Cubic C8: An Observable Allotrope of Carbon?

Ab initio and DFT calculations are used to investigate the structure, electronic properties, spectra and reactivity of cubic C₈, which is predicted to be aromatic according to Hirsch′s rule. Although highly strained and with a small amount of diradical character, the carbon cube represents a surprisingly deep minimum and should therefore be observable as an isolated molecule. It is, however, predicted to be very reactive, both with itself and triplet oxygen. Calculated IR, Raman, and UV/Vis spectra are provided to aid identification of cubic C₈ should it be synthesized.     

DFT studies on the acid-catalyzed Curtius reaction: the Schmidt reaction

The Schmidt reaction is the acid-catalyzed analogue of the Curtius reaction and is extensively used in organic synthesis. In this work, the mechanism of this reaction has been explored using DFT calculations at the B3LYP/6-311+G(d,p) level. Protonated formyl azide may undergo rearrangement to the product, protonated isocyanic acid, with simultaneous extrusion of molecular nitrogen (concerted mechanism), or undergo rearrangement to the anti conformer, followed by removal of nitrogen to form the nitrenium ion, which then rearranges to the final product, protonated isocyanic acid (step-wise mechanism). Like the Curtius reaction, it is found that the concerted pathway is definitely preferred. The key role of acidification in decreasing the overall energy barrier is more highlighted in case of phenyl substitution, with negligible effect on the lower homologues. For methoxy and amine substituents, there is very little difference in the activation energies of the concerted and step-wise reactions, with the former being still slightly preferred. Unlike the parent compound, the rearrangement of substituted nitrenium ion in some cases involves side reactions like C-H insertion and cyclization.     

Measurement of mean rotation and strain-rate tensors by using stereoscopic PIV

A technique is described for measuring the mean velocity gradient (rate-of-displacement) tensor by using a conventional stereoscopic particle image velocimetry (SPIV) system. Planar measurement of the mean vorticity vector, rate-of-rotation and rate-of-strain tensors and the production of turbulent kinetic energy can be accomplished. Parameters of the Q criterion and negative λ₂ techniques used for vortex identification can be evaluated in the mean flow field. Experimental data obtained for a circular turbulent jet issuing normal to a crossflow in a low speed wind tunnel for a jet-to-crossflow velocity ratio of 3.3 are presented to show the applicability of the proposed technique. The results reveal the presence of a secondary counter-rotating vortex pair (SCVP) which is located within the jet core and has a sense of rotation opposite to that of the primary one (PCVP). Consistency of the measurements is verified by the agreement of data obtained in two perpendicular planes. Accuracy of the data is discussed and algebraic relations for some measurement uncertainties are presented.     

Untersuchung des lokalen Stoffüberganges am laminaren und turbulenten Rieselfilm

Zusammenfassung Der lokale Stoffübergang wurde in Abhängigkeit von der Meßlänge, dem Startort und der Zulaufhöhe gemessen. Der Gültigkeitsbereich der Theorie von Nusselt wird ermittelt. Die Reynolds-Zahl nahm Werte zwischen 3,86 und 2496 an. Die örtlich wirkende Hydrodynamik ist entscheidend für das Anwachsen der örtlichen Sherwood-Zahl. Die Genauigkeit aller Versuchsergebnisse kann auf ± 5% abgeschätzt werden.

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Investigation of the local mass transfer of a laminar and turbulent falling liquid film

The local mass transfer was measured as a function of the measuring length, the starting point and the liquid height above the ring-slot. The range of the Reynolds number was 3,86 Re 2496. The validity of the Nusselt theory and the range of it is shown. The local hydrodynamic is the most important factor of the increase of the local Sherwood number. The accuracy of the measurements is ± 5%.

