The role of the gold-platinum interface in AuPt/TiO2-catalyzed plasmon-induced reduction of CO2 with water.

Bimetallic gold-platinum nanoparticles have been widely studied in the fields of nanoalloys, catalysis and plasmonics. Many preparation methods can lead to the formation of these bimetallic nanoparticles (NPs), and the structure and related properties of the nanoalloy often depend on the preparation method used. Here we investigate the ability of thermal dimethylformamide (DMF) reduction to prepare bimetallic gold-platinum sub-nm clusters supported on titania. We find that deposition of Pt preferentially occurs on gold. Formation of sub-nm clusters (vs. NPs) appears to be dependent on the metal concentration used: clusters can be obtained for metal loadings up to 4 wt% but 7-8 nm NPs are formed for metal loadings above 8 wt%, as shown using high resolution transmission electron microscopy (HRTEM). X-ray photoelectron spectroscopy (XPS) shows electron-rich Au and Pt components in a pure metallic form and significant platinum enrichment of the surface, which increases with increasing Pt/Au ratio and suggests the presence of Au@Pt core-shell type structures. By contrast, titania-supported bimetallic particles (typically >7 nm) obtained by sodium borohydride (NaBH4) reduction in DMF, contain Au/Pt Janus-type objects in addition to oxidized forms of Pt as evidenced by HRTEM, which is in agreement with the lower Pt surface enrichment found by XPS. Both types of supported nanostructures contain a gold-platinum interface, as shown by the chemical interface damping, i.e. gold plasmon damping by Pt, found using UV-visible spectroscopy. Evaluation of the materials for plasmon-induced continuous flow CO2 reduction with water, shows that: (1) subnanometer metallic clusters are not suitable for CO2 reduction with water, producing hydrogen from the competing water reduction instead, thereby highlighting the plasmonic nature of the reaction; (2) the highest methane production rates are obtained for the highest Pt enrichments of the surface, i.e. the core-shell-like structures achieved by the thermal DMF reduction method; (3) selectivity towards CO2 reduction vs. the competing water reduction is enhanced by loading of the plasmonic NPs, i.e. coverage of the titania semi-conductor by plasmonic NPs. Full selectivity is achieved for loadings above 6 wt%, regardless of the NPs composition and alloy structure.

Plasmonic photocatalysis applied to solar fuels.

The induction of chemical processes by plasmonic systems is a rapidly growing field with potentially many strategic applications. One of them is the transformation of solar energy into chemical fuel by the association of plasmonic metal nanoparticles (M NPs) and a semi-conductor (SC). When the localized surface plasmon resonance (LSPR) and the SC absorption do not match, one limitation of these systems is the efficiency of hot electron transfer from M NPs to SC through the Schottky barrier formed at the M NP/SC interfaces. Here we show that high surface area 1 wt% Au/TiO2-UV100, prepared by adsorption of a NaBH4-protected 3 nm gold sol, readily catalyzes the photoreduction of carbon dioxide with water into methane under both solar and visible-only irradiation with a CH4vs. H2 selectivity of 63%. Tuning Au NP size and titania surface area, in particular via thermal treatments, highlights the key role of the metal dispersion and of the accessible Au-TiO2 perimeter interface on the direct SC-based solar process. The impact of Au NP density in turn provides evidence for the dual role of gold as co-catalyst and recombination sites for charge carriers. It is shown that the plasmon-induced process contributes up to 20% of the solar activity. The plasmon-based contribution is enhanced by a large Au NP size and a high degree of crystallinity of the SC support. By minimizing surface hydroxylation while retaining a relatively high surface area of 120 m2 g-1, pre-calcining TiO2-UV100 at 450 °C leads to an optimum monometallic system in terms of activity and selectivity under both solar and visible irradiation. A state-of-the-art methane selectivity of 100% is achieved in the hot electron process.

TiO2 photocatalysis damages lipids and proteins in Escherichia coli.

