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Scorodite (FeAsO

Excessive consumption of energy and resources is a major challenge in wastewater treatment. Here, a novel heterogeneous Fenton-like catalyst consisting of Cu-doped graphene-like catalysts (Cu-GCD NSs) was first synthesized by an enhanced carbothermal reduction of β-cyclodextrin (β-CD). The catalyst exhibits excellent Fenton-like catalytic activity for the degradation of various pollutants under neutral conditions, accompanied by low H

In photosynthetic reaction centers from purple bacteria (PbRCs) and photosystem II (PSII), the photoinduced charge separation is terminated by an electron transfer between the primary (Q

Photosynthetic reaction centers from a green sulfur bacterium (GsbRC), the PscA/PscA proteins, and photosystem I (PSI), PsaA/PsaB proteins, share structural similarities. Here, we report the redox potential (

Flatbands have become a cornerstone of contemporary condensed-matter physics and photonics. In electronics, flatbands entail comparable energy bandwidth and Coulomb interaction, leading to correlated phenomena such as the fractional quantum Hall effect and recently those in magic-angle systems. In photonics, they enable properties including slow light

The degradation and mineralization of volatile organic compounds (VOCs) in gas-solid phase photocatalytic systems suffer great challenges due to the low electron transfer efficiency and slow benzene ring-opening kinetics. Hence, a heterojunction photocatalyst of Bi

International audience; Interfaces and their understanding/control are the key to pave the way for the development of solid-state batteries. This work focuses on the development of operando Auger cycling using an electron beam to investigate the Li/solid electrolyte (SE) interphases. To do so, the fully tunable electron gun of the Auger was applied on top of a model Li/Li6PS5Cl(Arg) stack, allowing charge build up at the Arg surface and Li+ migration from the lithium electrode followed by SE interphase formation and Li plating. Overall, it is found that (i) Li6PS5Cl is first reduced to Li2S, LiCl and Li3P while (ii) Li plating occurs almost concomitantly and (iii) proceeds until the end of the operando cycling. These results were then confirmed by operando XPS using an electron beam. Importantly, this study highlights that operando Auger is more powerful than operando XPS as it provides visual observation of the dynamics/morphology of both Li/solid electrolyte interphase formation and Li plating together with reliable chemical information. This study thus opens the door for future development of operando Auger cycling using an electron beam as a powerful approach to better understand the interfaces in solid-state batteries.

Maximizing the usable space of electrocatalysts and fine-tuning the interface geometry as well as the electronic structure to facilitate hydrogen and oxygen evolution reactions (HER and OER) have always been the focus of research. Herein, a homogeneous porous nanoparticle construction strategy was proposed, in which molybdenum nitride (Mo

The creation of ultrafine alloy nanoparticles (5 nm) that can maintain surface activity and avoid aggregation for heterogeneous catalysis has received much attention and is extremely challenging. Here, ultrafine PtRh alloy nanoparticles imprisoned by the cavities of reduced chiral covalent imine cage (PtRh@RCC3) are prepared successfully by an organic molecular cage (OMC) confinement strategy, while the soluble RCC3 can act as a homogenizer to homogenize the heterogeneous PtRh alloy in solution. Moreover, the X-ray absorption near-edge structure (XANES) results show that the RCC3 can act as an electron-acceptor to withdraw electrons from Pt, leading to the formation of higher valence Pt atoms, which is beneficial to improving the catalytic activity for the reduction of 4-nitrophenol. Attributed to the synergistic effect of Pt/Rh atoms and the unique function of the RCC3, the reaction rate constants of Pt

