We have designed and fabricated efficient photocatalysts sensitive to visible light, metal ion-grafted TiO 2 after the knowledge of the photoinduced interfacial charge transfer from a semiconductor to an adsorbed molecular species and the catalytic multi-electron reduction of oxygen by electron-injected metal ions.

In order to reduce infection risk of novel coronavirus (SARS-CoV-2), we developed nano-photocatalysts with nanoscale rutile TiO 2 (4–8 nm) and Cu x O (1–2 nm or less). Their extraordinarily small size leads to high dispersity and good optical transparency, besides large active surface area. Those photocatalysts can be applied to white and translucent latex paints. Although Cu 2 O clusters involved in the paint coating undergo gradual aerobic oxidation in the dark, the oxidized clusters are re-reduced under > 380 nm light. The paint coating inactivated the original and alpha variant of novel coronavirus under irradiation with fluorescent light for 3 h. The photocatalysts greatly suppressed binding ability of the receptor binding domain (RBD) of coronavirus (the original, alpha and delta variants) spike protein to the receptor of human cells. The coating also exhibited antivirus effects on influenza A virus, feline calicivirus, bacteriophage Qβ and bacteriophage M13. The photocatalysts would be applied to practical coatings and lower the risk of coronavirus infection via solid surfaces.

The aspects of photoinduced superhydrophilic TiO 2 surface and the mechanistic approaches for the superhydrophilicity were overviewed. We propose that the surface energy of the TiO 2 surface increases by being covered with the thermodynamically less stable OH groups, resulting in the generation of the superhydrophilicity.

Accelerating electron-transfer in c-type cytochrome (Cyt) complexes is critical for efficient energy harvesting in bacterial bio-electrocatalysis. While the importance of the counter cation was recently shown, a rate-limiting protonation site remains unclear. We demonstrate here that increasing the basicity of N5-nitrogen atom in isoalloxazine ring of a bound cofactor in Cyt enhances electron transfer. Methylene blue, a phenothiazine derivative with a high pK>a(N5), acts as a bound cofactor in Cyts, enhancing current production of Geobacter by a factor of 113±43 at 500 nM and Shewanella by a factor of 23.5±9.4 at 2.0 μM. Significant kinetic isotope effects and electron-transfer rate enhancements dependent on the pK>a(N5) of phenothiazine derivatives strongly suggest that N5 protonation dictates electron transfer kinetics. In contrast to electron shuttles that are used at more-than hundreds µM, the basified cofactors exhibit their effects at much lower levels, facilitating the development of scalable, low-cost, and high-performance microbial electrochemical reactors.

In order to reduce infection risk of novel coronavirus (SARS-CoV-2), we developed photocatalysts with nanoscale rutile TiO2 (4–8 nm) and CuxO (1–2 nm or less). Their extraordinarily small size leads to high dispersity and good optical transparency, besides large active surface area. Those photocatalysts can be applied to white and translucent latex paints and a transparent varnish. Although Cu2O clusters involved in the paint coating undergo gradual aerobic oxidation in the dark, the oxidized clusters are re-reduced under >380 nm light. The paint coating inactivated novel coronavirus and its alpha (B.1.1.7) variant under irradiation with fluorescent light for 3 h. The coating also exhibited antivirus effects on influenza A virus, feline calicivirus and bacteriophage Qβ. The photocatalysts would be applied to practical coatings and lower the risk of coronavirus infection via solid surfaces.

Science and Technology of Materials Science (STAM) celebrated its 20th anniversary in 2019 [1]. Thanks to the continuous efforts of former Editors-in-Chief, editorial board members, and members of ...

The International Organization for Standardization (ISO) was used to evaluate antibacterial activity by titanium dioxide (TiO 2 ) photocatalysis since 2006. We evaluated photocatalytic inactivation of Qβ and T4 bacteriophages induced by low-intensity, long-wavelength ultraviolet A (UVA; 0.1 mW cm −2 and 0.001 mW cm −2 ) irradiation on a TiO 2 -coated glass plate using the ISO methodology. The results indicated that both bacteriophages were inactivated at 0.001 mW cm −2 UVA. The intensity of UV light, including long-wavelength light (UVA), is very low in an actual indoor environment. Thus, TiO 2 photocatalysis can be beneficial for inactivating viruses in an indoor environment. Experiments using qPCR and bovine serum albumin degradation assume that viral inactivation is caused by outer viral protein disorder and not by viral RNA reduction by reactive oxygen species produced during TiO 2 photocatalysis. Furthermore, we showed that the ISO methodology for standard testing of antibacterial activity by TiO 2 photocatalysis can be applied to assess antiviral activity.

