Kinetics study of ultrafast electron transfer from sensitized dyes to silver halide microcrystals

Spectral sensitization micromechanism of cyanine dyes J-aggregate adsorbed on the tabular and cubic AgBr microcrystals with different dye concentrations is studied by using picosecond time-resolved fluorescence spectroscopy, and the dependences of electron transfer and spectral efficiency sensitization on different conditions are analysed in detail, With the steady spectroscopy, the wavelengths of absorption and fluorescence of J-aggregate adsorbed on AgBr microcrystals are found to shift to red relative to dye monomer. The spectrum of fluorescence has a red shift relative to the absorption peak. With the time-resolved fluorescence spectroscopy, the fluorescence decay curves of cyanine dyes J-aggregate adsorbed on the tabular and cubic AgBr grains are found to be fitted well by a double-exponential decay function. The fitting curves consist of a fast and a slow component. Because of the large amplitude of the fast component, this fast decay should be attributable mainly to the electron transfer from J-aggregate of dye to a conduction band of AgBr.

Conduction mechanism studies on electron transfer of disordered system

Using the negative eigenvalue theory and the infinite order perturbation theory, a new method was developed to solve the eigenvectors of disordered systems. The result shows that eigenvectors change from the extended state to the localized state with the increase of the site points and the disordered degree of the system. When electric field is exerted, the electrons transfer from one localized state to another one. The conductivity is induced by the electron transfer. The authors derive the formula of electron conductivity and find the electron hops between localized states whose energies are close to each other, whereas localized positions differ from each other greatly. At low temperature the disordered system has the character of the negative differential dependence of resistivity and temperature.

Direct Electron Transfer Reactions of Glucose Oxidase and D-Amino Acid Oxidase at a Glassy Carbon Electrode in Organic Media

Cyclic voltammetry is employed to demonstrate feasibility of direct electron transfer of glucose oxidase and D amino acid oxidase at a glassy carbon electrode in organic media. The reversible slight conformational change of glucose oxidase is observed by changing 0.1 mol/L phosphate buffer to acetonitrile containing 10% v/v of water and 0.05 mol/L tetrabutyalammonium perchlorate, and vice versa.

PRESSURE－INDUCED 4p→4s ELECTRON TRANSFER AND ITS EFFECT ON ELECTRICAL TRANSPORT OF COPPER

ＰＲＥＳＳＵＲＥ－ＩＮＤＵＣＥＤ４ｐ→４ｓＥＬＥＣＴＲＯＮＴＲＡＮＳＦＥＲＡＮＤＩＴＳＥＦＦＥＣＴＯＮＥＬＥＣＴＲＩＣＡＬＴＲＡＮＳＰＯＲＴＯＦＣＯＰＰＥＲＰＲＥＳＳＵＲＥ－ＩＮＤＵＣＥＤ４ｐ→４ｓＥＬＥＣＴＲＯＮＴＲＡＮＳＦＥＲＡＮＤＩＴＳＥＦＦＥ...

P-induced electron transfer interaction for enhanced selective hydrogenation rearrangement of furfural to cyclopentanone

Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-doping bifunctional catalyst(Ni-P/mSiO_(2))that achieved 96.6%yield for the hydrogenation rearrangement of furfural to cyclopentanone at mild conditions(1 MPaH_(2),150°C).The turnover frequency of Ni-P/mSiO_(2)was 411.9 h^(-1),which was 3.2-fold than that of Ni/mSiO_(2)(127.2 h^(-1)).Detailed characterizations and differential charge density calculations revealed that the electron-deficient Niδ+species were generated by the electron transfer from Ni to P,which promoted the ring rearrangement reaction.Density functional theory calculations illustrated that the presence of P atoms endowed furfural tilted adsorb on the Ni surface by the C=O group and facilitated the desorption of cyclopentanone.This work unraveled the connection between the localized electronic structures and the catalytic properties,so as to provide a promising reference for designing advanced catalysts for biomass valorization.

