Die UV-Absorptionsspektren einiger einfacher Chinoxalin-Derivate

Die UV-Absorptionsspektren 13 einfacher Chinoxalin-Derivate, bei denen die Substituenten keinen Anlaß zu tautomeren Wechselwirkungen geben, wurden in verschiedenen Lösungsmitteln gemessen und diskutiert. An Hand der Feinstruktur der UV-Absorptionsspektren der 2.3-Di-methoxy- und iso-propoxy-Derivate und deren Fluoreszenzspektren sowie der Lösungsmittelabhängigkeit aller Absorptionsspektren wird versucht, eine Zuordnung der langwelligen, überlagerten 1L-Banden zu treffen. © 1962, Walter de Gruyter. Alle Rechte vorbehalten

Electronic excited state of protonated aromatic molecules: protonated Fluorene

The photo-fragmentation spectrum of protonated fluorene has been recorded in the visible spectral region, largely red shifted as compared to the first excited state absorption of neutral fluorene. The spectrum shows two different vibrational progressions, separated by 0.19 eV that are assigned to the absorption of two isomers. As in protonated linear PAHs, comparison with ab-initio calculations indicates that the red shift is due to the charge transfer character of the excited state

Mechanically stacked 1 nm thick carbon nanosheets: Ultrathin layered materials with tunable optical, chemical and electrical properties

Carbon nanosheets are mechanically stable free-standing two-dimensional materials with a thickness of ~1 nm and well defined physical and chemical properties. They are made by radiation induced cross-linking of aromatic self-assembled monolayers. Here we present a route to the scalable fabrication of multilayer nanosheets with tunable electrical, optical and chemical properties on insulating substrates. Stacks up to five nanosheets with sizes of ~1 cm^2 on oxidized silicon were studied. Their optical characteristics were investigated by visual inspection, optical microscopy, UV/Vis reflection spectroscopy and model calculations. Their chemical composition was studied by X-ray photoelectron spectroscopy. The multilayer samples were then annealed in ultra high vacuum at various temperatures up to 1100 K. A subsequent investigation by Raman, X-ray photoelectron and UV/Vis reflection spectroscopy as well as by electrical four-point probe measurements demonstrates that the layered nanosheets transform into nanocrystalline graphene. This structural and chemical transformation is accompanied by changes in the optical properties and electrical conductivity and opens up a new path for the fabrication of ultrathin functional conductive coatings.Comment: 36 pages, 7 Figure

Instrumentation-related uncertainty of reflectance and transmittance measurements with a two-channel spectrophotometer

Spectrophotometers are operated in numerous fields of science and industry for a variety of applications. In order to provide confidence for the measured data, analyzing the associated uncertainty is valuable. However, the uncertainty of the measurement results is often unknown or reduced to sample-related contributions. In this paper, we describe our approach for the systematic determination of the measurement uncertainty of the commercially available two-channel spectrophotometer Agilent Cary 5000 in accordance with the Guide to the expression of uncertainty in measurements. We focus on the instrumentation-related uncertainty contributions rather than the specific application and thus outline a general procedure which can be adapted for other instruments. Moreover, we discover a systematic signal deviation due to the inertia of the measurement amplifier and develop and apply a correction procedure. Thereby we increase the usable dynamic range of the instrument by more than one order of magnitude. We present methods for the quantification of the uncertainty contributions and combine them into an uncertainty budget for the device. © 2017 Author(s)

An Alternative Procedure to Quantify Soot in Engine Oil by Ultraviolet-Visible Spectroscopy

