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31.
Chmielewski MK Marchán V Cieślak J Grajkowski A Livengood V Münch U Wilk A Beaucage SL 《The Journal of organic chemistry》2003,68(26):10003-10012
Thermolytic groups structurally related to well-studied heat-sensitive phosphate/thiophosphate protecting groups have been evaluated for 5'-hydroxyl protection of deoxyribonucleosides as carbonates and for potential use in solid-phase oligonucleotide synthesis. The spatial arrangement of selected functional groups forming an asymmetric nucleosidic 5'-O-carbonic acid ester has been designed to enable heat-induced cyclodecarbonation reactions, which would result in the release of carbon dioxide and the generation of a nucleosidic 5'-hydroxyl group. The nucleosidic 5'-O-carbonates 3-8, 10-15, and 19-21 were prepared and were isolated in yields ranging from 45 to 83%. Thermolytic deprotection of these carbonates is preferably performed in aqueous organic solvent at 90 degrees C under near neutral conditions. The rates of carbonate deprotection are dependent on the nucleophilicity of the functional group involved in the postulated cyclodecarbonation reaction and on solvent polarity. Deprotection kinetics increase according to the following order: 4 < 5 < 10 < 6 < 12 < 7 < 13 < 8 < 14 congruent with 19-21 and CCl4 < dioxane < MeCN < t-BuOH < MeCN:phosphate buffer (3:1 v/v, pH 7.0) < EtOH:phosphate buffer (1:1 v/v, pH 7.0). Complete thermolytic deprotection of carbonates 7, 8, 13, and 14 is achieved within 20 min to 2 h under optimal conditions in phosphate buffer-MeCN. The 2-(2-pyridyl)amino-1-phenylethyl and 2-[N-methyl-N-(2-pyridyl)]aminoethyl groups are particularly promising for 5'-hydroxyl protection of deoxyribonucleosides as thermolytic carbonates. 相似文献
32.
This paper compares model development strategies based on different performance metrics. The study was conducted in the area of credit risk modeling with the usage of diverse metrics, including general-purpose Area Under the ROC curve (AUC), problem-dedicated Expected Maximum Profit (EMP) and the novel case-tailored Calculated Profit (CP). The metrics were used to optimize competitive credit risk scoring models based on two predictive algorithms that are widely used in the financial industry: Logistic Regression and extreme gradient boosting machine (XGBoost). A dataset provided by the American Fannie Mae agency was utilized to conduct the study. In addition to the baseline study, the paper also includes a stability analysis. In each case examined the proposed CP metric that allowed us to achieve the most profitable loan portfolio. 相似文献
33.
Roman Major Grayna Wilczek Justyna Wicek Maciej Gawlikowski Hanna Plutecka Katarzyna Kasperkiewicz Marcin Kot Magorzata Pomorska Roman Ostrowski Magdalena Kopernik 《Molecules (Basel, Switzerland)》2022,27(17)
The aim of this study was to minimize the risk of life-threatening thromboembolism in the ventricle through the use of a new biomimetic heart valve based on metal–polymer composites. Finite volume element simulations of blood adhesion to the material were carried out, encompassing radial flow and the cone and plane test together with determination of the effect of boundary conditions. Both tilt-disc and bicuspid valves do not have optimized blood flow due to their design based on rigid valve materials (leaflet made of pyrolytic carbon). The main objective was the development of materials with specific properties dedicated to contact with blood. Materials were evaluated by dynamic tests using blood, concentrates, and whole human blood. Hemostability tests under hydrodynamic conditions were related to the mechanical properties of thin-film materials obtained from tribological tests. The quality of the coatings was high enough to avoid damage to the coating even as they were exposed up to maximum loading. Analysis towards blood concentrates of the hydrogenated carbon sample and the nitrogen-doped hydrogenated carbon sample revealed that the interaction of the coating with erythrocytes was the strongest. Hemocompatibility evaluation under hydrodynamic conditions confirmed very good properties of the developed coatings. 相似文献
34.