Similar to other radiation therapy techniques, intraoperative electron radiation therapy (IOERT) can benefit from an online treatment planning system (TPS). Among all the analytical electron dose calculation algorithms, pencil beam redefinition algorithm (PBRA) has shown an acceptable accuracy in inhomogeneities. The input dataset for PBRA includes electron planar fluence, mean direction and root mean square (RMS) spread about the mean direction which had been introduced based on the conventional linear accelerator geometry in former studies. Herein, three methods for implementing PBRA for IOERT system are presented.The initialization parameters were identified using Monte Carlo (MC) simulation of a dedicated IOERT system equipped with a cylindrical 10 cm applicator, irradiating a water phantom. Phase space distribution of electrons was recorded on a plane below the applicator. The input dataset was extracted for 2 × 2 mmPBRA was implemented with three initialization methods and compared to MC. The 3D gamma analysis of the algorithm with the Formula method, which was in best agreement with MC in a simple water phantom, showed passing rates of more than 99 % for all nominal energies and it was 97.1 % for 8 MeV in the presence of protecting disk and irregular surface. Implementing PBRA on CUDA C++ resulted in 5 s run time for 8 MeV nominal energy in a water phantom.The agreement between PBRA dose calculation and MC is promising for the development of an intraoperative TPS for IOERT.

Semiconductor nanocrystals (NCs) interfaced with molecular ligands that function as charge and energy acceptors are an emerging platform for the design of light-harvesting, photon-upconverting, and photocatalytic materials. However, NC systems explored for these applications often feature high concentrations of bound acceptor ligands, which can lead to ligand-ligand interactions that may alter each system's ability to undergo charge and energy transfer. Here, we demonstrate that aggregation of acceptor ligands impacts the rate of photoinduced NC-to-ligand charge transfer between lead(II) sulfide (PbS) NCs and perylenediimide (PDI) electron acceptors. As the concentration of PDI acceptors is increased, we find the average electron transfer rate from PbS to PDI ligands decreases by nearly an order of magnitude. The electron transfer rate slowdown with increasing PDI concentration correlates strongly with the appearance of PDI aggregates in steady-state absorption spectra. Electronic structure calculations and molecular dynamics (MD) simulations suggest PDI aggregation slows the rate of electron transfer by reducing orbital overlap between PbS charge donors and PDI charge acceptors. While we find aggregation slows electron transfer in this system, the computational models we employ predict ligand aggregation could also be used to speed electron transfer by producing delocalized states that exhibit improved NC-molecule electronic coupling and energy alignment with NC conduction band states. Our results demonstrate that ligand aggregation can alter rates of photoinduced electron transfer between NCs and organic acceptor ligands and should be considered when designing hybrid NC:molecule systems for charge separation.

There have been many examples of the accelerating effects of acids in electron transfer (ET), oxygen atom transfer (OAT), and hydrogen atom transfer (HAT) reactions. Herein, we report a contrasting effect of acids in the ET, OAT, and HAT reactions of a nickel(III) complex, [Ni

Ascidians use a class of cysteine-rich proteins generally referred to as vanabins to reduce vanadium ions, one of the many biological processes that involve the redox conversion between disulfide and dithiolate mediated by transition-metal ions. To further understand the nature of disulfide/dithiolate exchange facilitated by a vanadium center, we report herein a six-coordinate non-oxido V

We have developed a general process for the formation of α-arylethers via the Pd-catalyzed arylation of secondary α-alkoxytricyclohexylstannanes. Incorporation of cyclohexyl spectator ligands into the alkylstannane and the use of the electron-deficient ligand JackiePhos (1) are critical for achieving selective alkyl transfer in this process. This system circumvents the need for a coordinating/directing oxygen-protecting group to promote selective alkyl transfer and enables α-tetrahydropyran, α-tetrahydrofuran, and open-chain secondary α-alkoxy groups to be employed efficiently in Pd-catalyzed Stille reactions with a broad range of aryl electrophiles. These findings suggest that selective transmetalation of a single marginally activated secondary alkyl unit from Sn to Pd should be broadly achievable provided that unactivated secondary alkyl ligands comprise the other three groups of the tetraalkylstannane.

The exploration of organic fluorescent sensing materials and mechanisms is of great significance, especially for the deep understanding of twisted intramolecular charge transfer (TICT). Here, the electron-donating ability of a chemically protonated amino group and the corresponding excitation primarily ensure the occurrence of excited-state intramolecular proton transfer. Due to the hybridization of the amino group from sp

The electron transfer (ET) from the conduction band of the semiconductor to surface-bound species is a key step in the photocatalytic reaction and strongly affects the reactivity and selectivity, while the effect of catalyst surface structure on this process has rarely been explored due to the lack of an effective method. Herein, we have developed a strategy to detect and measure surface electrons' transfer energy to the adsorbates and disclosed a facet-dependent electron transfer energy over anatase TiO

