Reaction Of Diazonium Salts Research Articles

The Prospect of Improving Pancreatic Cancer Diagnostic Capabilities by Implementing Blood Biomarkers: A Study of Evaluating Properties of a Single IL-8 and in Conjunction with CA19-9, CEA, and CEACAM6.

Background/Objectives: This study aims to evaluate the possible clinical application of interleukin 8 (IL-8) as a single biomarker and its capabilities in combination with carbohydrate antigen (CA19-9), carcinoembryonic antigen (CEA), and carcinoembryonic antigen cell adhesion molecule 6 (CEACAM6) as diagnostic and prognostic tools for pancreatic ductal adenocarcinoma (PDAC). Methods: A total of 170 serum samples from patients with PDAC (n = 100), chronic pancreatitis (CP) (n = 39), and healthy individuals (n = 31) were analysed. IL-8 and CEACAM6 were measured by an enzyme-linked immunosorbent assay (ELISA). CA19-9 and CEA were determined by chemiluminescent microparticle immunoassay, and bilirubin was quantified using a diazonium salt reaction. Receiver operating characteristic curve analysis, logistic regression, and Kaplan-Meier analyses were performed to evaluate the properties of a single IL-8 and in combination with other biomarkers. Results: The concentrations of IL-8 were statistically significantly higher in the PDAC group compared to the CP and control groups. Heterogeneous levels of IL-8 correlated with PDAC stages (p = 0.007). IL-8 had good and satisfactory diagnostic efficacy in differentiating PDAC from controls (0.858; p < 0.001) and patients with CP (0.696; p < 0.001), respectively. High and low expressions of IL-8 were not significantly associated with overall survival (OS) or disease-free survival (DFS). A combination of IL-8, CEACAM6, and CA19-9 reached the highest AUC values for differentiating PDAC from the control group. The best classification score between PDAC and the control group with CP patients was obtained by merging IL-8 and CA19-9 (0.894; p < 0.001). Conclusions: These results provide compelling evidence of IL-8 as a promising diagnostic biomarker. Nonetheless, due to the high complexity of PDAC, only the conjunction of IL-8, CA19-9, and CEACAM6 integrates sufficient diagnostic capabilities.

Nano-synthesis, characterization, theoretical, biological and catalytic studies of Mn(II), Cu(II), Cd(II), and Th(IV) complexes based on antipyrine azo dye ligand

The design and detailed characterization of the azo dye ligand obtained from the reaction of 4-aminoantipyrine diazonium salt with 3-hydroxybenzaldehyde (HL) and its novel metal chelates with Mn2+, Cu2+, Cd2+ and Th4+ ions have been presented. Utilizing modern spectroscopic and analytical techniques, these complexes were found to adopt an octahedral geometry, demonstrate inner sphere d2sp3 hybridization for Th(IV) complex and outer sphere sp3d2 hybridization for other complexes. Particle sizes calculated using the Debye-Scherrer equation on XRD patterns were 32.05 nm for Mn(II), 34.07 nm for Cu(II), 30.90 nm for Cd(II), and 22.05 nm for Th(IV). These substances' anticancer activity was assessed on human lung cancer cells (A-549) and pancreatic carcinoma cell lines (PANC-1). Cd(II) complex exhibited higher cytotoxicity against the A-549 cell line than the reference drug vinblastine sulfate which revealing its potential application as a new anticancer agent. Quantum chemical computations using the DMOL3 module's density functional theory (DFT) and molecular docking studies with the Schrödinger suite demonstrated significant inhibitory effects of the free organic compound and Cu(II) chelate on the FGFR1 protein, crucial for cell development and differentiation. Additionally, the study examined the catalytic activity of HL and its metal chelates in the oxidative degradation of methyl violet 2B dye in presence of H2O2. The order was followed by the pseudo-first-order rate constants: Th(IV) chelate (0.9556 min⁻¹) > HL (0.4911 min⁻¹) > Cu(II) chelate (0.5979 min⁻¹) > Mn(II) chelate (0.2645 min⁻¹) > Cd(II) chelate (0.2280 min⁻¹).