This study investigates the mechanisms of UV-A (315 to 400 nm) photocatalysis with titanium dioxide (TiO2) applied to the degradation of Escherichia coli and their effects on two key cellular components: lipids and proteins. The impact of TiO2 photocatalysis on E. coli survival was monitored by counting on agar plate and by assessing lipid peroxidation and performing proteomic analysis. We observed through malondialdehyde quantification that lipid peroxidation occurred during the photocatalytic process, and the addition of superoxide dismutase, which acts as a scavenger of the superoxide anion radical (O2·(-)), inhibited this effect by half, showing us that O2·(-) radicals participate in the photocatalytic antimicrobial effect. Qualitative analysis using two-dimensional electrophoresis allowed selection of proteins for which spot modifications were observed during the applied treatments. Two-dimensional electrophoresis highlighted that among the selected protein spots, 7 and 19 spots had already disappeared in the dark in the presence of 0.1 g/liter and 0.4 g/liter TiO2, respectively, which is accounted for by the cytotoxic effect of TiO2. Exposure to 30 min of UV-A radiation in the presence of 0.1 g/liter and 0.4 g/liter TiO2 increased the numbers of missing spots to 14 and 22, respectively. The proteins affected by photocatalytic oxidation were strongly heterogeneous in terms of location and functional category. We identified several porins, proteins implicated in stress response, in transport, and in bacterial metabolism. This study reveals the simultaneous effects of O2·(-) on lipid peroxidation and on the proteome during photocatalytic treatment and therefore contributes to a better understanding of molecular mechanisms in antibacterial photocatalytic treatment.

On the use of capillary cytometry for assessing the bactericidal effect of TiO2. Identification and involvement of reactive oxygen species.

The photocatalytic antimicrobial properties of TiO2 were studied on Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa bacterial strains taken as model strains for pathogenic species mainly implied in nosocomial infections. Capillary cytometry, coupled to a double-staining method for visualizing membrane integrity as a cell viability indicator, was highlighted as a rapid, easy-to-use, and automated numeration technique for quantitative and reproducible determination of cellular viability and thus, was able to give an accurate evaluation of the bactericidal effect of UV-A photocatalysis. Cytometry also enabled the study of TiO2-bacteria interactions and aggregation in the dark as well as TiO2 cytotoxicity. Compared with the traditional agar plate cultivation method, a significatively weaker reduction in cell viability was recorded by cytometry whatever the bacteria, TiO2 concentration, and duration of the photocatalytic treatment. The mismatch between both numeration methods was attributed to: (i) the presence of mixed bacteria-TiO2 aggregates that could interfere with bacteria measurement on plates, (ii) prolonged contact of the bacteria with TiO2 during incubation, which could cause additional cytotoxic damage to the bacterial wall, and (iii) the counting of viable but non-culturable bacteria as live bacteria in cytometry, whereas they cannot grow on solid media. A more pronounced difference was observed for P. aeruginosa and S. aureus bacteria, for which 2.9 and 1.9 log10 survival reduction overestimations were measured by plate counting, respectively. Using chemiluminescence, full restoration of cell viability by controlled addition of the O2˙(-) scavenger superoxide dismutase enzyme suggests that O2˙(-) acts, in our conditions, as the main reactive oxygen species responsible for the photocatalytic attack towards the targeted bacteria.

Failed in aging? Queering in living with dementia.

This article explored the ways in which living with dementia brings potentials to queer the concept of "successful aging" and associated notions of being human. Regarding the progressive development of dementia, it can be assumed that people affected, no matter how hard they try, will sooner or later fail to age successfully. They increasingly become a symbol of what is called the "fourth age" and are framed as an essentialized other. Based on statements of people with dementia, it will be examined to what extent the position on the outside enables people affected to abandon societal guiding ideals and undermine hegemonic-dominant notions of aging. It is shown how they develop life-affirming ways of being-in-the-world that run counter to the idea of the rational, autonomous, consistent, active, productive, and healthy human beings.

MOF-Derived Defective Co3O4 Nanosheets in Carbon Nitride Nanocomposites for CO2 Photoreduction and H2 Production.

