Trans-amidate platinum complexes anchoring water and N-donor molecules. The importance of hydrogen bonding

The square planar bisnitrile platinum(II) derivatives PtCl2(NCR)2 (R=Ph (1 a); Et (1 b); p-C6H4F (1 c); p-C6H4tBu (1 d); m-C6H3Me2 (1 e); o, p-C6H2Me3 (1 f)) react with tetrabutylammonium hydroxide to render the monoaquo NBu4]trans-PtCl(HNCOR)2(OH2)] (2 a–2 f). The water molecule is s-coordinated to platinum and the binding is reinforced by two strong hydrogen bonds to the neighboring amidate ligands (OH···OC). Substitution of water in 2 a by N-donor ligands can be efficiently achieved only in the presence of a dehydrating agent as magnesium sulphate or 4 Å molecular sieves. By following this strategy, compounds NBu4]trans-PtCl(HNCOPh)2(NH2R’)] (R’=H (3), NH2 (4), tBu (5 a), p-C6H4Me (5 b) have been isolated. The incoming ligands are s-coordinated to platinum and also establish strong hydrogen bonds to the amidates (NH···OC). Treatment of 2 a with halogens causes oxidation at the metal center, rendering the platinum(IV) derivatives NBu4]PtClX2(HNCOPh)2(OH2)] (X=Cl (6 a), Br (6 b), I (6 c))

Metal-Metal Cooperation in the Oxidation of a Flapping Platinum Butterfly by Haloforms: Experimental and Theoretical Evidence

The model 1-DFT for the butterfly complex [{Pt(C¿C*)(µ-pz)}2] (1; HC¿C* = 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene) shows two minima in the potential energy surface of the ground state in acetone solution: the butterfly-wing-spreading molecules 1-s, (dPt-Pt ˜ 3.20 Å) and the wing-folding molecules 1-f (dPt-Pt = 3.00 Å). Both minima are very close in energy (¿G° = 1.7 kcal/mol) and are connected through a transition state, which lies only 1.9 kcal/mol above 1-s and 0.2 kcal/mol above 1-f. These very low barriers support a fast interconversion process, resembling a butterfly flapping, and the presence of both conformers in acetone solution. However, the 1-f ratio is so low that it is undetectable in the excitation and emission spectra of 1 in 2-MeTHF of diluted solutions (10-5 M) at 77 K, while it is seen in more concentrated solutions (10-3 M). In acetone solution, 1 undergoes a [2c, 2e] oxidation by CHX3 (X = Cl, Br) in the sunlight to render the Pt2(III, III) compounds [{Pt(C¿C*)(µ-pz)X)}2] (X = Cl (2-Cl), Br (2-Br)). In concentrated solutions, 1 can react with CHCl3 under blue light to give 2-Cl and with CHBr3 in the dark, the latter rendering the compound [BrPt(C¿C*)(µ-pz)2Pt(C¿C*)CHBr2] (3-Br) or mixtures of 2-Br and 3-Br if the reaction is performed under an argon atmosphere or in the air, respectively. Mechanistic studies showed that in concentrated solutions the oxidation processes follow a radical mechanism being the MMLCT-based species 1-f, those which trigger the reaction of 1 with CHBr3 and CHCl3. In the ground state (S0f), it promotes the thermal oxidation of 1 by CHBr3 and in the first singlet excited state (S1f) the blue-light-driven photooxidation of 1 by CHCl3. Complexes, 2-Cl, 2-Br, and 3-Br were selectively obtained and fully characterized, showing Pt-Pt distances (ca. 2.6 Å) shorter than that of the starting complex, 1. They are, together with the analogous [{Pt(C¿C*)(µ-pz)I)}2] and [IPt(C¿C*)(µ-pz)2Pt(C¿C*)CHI2], the only dinuclear metal-metal-bonded PtIII(µ-pz)2PtIII compounds reported to date

A study on the interaction between local flow and flame structure for mixing-controlled Diesel sprays

[EN] A detailed study on the spray local flow and flame structure has been performed by means of PIV and laser-sheet LIF techniques under Diesel spray conditions. Operating conditions were based on Engine Combustion Network recommendations. A consistent comparison of inert and reacting axial velocity fields has produced quantitative information on the effect of heat release on the local flow. Local axial velocity has been shown to increase 50-60% compared to the inert case, while the combustion-induced radial expansion of the spray has been quantified in terms of a 0.9-2.1 mm radius increase. As a result, the drop in entrainment rate has been quantified around 25% compared to the inert case. Streamline analysis also hints at a reduced entrainment under reacting conditions. A 1D spray model under reacting condition has been used, which confirms the modifications obtained in the main flow metrics when moving from inert to reacting conditions. When comparing the flow evolution with the flame structure, little effect of chemical activity on the spray flow upstream the lift-off length has been evidenced, in spite of the presence of formaldehyde in such regions. Only downstream of the lift-off length, as defined by OH LIF, has a strong change in flow pattern been observed as a result of combustion-induced heat release. (C) 2017 The Combustion Institute. Published by Elsevier Inc. All rights reserved.This work was carried out during a scientific visit period by J.M. Garcia-Oliver at IFPEN in 2015, which was funded by the Spanish Ministry of Education, Culture and Sport (Grant PRX14/00192). This study was partially funded by the Spanish Ministry of Economy and Competitiveness in the frame of the COMEFF (TRA2014-59483-R) project.García-Oliver, JM.; Malbec, L.; Toda, HB.; Bruneaux, G. (2017). A study on the interaction between local flow and flame structure for mixing-controlled Diesel sprays. Combustion and Flame. 179:157-171. https://doi.org/10.1016/j.combustflame.2017.01.023S15717117