Balancing electron transfer and intermediate adsorption ability of metallic Ni-Fe-RE-P bifunctional catalysts via 4f-2p-3d electron interaction for enhanced water splitting

Balancing electron transfer and intermediate adsorption ability of bifunctional catalysts via tailoring electronic structures is crucial for green hydrogen production,while it still remains challenging due to lacking efficient strategies.Herein,one efficient and universal strategy is developed to greatly regulate electronic structures of the metallic Ni-Fe-P catalysts via in-situ introducing the rare earth(RE)atoms(Ni-Fe-RE-P,RE=La,Ce,Pr,and Nd).Accordingly,the as-prepared optimal Ni-Fe-Ce-P/CC self-supported bifunctional electrodes exhibited superior electrocatalytic activity and excellent stability with the low overpotentials of 247 and 331 mV at 100 mA cm^(-2) for HER and OER,respectively.In the assembled electrolyzer,the Ni-Fe-Ce-P/CC as bifunctional electrodes displayed low operation potential of 1.49 V to achieve a current density of 10 mA cm^(-2),and the catalytic performance can be maintained for 100 h.Experimental results combined with density functional theory(DFT)calculation reveal that Ce doping leads to electron decentralization and crystal structure distortion,which can tailor the band structures and d-band center of Ni-Fe-P,further increasing conductivity and optimizing intermediate adsorption energy.Our work not only proposes a valuable strategy to regulate the electron transfer and intermediate adsorption of electrocatalysts via RE atoms doping,but also provides a deep under-standing of regulation mechanism of metallic electrocatalysts for enhanced water splitting.

Analysis of the electron transfer pathway in small laccase by EPR and UV-vis spectroscopy coupled with redox titration

Bacterial small laccases(SLAC) are promising industrial biocatalysts due to their ability to oxidize a broad range of substrates with exceptional thermostability and tolerance for alkaline p H. Electron transfer between substrate, copper centers, and O2is one of the key steps in the catalytic turnover of SLAC. However, limited research has been conducted on the electron transfer pathway of SLAC and SLAC-catalyzed reactions, hindering further engineering of SLAC to produce tunable biocatalysts for novel applications. Herein, the combinational use of electron paramagnetic resonance(EPR) and ultraviolet-visible(UV-vis) spectroscopic methods coupled with redox titration were employed to monitor the electron transfer processes and obtain further insights into the electron transfer pathway in SLAC. The reduction potentials for type 1 copper(T1Cu), type 2 copper(T2Cu) and type 3copper(T3Cu) were determined to be 367 ± 2 mV, 378 ± 5 m V and 403 ± 2 mV,respectively. Moreover, the reduction potential of a selected substrate of SLAC, hydroquinone(HQ), was determined to be 288 mV using cyclic voltammetry(CV). In this way, an electron transfer pathway was identified based on the reduction potentials. Specifically,electrons are transferred from HQ to T1Cu, then to T2Cu and T3Cu, and finally to O2.Furthermore, superhyperfine splitting observed via EPR during redox titration indicated a modification in the covalency of T2Cu upon electron uptake, suggesting a conformational alteration in the protein environment surrounding the copper sites, which could potentially influence the reduction potential of the copper sites during catalytic processes. The results presented here not only provide a comprehensive method for analyzing the electron transfer pathway in metalloenzymes through reduction potential measurements, but also offer valuable insights for further engineering and directed evolution studies of SLAC in the aim for biotechnological and industrial applications.

