Dye Derivatives Research Articles

Computational studies of the thermodynamic properties, and global and reactivity descriptors of fluorescein dye derivatives in acetonitrile using density functional theory

This work reports density functional theory calculations of the optimized geometries, molecular reactivity, energy gap, and thermodynamic properties of molecular dyes fluorescein (FS), fluorescein attached with methoxy (FSO), fluorescein attached with amine (FSA), fluorescein attached with methane (FSM), fluorescein attached with ethene (FSE), and fluorescein attached with thiophene (FST) using the hybrid functional B3LYP and 6-311G basis sets. When donating groups are attached to the molecular dye, the bond lengths are slightly decreased which is important for easy transfer of electron from donating to the accepting group. For all dyes, highest occupied molecular orbital/lowest occupied molecular orbital analysis results in positive outcomes upon electron injection to semiconductors and subsequent dye regeneration by the electrolyte. The ionization potential increases with increasing conjugation; therefore, the molecular dye attached to thiophene has the highest ionization potential. Meanwhile, a donating group with increased conjugation results in low electron affinity.

The ability of 2,5-disubstituted oxazole dyes derivatives to generate two-photon upconversion photoluminescence and its brightness evaluation

The brightness study of emissive compounds is one of the fundamental spectroscopic characterizations. In this work, we assessed the brightness values of eight 2,5-disubstituted oxazole dyes derivatives by combining linear and nonlinear spectroscopic parameters. The range of the brightness values obtained is from 0.26 GM to 15.15 GM. The highest value belongs to compound 14 m, which, compared to previously investigated compounds of similar π-conjugation length, is at least two times higher. Brightness values were determined in the spectral region between 700 nm–720 nm, revealing this class of dyes' potential to be used as photoluminescence bioprobes excited by two-photons.

Construction of 2-pyridones via oxidative cyclization of enamides: access to Pechmann dye derivatives.

An efficient protocol for the construction of structurally diverse 2-pyridone derivatives from imines and α,β-unsaturated acid chlorides in a single operation is reported. The target compounds, including coumarin-8-oxoprotoberbine analogues and lamellarin G isomers, were prepared via thermal cyclization of the in situ generated enamides followed by thermal dehydrogenation. The cyclization of enamides was achieved by the introduction of an electron-withdrawing group on the α-carbon of acid chlorides. This methodology allows quick access to polycyclic Pechmann dyes via rare double oxidative cyclizations of dienamides under mild conditions.

Correction: A computational probe granting insight into intra and inter-stacking interactions in squaraine dye derivatives.

Correction for 'A computational probe granting insight into intra and inter-stacking interactions in squaraine dye derivatives' by Krishna Chaitanya Gunturu et al., Phys. Chem. Chem. Phys., 2021, DOI: .

A computational probe granting insight into intra and inter-stacking interactions in squaraine dye derivatives.

In order to decipher structure function relationships regarding the optoelectronic properties of organic functional materials, two sets of anilinosquaraine dye derivatives were analysed computationally. 2,4-Bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl]squaraine exhibits orthorhombic and monoclinic polymorphs (motif-1 and motif-2) in bulk and spin coated films, respectively, and concomitant J- and H-aggregate spectral features. In the second set, in spite of variation in the n-alkyl chain of the anilinosquaraine derivatives (n-propyl vs. n-butyl; motif-3 and motif-4), both acquired triclinic morphology and intermolecular charge transfer had been identified as the origin of their panchromaticity. The differences between these motifs were closely inspected at the theoretical level including geometrical parameters, internal reorganization energies, charge transfer integrals, drift mobilities, interaction energies and lattice energies along with a comprehensive Hirshfeld surface analysis. A correlation was established between C⋯C type intra-stack interactions with the observed red-shifted absorption patterns in the order motif-1 > motif-3 > motif-4. Hydrophobic interactions, π-π interactions and hydrogen bonds were found to influence the crystal packing patterns and concomitantly the overall molecule planarity and thereby the extent of π-bond delocalization/resonance. Insights into intra-stack and inter-stack interactions based on crystal packing effects are provided, which support and potentially guide the experimentalists' key ideas for shaping and encompassing the applications of promising squaraine derivative materials.

