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At least 73 records · Page 4

Reductive Dynamic and Static Excited State Quenching of a Homoleptic Ruthenium Complex Bearing Aldehyde Groups

A new homoleptic Ru polypyridyl complex bearing two aldehyde groups on each bipyridine ligand, [Ru(dab) 3 ](PF 6 ) 2 , where dab is 4,4′-dicarbaldehyde-2,2′-bipyridine, was synthesized, characterized, and utilized for iodide photo-oxidation studies. In acetonitrile (CH 3 CN) solution, the complex displayed an intense metal-to-ligand charge transfer (MLCT) absorbance maximum at 475 nm (ε = 22,000 M –1 cm –1 ) and an infrared (IR) band at 1712 cm –1 assigned to the pendent aldehyde groups. Visible light excitation in air-saturated solution resulted in room temperature photoluminescence (PL) with a maximum at 675 nm, a quantum yield, ϕ PL = 0.048, and an excited state lifetime, τ ο = 440 ns, from which radiative and nonradiative relaxation rate constants were extracted, k r = 9.1 × 10 4 s –1 and knr = 1.8 × 10 6 s –1 . Pulsed visible light excitation yielded transient UV–vis and IR absorption spectra consistent with an MLCT excited state; relaxation occurred with the maintenance of two isosbestic points in the visible region, and a lifetime that agreed with that measured by time-resolved PL. Cyclic voltammetry studies in a CH 3 CN solution with 0.1 M TBAPF 6 electrolyte revealed a quasi-reversible oxidation, E°(Ru III/II ) = +1.25 V vs. Fc +/0 , and three sequential one-electron reductions at −1.10, −1.25, and −1.54 V vs. Fc +/0 . Here, an excited state reduction potential of E°(Ru *2+/+ ) = +0.89 V vs. Fc +/0 was estimated with the Rehm–Weller expression. Titration of tetrabutylammonium iodide, TBAI, into a CD 3 CN solution of [Ru(dab) 3 ](PF 6 ) 2 resulted in significant shifts in the aldehyde H atom and 3,3′-biypridyl resonances that were analyzed with a 1:1 equilibrium model, from which K eq = 460 M –1 was extracted, increasing to 5800 M –1 when the solvent was changed to acetone-d 6 . Iodide titrations resulted in a significant quenching of the [Ru(dab) 3 ] *2+ lifetime and quantum yield in both CH 3 CN and acetone solvents. In CH 3 CN, the quenching was mainly dynamic and well described by the Stern–Volmer model, from which a quenching rate constant, k q , of 4.5 × 10 10 M –1 s –1 and an equilibrium constant, K eq , of 8.3 × 10 3 M –1 were obtained. In acetone, the static quenching pathway by iodide was greatly enhanced, with a K eq of 1.2 × 10 4 M –1 and a higher k q of 9.2 × 10 10 M –1 s –1 .

Aldehydes↗

Dynamic behavior of a magnetic bearing supported jet engine rotor with auxiliary bearings

This paper presents a study of the dynamic behavior of a rotor system supported by auxiliary bearings. The steady-state behavior of a simulation model based upon a production jet engine is explored over a wide range of operating conditions for varying rotor imbalance, support stiffness and damping. Interesting dynamical phenomena, such as chaos, subharmonic responses, and double-valued responses, are presented and discussed.

Homaifar, Abdollah↗

Dynamic behavior of a magnetic bearing supported jet engine rotor with auxiliary bearings

This paper presents a study of the dynamic behavior of a rotor system supported by auxiliary bearings. The steady-state behavior of a simulation model based upon a production jet engine is explored over a wide range of operating conditions for varying rotor imbalance, support stiffness, and damping. Interesting dynamical phenomena, such as chaos, subharmonic responses, and double-valued responses, are presented and discussed.

Flowers, George T.↗

Effect of Roller Profile on Cylindrical Roller Bearing Life Prediction: Comparison of Bearing Life Theories - Part 1

Four rolling-element bearing life theories were chosen for analysis and compared for a simple roller-race geometry model. The life theories were those of Weibull; Lundberg and Palmgren; Ioannides and Harris; and Zaretsky. The analysis without a fatigue limit of Ioannides and Harris is identical to the Lundberg and Palmgren analysis, and the Weibull analysis is similar to that of Zaretsky if the exponents are chosen to be identical. The resultant predicted life a each stress condition not only depends on the life equation used but also on the Weibull slope assumed. The least variation in predicted life with Weibull slope comes with the Zaretsky equation. Except for a Weibull slope of 1.11, at which the Weibull equation predicts the highest lives, the highest lives are predicted for the Zaretsky equation. For Weibull slopes of 1.5 and 2, both the Lundherg-Palmgren and Ioannides-Harris (where tau(sub u) = 0) equations predict lower lives than the ANSI/ABMA/ISO standard. Based upon the Hertz stresses for line contact, the accepted load-life exponent of 10/3 results in a maximum Hertz stress-life exponent equal to 6.6. This value is inconsistent with that experienced in the field. The assumption of as shear stress fatigue limit tau(sub u) results in Hertz stress-life exponents greater than are experimentally verifiable.

Poplawski, Joseph V.↗

Experimental Acid Weathering of Fe-Bearing Mars Analog Minerals and Rocks: Implications for Aqueous Origin of Hematite-Bearing Sediments in Meridiani Planum, Mars

A working hypothesis for Meridiani evaporite formation involves the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [1, 2]. However, there are no reported experimental studies for the formation of jarosite and gray hematite (spherules), which are characteristic of Meridiani rocks from Mars analog precursor minerals. A terrestrial analog for hematite spherule formation from basaltic rocks under acidic hydrothermal conditions has been reported [3], and we have previously shown that the hematite spherules and jarosite can be synthetically produced in the laboratory using Fe3+ -bearing sulfate brines under hydrothermal conditions [4]. Here we expand and extend these studies by reacting Mars analog minerals with sulfuric acid to form Meridiani-like rock-mineral compositions. The objective of this study is to provide environmental constraints on past aqueous weathering of basaltic materials on Mars.

Golden, D. C.↗