"This is an Accepted Manuscript of an article published by Taylor & Francis in Tribology Transactions on 02-11-2019, available online: https://www.tandfonline.com/doi/full/10.1080/10402004.2019.1645255."[EN] Due to new pollutant emissions standards, internal combustion engines need several emission control strategies (and related procedures) such as exhaust gas recirculation, diesel/gasoline particulate filters, and selective catalyst reduction that allow them to comply with complete requirements defined on those standards. These strategies result in faster degradation of engine oil, one of the most relevant consequences of which is an increase in soot contamination level. All of these strategies facilitate soot generation. Consequently, soot is one of the most important contaminants present in engine oil. The main technique to measure the content of soot in oil is thermogravimetric analysis (TGA), but this technique has certain limitations. TGA requires a long and specific procedure and has limitations in measuring small concentrations of soot in oil. Therefore, the design of an alternative technique to quantify soot in oil is relevant. One alternative is Fourier transform infrared (FTIR) spectroscopy, but it also has limitations related to low concentrations of soot in oil. This work presents an alternative technique based on ultraviolet-visible (UV-Vis) spectroscopy that allows quantification of small soot contents in used engine oil samples and avoids potential interference from other typical contaminants or those related to measurement processes, such as sample cuvette material.Antonio Garcia-Barbera was supported through the Programa Nacional de Formacion de Recursos Humanos de Investigacion of Spanish Ministerio de Ciencia e Innovacion (Grant Number BES-2016-078073).Macian Martinez, V.; Tormos, B.; Ruiz-Rosales, S.; García-Barberá, A. (2019). An Alternative Procedure to Quantify Soot in Engine Oil by Ultraviolet-Visible Spectroscopy. Tribology Transactions. 62(6):1063-1071. https://doi.org/10.1080/10402004.2019.1645255S10631071626Squaiella, L. L. F., Martins, C. A., & Lacava, P. T. (2013). Strategies for emission control in diesel engine to meet Euro VI. Fuel, 104, 183-193. doi:10.1016/j.fuel.2012.07.027Piock, W., Hoffmann, G., Berndorfer, A., Salemi, P., & Fusshoeller, B. (2011). Strategies Towards Meeting Future Particulate Matter Emission Requirements in Homogeneous Gasoline Direct Injection Engines. SAE International Journal of Engines, 4(1), 1455-1468. doi:10.4271/2011-01-1212Johnson, B. T. (2008). Diesel Engine Emissions and Their Control. Platinum Metals Review, 52(1), 23-37. doi:10.1595/147106708x248750Johnson, T. V. (2008). Diesel Emission Control in Review. SAE International Journal of Fuels and Lubricants, 1(1), 68-81. doi:10.4271/2008-01-0069Mohan, B., Yang, W., & Chou, S. kiang. (2013). Fuel injection strategies for performance improvement and emissions reduction in compression ignition engines—A review. Renewable and Sustainable Energy Reviews, 28, 664-676. doi:10.1016/j.rser.2013.08.051ALKEMADE, U., & SCHUMANN, B. (2006). Engines and exhaust after treatment systems for future automotive applications. Solid State Ionics, 177(26-32), 2291-2296. doi:10.1016/j.ssi.2006.05.051Bensaid, S., Caroca, C. J., Russo, N., & Fino, D. (2011). Detailed investigation of non-catalytic DPF regeneration. The Canadian Journal of Chemical Engineering, 89(2), 401-407. doi:10.1002/cjce.20408E, J., Xie, L., Zuo, Q., & Zhang, G. (2016). Effect analysis on regeneration speed of continuous regeneration-diesel particulate filter based on NO 2 -assisted regeneration. Atmospheric Pollution Research, 7(1), 9-17. doi:10.1016/j.apr.2015.06.012Tripathi, A., & Vinu, R. (2015). Characterization of Thermal Stability of Synthetic and Semi-Synthetic Engine Oils. Lubricants, 3(1), 54-79. doi:10.3390/lubricants3010054Karacan, Ö., Kök, M. V., & Karaaslan, U. (1999). Journal of Thermal Analysis and Calorimetry, 55(1), 109-114. doi:10.1023/a:1010136222719Heredia-Cancino, J. A., Ramezani, M., & Álvarez-Ramos, M. E. (2018). Effect of degradation on tribological performance of engine lubricants at elevated temperatures. Tribology International, 124, 230-237. doi:10.1016/j.triboint.2018.04.015Wattrus, M. (2013). Fuel Property Effects on Oil Dilution in Diesel Engines. SAE International Journal of Fuels and Lubricants, 6(3), 794-806. doi:10.4271/2013-01-2680Sharma, V., Uy, D., Gangopadhyay, A., O’Neill, A., Paxton, W. A., Sammut, A., … Aswath, P. B. (2016). Structure and chemistry of crankcase and exhaust soot extracted from diesel engines. Carbon, 103, 327-338. doi:10.1016/j.carbon.2016.03.024Pfau, S. A., La Rocca, A., Haffner-Staton, E., Rance, G. A., Fay, M. W., Brough, R. J., & Malizia, S. (2018). Comparative nanostructure analysis of gasoline turbocharged direct injection and diesel soot-in-oil with carbon black. Carbon, 139, 342-352. doi:10.1016/j.carbon.2018.06.050George, S., Balla, S., Gautam, V., & Gautam, M. (2007). Effect of diesel soot on lubricant oil viscosity. Tribology International, 40(5), 809-818. doi:10.1016/j.triboint.2006.08.002Antusch, S., Dienwiebel, M., Nold, E., Albers, P., Spicher, U., & Scherge, M. (2010). On the tribochemical action of engine soot. Wear, 269(1-2), 1-12. doi:10.1016/j.wear.2010.02.028Green, D. A., & Lewis, R. (2008). The effects of soot-contaminated engine oil on wear and friction: A review. Proceedings of the Institution of Mechanical Engineers, Part D: Journal of Automobile Engineering, 222(9), 1669-1689. doi:10.1243/09544070jauto468Bredin, A., Larcher, A. V., & Mullins, B. J. (2011). Thermogravimetric analysis of carbon black and engine soot—Towards a more robust oil analysis method. Tribology International, 44(12), 1642-1650. doi:10.1016/j.triboint.2011.06.002VAN DE VOORT, F. R., SEDMAN, J., COCCIARDI, R. A., & PINCHUK, D. (2006). FTIR Condition Monitoring of In-Service Lubricants: Ongoing Developments and Future Perspectives. Tribology Transactions, 49(3), 410-418. doi:10.1080/10402000600781432Van de Voort, F. R., Ghetler, A., García-González, D. L., & Li, Y. D. (2008). Perspectives on Quantitative Mid-FTIR Spectroscopy in Relation to Edible Oil and Lubricant Analysis: Evolution and Integration of Analytical Methodologies. Food Analytical Methods, 1(3), 153-163. doi:10.1007/s12161-008-9031-6Ess, M. N., Ferry, D., Kireeva, E. D., Niessner, R., Ouf, F.-X., & Ivleva, N. P. (2016). In situ Raman microspectroscopic analysis of soot samples with different organic carbon content: Structural changes during heating. Carbon, 105, 572-585. doi:10.1016/j.carbon.2016.04.056Russo, C., Apicella, B., Lighty, J. S., Ciajolo, A., & Tregrossi, A. (2017). Optical properties of organic carbon and soot produced in an inverse diffusion flame. Carbon, 124, 372-379. doi:10.1016/j.carbon.2017.08.07

