Novel Alkyne And Phosphaalkyne Coupling On An Ir4 Cluster: Synthesis And Molecular Structure Of [ir4(μ-co)(co) 7{μ4-η3-ph2 Pc(h)c(ph)pcbut}(μ-pph2)]

The cluster compound [(μ-H)Ir4(CO)9(Ph 2PCCPh)(μ-PPh2)] 1 reacts with the phosphaalkyne ButCP to yield [Ir4(μ-CO)(CO) 7{μ4-η3-Ph2 PC(H)C(Ph)PCBut}(μ-PPh2)] 3, containing the novel 2-phosphabutadienylphosphine fragment as a result of the coupling of Bu tCP with the diphenylphosphinoalkyne ligand and incorporation of the cluster bound H atom.161869187

A new LED-LED portable CO2 gas sensor based on an interchangeable membrane system for industrial applications

A new system for CO2 measurement (0-100%) by based on a paired emitter-detector diode arrangement as a colorimetric detection system is described. Two different configurations were tested: configuration 1 (an opposite side configuration) where a secondary inner-filter effect accounts for CO2 sensitivity. This configuration involves the absorption of the phosphorescence emitted from a CO2-insensitive luminophore by an acid-base indicator and configuration 2 wherein the membrane containing the luminophore is removed, simplifying the sensing membrane that now only contains the acid-base indicator. In addition, two different instrumental configurations have been studied, using a paired emitter-detector diode system, consisting of two LEDs wherein one is used as the light source (emitter) and the other is used in reverse bias mode as the light detector. The first configuration uses a green LED as emitter and a red LED as detector, whereas in the second case two identical red LEDs are used as emitter and detector. The system was characterised in terms of sensitivity, dynamic response, reproducibility, stability and temperature influence. We found that configuration 2 presented a better CO2 response in terms of sensitivity

Relevant developments and new insights on Sonoelectrochemistry

AbstractSonoelectrochemistry is undergoing a reemerging activity in the last years with an increasing number of papers appearing in a wide range of peer review journals. Applied studies cover environmental treatments, synthesis and characterization of nanostructures, polymeric materials synthesis, analytical procedures, films preparations, membrane preparations among other interesting applications. Fundamental analyses are also carried out focused on electrochemical processes using unconventional solvents, elucidation of mechanisms and combination with other techniques. The interrelation between Electrochemistry and Acoustics presents mutual benefits for both disciplines, providing interesting information about the bubble dynamics for acoustics physicists and a higher number of possible applications for electrochemists. However, the vast majority of this research has been carried out at laboratory scale with individually designed systems based on ultrasonic horns dipped into traditional glass electrochemistry vessels. It is remarkable that even with this rudimentary experimental set-up many interesting results have been generated. However sonoelectrochemistry has suffered a few drawbacks related to reproducibility, scale-up and design aspects which have slowed its development. Almost certainly the reason for this is the lack of reactors that have been purpose built for sonoelectrochemistry. There have been many attempts to build lab-scale systems e.g. for electroanalysis, nanomaterials synthesis and the electrooxidation of organic pollutants but the results are often contradictory. A few groups have attempted to characterize lab-scale sonochemical reactors adapted as sonoelectrochemical reactors but the true optimization of such reactors requires contributions from many disciplines including physics, fundamental and applied electrochemistry, chemical engineering and material science

Thermal Decomposition Of [m3(co)12] (m = Ru, Os) Physisorbed Onto Porous Vycor Glass: A Route To A Glass/ruo2 Nanocomposite

