One-pot Synthesis and Photophysical Studies of Α-cycloamino-substituted 5-aryl-2,2'-bipyridines.

A series of α-cycloamine substituted 2,2'-bipyridines 3ae'-3ce' was obtained via the one-pot approach based on ipso-substitution of a cyano-group in 1,2,4-triazines, followed by aza-Diels-Alder reaction in good yields. Photophysical properties, including fluorosolvatochromism, were studied for 3ae'-3ce' and were compared with α-unsubstituted 2,2'-bipyridines. In addition, dipole moments differences in ground and excited states were calculated by both Lippert-Mataga equation and DFT studies and were compared to each other. The correlation between the size of cycloamine unit and the dipole moments differences value (based on Lippert-Mataga equation) was observed. In addition charge transfer indices (DCT, Λ, H and t) were calculated to demonstrate influence of molecular structure on the intramolecular charge transfer degree.

Application of Bimetallic Hydroxide/Graphene Composites in Wastewater Treatment.

The increasing discharge of antibiotic wastewater leads to increasing water pollution. Most of these antibiotic wastewaters are persistent, strongly carcinogenic, easy to bioaccumulate, and have other similar characteristics, seriously jeopardizing human health and the ecological environment. As a commonly used wastewater treatment technology, non-homogeneous electro-Fenton technology avoids the hazards of H2O2 storage and transportation as well as the loss of desorption and reabsorption. It also facilitates electron transfer on the electrodes and the reduction of Fe3+ on the catalysts, thereby reducing sludge production. However, the low selectivity and poor activity of electro-synthesized H2O2, along with the low concentration of its products, combined with the insufficient activity of electrically activated H2O2, results in a low ∙OH yield. To address the above problems, composites of layered bimetallic hydroxides and carbon materials were designed and prepared in this paper to enhance the performance of electro-synthesized H2O2 and non-homogeneous electro-Fenton by changing the composite mode of the materials. Three composites, NiFe layered double hydroxides (LDHs)/reduced graphene oxide (rGO), NiMn LDHs/rGO, and NiMnFe LDHs/rGO, were constructed by the electrostatic self-assembly of exfoliated LDHs with few-layer graphene. The LDHs/rGO was loaded on carbon mats to construct the electro-Fenton cathode materials, and the non-homogeneous electro-Fenton oxidative degradation of organic pollutants was realized by the in situ electrocatalytic reduction of O2 to ∙OH. Meanwhile, the effects of solution pH, applied voltage, and initial concentration on the performance of non-homogeneous electro-Fenton were investigated with ceftazidime as the target pollutant, which proved that the cathode materials have an excellent electro-Fenton degradation effect.

Design, Synthesis, and Photophysical Properties of 5-Aminobiphenyl Substituted [1,2,4]Triazolo[4,3-c]- and [1,2,4]Triazolo[1,5-c]quinazolines.

Two series of novel [1,2,4]triazolo[4,3-c]- and [1,2,4]triazolo[1,5-c]quinazoline fluorophores with 4'-amino[1,1']-biphenyl residue at position 5 have been prepared via Pd-catalyzed cross-coupling Suzuki-Miyaura reactions. The treatment of 2-(4-bromophenyl)-4-hydrazinoquinazoline with orthoesters in solvent-free conditions or in absolute ethanol leads to the formation of [4,3-c]-annulated triazoloquinazolines, whereas [1,5-c] isomers are formed in acidic media as a result of Dimroth rearrangement. A 1D-NMR and 2D-NMR spectroscopy, as well as a single-crystal X-ray diffraction analysis, unambiguously confirmed the annelation type and determined the molecular structure of p-bromophenyl intermediates and target products. Photophysical properties of the target compounds were investigated in two solvents and in the solid state and compared with those of related 3-aryl-substituted [1,2,4]triazolo[4,3-c]quinazolines. The exclusion of the aryl fragment from the triazole ring has been revealed to improve fluorescence quantum yield in solution. Most of the synthesized structures show moderate to high quantum yields in solution. Additionally, the effect of solvent polarity on the absorption and emission spectra of fluorophores has been studied, and considerable fluorosolvatochromism has been stated. Moreover, electrochemical investigation and DFT calculations have been performed; their results are consistent with the experimental observation.

Pillararenes as Promising Carriers for Drug Delivery.