Coordination of alcohols to the single-electron reductant samarium diiodide (SmI

Exploration of a novel and efficient sensing mechanism of Au nanocluster (AuNC)-based electrochemiluminescence (ECL) sensors is still a great challenge and opportunity for further applications. Herein, we proposed that the electron transfer (ET) could be used as a novel sensing regulation factor for the construction of an ECL-sensing platform based on the AuNC probe. As a proof-of-concept, the ECL quenching effect and mechanism of Cu

Carbon nitride (g-C

A characteristic of living systems is their ability to self-organize. Using appropriate quantum mechanical and mathematical tools, we show that this ability may also be a characteristic of non-living systems, such as the electron, thus establishing an unsuspected relationship between biology and physics, whereby "biology precedes physics". Planck's constant h is not a pure number but an elementary quantum of action, a "real atom" according to Henri Poincaré. Consequently, Louis de Broglie's equation λ = h/p must be rewritten in the form h = λp or lp. This approach gives a new meaning to quantum physics: the precise equivalence lp = h = Ed combined with the conceptual tools of Laurent Nottale's scale relativity allows the reunification of physics and support the development of promising engineering applications, notably in systems biology and medicine.

The reorganization energy (λ) for interfacial electron transfer (ET) and proton-coupled ET (PCET) from a conductive metal oxide (In

Good brain health refers to a condition in which a person may fully realize their talents and improve their psychological, emotional, cognitive, and behavioral functioning to cope with life's challenges. Various causes of CNS diseases are now being investigated. Radiation is one of the factors that affects the brain and causes a variety of problems. The emission or transmission of energy in the form of waves or particles via space or a material medium is known as radiation. Particle beams and electromagnetic waves are two types of ionizing radiation that have the potential to ionize atoms in a material (separating them into positively charged ions and negatively charged electrons). Radiation to the CNS can induce delayed puberty, which can lead to hyperprolactinemia, and the hypothalamic-pituitary axis can lead to gonadotropin deficit if the hypothalamic-pituitary axis is involved in the radiation field. Ionizing radiation is the most common kind of radiation. Here, we focus on the different effects of radiation on brain health. In this article, we will look at a variety of CNS diseases and how radiation affects each one, as well as how it affects the brain's numerous processes.

Chiral π-conjugated molecules bring new functionality to technological applications and represent an exciting, rapidly expanding area of research. Their functional properties, such as the absorption and emission of circularly polarized light or the transport of spin-polarized electrons, are highly anisotropic. As a result, the orientation of chiral molecules critically determines the functionality and efficiency of chiral devices. Here we present a strategy to control the orientation of a small chiral molecule (2,2'-dicyano[6]helicene) by the use of organic and inorganic templating layers. Such templating layers can either force 2,2'-dicyano[6]helicene to adopt a face-on orientation and self-assemble into upright supramolecular columns oriented with their helical axis perpendicular to the substrate, or an edge-on orientation with parallel-lying supramolecular columns. Through such control, we show that low- and high-energy chiroptical responses can be independently 'turned on' or 'turned off'. The templating methodologies described here provide a simple way to engineer orientational control and, by association, anisotropic functional properties of chiral molecular systems for a range of emerging technologies.

Excitation-energy transfer is a key step in processes such as photosynthesis that convert light into other forms of energy. Time-dependent density functional theory (DFT) in real time is ideal for the first-principles simulation of such processes due to its computational efficiency. We here demonstrate how real-time DFT can be used for analyzing excitation-energy transfer from first-principles. We discuss several measures of energy transfer that are based solely on the time-dependent density, are well founded in the DFT framework, allow for intuitive understanding and visualization, and reproduce important limiting cases of an analytical model. We demonstrate their usefulness in calculations for model systems, both with static nuclei and in the context of DFT-based Ehrenfest dynamics.

