Azo Derivatives Research Articles

Smart gated magnetic silica mesoporous particles for targeted colon drug delivery: New approaches for inflammatory bowel diseases treatment

Magnetic mesoporous silica microparticles were loaded with safranin O (S1) and with hydrocortisone (S2) and the outer surface functionalized with a bulky azo derivative bearing urea moieties. Aqueous suspensions of both solids at pH 7.4 showed negligible payload release whereas a marked delivery was observed in the presence of sodium dithionite due to the rupture of the azo bonds. Besides, a moderate cargo release was observed at acidic pH due to the hydrolysis of the urea bonds that linked the azo derivative onto the external surface of the inorganic scaffolds. In vitro digestion models showed that S1 and S2 microparticles could be used for the controlled release of payload in the reducing colon environment (in which azoreductase enzymes are present). On the other hand, in vivo pharmacokinetic studies in rats showed that safranine O release from S1 microparticles was concentrated in colon. The performance of S2 microparticles for the treatment of colitis in rats (induced by oral administration of a 2,4,6-trinitrobenzenesulfonic acid solution) was tested. The controlled release of hydrocortisone from S2 in the colon of injured rats induced marked reduction in colon/body weight ratio and in clinical activity score. Also, histological studies showed a marked decrease in inflammation followed by intensive regeneration and almost normal mucosal structure of the individuals treated with S2. Besides, the use of a magnetic belt increased the therapeutic performances of S2 due to an enhanced retention time of the particles in the colon.

Azo dye with nitrogen donor sets of atoms and its metal complexes: Synthesis, characterization, DFT, biological, anticancer and Molecular docking studies

An azo derivative was synthesized by coupling diazotized 2,6‐diaminopyridine with p‐dimethyl amino benzaldehyde and this new ligand formed a series of metal complexes with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) salts. These complexes were characterized on the basis of elemental analyses, molar conductance, infrared spectroscopy, UV–Vis, 1H NMR, mass spectrometry, electronic spectra, magnetic susceptibility and ESR spectral studies, conductivity measurements, thermogravimetric analyses (TG‐DTG). The molecular and electronic structure of the azo ligand was optimized theoretically and the quantum chemical parameters were calculated. The ligand and its metal complexes were subjected to X‐ray powder diffraction study. The thermal stability of the ligand and its metal complexes was examined by thermogravimetry. The ligand and its complexes were tested for their in vitro antimicrobial activity, some of the complexes showed good antimicrobial activities against some selected bacterial and fungal strains. Anticancer activity of the ligand and its metal complexes are evaluated against human cancer (MCF‐7 cells viability). Molecular docking was used to predict the binding between azo ligand and the receptors of nucleoside diphosphate kinase of Staphylococcus aureus (3Q8U) and (3HB5) which is breast cancer mutant oxidoreductase. The docking study provided useful structural information for inhibition studies.

Azo Derivatives of Phenol and 1-Naphthol as Flotation Collector of Sulfide Ore of Non-Ferrous Metals

Nine heterocyclic and aromatic azo derivatives of phenol and 1-naphthol were studied as flotation collectors of sulfide ores of non-ferrous metals. The constants of acid dissociation of compounds in aqueous solutions and their solubility in alkaline media are determined. It has been established that the adsorption of reagents on the surface of sulfide copper-nickel ore has a physical character. The adsorption constants are calculated. It is shown that the reagents under study exhibit collective properties with respect to the sulfide minerals of copper, cobalt and nickel. The use of mixtures of azo compounds with potassium butyl xanthate leads to an increase in both the recovery degree and the quality of the concentrate for nickel and copper in comparison with a single butyl xanthate.

A concept for stimulated proton transfer in 1-(phenyldiazenyl)naphthalen-2-ols

A series of aryl azo derivatives of naphthols (1–3) were studied by means of UV–Vis and NMR spectroscopy in different solvents as well as by quantum chemical calculations and X-ray analysis. Previous studies have shown that Sudan I (1) exists as a tautomeric mixture. The effect of the solvents is minimized by the existing intramolecular hydrogen bond. Therefore, the influence on the tautomeric state in structurally modified 1 has been investigated. Structure 2 contains an additional OH-group, which deprotonates easily and affects the position of the tautomeric equilibrium by changing the electronic properties of the substituent. The implementation of a sidearm in 3 creates a condition for competition between the nitrogen from the azo group and from the piperidine unit for the tautomeric proton. In this case the use of acid as a stimulus for controlling the tautomeric process was achieved.