Enhancing color brilliance and fastness of polyester dyeing with antipyrine-derived disperse dyes

Disperse azo dyes are important colorants for dyeing polyester fabrics, but developing optimized disperse azo dyes remains a challenge. This work details the synthesis of seven new disperse azo dyes 3a-g derived from the coupling reaction of 4-aminoantipyrine diazonium salt with various phenolic precursors including phenol (3a), salicylic acid (3b), salicylaldehyde (3c), cresols (3d-f), and resorcinol (3g). The dyes were characterized by spectroscopic techniques. Their UV–visible absorption spectra were studied, revealing bathochromic shifts for 3d-g containing electron-donating methyl and hydroxyl substituents compared to parent dye 3a while dyes 3b-c showed hypsochromic shifts. The impact of acid and base on the absorption spectra indicates azo-hydrazone tautomerism for 3f-g but predominant azo form for 3a-e. The dyes showed excellent dyeing on polyester fabrics with up to 97.86 % dye exhaustion. High wash, light and perspiration fastness was exhibited while fastness to respiration varied. The strongest color yield on polyester was achieved with 3g derived from resorcinol coupler. Density functional theory calculations were performed to elucidate relationships between substituent effects and spectral attributes. Lower energy gaps were computed for 3f-g, consistent with enhanced reactivity. This work expands disperse azo dye precursors while offering fundamental structure-performance insight to guide future design. The potent polyester coloration and good fastness properties warrant ongoing investigation of these dyes.

B-diketon Derived Ligands Metal Complexes, Synthesize, Characterization, and Bioactivity Studies

The precursor in our study 2, 2’- ((1E,1’E) - (4,4’- diamino - 5, 5’- dimethyl - [1,1’-biphenyl]-3, 3’-diyl) bis(diazene-2,1-diyl) diphenol (W1) or (W2) 3,3’-dimethyl-5,5’-bis((E)-pyridin-3-yldiazenyl)-[1,1’-biphenyl]-4,4’-diamine were obtained from reaction of diazonium salt with tolidin. The both precursors used for synthesis of the ligands [H4L1] and [H2L2] by reaction with di benzyl methan to produce the ligands [H4L1]2,2’-((1E,1’E)-(4,4’-bis((3-hydroxy-1,3-diphenylpropylidene)amino)-5,5’-dimethyl-[1,1’-biphenyl]-3,3’-diyl)bis(diazene-2,1-diyl))diphenoland [H2L2] 3,3’-((3,3’-dimethyl-5,5’-bis((E)-pyridin-3-yldiazenyl)-[1,1’-biphenyl]-4,4’-diyl)bis(azaneylylidene))bis(1,3-diphenylpropan-1-ol). Elemental microanalysis, 1H and 13C-NMR, FT-IR, U.V, mass spectroscopies were used to describe the structure of the ligands. In this research we also reported the complexes synthesis via reaction of of [NiII, MnII, CoII, CdII, CuII] chloride salts with ligands, using KOH as a base and ethanol as a solvent, under reflux. Complexes were characterized by atomic absorption, (FT-I.R, U.V-Vis, 1H and 13C-NMR and mass) spectroscopies along with conductivity, magnetic susceptibility and melting point measurements. The presence of crystallized water molecule insured by thermal analysis in some complexes structure. Finally, the synthesized ligands and complexes biological activity studied against selected organisms.