The CC2 and ADC(2) wave function models and their spin-component scaled modifications are adopted for predicting vertical ionization potentials (VIPs) and electron affinities (VEAs). The ionic solutions are obtained as electronic excitations in the continuum orbital formalism, making possible the use of existing, widespread quantum chemistry codes with minimal modifications, in full consistency with the treatment of charge transfer excitations. The performance of different variants is evaluated via benchmark calculations on various sets from previous works, containing small and medium-sized systems, including the nucleobases. It is shown that with the spin-scaled approximate methods, in particular the scaled opposite-spin variant of the ADC(2) method the accuracy of EOM-CCSD is achievable at a fraction of the computational cost, also outperforming many common electron propagator approaches.

Organometallic sandwich complexes are versatile molecular systems that have been recently employed for single-molecule manipulation and spin sensing experiments. Among related organometallic compounds, the mixed-sandwich

The quantitative characterization of the degree of randomness and aggregation of surface micro and nanostructures is critical to evaluate their effects on targeted functionalities. To this end, the methods of Point Pattern Analysis (PPA), largely used in ecology and medical imaging, seem to provide a powerful toolset. However, the application of these techniques requires the extraction of the point pattern of nanostructures from their microscope images. In this work, we address the issue of the impact that Scanning Electron Microscope (SEM) image processing may have on the fundamental metric of PPA, i.e. the Nearest Neighbour Index (NNI). Using as examples two typical SEM images of polymer micro- and nanostructures taken from secondary and backscattered electrons, we report the effects of the a) noise filtering and b) binarization threshold on the value of NNI as well as the impact of the image finite size effects. Based on these results, we draw conclusions for the safe choice of SEM settings to provide accurate measurement of nanostructure randomness through NNI estimation.

A common strategy to exploring the properties and reactivity of complex systems is to use quantum mechanics/molecular mechanics (QM/MM) embedding, wherein a QM region is defined and treated with electronic structure theory and the remainder of the system is treated with a forcefield. Of equal importance to the level of quantum chemical theory used for the QM region and the quality of the forcefield is the treatment of the coupling between the QM and MM subsystems. The state-of-the-art is to use a polarizable forcefield for the MM region and mutually couple the QM wavefunction and MM induced dipoles, in addition to the usual electrostatic embedding, yielding a polarizable embedding (QM/MM-Pol) approach. However, extensions to electronic excited states are less well developed, and we showed previously that current popular QM/MM-Pol approaches exhibit issues of root flipping and/or incorrect descriptions of electronic crossings in multistate calculations.[J. Chem. Theory Comput. 14, 2137 (2018)] Here we demonstrate a solution to these problems with an integral-exact reformulation of the Direct Reaction Field approach of Thole and Van Duijnen (QM/MM-IEDRF). The resulting embedding potential includes one- and two-electron operators, and many-body dipole-induced dipole interactions, and thus includes a natural description of the screening of electron-electron interactions by the MM induced dipoles. Pauli repulsion from the environment is mimicked by effective core potentials on the MM atoms. Inherent to the DRF approach is the assumption that MM dipoles respond instantaneously to the positions of the QM electrons, therefore dispersion interactions are captured approximately. All electronic states are eigenfunctions of the same Hamiltonian while the polarization induced in the environment and the associated energetic stabilization are unique to each state. This allows for a consistent definition of transition properties and state crossings. We demonstrate QM/MM-IEDRF by exploring the influence of a (polarizable) inert xenon matrix environment on the conical intersection underlying cis-trans isomerization of ethylene.

A mild photoredox approach enabling the first one-step synthesis of thiolated 2-aminothiazoles has been reported. Notably, the incorporation of thio group on electron-rich heteroarenes such as aminothiazoles via conventional nucleophilic aromatic substitution (SsubN/subAr) presents a significant challenge owing to polarity mismatch. Herein, we present a remarkable site-selective installation of thio group at the C-5 position of the electron-rich aminothiazole skeleton and successfully used them for the postfunctionalization of drugs and natural products.

