Chemistry of Pyruvate Enolates: anti‐Selective Direct Aldol Reactions of Pyruvate Ester with Sugar Aldehydes Promoted by a Dinuclear Zinc Catalyst

A chiral dinuclear zinc complex can effectively catalyse the direct aldol reactions of pyruvic acid ester with various chiral sugar aldehydes, thus functionally mimicking the pyruvate‐dependent type II aldolases. Application of sterically hindered aryl esters allows for the elusive aldol reaction of the pyruvate donor with controlled anti‐selectivity en route to the short and efficient synthesis of 3‐deoxy‐2‐ulosonic acids. Pyruvic acid ester is here used as a chemical equivalent of phosphoenol pyruvate (PEP) in imitation of the synthetic principle used in nature. The presented biomimetic methodologies use enol formation for the highly efficient and flexible formation of various C₆–C₉ ulosonic acids. Particularly, efficient and concise syntheses of 3‐deoxy‐D ‐erythro‐hex‐2‐ulosonic acid (KDG, overall 50% yield), 3‐deoxy‐D ‐ribo‐hept‐2‐ulosonic acid (DRH, overall 53% yield) and 3‐deoxy‐D ‐glycero‐D ‐talo‐non‐2‐ulosonic acid (4‐epi‐KDN, overall 78% yield) are described. This direct efficient application of pyruvic esters does not require additional demasking steps and thus surpassess previously methodologies utilising masked pyruvic synthons such 2‐acetylthiazole and pyruvic aldehyde dimethyl acetal.

     

Constraints on the applicability range of Hill’s criterion: strong orthotropy or transverse isotropy

Commonly used orthotropic Hill’s criterion of plastic flow initiation (Hill in Proc R Soc Lond A 193:281–297, 1948) suffers from some constraints and inconsistencies, which are of two different origins. Firstly, in case of high orthotropy degree, the quadratic form corresponding to Hill’s criterion may change type from convex and closed elliptic to concave and open hyperbolic in the deviatoric stress space (Ottosen and Ristinmaa in the mechanics of constitutive modeling, Elsevier, Amsterdam, 2005). Secondly, application of classical Hill’s criterion to transversely isotropic materials shows a discrepancy between Hill’s limit curves in the transverse isotropy plane and the Huber-von Mises prediction for isotropic materials (Huber 1904; von Mises 1913). The basic result of the present paper is to propose the new transversely isotropic von Mises–Hu–Marin’s-type criterion of hexagonal symmetry that is free from both constraints. The new enhanced Hu–Marin’s-type limit surface represents an elliptic cylinder, the axis of which is proportional to stress/strength, in contrast to Hill’s-type limit surface possessing the hydrostatic axis. Hence, this condition does not exhibit the deviatoricity property, which is a price for coincidence with the Huber–von Mises condition in the transverse isotropy plane, but with cylindricity ensured for an arbitrarily high orthotropy degree. The hybrid-type transversely isotropic Hu–Marin’s criterion of mixed symmetry based on additional biaxial bulge test, capable of fitting experimental findings for some complex composites, is also proposed. Application of this criterion has been verified for a unidirectional SiC/Ti composite examined by Herakovich (Thermal stresses V, Lastran Corp. Publ. Division, pp 1–142, 1999).     

Occurrence and transport of tetracycline, sulfonamide, quinolone, and macrolide antibiotics in the Haihe River Basin, China

The occurrence and transport of 12 antibiotics (from the tetracycline, sulfonamide, quinolone, and macrolide families) was studied in a 72-km stretch of the Haihe River, China, and in six of its tributaries. Aqueous and sediment samples were analyzed by HPLC-MS/MS. Sulfonamides were detected at the highest concentrations (24-385 ng/L) and highest frequencies (76-100%). Eight of the 12 antibiotics likely originated from veterinary applications in swine farms and fishponds, and concentrations at these sources (0.12-47 μg/L) were 1-2 orders of magnitude higher than in the effluent of local wastewater treatment plants. Sulfachloropyridazine (SCP) was detected in all swine farm and fishpond samples (maximum concentration 47 μg/L), which suggests its potential usefulness to indicate livestock source pollution in the Haihe River basin. Hydrological and chemical factors that may influence antibiotic distribution in the Haihe River were considered by multiple regression analysis. River flow rate exerted the most significant effect on the first-order attenuation coefficient (K) for sulfonamides, quinolones, and macrolides, with higher flow rates resulting in higher K, probably due to dilution. For tetracyclines, sediment total organic matter and cation exchange capacity exerted a greater impact on K than flow rate, indicating that adsorption to sediments plays an important role in attenuating tetracycline migration. Overall, the predominance of sulfonamides in the Haihe River underscores the need to consider regulating their veterinary use and improving the management and treatment of associated releases.     

Attenuation by leptin of the effects of fasting on ovarian function in hens (Gallus domesticus)

Thirty-four-week-old laying hens received injections of recombinant chicken leptin to assess the role of leptin in avian ovarian function. In the first experiment, the hens (n=60) were divided into three groups: (i). fed ad libitum; (ii). fasted; and (iii). fasted + leptin. Hens were fasted for 5 days and those treated with leptin received 250 microg leptin kg-1 body weight twice a day, i.p. In the second experiment, the hens (n=72) were divided into four groups: (i). fed ad libitum; (ii). fasted; (iii). fasted + leptin given only during fasting (5 days); or (iv). fasted and leptin given during both fasting and 5 days of re-feeding (10 days). LH was measured in blood plasma, and progesterone and oestradiol were measured in blood plasma and the ovary by radioimmunoassay. Apoptosis was examined in the walls of the three largest yellow hierarchical follicles (F3-F1; F38-12 mm), and the granulosa layer of F3 follicles. The expression of leptin receptor in the granulosa layer of F2 and F1 follicles was barely detectable. This was in contrast to a much higher expression of leptin receptor maintained in the theca layer of F3-F1 follicles. The present results indicate that in chickens leptin might be involved in the adaptation to starvation due to attenuation of follicular apoptosis. The presence of leptin receptors in the ovary indicates the possibility of a peripheral effect of the hormone.     

