An innovative, highly stable Ag/ZIF-67@GO nanocomposite with exceptional peroxymonosulfate (PMS) activation efficacy, for the destruction of chemical and microbiological contaminants under visible light.

In this work, Ag nanoparticles were loaded on ZIF-67 covered by graphene oxide (Ag/ZIF-67@GO), and its catalytic performance was studied for the heterogeneous activation of peroxymonosulfate (PMS) under visible-light. The catalyst surface morphology and structure were analyzed by FT-IR, XRD, XPS, DRS, FE-SEM, EDX, TEM, BET, ICP-AES and TGA analysis. The efficacy of PMS activation by the Ag/ZIF-67@GO under visible light was assessed by phenol degradation and E. coli inactivation. Phenol was completely degraded within 30 min by HO•, SO4•- and O2•- generated through the photocatalytic PMS activation. In addition, total E. coli inactivation was attained in 15 min that confirmed the highly efficient catalytic activation of PMS by the as-made nanocomposite under visible light. The reaction mechanism was elucidated and the importance of the generated reactive species followed the order of: HO• > SO4•- > O2•- > h+, implying a radical-pathway dominated process.

An Unconventional Iron Nickel Catalyst for the Oxygen Evolution Reaction.

The oxygen evolution reaction (OER) is a key process that enables the storage of renewable energies in the form of chemical fuels. Here, we describe a catalyst that exhibits turnover frequencies higher than state-of-the-art catalysts that operate in alkaline solutions, including the benchmark nickel iron oxide. This new catalyst is easily prepared from readily available and industrially relevant nickel foam, and it is stable for many hours. Operando X-ray absorption spectroscopic data reveal that the catalyst is made of nanoclusters of γ-FeOOH covalently linked to a γ-NiOOH support. According to density functional theory (DFT) computations, this structure may allow a reaction path involving iron as the oxygen evolving center and a nearby terrace O site on the γ-NiOOH support oxide as a hydrogen acceptor.

Iron oxide-mediated semiconductor photocatalysis vs. heterogeneous photo-Fenton treatment of viruses in wastewater. Impact of the oxide particle size.

The photo-Fenton process is recognized as a promising technique towards microorganism disinfection in wastewater, but its efficiency is hampered at near-neutral pH operating values. In this work, we overcome these obstacles by using the heterogeneous photo-Fenton process as the default disinfecting technique, targeting MS2 coliphage in wastewater. The use of low concentrations of iron oxides in wastewater without H2O2 (wüstite, maghemite, magnetite) has demonstrated limited semiconductor-mediated MS2 inactivation. Changing the operational pH and the size of the oxide particles indicated that the isoelectric point of the iron oxides and the active surface area are crucial in the success of the process, and the possible underlying mechanisms are investigated. Furthermore, the addition of low amounts of Fe-oxides (1mgL-1) and H2O2 in the system (1, 5 and 10mgL-1) greatly enhanced the inactivation process, leading to heterogeneous photo-Fenton processes on the surface of the magnetically separable oxides used. Additionally, photo-dissolution of iron in the bulk, lead to homogeneous photo-Fenton, further aided by the complexation by the dissolved organic matter in the solution. Finally, we assess the impact of the presence of the bacterial host and the difference caused by the different iron sources (salts, oxides) and the Fe-oxide size (normal, nano-sized).

Interstitial fluid pressure: A novel biomarker to monitor photo-induced drug uptake in tumor and normal tissues.