Synthesis, Characterization and Biological Activity Evaluation of Some New Azo Derivatives from 2- Amino Benzothiazole and Their Derivatives

This study includes synthesis 2-amino benzothiazole and its substitutes (M1-M14) by the reaction of aniline derivatives with KSCN in presence of Br2 and glacial acetic acid then neutralize by concentrated ammonia solution or (by 50% NaOH). The prepared compounds (M3-M5-M6-M11) were used for preparation diazonium salts through reaction with NaNO2 and HCl, at that point diazonium salts were utilized specifically interaction with 4-amino antipyrine and 4-amino-3-hydroxy-1-naphthalene sulphonic acid (in alkaline medium) to produce azo dyes (M15-M22). These compounds were characterized by their physical properties, spectroscopic information (FT-IR, 1H-NMR, 13C-NMR and CHNS elemental analysis), and also to systematically defining of a few active functional groups for these prepared compounds. The biological activity evaluated for four of prepared compounds towards four kinds of bacteria

Synthesis, properties and structure of copper(II) complexes of quinolyl azo derivatives of pyrazole-5-one(thione)

The interaction of 5-methyl-2-phenyl-4-[(8-quinolylhydrazono)]pyrazol-3-one (2) and 5-methyl-2-phenyl-4-(8-quinolylhydrazono)pyrazole-3-thione (4) with copper(II) acetate monohydrate under reflux in ethanol results in the formation of copper(II) azo chelates incorporating CuN4O2 (5) and CuN3S2 (6) chromophores. All the compounds were characterized with FT-IR, EPR, X-ray absorption spectroscopy and magnetic measurements. The structures of complexes 5 and 6 were determined by X-ray single-crystal diffraction. Complex 5 adopts a pseudo-octahedral geometry with a cis disposition of the oxygen atoms around the copper(II) centre, whilst in 6 the copper(II) ion displays a square-pyramidal geometry with a {N3S2} ligand environment.

Cis-to- Trans Isomerization of Azobenzene Derivatives Studied with Transition Path Sampling and Quantum Mechanical/Molecular Mechanical Molecular Dynamics.

Azobenzene-based molecular photoswitches are becoming increasingly important for the development of photoresponsive, functional soft-matter material systems. Upon illumination with light, fast interconversion between a more stable trans and a metastable cis configuration can be established resulting in pronounced changes in conformation, dipole moment or hydrophobicity. A rational design of functional photosensitive molecules with embedded azo moieties requires a thorough understanding of isomerization mechanisms and rates, especially the thermally activated relaxation. For small azo derivatives considered in the gas phase or simple solvents, Eyring's classical transition state theory (TST) approach yields useful predictions for trends in activation energies or corresponding half-life times of the cis isomer. However, TST or improved theories cannot easily be applied when the azo moiety is part of a larger molecular complex or embedded into a heterogeneous environment, where a multitude of possible reaction pathways may exist. In these cases, only the sampling of an ensemble of dynamic reactive trajectories (transition path sampling, TPS) with explicit models of the environment may reveal the nature of the processes involved. In the present work we show how a TPS approach can conveniently be implemented for the phenomenon of relaxation-isomerization of azobenzenes starting with the simple examples of pure azobenzene and a push-pull derivative immersed in a polar (DMSO) and apolar (toluene) solvent. The latter are represented explicitly at a molecular mechanical (MM) and the azo moiety at a quantum mechanical (QM) level. We demonstrate for the push-pull azobenzene that path sampling in combination with the chosen QM/MM scheme produces the expected change in isomerization pathway from inversion to rotation in going from a low to a high permittivity (explicit) solvent model. We discuss the potential of the simulation procedure presented for comparative calculation of reaction rates and an improved understanding of activated states.

Functional Magnetic Mesoporous Silica Microparticles Capped with an Azo-Derivative: A Promising Colon Drug Delivery Device.