Photocatalysis is an effective technology for preventing the spread of pandemic-scale viruses. This review paper presents an overview of the recent progress in the development of an efficient visible light-sensitive photocatalyst, i.e., a copper oxide nanoclusters grafted titanium dioxide (CuxO/TiO2). The antiviral CuxO/TiO2 photocatalyst is functionalised by a different mechanism in addition to the photocatalytic oxidation process. The CuxO nanocluster consists of the valence states of Cu(I) and Cu(II); herein, the Cu(I) species denaturalizes the protein of the virus, thereby resulting in significant antiviral properties even under dark conditions. Moreover, the Cu(II) species in the CuxO nanocluster serves as an electron acceptor through photo-induced interfacial charge transfer, which leads to the formation of an anti-virus Cu(I) species and holes with strong oxidation power in the valence band of TiO2 under visible-light irradiation. The antiviral function of the CuxO/TiO2 photocatalyst is maintained under indoor conditions, where light illumination is enabled during the day but not during the night; this is because the remaining active Cu(I) species works under dark conditions. The CuxO/TiO2 photocatalyst can thus be used to reduce the risk of virus infection by acting as an antiviral coating material.

The influence of pre-coating Li7La3Zr2O12 (LLZ) with Au on the charge transfer resistance (R-int) at the interface of LLZ and lithium (Li) is examined by AC impedance spectroscopy using a three-electrode system. The Au diffuses into Li after physical contact with Li, and the open-circuit potential reaches approximately 0 mV (vs. Li/Li +) accompanied by a decrease in R-int. During the Li dissolution/deposition cycles, the electrode potential changes with 0 mV as the central potential, indicating that Li metal dissolution/deposition on Li metal proceeds predominantly at the interface. R-int increases and decreases during Li dissolution and deposition, respectively, regardless of the presence or absence of the Au coating; however, the increase in R-int during Li dissolution is suppressed at the Li/Au-coated LLZ (Au-LLZ) interface. The decreased R-int is considered to be due to an increase in the effective contact area at the electrode/LLZ interface, which is achieved by pre-coating Au onto the LLZ surface.

AbstractExtracellular electron transport (EET) occurs in environmental iron-reducing bacteria and is mediated by an outer membrane multi-heme cytochrome complex (Cyts). It has critical implications for global mineral cycling and electrochemical microbial catalysis. The rate of EET mediated by multiple heme redox centers significantly increases in the presence of flavins and quinones. Their electron free energy does not entirely account for the fact that differential effects on EET rate enhancement vary significantly by factors ≥100. Here, we report on whole-cell electrochemical analysis ofShewanella oneidensisMR-1 using six flavin analogs and four quinones. We demonstrated that protonation of the nitrogen atom at position 5 (N5) of the isoalloxazine ring is essential for electron outflow acceleration as a bound non-covalent cofactor of Cyts. EET mediated by Cyts was accelerated at a rate dependent on pKa(N5). The EET rate largely decreased in response to the addition of deuterated water (D2O), while low concentration of D2O (4 %) had little impact on electron free energy difference of the heme and non-covalent bound cofactors, strongly suggesting that the protonation of N5 limits the rate of EET. Our findings directly link EET kinetics to proton transport reaction via N5 and provide a basis for the development of novel strategies for controlling EET-associated biological reactions.Significance statementThe potential of various small molecules such as flavins and quinones to enhance the rate of extracellular electron transport (EET) has been exploited to develop environmental energy conversion systems. Flavins and quinones have similar molecular structures but their abilities to enhance EET vary by >100× inShewanella oneidensisMR-1. These large differences are inconsistent with conventional models, which rely on redox potentials or diffusion constant of shuttling electron mediators. In this study, we demonstrated that the basicity of the nitrogen atom of the isoalloxazine ring (N5) enhances the rate of electron outflow when a flavin or quinone is a non-covalent cofactor ofS. oneidensisMR-1 outer membranec-type cytochromes.

Extracellular electron transport (EET) occurs in environmental iron-reducing bacteria and is mediated by an outer membrane multi-heme cytochrome complex (Cyts). It has critical implications for global mineral cycling and electrochemical microbial catalysis. The rate of EET mediated by multiple heme redox centers significantly increases in the presence of flavins and quinones. Their electron free energy does not entirely account for the fact that differential effects on EET rate enhancement vary significantly by factors ≥100. Here, we report on whole-cell electrochemical analysis of MR-1 using six flavin analogs and four quinones. We demonstrated that protonation of the nitrogen atom at position 5 (N5) of the isoalloxazine ring is essential for electron outflow acceleration as a bound non-covalent cofactor of Cyts. EET mediated by Cyts was accelerated at a rate dependent on p(N5). The EET rate largely decreased in response to the addition of deuterated water (DO), while low concentration of DO (4 %) had little impact on electron free energy difference of the heme and non-covalent bound cofactors, strongly suggesting that the protonation of N5 limits the rate of EET. Our findings directly link EET kinetics to proton transport reaction via N5 and provide a basis for the development of novel strategies for controlling EET-associated biological reactions.

