Mechanistic Insights into Enantioselective C?H Photooxygenation of Aldehydes via Enamine Catalysis

Organocatalytic photooxygenation of aldehydes at the α‐position proceeds via enamine catalysis, though enamines should be easily oxidized by singlet oxygen respectively to amides and carbonyl compounds. Moreover, the formation of a zwitterionic enamine peroxide intermediate was postulated based on experimental and theoretical data. The reaction affords desired diols (after in situ reduction) in a decent yield and (S)‐ or (R)‐enantioselectivity depending on a catalyst used. The (S)‐enantiomer predominated in imidazolidinone‐catalyzed reactions, while prolineamides assured the formation of the (R)‐stereoisomer. DFT calculation suggests that the enamine–oxygen complex with the lowest energy has the E, s‐cis conformation for the prolineamide derivative and E, s‐trans for the imidazolidinone catalyst, explaining the opposite stereoselectivity in the photooxygenation reaction.

     

Symbiotic Activity of Pea (Pisum sativum) after Application of Nod Factors under Field Conditions

Growth and symbiotic activity of legumes are mediated by Nod factors (LCO, lipo-chitooligosaccharides). To assess the effects of application of Nod factors on symbiotic activity and yield of pea, a two-year field experiment was conducted on a Haplic Luvisol developed from loess. Nod factors were isolated from Rhizobium leguminosarum bv. viciae strain GR09. Pea seeds were treated with the Nod factors (10⁻¹¹ M) or water (control) before planting. Symbiotic activity was evaluated by measurements of nitrogenase activity (acetylene reduction assay), nodule number and mass, and top growth by shoot mass, leaf area, and seed and protein yield. Nod factors generally improved pea yield and nitrogenase activity in the relatively dry growing season 2012, but not in the wet growing season in 2013 due to different weather conditions.     

Phospholipids and Fatty Acids Affect the Colonization of Urological Catheters by Proteus mirabilis

Proteus mirabilis-mediated CAUTIs are usually initiated by the adherence of bacteria to a urinary catheter surface. In this paper, three isolates of different origin and exhibiting different adhesion abilities were investigated in search of any changes in lipidome components which might contribute to P. mirabilis adhesion to catheters. Using GC-MS and LC-MS/MS techniques, 21 fatty acids and 27 phospholipids were identified in the examined cells. The comparison of the profiles of phospholipids and fatty acids obtained for catheter-attached cells and planktonic cells of the pathogens indicated C11:0 and PE 37:2 levels as values which could be related to P. mirabilis adhesion to a catheter, as well as cis C16:1, PE 32:0, PE 33:0, PE 38:2, PG 33:1, PG 34:0, PE 30:1, PE 32:1 and PG 30:2 levels as values which could be associated with cell hydrophobicity. Based on DiBAC₄ (3) fluorescence intensity and an affinity to p-xylene, it was found that the inner membrane depolarization, as well as strong cell-surface hydrophobicity, were important for P. mirabilis adhesion to a silicone catheter. A generalized polarization of Laurdan showed lower values for P. mirabilis cells attached to the catheter surface than for planktonic cells, suggesting lower packing density of membrane components of the adherent cells compared with tightly packed, stiffened membranes of the planktonic cells. Taken together, these data indicate that high surface hydrophobicity, fluidization and depolarization of P. mirabilis cell membranes enable colonization of a silicone urinary catheter surface.     

Identification of drugs and other toxic compounds from their ultraviolet spectra. Part III: Ultraviolet absorption properties of 22 structural groups

The ultraviolet absorption spectra of 22 different chemical (structural) groups of drugs and toxic compounds were studied. This paper completes a three-part series in which more than 500 individual compounds have been grouped according to structure as it pertains to characteristics of the ultraviolet absorption scan. Each group has a typical absorption profile with respect to the number of bands between 200 and 340 nm, the intensity of the band(s), and the changes in absorption pattern with solvent and pH changes. Phenothiazines, xanthines, coumarins, quinolines, naphthalene derivatives. O-alkyl benzene derivatives, opiates, ergot alkaloids, benzodiazepines, and various heterocyclic compounds are among the groups of compounds covered in this paper.     