Magnetic micro-sized mesoporous silica particles were used for the preparation of a gated material able to release an entrapped cargo in the presence of an azo-reducing agent and, to some extent, at acidic pH. The magnetic mesoporous microparticles were loaded with safranin O and the external surface was functionalized with an azo derivative 1 (bearing a carbamate linkage) yielding solid S1. Aqueous suspensions of S1 at pH 7.4 showed negligible safranin O release due to the presence of the bulky azo derivative attached onto the external surface of the inorganic scaffold. However, in the presence of sodium dithionite (azoreductive agent), a remarkable safranin O delivery was observed. At acidic pH, a certain safranin O release from S1 was also found. The pH-triggered safranin O delivery was ascribed to the acid-induced hydrolysis of the carbamate moiety that linked the bulky azo derivatives onto the mesoporous inorganic magnetic support. The controlled release behavior of S1 was also tested using a model that simulated the gastro intestinal tract.

Greener synthesis, antimicrobial screening and plant growth regulator (PGR) evaluation of some novel azo (dipyrano) derivatives

Greener synthesis, antimicrobial screening and plant growth regulator (PGR) evaluation of some novel azo (dipyrano) derivatives

Activation volumes for cis-to-trans isomerisation reactions of azophenols: a clear mechanistic indicator?

The thermal cis-to-trans isomerisation reaction of a series of hydroxy-substituted azo derivatives was studied kinetico-mechanistically as a function of temperature and pressure in order to investigate the possible role of the solvent in controlling the isomerisation mechanism, viz. inversion versus rotation. The variation of the observed first order rate constants for kinetic runs carried out at different temperatures and pressures was used to determine the thermal activation parameters ΔH‡ and ΔS‡, and the pressure activation parameter ΔV‡. In addition, some experiments with deuterated species or solvents were also performed. The reported results could be interpreted as indicative of a changeover from an inversion mechanism for non-polar solvents to a rotational mechanism for polar solvents, capable of hydrogen bonding, for some of the systems studied. However, the operation of a rotational mechanism in all studied cases can account more consistently for the data observed.

Evaluation of oxidative enzymes for efficient oxidation of aniline and phenolic pollutants

Tyrosinases, laccases, and peroxidases are three important groups of oxidative enzymes. A characteristic feature of these enzymes is their ability for the oxidation of aniline and phenolic compounds. Literature review reveals some overlap between the organic substrates of these enzymes, but how exactly they are different and how much they have in common from both substrate structure and rate of oxidation points of views. Can they complete functional efficiency of each other when co-immobilized in a multi-enzymes system? To address these questions, edible mushroom (Agaricus bisporus) tyrosinase, Neurospora crassa laccase, and horseradish peroxidase were examined for the oxidation of azo derivatives of anilines and phenols. These substances were selected because their enzymatic degradation is of interest to environmentalists and can be followed spectrophotometrically. Experiments showed that tyrosinase and laccase had limitations in oxidizing these substances, especially anilines, while peroxidase oxidized all the selected compounds. However, substrates carrying electron-withdrawing substituents had slower oxidation. Co-immobilization of tyrosinase and laccase would be effective against phenolic compounds, but phenols oxidation proceeds faster (between 100 and 500 times) if peroxidase and H2O2 are used. Combination of peroxidase and H2O2, instead of co-immobilization of tyrosinase, laccase, and peroxidase, seems to be more promising for the removal of organic pollutants from contaminated water resources.

Synthesis and characterization of mixed Amides-Imines and Amides-Azo Compound derived from Chrysanthemic acid and trimethoprim and study their biological activities

Chrysanthemic acid, Trimethoprim, amides, Imines and azo compound : all found to have enormous biological activities in different directions such as medical , pharmaceutical pesticidal …etc. Accordingly combination of these functional in on compound expected to enhances their activities. Therefore mixed amides – imines and amides – diazo derived from trimethoprim and chrysanthemic acid, have been prepared by reaction of equimolar amount of these compound to form the corresponding mono amides , which on treatment of the remaining amino group of the trimethoprim with some aromatic aldehydes give the corresponding imines ; or diazo compounds on reaction with nitrous acid followed by reaction with aromatic phenols and naphthols . The structures of these derivatives were confirmed by their physical properties and spectroscopic techniques such as FT-IR ; 1Hnmr and mass spectrometry for selected compound. In addition the biological evaluation of the synthesized compound have been studied through the investigation of its capacity to scavenge the free radical (DPPH.) to give an inhibition at 50% concentration (IC50) , using the butylated hydroxyl toluene (BHT) as a control. This study reveals the highest scavenging for the azo derivatives .

