Photosensitive Bent-Core Liquid Crystals with Laterally Substituted Azobenzene Unit

Photosensitive liquid crystals represent an important class of functional materials that experience rapid development. Hereby, we present novel bent-core liquid crystals bearing a lateral substitution on the central core and in the vicinity of the photosensitive unit—an azo group. The azo group enables fast (E)-to-(Z)-isomerization upon irradiation with UV-light and visible light, while the substitution facilitates the high stability of the photochemically formed (Z)-isomer. The effectiveness of the irradiation and the composition of photostationary states was determined by UV/Vis and 1H NMR spectroscopy. A nematic phase formed by the materials was characterized by differential scanning calorimetry and optical polarizing microscopy. We show that the materials easily change their relative configuration of the N=N double bond not only in solution, but also in the mesophase, which leads to fast isothermal phase transition from the nematic phase to isotropic liquid.

Flavylium-Based Hypoxia-Responsive Probe for Cancer Cell Imaging

A hypoxia-responsive probe based on a flavylium dye containing an azo group (AZO-Flav) was synthesized to detect hypoxic conditions via a reductase-catalyzed reaction in cancer cells. In in vitro enzymatic investigation, the azo group of AZO-Flav was reduced by a reductase in the presence of reduced nicotinamide adenine dinucleotide phosphate (NADPH) followed by fragmentation to generate a fluorescent molecule, Flav-NH2. The response of AZO-Flav to the reductase was as fast as 2 min with a limit of detection (LOD) of 0.4 μM. Moreover, AZO-Flav displayed high enzyme specificity even in the presence of high concentrations of biological interferences, such as reducing agents and biothiols. Therefore, AZO-Flav was tested to detect hypoxic and normoxic environments in cancer cells (HepG2). Compared to the normal condition, the fluorescence intensity in hypoxic conditions increased about 10-fold after 15 min. Prolonged incubation showed a 26-fold higher fluorescent intensity after 60 min. In addition, the fluorescence signal under hypoxia can be suppressed by an electron transport process inhibitor, diphenyliodonium chloride (DPIC), suggesting that reductases take part in the azo group reduction of AZO-Flav in a hypoxic environment. Therefore, this probe showed great potential application toward in vivo hypoxia detection.

Substituent and Solvent Polarity on the Spectroscopic Properties in Azo Derivatives of 2-Hydroxynaphthalene and Their Difluoroboranes Complexes

Novel fluorescent dyes such as difluoroborane complexes of 1-phenylazonaphthalen-2-ol derivatives were successfully synthesized and characterized with a focus on the influence of a substituent and a solvent on the basic photophysical properties. 1H, 11B, 13C, 15N, and 19F nuclear magnetic resonance (NMR) spectra of substituted 1-phenylazonaphthalen-2-ol difluoroboranes and their parent azo dyes were recorded and discussed. The absorption and emission properties of synthesized compounds were investigated in solvents of varying polarity. They were found to be fluorescent despite the presence of the azo group. The azo group rotation was blocked by complexing with -BF2 to get a red shift in absorption. Solvent-dependent spectral properties of compounds were investigated using Lipper-Mataga and Bakhshiev plot. The calculated DFT energies and Frontier Molecular Orbitals calculations of the studied compounds were proved to be consistent with the experimental observations.

Azopyridine-based chiral oxazolines with rare-earth metals for photoswitchable catalysis

An azopyridine-based oxazoline was developed for utilizing azo group coordination and isomerization as a photoswitchable ligand. The ligand coordinated to rare-earth metal (RE) catalyst underwent efficient E/Z photoisomerization, suggesting tri-...

INFLUENCE OF ADDITIVES OF ACID ON STAGE OF TRANSFORMATIONS OF 4-NITRO-2'-HYDROXY-5'-METHYLASOBENZENE ON SKELETONIC NICKEL IN WATER SOLUTION OF 2-PROPANOL