The current study investigated epithelial modification of embryonic quail esophagus using gross examination, light microscopy, transmission and scanning electron microscopy. By semithin sections, the pre-gastric modified region had unfolded mucosa, formed epithelial flabs and pockets, and had reduced muscularis mucosae, thin muscular layer, less glandular tissue, and outer esophageal groove. Conversely, the normal esophageal mucosa was folded, had abundant glandular tissue and prominent muscularis mucosae, with two muscular layers; the outer and the inner. The modified epithelium resembled stratified squamous type that had a high affinity for PAS, methylene blue, and PAP stains. Ultra-structural features of the modified esophageal epithelium resembled stratified squamous epithelium and contained hypertrophic Keratinocytes; dark and light. Hypertrophic keratinocytes had RER organized, few ribosomes, and developed loose bundle of cytokeratin compared with squamous keratinocytes. Hypertrophic Keratinocytes synthesize two types of granules; peripherally located small electron-dense granules and large electron-lucent granules. Hypertrophic keratinocytes had peroxisomes that were identified by the crystalline core of the urate oxidase. In conclusion, epithelia modification may have secretory function. Further studies should be carried out to explain the exact function of this type of modified epithelium.

Role of biochar in promoting methanogenesis during anaerobic processes was investigated in this research. Biochar produced from Himalayan pine needles was used as medium for conductive material mediated interspecies electron transfer (CM-IET) amongst the electron producing microorganisms and electron consuming methanogenic archaea. Three anaerobic continuous stirrer tank reactors (CSTRs) with 0, 5 and 10 g/L pine needle biochar (PNB) were operated at steady state organic loading rate (OLR) of 2.0–2.5 kgCOD/(m3.d). R0 (0 g/L PNB), representing indirect interspecies electron transfer (IIET), failed at an OLR of 2.0 kgCOD/(m3.d) due to the highest volatile fatty acid (VFA) concentration of 6,300 mg/L among the three CSTRs. On the other hand, at an OLR of 2.5 kgCOD/(m3.d), R2 (10 g/L PNB) showed the most superior performance with chemical oxygen demand (COD) removal of 55% and volatile fatty acid (VFA) concentration of 3,500 mg/L, while R1 (5 g/L PNB) recorded COD removal of 45% and VFA concentration of 4,400 mg/L. In comparison, fixed biofilm reactor (FBR) with 80 g/L of PNB as support material operated satisfactorily at OLR of 13.8 kgCOD/(m3.d) with 70% COD removal and VFA concentration of 1,400 mg/L. These investigations confirmed the beneficial role of biochar in anaerobic processes by promoting CM-IET amongst VFA degrading bacteria and methane producing archaea.

Significant progress in understanding the key enzymes or species of anammox has been made; however, the nitrogen removal mechanism in complex coupling systems centered on anammox remains limited. In this study, by the combination of metagenomics-metatranscriptomics analyses, the nitrogen removal in the anammox-centered coupling system that entails partial denitrification (PD) and hydrolytic acidification (HA, A-PDHA) was elucidated to be the nitrogen transformation driven by the electron generation-transport-consumption process. The results showed that a total nitrogen (TN) removal efficiency of98%, with a TN effluence of1 mg/L and a TN removal contribution via anammox of98%, was achieved after 59 days under famine operation and alkaline conditions during the start-up process. Further investigation confirmed that famine operation promoted the activity of genes responsible for electron generation in anammox, and increased the abundance or expression of genes related to electron consumption. Alkaline conditions enhanced the electron generation for PD by upregulating the activity of glyceraldehyde 3-phosphate dehydrogenase and strengthened electron transfer by increasing the gene encoding quinone pool. Altogether, these variations in the electron flow led to efficient nitrogen removal. These results improve our understanding of the nitrogen removal mechanism and application of the anammox-centered coupling systems in treating nitrogen wastewater.

One of the fundamental limitations of accurately modeling biomolecules like DNA is the inability to perform quantum chemistry calculations on large molecular structures. We present a machine learning model based on an equivariant Euclidean neural network framework to obtain accurate ab initio electron densities for arbitrary DNA structures that are much too large for conventional quantum methods. The model is trained on representative B-DNA basepair steps that capture both base pairing and base stacking interactions. The model produces accurate electron densities for arbitrary B-DNA structures with typical errors of less than 1%. Crucially, the error does not increase with system size, which suggests that the model can extrapolate to large DNA structures with negligible loss of accuracy. The model also generalizes reasonably to other DNA structural motifs such as the A- and Z-DNA forms, despite being trained on only B-DNA configurations. The model is used to calculate electron densities of several large-scale DNA structures, and we show that the computational scaling for this model is essentially linear. We also show that this machine learning electron density model can be used to calculate accurate electrostatic potentials for DNA. These electrostatic potentials produce more accurate results compared with classical force fields and do not show the usual deficiencies at short range.