GlcNAcstatins are nanomolar inhibitors of human O-GlcNAcase inducing cellular hyper-O-GlcNAcylation

O-GlcNAcylation is an essential, dynamic and inducible post-translational glycosylation of cytosolic proteins in metazoa and can show interplay with protein phosphorylation. Inhibition of OGA (O-GlcNAcase), the enzyme that removes O-GlcNAc from O-GlcNAcylated proteins, is a useful strategy to probe the role of this modification in a range of cellular processes. In the present study, we report the rational design and evaluation of GlcNAcstatins, a family of potent, competitive and selective inhibitors of human OGA. Kinetic experiments with recombinant human OGA reveal that the GlcNAcstatins are the most potent human OGA inhibitors reported to date, inhibiting the enzyme in the sub-nanomolar to nanomolar range. Modification of the GlcNAcstatin N-acetyl group leads to up to 160-fold selectivity against the human lysosomal hexosaminidases which employ a similar substrate-assisted catalytic mechanism. Mutagenesis studies in a bacterial OGA, guided by the structure of a GlcNAcstatin complex, provides insight into the role of conserved residues in the human OGA active site. GlcNAcstatins are cell-permeant and, at low nanomolar concentrations, effectively modulate intracellular O-GlcNAc levels through inhibition of OGA, in a range of human cell lines. Thus these compounds are potent selective tools to study the cell biology of O-GlcNAc

Electrophilicity of neutral square-planar organosilver(III) compounds

Neutral Ag(III) complexes stabilised with just monodentate ligands are here unambiguously established. In a series of square-planar (CF3)3Ag(L) compounds with hard and soft Group 15 donor ligands, L, the metal center has been found to exhibit substantial acidity favouring apical coordination of an additional ligand under no coordination constraints

Using Dedal to share and reuse distributed engineering design information

The overall goal of the project is to facilitate the reuse of previous design experience for the maintenance, repair and redesign of artifacts in the electromechanical engineering domain. An engineering team creates information in the form of meeting summaries, project memos, progress reports, engineering notes, spreadsheet calculations and CAD drawings. Design information captured in these media is difficult to reuse because the way design concepts are referred to evolve over the life of a project and because decisions, requirements and structure are interrelated but rarely explicitly linked. Based on protocol analysis of the information seeking behavior of designer's, we defined a language to describe the content and the form of design records and implemented this language in Dedal, a tool for indexing, modeling and retrieving design information. We first describe the approach to indexing and retrieval in Dedal. Next we describe ongoing work in extending Dedal's capabilities to a distributed environment by integrating it with World Wide Web. This will enable members of a design team who are not co-located to share and reuse information

Field Sampling and Necropsy Examination of Fish

This paper presents an overview of observational and fish sampling tech­niques for investigating fish lesions, morbidity and mortality. These sam­pling techniques and investigations are much like detective work and require attention to detail, common sense, technical proficiency and experience. To solve the mystery of a fish kill, the investigator must use available evidence and clues to piece together a series of events that often have long since passed. The cause of these field events may be chemical, biological or physical; more often, it is some combination of these. An initial categorization approach may be used to reduce the great number of possible causes of a fish kill to something more reasonable. Through proper observations, the most probable cause may be placed in one of four broad categories (although additional secondary relationships should also be recognized). These broad categories include oxygen related, toxics or water quality related, disease or population related and trauma related events, and may be based on defined criteria Caution should be taken on making etiologic generaliz.ations since many types of lesions or mortality events may appear similar. This paper provides support for making consistent observations; taking photographs, tissue and water samples; classifying external lesions and choosing appropriate ne­cropsy methods. A bibliography is provided to reference information perti­nent to fish kill investigations and fish disease, anatomy and taxonomy

Black-boxing Sustainable Development: Environmental Impact Assessment on the River Uruguay

International audienceThis chapter offers an original account of Environmental Impact Assessment (EIA) as a technology that scripts collective action through black-boxing the politics of governance. After tracing the global trajectory of the instrument, the chapter looks at EIA struggles in the case of pulp mills on the River Uruguay. As actors seeking to halt projects because of their potential harmful impact follow the choreography of EIA, the authoritative governance script is reinforced rather than undermined. There is a tragic aspect to this, in that those wishing to block a project are actually making it stronger. This points to a subtle de-politicization resulting from the evolution of instruments in use, and a need for their re-politicization