In photocatalysis, especially in CO2 reduction and H2 production, the development of multicomponent nanomaterials provides great opportunities to tune many critical parameters toward increased activity. This work reports the development of tunable organic/inorganic heterojunctions comprised of cobalt oxides (Co3O4) of varying morphology and modified carbon nitride (CN), targeting on optimizing their response under UV-visible irradiation. MOF structures were used as precursors for the synthesis of Co3O4. A facile solvothermal approach allowed the development of ultrathin two-dimensional (2D) Co3O4 nanosheets (Co3O4-NS). The optimized CN and Co3O4 structures were coupled forming heterojunctions, and the content of each part was optimized. Activity was significantly improved in the nanocomposites bearing Co3O4-NS compared with the corresponding bulk Co3O4/CN composites. Transient absorption spectroscopy revealed a 100-fold increase in charge carrier lifetime on Co3O4-NS sites in the composite compared with the bare Co3O4-NS. The improved photocatalytic activity in H2 production and CO2 reduction is linked with (a) the larger interface imposed from the matching 2D structure of Co3O4-NS and the planar surface of CN, (b) improvements in charge carrier lifetime, and (c) the enhanced CO2 adsorption. The study highlights the importance of MOF structures used as precursors in forming advanced materials and the stepwise functionalization of the individual parts in nanocomposites for the development of materials with superior activity.

Acute effects of an isometric neck warm-up programme on neck performance characteristics and ultrasound-based morphology.

OBJECTIVE: Athletic performance can be enhanced immediately after an isometric warm-up, a phenomenon termed post-activation performance enhancement (PAPE). While isometric warm-ups can improve lower extremity sprint and jump performance, neck-specific isometric warm-ups need development and validation for mild traumatic brain disorders and neck pain. This study examined acute effects of isometric warm-ups on neck performance and morphology. METHODS: Arm 1: Twenty-six adults (13 M:13F) completed neck performance testing before and after a 10-minute neck isometric warm-up or stationary bike (sham) between two visits. Testing included visual-motor reaction time, peak force, rate of force development, force steadiness, and force replication/proprioception measured by a 6-axis load cell. An inclinometer assessed range-of-motion. Paired t-tests and two-way ANOVA examined effects of neck/bike warm-up and interaction effects, respectively. Arm 2: 24 adults (11 M:13F) completed ultrasound scans of cervical muscles: before 20-minute rest (sham), and before/after a 5-min neck isometric warm-up. Longus colli cross-sectional area and sternocleidomastoid/upper trapezius thickness and stiffness, and cervical extensors thickness was assessed. One-way ANOVA compared morphological values at sham, before, and after warm-up. Significance was set at p < 0.05. RESULTS: Isometric neck warm-up increased rate of force development in flexion (p = 0.022), extension (p = 0.001-0.003), right lateral flexion (p = 0.004-0.032), left lateral flexion (p = 0.005-0.014), while peak force improved only in left lateral flexion (p = 0.032). Lateral flexion range-of-motion increased after neck warm-up (p = 0.003-0.026). Similarly, longus colli cross-sectional area (p = 0.016) and sternocleidomastoid thickness (p = 0.004) increased. CONCLUSIONS: Increased neck performance characteristics and morphology are likely due to PAPE effects of isometric neck warm-up. For coaches and athletes, simple isometric contractions could be added to existing warm-ups to reduce prevalence, incidence, and severity of mild traumatic brain injuries and neck pain.

Photocatalytically active polyelectrolyte/nanoparticle films for the elimination of a model odorous gas.

Virtually transparent films of Aeroxide TiO(2) P25 were fabricated via layer-by-layer assembly with sodium poly(styrene sulfonate). Nanoscale films are formed on model surfaces for characterization or inside of cylindrical reactors for investigating the catalytic properties. Films are fairly homogeneous and smooth over large areas and show different optical interference colors depending on film thickness. The application-relevant photocatalytic performance of such films toward on-flow degradation of hydrogen sulfide under UV-A irradiation was investigated. Scanning electron microscopy reveals a nanoporous structure allowing for the permeation of gas. Consequently, the catalytic efficiency of the films increases with increasing film thickness retaining a considerable activity of the corresponding nanoparticle powder. Scheme 1 depicts in a general way the functionalized reactor and the principle of the measurement.

The dual mode of action of bistramide A entails severing of filamentous actin and covalent protein modification.