Anticancer activity of novel Schiff bases and azo dyes derived from 3-amino-4-hydroxy-2H-pyrano[3,2-c]quinoline-2,5(6H)-dione

Abstract New Schiff bases and azo dyes derivatives have been synthesized via appropriate conventional methods using pyranoquinolinone as a starting material. The compounds obtained were characterized by spectral analysis and evaluated for anticancer activity in several human tumor cell lines: MCF-7 breast cancer, HepG2 liver cancer and HCT-116 colon carcinoma. 5-fluorouracil was used as a reference drug. The in vitro cytotoxicity screening results revealed that all tested compounds showed promising activity against MCF-7 cells. In particular, compounds 6a, 6b, and 7b showed excellent activity against the three human tumor cell lines. Structure-activity relationship studies indicated that the azo derivative with a trifluoromethoxy group (compound 7b) was the most potent candidate against the three human tumor cell lines (IC50, 1.82-8.06 μg/mL). Our findings highlight pyranoquinolinone analogues as a promising class of compounds for new anticancer therapies.

Luminescence Color Control Based on Electrochromic Reaction Using Luminescent Leuco Dye Derivatives

Luminescence Color Control Based on Electrochromic Reaction Using Luminescent Leuco Dye Derivatives

Design and theoretical study of phenothiazine-based low bandgap dye derivatives as sensitizers in molecular photovoltaics

Modulation of metal free organic (MFO) molecules become imperative to researchers to obtain low-cost sensitizer for dye sensitized solar cells (DSSCs) purposes. A series of metal free phenothiazine-based (PTZ) organic dyes are designed and optimized as sensitizers for DSSCs application. Their electronic and optical properties were probed using Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) approaches. Effects of additional donor unit, π-conjugation bridges, and benzothiadiazole (BTDA) were investigated. Introducing BTDA in the acceptor unit leads to the tailoring of the energy band gap and promotion of charge transfer within donor and anchor groups with increased effective parameters in DSSC efficiency. The addition of diphenylamine, triphenylamine, or hexyloxyphenyl to the PTZ unit increased electron delocalization and enhanced intramolecular charge transfer. Changing π-spacer from phenyl to thiophene has a great effect on the electronic properties and absorption spectra of the dyes. The relationship between light harvesting efficiency (LHE) and chemical hardness (ƞ) shows that structural design that consists of BTDA and thiophene as π-spacer tends most towards excellent performance as dye sensitizers in DSSCs.

Stereochemistry-Controlled Supramolecular Architectures of New Tetrahydroxy-Functionalised Amphiphilic Carbocyanine Dyes.

The syntheses of novel amphiphilic 5,5′,6,6′‐tetrachlorobenzimidacarbocyanine (TBC) dye derivatives with aminopropanediol head groups, which only differ in stereochemistry (chiral enantiomers, meso form and conformer), are reported. For the achiral meso form, a new synthetic route towards asymmetric cyanine dyes was established. All compounds form J aggregates in water, the optical properties of which were characterised by means of spectroscopic methods. The supramolecular structure of the aggregates is investigated by means of cryo‐transmission electron microscopy, cryo‐electron tomography and AFM, revealing extended sheet‐like aggregates for chiral enantiomers and nanotubes for the mesomer, respectively, whereas the conformer forms predominately needle‐like crystals. The experiments demonstrate that the aggregation behaviour of compounds can be controlled solely by head group stereochemistry, which in the case of enantiomers enables the formation of extended hydrogen‐bond chains by the hydroxyl functionalities. In case of the achiral meso form, however, such chains turned out to be sterically excluded.

Colorimetric Chemosensor and Turn on Fluorescence Probe for pH Monitoring Based on Xanthene Dye Derivatives and its Bioimaging of Living Escherichia coli Bacteria.