Coupling ferromagnetic ordering electron transfer channels and surface reconstructed active species for spintronic electrocatalysis of water oxidation

Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using modeled ZnFe_(2-x)Ni_xO_(4)(0 ≤ x ≤ 0.4) spinel oxides, we aim to develop better OER electrocatalyst through combining the construction of ferromagnetic(FM) ordering channels and generation of highly active reconstructed species. The number of symmetry-breaking Fe–O–Ni structure links to the formation of FM ordering electron transfer channels. Meanwhile, as the number of Ni^(3+)increases, more ligand holes are formed, beneficial for redirecting surface reconstruction. The electro-activated ZnFe_(1.6)Ni_(0.4)O_(4) shows the highest specific activity, which is 13 and 2.5 times higher than that of ZnFe_(2)O_(4) and unactivated ZnFe_(1.6)Ni_(0.4)O_(4), and even superior to the benchmark IrO_(2) under the overpotential of 350 mV. Applying external magnetic field can make electron spin more aligned, and the activity can be further improved to 39 times of ZnFe_(2)O_(4). We propose that intriguing FM exchange-field interaction at FM/paramagnetic interfaces can penetrate FM ordering channels into reconstructed oxyhydroxide layers, thereby activating oxyhydroxide layers as spin-filter to accelerate spin-selective electron transfer. This work provides a new guideline to develop highly efficient spintronic catalysts for water oxidation and other spin-forbidden reactions.

Promoting and controlling electron transfer of furfural oxidation efficiently harvest electricity,furoic acid,hydrogen gas and hydrogen peroxide

Conventional chemical oxidation of aldehydes such as furfural to corresponding acids by molecular oxygen usually needs high pressure to increase the solubility of oxygen in aqueous phase,while electrochemical oxidation needs input of external electric energy.Herein,we developed a liquid flow fuel cell(LFFC)system to achieve oxidation of furfural in anode for furoic acid production with co-production of hydrogen gas.By controlling the electron transfer in cathode for reduction of oxygen,efficient generation of electricity or production of H_(2)O_(2)were achieved.Metal oxides especially Ag_(2)O have been screened as the efficient catalyst to promote the oxidation of aldehydes,while liquid redox couples were used for promoting the kinetics of oxygen reduction.A novel alkaline-acidic asymmetric design was also used for anolyte and catholyte,respectively,to promote the efficiency of electron transfer.Such an LFFC system achieves efficient conversion of chemical energy of aldehyde oxidation to electric energy and makes full use the transferred electrons for high-value added products without input of external energy.With(VO_(2))_(2)SO_(4)as the electron carrier in catholyte for four-electron reduction of oxygen,the peak output power density(Pmax)at room temperature reached 261 mW/cm^(2)with furoic acid and H_(2)yields of 90%and 0.10 mol/mol furfural,respectively.With anthraquinone-2-sulfonate(AQS)as the cathodic electron carrier,Pmaxof 60 mW/cm^(2)and furoic acid,H_(2)and H_(2)O_(2)yields of 0.88,0.15 and 0.41 mol/mol furfural were achieved,respectively.A new reaction mechanism on furfural oxidation on Ag_(2)O anode was proposed,referring to one-electron and two-electron reaction pathways depending on the fate of adsorbed hydrogen atom transferred from furfural aldehyde group.

Activating coordinative conjugated polymer via interfacial electron transfer for efficient CO_(2) electroreduction

With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).

Influence of dye molecular structure on electron transfer in 2,9,16,23-tetracarboxy zinc phthalocyanine sensitized solar cell

2, 9, 16, 23-tetracarboxy zinc phthalocyanine （ZnTCPc） is synthesized and characterized by physicochemical and theoretical methods and it is used as a photosensitizer in dye-sensitized solar cells （DSSC）. The excited lifetime, band gap and frontier orbital distribution of ZnTCPc are investigated by fluorescence spectra, cyclic voltammetry and quantum calculation. The results show that the excited lifetime and band gap are 0. 1 ns and 1.81 eV, respectively. Moreover, it is found that the highest occupied molecular orbital （HOMO） location is not shared by both the zinc metal and the isoindoline ligands, and the lowest unoccupied molecular orbital（LUMO） location does not strengthen the interaction coupling between ZnTCPc and TiO：. As a result, the ZnTCPc-DSSC gains a short-circuit current density of 0. 147 mA/cm2, an open-circuit photovoltage of 277 mV, a fill factor of 0. 51 and an overall conversion efficiency of 0. 021%.

