Nonlinear modeling and analysis of rotors supported by magnetorheological squeeze film journal bearings

Meccanica - The driver coupled to a driven system through mechanical couplings is very common in rotating machinery. These couplings can present angular and parallel misalignments with more or less...     

Influence of stereoelectronic effects on the 1JC─F spin–spin coupling constant in fluorinated heterocyclic compounds

The Perlin effect and its analog for fluorinated compounds (the fluorine Perlin-like effect) manifest on one-bond C─H (C─F for the fluorine Perlin-like effect) spin–spin coupling constants (SSCCs) in six-membered rings. These effects can be useful to probe the stereochemistry (axial or equatorial) of the C─H and C─F bonds, respectively. The origin of these effects has been debatable in the literature as being due to hyperconjugative interactions, dipolar effects, and induced current density. Accordingly, a variety of model compounds has been used to probe such effects since the cyclohexanone carbonyl group and the endocyclic heteroatom lone pairs play different roles on the above-mentioned effects. Thus, the ¹J_C─F SSCC in fluorinated lactams and lactones were theoretically studied to gain further insight on the nature of the fluorine Perlin-like effect. In addition, because the intramolecular α-effect has recently gained attention for its importance in the reactivity and stereoelectronic interactions in peroxide compounds, some fluorinated 1,2-dioxanes and 1,2-dithianes were studied to evaluate the role of the α-effect on the behavior of ¹J_C─F SSCCs. Differently from fluorinated ketones and ethers, the fluorine Perlin-like effect in the amides and esters cannot be explained by hyperconjugative or dipolar interactions alone, because the resonance in these groups affect the ¹J_C─F values. The O─O and S─S-containing systems exhibit a strong fluorine Perlin-like effect, but unlike the α-effect, this behavior cannot be explained neither by hyperconjugation nor by dipolar interactions alone; the spatial proximity of the C─F and O─O/S─S bonds is proposed to affect the magnitude of the ¹J_C─F SSCC.     

Impact of malolactic fermentation on low molecular weight phenolic compounds

A reversed phase liquid chromatography-DAD method is proposed for analysis of major non-flavonoid phenolic compounds in wines. The method employed a mixture of acetic acid, water and methanol as eluents and was used to evaluate the impact of malolactic fermentation in low molecular phenolic compounds.

The wines analyzed underwent different treatments, like the addition of a pectolytic enzyme or lysozyme, and the way malolactic fermentation was carried out—spontaneously or with the inoculation of two different commercial lactic bacteria.

The main result observed was the disappearance of hydroxycinnamoyltartaric acids and the increase of resultant free forms, regardless the way malolactic fermentation was carried out.     

Identifying chemical sources of airborne contamination in lichen biomonitors through instrumental neutron activation analysis

Chemical elements were determined in epiphytic lichens from Terceira and Santa Maria islands (Azores, Portugal), by k ₀-standardized, instrumental neutron activation analysis. Abundance ranges were generally below those in mainland Portugal, except for Br (Terceira), Cl (Santa Maria), Na (Santa Maria), and Se (both islands). Elemental (averaged) contents of As, Br, Cl, Co, Cr, Mg, Na, Se, Hg and Zn were significantly different between the islands. Anthropogenic influence was discernible in Terceira if not in Santa Maria, where only crustal and marine sources are apparent.     

The Biochemical Mechanisms of Antimicrobial Photodynamic Therapy†

The unbridled dissemination of multidrug-resistant pathogens is a major threat to global health and urgently demands novel therapeutic alternatives. Antimicrobial photodynamic therapy (aPDT) has been developed as a promising approach to treat localized infections regardless of drug resistance profile or taxonomy. Even though this technique has been known for more than a century, discussions and speculations regarding the biochemical mechanisms of microbial inactivation have never reached a consensus on what is the primary cause of cell death. Since photochemically generated oxidants promote ubiquitous reactions with various biomolecules, researchers simply assumed that all cellular structures are equally damaged. In this study, biochemical, molecular, biological and advanced microscopy techniques were employed to investigate whether protein, membrane or DNA damage correlates better with dose-dependent microbial inactivation kinetics. We showed that although mild membrane permeabilization and late DNA damage occur, no correlation with inactivation kinetics was found. On the other hand, protein degradation was analyzed by three different methods and showed a dose-dependent trend that matches microbial inactivation kinetics. Our results provide a deeper mechanistic understanding of aPDT that can guide the scientific community toward the development of optimized photosensitizing drugs and also rationally propose synergistic combinations with antimicrobial chemotherapy.     

Synthesis and characterization of nanostructured iron compounds prepared from the decomposition of iron pentacarbonyl dispersed into carbon materials with varying porosities

This work describes the production and characterization of carbon-iron nanocomposites obtained from the decomposition of iron pentacarbonyl (Fe(CO)₅) mixed with different carbon materials: a high surface area activated carbon (AC), powdered graphite (G), milled graphite (MG), and carbon black (CB). The nanocomposites were prepared either under argon or in ambient atmosphere, with a fixed ratio of Fe(CO)₅ (4.0 mL) to carbon precursor (2.0 g). The images of scanning electron microscopy and the analysis of textural properties indicated the presence of nanostructured Fe compounds homogeneously dispersed into the different classes of pores of the carbon matrices. The elemental Fe content was always larger for samples prepared in ambient atmosphere, reaching values in the range of 20–32 wt%. On the other hand, samples prepared under argon showed reduced Fe content, with values in the range 5–10 wt% for samples prepared from precursors with low surface area (G, MG, and CB) and a much higher value (~19 wt%) for samples prepared from the precursor of high surface area (AC). Mössbauer spectroscopy and X-ray diffractometry showed that the nanoparticles were mostly composed of iron oxides in the case of the samples prepared in oxygen-rich ambient atmosphere and also for the AC-derived nanocomposite prepared under argon, which is consistent with the large oxygen content of this precursor. For the other precursors, with reduced or no oxygen content, metallic iron and iron carbides were found to be the dominant phases in samples prepared under oxygen-free atmosphere. The samples prepared in ambient atmosphere and the AC-derived sample prepared under argon exhibited superparamagnetic behavior at room temperature, as revealed by temperature-dependent magnetization curves and Mössbauer spectroscopy.     

Spectrometric and theoretical investigation of the structures of Cu and Pb/DTPA complexes

Spectrometric and theoretical tools have been employed in this study in order to elucidate the structures of DTPA (diethylenetriaminepentaacetic acid) complexed to copper and lead. Mass spectrometry allowed determining the 1:1 stoichiometry of metal:ligand, while infrared spectroscopy demonstrated that both N and O are sites for complexation. ¹³C NMR analysis showed the existence of free and complexed carboxyl groups, due to a straight singlet at 180.7 ppm (free carboxylic ¹³C) and to a broad signal at 179.3 ppm (complexed carboxylic ¹³C, ² J _Pb…O=C). A distorted NMR signal were observed for the Cu–DTPA carboxyl group, due to the Cu²⁺ paramagnetism. Based on the spectrometric evidences for the metal–DTPA structures, DFT optimizations were carried out and an octahedral-like arrangement for the Cu complex and a “shell-like” arrangement for the Pb complex, both hexa-coordinated, were then proposed for the structures of the titled compounds.