Elucidating the mechanism that differentiates the oxygen-evolving center of photosystem II with its inorganic counterpart is crucial to develop efficient catalysts for the oxygen evolution reaction (OER). Previous studies have suggested that the larger overpotential for MnO2 catalysts under neutral conditions may result from the instability of the Mn3+ intermediate to charge disproportionation. Here, by monitoring the surface intermediates of electrochemical OER on rutile MnO2 with different facet orientations, a correlation between the stability of the intermediate species and crystal facets is confirmed explicitly for the first time. The coverage of the Mn3+ intermediate is found to be 11-fold higher on the metastable (101) surfaces compared to (110) surfaces, leading to the superior OER activity of (101) surfaces. The difference in OER activity may result from the difference in surface electronic states of Mn3+, where interlayer charge comproportionation of Mn2+ and Mn4+ to generate two Mn3+ species is favored on (101) facets. Considering the fact that the OER enzyme accommodates Mn3+ stably during the Kok cycle, the enhanced OER activity of the rutile MnO2 catalyst with a metastable surface highlights the importance of mimicking not only the crystal structure but also the electronic structure of the targeted natural enzyme.

Linear polydimethylsiloxane (PDMS) was investigated as a solubilizing group for π-conjugated polymers with the aim of combining high solubility in organic solvents with the molecular packing in solid films that is advantageous for charge transport. Diketopyrrolopyrrole-based copolymers with different contents and substitution patterns of the PDMS side chains were synthesized and evaluated for application in organic field-effect transistors. The PDMS side chains greatly increased the solubility of the polymers and led to shorter d -spacings of the π-stacking in the thin films compared with polymers containing conventional branched alkyl side chains.

Understanding the design strategy of photosynthetic and respiratory enzymes is important to develop efficient artificial catalysts for oxygen evolution and reduction reactions. Here, based on a bioinformatic analysis of cyanobacterial oxygen evolution and reduction enzymes (photosystem II: PS II and cytochrome c oxidase: COX, respectively), the gene encoding the catalytic D1 subunit of PSII was found to be expressed individually across 38 phylogenetically diverse strains, which is in contrast to the operon structure of the genes encoding major COX subunits. Selective synthesis of the D1 subunit minimizes the repair cost of PSII, which allows compensation for its instability by lowering the turnover number required to generate a net positive energy yield. The different bioenergetics observed between PSII and COX suggest that in addition to the catalytic activity rationalized by the Sabatier principle, stability factors have also provided a major influence on the design strategy of biological multi-electron transfer enzymes.

Dynamic changes in the charge-transfer resistance at a Li/Li7La3Zr2O12 (LLZ) interface during lithium (Li) dissolution/deposition cycles are investigated with an alternative current (AC) impedance technique in a three-electrode system. The resistance respectively increases and decreases during electrodissolution and electrodeposition of Li. The resistance does not return to the initial value after one cycle of Li dissolution and deposition, which indicates that the change in resistance during dissolution is larger than that during deposition. Furthermore, the resistance is almost constant when Li deposition proceeds without prior Li dissolution. The respective increase and decrease in the interfacial resistance during Li dissolution and deposition is most likely due to the formation and disappearance of voids at the Li/LLZ interface, and the voids formation during Li dissolution is suggested to be a critical factor that influences the interfacial resistance.

We established whole-cell circular dichroism difference spectroscopy to identify the inter-heme interaction in deca-heme cytochrome protein MtrC in whole cell. Our data showed that the heme alignment of reduced MtrC in whole cell is distinct from that in purified one, suggesting the in vivo specific electron transport kinetics.

A poly(3-butylthiophene) derivative with an end group of 1,1,1,3,3,5,5-heptamethyl trisiloxane group (P3BT-Si) was synthesized for the application of surface segregated monolayer (SSM) in polymer films. The surface segregation behaviors, thermal properties and chain orientation of P3BT-Si were investigated. The formation of the surface layer of P3BT-Si was confirmed in the blend films with polystyrene. In contrast to the fluoroalkyl-terminated polymer (P3BT-F 17 ) that shows strong end-on orientation in the SSM with high crystallinity, P3BT-Si showed edge-on orientation in the SSM with low crystallinity. The difference can be attributed to the more flexible structure of trisiloxane group than the fluoroalkyl chain.

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