evolutionary significance of these variations in PSI charge separation, this study sets the stage for future investigations into the complex interplay between protein structure, ET pathways, and the environmental adaptations of photosynthetic organisms. Full article

High light (HL) significantly impacts plant photosynthesis. This study investigated the effects of different magnesium (Mg) levels (0, 1, 2, and 5 mol Mg plant⁻¹; HMg0, HMg1, HMg2, and HMg5) on tobacco (Nicotiana tabacum L. cv. Cuibi No. 1) under HL (1500 μmol m⁻² s⁻¹), aiming to understand the role of Mg in mitigating the impact of HL on photosynthesis and carbon–nitrogen metabolism. Plants treated with 1 mol Mg plant⁻¹ under 750 μmol m⁻² s⁻¹ light conditions served as the control. HL led to a reduced chlorophyll (Chl) content and inhibited the maximum photosynthetic rate (Pmax). It also decreased energy involved in photosynthetic electron transfer (ET) and electron flux to reduction end-electron acceptors at the photosystems I (PSI) acceptor side (RE) and caused photosynthetic system damage. H₂O₂ accumulation exacerbated membrane lipid peroxidation damage, disrupting carbon and nitrogen metabolism, and inducing antioxidant enzyme activity. HMg2 increased Chl content, stomatal conductance, intercellular CO₂ concentration, and the net photosynthetic rate compared to HMg0. It enhanced ET efficiency, PSI and PSII functionality, reduced dissipated energy flux (DI), and minimized photosynthesis damage. Conversely, excessive Mg application (HMg5) decreased Pmax and PSII activity, increasing DI. Adequate Mg supply alleviated HL’s detrimental effects by enhancing Chl content and ET and RE efficiency. Full article

Molecular hydrogen (H₂) has been recognized as a novel medical gas with antioxidant and anti-inflammatory effects. Non-alcoholic fatty liver disease (NAFLD) is a liver pathology with increased fat accumulation in liver tissue caused by factors other than alcohol consumption. Platelet mitochondrial function is considered to reflect systemic mitochondrial health. We studied the effect of adjuvant therapy with hydrogen-rich water (HRW) on coenzyme Q₁₀ (CoQ₁₀) content and platelet mitochondrial bioenergetics in patients with NAFLD. A total of 30 patients with NAFLD and 15 healthy volunteers were included in this clinical trial. A total of 17 patients (H₂ group) drank water three × 330 mL/day with tablets producing HRW (>4 mg/L H₂) for 8 weeks, and 13 patients (P group) drank water with placebo tablets producing CO₂. The concentration of CoQ_10-TOTAL was determined by the HPLC method, the parameter of oxidative stress, thiobarbituric acid reactive substances (TBARS), by the spectrophotometric method, and mitochondrial bioenergetics in platelets isolated from whole blood by high-resolution respirometry. The patients with NAFLD had lower concentrations of CoQ_10-TOTAL in the blood, plasma, and platelets vs. the control group. Mitochondrial CI-linked LEAK respiration was higher, and CI-linked oxidative phosphorylation (OXPHOS) and CII-linked electron transfer (ET) capacities were lower vs. the control group. Plasma TBARS concentrations were higher in the H₂ group. After 8 weeks of adjuvant therapy with HRW, the concentration of CoQ₁₀ in platelets increased, plasma TBARS decreased, and the efficiency of OXPHOS improved, while in the P group, the changes were non-significant. Long-term supplementation with HRW could be a promising strategy for the acceleration of health recovery in patients with NAFLD. The application of H₂ appears to be a new treatment strategy for targeted therapy of mitochondrial disorders. Additional and longer-term studies are needed to confirm and elucidate the exact mechanisms of the mitochondria-targeted effects of H₂ therapy in patients with NAFLD. Full article