Theoretical Studies on the Mechanism of the Proton-transfer-coupled Electron Transfer Reactions Between Menaquinone Q_A and Ubiquinone Q_B in the Bacterial Photosynthetic Reaction Center of Rhodopseudomona viridis

The mechanism of the proton_transfer_coupled electron transfer (PT_ET) reactions between the menaquinone Q A (MQ 1) and ubiquinone Q B (UQ 1) in the bacterial photosynthetic reaction center of Rhodopseudomona viridis was studied by using the B3LYP/6_31G(d) method. The changes of standard Gibbs free energy ΔG 0 of all possible reactions followed the ET reaction (1) were calculated. The results indicated that: (1) according to the ΔG 0 values of corresponding reactions, UQ 1 could not accept two electrons from MQ - 1 continually without the coupled proton transfer reactions. Because of ΔG 0 2b 0, ΔG 0 3b 0 and ΔG 0 4b 0, the corresponding PT_ET reactions could take place along with reactions (2b), (3b) and (4b) sequentially; (2) on the gaseous condition, the first and second transferred protons (H +(1) and H +(2)) from the surrounding amino acid residues or water molecules will combine with the oxygen No.7 and oxygen No.8 of UQ 1, respectively. On the condition of protein surroundings (by SCRF model, ε =4.0), the results are converse but the energy difference between the combination of H +(1) and H +(2) with UQ - 1 is quite small. The difference of ΔG 0 values between the corresponding reactions in gaseous surroundings and the SCRF model is not significant; (3) the PT_ET reactions between MQ 1 - and UQ 1 - should be as follows: MQ 1 -+UQ 1→MQ 1+UQ 1 - (1) UQ 1 - ( O (7) )+H +( HisL 190)→UQ 1H(2b) ( Gas ) or UQ 1 - ( O (8) )+H +(H 2O)→UQ 1H (2b') ( SCRF ) or UQ 1 - ( O (8) )+H + ( ArgL 217)→UQ 1H(2b') ( SCRF ) MQ 1 -+UQ 1H→MQ 1+UQ 1H - (3b) ( Gas ) MQ 1 -+UQ 1H→MQ 1+UQ 1H -(3b') ( SCR F) UQ 1H -+H +(H 2O)→UQ 1H 2(4b) ( Gas ) or UQ 1H -+H + ( ArgL 217)→UQ 1H 2 (4b) ( Gas ) or UQ 1H -+H + ( HisL 190)→UQ 1H 2 (4b') ( SCRF )

Photochemical Hydrogen Abstraction and Electron Transfer Reactions of Tetrachlorobenzoquinone with Pyrimidine Nucleobases

Pentachlorophenol, a widespread environmental pollutant that is possibly carcinogenic to humans, is metabolically oxidized to tetrachloroquinone （TCBQ） which can result in DNA damage. We have investigated the photochemical reaction dynamics of TCBQ with two pyrimidine type nucleobases （thymine and uracil） upon UVA （355 ran） excitation using the technique of nanosecond time-resolved laser flash photolysis. It has been found that 355 nm excitation populates TCBQ molecules to their triplet state 3TCBQ＊, which are highly reactive towards thymine or uracil and undergo two parallel reactions, the hydrogen abstraction and electron transfer, leading to the observed photoproducts of TCBQH. and TCBQ.- in transient absorption spectra. The concomitantly produced nucleobase radicals and radical cations are expected to induce a series of oxidative or strand cleavage damage to DNA afterwards. By characterizing the photochemical hydrogen abstraction and electron transfer reactions, our results provide potentially important molecular reaction mechanisms for understanding the carcinogenic effects of pentachlorophenol and its metabolites TCBQ.