Energy consumption and CO2 emissions of the European glass industry

An in-depth analysis of the energy consumption and CO₂ emissions of the European glass industry is presented. The analysis is based on data of the EU ETS for the period 2005–2007 (Phase I). The scope of this study comprises the European glass industry as a whole and its seven subsectors. The analysis is based on an assignment of the glass installations (ca. 450) within the EU ETS to the corresponding subsectors and an adequate matching of the respective production volumes. A result is the assessment of the overall final energy consumption (fuel, electricity) as well as the overall CO₂ emissions (process, combustion and indirect emissions) of the glass industry and its subsectors in the EU25/27. Moreover, figures on fuel mix as well as fuel intensity and CO₂ emissions intensity (i.e. carbon intensity) are presented for each of the subsectors on aggregated levels and for selected EU Member States separately. The average intensity of fuel consumption and direct CO₂ emissions of the EU25 glass industry decreased from 2005 to 2007 by about 4% and amounted in 2007 to 7.8 GJ and 0.57 _tCO₂${\mathrm{t}}_{{\text{CO}}_{\mathrm{2}}}$ per tonne of saleable product, respectively. The economic energy intensity was evaluated with 0.46 toe/1000€ (EU27).     

Comparison of bioactive compounds,antioxidant and antiproliferative activities of Mon Thong durian during ripening

The aim of this investigation was to compare the bioactive and nutrient compounds, fatty acids, and antioxidant and antiproliferative activities of Mon Thong durian at different stages of ripening. It was found that the total polyphenols, flavonoids, flavanols, ascorbic acid, tannins and the antioxidant activity determined by four assays (CUPRAC, DPPH, ABTS and FRAP) differed in immature, mature, ripe and overripe samples. The content of polyphenols and antioxidant activity were the highest in overripe durian, flavonoids were the highest in ripe durian, and flavanols and antiproliferative activity were the highest in mature durian (p < 0.05). FTIR spectra of polyphenols, HPLC profiles of fatty acids, the antioxidant and antiproliferative activities can be used as indicators to characterise different stages of durian ripening.     

The effect of titanium ion implantation into carbon ceramic on its wettability by liquid copper

There is a growing interest in the carbon ceramics and their use in present technology. Among other problems, the joining of such ceramics with other materials presents an important challenge. Since joining with metals is associated with wetting, we studied the effect of ion implantation on wetting of various forms of carbon and of silicon carbide by copper. An essential result is that Ti ion implantation followed by ArcPVD Ti deposition results in excellent wettability in all studied cases.     

May Staphylococcus lugdunensis Be an Etiological Factor of Chronic Maxillary Sinuses Infection?

Staphylococcus lugdunensis is an opportunistic pathogen found in the healthy human skin microbiome bacterial community that is able to cause infections of diverse localization, manifestation, and course, including laryngological infections, such as necrotizing sinusitis. Chronic maxillary sinusitis is a disease present in up to one third of European and American populations, and its etiology is not fully described. Within this study, we aimed to characterize 18 S. lugdunensis strains recovered from maxillary sinuses and evaluate them as etiological agents of chronic disease. We performed MLST analysis, the complex analysis of both phenotypic and genetic virulence factors, antibiotic susceptibility profiles, and biofilm formation assay for the detection of biofilm-associated genes. Altogether, S. lugdunensis strains were clustered into eight different STs, and we demonstrated several virulence factors associated with the chronic disease. All tested strains were able to produce biofilm in vitro with numerous strains with a very strong ability, and overall, they were mostly susceptible to antibiotics, although we found resistance to fosfomycin, erythromycin, and clindamycin in several strains. We believe that further in-depth analysis of S. lugdunensis strains from different niches, including the nasal one, should be performed in the future in order to reduce infection rate and broaden the knowledge about this opportunistic pathogen that is gaining attention.     

Establishment of In Vitro and In Vivo Anticolorectal Cancer Efficacy of Lithocholic Acid-Based Imidazolium Salts

Imidazolium salts (IMSs) are the subject of many studies showing their anticancer activities. In this research, a series of novel imidazolium salts substituted with lithocholic acid (LCA) and alkyl chains of various lengths (S1–S10) were evaluated against colon cancer cells. A significant reduction in the viability and metabolic activity was obtained in vitro for DLD-1 and HT-29 cell lines when treated with tested salts. The results showed that the activities of tested agents are directly related to the alkyl chain length, where S6–S8 compounds were the most cytotoxic against the DLD-1 line and S4–S10 against HT-29. The research performed on the xenograft model of mice demonstrated a lower tendency of tumor growth in the group receiving compound S6, compared with the group receiving 5-fluorouracil (5-FU). Obtained results indicate the activity of S6 in the induction of apoptosis and necrosis in induced colorectal cancer. LCA-based imidazolium salts may be candidates for chemotherapeutic agents against colorectal cancer.