BACKGROUND: Low-dose photodynamic therapy PDT (photoinduction) can modulate tumor vessels and enhance the uptake of liposomal cisplatin (Lipoplatin®) in pleural malignancies. However, the photo-induction conditions must be tightly controlled as overtreatment shuts down tumor vessels and enhances normal tissue drug uptake. MATERIAL AND METHODS: In a pleural sarcoma and adenocarcinoma rat model (n = 12/group), we applied photoinduction (0.0625 mg/kg Visudyne®, 10 J/cm2 ) followed by intravenous Lipoplatin® (5 mg/kg) administration. Tumor and normal tissue IFP were assessed before and up to 1 hour following photoinduction. Lipoplatin® uptake was determined 60 minutes following photoinduction. We then treated the pleura of tumor-free minipigs with high dose photodynamic therapy (PDT) (0.0625 mg/kg Visudyne®, 30 J/cm2 , n = 5) followed by Lipoplatin (5 mg/kg) administration. RESULTS: In rodents, photoinduction resulted in a significant decrease of IFP (P < 0.05) in both tumor types but not in the surrounding normal lung, equally exposed to light. Also, photoinduction resulted in a significant increase of Lipoplatin® uptake in both tumor types (P < 0.05) but not in normal lung. Tumor IFP variation and Lipoplatin® uptake fitted an inverted parabola. In minipigs, high dose photodynamic treatment resulted in pleural IFP increase of some animals which predicted higher Lipoplatin® uptake levels. CONCLUSION: Normal and tumor vasculatures react differently to PDT. Continuous IFP monitoring in normal and tumor tissues is a promising biomarker of vessel photoinduction. Moderate drop in tumor with no change in normal tissue IFP are predictive of specific Lipoplatin® uptake by cancer following PDT. Lasers Surg. Med. 49:773-780, 2017. © 2017 Wiley Periodicals, Inc.

Treatment of pleural malignancies by photo-induction combined to systemic chemotherapy: Proof of concept on rodent lung tumors and feasibility study on porcine chest cavities.

BACKGROUND: Low-dose, Visudyne®-mediated photodynamic therapy (photo-induction) was shown to selectively enhance tumor vessel transport causing increased uptake of systemically administered chemotherapy in various tumor types grown on rodent lungs. The present experiments explore the efficacy of photo-induced vessel modulation combined to intravenous (IV) liposomal cisplatin (Lipoplatin®) on rodent lung tumors and the feasibility/toxicity of this approach in porcine chest cavities. MATERIAL AND METHODS: Three groups of Fischer rats underwent orthotopic sarcoma (n = 14), mesothelioma (n = 14), or adenocarcinoma (n = 12) implantation on the left lung. Half of the animals of each group had photo-induction (0.0625 mg/kg Visudyne®, 10 J/cm(2) ) followed by IV administration of Lipoplatin® (5 mg/kg) and the other half received Lipoplatin® without photo-induction. Then, two groups of minipigs underwent intrapleural thoracoscopic (VATS) photo-induction (0.0625 mg/kg Visudyne®; 30 J/cm(2) hilum; 10 J/cm(2) apex/diaphragm) with in situ light dosimetry in combination with IV Lipoplatin® administration (5 mg/kg). Protocol I (n = 6) received Lipoplatin® immediately after light delivery and Protocol II (n = 9) 90 minutes before light delivery. Three additional animals received Lipoplatin® and VATS pleural biopsies but no photo-induction (controls). Lipoplatin® concentrations were analyzed in blood and tissues before and at regular intervals after photo-induction using inductively coupled plasma mass spectrometry. RESULTS: Photo-induction selectively increased Lipoplatin® uptake in all orthotopic tumors. It significantly increased the ratio of tumor to lung Lipoplatin® concentration in sarcoma (P = 0.0008) and adenocarcinoma (P = 0.01) but not in mesothelioma, compared to IV drug application alone. In minipigs, intrapleural photo-induction combined to systemic Lipoplatin® was well tolerated with no toxicity at 7 days for both treatment protocols. The pleural Lipoplatin® concentrations were not significantly different at 10 and 30 J/cm(2) locations but they were significantly higher in protocol I compared to II (2.37 ± 0.7 vs. 1.37 ± 0.7 ng/mg, P < 0.001). CONCLUSION: Visudyne®-mediated photo-induction selectively enhances the uptake of IV administered Lipoplatin® in rodent lung tumors. Intrapleural VATS photo-induction with identical treatment conditions combined to IV Lipoplatin chemotherapy is feasible and well tolerated in a porcine model. Lasers Surg. Med. 47:807-816, 2015. © 2015 Wiley Periodicals, Inc.