The apicoplast, a relict plastid found in most species of the phylum Apicomplexa, harbors the ferredoxin redox system which supplies electrons to enzymes of various metabolic pathways in this organelle. Recent reports in Toxoplasma gondii and Plasmodium falciparum have shown that the iron-sulfur cluster (FeS)-containing ferredoxin is essential in tachyzoite and blood-stage parasites, respectively. Here we review ferredoxin's crucial contribution to isoprenoid and lipoate biosynthesis as well as tRNA modification in the apicoplast, highlighting similarities and differences between the two species. We also discuss ferredoxin's potential role in the initial reductive steps required for FeS synthesis as well as recent evidence that offers an explanation for how NADPH required by the redox system might be generated in Plasmodium spp.

In this work, novel biocompatible and reduction-responsive soft hydrogels were formulated from norbornene (Nb)-functionalized carboxymethyl cellulose (CMCNb). To cross-link the CMC-Nb via a highly bioorthogonal inverse electron demand Diels-Alder (IEDDA) reaction, we employed a water-soluble and reduction-responsive diselenide-based cross-linker possessing two terminal tetrazine (Tz) groups with varying molar concentrations (Nb/Tz molar ratios of 10/10, 10/05, and 10/2.5). The N

Addition of NO to a nonheme dithiolate-ligated iron(II) complex, Fe

Traditionally, the ferritin-like superfamily of proteins was thought to exclusively use a diiron active site in catalyzing a diverse array of oxygen-dependent reactions. In recent years, novel redox-active cofactors featuring heterobimetallic Mn/Fe active sites have been discovered in both the radical-generating R2 subunit of class Ic (R2c) ribonucleotide reductases (RNRs) and the related R2-like ligand-binding oxidases (R2lox). However, the protein-specific factors that differentiate the radical reactivity of R2c from the C-H activation reactions of R2lox remain unknown. In this work, multifrequency pulsed electron paramagnetic resonance (EPR) spectroscopy and ligand hyperfine techniques in conjunction with broken-symmetry density functional theory calculations are used to characterize the molecular and electronic structures of two EPR-active intermediates trapped during aerobic assembly of the R2lox Mn/Fe cofactor. A Mn

An (N-heterocyclic carbene)nickel(I) cation precursor reacts with the corresponding nickel(0) complex to form a dinickel(I,0) monocation. The Ni···Ni distance in this cation is 0.93 Å shorter than in the analogous dinickel(0) complex. Although the solid-state structure shows equivalent Ni centers, density functional theory calculations indicate significant electronic localization. Reactions with CO and NO form mononuclear carbonyl and nitrosyl complexes. Oxidative addition of an aryl bromide results in

Ultrafast triplet formation in donor-acceptor (D-A) systems typically occurs by spin-orbit charge-transfer intersystem crossing (SOCT-ISC), which requires a significant orbital angular momentum change and is thus usually observed when the adjacent π systems of D and A are orthogonal; however, the results presented here show that subnanosecond triplet formation occurs in a series of D-A cocrystals that form one-dimensional cofacial π stacks. Using ultrafast transient absorption microscopy, photoexcitation of D-A single cocrystals, where D is coronene (Cor) or pyrene (Pyr) and A is

The enzyme nicotine oxidoreductase (NicA2) is a member of the flavoprotein amine oxidase family that uses a cytochrome c protein (CycN) as its oxidant instead of dioxygen, which is the oxidant used by most other members of this enzyme family. We recently identified a potential binding site for CycN on the surface of NicA2 through rigid body docking [J. Biol. Chem. (2022) 298(8), 102251]. However, this potential binding interface has not been experimentally validated. In this paper, we used unnatural amino acid incorporation to probe the binding interface between NicA2 and CycN. Our results are consistent with a structural model of the NicA2-CycN complex predicted by protein-protein docking and AlphaFold, suggesting that this is the binding site for CycN on NicA2’s surface. Based on additional mutagenesis of potentially redox active residues in NicA2, we propose that electron transfer from NicA2’s flavin to CycN’s heme occurs without the assistance of a protein-derived wire.

