Solid-phase synthesis of thioether-linked glycopeptide mimics for application to glycoprotein semisynthesis

[reaction: see text]. Glycoproteins are particularly suited to protein semisynthesis since homogeneous samples for biological analyses are not readily available using traditional recombinant techniques. Here we apply glycosyl iodoacetamides, normally used for the modification of bacterially derived proteins, to solid-phase glycopeptide synthesis. This provides access to glycopeptide alpha-thioesters, which may lend themselves to the semisynthesis of homogeneous N-linked glycoprotein mimics and novel glycopeptide libraries.     

In Vitro Human Skin Penetration,Antioxidant and Antimicrobial Activity of Ethanol-Water Extract of Fireweed (Epilobium angustifolium L.)

Epilobium angustifolium L. is applied as an antiseptic agent in the treatment of skin diseases. However, there is a lack of information on human skin penetration of active ingredients with antioxidative potential. It seems crucial because bacterial infections of skin and subcutaneous tissue are common and partly depend on oxidative stress. Therefore, we evaluated in vitro human skin penetration of fireweed ethanol-water extracts (FEEs) by determining antioxidant activity of these extracts before and after penetration study using 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), and Folin–Ciocalteu methods. Microbiological tests of extracts were done. The qualitative and quantitative evaluation was performed using gas chromatography-mass spectrometry (GC-MS) and high-performance liquid chromatography (HPLC-UV) methods. The in vitro human skin penetration using the Franz diffusion chamber was assessed. The high antioxidant activity of FEEs was found. Gallic acid (GA), chlorogenic acid (ChA), 3,4-dihydroxybenzoic acid (3,4-DHB), 4-hydroxybenzoic acid (4-HB), and caffeic acid (CA) were identified in the extracts. The antibacterial activities were found against Serratia lutea, S. marcescens, Bacillus subtilis, B. pseudomycoides, and B. thuringiensis and next Enterococcus faecalis, E. faecium, Streptococcus pneumoniae, Pseudomonas aeruginosa, and P. fluorescens strains. In vitro penetration studies showed the penetration of some phenolic acids and their accumulation in the skin. Our results confirm the importance of skin penetration studies to guarantee the efficacy of formulations containing E. angustifolium extracts.     

Relationships between the Content of Phenolic Compounds and the Antioxidant Activity of Polish Honey Varieties as a Tool for Botanical Discrimination

The study compared the content of eight phenolic acids and four flavonoids and the antioxidant activity of six Polish varietal honeys. An attempt was also made to determine the correlations between the antioxidant parameters of the honeys and their polyphenol profile using principal component analysis. Total phenolic content (TPC), total flavonoid content (TFC), antioxidant activity (ABTS) and reduction capacity (FRAP) were determined spectrophotometrically, and the phenolic compounds were determined using high-performance liquid chromatography (HPLC). The buckwheat honeys showed the strongest antioxidant activity, most likely because they had the highest concentrations of total phenols, total flavonoids, p-hydroxybenzoic acid, caffeic acid, p-coumaric acid, vanillic acid and chrysin. The principal component analysis (PCA) of the data showed significant relationships between the botanic origin of the honey, the total content of phenolic compounds and flavonoids and the antioxidant activity of the six Polish varietal honeys. The strongest, significant correlations were shown for parameters of antioxidant activity and TPC, TFC, p-hydroxybenzoic acid, caffeic acid and p-coumaric acid. Analysis of four principal components (explaining 86.9% of the total variance), as a classification tool, confirmed the distinctiveness of the Polish honeys in terms of their antioxidant activity and content of phenolic compounds.     

Enhanced Adhesion Properties,Structure and Sintering Mechanism of Hydroxyapatite Coatings Obtained by Plasma Jet Deposition

Plasma Chemistry and Plasma Processing - Hydroxyapatite (HA) coatings were deposited on high purity titanium substrate by atmospheric plasma spraying (APS) with high electric energy input....     

The role of phytochelatins in Sinapis alba L. response to stress caused by two toxic elements As and Tl

Phytochelatins (PCs) play an important role in the detoxification and homeostasis processes in plants, since xenobiotics complexed by sulfhydryl groups are less toxic than the free ions. This paper describes studies related to PCs synthesis in Sinapis alba L. exposed to As and Tl salts, and in particular to the identification of the PC complexes that are formed in white mustard tissues. To reach the goal, two analytical methods were applied – high-performance liquid chromatography with fluorescent detection analysis after derivatisation of thiol compounds and high-performance liquid chromatography with electrospray ionization mass spectrometry (HPLC ESI MS). The study confirmed the synthesis of PCs in all plant organs under the influence of As salt. Moreover two As-PC complexes were identified: As-PC₃ and As-PC₄. While in the case of Tl – although that element strongly influenced the growth of Sinapis alba L. and to a great extent was transported to above-ground organs – no PC complexes or free PCs were found in plants exposed to Tl salt. Although both elements exist in mustard plant tissues at their trivalent oxidation state, showing high affinity to thiol groups, a defence mechanism associated with the synthesis of PC occurred only in case of arsenic.     

Spheroid cultivation of HT-29 carcinoma cell line in liquid marbles

The ability to simulate the 3D structure of a human body is essential to increase the efficiency of drug development. In vivo conditions are significantly different in comparison to in vitro conditions. A standardly used cell monolayer on tissue culture plastic (2D cell culture) is not sufficient to simulate the transfer phenomena occurring in living organisms, therefore, cell growth in a 3D space is desired. Drug absorption, distribution, metabolism, excretion and toxicity could be tested on 3D cell aggregates called spheroids, decrease the use of animal models and accelerate the drug development. In this work, the formation of spheroids from HT-29 human colorectal adenocarcinoma cells was successfully achieved by means of the so-called liquid marbles, which are liquid droplets encapsulated by a hydrophobic powder. During the cultivation in the medium inside the liquid marbles, cells spontaneously formed spherical agglomerates (spheroids) without the need of any supporting scaffold. The study focused on the influence of different parameters—namely liquid marble volume, seeding cell density and time of cultivation—on the final yield and quality of spheroids. This work has shown that using liquid marbles as microbioreactors is a suitable method for the cultivation of HT-29 cells in the form of spheroids.     

Determination of the cation-chelating potential of C-methylthiolated beta-lactams and their sulfones by electrospray ionization mass spectrometry

The chelation potential of highly lipophilic C-dimethylthiolated monocyclic beta-lactams was examined using electrospray ionization mass spectrometry (ESI-MS). The metal salts NaCl, KCl, CaCl2, ZnCl2, Cu(NO3)2, CdSO4, MnCl2, and Mg(NO3)2 were used for the analysis. The K+ adducts of the compounds studied were more responsive in ESI analysis, compared to their Na+ adducts, regardless of the oxidation state of the sulfur (in the methylthio or the sulfone groups) and the type of the group adjacent to the lactam carbonyl. Opening of the beta-lactam ring, leading to formation of a chargeable N-atom, had little to no effect on the K+ adduct formation. Interactions of the methylthio group with the divalent zinc ion were also observed.