Supramolecular 3D Zn(II) coordination polymer {[Zn(bim)(bdc)]⋅0.8DMF⋅0.4EtOH⋅0.1H₂O }_n (Zn-MOF), constructed from Zn²⁺ ions, bis(imidazol-1-yl)methane (bim) and terephthalate (bdc²⁻) anions, was synthesized and structurally characterized. Zn-MOF crystallizes in the tetragonal crystal system, space group P4₂/n. Each Zn(II) ion coordinates two neutral bim molecules in a bridging bidentate coordination mode via nitrogen atoms at position 3 of the imidazole rings and two bdc²⁻ anions, with monodentate coordination of the carboxylate group for one of them and bidentate coordination for another. Zn(II) cations are in a distorted square pyramidal ZnN₂O₃ coordination environment. Metal cations are alternately linked by the bim and bdc²⁻ ligands, forming a two-dimensional layered structure along the crystallographic plane ab. As a result of layer interpenetration, a supramolecular 3D network is formed. Zn-MOF demonstrated blue (aquamarine) emission with a maximum at 430 nm upon excitation at 325 nm. The luminescence lifetime of 6 ns is characteristic for ligand-centered fluorescence. The luminescent sensing properties of Zn-MOF in ethanol suspension toward inorganic cations and anions were evaluated and an emission quenching response was observed for Fe³⁺ and chromate/dichromate ions. Photoinduced electron transfer from Zn-MOF to Fe³⁺ was elucidated as a possible quenching mechanism on the basis of DFT calculations. Full article

Stimuli-responsive drug release and photodynamic therapy (PDT) have aroused extensive attention for their enormous potential in antitumor treatment. pH-responsive drug delivery systems (PFE-DOX-1 and PFE-DOX-2) based on water-soluble conjugated polymers were constructed in this work for high-performance synergistic chemo-/PDT therapy, in which the anticancer drug doxorubicin (DOX) is covalently attached to the side chains of the conjugated polymers via acid-labile imine and acylhydrazone bonds. Concurrently, the intense fluorescence of poly(fluorene-co-ethynylene) (PFE) is effectively quenched due to the energy/electron transfer (ET) between the PFE-conjugated backbone and DOX. Effective pH-responsive drug release from PFE-DOX-2 is achieved by the cleavage of acylhydrazone linkages in the acidic tumor intracellular microenvironment. Additionally, the drug release process can be monitored by the recovered fluorescence of conjugated polymers. Furthermore, the conjugated polymers can produce reactive oxygen species (ROS) under light irradiation after drug release in an acidic environment, which prevents possible phototoxicity to normal tissues. It is noted that PFE-DOX-2 demonstrates remarkable antitumor cell performance, which is attributed to its efficient cell uptake and powerful synergistic chemo-/PDT therapeutic effectiveness. This report thus provides a promising strategy for in vivo anticancer treatment with the construction of a stimuli-responsive multifunctional drug delivery system. Full article

Photocatalytic systems for CO₂ reduction operate via complicated multi-electron transfer (ET) processes. A complete understanding of these ET dynamics can be challenging but is key to improving the efficiency of CO₂ conversion. Here, we report the ET dynamics of a series of zinc porphyrin derivatives (ZnPs) in the photosensitization reactions where sequential ET reactions of ZnPs occur with a sacrificial electron donor (SED) and then with TiO₂. We employed picosecond time-resolved fluorescence spectroscopy and femtosecond transient absorption (TA) measurement to investigate the fast ET dynamics concealed in the steady-state or slow time-resolved measurements. As a result, Stern-Volmer analysis of fluorescence lifetimes evidenced that the reaction of photoexcited ZnPs with SED involves static and dynamic quenching. The global fits to the TA spectra identified much faster ET dynamics on a few nanosecond-time scales in the reactions of one-electron reduced species (ZnPs^•–) with TiO₂ compared to previously measured minute-scale quenching dynamics and even diffusion rates. We propose that these dynamics report the ET dynamics of ZnPs^•– formed at adjacent TiO₂ without involving diffusion. This study highlights the importance of ultrafast time-resolved spectroscopy for elucidating the detailed ET dynamics in photosensitization reactions. Full article

Many specific features of ultrafast electron transfer (ET) reactions in macromolecular compounds can be attributed to nonequilibrium configurations of intramolecular vibrational degrees of freedom and the environment. In photoinduced ET, nonequilibrium nuclear configurations are often produced at the stage of optical excitation, but they can also be the result of electron tunneling itself, i.e., fast redistribution of charges within the macromolecule. A consistent theoretical description of ultrafast ET requires an explicit consideration of the nuclear subsystem, including its evolution between electron jumps. In this paper, the effect of the multi-timescale nuclear reorganization on ET transitions in macromolecular compounds is studied, and a general theory of ultrafast ET in non-Debye polar environments with a multi-component relaxation function is developed. Particular attention is paid to designing the multidimensional space of nonequilibrium nuclear configurations, as well as constructing the diabatic free energy surfaces for the ET states. The reorganization energies of individual ET transitions, the equilibrium energies of ET states, and the relaxation properties of the environment are used as input data for the theory. The effect of the system-environment interaction on the ET kinetics is discussed, and mechanisms for enhancing the efficiency of charge separation in macromolecular compounds are analyzed. Full article