This study provides comprehensive characterization of the mode of action of bistramide A and identifies structural requirements of bistramide-based compounds that are responsible for severing actin filaments and inhibiting growth of cancer cells in vitro and in vivo. We rationally designed and assembled a series of structural analogs of the natural product, including a fluorescently labeled conjugate. We used TIRF microscopy to directly observe actin filament severing by this series of small molecules, which established that the combination of the spiroketal and the amide subunits was sufficient to enable rapid actin filament disassembly in vitro. In addition, we demonstrated that the enone subunit of bistramide A is responsible for covalent modification of the protein in vitro and in A549 cells, resulting in further increase in the cytotoxicity of the natural product. Our results demonstrate that bistramide A elicits its potent antiproliferative activity by a dual mechanism of action, which entails both severing of actin filaments and covalent sequestration of monomeric actin in the cell.

Titania-Carbon Nitride Interfaces in Gold-Catalyzed CO Oxidation.

Gold-catalyzed CO oxidation is a reaction of both practical and fundamental interest. In particular, rate-determining oxygen activation pathways have attracted a lot of attention. They have been found to depend on the surface chemistry of the catalyst support, titania providing the most active catalysts and carbon nitride leading to inactive catalysts. Here, we show that C3N4-TiO2 composites with rather similar surface chemistries can be engineered by using titania nanotubes as hard templates and by performing the polycondensation of melamine and dicyandiamide in air and in ammonia. By varying the C3N4 content from 2 to 75 wt %, the mesoporosity can be tuned from 8 to 40 nm. A systematic study of CO oxidation turnover numbers in the absence and in the presence of hydrogen over the composites loaded with well-calibrated 2-4 nm gold nanoparticles clearly shows that (1) the chemical composition of the support surface has much less impact on PROX (preferential oxidation of CO in excess hydrogen) than on dry CO oxidation, (2) NH2-terminated supports are as active as OH-terminated supports in PROX, (3) hydrogen/water-mediated CO oxidation pathways are active on C3N4-based Au catalysts, and (4) PROX activity requires a rather large porosity (40 nm), which suggests the involvement of much larger intermediates than the usually postulated peroxo-type species.

Tunable generation and adsorption of energetic compounds in the vapor phase at trace levels: a tool for testing and developing sensitive and selective substrates for explosive detection.

Among various methods for landmine detection, as well as soil and water pollution monitoring, the detection of explosive compounds in air is becoming an important and inevitable challenge for homeland security applications, due to the threatening increase in terrorist explosive bombs used against civil populations. However, in the last case, there is a crucial need for the detection of vapor phase traces or subtraces (in the ppt range or even lower). A novel and innovative generator for explosive trace vapors was designed and developed. It allowed the generation of theoretical concentrations as low as 0.24 ppq for hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in air according to Clapeyron equations. The accurate generation of explosive concentrations at subppt levels was verified for RDX and 2,4,6-trinitrotoluene (TNT) using a gas chromatograph coupled to an electron capture detector (GC-ECD). First, sensing material experiments were conducted on a nanostructured tungsten oxide. The sensing efficiency of this material determined as its adsorption capacity toward 54 ppb RDX was calculated to be five times higher than the sensing efficiency of a 54 ppb TNT vapor. The material sensing efficiency showed no dependence on the mass of material used. The results showed that the device allowed the calibration and discrimination between materials for highly sensitive and accurate sensing detection in air of low vapor pressure explosives such as TNT or RDX at subppb levels. The designed device and method showed promising features for nanosensing applications in the field of ultratrace explosive detection. The current perspectives are to decrease the testing scale and the detection levels to ppt or subppt concentration of explosives in air.

Silver-Catalyzed Aldehyde Olefination Using Siloxy Alkynes.

We describe the development of a silver-catalyzed carbonyl olefination employing electron rich siloxy alkynes. This process constitutes an efficient synthesis of trisubstituted unsaturated esters, and represents an alternative to the widely utilized Horner-Wadsworth-Emmons reaction. Excellent diastereoselectivities are observed for a range of aldehydes using either 1-siloxy-1-propyne or 1-siloxy-1-hexyne. This mild catalytic process also enables chemoselective olefination of aldehydes in the presence of either ester or ketone functionality. Furthermore, since no by-products are generated, this catalytic process is perfectly suited for development of sequential reactions that can be carried out in a single flask.