Synthesis and characterization of a new azo quinoline ligand and its metal complexes with spectrophotometric determination and biological efficacy study of its Hg(II) complex

ABSTRACT. An azo quinoline ligand, (E)-2-((4-iodophenyl)diazenyl)-8-hydroxyquinoline (IPDHQ), was synthesized by the coupling reaction of 4-iodoaniline diazonium salt with 8-hydroxyquinoline. The synthesized ligand and its Cd(II), Pd(II), Cu(II) and Hg(II) complexes were spectrally characterized by UV‒Vis spectrophotometry, FT-IR, mass spectral analysis, 1H-NMR, magnetic sensitivity and molar conductivity. The general formula of the Cd(II), Cu(II) and Hg(II) complexes is [M(L)2].Cl2.H2O with octahedral geometry, while the general formula of the Pd(II) complex is [M(L).Cl2].H2O with square planer geometry. A simple and rapid spectrophotometric procedure was suggested for the determination of Hg(II) using the synthesized ligand as a spectrophotometric reagent. By measuring the absorbance for the resulting orange complex at 430 nm, the linearity range was 0.5-15 µg mL-1, and the interfering effect was also studied. The synthesized azo ligand and its Hg(Ⅱ) complex were tested for their biological activity against four bacterial strains.&#x0D; KEY WORDS: Azo quinoline ligand, 8-Hydroxy quinoline, 4-Iodoaniline, Azo metal complexes, Spectrophotometric determination, Biological efficacy study&#x0D; Bull. Chem. Soc. Ethiop. 2023, 37(6), 1459-1470. DOI: https://dx.doi.org/10.4314/bcse.v37i6.13

New substituted pentazadienes as initiators of free-radical polymerization: synthesis, photochemical properties and perspectives for holographic media

The series of 4,4′-substituted 3-hydroxyethyl-pentaza-1,4-dienes were synthesized in the reaction of aromatic diazonium salts with an ethanol amine. Photolysis of pentaza-1,4-dienes was investigated by means of UV/Vis spectroscopy. Electron donating methyl and methoxy substituents were found to increase photosensitivity whereas electron withdrawing chloro-substituents cause higher photolytic stability. 3-hydroxyethyl-pentaza-1,4-dienes as a radical polymerization initiator has been successfully investigated in 10% methyl methacrylate solution in DMF. Gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) were used for obtained polymers characteristics evaluation. The highest values of PMMA Mn and Đ can be obtained in the case of chloro-substituted derivative. The holograms of a plane wavefront were recorded in media based on obtained PMMA doped by azo-dye by a 532 nm laser in a ∼1-μm-thick sample. The diffraction efficiency values for parallel polarized acting light increased in Cl→Me→OMe series.

Host-aided pH-controlled substitution reaction of aryl diazonium salts and sodium azide

Host-aided pH-controlled substitution reaction of aryl diazonium salts and sodium azide

Composite Interlaminar Fracture Toughness Enhancement Using Electrospun PPO Fiber Veils Regulated by Functionalized CNTs.

In this study, carbon nanotubes (CNTs) are functionalized through diazonium salt reaction to introduce polar groups onto their surfaces. These functionalized CNTs (FCNTs) are added into PPO solutions at different loadings (0 wt%, 0.5 wt%, 1 wt%, 1.5 wt%) and used for electrospinning. The results show that the addition of FCNTs facilitate the production of PPO veils having small fiber diameters. The veils are used as interleaves in CF/EP composite laminates. The Mode I and Mode II interlaminar fracture toughness tests reveal that PPO veils containing 0.5 wt% FCNTs exhibit the optimal toughening. GICini and GIIC have an improvement of approximately 120% and 180% over the untoughened samples, respectively, which is 15% and 26% higher than that of PPO veils containing no CNTs, respectively. The toughening mechanism is also analyzed using scanning electron microscopy (SEM).

Adsorption-Assisted Redox Center in Porous Organic Frameworks for Boosting Lithium Storage.