A new turn on fluorescence probe based on 3',6'-dihydroxy-6-methyl-2-((pyridin-2-ylmethylene)amino)-4-(p-tolyl)spiro[benzo[f]isoindole-1,9'-xanthen]-3(2H)-one (BFFPH) derived from benzo[f]fluorescein was prepared. Full characterization of the prepared probe using spectroscopic analysis was described such as IR, NMR and MS spectra. The sensitivity of BFFPH for monitoring of pH change in alkaline medium was studied. BFFPH exhibited a high sensitivity to alkaline pH by two pKa values at 8.82 and 10.66 in UV/vis spectroscopy titration. The pH monitoring was studied in broad range of pH values (2.5-12.2) at two pKa values at 8.72 and 10.73 by recording the effect of pH on the fluorescence intensity of BFFPH. The acid-base reversibility character of the probe was investigated as well as the effect of the pH change on the fluorescence quantum yield. The application of the prepared BFFPH probe for detection of living Escherichia coli (E. coli) bacteria using confocal fluorescence microscope was investigated.

Synthesis of azo and anthraquinone dyes and dyeing of nylon-6,6 in supercritical carbon dioxide

In this work, thiazole based azo dyes (6A and 6B) and anthraquinone dye derivatives (6C, 6D and 6E) were synthesized from commercially inexpensive starting materials.The advantage of the synthesis of these dyes are quite facile and scale-up is feasible, which favors for an industrial dyeing applications. All the dyes were characterized by spectroscopic techniques such as IR, NMR (1H and 13C), HRMS and UV–vis spectroscopy. Preliminary dyeing experiments were carried out with these dye stuffs on nylon 6,6 fabrics to examine the possibility of scaling up supercritical carbon dioxide dyeing to a factory level. All the five dyes (6A-6E) showed good color strength and especially two dyes 6A and 6C exhibited excellent dye fixation. Remarkable results obtained for washing fastness (fading and staining grade of 4–5) and sweat fastness (fading and staining grade of 4–5) for all the dyes (6A-6E). Based on the results, the synthesized dyes could be hopefully applied in near future for the dyeing of nylon 6,6 fabrics on an industrial scale under the ecofriendly and energy-efficient supercritical carbon dioxide medium.

Novel synthesized azo-benzylidene-thiourea as dual naked-eye chemosensor for selective detection of Hg2+ and CN¯ ions

Seven novel chemosensors contain azo chromophore and phenylthiourea, were synthesized and applied as colorimetric probes in aqueous solutions of dimethyl sulfoxide. The anion recognition studies exhibited that the synthesized azo dye derivatives act as a highly dual-sensitive and selective chromogenic sensor for naked-eye detection of Hg2+ and CN¯ ions, with a different color change from yellow to colorless and yellow to red, respectively. The limit of detection (LOD) was found for 3c toward Hg2+ and CN¯ ions to be 4.89 μM and 2.23 μM, respectively. The result of the Job's plot indicating that the stoichiometry binding ratios of compound 3c to Hg2+ is 1:1 and to CN¯ is 1:2. These results were confirmed by 1H NMR titration experiments.

Evaluation of Antibacterial Potential of New Acid Dyes Based on Substituted Aryl Amines and Amino Hydroxy Sulfonic Acid

Six newly synthesized acid dye derivatives were evaluated for their in vitro antimicrobial activity against four (04) Gram positive (Staphylococcus aureus, Staphylococcus lugdunensis, Streptococcus pneumoniae and Bacillus subtilis) and six (06) Gram negative (Pseudomonas aeruginosa, Acinetobacter baumannii, Citrobacter freundii, Klebsiella pneumoniae,Pseudomonas fluorescens and Shigella sonnei) bacterial strains. The dyes were synthesized using substituted aryl amines and substituted amino hydroxy sulfonic acid as diazo and coupling components, respectively. The antimicrobial activity was explored by Agar-Well Diffusion method using 100 mg/ml dye concentration. The results demonstrated that the dyes possess varying degrees of activities against the bacterial strains tested and the structure of the dye molecules was found to have considerable influence on their antimicrobial activity.

Evaluation of Antibacterial Potential of New Acid Dyes Based on Substituted Aryl Amines and Amino Hydroxy Sulfonic Acid

Six newly synthesized acid dye derivatives were evaluated for their in vitro antimicrobial activity against four (04) Gram positive (Staphylococcus aureus, Staphylococcus lugdunensis, Streptococcus pneumoniae and Bacillus subtilis) and six (06) Gram negative (Pseudomonas aeruginosa, Acinetobacter baumannii, Citrobacter freundii, Klebsiella pneumoniae,Pseudomonas fluorescens and Shigella sonnei) bacterial strains. The dyes were synthesized using substituted aryl amines and substituted amino hydroxy sulfonic acid as diazo and coupling components, respectively. The antimicrobial activity was explored by Agar-Well Diffusion method using 100 mg/ml dye concentration. The results demonstrated that the dyes possess varying degrees of activities against the bacterial strains tested and the structure of the dye molecules was found to have considerable influence on their antimicrobial activity.