Effects of Membrane Lipids on the Electron Transfer Activity of Cytochrome b_6f Complex from Spinach

A lipid_depleted cytochrome b 6f (Cyt b 6f) preparation was obtained from spinach (Spinacia oleracea L.) chloroplasts. Upon reconstitution of this preparation with the membrane lipids purified from spinach thylakoid, the effects of different membrane lipids on the electron transfer activity were studied. The results show that the electron transfer activity of Cyt b 6f is obviously stimulated to different extents, respectively, by monogalactosyldiacylglycerol (MGDG), digalactosyldiacylglycerol (DGDG), phosphatidylcholine (PC), phosphatidylglycerol (PG) and sulfoquinovosyldiacylglycerol (SQDG), and that the extents of stimulation may be closely related to the charge of the membrane lipids. The stimulation of non_charged lipids (MGDG, DGDG) and neutrally_charged lipid (PC) was high with a maximum enhancement of 89%, 75% and 77%, respectively; but the stimulation of two kinds of negatively_charged lipid (PG and SQDG) was relatively low with a maximum enhancement of 43% and 26%, respectively.

Skeletal Muscle Magnetic Resonance Imaging of the Lower Limbs in Late-onset Lipid Storage Myopathy with Electron Transfer Flavoprotein Dehydrogenase Gene Mutations

Background： Lipid storage myopathy （LSM） is a genetically heterogeneous group with variable clinical phenotypes. Late-onset multiple acyl-coenzyme A dehydrogenation deficiency （MADD） is a rather common form of LSM in China. Diagnosis and clinical management of it remain challenging, especially without robust muscle biopsy result and genetic detection. As the noninvasion and convenience, muscle magnetic resonance imaging （MRI） is a helpful assistant, diagnostic tool for neuromuscular disorders. However, the disease-specific MRI patterns of muscle involved and its diagnostic value in late-onset MADD have not been systematic analyzed. Methods： We assessed the MRI pattern and fat infiltration degree of the lower limb muscles in 28 late-onset MADD patients, combined with detailed clinical features and gene spectrum. Fat infiltration degree of the thigh muscle was scored while that ofgluteus was described as obvious or not. Associated muscular atrophy was defined as obvious muscle bulk reduction. Results： The mean scores were significantly different among the anterior, medial, and posterior thigh muscle groups. The mean of fat infiltration scores on posterior thigh muscle group was significantly higher than either anterior or medial thigh muscle group （P 〈 0.00 l）. Moreover, the mean score on medial thigh muscle group was significantly higher than that of anterior thigh muscle group （P 〈 0.01）. About half of the patients displayed fat infiltration and atrophy in gluteus muscles. Of 28 patients, 12 exhibited atrophy in medial and/ or posterior thigh muscle groups, especially in posterior thigh muscle group. Muscle edema pattern was not found in all the patients. Conclusions： Late-onset MADD patients show a typical muscular imaging pattern of fat infiltration and atrophy on anterior, posterior, and medial thigh muscle groups, with major involvement of posterior thigh muscle group and gluteus muscles and a sparing involvement of anterior thigh compartment. Our findings also suggest that muscle MRI of lower limbs is a helpful tool in guiding clinical evaluation on late-onset MADD.

Combined pretreatment using CaO and liquid fraction of digestate of rice straw: Anaerobic digestion performance and electron transfer

To improve anaerobic digestion(AD)efficiency of rice straw,solid alkaline CaO and the liquid fraction of digestate(LFD)were used as pretreatment agents of rice straw.The results showed that AD performance of rice straw with CaOLFD pretreatment was optimal in different pretreatment methods of the CaO+LFD,CaOLFD,LFD+CaO,CaO,and LFD.The maximum methane yield(314 ml(g VS)^(-1))and the highest VFAs concentration(14851 mg·L^(-1) on day 3)of the CaOLFD pretreatment group were 81%and 118%higher than that of the control group,respectively.Under the action of solid alkaline CaO,the bacteria of Clostridium,Atopostipes,Sphaerochaeta,Tissierella,Thiopseudomonas,Rikenellaceae,and Sedimentibacter could build up co-cultures with the archaeal of Methanosaeta,Methanobacterium,and Methanosarcina performing direct interspecies electron transfer(DIET)and improving AD performance of rice straw.Therefore,the combined pretreatment using CaO and LFD could not only pretreat rice straw but also stimulate co-cultures of microorganism to establish DIET enhancing AD efficiency.

