Oxygen vacancies as active sites for water dissociation on rutile TiO2(110)

Through an interplay between scanning tunneling microscopy experiments and density functional theory calculations, we determine unambiguously the active surface site responsible for the dissociation of water molecules adsorbed on rutile TiO2(110). Oxygen vacancies in the surface layer are shown to dissociate H2O through the transfer of one proton to a nearby oxygen atom, forming two hydroxyl groups for every vacancy. The amount of water dissociation is limited by the density of oxygen vacancies present on the clean surface exclusively. The dissociation process sets in as soon as molecular water is able to diffuse to the active site.

Bonding of gold nanoclusters to oxygen vacancies on rutile TiO2(110)

Through an interplay between scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we show that bridging oxygen vacancies are the active nucleation sites for Au clusters on the rutile TiO2(110) surface. We find that a direct correlation exists between a decrease in density of vacancies and the amount of Au deposited. From the DFT calculations we find that the oxygen vacancy is indeed the strongest Au binding site. We show both experimentally and theoretically that a single oxygen vacancy can bind 3 Au atoms on average. In view of the presented results, a new growth model for the TiO2(110) system involving vacancy-cluster complex diffusion is presented.

Prognostic Importance of the Cuse of Renal Failure in Patients With Cirrhosis

BACKGROUND & AIMS: The prognostic value of the different causes of renal failure in cirrhosis is not well established. This study investigated the predictive value of the cause of renal failure in cirrhosis. METHODS: Five hundred sixty-two consecutive patients with cirrhosis and renal failure (as defined by serum creatinine 1.5 mg/dL on 2 successive determinations within 48 hours) hospitalized over a 6-year period in a single institution were included in a prospective study. The cause of renal failure was classified into 4 groups: renal failure associated with bacterial infections, renal failure associated with volume depletion, hepatorenal syndrome (HRS), and parenchymal nephropathy. The primary end point was survival at 3 months. RESULTS: Four hundred sixty-three patients (82.4%) had renal failure that could be classified in 1 of 4 groups. The most frequent was renal failure associated with infections (213 cases; 46%), followed by hypovolemia-associated renal failure (149; 32%), HRS (60; 13%), and parenchymal nephropathy (41; 9%). The remaining patients had a combination of causes or miscellaneous conditions. Prognosis was markedly different according to cause of renal failure, 3-month probability of survival being 73% for parenchymal nephropathy, 46% for hypovolemia-associated renal failure, 31% for renal failure associated with infections, and 15% for HRS (P .0005). In a multivariate analysis adjusted for potentially confounding variables, cause of renal failure was independently associated with prognosis, together with MELD score, serum sodium, and hepatic encephalopathy at time of diagnosis of renal failure. CONCLUSIONS: A simple classification of patients with cirrhosis according to cause of renal failure is useful in assessment of prognosis and may help in decision making in liver transplantation.

The Role of Canyons in Strata Formation

This paper provides a spatial and temporal multi-scale approach of European submarine canyons. We fi rst present the long-term geologic view of European margins as related to controls on submarine canyon development. Then we discuss the extent to which submarine canyon systems resemble river systems because both essentially form drainage networks. Finally, we deal with the hortest-term, highestresolution scale to get a fl avor of the current functioning and health of modern submarine canyons in the northwestern Mediterranean Sea. Submarine canyons are unique features of the seafl oor whose existence was known by European fi shermen centuries ago, especially for those canyons that have their heads at short distance from shoreline. Popular names given to specifi c canyons in the different languages spoken in European coastal communities refer to the concepts of a"deep" or"trench." In the old times it was also common thinking that submarine canyons where so deep that nobody could measure their depth or even that they had no bottom. Submarine canyons are just one of the seven different types of seafl oor valleys identifi ed by Shepard (1973) in his pioneering morphogenetic classifi cation. Shepard (1973) defined submarine canyons as"steep-walled, sinuous valleys, with V-shaped cross sections, and relief comparable even to the largest of land canyons; tributaries are found in most of the canyons and rock outcrops abound on their walls." Canyons are features typical of continental slopes with their upper reaches and heads cut into the continental shelf.

A mechanistic approach to methylene blue sorption on two vegetable wastes: Cork bark and grape stalks

Two vegetable wastes, cork bark and grape stalks, were investigated for the removal of methylene blue from aqueous solution. The effects of contact time, dye concentration, pH, and temperature on sorption were studied relative to adsorption on a commercially-activated carbon. The highest adsorption yield was obtained within the pH range 5 to 10 for grape stalks and 7 to 10 for cork bark. The sorption kinetics of dye onto activated carbon and grape stalks was very fast. Kinetics data were fitted to the pseudo-first and second order kinetic equations, and the values of the pseudo-second-order initial rate constants were found to be 1.69 mg g-1 min-1 for activated carbon, 2.24 mg g-1 min-1 for grape stalks, and 0.90 mg g-1 min-1 for cork bark. Langmuir maximum sorption capacities for activated carbon, grape stalks, and cork bark for methylene blue estimated by the Orthogonal Distance Regression method (ODR) were 157.5 mg g-1, 105.6 mg g-1, and 30.52 mg g-1, respectively. FTIR spectra indicated that carboxylic groups and lignin play a significant role in the sorption of methylene blue. Electrostatic forces, n-p interactions, cation-p, and p-p stacking interactions contribute to methylene blue sorption onto grape stalks and cork bark. Grape stalks can be considered an efficient biosorbent and as a viable alternative to activated carbon and ion-exchange resins for the removal of methylene blue

Triggering the generation of an iron(IV)-oxo compound and its reactivity toward sulfides by RuII photocatalysis

The preparation of [FeIV(O)(MePy2tacn)]2+ (2, MePy2tacn = N-methyl-N,N-bis(2-picolyl)-1,4,7-triazacyclononane) by reaction of [FeII(MePy2tacn)(solvent)]2+ (1) and PhIO in CH3CN and its full characterization are described. This compound can also be prepared photochemically from its iron(II) precursor by irradiation at 447 nm in the presence of catalytic amounts of [Ru II(bpy)3]2+ as photosensitizer and a sacrificial electron acceptor (Na2S2O8). Remarkably, the rate of the reaction of the photochemically prepared compound 2 toward sulfides increases 150-fold under irradiation, and 2 is partially regenerated after the sulfide has been consumed; hence, the process can be repeated several times. The origin of this rate enhancement has been established by studying the reaction of chemically generated compound 2 with sulfides under different conditions, which demonstrated that both light and [Ru II(bpy)3]2+ are necessary for the observed increase in the reaction rate. A combination of nanosecond time-resolved absorption spectroscopy with laser pulse excitation and other mechanistic studies has led to the conclusion that an electron transfer mechanism is the most plausible explanation for the observed rate enhancement. According to this mechanism, the in-situ-generated [RuIII(bpy)3] 3+ oxidizes the sulfide to form the corresponding radical cation, which is eventually oxidized by 2 to the corresponding sulfoxide