Since their discovery in 2008 by N. Ogoshi and co-authors, pillararenes (PAs) have become popular hosts for molecular recognition and supramolecular chemistry, as well as other practical applications. The most useful property of these fascinating macrocycles is their ability to accommodate reversibly guest molecules of various kinds, including drugs or drug-like molecules, in their highly ordered rigid cavity. The last two features of pillararenes are widely used in various pillararene-based molecular devices and machines, stimuli-responsive supramolecular/host-guest systems, porous/nonporous materials, organic-inorganic hybrid systems, catalysis, and, finally, drug delivery systems. In this review, the most representative and important results on using pillararenes for drug delivery systems for the last decade are presented.

Comparison of Photophysical Properties of Lanthanide(III) Complexes of DTTA- or DO3A-Appended Aryl-2,2'-Bipyridines.

New Tb(III) and Eu(III) complexes based on aryl-2,2'-bipyridine ligands with a cyclic DO3A chelating unit appended in the alpha position of the bipyridine core were synthesized. The photophysical properties of these complexes were compared with those of complexes of ligands with identical aryl-2,2'-bipyridine chromophores, but with an acyclic DTTA residue as an additional chelating site in the alpha position of the bipyridine core. The nature of the polyaminocarboxylic acid fragments was found to have a significant influence on the luminescence. For some of the Eu(III) complexes, upon the transition from acyclic DTTA- to the cyclic DO3A-appended ligands, a noticeable increase in the intensity of Eu(III) luminescence was observed, with an increase in the quantum yield of up to 2.55 times. In contrast, for most of the Tb(III) complexes, a similar transition resulted in a noticeable decrease in the luminescence intensity of the Tb(III) cation.

3-Aryl-5-aminobiphenyl Substituted [1,2,4]triazolo[4,3-c]quinazolines: Synthesis and Photophysical Properties.

Amino-[1,1']-biphenyl-containing 3-aryl-[1,2,4]triazolo[4,3-c]quinazoline derivatives with fluorescent properties have been designed and synthesized. The type of annelation of the triazole ring to the pyrimidine one has been unambiguously confirmed by means of an X-ray diffraction (XRD) method; the molecules are non-planar, and the aryl substituents form the pincer-like conformation. The UV/Vis and photoluminescent properties of target compounds were investigated in two solvents of different polarities and in a solid state. The samples emit a broad range of wavelengths and display fluorescent quantum yields of up to 94% in toluene solutions. 5-(4'-Diphenylamino-[1,1']-biphenyl-4-yl)-3-(4-(trifluoromethyl)phenyl)-[1,2,4]triazolo[4,3-c]quinazoline exhibits the strongest emission in toluene and a solid state. Additionally, the solvatochromic properties were studied for the substituted [1,2,4]triazolo[4,3-c]quinazolines. Moreover, the changes in absorption and emission spectra have been demonstrated upon the addition of water to MeCN solutions, which confirms aggregate formation, and some samples were found to exhibit aggregation-induced emission enhancement. Further, the ability of triazoloquinazolines to detect trifluoroacetic acid has been analyzed; the presence of TFA induces changes in both absorption and emission spectra, and acidochromic behavvior was observed for some triazoloquinazoline compounds. Finally, electronic-structure calculations with the use of quantum-chemistry methods were performed for synthesized compounds.

New Degradable Semiconducting Polymers for Photoacoustic Imaging of λ-Carrageenan-Induced Arthritis Mouse Model.

Semiconducting polymer has a high extinction coefficient and a long band absorption and can be used as a photoacoustic imaging contrast agent. However, nonbiodegradable semiconducting polymers may cause biosafety issues due to being retained in the body. Therefore, developing degradable semiconducting polymers is necessary for in vivo imaging. Herein, we developed three degradable semiconducting polymers with unique optical properties. We adjusted the optical properties of semiconducting polymers by designing the molecular structure of semiconducting polymers. Polymers with a donor-π-acceptor structure could easily improve the optical properties through adjusting the donor or acceptor units. Through adjusting the electron-donor and -acceptor units, three diketopyrrolopyrrole derivative polymers (DPPTz, DPPQu, and DPPWu) were synthesized and converted into nanosize particles. By introducing the degradable chemical groups in the main chain structure of semiconducting polymers, diketopyrrolopyrrole polymers could be degraded by ClO-. Among these nanosize particles, DPPTz NPs and DPPQu NPs were used to achieve the in vivo photoacoustic imaging of λ-carrageenan-induced arthritis mouse model. This work provides a novel design idea for the designing of red-shifted semiconducting polymer with degradable properties.