Katarzyna Gawe-Bben Karolina Czech Marcelina Strzpek-Gomka Marcin Czop Monika Szczepanik Anna Lichtarska Wirginia Kukula-Koch 《Molecules (Basel, Switzerland)》2022,27(21)
By-products of cultivated plants are one of the major environmental concerns worldwide. Due to the high concentration of bioactive chemicals, such waste may be considered hazardous due to the interference with the plant growth, deterioration of the drinking water quality or toxic effects on sensitive marine organisms. Moreover, plant-derived by-products, with proper handling, may represent a low-cost source of bioactive compounds potentially important for pharmaceutical and cosmetics industries. The aim of the study was to evaluate the phytochemical composition, antioxidant activity, the influence of tyrosinase activity, in vitro sun protecting factor and cytotoxicity of 15 extracts from peels of five cultivars of Cucurbita maxima and C. moschata. The extracts were prepared using “green solvents” (water, 50% propylene glycol, and 20% ethanol) and ultrasound-assisted extraction. The performed analysis showed that the peel extracts from various cultivars differ significantly in respect to the phytochemical content and activity. The type of solvent also had a significant impact on the extract’s composition and bioactivity. Aqueous peel extracts contained the highest amounts of flavonoids, showed the greatest antioxidant potential and the most significant in vitro SPF values. In vitro studies showed that the analyzed peel extracts are not cytotoxic for human keratinocytes up to the concentration of 1000 µg/mL and thus might be considered as non-irritant for the skin. The study confirms the potential application of peel extracts from Cucurbita spp. cultivars in cosmetic products. 相似文献
35.
Karolina Ciesielska Marcin Hoffmann Maciej Kubicki Donata Pluskota-Karwatka 《Molecules (Basel, Switzerland)》2022,27(14)
A number of imines, including 12 new compounds, previously not reported in the literature, derived from variously fluorinated benzaldehydes and different anilines or chiral benzylamines were synthesized by a solvent-free mechanochemical method, which was based on the manual grinding of equimolar amounts of the substrates at the room temperature. In a very short reaction time of only 15 min, the method produced the expected products with good-to-excellent yields. The yields were comparable or significantly higher than those reported in the literature for the imines synthesized by other methods. Importantly, the conditions used for the reactions with aniline derivatives also resulted in the high yields of imines obtained from chiral benzylamines, and can be extended to the synthesis with other similar amines. Structures of all imines were confirmed by NMR spectroscopy: 1H, 13C and 19F. For four compounds, X-ray structures were also obtained. The synthetic approach presented in this paper contributes to the prevention of environmental pollution and can be easily extended for larger-scale syntheses. The mechanochemical solvent-free method provides a convenient strategy particularly useful for the preparation of fluorinated imines being versatile intermediates or starting material in the synthesis of drugs and other fine chemicals. 相似文献
36.
Ewelina Pogorzelska-Nowicka Marcin Kurek Monika Hanula Agnieszka Wierzbicka Andrzej Ptorak 《Molecules (Basel, Switzerland)》2022,27(14)
Meat is a rich source of various nutrients. However, it needs processing before consumption, what in turn generates formation of carcinogenic compounds, i.a., polycyclic aromatic hydrocarbons (PAH), nitrosamines (NOCs), and the most mutagenic heterocyclic aromatic amines (HAAs). It was widely found that many factors affect the content of carcinogens in processed meat. However, it has recently been discovered that after digestion free HAAs are released, which are not detectable before enzymatic treatment. It was established that the highest percentage of carcinogens is released in the small intestine and that its amount can be increased up to 6.6-fold. The change in free HAAs content in analyzed samples was dependent on many factors such as meat type, doneness, particle size of meat, and the enzyme concentration used for digestion. In turn, introduction of bacteria naturally occurring in the human digestive tract into the model significantly decreases total amount of HAAs. Contrary, the addition of food ingredients rich in polyphenols, fiber, and water (pepper powder, onions, apples) increases free HAAs’ release up to 56.06%. Results suggests that in vitro digestion should be an integral step of sample preparation. Artificial digestion introduced before chromatographic analysis will allow to estimate accurately the content of carcinogens in processed meat. 相似文献
37.