The article is devoted to the analysis of the reaction kinetics of hydrogenation of 4-nitro-2'-hydroxy-5'-methylazobenzene in an aqueous solution of 2-propanol with acetic acid addition on skeletal nickel at different initial quantity of the starting compound. Clarification of the sequence of transformations of compounds containing several reactive groups, and the development of approaches to controlling the selectivity of processes with their participation is a practically significant task. According to the data obtained, at both low and high initial concentrations the hydrogenation of 4-nitro-2'-hydroxy-5'-methylazobenzene on skeletal nickel in a 2-propanol aqueous solution-0.01 M CH3COOH solvent proceeds in two parallel directions. The largest contribution in the first phase of the reaction is made by the azo group conversion of the starting compound, in contrast to the reaction in an aqueous solution of 2-propanol without acid addition. An increase in the initial quantity of the hydrogenated compound above its solubility limit leads to an increase in the rate of conversion of the azo group in 4-nitro- and 2-amino-2'-hydroxy-5'-methylazobenzene. Consequently, optimum quantity of 4-nitroaniline and 2-amino-2'-hydroxy-5'-methylazobenzene in the bulk solution during hydrogenation of the specified quantity of 4-nitro-2'-hydroxy-5'-methylazobenzene practically didn’t change, in contradiction to the hydrogenation on skeletal nickel in a neutral aqueous solution of 2-propanol. In a neutral aqueous solution of 2-propanol, when passing to high concentrations of the hydrogenated compound, the maximum yield of 4-nitroaniline increases twice as long the better, while as 4-amino-2'-hydroxy-5'-methylazobenzene, is reduced conversely. The results obtained do not contradict the concept of a parallel-sequential scheme for the conversion of 4-nitro-2'-hydroxy-5'-methylazobenzene. One of the directions involves the conversion of 4-nitro-2'-hydroxy-5'-methylazobenzene through 4-nitroaniline and 2-amino-4-methylphenol due to the hydrogenation of the azo group, and the second is the conversion of 4-nitro-2'-hydroxy-5'- methylazobenzene via 4-amino-2'-hydroxy-5'-methylazobenzene by reduction of the nitro group. At the end of the reaction, all the intermediate compounds are reduced to 2-amino-4-methylphenol and 1,4-phenylenediamine. When acetic acid is introduced into the composition of the neutral solvent 2-propanol-water, the contribution of the direction that ensures the formation of 4-nitroaniline and 2-amino-4-methylphenol to the overall reaction rate increases. An increase in the initial amount of 4-nitro-2′-hydroxy-5′-methyl-azobenzene leads to an increase in the rate of conversion of the azo group in the starting compound and to a decrease in the rate of conversion of 4-amino-2′-hydroxy-5′-methylazobenzene. The effect of the acid on the change in the conversion rates of nitro and azo groups to 4-nitro-2′-hydroxy-5′-methylazobenzene does not contradict the previously obtained results for the hydrogenation of its analogue, 2-nitro-2′-hydroxy-5-methylazobenzene, as well as individual compounds containing a nitro and azo group.

HYDROGEN ROLE IN SELECTIVITY OF SUBSTITUTED NITRO-AZOBENENES HYDROGENI-ZATION ON SKELETAL NICKEL IN 2-PROPANOL AQUEOUS SOLUTIONS

Elucidation of the substituted nitrobenzenes transformations sequence, in particular, containing several reactive groups and the development of approaches to the control of the selectivity of processes involving them is of interest from both theoretical and practical points of view. The article is devoted to the analysis of the hydrogenation kinetics of 2-nitro-2'-hydroxy-5'-methylazobenzene, 4-nitro-2'-hydroxy-5'-methyl-isobenzene, 4-nitroaniline, 4-amino-2'-hydroxy-5'-methylazobenzene on skeletal nickel in 2-propanol aqueous solutions of different composition, including with the addition of acetic acid or sodium hydroxide with various initial amounts of organic compound. The rise in the 4-nitro-2'-hydroxy-5'-methylazobenzene initial amount leads to increase in the nitro group transformation rate in the starting compound and to decrease in the azo-group transformation rate. The effect of sodium hydroxide additives in the 2-propanol aqueous solution on the nitro- and azo-groups conversion rate into 4-nitro-2'-hydroxy-5'-methyl-isobenzene is analogous to the change in the individual compounds hydrogenation rates (4-nitroaniline and 4-amino-2'-hydroxy-5'-methylazobenzene). Obtained results do not contradict the parallel-sequential scheme concept for the 4-nitro-2'-hydroxy-5'-methylazobenzene transformations. One of the directions is associated with the azo-group transformation into 4-nitro-2'-hydroxy-5'-methylazobenzene and 4-nitroaniline and 2-amino-4-methylphenol formation, and the second with the 4-nitro-2'-hydroxy-5'-methyl-isobenzene conversion through 4-amino-2'-hydroxy-5'-methyl-isobenzene by the nitro-group reducing. At the reaction end, all intermediate compounds are reduced to 2-amino-4-methylphenol and 1,4-phenylenediamine. When 2-nitro-2'-hydroxy-5'-methylazobenzene is hydrogenated, one of the directions leads to the 2-nitro-2'-hydroxy-5'-methylhydrazobenzene formation, and the second to the product containing the triazole cycle - N-oxide 2-2'-hydroxy-5'-methylphenylbenzotriazole. At the reaction end, these compounds are reduced to 2-2'-hydroxy-5'-methylphenylbenzotriazole and 2-amino-4-methylphenol and 1,2-phenylenediamine, respectively. In the solution at the sodium hydroxide presence, 2-nitro-2'-hydroxy-5'-methylhydrazobenzene transforms into the N-oxide 2-2'-hydroxy-5'-methylphenylbenzotriazole as a result of intramolecular rearrangement.