Optical limiting behavior of carbon nanotubes exposed to infrared laser irradiations studied by the Z-scan technique.

The optical limiting behavior of multiwalled carbon nanotube (MWCNT) powder in chloroform solution under CO(2) infrared laser irradiations is reported for, to our knowledge, the first time. Here we demonstrate the pure thermal origin of the optical limiting effect in the 160 ns time scale studied. The Z-scan technique appears to be an excellent tool for experimental evaluation of the nonlinear refractive index. An experimental model for the optical limiting behavior of MWCNT suspensions in chloroform is presented. The occurrence of a laser-induced thermal lens through the absorption of energy by the MWCNTs and subsequent heat transfer to the solvent, followed by solvent vapor bubble growth, is the main factor governing the observed drop in transmittance. Pump-probe experiments have been performed to obtain some quantitative estimation of both the rise and decay times of the thermal lensing phenomenon. It was found that the early probe signal decay, tau(1)=149 ns, was of the same order of magnitude as the rise time of the thermal lens, tau(r)=121 ns. When the nonlinear scattering was considered, a total decay time of tau=1.8 micros was obtained. A recovery time for the thermal lens of several tens of milliseconds has been experimentally determined, which is in good accordance with the theoretical value.

Antibacterial and Biofilm-Preventive Photocatalytic Activity and Mechanisms on P/F-Modified TiO2 Coatings.

Photocatalytic antibacterial and biofilm-preventive activity in liquid of heavy-metal-free coatings based on a phosphorus (P)- and fluorine (F)-modified TiO2 photocatalyst has been investigated. They reveal significantly higher immediate and longer-term (biofilm-preventive) inactivation capacity than a reference coating made of the commercial photocatalyst TiO2 P25 on three bacterial species differing in cell wall type and ability to resist oxidative stress (Escherichia coli, Staphylococcus epidermidis, Pseudomonas fluorescens) (up to more than 99% reduction of colonization on P/F-modified TiO2 coating compared to about 50% on P25 TiO2 coating for 10 min UV-A illumination). This results from the P- and F-induced improvement of photocatalyst properties and from the smoother surface topography, which shortens reactive oxygen species (ROS) diffusion to the outer membrane of the targeted adhered bacteria. Decrease in ROS-related impairment of cell wall, respiratory, and enzymatic activities confirms the loss of ROS throughout the bacterial cell degradation. Staphylococcus epidermidis and Pseudomonas fluorescens are less sensitive than Escherichia coli, with a probable relation to the bacterial oxygen stress defense mechanism. The coating antibacterial efficacy was highly affected by phosphate ions and the richness in dissolved oxygen of the reaction medium.

Double side nanostructuring of microcantilever sensors with TiO2-NTs as a route to enhance their sensitivity.

We reported a new strategy to enhance the sensing performances of a commercial microcantilever with optical readout in dynamic mode for the vapor detection of organophosphorus compounds (OPs). In order to increase significantly the surface area accessible to the molecules in the vapor phase, we nanostructured both sides of the microcantilever with ordered, open and vertically oriented amorphous titanium dioxide nanotubes (TiO2-NTs) in one step by an anodization method. However, due to the aggressive conditions of anodization synthesis it remains a real challenge to nanostructure both sides of the microcantilever. Consequently, we developed and optimized a protocol of synthesis to overcome these harsh conditions which can lead to the total destruction of the silicon microcantilever. Moreover, this protocol was also elaborated in order to maintain a good reflection of the laser beam on one side of the microcantilever towards the position sensitive photodiode and limit the light diffusion by the NTs film. The results related to the detection of dimethyl methylphosphonate (DMMP) showed that TiO2 and the nanostructuring on both sides of the microcantilever with NTs indeed improved the response of the sensor to vapors compared to a microcantilever nanostructured on only one side. The dimensions and morphology of NTs guaranteed the access of molecules to the surface of NTs. This approach showed promising prospects to enhance the sensing performances of microcantilevers.

Functionalized TiO2 Nanorods on a Microcantilever for the Detection of Organophosphorus Chemical Agents in Air.