Krzysztof Bartkowski Paola Zimmermann Crocomo Micha Andrzej Kochman Dharmandra Kumar Adam Kubas Przemysaw Data Marcin Lindner 《Chemical science》2022,13(34):10119
Hyperfluorescence (HF), a relatively new phenomenon utilizing the transfer of excitons between two luminophores, requires careful pairwise tuning of molecular energy levels and is proposed to be the crucial step towards the development of new, highly effective OLED systems. To date, barely few HF yellow emitters with desired narrowband emission but moderate external quantum efficiency (EQE < 20%) have been reported. This is because a systematic strategy embracing both Förster resonance energy transfer (FRET) and triplet to singlet (TTS) transition as complementary mechanisms for effective exciton transfer has not yet been proposed. Herein, we present a rational approach, which allows, through subtle structural modification, a pair of compounds built from the same donor and acceptor subunits, but with varied communication between these ambipolar fragments, to be obtained. The TADF-active dopant is based on a naphthalimide scaffold linked to the nitrogen of a carbazole moiety, which through the introduction of an additional bond leads not only to π-cloud enlargement, but also rigidifies and inhibits the rotation of the donor. This structural change prevents TADF, and guides bandgaps and excited state energies to simultaneously pursue FRET and TTS processes. New OLED devices utilizing the presented emitters show excellent external quantum efficiency (up to 27%) and a narrow full width at half maximum (40 nm), which is a consequence of very good alignment of energy levels. The presented design principles prove that only a minor structural modification is needed to obtain commercially applicable dyes for HF OLED devices.The rigidification with simultaneous π-extension of TADF-active dye leads to fluorescent dopant with fine-tuned energy levels. These used as hyperfluorescent OLED device shows extraordinary EQE and brightness due to effective FRET and TTS processes. 相似文献
38.
Marcin Feldo Magdalena Wjciak Aleksandra Ziemlewska Sawomir Dresler Ireneusz Sowa 《Molecules (Basel, Switzerland)》2022,27(13)
Diosmin is widely used as a venoactive drug in the pharmacological treatment of chronic venous disorders. It exerts a strong protective effect on blood vessels via an increase in the elasticity of vessel walls and reduces the permeability of capillary walls, thereby producing an anti-edematous effect. In this paper, we investigated the effectiveness of diosmin and diosmetin in modulating the level of proinflammatory factors in human skin fibroblasts treated with lipopolysaccharide (LPS). Two variants of the experiments were performed: the flavonoid was added 2 h prior to or 24 h after LPS stimulation. Our study revealed that both flavonoids reduced the levels of IL-6 and Il-1β as well as COX-2 and PGE2 but had no impact on IL-10. However, the addition of the compounds prior to the LPS addition was more effective. Moreover, diosmetin modulated the proinflammatory factors more strongly than diosmin. Our investigations also showed that both flavonoids were potent inhibitors of elastase and collagenase activity, and no differences between the glycoside and aglycone forms were observed. 相似文献
39.
Magdalena
widro-Pito Alicja Chromiec Marcin Zawadzki Renata Wietecha-Posuszny 《Molecules (Basel, Switzerland)》2022,27(13)
The present investigation utilised the quick and easy SPME/LC-MS method to determine selected narcotic substances and their metabolites in whole blood. The study included qualitative analysis and validation of the method. Analytes were determined in the linearity range of 25–300 ng/mL. The precision during and between days (in general CV < 13.41%), and the LOD which results in between 0.36 and 11.08 ng/mL, and the LOQ between 1.20 and 36.90 ng/mL were investigated. The validation results obtained, as well as the results of subsequent in-laboratory tests, confirmed the applicability of the method in the analysis of blood samples. An attempt to apply the method to the analysis of bone marrow samples has yielded promising results; however, more detailed studies are needed in this area. 相似文献
40.
Agnieszka Lewiska Marta Doma-Kdzia Kinga Kierul Micha Bochynek Dominika Pannert Piotr Nowaczyk Marcin ukaszewicz 《Molecules (Basel, Switzerland)》2021,26(4)
The skin is constantly exposed to external and internal factors that disturb its function. In this work, two nanosystems-levan nanoparticles and a surfactin-stabilized nanoemulsion were preserved (tested for microbial growth) and characterized (size, polydispersity, Zeta potential, and stability). The nanosystems were introduced in the model formulations-cream, tonic, and gel, and confirmed by TEM. The analysis showed that nanoemulsion has a spherical morphology and size 220–300 nm, while levan nanoparticles had irregular shapes independently of the use of matrix and with particle size (130–260 nm). Additionally, we examined the antiradical effect of levan nanoparticles and nanoemulsion in the prototype of formulations by scavenging DPPH (2,2-diphenyl-1-picrylhydrazyl; EPR spectroscopy). The model cream with both nanosystems and the whole range of products with nanosystems were evaluated in vivo for hydration, elasticity, smoothness, wrinkles and vascular lesions, discoloration, respectively. The cream improved skin condition in all tested parameters in at least 50% of volunteers. The use of more comprehensive care, additionally consisting of a tonic and gel, reduced the previously existing skin discoloration to 10.42 ± 0.58%. The presented prototype formulations are promising in improving skin conditions. 相似文献