Optimisation of the epi-ready semi-insulating GaAs wafer preparation procedure

The surface quality is crucial for growth of epitaxial layers on III-V semiconductor substrates. In this work the procedures of epi-ready semi-insulating (SI) GaAs wafer preparation were developed. The atomic force microscopy (AFM), triple crystal X-ray diffraction (TCD) and X-ray photoelectron spectroscopy (XPS) were used to monitor morphology and composition of substrates with different chemical treatment history. We propose an optimised epi-ready SI GaAs wafer preparation procedure involving NH₄OH:H₂O₂:H₂O/NaOCl:H₂O₂:H₂O etching/polishing.     

Coating of intravascular balloon with paclitaxel prevents constrictive remodeling of the dilated porcine femoral artery due to inhibition of intimal and media fibrosis

Here we investigated how a coating of intravascular balloon with paclitaxel (drug-coated balloon; DCB, Freeway?) impacted porcine peripheral artery vascular function and remodeling. Domestic swine (n = 54) underwent percutaneous overstretch balloon dilation of femoral and iliac arteries, controlled by angiography and optical coherence tomography (OCT). Paclitaxel tissue uptake was measured at 1 h and 1, 3, and 9 days post-dilation. At these time-points and at 32 ± 2 days, vascular function of the dilated arteries was assessed using the organ chamber model. Neointimal growth and remodeling indices were determined using OCT and histology at 32 ± 2 days. Intima and media fibrosis were quantified by picrosirius red staining. Post-inflation femoral artery tissue drug levels were 460 ± 214, 136 ± 123, 14 ± 6, and 0.1 ± 0.1 ng/mg at 1 h and 1, 3, and 9 days, respectively. Compared to plain balloon, Freeway? resulted in a significantly smaller neointimal area (P < 0.05), less tunica intima (8.0 ± 5.4 vs 14.2 ± 4.7 %) and media fibrosis (15.6 ± 7.7 vs 24.5 ± 5.4 %), and less femoral artery constrictive remodeling (remodeling index: 1.08 ± 0.08 vs 0.94 ± 0.08). The DCB was associated with significantly increased vasoconstrictor tone and endothelium-dependent vasodilation impairment shortly after post-overstretch injury. Overall, DCB dilation of peripheral arteries resulted in high drug uptake into arterial tissue. Compared with the plain balloon, the DCB was associated with decreased vessel wall fibrosis after balloon overstretch injury, and reduced degrees of constrictive remodeling and neointimal hyperplasia.     

Activity of CdTe Quantum-Dot-Tagged Superoxide Dismutase and Its Analysis in Capillary Electrophoresis

Quantum dots (QDs) have a broad range of applications in cell biolabeling, cancer treatment, metastasis imaging, and therapeutic drug monitoring. Despite their wide use, relatively little is known about their influence on other molecules. Interactions between QDs and proteins can influence the properties of both nanoparticles and proteins. The effect of mercaptosuccinic acid-capped CdTe QDs on intercellular copper–zinc superoxide dismutase (SOD1)—one of the main enzymatic antioxidants—was investigated. Incubation of SOD1 with QDs caused an increase in SOD1 activity, unlike in the case of CdCl₂, which inhibited SOD1. Moreover, this effect on SOD1 increased with the size and potential of QDs, although the effect became clearly visible in higher concentrations of QDs. The intensity of QD-SOD1 fluorescence, analyzed with the use of capillary electrophoresis with laser-induced fluorescence detection, was dependent on SOD1 concentration. In the case of green QDs, the fluorescence signal decreased with increasing SOD1 concentration. In contrast, the signal strength for Y-QD complexes was not dependent on SOD1 dilutions. The migration time of QDs and their complexes with SOD1 varied depending on the type of QD used. The migration time of G-QD complexes with SOD1 differed slightly. However, in the case of Y-QD complexes with SOD1, the differences in the migration time were not dependent on SOD concentration. This research shows that QDs interact with SOD1 and the influence of QDs on SOD activity is size-dependent. With this knowledge, one might be able to control the activation/inhibition of specific enzymes, such as SOD1.