Markovian Solutions of Inviscid Burgers Equation

For solutions of (inviscid, forceless, one dimensional) Burgers equation with random initial condition, it is heuristically shown that a stationary Feller–Markov property (with respect to the space variable) at some time is conserved at later times, and an evolution equation is derived for the infinitesimal generator. Previously known explicit solutions such as Frachebourg–Martin's (white noise initial velocity) and Carraro–Duchon's Lévy process intrinsic-statistical solutions (including Brownian initial velocity) are recovered as special cases.     

Electrochemical reduction of oxygen catalyzed by a wide range of bacteria including Gram-positive

Most bacteria known to be electrochemically active have been harvested in the anodic compartments of microbial fuel cells (MFCs) and are able to use electrodes as electron acceptors. The reverse phenomenon, i.e. using solid electrodes as electron donors, is not so widely studied. To our knowledge, most of the electrochemically active bacteria are Gram-negative. The present study implements a transitory electrochemical technique (cyclic voltammetry) to study the microbial catalysis of the electrochemical reduction of oxygen. It is demonstrated that a wide range of aerobic and facultative anaerobic bacteria are able to catalyze oxygen reduction. Among these electroactive bacteria, several were Gram-positive. The transfer of electrons was direct since no activity was obtained with the filtrate. These findings, showing a widespread property among bacteria including Gram-positive ones, open new and interesting routes in the field of electroactive bacteria research.     

Lévy-Process Intrinsic Statistical Solutions of a Randomly Forced Burgers Equation

We consider Burgers equation forced by a brownian in space and white noise in time process \(\partial_{t}u+\frac{1}{2}\partial_{x}(u)^{2}=f(x,t)\), with \(E(f(x,t)f(y,s))=\frac{1}{2}(|x|+|y|-|x-y|)\*\delta(t-s)\) and we show that there exist intrinsic statistical solutions that are Lévy processes at any given positive time. We give the evolution equation for the characteristic exponent of such solutions; in particular we give the explicit solution in the case u ₀(x)=0.     

Geobacter sulfurreducens can protect 304L stainless steel against pitting in conditions of low electron acceptor concentrations

The effect of Geobacter sulfurreducens cells was studied on the electrochemical behaviour of 304L stainless steel, emphasizing the role of the soluble electron acceptor (fumarate). In fumarate-lacking media, the presence of G. sulfurreducens induced free potential ennoblement in a few hours. This ennoblement has already been observed in standard media that contained fumarate. Our previous studies have shown that G. sulfurreducens shifted the pitting potential toward the positive values. The pits induced by the presence of the bacteria were wider and deeper than in the absence of bacteria. Here, in fumarate-lacking media, similar shift in pitting potential was observed, but the repassivation phase was strongly improved. AFM analysis showed that pits were identical with those observed in the absence of bacteria at lower potential. In contrast with all the previous work where G. sulfurreducens enhanced corrosion, here at a low concentration of electron acceptor, the presence of the bacteria protected the steel against pitting.     

Towards an engineering-oriented strategy for building microbial anodes for microbial fuel cells

The objective of the work was to give some first insight into an engineering-oriented approach to MFC design by focusing on anode optimisation. The effect of various parameters was firstly investigated in half cell set-ups under well-controlled conditions. Microbial anodes were formed from soil leachate under polarisation at -0.2 V vs. SCE with different concentrations of substrate, salt and buffer. It was shown that non-turnover CV could be used to assess the electroactive maturity of the anodes during polarisation. This first phase resulted in the definition of a set of optimal parameter values. In the second phase, an optimal anode was formed in a half-cell under the defined optimal conditions. A numerical approach was then developed to calculate the theoretical maximum power that the anode could provide in an ideal MFC. The concept of "ideal MFC" introduced here allowed the theoretical maximum power to be calculated on the sole basis of the kinetic characteristics of the anode. Finally, a MFC designed in the aim of approaching such ideal conditions generated stable power densities of 6.0 W m(-2), which were among the highest values reported so far. The discrepancy between the theoretical maximum (8.9 W m(-2)) and the experimental results pointed out some limit due to the source of inoculum and suggested possible paths to improvement.     

Syntheses and characterization of dicarbonyl-nitrosyl complexes of technetium(I) and rhenium(I) in aqueous media: spectroscopic, structural, and DFT analyses