Structural and catalytic properties of some azo-rhodanine Ruthenium(III) complexes

Novel azo-rhodanine ruthenium(III) complexes of the type trans-[Ru(Ln)2(AsPh3)2]Cl (Ln = monobasic bidentate anions of 5-(4′-methoxyphenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL1), 5-(phenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL2) and 5-(4′-chlorophenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL3); AsPh3 = triphenylarsine) have been synthesized and characterized by elemental analysis, spectroscopic (IR, 1H NMR and UV–VIS), magnetic, X-ray diffraction, mass spectra and thermal analysis techniques. These techniques confirm the formation of octahedral ruthenium(III) complexes. The Ru(III) complexes were tested as a catalysts for the oxidation of benzyl alcohol to benzaldehyde with N-methylmorpholine-N-oxide as a co-oxidant. The effect of time, temperature, and solvent were also studied and the mechanism of this catalytic oxidation reaction is suggested. Molecular docking was used to predict the binding between azo rhodanine derivatives (HLn) with the receptor of 3qum- immune system receptor of human prostate specific antigen (PSA) in a Fab sandwich with a high affinity and a PCa selective antibody.

Design and synthesis of three series of novel antitumor–azo derivatives

Three new series of thiazoles, quinolones, and thiazolidinones merged with benzimidazole, benzoxazole, and benzothiazole nuclei were synthesized. The compounds were subjected to Infrared, 1H nuclear magnetic resonance, 13C nuclear magnetic resonance, mass spectrometry, and elemental analyses. Cytotoxic activity of compounds were evaluated against breast (MCF-7) and colon (HCT-116) cell lines. Seven of the compounds had IC50 values between 0.0112 and 0.0198 µM and are hence more potent than the reference drug doxorubicin (IC50 = 0.0084 and 0.0088 µM against MCF-7 and HCT-116, respectively).

The novel photoresponsive oligomers containing azo derivatives of sulfamerazine for spontaneous surface relief grating inscription

In this work, a novel photoresponsive materials has been successfully developed. We have synthesized the series of azopolymers containing derivatives of sulfamerazine and studied their photochromic properties. The polymers were obtained from methacrylate azomonomers, butyl methacrylate and isobornyl methacrylate by radical polymerization. Spectral properties and photoisomerization kinetic constants were determined for thin transparent films, using UV–Vis spectroscopy. The maximum absorption of the films was observed at 432–440nm. The obtained materials showed ability to reversible trans–cis photoisomerization. Reversibility of the process was confirmed during ellipsometric measurements. The change of the real part of the complex refractive index induced by laser irradiation was between 0.010 and 0.053. Additionally, some properties of described polymers and azobenzene derivatives were calculated and were utilized in order to better understand the differences in the photochromic behaviour of the new materials. Moreover, we determined the suitability of the obtained azopolymers for spontaneous surface relief grating inscription. Spontaneous surface relief grating recording on the thin azopolymer films was carried out using set-up with one laser beam. The spontaneous SRG was successfully recorded in all investigated polymers.