Synthetic approaches to 1,2,4-triazolo[5,1-c][1,2,4]triazin-7-ones as basic heterocyclic structures of the antiviral drug Riamilovir ("Triazavirin®") active against SARS-CoV-2 (COVID-19).

Fragments of 1,2,4-triazolo[5,1-c][1,2,4]triazin-7-one are found in many compounds with various types of biological activities, including the antiviral drug Riamilovir (Triazavirin®), which shows activity against SARS-CoV-2 (COVID-19). Therefore, the development of convenient methods for the synthesis of new derivatives of 1,2,4-triazolo[5,1-c][1,2,4]triazin-7-one is always in demand. This review systematizes the information on the most common synthetic methods for constructing the 1,2,4-triazolo[5,1-c][1,2,4]triazin-7-one heterocyclic system.

Asymmetrically Functionalized 1,3-Di(2-pyridyl)benzenes: Synthesis and Photophysical Studies.

A convenient synthetic approach to asymmetrically functionalized 1,3-di(2-pyridyl)benzenes starting from 3-(3-bromophenyl)-1,2,4-triazines using sequential aza-Diels-Alder reactions and Stille cross-coupling is reported. Photophysical properties of the obtained compounds are studied.

Mechanochemical Approach towards Multi-Functionalized 1,2,3-Triazoles and Anti-Seizure Drug Rufinamide Analogs Using Copper Beads.

Highly regiospecific, copper-salt-free and neat conditions have been demonstrated for the 1,3-dipolar azide-alkyne cycloaddition (AAC) reactions under mechanochemical conditions. A group of structurally challenging alkynes and heterocyclic derivatives was efficiently implemented to achieve highly functionalized 1,4-disubstituted-1,2,3-triazoles in good to excellent yield by using the Cu beads without generation of unwanted byproducts. Furthermore, the high-speed ball milling (HSBM) strategy has also been extended to the synthesis of the commercially available pharmaceutical agent, Rufinamide, an antiepileptic drug (AED) and its analogues. The same strategy was also applied for the synthesis of the Cl-derivative of Rufinamide. Analysis of the single crystal XRD data of the triazole was also performed for the final structural confirmation. The Cu beads are easily recoverable from the reaction mixture and used for the further reactions without any special treatment.

Synthesis and Photophysical Properties of α-(N-Biphenyl)-Substituted 2,2'-Bipyridine-Based Push-Pull Fluorophores.

A series of new α-(N-biphenyl)-substituted 2,2'-bipyridines were obtained through the combination of the ipso-nucleophilic aromatic substitution of the C5-cyano group, aza-Diels-Alder and Suzuki cross-coupling reactions, starting from 5-cyano-1,2,4-triazines. For the obtained compounds, photophysical and fluorosolvatochromic properties were studied. Fluorophores 3l and 3b demonstrated unexpected AIEE activity, while 3a and 3h showed promising nitroexplosive detection abilities.

Fluorescent Pyranoindole Congeners: Synthesis and Photophysical Properties of Pyrano[3,2-f], [2,3-g], [2,3-f], and [2,3-e]Indoles.

This paper reports the synthesis of four types of annulated pyranoindole congeners: pyrano[3,2-f]indole, pyrano[2,3-g]indole, pyrano[2,3-f]indole, and pyrano[2,3-e]indole and photophysical studies in this series. The synthesis of pyrano[3,2-f], [2,3-g], and [2,3-e]indoles involve a tandem of Bischler-Möhlau reaction of 3-aminophenol with benzoin to form 6-hydroxy- or 4-hydroxyindole followed by Pechmann condensation of these hydroxyindoles with ß-ketoesters. Pyrano[2,3-f]indoles were synthesized through the Nenitzescu reaction of p-benzoquinone and ethyl aminocrotonates and subsequent Pechmann condensation of the obtained 5-hydroxyindole derivatives. Among the pyranoindoles studied, the most promising were pyrano[3,2-f] and [2,3-g]indoles. These compounds were characterized by moderate to high quantum yields (30-89%) and a large (9000-15,000 cm-1) Stokes shift. More detailed photophysical studies were carried out for a series of the most promising derivatives of pyrano[3,2-f] and [2,3-g]indoles to demonstrate their positive solvatochromism, and the data collected was analyzed using Lippert-Mataga equation. Quantum chemical calculations were performed to deepen the knowledge of the absorption and emission properties of pyrano[3,2-f] and [2,3-g]indoles as well as to explain their unusual geometries and electronic structures.