Decavanadate interactions with actin: inhibition of G-actin polymerization and stabilization of decameric vanadate

Decameric vanadate species (V10) inhibit the rate and the extent of G-actin polymerization with an IC50 of 68 ± 22 lM and 17 ± 2 lM, respectively, whilst they induce F-actin depolymerization at a lower extent. On contrary, no effect on actin polymerization and depolymerization was detected for 2 mM concentration of ‘‘metavanadate’’ solution that contains ortho and metavanadate species, as observed by combining kinetic with 51V NMR spectroscopy studies. Although at 25 C, decameric vanadate (10 lM) is unstable in the assay medium, and decomposes following a first-order kinetic, in the presence of G-actin (up to 8 lM), the half-life increases 5-fold (from 5 to 27 h). However, the addition of ATP (0.2 mM) in the medium not only prevents the inhibition of G-actin polymerization by V10 but it also decreases the half-life of decomposition of decameric vanadate species from 27 to 10 h. Decameric vanadate is also stabilized by the sarcoplasmic reticulum vesicles, which raise the half-life time from 5 to 18 h whereas no effects were observed in the presence of phosphatidylcholine liposomes, myosin or G-actin alone. It is proposed that the ‘‘decavanadate’’ interaction with G-actin, favored by the G-actin polymerization, stabilizes decameric vanadate species and induces inhibition of G-actin polymerization. Decameric vanadate stabilization by cytoskeletal and transmembrane proteins can account, at least in part, for decavanadate toxicity reported in the evaluation of vanadium (V) effects in biological systems