Fluorescent Sensor Based on 1H-Pyrazolo[3,4-b]quinoline Derivative for Detecting Zn2+ Cations.

The photophysical and sensory properties of the donor-acceptor pyrazoloquinoline derivative (PQPc) were investigated using absorption, steady-state, and time-resolved fluorescence measurements. The compound synthesized from commercial, readily available substrates exhibited absorptions in the UV-Vis range, with a maximum of the longwave band around 390 nm. The maximum fluorescence was around 460-480 nm, depending on the solvent. The quantum yield was between 12.87% (for n-hexane) and 0.75% (for acetonitrile) and decreased with increasing solvent polarity. The PET mechanism was implicated as the cause of fluorescence quenching. Divalent ions such as Zn2+, Pb2+, Cd2+, Ca2+, Mg2+, Co2+, Ni2+, and Cu2+ were introduced to study the fluorescent response of PQPc. A 13-times increase in fluorescence quantum yield was observed after the addition of Zn2+ ions. Detailed research was carried out for the PQPc-Zn2+ system in order to check the possibility of analytical applications of PQPc as a fluorescent sensor. A detection limit of Zn2+ was set at the value level 1.93 × 10-7 M. PQPc-Zn2+ complexes had a stoichiometry of 1:1 with a binding constant of 859 M-1. Biological studies showed that the sensor was localized in cells near the membrane and cytoplasm and may be used to detect zinc ions in eukaryotic cells.

Spectral Properties of Highly Emissive Derivative of Coumarin with N,N-Diethylamino, Nitrile and Tiophenecarbonyl Moieties in Water-Methanol Mixture.

The new derivative of coumarin (E)-3-[7-(diethyloamino)-2-oxo-chromen-3yl]-2-(tiophene-2-carbonyl)prop-2-enenitrile (NOSQ) was easy synthesized with commercial substrates as a result of the search of new Michael type addition sensors based on coumarins. Spectral properties of highly emissive NOSQ were investigated by steady state analysis (absorption and fluorescence measurements) and time-resolved analysis (fluorescence lifetime measurements). The effect of water-methanol mixture on the photophysical properties of the NOSQ molecule was analyzed. With increasing of volumetric fraction of water the intensity of absorbance and fluorescence was strongly reduced. The NOSQ quantum yield in methanol was quite high and the first portions of water caused a significant increase in this value. Water, which is usually a quencher, in this case caused the increase in the quantum yield. The fluorescence lifetimes had second-order decay and the values of fluorescence lifetime increased with increasing alcohol content. Density functional theory (DFT) calculations and experimental data remained in agreement and showed that the interaction between the NOSQ molecule and the solvent affects the appearance of the new conformer.

Synthesis and Characterization of Halloysite/Carbon Nanocomposites for Enhanced NSAIDs Adsorption from Water.

The adsorption of ketoprofen, naproxen, and diclofenac (non-steroidal anti-inflammatory drugs, NSAIDs) on halloysite/carbon nanocomposites and non-modified halloysite were investigated in this work. Halloysite/carbon nanocomposites were obtained through liquid phase impregnation and carbonization using halloysite as the template and saccharose as the carbon precursor. Scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier-transform infrared spectrometry (FT-IR), and low-temperature nitrogen adsorption method were employed to study the morphological and structural changes of the halloysite/carbon nanocomposites. The effects of contact time, initial concentration of adsorbates, pH of solution, and mass of adsorbent on the adsorption were studied. Adsorption mechanism was found to fit pseudo-second-order and intra-particle diffusion models. The obtained experimental adsorption data were well represented by the Langmuir multi-center adsorption model. Adsorption ability of halloysite/carbon nanocomposites was much higher for all the studied NSAIDs in comparison to non-modified halloysite. Optimized chemical structures of ketoprofen, naproxen, and diclofenac obtained by Density Functional Theory (DFT) calculation showed that charge distributions of these adsorbate molecules and their ions can be helpful to explain the details of adsorption mechanism of NSAIDs on halloysite/carbon nanocomposites.

The self-disproportionation of enantiomers (SDE) of α-amino acid derivatives: facets of steric and electronic properties.

α-Amino acids (α-AAs) are in extremely high demand in nearly every sector of the food and health-related chemical industries and continue to be the subject of intense multidisciplinary research. The self-disproportionation of enantiomers (SDE) is an emerging and one of the least studied areas of α-AA or enantiomeric properties, critically important for their production and application. In the present work, we report a detailed study of the SDE via achiral, gravity-driven column chromatography for a set of N-acylated, N-carbonylated, N-fluoroacylated, and N-thioacylated α-amino acid esters. As well as thioacylation, attention was paid to the effect of altering the R group of the ester functionality, the side chain, or that of the acyl group attached to the amide nitrogen, whereby it was found that electron-withdrawing groups in the latter moiety had a pronounced effect on the magnitude and behavior of the resulting SDE phenomenon. Intriguingly, in the case of N-fluoroacylated derivatives, by favoring the formation of dimeric associates and effecting a strong bias toward homochiral associates over heterochiral associates, the SDE magnitude was greatly reduced contrary to intuitive expectations. Energy estimates resulted from DFT calculations.

Stationary and time-resolved spectra analysis of pyrazoloquinoline derivatives with pyridyl moiety.

Two derivatives of pyrazoloquinoline with pyridyl moiety: 6-N,N-dimethyl-3-phenyl-1-(2-pyridyl)-1H-pyrazolo[3,4-b]quinoline (DMA-1PPhPQ) and 6-N,N-dimethyl-1,3-(di-2-pyridyl)-1H-pyrazolo[3,4-b]quinoline (DMA-1,3PPQ) were synthesized with commercial substrates. The theoretical characterization of both compounds was done. Geometry optimizations give not flat structure with the first absorption band at the wavelength about 390nm for both compounds. Several electro-optical parameters were also calculated. The optical properties of DMA-1PPHPQ and DMA-1,3PPQ were investigated by ultraviolet-visible spectroscopy and stationary as well as time-resolved fluorescence. The fluorescence maximum and fluorescence quantum yield are strongly dependent on solvent polarity function. Results indicate CT fluorescence for both compounds. Because of high emission the investigated pyrazoloquinoline derivatives can be potential candidates for fabrications of electroluminescent devices.

Coherence resonances in an excitable thermochemical system with multiple stationary states.

A master equation approach is used to study the influence of internal fluctuations on the dynamics of three excitable thermochemical systems exhibiting continuous as well as discrete changes of temperature. The systems differ by the types of excitability. The dependences of the relative deviations from mean values of the interspike intervals and escape times from the stable stationary state on the size of the systems calculated from simulations of stochastic trajectories exhibit minima, which testify to the appearance of resonance phenomena. An explanation for the appearance of the stochastic resonances is presented.