Small-Molecule Activation Mediated by a Uranium Bipyridyl Metallocene

Addition of potassium graphite (KC8) to a solution of (η5-C5Me5)2UCl2 (1) and 2,2′-bipyridine (bipy) gives the uranium bipyridyl metallocene (η5-C5Me5)2U(bipy) (2) in good yield. In complex 2 a bipy radical anion is coordinated to a U(III) atom, and it is therefore an ideal starting material for small-molecule activation: e.g., it serves as a synthetic equivalent for the (η5-C5Me5)2UII fragment on treatment with conjugated alkynes and a variety of heterounsaturated molecules such as imines, carbodiimide, organic azides, hydrazine, and azo derivatives. Alternatively, it may also react with aldehydes, ketones, nitriles, and α,β-unsaturated reagents such as p-ClPhCHO, (CH2)5CO, PhCN, and methyl methacrylate (MMA), forming the C–C bond coupling products (η5-C5Me5)2U[(bipy)(p-ClPhCHO)] (10), (η5-C5Me5)2U[(bipy){(CH2)5CO}] (11), (η5-C5Me5)2U[(bipy)(PhCN)] (12), (η5-C5Me5)2U[(bipy){CH2═C(Me)CO(OMe)] (13a), and [(η5-C5Me5)2U{OC(OMe)═C(Me)CH2–3-bipy}]2 (13b), respectively, in quantitative conversion. Furthermore, ...

Synthesis and antimicrobial evaluation of some new hydrazo, dihydropyridazinyl and triazolyl derivatives containing indole nucleus

PurposeThe aim of this paper is synthesis of some new hydrazo, dihydropyridazinyl and triazolyl derivatives containing indole nucleus and their antimicrobial evaluation.Design/methodology/approachTreatment of 3-(1H-indol-3-yl)-3-oxopropanenitrile (1) with different aryl diazonium salts 2a-j gave the corresponding arylazohydrazone derivatives 3a-j. The azo derivatives 3d and 3e were used as the key intermediate for the synthesis of some new diazines 5d, e and triazoles 7d, e. The newly synthesized compounds were characterized by electronic absorption properties – IR, 1HNMR and MS studies – and screened for their biological evaluation. Compounds 3a-j, 5d, e and 7d, e showed promising results as antimicrobial agents.FindingsCompounds 3a-j, 5d, e and 7d, e showed promising results as antimicrobial agents.Originality/valueNo details regarding the synthesis of such dyes are reported before in the literature.

Copper‐Catalyzed Chelation‐Assisted Synthesis of Unsymmetrical Aliphatic Azo Compounds

AbstractAn unprecedented and convenient synthetic approach to a new class of unsymmetrical azo compounds is developed through a chelation‐assisted copper‐catalysis using cheap commercial reagents. The reactions proceed rapidly at room temperature (typically one hour) and were performed in aqueous medium as well as in solvent‐free conditions, delivering structurally diverse alkyl aryl azo compounds in good yields. It has been observed that these novel pyridine hinged azo derivatives exhibit “turn on” fluorescence response in the presence of copper(II) ion in aqueous medium.

Synthesis and Anticancer Activities of 4-[(Halophenyl)diazenyl]phenol and 4-[(Halophenyl)diazenyl]phenyl Aspirinate Derivatives against Nasopharyngeal Cancer Cell Lines

Aspirin and azo derivatives have been widely studied and have drawn considerable attention due to diverse biological activities. In this study, a series of 4-[(halophenyl)diazenyl]phenyl aspirinate derivatives were synthesized from the reaction of aspirin with 4-[(halophenyl)diazenyl]phenol via esterification, in the presence of DCC/DMAP in DCM with overall yield of 45–54%. 4-[(Halophenyl)diazenyl]phenol was prepared prior to esterification from coupling reaction of aniline derivatives and phenol in basic solution. All compounds were characterized using elemental analysis, FTIR, and 1H and 13C NMR spectroscopies. All compounds were screened for their anticancer activities against nasopharyngeal cancer (NPC) HK-1 cell lines and the viability of cultured cells was determined by MTS [3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxylmethoxylphenyl)-2-(4-sulfophenyl)-2H-tetrazolium]-based colorimetric assay. 4-[(E)-(Fluorophenyl)diazenyl]phenol showed the highest anticancer activity against NPC HK-1 cell lines compared to other synthesized compounds. 4-[(Halophenyl)diazenyl]phenyl aspirinate showed low cytotoxicity against NPC HK-1 cell lines compared to 4-[(halophenyl)diazenyl]phenol but better anticancer activity than aspirin alone.

Hünlich base derivatives as photo-responsive Λ-shaped hinges

The azo derivatives of the Hünlich base are introduced as a set of molecular switches with unique shapes and properties.