Due to the designable structure and capacity, organic materials are promising candidates for lithium-ion batteries. Herein, we report a novel type of porous organic frameworks (POFs) based on the coupling reaction of diazonium salt as the anodes for lithium ion storage. The active center containing an azo group and the adjacent lithium-philic adsorption site is constructed to investigate the electrochemical behaviors and reaction mechanism. As synthesized POF material (named as POF-AN) exhibits high reversible lithium storage capacities of 523 mAh g-1 at 0.5 A g-1 and 445 mAh g-1 at 2.0 A g-1 after 1500 cycles, showing excellent cycle stability and rate performance. The detailed characterizations reveal that the azo group can act as an electrochemical active site that reversibly bonds with Li-ions, and the adjacent oxygen atoms can electrostatically adsorb with Li-ions to promote the lithium storage reaction. This adsorption-assisted three-atom redox center is beneficial to synergistically enhance the adsorption and intercalation of lithium ions, which can further improve the capacity and cycle stability. By replacing the precursor, it is also facile to synthesize more similar structure types. The reversible redox chemistry of the adsorption-assisted three-atom active center provides new opportunities for the development of long lifespan and high-rate organic anodes.

Air and moisture stable robust bio-polymeric palladium catalyzed C[sbnd]C bond formation and its application to the synthesis of fungicidal

Cellulose supported bio-heterogeneous polymeric Pd(II) catalyst, stable to air and moisture, was designed and characterized with different spectroscopic techniques including FESEM, TEM, XPS, XRD, ICP-AES and EDX. The Pd(II) catalyst showed high catalytic performance (0.2 to 0.0009 mol%) to the Suzuki-Miyaura CC cross-coupling reaction of aromatic halides and aryl diazonium salts with a range of organoboronic acids to produce the respective biaryl product in up to 97% yield. Biologically active Boscalid, a fungicide that effectively inhibits the growth of fungal pathogens like ascomycetes on fruits and plants, could also be constructed through using this catalyst. Additionally, it was possible to recover the Pd(II) catalyst from the reaction medium and reused it repeatedly without significantly degrading its catalytic efficiency.

Effect of Surface Modification on the Fundamental Electrical Characteristics of Solution-Gated Indium Tin Oxide-Based Thin-Film Transistor Fabricated by One-Step Sputtering.

Our solution-gated indium tin oxide (ITO)-based thin-film transistor (TFT) produced by single-step sputtering has great future potential in bioelectronics. In particular, chemical modifications of the ITO channel surface are expected to contribute to biomolecular recognition with ultrahigh sensitivity owing to a remarkably steep subthreshold slope (SS). In this study, we investigate the effect of a chemical modification of an aptamer as a receptor molecule at the ITO channel surface on the electrical characteristics of the solution-gated TFT. In this case, a SARS-CoV-2 aptamer is immobilized using a spacer molecule on an aryl diazonium monolayer that is electrochemically deposited with a radical scavenger. The monolayer is expected to not only passivate the ITO channel surface but also change the electron density in the ITO channel owing to the reduction reaction of aryl diazonium salts. Indeed, the electrochemical deposition of aryl diazonium salts decreases the leakage current through the ITO channel surface and provides a steep SS, which is near the thermal limit at 300 K, owing to the decrease in depletion layer capacitance. After the aptamer immobilization, the leakage current and SS unexpectedly return close to their original values before the surface modifications. This finding indicates that aptamer molecules should be carefully used because their negative charges would attract cations around the detection interface. Eventually, the solution-gated ITO-based TFT with the SARS-CoV-2 aptamer clearly responds to inactivated SARS-CoV-2 particles owing to the successful surface modification.

Transition metal-free, photocatalytic arylation and dioxygenation for vicinal diketone synthesis using alkynes and arene diazonium salts

A metal-free dioxygenative reaction of aryl diazonium salts with aryl alkynes for vicinal diketone synthesis is developed.