This paper reports the preparation and characterization of oxide/glass nanocomposites, obtained by the impregnation and thermal decomposition of the trinuclear metal carbonyl clusters[M3(CO)12] (M = Ru, Os) inside the pores of porous Vycor glass (PVG). The intermediate species formed during the thermal treatment of the [M3(CO)12] adsorbed PVG materials were studied by UV-VIS-NIR and diffuse reflectance infrared (DR-IR) spectroscopy. At 65°C (M-Ru) and 110°C (M = Os), formation of surface bound [HM3(CO)10(μ- OSi≃)] species occurs, as a result of oxidative addition of a PVG surface silanol group to a cluster M-M bond. At T > 130°C (M = Ru) and T > 200°C (M = Os) cluster breakdown is observed, with formation of [M(CO)(n)(OSi≃)2] (n = 2 and/or 3) species. When [Ru3(CO)12] incorporated PVG is heated in air at T >250°C, decomposition of the cluster and formation of RuO2 nanoparticles are observed. AT 1200 °C, collapse of the glass pores leads to the formation of a transparent silica glass/RuO2 nanocomposite of particle average size 45 Å.92519523Borreli, N.F., Morse, D.L., (1983) Appl. Phys. Lett., 43, p. 1Borreli, N.F., Morse, D.L., Schreus, J.W.H., (1983) J. Appl. Phys., 54, p. 3344Simon, R., Gafney, H.D., (1983) Inorg. Chem., 22, p. 573Darsillo, M.S., Gafney, H.D., Paquete, M.S., (1987) J. Am. Chem. Soc., 109, p. 3275Simon, R.C., Gafney, H.D., Morse, D.L., (1985) Inorg. Chem., 24, p. 2565Gafney, H.D., (1990) J. Macromol. Sci-Chem. A, 27, p. 1187Sunil, D., Sokolov, J., Rafailovich, M.H., Duan, X., Gafney, H.D., (1993) Inorg. Chem., 32, p. 4489Mendoza, E.A., Wolkow, E., Sunil, D., Wong, P., Sobokov, J., Rafailovich, M.H., DeuBoer, M., Gafney, H.D., (1991) Langmuir, 7, p. 3046Sunil, D., Sokolov, J., Rafailovich, M.H., Kotyuzhanskii, B., Gafney, H.D., Wilkens, B.J., Harson, A.L., (1993) J. Appl. Phys., 74, p. 3768Gafney, H.D., Xu, S.P., (1995) Inorg. Chim. 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Facile And Reversible Co Insertion Into The Ir-ch3 Bond Of [ir4(ch3)(co)8(μ4- η3-ph2pccph)(μ-pph2)]

Reaction of [Ir4H(CO)10 (μ-PPh2)] with BuLi, Ph2PC≡CPh and then Mel gives [Ir4 (CH 3)(CO)8 (μ4-η3-Ph 2PCCPh)(μ-PPh2)], which undergoes a reversible two-step CO insertion under extremely mild conditions to yield Ir4{(CH 3C(O)}(CO)8-(μ4:η3-Ph 2PCCPh)(μ-PPh2)] as the final product; the structures of both species have been established by X-ray diffraction studies.121008101

Dipstick proteinuria is an independent predictor of high on treatment platelet reactivity in patients on clopidogrel, but not aspirin, admitted for major adverse cardiovascular events.

Abstract The effectiveness of aspirin and clopidogrel in patients with chronic kidney disease (CKD) suffering from acute cardiovascular events is unclear. High on treatment platelet reactivity (HTPR) has been associated with worse outcomes. Here, we assessed the association of dipstick proteinuria (DP) and renal function on HTPR and clinical outcomes. Retrospective cohort analysis of 261 consecutive, non-dialysis patients admitted for Major Adverse Cardiovascular Events (MACE) that had VerifyNow P2Y12 and VerifyNow Aspirin assays performed. HTPR was defined as P2Y12 reactivity unit (PRU) \u3e 208 for clopidogrel and aspirin reaction units (ARU) \u3e 550 for aspirin. Renal function was classified based on the estimated glomerular filtration rate (eGFR), and dipstick proteinuria was defined as ≥30 mg/dl of albumin detected on a spot analysis. All cause mortality, readmissions, and cardiac catheterizations were reviewed over 520 days. In patients on clopidogrel (n = 106), DP was associated with HTPR, independent of eGFR, diabetes mellitus, smoking or use of proton pump inhibitor (AOR = 4.76, p = 0.03). In patients with acute coronary syndromes, HTPR was associated with more cardiac catheterizations (p = 0.009) and readmissions (p = 0.032), but no differences in in-stent thrombosis or re-stenosis were noted in this cohort. In patients on aspirin (n = 155), no associations were seen between DP and HTPR. However, all cause mortality was significantly higher with HTPR in this group (p = 0.038). In this cohort, DP is an independent predictor of HTPR in patients on clopidogrel, but not aspirin, admitted to the hospital for MACE