New TEMPO-Appended 2,2'-Bipyridine-Based Eu(III), Tb(III), Gd(III) and Sm(III) Complexes: Synthesis, Photophysical Studies and Testing Photoluminescence-Based Bioimaging Abilities.

Linked to Alzheimer's disease (AD), amyloids and tau-protein are known to contain a large number of cysteine (Cys) residues. In addition, certain levels of some common biogenic thiols (cysteine (Cys), homocysteine (Hcy), glutathione (GSH), etc.) in biological fluids are closely related to AD as well as other diseases. Therefore, probes with a selective interaction with the above-mentioned thiols can be used for the monitoring and visualizing changes of (bio)thiols in the biological fluids as well as in the brain of animal models of Alzheimer's disease. In this study, new Eu(III), Tb(III), Gd(III) and Sm(III) complexes of 2,2'-bipyridine ligands containing TEMPO fragments as receptor units for (bio)thiols are reported. The presence of free radical fragments of the ligand in the complexes was proved by using the electronic paramagnetic resonance (EPR) method. Among all the complexes, the Eu(III) complex turned out to be the most promising one as luminescence- and spin-probe for the detection of biogenic thiols. The EPR and fluorescent titration methods showed the interaction of the resulting complex with free Cys and GSH in solution. To study the practical applicability of the probes for the monitoring of AD in-vivo, by using the above-mentioned Eu(III)-based probe, the staining of the brain of mice with amyloidosis and Vero cell cultures supplemented with the cysteine-enriched medium was studied as well as the fluorescence titration of Bovine Serum Albumin, BSA (as the model for the thiol moieties containing protein), was carried out. Based on the results of fluorescence titration, the formation of a non-covalent inclusion complex between the above-mentioned Eu(III) complex and BSA was suggested.

4-(Aryl)-Benzo[4,5]imidazo[1,2-a]pyrimidine-3-Carbonitrile-Based Fluorophores: Povarov Reaction-Based Synthesis, Photophysical Studies, and DFT Calculations.

A series of novel 4-(aryl)-benzo[4,5]imidazo[1,2-a]pyrimidine-3-carbonitriles were obtained through the Povarov (aza-Diels-Alder) and oxidation reactions, starting from benzimidazole-2-arylimines. Based on the literature data and X-ray diffraction analysis, it was discovered that during the Povarov reaction, [1,3] sigmatropic rearrangement leading to dihydrobenzimidazo[1,2-a]pyrimidines took place. The structures of all the obtained compounds were confirmed based on the data from 1H- and 13C-NMR spectroscopy, IR spectroscopy, and elemental analysis. For all the obtained compounds, their photophysical properties were studied. In all the cases, a positive emission solvatochromism with Stokes shifts from 120 to 180 nm was recorded. Aggregation-Induced Emission (AIE) has been illustrated for compound 6c using different water fractions (fw) in THF. The compounds 6c and 6f demonstrated changes in emission maxima or/and intensities after mechanical stimulation.

5-Aryl-6-arylthio-2,2'-bipyridine and 6-Arylthio-2,5-diarylpyridine Fluorophores: Pot, Atom, Step Economic (PASE) Synthesis and Photophysical Studies.

A PASE (pot, step, atom, economic) synthetic approach to 5-aryl-6-arylthio-2,2'-bipyridine and 6-arylthio-2,5-diarylpyridine ligands/fluorophores has been reported via SNH in 6-aryl-5H-1,2,4-triazines/aza-Diels-Alder reaction sequence. In this article, the "1,2,4-triazine" methodology was successfully used for the synthesis of C6-thiophenol-substituted (2,2'-bi)pyridines as it is well known that thio-substituted (bi)pyridines and their aza-analogs are of wide practical interest. The photophysical properties of the obtained compounds are studied and compared with those reported earlier for 6-substituted 2,2'-bipyridines. The influence of the nature of substituents in the 6-arylthio(bi)pyridine core on the photophysical properties is discussed. It was observed that the new compounds exhibited promising photophysical properties and could be considered as potential push-pull fluorophores. In addition, they demonstrated greater Stokes shift values compared to the previously described 6-H, 6-arylamino and 6-pentafluoro-2,2'-bipyridines and higher fluorescence quantum yields values compare to pentafluorophenyl-substituted 2,2'-bipyridines. Depending on a nature of (bi)pyridine fluorophore LE (locally excited) and/or ICT (intramolecular charge transfer) state were prevailing in emission spectra.