Electro-polymerization rates of diazonium salts are dependent on the crystal orientation of the surface

Electro-polymerization of diazonium salts is widely used for modifying surfaces with thin organic films. Initially this method was primarily applied to carbon, then to metals, and more recently to semiconducting Si. Unlike on other surfaces, electrochemical reduction of diazonium salts on Si, which is one of the most industrially dominant material, is not well understood. Here, we report the electrochemical reduction of diazonium salts on a range of silicon electrodes of different crystal orientations (111, 211, 311, 411, and 100). We show that the kinetics of surface reaction and the reduction potential is Si crystal-facet dependent and is more favorable in the hierarchical order (111) > (211) > (311) > (411) > (100), a finding that offers control over the surface chemistry of diazonium salts on Si. The dependence of the surface reaction kinetics on the crystal orientation was found to be directly related to differences in the potential of zero charge (PZC) of each crystal orientation, which in turn controls the adsorption of the diazonium cations prior to reduction. Another consequence of the effect of PZC on the adsorption of diazonium cations, is that molecules terminated by distal diazonium moieties form a compact film in less time and requires less reduction potentials compared to that formed from diazonium molecules terminated by only one diazo moiety. In addition, at higher concentrations of diazonium cations, the mechanism of electrochemical polymerization on the surface becomes PZC-controlled adsorption-dominated inner-sphere electron transfer while at lower concentrations, diffusion-based outer-sphere electron transfer dominates. These findings help understanding the electro-polymerization reaction of diazonium salts on Si en route towards an integrated molecular and Si electronics technology.

A Fruitful Decade of Organofluorine Chemistry: New Reagents and Reactions

A Fruitful Decade of Organofluorine Chemistry: New Reagents and Reactions

Preparation, DFT and optical nonlinear studies of a novel azo-(β)- diketone dye

New azo compound containing an antipyrine moiety is prepared via interaction of 4-aminoantipyrine with benzoylacetone. The coupling reaction of diazonium salt with benzoylacetone is employed to prepare the azo compound. The FTIR, 1H NMR and mass spectroscopies are used for the characterization of the new azo compound. Density function theory DFT calculations are carried out to study the electronic structure and vibrational frequencies of the prepared azo compound. A linear correlation appeared between the Mulliken atomic charge of oxygen atoms and the values of calculated wavenumbers. The nonlinear optical NLO properties of the prepared compound solution are studied using 473 nm, continuous wave cw, single fundamental mode, low power laser beam via the diffraction ring patterns DRPs and the Z-scan techniques. The optical limiting OLg property of the compound solution is examined. The DRPs are simulated numerically using the Fresnel-Kirchhoff integral with reasonable accord compared to the experimental findings.

SYNTHESIS OF NEW SUBSTITUTED PROCAINE HYDROCHLORIDE COMPOUNDS AND THEIR USE IN SPECTROPHOTOMETRIC DETERMINATION OF TETRACYCLINE HYDROCHLORIDE THROUGH DIAZOTIZATION-COUPLING REACTIONS

Background: Tetracycline is one of the most important antibiotics. It is used to treat many different bacterial infections. It is often used in treating severe acne, or sexually transmitted diseases such as syphilis, gonorrhea, or chlamydia. In some cases, tetracycline is used when penicillin or another antibiotic cannot be used to treat serious infections such as the ones caused by Bacillus anthracis, Listeria, Clostridium, Actinomyces. Aim: synthesized a new novel reagent used to determine TCH spectrophotometrically by using diazonium and coupling reaction. Methods: Four new substituted procaine derivatives were prepared by simple organic methods using aniline derivatives. A spectrophotometric approach was established for the micro-determination of TCH. The stoichiometry was investigated using mole ratio and continuous variation methods, and the stability constant was also estimated. The ΔG, ΔH, and ΔS were determined as thermodynamic parameters for evaluating the effect of temperature on the reaction. Results: Substituted procaine derivatives were prepared, and o-hydroxy procaine seems to be the best reagent used to determine TCH by diazotization and coupling reaction. The result was a yellow water-soluble dye with a maximum absorbance of 380 nm. The reaction conditions were studied and optimized. Beers law was obeyed over a concentration range (2.5–50) μg.mL-1 for TCH. The molar absorptivity was (14.4669.103) L.mol-1.cm-1, and the detection limit was (0.5052) μg.mL-1. The stoichiometry of the formed product was found 1:1 (o-hydroxyprocaine: TCH). The stability constant indicated that the product formed was stable, and the thermodynamic parameters showed that the diazonium salt reaction was preferred to occur at a low temperature. Conclusions: a simple, accurate, and fast method was developed to determine TCH in pure form and pharmaceuticals by coupling the TCH with a newly synthesized procaine derivative reagent (o-hydroxy procaine) in a basic medium.