Effect of surface pretreatment of TiO2 films on interfacial processes leading to bacterial inactivation in the dark and under light irradiation.

Evidence is presented for radio-frequency plasma pretreatment enhancing the amount and adhesion of TiO2 sputtered on polyester (PES) and on polyethylene (PE) films. Pretreatment is necessary to attain a suitable TiO2 loading leading to an acceptable Escherichia coli reduction kinetics in the dark or under light irradiation for PES-TiO2 and PE-TiO2 samples. The amount of TiO2 on the films was monitored by diffuse reflectance spectroscopy and X-ray fluorescence. X-ray electron spectroscopy shows the lack of accumulation of bacterial residues such as C, N and S during bacterial inactivation since they seem to be rapidly destroyed by TiO2 photocatalysis. Evidence was found for Ti(4+)/Ti(3+) redox catalysis occurring on PES-TiO2 and PE-TiO2 during the bacterial inactivation process. On PE-TiO2 surfaces, Fourier transform infrared spectroscopy (ATR-FTIR) provides evidence for a systematic shift of the na(CH2) stretching vibrations preceding bacterial inactivation within 60 min. The discontinuous IR-peak shifts reflect the increase in the C-H inter-bond distance leading to bond scission. The mechanism leading to E. coli loss of viability on PES-TiO2 was investigated in the dark up to complete bacterial inactivation by monitoring the damage in the bacterial outer cell by transmission electron microscopy. After 30 min, the critical step during the E. coli inactivation commences for dark disinfection on 0.1-5% wt PES-TiO2 samples. The interactions between the TiO2 aggregates and the outer lipopolysaccharide cell wall involve electrostatic effects competing with the van der Waals forces.

Easily-prepared dinickel phosphide (Ni2P) nanoparticles as an efficient and robust electrocatalyst for hydrogen evolution.

Polydispersed dinickel phosphide (Ni2P) nanoparticles were synthesized by a simple and scalable solid-state reaction. These nanoparticles are an excellent and robust catalyst for the electrochemical hydrogen evolution reaction, operating in both acidic and basic solutions.

Mesoscopic photosystems for solar light harvesting and conversion: facile and reversible transformation of metal-halide perovskites.

Recently, hybrid organic-inorganic metal halide perovskites have gained prominence as potent light harvesters in thin film solid-state photovoltaics. In particular the solar-to-electric power conversion efficiency (PCE) of devices using CH(3)NH(3)PbI(3) as sensitizer has increased from 3 to 20.1% within only a few years. This key material can be prepared by solution processing from PbI(2) and CH(3)NH(3)I in one step or by sequential deposition. In the latter case an electron capturing support such as TiO(2) is first covered with PbI(2), which upon exposure to a CH(3)NH(3)I solution is converted to the perovskite. Here we apply for the first time quartz crystal microbalance (QCMD) measurements in conjunction with X-ray diffraction and scanning electron microscopy to analyse the dynamics of the conversion of PbI(2) to CH(3)NH(3)PbI(3). Employing 200 nm thick PbI(2) films as substrates we discover that the CH(3)NH(3)I insertion in the PbI(2) is reversible, with the extraction into the solvent isopropanol occurring on the same time scale of seconds as the intercalation process. This offers an explanation for the strikingly rapid and facile exchange of halide ions in CH(3)NH(3)PbX(3) by solution processing at room temperature.

Over-expression of PHO1 in Arabidopsis leaves reveals its role in mediating phosphate efflux.