Synthesis And Structural Characterisation Of [ir4(co)8(ch3)(μ4-η 3-ph2pccph)(μ-pph2)] And Of The Carbonylation Product [ir4(co)8{c(o)ch3}(μ4-η 3-ph2pccph)(μ-pph2)]

Deprotonation of [(μ-H)Ir4(CO)10(μ-PPh2)], 1, gives [Ir4(CO)10(μ-PPh2)]- that reacts with Ph2PCCPh and CH3I to afford [Ir4(CO)8(CH3)(μ4-η 3-Ph2PCCPh)(μ-PPh2)], 2 (34%), besides [Ir4(CO)9(μ3-η3-Ph 2PC(H)CPh)(μ-PPh2)] and [(μ-H)Ir4(CO)9(Ph2PC≡CPh)(μ-PPh2)]. Compound 2 was characterised by a single crystal X-ray diffraction analysis and exhibits a flat butterfly of metal atoms, with the Ph2PCCPh ligand interacting with all four Ir atoms and the methyl group bonded terminally to a wingtip Ir atom. Carbonylation of 2 yields initially (25°C, 20 min) a CO addition product that, according to VT 31P{1H} and 13C{1H} studies, exists in solution in the form of two isomers 4A and 4B (8:1), and then (40°C, 7 h), the CO insertion product [Ir4(CO)8{C(O)CH3}-(μ4-η 3-Ph2PCCPh)(μ-PPh2)], 5. The molecular structure of 5, established by an X-ray analysis, is similar to that of 2, except for the acyl group that remains bound to the same Ir atom. The process is reversible at both stages. Treatment of 2 with PPh3 and P(OMe)3 affords the CO substitution products [Ir4(CO)7L(CH3)(μ4-η 3-Ph2PCCPh)(μ-PPh2)] (L = PPh3, 6 and P(OMe)3, 7), instead of the expected CO inserted products. According to the 1H and 31P{1H} NMR studies, the PPh3 derivative 6 exists in the form of two isomers (1:1) that differ with respect to the position of this ligand.1013545Hoffmann, R., (1982) Angew. Chem. Int. Ed. Engl., 21, p. 711Bau, R., Chiang, M.Y., Wei, C.-Y., Garlaschelli, L., Martinengo, S., Koestzle, T.F., (1984) Inorg. Chem., 23, p. 4758Ragaini, F., Porta, F., Demartin, F., (1991) Organometallics, 10, p. 185Albano, V.G., Canziani, F., Ciani, G., Chini, P., Martinengo, S., Manassero, M., Giordano, G., (1978) J. Organomet. Chem., 150, pp. C17Chinara, T., Aoki, K., Yamazaki, H., (1990) J. Organomet. Chem., 353, p. 367Chinara, T., Aoki, K., Yamazaki, H., (1994) J. Organomet. Chem., 473, p. 273González-Moraga, (1993) Cluster Chemistry, , Chapter 3, Springer-Verlag, BerlinBenvenutti, M.H.A., Vargas, M.D., Braga, D., Grepioni, F., Parisini, E., Mann, B.E., (1993) Organometallics, 12, p. 2955Benvenutti, M.H.A., Vargas, M.D., Braga, D., Grepioni, F., Mann, B.E., Naylor, S., (1993) Organometallics, 12, p. 2947Yamamoto, A., (1986) Organotransition Metal Chemistry, , WileyMorison, E.D., Bassner, L.S.L., Geoffroy, G.L., (1986) Organometallics, 5, p. 408Pereira, R.M.S., Fujiwara, F.Y., Vargas, M.D., Braga, D., Grepioni, F., (1997) Organometallics, 16, p. 4833Delgado, E., Chi, Y., Wang, W., Horgath, G., Low, P.J., Enright, G.D., Peng, S.-M., Carty, A.J., (1998) Organometallics, 17, p. 2936Vargas, M.D., Pereira, R.M.S., Braga, D., Grepioni, F., (1993) J. Chem. Soc. Chem. Commun., p. 1008Hengefelt, A., Nast, R., (1983) Chem. Ber., 116, p. 2025Livotto, F.S., Raithby, P.R., Vargas, M.D., (1993) J. Chem. Soc. Dalton Trans., p. 1797Brauer, G., (1965) Handboock of Preparative Inorganic Chemistry, 1, p. 645Sheldrick, G.M., (1990) Acta Crystallogr., A46, p. 467Sheldrick, G.M., (1976) SHELX76, Program for Crystal Structure Determination, , University of Cambridge, Cambridge, EnglandWalker, N., Stuart, D., (1983) Acta Crystallogr., Sect. B, 39, p. 158Keller, E., (1992) SHAKAL92, Graphical Representation of Molecular Models, , University of Freiburg, FRGKubota, M., McClesky, T.M., Hayashi, R.K., Carl, G., (1987) J. Am. Chem. Soc., 109, p. 7569Wade, K., (1976) Adv. Inorg. Chem. Radiochem., 18, p. 1Benvenutti, M.H.A., Vargas, M.D., Hitchcock, P.B., Nixon, J.F., (1995) J. Chem. Soc. Chem. Commun., p. 866Carty, A.J., Mac Laughlin, S.A., Nucciaroni, D., (1987) Phosphorus 31-NMR Spectroscopy in Steereochemical Analysis of Organic Compounds and Metal Complexes, , Chapter 16Verkade, J. G.Quin, L. D. EdsVCHKeister, J.B., (1980) J. Organomet. Chem., 190, pp. C36Aime, S., Dastrù, W., Gobetto, R., Viale, A., (1998) Organometallics, 17, p. 3182Johnson, B.F.G., Lewis, J., Orpen, A.G., Raithby, P.R., Süss, G., (1979) J. Organomet. Chem., 173, p. 187Araujo, M.H., Vargas, M.D., unpublished resultsMonti, D., Frachey, G., Bassetti, M., Haynes, A., Sunley, G.J., Maitlis, P.M., Cantoni, A., Bocelli, G., (1995) Inorg. Chim. Acta, 240, p. 485Garcia Alonso, J., Llamazares, A., Riera, V., Diaz, M.R., García Grande, S., (1991) J. Chem. Soc. Chem. Commun., p. 1058Cotton, J.D., Crisp, G.T., Daly, V.A., (1981) Inorg. Chim. Acta, 47, p. 165Bondietti, G., Laurenczy, G., Ross, R., Roulet, R., (1994) Helv. Chim. Acta, 77, p. 1869Laurenczy, G., Bondietti, G., Merbach, A.E., Moulet, B., Roulet, R., (1994) Helv. Chim. Acta, 77, p. 547Braga, D., Grepioni, F., Vargas, M.D., Ziglio, C.M., manuscript in preparatio