Recent advances in the synthesis of fluorinated compounds via an aryne intermediate.

The development of new methodologies for the synthesis of fluorinated organic molecules is in high demand due to their wide applications in agriculture and pharmaceutical sciences. Various strategies have been employed for this purpose for a long time. Arynes are well known synthetic intermediates and have gained the attention of synthetic chemists for the synthesis of various functionalized organic molecules. Consequently, these synthetic intermediates have been successfully employed in the synthesis of fluorinated organic moieties. Various useful fluorinated aromatic and heterocyclic molecules have been synthesized employing aryne intermediates. In this review, we will discuss all these methodologies developed in the last decade via aryne intermediates.

Studies on the interactions of 5-R-3-(2-pyridyl)-1,2,4-triazines with arynes: inverse demand aza-Diels-Alder reaction versus aryne-mediated domino process.

The interactions between substituted 5-R-3-(pyridyl-2)-1,2,4-triazines with in situ generated substituted aryne intermediates have been studied. The reaction afforded either inverse demand (ID) aza-Diels-Alder products or 1,2,4-triazine ring rearrangement (domino) products as major ones depending on the nature of both the substituents at the C5 position of the 1,2,4-triazine core or in the aryne moiety. The structures of the key products were confirmed based on X-ray data. Based on the density functional theoretical (DFT) studies of the Diels-Alder transition state geometries, the influence of the nature of arynes on the direction of the 1,2,4-triazine transformation has been proposed.

Mechanosynthesis of Polyureas and Studies of Their Responses to Anions.

Polyureas (PUs) have already found wide practical applications, and various methods of their synthesis have been reported. In this manuscript, we wished to report the very first mechanochemical approach towards aromatic PUs via reactions between isomeric 2,2'-, 3,3'-, and 4,4'-diaminobiphenyls and triphosgene under solvent-free conditions following ball-milling. By using this synthetic approach, both PUs and azomethine-capped Pus were obtained. The fluorescence response of the above-mentioned PUs towards various anions in solutions were studied and selective fluorescence responses towards the hydroxyl and fluoride anions were observed.

Polymers and Polymer-Based Materials for the Detection of (Nitro-)explosives.

Methods for the remote detection of warfare agents and explosives have been in high demand in recent times. Among the several detection methods, fluorescence methods appear to be more convenient due to their low cost, simple operation, fast response time, and naked-eye-visible sensory response. For fluorescence methods, a large variety of fluorescent materials, such as small-molecule-based fluorophores, aggregation-induced emission fluorophores/materials, and supramolecular systems, have been reported in the literature. Among them, fluorescent (bio)polymers/(bio)polymer-based materials have gained wide attention due to their excellent mechanical properties and sensory performance, their ability to recognize explosives via different sensing mechanisms and their combinations, and, finally, the so-called amplification of the sensory response. This review provides the most up-to-date data on the utilization of polymers and polymer-based materials for the detection of nitroaromatic compounds (NACs)/nitro-explosives (NEs) in the last decade. The literature data have been arranged depending on the polymer type and/or sensory mechanism.

Xanthone-1,2,4-triazine and Acridone-1,2,4-triazine Conjugates: Synthesis and Anticancer Activity.

A total of 21 novel xanthone and acridone derivatives were synthesized using the reactions of 1,2,4-triazine derivatives with 1-hydroxy-3-methoxy-10-methylacridone, 1,3-dimethoxy-, and 1,3-dihydroxanthone, followed by optional dihydrotiazine ring aromatization. The synthesized compounds were evaluated for their anticancer activity against colorectal cancer HCT116, glioblastoma A-172, breast cancer Hs578T, and human embryonic kidney HEK-293 tumor cell lines. Five compounds (7a, 7e, 9e, 14a, and 14b) displayed good in vitro antiproliferative activities against these cancer cell lines. Compounds 7a and 7e demonstrated low toxicity for normal human embryonic kidney (HEK-293) cells, which determines the possibility of further development of these compounds as anticancer agents. Annexin V assay demonstrated that compound 7e activates apoptotic mechanisms and inhibits proliferation in glioblastoma cells.