RESUMO
1,4-Bis(5-phenyl-2-oxazolyl)benzene (POPOP) is a common scintillation fluorescent laser dye. In this manuscript, the synthesis of 2-Ar-5-(4-(4-Ar'-1H-1,2,3-triazol-1-yl)phenyl)-1,3,4-oxadiazoles (Ar, Ar' = Ph, naphtalenyl-2, pyrenyl-1, triphenilenyl-2), as PAH-based aza-analogues of POPOP, by means of Cu-catalyzed click reaction between 2-(4-azidophenyl)-5-Ar-1,3,4-oxadiazole and terminal ethynyl-substituted PAHs is reported. An investigation of the photophysical properties of the obtained products was carried out, and their sensory response to nitroanalytes was evaluated. In the case of pyrenyl-1-substituted aza-POPOP, dramatic fluorescence quenching by nitroanalytes was observed.
Assuntos
Hidrocarbonetos , FluorescênciaRESUMO
As a result of bright complexation properties, easy functionalization and the ability to self-organize in an aqueous solution, amphiphilic supramolecular macrocycles are being actively studied for their application in nanomedicine (drug delivery systems, therapeutic and theranostic agents, and others). In this regard, it is important to study their potential toxic effects. Here, the synthesis of amphiphilic calix[4]resorcinarene carboxybetaines and their esters and the study of a number of their microbiological properties are presented: cytotoxic effect on normal and tumor cells and effect on cellular and non-cellular components of blood (hemotoxicity, anti-platelet effect, and anticoagulant activity). Additionally, the interaction of macrocycles with bovine serum albumin as a model plasma protein is estimated by various methods (fluorescence spectroscopy, synchronous fluorescence spectroscopy, circular dichroic spectroscopy, and dynamic light scattering). The results demonstrate the low toxicity of the macrocycles, their anti-platelet effects at the level of acetylsalicylic acid, and weak anticoagulant activity. The study of BSA-macrocycle interactions demonstrates the dependence on macrocycle hydrophilic/hydrophobic group structure; in the case of carboxybetaines, the formation of complexes prevents self-aggregation of BSA molecules in solution. The present study demonstrates new data on potential drug delivery nanosystems based on amphiphilic calix[4]resorcinarenes for their cytotoxicity and effects on blood components.
Assuntos
Ésteres , Soroalbumina Bovina , Ésteres/farmacologia , Soroalbumina Bovina/química , Espectrometria de Fluorescência , Interações Hidrofóbicas e Hidrofílicas , Água/químicaRESUMO
This study aimed to evaluate the suitability of two bioaerosol generation systems (dry and wet generation) for the aerosolization of microorganisms isolated from the International Space Station, and to calibrate the produced bioaerosols to fulfill the requirements of computational fluid dynamics model (CFD) validation. Concentration, stability, size distribution, agglomeration of generated bioaerosol and deposition of bioaerosols were analyzed. In addition, the dispersion of non-viable particles in the air was studied. Experiments proved that wet generation from microbial suspensions could be used for the production of well-calibrated and stabile bioaerosols for model validation. For the simulation of the natural release of fungal spores, a dry generation method should be used. This study showed that the used CFD model simulated the spread of non-viable particles fairly well. The mathematical deposition model by Lai and Nazaroff could be used to estimate the deposition velocities of bioaerosols on surfaces, although it somewhat underestimated the measured deposition velocities.
Assuntos
Aerossóis/análise , Microbiologia do Ar , Monitoramento Ambiental , Modelos Teóricos , Astronave , Poluição do Ar em Ambientes Fechados/análise , Poluição do Ar em Ambientes Fechados/estatística & dados numéricos , Bactérias/isolamento & purificação , Fungos/isolamento & purificaçãoRESUMO
Long-term human Space missions depend on regenerative life support systems (RLSS) to produce food, water and oxygen from waste and metabolic products. Microbial biotechnology is efficient for nitrogen conversion, with nitrate or nitrogen gas as desirable products. A prerequisite to bioreactor operation in Space is the feasibility to reactivate cells exposed to microgravity and radiation. In this study, microorganisms capable of essential nitrogen cycle conversions were sent on a 44-days FOTON-M4 flight to Low Earth Orbit (LEO) and exposed to 10-3-10-4 g (gravitational constant) and 687 ± 170 µGy (Gray) d-1 (20 ± 4 °C), about the double of the radiation prevailing in the International Space Station (ISS). After return to Earth, axenic cultures, defined and reactor communities of ureolytic bacteria, ammonia oxidizing archaea and bacteria, nitrite oxidizing bacteria, denitrifiers and anammox bacteria could all be reactivated. Space exposure generally yielded similar or even higher nitrogen conversion rates as terrestrial preservation at a similar temperature, while terrestrial storage at 4 °C mostly resulted in the highest rates. Refrigerated Space exposure is proposed as a strategy to maximize the reactivation potential. For the first time, the combined potential of ureolysis, nitritation, nitratation, denitrification (nitrate reducing activity) and anammox is demonstrated as key enabler for resource recovery in human Space exploration.