Inorganic phosphate (Pi) homeostasis in multi-cellular eukaryotes depends not only on Pi influx into cells, but also on Pi efflux. Examples in plants for which Pi efflux is crucial are transfer of Pi into the xylem of roots and release of Pi at the peri-arbuscular interface of mycorrhizal roots. Despite its importance, no protein has been identified that specifically mediates phosphate efflux either in animals or plants. The Arabidopsis thaliana PHO1 gene is expressed in roots, and was previously shown to be involved in long-distance transfer of Pi from the root to the shoot. Here we show that PHO1 over-expression in the shoot of A. thaliana led to a two- to threefold increase in shoot Pi content and a severe reduction in shoot growth. (31) P-NMR in vivo showed a normal initial distribution of intracellular Pi between the cytoplasm and the vacuole in leaves over-expressing PHO1, followed by a large efflux of Pi into the infiltration medium, leading to a rapid reduction of the vacuolar Pi pool. Furthermore, the Pi concentration in leaf xylem exudates from intact plants was more than 100-fold higher in PHO1 over-expressing plants compared to wild-type. Together, these results show that PHO1 over-expression in leaves leads to a dramatic efflux of Pi out of cells and into the xylem vessel, revealing a crucial role for PHO1 in Pi efflux.

The diffuse infiltration of road runoff: an environmental improvement.

The Laboratory of Engineering and Environmental Geology (GEOLEP) has been mandated by Swiss authorities (Swiss Federal Road Office FedRO) to test a new road runoff management concept. This concept promotes the diffuse infiltration of road runoff into infiltration slopes designed for this purpose. Soils retain particles and contaminants; this lowers the road impact on the environment and simultaneously improves aquifer recharge. This concept has to be adapted to aquifer vulnerability and traffic conditions. Thus, a real-scale experimental station was designed and built in Switzerland to assess the feasibility of this new concept. This station allowed the testing of two lysimeters composed of 80 cm of A and B-horizons. Water and chemical fluxes were measured at the lysimeter bases. Road runoff was sampled in a distinct collector. Infiltration of road runoff into the local aquifer was monitored thanks to six piezometers. Water quality and quantity were therefore measured at each step of the infiltration process. Results provided by 112 natural events showed that soil horizons accommodated road runoff flows. The least favourable conditions for contaminant retention are encountered during thunderstorms, when high concentrations of substances deposited on the road are remobilised within a short time and rapidly percolates through soil horizons. Thus, three artificial events were designed to mimic heavy thunderstorms. Concentrations measured in road runoff notably decreased after soil filtration. Substances with high distribution coefficients Kd (low mobility) had concentrations reduced to lower values (1/1000 to 1/10,000), while those with high mobility retained similar concentrations even after soil filtration. However, these mobile substances exhibited low concentrations in the underlying aquifer due to dilution. This innovative road runoff management concept can thus be readily implemented outside groundwater protection zones where aquifers are slightly vulnerable; it undoubtedly lowers the environmental impact of roads, does not endanger road integrity, and locally increases aquifer recharge.

Participation of G proteins in natriuretic peptide hormone secretion from heart atria.

The involvement of G proteins in the mechanism underlying the increased atrial natriuretic factor (ANF) secretion observed after atrial muscle stretch (stretch-secretion coupling) was assessed using a combined pharmacological, immunocytochemical, and tissue fractionation approach. It was found that G(i/o) inhibition by pertussis toxin (PTX) abolished stretch-secretion coupling without affecting baseline secretion through a mechanism that is independent of G(q) signaling agonists. Mastoparan-7, a G(i/o) agonist, significantly increased ANF secretion even in the absence of muscle stretch through a PTX-sensitive mechanism. By confocal and electron immunocytochemistry, ANF and G(o) partially colocalized, whereas ultracentrifugation analysis suggested the presence of two populations of granules, one of which was partially associated with G(o), as demonstrated by Western blotting. PTX did not affect basal or endothelin-1-stimulated ANF secretion, in line with the view that endothelin-1 signals mainly through G(q). It is concluded there are at least two types of regulated secretory processes in atrial cardiocytes: one is acutely responsive to muscle stretch and is PTX sensitive, and the other is G(q)mediated and PTX insensitive and may be responsible for changes in secretion after chronic changes in the neuroendocrine environment.