PI3K/AKT/mTOR pathway activation in actinic cheilitis and lip squamous cell carcinomas

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/156448/2/jdv16420_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/156448/1/jdv16420.pd

A new LED-LED portable CO2 gas sensor based on an interchangeable membrane system for industrial applications

CO2 monitoring is important for many areas of high economic relevance, like environmental monitoring, control of biotechnological processes in bio-pharmaceutical industries, and the food industry, particularly controlled atmosphere storage rooms and modified atmosphere packaging [ ]. CO2 sensing is not a trivial area of research, as is testified by the increasing numbers of publications regarding this topic over the past decade. The main reason is that CO2 chemically is relatively unreactive, and therefore finding a mechanism for signal generation is difficult. Most publications are based on its well-known acidic properties. In this communication, we present a portable optical sensor for gaseous CO2 detection based on the phosphorescence intensity variation of a platinum octaethylporphyrin (PtOEP) complex trapped in oxygen-insensitive poly(vinylidene chloride-co-vinyl chloride) (PVCD) membranes. The sensing mechanism arises from the increasing displacement of the α-naphtholphthalein acid–base equilibrium with rising CO2 concentrations [ ]. The low-power LED-based optical sensing instrumentation for monitoring CO2 is based on a pair of light emitting diodes (LEDs) arranged to face each other, wherein one LED functions as the light source and the other LED is reverse biased to function as a light detector [ ]. A transparent polymer substrate coated on both sides with the CO2 sensitive membrane placed between the two LEDs serves as a chemically responsive filter between the light source and the detector