High-Resolution Mass Spectrometry Analysis of Reactive Dye Derivatives Removed from Biodegraded Dyed Cotton by Chemical and Enzymatic Methods

The purpose of this study was to determine and characterize the biodegradation of reactive dyes on cotton jersey fabrics buried in soil. Four commonly-used reactive dyes, C.I. Reactive Black 5 (RBlk5), C.I. Reactive Red 198 (RR198), C.I. Reactive Blue 49 (RB49), and C.I. Reactive Orange 35 (RO35), were used in this study. Degradation products were characterized and proposed based on high-performance liquid chromatography (HPLC) coupled with high-resolution mass spectrometry (HRMS). A chemical method and an enzymatic digestion were developed and used to remove the reactive dye from the control and degraded cotton fabrics. Hydrolyzed reactive dyes and reactive dyes having cellobiose units were synthesized and used as standards for comparison in this study. The possible degradation mechanism pathways of the reactive dyes bonded to cotton fabrics depends on the chemical structure of each dye.

The nonlinear optical properties of acyclic triarylamine-conjugated dimethyl diethynylfumarate and its two cyclic Pechmann dyes derivatives: A theoretical study

DFT and TDDFT calculations were used to investigate the potential use of two Pechmann dyes as efficient nonlinear optical (NLO) compounds. The two Pechmann dyes are with cyclic cores formed by acid-induced double lactonization from their parent acyclic core compound dimethyl 2,3-bis((4-(bis(4-methoxyphenyl)amino)phenyl)ethynyl)fumarate (parent compound; E1). The two Pechmann dyes are (E)-5,5′-bis(4-(bis(4-methoxyphenyl)amino)phenyl)-2H,2′H-[3,3′ bifuranylidene]-2,2′-dione (P55), and 3,7-bis(4-(bis(4-methoxyphenyl)amino)phenyl)pyrano[4,3-c]pyran-1,5-dione (P66). The polarizability parameters were calculated and analyzed. To rationalize the NLO response, the following parameters were calculated and discussed: (1) the charge transfer descriptors, (2) the linear optical properties, (3) Fukui indices, and (4) the two-level model. According to the calculated parameters, the better performance of P66 as NLO material was ascribed to the improved intramolecular charge transfer (IACT) properties of this molecule.

A Novel Natural Dye Derivative for Natural Fabric Supercritical Carbon Dioxide Dyeing Technology

The supercritical carbon dioxide (SC-CO2) dyeing technology is a green dyeing technology, and the usage of natural dye makes SC-CO2 dyeing technology safer and more environment-friendly. Nevertheless, after using natural dye in SC-CO2 dyeing, the color depth and fastness of dyed natural fabric are poor. In this study, alkyl and hydroxyalkyl groups were grafted onto alizarin, which is a natural dye, to elevate the color depths and fastness of alizarin-derivative-dyed natural fabric. The results demonstrate that the color depths of alkyl-alizarin-dyed and hydroxyalkyl-alizarin-dyed natural fabrics were increased. This has to do with the increase in the solubilities of alkyl alizarin and hydroxyalkyl alizarin in SC-CO2. The hydroxybutyl-alizarin-dyed wool displayed the best color depth (K/S value: 6.44). And the hydroxyalkyl-alizarin-dyed natural fabric showed good washing fastness and rubbing fastness (about 4–5 level), because that hydroxyalkyl alizarin could be linked by a covalent bond to the natural fabric.

Photostable Voltage-Sensitive Dyes Based on Simple, Solvatofluorochromic, Asymmetric Thiazolothiazoles.