We discuss the problem of electron transfer (ET) in mixed valence (MV) molecules that is at the core of molecular Quantum Cellular Automata (QCA) functioning. Theoretical modelling of tetrameric bi-electronic MV molecular square (prototype of basic QCA cell) is reported. The model involves interelectronic Coulomb repulsion, vibronic coupling and ET between the neighboring redox sites. Unlike the majority of previous studies in which molecular QCA have been analyzed only for particular case when the Coulomb repulsion energy significantly exceeds the ET energy, here we do not imply assumptions on the relative strength of these two interactions. Moreover, in the present work we go beyond the adiabatic semiclassical approximation often used in theoretical analysis of such systems in spite of the fact that this approximation ignores such an important phenomenon as quantum tunneling. By analyzing the electronic density distributions in the cells and the ell-cell response functions obtained from a quantum-mechanical solution of a complex multimode vibronic problem we have concluded that such key features of QCA cell as bistability and switchability can be achieved even under failure of the condition of strong Coulomb repulsion provided that the vibronic coupling is strong enough. We also show that the semiclassical description of the cell-cell response functions loses its accuracy in the region of strong non-linearity, while the quantum-mechanical approach provides correct results for this critically important region. Full article

Perfluorooctanoic acid (PFOA) that accumulates in wastewater and excess sludge interact with the anaerobes and deteriorate the energy recovery and pollutants removal performance in the anaerobic digestion (AD) system. However, the interaction between PFOA and microbial metabolism in the AD systems remains unclear. This study aimed to clarify the effects and mechanism of PFOA on the AD process as well as the removal pathways of PFOA in an AD system. The results showed that the methane recovery efficiency was inhibited by 7.6–19.7% with the increased PFOA concentration of 0.5–3.0 mg/L, and the specific methanogenesis activity (SMA) was inhibited by 8.6–22.3%. The electron transfer system (ETS) was inhibited by 22.1–37.3% in the PFOA-containing groups. However, extracellular polymeric substance (EPS) gradually increased due to the toxicity of PFOA, and the ratio of protein to polysaccharide shows an upward trend, which led to the formation of sludge aggregates and resistance to the toxic of PFOA. The PFOA mass balance analysis indicated that 64.2–71.6% of PFOA was removed in the AD system, and sludge adsorption was the main removal pathway, accounting for 36.1–61.2% of the removed PFOA. In addition, the anaerobes are proposed to have the potential to reduce PFOA through biochemical degradation since 10.4–28.2% of PFOA was missing in the AD system. This study provides a significant reference for the treatment of high-strength PFOA-containing wastes. Full article

Digital signatures are unsuitable for specific applications that are sensitive on a personal or commercial level because they are universally verifiable. Jakobsson et al. proposed the Designated Verifier Signature (DVS) system, which only allows the intended verifier to validate a message’s signature. It prohibits the disclosure of a conviction to a third party. This functionality is useful in applications that require both authenticity and signer privacy, such as electronic voting and tender calls. The vast majority of current DVS schemes are based on difficult number theory problems such as integer factorization or discrete log problems over various groups. The development of a large-scale quantum computer would render these schemes unsafe. As a result, it is critical to develop quantum-resistant DVS methods. In both quantum and classical computers, signatures based on one-way functions are more efficient and secure. They have several advantages over digital signatures based on trapdoor functions. As a result, hash-based signatures are now considered viable alternatives to number-theoretic signatures. Existing hash-based signatures, on the other hand, are easily verifiable by anyone. As a result, they do not protect the signer’s identity. In addition, they are one-time signatures. This paper presents a hash-based multi-time designated verifier signature scheme that ensures signer anonymity. The unforgeability of the signature scheme is also tested in the random oracle model under chosen message attack. The properties such as non-transferability and non-delegatability are investigated. Full article