This work describes new synthetic routes to produce mixed carbonyl-nitrosyl complexes of technetium(I) and rhenium(I) in aqueous media. NaNO2, NOHSO4, and NO2(g) have been used to produce in situ nitrous acid as the primary source of NO+. Starting from the organometallic precursor fac-[MX3(CO)3]+, 1 (M = 99Tc, Re; X = Cl, Br), the formation of mixed dicarbonyl-mononitrosyl complexes was observed in aqueous hydrochloric and hydrobromic acid. Time-dependent analyses of the reactions by means of HATR-IR and 99Tc NMR spectroscopy in solution revealed the almost quantitative substitution of one CO ligand by NO+ and, thus, the formation of complexes with facial arrangement of the three pi-acceptor ligands. In the case of technetium, the monomeric complex (NEt4)[TcCl3(CO)2NO] (3a) and the dimeric, chloride-bridged, neutral complex [TcCl(mu-Cl)(CO)2NO]2 (4a) were produced. In the case of rhenium, the monomeric species (NEt4)[ReBr2X(CO)2NO] (X = Br (3b), NO3 (5)) was solely isolated. The X-ray structure of complexes 4a and 5 are discussed. The crystallographic analyses revealed the coordination of the NO+ group trans to the terminal chloride (4a) or the bromide (5), respectively. Crystal data: complex 4a (C4Cl4N2O(6)Tc2), monoclinic, Cc, a = 18.82(3) A, b = 6.103(6) A, c = 12.15(2) A, alpha = 90 degrees , beta = 105.8(2) degrees , gamma = 90 degrees , V = 1343(3) A(3), Z = 4; complex 5 (C10H20N3O(6)Br2Re), orthorhombic, P2(1)2(1)2(1), a = 10.2054(5) A, b = 12.5317(7) A, c = 13.9781(7) A, V = 1787.67(16) A(3), Z = 4. The isolated complexes and their potential facial isomers have been further investigated by density functional theory (DFT) calculations. The energy differences of the isomers are relatively small; however, the calculated energies are consistent with the formation of the observed and isolated compounds. The calculated bond lengths and angles of complex 5 are in good agreement with the data determined by X-ray diffraction. Experiments on the no-carrier-added level starting from fac-[99mTc(H2O)3(CO)3]+ revealed the formation of the complex fac-[99mTcCl(H2O)2(CO)2NO]+ in reasonable good yields. This aqueous-based, synthetic approach will enable the future evaluation of this novel, low-valent metal precursor for potential use in radiopharmacy.     

Stabilization of molecular LiF and LiFHF inside metallamacrocyclic hosts

Complexes of molecular LiF and LiFHF were synthesized using the metallamacrocyclic receptors [(cymene)Ru(C(5)H(3)NO(2))](3) (1), [CpRh(C(5)H(3)NO(2))](3) (2), and [CpIr(C(5)H(3)NO(2))](3) (3). LiBF(4) complexes of 1-3 were prepared and subsequently treated with F(-) or FHF(-) to give the desired products in an anion-exchange reaction. All complexes were characterized by multinuclear NMR spectroscopy ((1)H, (13)C, (19)F, (7)Li). Strong scalar coupling between (7)Li and (19)F is observed for the LiF and the LiFHF complexes ((1)J(LiF) = 91-103 Hz). The LiFHF adduct of 1 displays fluxional behavior with fast exchange of the two fluorine atoms. The structures of the complexes 1.LiBF(4), 2.LiBF(4), 1.LiF, 2.LiF, 1.LiFHF, and 3.LiFHF were determined by single-crystal X-ray analysis. Li-F bond lengths between 1.77 and 1.81 A were found. The LiFHF complexes show a hydrogen difluoride anion coordinated in a bent fashion via one fluorine atom to the lithium ion.     

Diastereoselective formation of metallamacrocyclic (arene)Ru(II) and CpRh(III) complexes

The reaction of [(arene)RuCl(2)](2) (arene = cymene, 1,3,5-C(6)H(3)Me(3)) and [CpRhCl(2)](2) half-sandwich complexes with tridentate heterocyclic ligands in the presence of base has been investigated. In all cases, the chloro-ligands were substituted to give metallacyclic products with ring sizes between 4 and 18 atoms. The cyclization occurs in a highly diastereoselective fashion with chiral recognition between the different metal fragments. The complexes were comprehensively characterized by elemental analysis, NMR spectroscopy, and single crystal X-ray crystallography. For 2-hydroxy-nicotinic acid and 2-amino-nicotinic acid, dinuclear structures were obtained (15-17) whereas for 2,3-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, and 6-methyl-2,3-phenazinediol, trimeric assemblies were found (19-22), and for 4-imidazolecarboxylic acid, a tetrameric assembly (18) was found.     

Geobacter species enhances pit depth on 304L stainless steel in a medium lacking with electron donor

Geobacter sulfurreducens bacteria increased the open circuit potential of 304L stainless steel by around 320 mV in only a few hours after inoculation. This represents a significant increase in the corrosion risk. In contrast, the oxidation of acetate, which is catalysed by well-established biofilms, shifted the pitting potential towards positive values. In acetate-lacking media, pitting occurred with and without bacteria in the same range of potential values, but the presence of bacteria drastically increased the size of pits. AFM showed pits more than 10 times broader and deeper due to the presence of bacteria.In the absence of acetate, the masking effect due to acetate oxidation disappeared and the full corrosive effect of the biofilm was revealed.This also fully explains why pitting was predominantly observed close to surface areas where bacterial settlement was the densest.