A family of asymmetric thiazolo[5,4-d]thiazole (TTz) fluorescent dye sensors has been developed, and their photophysical sensing properties are reported. The π-conjugated, TTz-bridged compounds are synthesized via a single-step, double condensation/oxidation of dithiooxamide and two different aromatic aldehydes: one with strong electron-donating characteristics and one with strong electron-accepting characteristics. The four reported dyes include electron-donating moieties (N,N-dibutylaniline and N,N-diphenylaniline) matched with three different electron-accepting moieties (pyridine, benzoic acid, and carboxaldehyde). The asymmetric TTz derivatives exhibit strong solvatofluorochromism with Stokes shifts between 0.269 and 0.750 eV (2270 and 6050 cm-1) and transition dipole moments (Δμ = 13-18 D) that are among the highest reported for push-pull dyes. Fluorescence quantum yields are as high as 0.93 in nonpolar solvents, and the fluorescence lifetimes (τF) vary from 1.50 to 3.01 ns depending on the solvent polarity. In addition, thermofluorochromic studies and spectrophotometric acid titrations were performed and indicate the possibility of using these dyes as temperature and/or acid sensors. In vitro cell studies indicate good cell membrane localization, negligible cytotoxicity, promising voltage sensitivities, and photostabilities that are 4 times higher than comparable dyes. Their ease of synthesis and purification, remarkable photophysical properties, and chemically sensitive TTz π-bridge make these asymmetric dye derivatives attractive for environmental and biological sensing or similar molecular optoelectronic applications.

A boronic acid based intramolecular charge transfer probe for colorimetric detection of hydrogen peroxide

Many oxidative stress related diseases and adverse health conditions have been associated with the negative effects of hydrogen peroxide and other similar reactive oxygen species in human body. Therefore, increasing attention has been attracted to the detection and monitoring of hydrogen peroxide in living organisms and food items. In this work, a simple, inexpensive colorimetric method for the quantitative determination of hydrogen peroxide in aqueous sample is described. This method utilizes the de-protection of aryl boronic acid to yield a strongly colored water-soluble dye, which is capable of absorbing and emitting in the red region of the spectrum. The mechanism is faster in alkaline condition and utilizes the intramolecular charge transfer between strong phenolate donor and TCF acceptor, thus allowing a naked eye detection of hydrogen peroxide within seconds. The method is unaffected by the presence of various salts, metal ions, and other interfering species, and it can provide a limit of detection as low as ~1 ppm in aqueous samples. This unique way of generating a fluorogenic donor-acceptor pair holds a potential of this dye and other related derivatives for understanding the role of hydrogen peroxide in physiology and pathology.

Pyridine azo disperse dye derivatives and their selenium nanoparticles (SeNPs): synthesis, fastness properties, and antimicrobial evaluations.

AimAiming to produce pyridine azo disperse dyes with good fastness properties and promising antimicrobial activity, a number of novel systems of polyfunctionalized pyridine azo dyes and their selenium nanoparticles (SeNPs) were synthesized.Materials and methodsThe synthesized products were formed by the reaction of diazotized aniline derivatives or diazotized amino antipyrene with any of dibenzoyl methane or benzoyl acetone and cyanoacetamide in boiling ethanolic sodium ethoxide. The structures of the newly synthesized compounds were elucidated by elemental analysis and spectral data. Moreover, (SeNPs) of the pyridine azo disperse dyes were characterized by Ultra-Violet -Visible spectrophotometry, dynamic light scattering , X-ray diffraction, and transmission electron microscope analysis. On the other hand, the synthesized dyes and its (SeNPs) were applied for disperse dyeing of nylon 66 and their fastness properties were measured, such as washing, rubbing, perspiration, and light fastness. In addition, the antimicrobial activities for all the synthesized compounds and for (SeNPs) prepared compounds (2bN, 2cN, 2fN, 2gN, 2hN) were evaluated.ResultsCompounds 2bN, 2c, 2cN, 2fN, 2gN, 2h, 2hN, and 2i were the most active compounds against all Gram-positive and Gram-negative bacterial species. While, compounds 2b, 2f, 2g, and 5b were the most active toward some of the bacterial strains (at least two from the selected four strains). Moreover, compounds 2bN, 2cN, 2fN, 2gN, 2h, 2hN showed higher activity toward the fungal strain. Also, the minimal inhibitory concentrations for all the most active compounds were determined.ConclusionFinally, all the (SeNPs) compounds revealed higher activity against bacterial and fungal strains than the other synthesized compounds.