Synthesis and characterization of pyrazole- and imidazole- derived energetic compounds featuring ortho azido/nitro groups

Two novel nitrogen-rich heterocyclic energetic compounds, 5-amino-3-azido-4-nitro-1H-pyrazole (3) and 5,5′-diazido-4,4′-dinitro-1H,1′H-2,2′-biimidazole(6), featuring ortho azido/nitro groups were designed and synthesized by reactions of diazonium salts with sodium azide. In addition, treatment of diazonium salts with a mixture of hydrazine monohydrate and sodium nitrite in acetic acid also gave the same products 3 and 6 in high yields. Both structures of the products were characterized by 1H NMR, 13C NMR, IR and elemental analysis, as well as single-crystal X-ray diffraction. Furthermore, their physicochemical and energetic properties were studied.

Electrochemical preparation of new graphene nanosheet derivatives for using in different applications

In this study, graphene oxide nanoscale sheets were prepared by the modified Hammer method. The phenolic compound was prepared through reactions of diazonium salts that occurred between diazonium salt concerning benzidine as well as diazonium salt concerning para-aminophenol and then reacted by electro-platinum electrodes, where the graphene oxide was decorated with the phenolic compound [1,1′:4,1:4,1-quaterphenyl)-4,4-diol by electrical reaction through platinum electrodes after converting it to the sodium salt of the phenolic compound, and this compound was used in the Preparation of cement mortar and upon mixing it with cement mortar gave high compressive strength results, indicating that the prepared compound has a strong effect and benefit in mixing it with cement mortar.

Biological activity and latent fingerprints detection by azo quinoline dye and its complexes

Azo dye of quinoline named 5-(3-pyridylazo)-8-hydroxyquinoline dye (PAHQ) was prepared via coupling reaction of diazonium salt of 3-aminopyridine and 8-hydroxyquinoline. he PAHQ dye was characterized by elemental analysis, mass spectroscopy and 1H-NMR. The complexes of PAHQ dye were prepared under 2:1 (L:M) mole ratio. The complexes were characterized by elemental analysis, infrared spectroscopy, UV-Vis, molar conductance, magnetic susceptibility. The IR spectra data indicate that PAHQ ligand is bidentate through deprotonated phenolic oxygen and nitrogen atom of azomethine of quinoline. The IR spectra also indicate to presence of water in coordination state to metals. The PAHQ and its complexes were found to have high biological activity against different organisms of bacteria and fungi. The PAHQ ligand and zinc complex exhibited high toxicity against MCF-7 with high different values between IC50 against infection cells and healthy cells.

How do arenediazonium salts behave in deep eutectic solvents? A combined experimental and computational approach

Despite the growing use of Deep Eutectic Solvents (DESs) as green reaction media in a number of organic syntheses, no significant reactions of diazonium salts in these solvents are known in the literature. In this paper, we present the behavior of arenediazonium tetrafluoroborates in new halide salts/polyol-based DESs, the nature of which is investigated by means of a combined computational and experimental approach. A relatively fast (strictly depending on the electronic effects of the substituents bound to the aromatic ring) reduction reaction occurs initiated by the formation of a glycerolate-like species as proved by a thorough computational study aiming at elucidating the involved mechanism.