The first enantioselective total synthesis of (+)-lucidumone is described through a 13-step synthetic pathway (longest linear sequence). The key steps involve the formation of a bridged bicyclic lactone by an enantioselective inverse-electron-demand Diels-Alder cycloaddition, C-O bond formation to assemble two fragments, and a one-pot retro-[4 + 2]/[4 + 2] cycloaddition cascade. The synthesis is scalable, and more than one gram of natural product was synthesized in one batch.

Electron transfer through the mitochondrial electron transport chain (ETC) can be critically blocked by the dysfunction of protein complexes. Redox-active molecules have been used to mediate the electron transfer in place of the dysfunctional complexes; however, they are limited to replacing complex I and are known to be toxic. Here we report artificial mitochondrial electron transfer pathways that enhance ETC activity by exploiting inner-membrane-bound gold nanoparticles (GNPs) as efficient electron transfer mediators. The hybridization of mitochondria with GNPs, driven by electrostatic interaction, is successfully visualized in real time at the level of a single mitochondrion. By observing quantized quenching dips via plasmon resonance energy transfer, we reveal that the hybridized GNPs are bound to the inner membrane of mitochondria irrespective of the presence of the outer membrane. The ETC activity of mitochondria with GNPs such as membrane potential, oxygen consumption, and ATP production is remarkably increasediin vitro/i.

ConspectusThe field of molecular electronics has grown rapidly since its experimental realization in the late 1990s, with thousands of publications on how molecules can act as circuit components and the possibility of extending microelectronic miniaturization. Our research group developed molecular junctions (MJs) using conducting carbon electrodes and covalent bonding, which provide excellent temperature tolerance and operational lifetimes. A carbon-based MJ based on quantum mechanical tunneling for electronic music represents the world's first commercial application of molecular electronics, with3000 units currently in consumer hands. The all-carbon MJ consisting of aromatic molecules and oligomers between vapor-deposited carbon electrodes exploits covalent, C-C bonding which avoids the electromigration problem of metal contacts. The high bias and temperature stability as well as partial transparency of the all-carbon MJ permit a wide range of experiments to determine charge transport mechanisms and observe photoeffects to both characterize and stimulate operating MJs. As shown in the Conspectus figure, our group has reported a variety of electronic functions, many of which do not have analogs in conventional semiconductors. Much of the described research is oriented toward the rational design of electronic functions, in which electronic characteristics are determined by molecular structure.In addition to the fabrication of molecular electronic devices with sufficient stability and operating life for practical applications, our approach was directed at two principal questions: how do electrons move through molecules that are components of an electronic circuit, and what can we do with molecules that we cannot do with existing semiconductor technology? The central component is the molecular junction consisting of a 1-20+ nm layer of covalently bonded oligomers between two electrodes of conducting, mainly sp

Selective catalytic ammonia-to-dinitrogen oxidation (NH

Fe(II)-catalyzed ferrihydrite transformation under anoxic conditions has been intensively studied, while such mechanisms are insufficient to be applied in oxic environments with depleted Fe(II). Here, we investigated expanded pathways of sunlight-driven ferrihydrite transformation in the presence of dissolved oxygen, without initial addition of dissolved Fe(II). We found that sunlight significantly facilitated the transformation of ferrihydrite to goethite compared to that under dark conditions. Redox active species (hole-electron pairs, reactive radicals, and Fe(II)) were produced from the ferrihydrite interface via the photoinduced electron transfer processes. Experiments with systematically varied wet chemistry conditions probed the relative contributions of three pathways for the production of hydroxyl radicals: (1) oxidation of water (5.0%); (2) reduction of dissolved oxygen (40.9%); and (3) photolysis of Fe(III)-hydroxyl complexes (54.1%). Results also showed superoxide radicals as the main oxidant for Fe(II) reoxidation under acidic conditions, thus promoting the ferrihydrite transformation. The presence of inorganic ions (chloride, sulfate, and nitrate) did not only affect the hydrolysis and precipitation of Fe(III) but also the generation of radicals via photoinduced charge transfer reactions. The involvement of redox active species and the accompanying mineral transformations would exert a profound effect on the fate of multivalent elements and organic contaminants in aquatic environments.