We report the fabrication of nanostructured microcantilevers employed as sensors for the detection of organophosphorus (OPs) vapors. These micromechanical sensors are prepared using a two-step procedure first optimized on a silicon wafer. TiO2 one-dimensional nanostructures are synthesized at a silicon surface by a solvothermal method and then grafted with bifunctional molecules having an oxime group known for its strong affinity with organophosphorus compounds. The loading of oxime molecules grafted on the different nanostructured surfaces was quantified by UV spectroscopy. It has been found that a wafer covered by vertically aligned rutile TiO2 nanorods (NRs), with an average length and width of 9.5 µm and 14.7 nm, respectively, provides an oxime function density of 360 nmol cm-2. The optimized TiO2 nanorod synthesis was successfully reproduced on the cantilevers, leading to a homogeneous and reproducible TiO2 NR film with the desired morphology. Thereafter, oxime molecules have been successfully grafted on the nanostructured cantilevers. Detection tests were performed in a dynamic mode by exposing the microcantilevers to dimethyl methylphosphonate (a model compound of toxic OPs agents) and following the shift of the resonant frequency. The nanostructure and the presence of the molecules on a TiO2 NR surface both improve the response of the sensors. A detection limit of 2.25 ppm can be reached with this type of sensor.

Wide band gap Ga2O3 as efficient UV-C photocatalyst for gas-phase degradation applications.

α, ß, γ, and δ polymorphs of 4.6-4.8 eV wide band gap Ga2O3 photocatalysts were prepared via a soft chemistry route. Their photocatalytic activity under 254 nm UV-C light in the degradation of gaseous toluene was strongly depending on the polymorph phase. α- and ß-Ga2O3 photocatalysts enabled achieving high and stable conversions of toluene with selectivities to CO2 within the 50-90% range, by contrast to conventional TiO2 photocatalysts that fully deactivate very rapidly on stream in similar operating conditions with rather no CO2 production, no matter whether UV-A or UV-C light was used. The highest performances were achieved on the high specific surface area ß-Ga2O3 photocatalyst synthesized by adding polyethylene glycol (PEG) as porogen before precipitation, with stable toluene conversion and mineralization rate into CO2 strongly overcoming those obtained on commercial ß-Ga2O3. They were attributed to favorable physicochemical properties in terms of high specific surface area, small mean crystallite size, good crystallinity, high pore volume with large size mesopore distribution and appropriate surface acidity, and to the possible existence of a double local internal field within Ga3+ units. In the degradation of hydrogen sulfide, PEG-derived ß-Ga2O3 takes advantage from its high specific surface area for storing sulfate, and thus for increasing its resistance to deactivation and the duration at total sulfur removal when compared to other ß-Ga2O3 photocatalysts. So, we illustrated the interest of using high surface area ß-Ga2O3 in environmental photocatalysis for gas-phase depollution applications.

One-pot synthesis of lightly doped Zn1-x Cu x O and Au-Zn1-x Cu x O with solar light photocatalytic activity in liquid phase.

We report on the facile and low-temperature one-pot chemical synthesis of lightly doped Zn1-x Cu x O and hybrid Au-Zn1-x Cu x O photocatalysts with low Cu molar content (0 < x < 0.7%) using 1,3-propanediol polyol simultaneously as solvent, reducing and a stabilizing agent, without any final thermal treatment. The photocatalysts have been characterized by X-ray diffraction, N2 adsorption study, UV-vis diffuse reflectance spectroscopy, inductively coupled plasma optical emission spectroscopy, and transmission electron microscopy. The lightly doped hybrid Au-Zn1-x Cu x O photocatalysts consisted in faceted quasi-spherical large-size Au nanoparticle cores surrounded by closely packed small-size Zn1-x Cu x O nanoparticles. Taking the photocatalytic degradation of Diuron under solar light as liquid-phase test reaction, the lightly doped Au-Zn1-x Cu x O hybrid photocatalysts with optimized x = 0.09% Cu content showed strongly enhanced photocatalytic activity when compared to the bare ZnO counterpart. The observed 16-fold higher degradation rate constant resulted jointly from the light doping of ZnO with Cu to form Zn1-x Cu x O photocatalyst and further from the addition of gold nanoparticles allowing interfacial oxide-to-metal electron transfer within the hybrid Au-Zn1-x Cu x O photocatalyst.