Assuntos
Archaea/metabolismo , Bactérias/metabolismo , Reatores Biológicos/microbiologia , Ciclo do Nitrogênio/fisiologia , Voo Espacial , Ausência de Peso , Amônia/metabolismo , Archaea/efeitos da radiação , Bactérias/efeitos da radiação , Desnitrificação/fisiologia , Nitritos/metabolismo , Oxirredução , AstronaveRESUMO
In order to obtain a non-toxic amphiphilic calixresorcinarene capable to form nanoconjugates for drug encapsulation, tetraundecylcalixresorcinarene functionalized by methoxy poly(ethylene glycol) chains has been synthesized. The macrocycle obtained is characterized by low hemotoxicity. In aqueous solution it forms nanoassociates that are able to encapsulate organic substrates of different hydrophobicity, including drugs (doxorubicin, naproxen, ibuprofen, quercetin). The micelles of the macrocycle slowed down the release of the hydrophilic substrates in vitro. In physiological sodium chloride solution and phosphate-buffered saline, the micelles of the macrocycle acquire thermoresponsive properties and exhibit a temperature-controlled release of doxorubicin in vitro. The combination of the low toxicity and the encapsulation properties of the obtained calixresorcinarene-mPEG conjugate shows promising potential for the use as a supramolecular drug-delivery system.
RESUMO
Some important and essential features of absorption and fluorescence spectra of prodan in homogeneous and binary mixes are studied. According to results obtained from experimental and quantum-chemical researches we show that the absorption spectrum of prodan in nonpolar solvent within 25,000-50,000 cm(-1) is formed by eight electronic transitions. Quantum-chemical calculations are performed in the geometry of both the ground and exited states of prodan. The rate constants of photoprocesses and the quantum yield of fluorescence are determined for the prodan and its complexes with water. A dramatic shift of the fluorescence band at changing from nonpolar solvent to isopropyl alcohol and water is explained. The roles of general solvent effects and specific interactions are separated. According to values of molecular electrostatic potential and charges on atoms the centers of possible interaction of prodan with a solvent are obtained. Possible models of prodan complexes in water are offered. The results of quantum-chemical calculation for offered complexes of prodan in water are compared with those for the free prodan molecule. The presence of the second band (about 24,000 cm(-1)) in fluorescence spectra of prodan in isopropyl (ethyl) alcohol-water solvents is explained.
Assuntos
2-Naftilamina/análogos & derivados , Espectrometria de Fluorescência/métodos , Espectrofotometria/métodos , 2-Naftilamina/análise , 2-Naftilamina/química , 2-Propanol/química , Técnicas de Química Analítica/métodos , Ligação de Hidrogênio , Luz , Modelos Químicos , Octanos/química , Teoria Quântica , Software , Solventes/química , Eletricidade EstáticaRESUMO
Quantum-chemical calculations of ground and excited states of fluorescent probe (laurdan) by ab initio and semiempirical methods were performed. The laurdan optimized geometries of S0 and S1 states were obtained. The influence of laurdan nonrigidity structure on dipole moments and location of energy levels were studied. The specific solvation centers of laurdan were obtained. The rate constants of photoprocesses and fluorescence quantum yield of laurdan in non-polar solvent were calculated.
Assuntos
2-Naftilamina/análogos & derivados , Lauratos/química , Luminescência , 2-Naftilamina/química , Absorção Fisico-Química , Hexanos/química , Cinética , Modelos Moleculares , Conformação Molecular , Solventes/química , Espectrometria de Fluorescência , Eletricidade Estática , TemperaturaRESUMO
Here, we report on a systematic study of six calix[4]resorcinarene macrocycles bearing eight carboxylic groups on the upper rim and four different lower rim substituents that are either aliphatic (2, 4, and 5) or alkylaromatic (1, 3, and 6). The macrocycles were studied in their individual aqueous solutions and in the presence of triphenylmethane dye crystal violet. It was found that binding of crystal violet with aggregated macrocycles shields it from the bulk of solution, preventing its discoloration under basic conditions and electrochemical reduction on the glassy carbon electrode. Most efficient shielding, reducing the rate of discoloration more than 173 times, as compared to solution with no macrocycle, was achieved with 6 forming aggregates of average 72 molecules in 0.1 mM solutions.
RESUMO
Supramolecular nanoaggregates formed through the association of amphiphilic sulfonatomethylated calix[4]resorcinarenes with different substituents on the lower rim (methyl, pentyl, heptyl) and number of aromatic, aliphatic, and cationic guests differing in their shapes and sizes were investigated in aqueous solution by various NMR techniques ((1)H, 2D NOESY, FT-PGSE). It was shown that slight variations of the alkyl chain length on the lower rim of calixresorcinarenes dramatically change their aggregation behavior. Unlike the other calixresorcinarenes studied, the "head-to-tail" packing mode is observed for calixresorcinarene with pentyl moieties on the lower rim, which is unusual for amphiphilic calixarene aggregates. This calixresorcinarene demonstrates the stronger binding capacity toward the guest molecules due to their encapsulation into the capsule-like aggregate subunits. The guest-host complexation modifies the properties of both components, with the size of the resulted colloid particles being controlled by the guest nature.
RESUMO
The interaction of a macrocycle's aggregates with a guest molecule has special interest due to the double role, both of macrocycle cavity and self-associates, in the binding of the guests. Here, we report on the interactions of nonaggregated methyl-substituted (SCA1) and aggregated penthyl-substituted (SCA2) tetramethylenesulfonated calix[4]resorcinarenes with pH indicators methyl yellow (MY) and methyl orange (MO) in aqueous solutions. It was found that the pH of aqueous solutions of SCA1 and SCA2 depends on their concentration; besides, variation of the concentration of SCA1 and SCA2 results in a shift of the absorption maxima and of pH-sensitive azo dyes. Association of the marocycles with azo dyes was demonstrated to follow a proton-transfer mechanism accompanied by protonation of the dyes; it was found that excess of the macrocycle in solution with the universal buffer background shifts the pK(a) values and stabilizes the protonated form of the dyes. Consideration of interactions of small dye molecules with large molecular associates, containing both individual and multimolecule binding sites, gives a closer approximation of synthetic biomimetics to their natural prototypes.