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Bezeichnungen a Temperaturleitfähigkeit m²/s=/(c_p) - c Konzentration, c=¯c + c kmol/m³ - c_i0 Konzentration im Flüssigkeitskern kmol/m³ - D Diffusionskoeffizient m²/s - EL-NR Elektrodennummer - Fa Faraday-Konstante A s/kgäq=96,5·10⁶ - g Erdbeschleunigung m/s² - i_G Grenzstromdichte A/m² - u Geschwindigkeit in x-Richtung, u= + u - U Umfang des Rohres m - v Geschwindigkeit in y-Rich- m/stung, v=¯v + v - V^* Volumenstrom m³/s - x Lauflänge, Koordinate in m Strömungsrichtung - x_M Meßlänge für den Stoff-Übergang m - x_ST Startort für den Stoff-Übergang m - y Wegkoordinate senkrecht zur Rohroberfläche m - z Wertigkeit der Elektro-denreaktion kgäq/kmol - ZH Zulaufhöhe m - Wärmeübergangskoeffizient W/m²C - Stoffübergangskoeffizient m/s - Filmdicke m - Wärmeleitfähigkeit W/(mC) - kinematische Viskosität m²/s - Re=u/=V^*/U Reynolds-Zahl - Pr=/a=c_p/ Prandtl-Zahl - Sc=/D Schmidt-Zahl - Nu= / Nusselt-Zahl - Sh= /D Sherwood-Zahl - SHL lokale Sherwood-Zahl - SHM mittlere Sherwood-Zahl - - zeitlich gemittelt - örtlich gemittelt Die Durchführung der Arbeit am Institut für Verfahrens — und Kältetechnik der ETH Zürich bei Prof. Dr. P. Grassmann wurde ermöglicht durch Zuschüsse der Kommission zur Förderung der wissenschaftlichen Forschung und meiner Eltern.     

Anti-Proliferative and Pro-Apoptotic Effects of Digested Aglianico Grape Pomace Extract in Human Colorectal Cancer Cells

Grape pomace (GP)—the major by-product of winemaking processes—still contains bioactive molecules with known beneficial properties for human health, such as an antiradical scavenging activity or an antiproliferative activity of tumors. In vitro studies have demonstrated that GP polyphenols specifically influence colon cancer cell proliferation. In addition to previously published work, we tested the phenolic compounds of Aglianico GP following an in vitro simulated gastrointestinal digestion on colorectal cancer cell lines at different degrees of differentiation. Our experiments, using HT29 and SW480 cells, confirmed the anti-proliferative effect of GP gastrointestinal digested extract and provided intriguing insights on the way it influences the cancer cell features (i.e., viability, proliferation, and apoptosis). We observed that Aglianico GP extract showed a great ability to affect cell proliferation and apoptosis. Interestingly, both HT29 and SW480 cells produced a significant increase in Bax, and a significant increase in the Bax/Bcl-2 ratio and caspase-3. The gastrointestinal digested GP extract was previously characterized both for antioxidant activity and phenolic composition. As a result, the TPC and the antioxidant activity reached high values in the Aglianico GP digested extract, and the main compounds assessed by UHPLC-DAD were anthocyanins, phenolic acids, and flavonoids. This work shed light on the use of digested GP extract as a dietary ingredient, a very sustainable source of nutritional compounds with potential health benefits for colon cancer cell proliferation.     

Potential Benefits of Black Chokeberry (Aronia melanocarpa) Fruits and Their Constituents in Improving Human Health

Aronia berry (black chokeberry) is a shrub native to North America, of which the fresh fruits are used in the food industry to produce different types of dietary products. The fruits of Aronia melanocarpa (Aronia berries) have been found to show multiple bioactivities potentially beneficial to human health, including antidiabetic, anti-infective, antineoplastic, antiobesity, and antioxidant activities, as well as heart-, liver-, and neuroprotective effects. Thus far, phenolic compounds, such as anthocyanins, cyanidins, phenolic acids, proanthocyanidins, triterpenoids, and their analogues have been identified as the major active components of Aronia berries. These natural products possess potent antioxidant activity, which contributes to the majority of the other bioactivities observed for Aronia berries. The chemical components and the potential pharmaceutical or health-promoting effects of Aronia berries have been summarized previously. The present review article focuses on the molecular targets of extracts of Aronia berries and the examples of promising lead compounds isolated from these berries, including cyanidin-3-O-galactoside, chlorogenic acid, quercetin, and ursolic acid. In addition, presented herein are clinical trial investigations for Aronia berries and their major components, including cancer clinical trials for chlorogenic acid and COVID-19 trial studies for quercetin. Additionally, the possible development of Aronia berries and their secondary metabolites as potential therapeutic agents is discussed. It is hoped that this contribution will help stimulate future investigations on Aronia berries for the continual improvement of human health.