Carbon dots regulate the interface electron transfer and catalytic kinetics of Pt-based alloys catalyst for highly efficient hydrogen oxidation

The regulation of interface electron-transfer and catalytic kinetics is very important to design the efficient electrocatalyst for alkaline hydrogen oxidation reaction(HOR).Here,we show the Pt-Ni alloy nanoparticles(PtNi_(2))have an enhanced HOR activity compared with single component Pt catalyst.While,the interface electron-transfer kinetics of PtNi_(2)catalyst exhibits a very wide electron-transfer speed distribution.When combined with carbon dots(CDs),the interface charge transfer of PtNi_(2)-CDs composite is optimized,and then the PtNi_(2)-5 mg CDs exhibits about 2.67 times and 4.04 times higher mass and specific activity in 0.1 M KOH than that of 20%commercial Pt/C.In this system,CDs also contribute to trapping H^(+)and H_(2)O generated during HOR,tuning hydrogen binding energy(HBE),and regulating interface electron transfer.This work provides a deep understanding of the interface catalytic kinetics of Pt-based alloys towards highly efficient HOR catalysts design.

Enhancing the dynamic electron transfer of Au species on wormhole-like TS-1 for boosting propene epoxidation performance with H_(2) and O_(2)

Engineering unique electronic structure of catalyst to boost catalytic performance is of prime scientific and industrial importance.Herein,the identification of intrinsic electronic sensitivity for direct propene epoxidation was first achieved over highly stable Au/wormhole-like TS-1 catalyst.Results show that the electron transfer of Au species can be regulated by manipulating the dynamic evolutions and contents of Au valence states,thus resulting in different catalytic performance in 100 h time-on-stream.By DFT calculations,kinetic analysis and multicharacterizations,it is found that the Au^(0) species with higher electronic population can easily transfer more electrons to activate surface O_(2) compared with Au^(1+) and Au^(3+) species.Moreover,there is a positive correlation between Au^(0) content and activity.Based on this correlation,a facile strategy is further proposed to boost Au^(0) percentage,resulting in the reported highest PO formation rate without adding promoters.This work harbors tremendous guiding significance to the design of highly efficient Au/Ti-containing catalyst for propene epoxidation with H_(2) and O_(2).

A high H_2 evolution rate under visible light of a CdS/TiO_2@Ni S catalyst due to a directional electron transfer between the phases

The photocatalytic activity of CdS can be greatly improved by co-modification of NiS and TiO_2 materials; furthermore the order of connection affects much. A directional electron transfer route via CdS → TiO_2→ NiS is found crucial to the enhancement of ternary catalyst, where TiO_2 acts as an electron reservoir and Ni S works as an effective cocatalyst. Cd S/TiO_2@Ni S with Ni S loaded on TiO_2 has an activity of H_2 evolution 2.5 times higher than NiS@Cd S/TiO_2 with Ni S pre-loaded on Cd S. Faster e-/h+separation rates is obtained of Cd S/TiO_2@Ni S under visible light than under extra UV light irradiation, which in turn demonstrates the importance of directional electron transfer route.

Electrons Transfer Between Mercaptoacetic Acid and ZnO Nanocrystal Thin Film

ZnO nanoorystals thin film were prepared by means of the self-assembly mothed. The complex films of mercaptoacetic acid(MPA) and ZnO nanocrystals(ZNCs) were prepared by means of the self-assembly technique. The interaction between the MPA and ZnO within the MPA and ZnO nanocrystal thin film decreases the photoluminescence intensity of the ZnO. The interaction was manifested by the X-ray photoelectron spectra. The intensity change of the photoluminescence of the ZnO is discussed on the basis of taking into account the process of electron transfer on the interface between the ZnO and MPA. The electron transfer of ZnO depends on the distance between the ZnO and MPA.