In this research article, we describe a 4H(+)/4e(−) electron-coupled-proton buffer (ECPB) based on Cu and a redox-active ligand. The protonated/reduced ECPB (complex 1: [Cu(8H(+)/14e(−))](1+)), consisting of Cu(I) with 2 equiv of the ligand ((cat)LH(4): 1,1′-(4,5-dimethoxy-1,2-phenylene)bis(3-(tert-butyl)urea)), reacted with H(+)/e(−) acceptors such as O(2) to generate the deprotonated/oxidized ECPB. The resulting compound, (complex 5: [Cu(4H(+)/10e(−))](1+)), was characterized by X-ray diffraction analysis, nuclear magnetic resonance ((1)H-NMR), and density functional theory, and it is electronically described as a cuprous bis(benzoquinonediimine) species. The stoichiometric 4H(+)/4e(−) reduction of 5 was carried out with H(+)/e(−) donors to generate 1 (Cu(I) and 2 equiv of (cat)LH(4)) and the corresponding oxidation products. The 1/5 ECPB system catalyzed the 4H(+)/4e(−) reduction of O(2) to H(2)O and the dehydrogenation of organic substrates in a decoupled (oxidations and reductions are separated in time and space) and a coupled fashion (oxidations and reductions coincide in time and space). Mechanistic analysis revealed that upon reductive protonation of 5 and oxidative deprotonation of 1, fast disproportionation reactions regenerate complexes 5 and 1 in a stoichiometric fashion to maintain the ECPB equilibrium.

Visual detection of analytes has been a significant challenge in the design and development of optical chemosensors. Sensing of analytes in aqueous solution by organic molecules has encountered some issues, such as poor water solubility and quenching of optical properties. In this study, a new category of smart dendritic macromolecules was designed and synthesized by functionalization of the poly(amidoamine) (PAMAM) dendrimer with spiropyran molecules to afford a photoluminescent dendritic structure (SP-PAMAM). Smart optical sensors were prepared by physical incorporation of four different oxazolidine derivatives containing hydroxyl and nitro substituted groups into the SP-PAMAM structure. Investigation of optical properties demonstrated photoinduced electron transfer (PET) between the spiropyran end group of SP-PAMAM and oxazolidine derivatives (in a concentration of about 0.0002 M), which can result in quenching of fluorescence emission of spiropyran photoswitch in the form of merocyanine (MC). Treatment of the oxazolidine-doped SP-PAMAM samples with metal ions resulted in changes in the PET mechanism (switching on or off), as observed in the case of Fe

The enantioconvergent cross-coupling of racemic alkyl halides represents a powerful tool for the synthesis of enantioenriched molecules. In this regard, the first-row transition metal catalysis provides a suitable mechanism for stereoconvergence by converting racemic alkyl halides to prochiral radical intermediates owing to their good single-electron transfer ability. In contrast to the noble development of chiral nickel catalyst, copper-catalyzed enantioconvergent radical cross-coupling of alkyl halides is less studied. Besides the enantiocontrol issue, the major challenge arises from the weak reducing capability of copper that slows the reaction initiation. Recently, significant efforts have been dedicated to basic research aimed at developing chiral ligands for copper-catalyzed enantioconvergent radical cross-coupling of racemic alkyl halides. This perspective will discuss the advances in this burgeoning area with particular emphasis on the strategic chiral anionic ligand design to tune the reducing capability of copper for the reaction initiation under thermal conditions from our research group.

In the management of patients with breast cancer (BC), a mammography contributed to screen an early-stage patient, to plan a therapy strategy, to evaluate a therapy outcome, to detect a recurrence, and to reduce a mortality. Currently, various imaging modalities, such as CT, MR, Ultrasound (US), SPECT/CT, PET/CT, PET/MR have been utilized for the management of BC patients. In order to overcome a limited spatial resolution and sensitivity of whole-body systems in nuclear medicine imaging, dedicated breast imaging modalities were developed. One is a gamma imaging system with single/dual head scintillation detectors or semiconductor detectors associated with light compression device for breast parenchyma. Radiopharmaceutical for the gamma imaging is