Synthesis and application of some novel antimicrobial monoazonaphthalimide dyes: synthesis and characterisation

A series of novel monoazo dyes based on N‐pyridine‐1,8‐naphthalimides were prepared using 4‐amino‐N‐2‐aminomethylpyridine‐1,8‐naphthalimide as the diazo component and N,N‐diethyl‐meta‐toluidine, 3‐(N,N‐diethylamino)acetanilide and N‐hydroxyethyl‐N‐ethylaniline as the coupling components. The synthesised dyes were purified by utilising column and preparative thin‐layer chromatography methods. The characterisations of the prepared dyes were carried out by differential scanning calorimetery, thin‐layer chromatography (R_f values), Fourier Transform infrared, and proton and carbon nuclear magnetic resonance techniques. The in vitro antibacterial activity of the novel synthesised compounds against Escherichia coli, Staphylococcus aureus, Bacillus subtilis and their antifungal activity against Candida albicans were evaluated by use of conventional agar dilution procedures and a minimum inhibitory concentration. Some of these synthesised dyes demonstrated antibacterial activity against Gram‐positive bacteria in addition to antifungal activities.     

Solubilisation kinetics of some monoazo naphthalimide disperse dyes containing butyric acid and investigation of fastness properties of the dyes on polyester

In this paper, the solubilisation kinetics of three novel monoazo disperse dyes based on naphthalimdes incorporating a butyric acid group were investigated in different conditions using spectrophotometry. All dyes showed a reasonable level of solubilisation in alkaline media. Kinetic studies of the solubilisation reaction of the dyes in alkaline media showed that the rate of solubilisation of all dyes is a pseudo first‐order reaction equation. The rate constants of the solubilisation reaction of the dyes in alkaline media indicated that dye 3 , which is prepared by the diazotisation of 4‐amino‐n‐butyric acid 1,8‐naphthalimide and coupled with N,N‐diethy‐n‐hydroxyethyllaniline, has the highest rate of reaction and dye 1 , which is prepared by the diazotisation of 4‐amino‐n‐butyric acid 1,8‐naphthalimide and coupled with N,N‐diethylaniline, has the lowest rate. The dyes were applied on polyester fabrics and their fastness properties were examined. The dyed fabrics showed a good to excellent degree of wash and rubbing fastnesses after replacing reduction clearing with alkali clearing.     

Novel hydrolysable azo disperse dyes based on N‐ester‐1,8‐naphthalimide: dyeing of polyester–cotton blends

The dyeing of polyester–cotton blends with new alkali‐hydrolysable azo disperse dyes based on N‐ester‐1,8‐naphthalimide was investigated. Polyester–cotton blend fabrics were dyed using both one‐ and two‐bath methods. Dyes 3 and 4 offered lower colour yield on polyester using the one‐bath method. For the rest of the dyes, employing either the one‐ or two‐bath method resulted in a similar colour yield on polyester fabric. The results for fastness properties and colour yield of the dyeings showed that the dyes were suitable for dyeing polyester–cotton blends using the one‐bath method. The kinetic study of hydrolysis of the dyes in alkali media obeyed the pseudo first‐order reaction rate.     

Synthesis of a novel fluorescent coloured copolymer based on 4‐butylthio‐1,8‐naphthalimide

A novel fluorescent coloured copolymer based on naphthalimide was prepared. Acenaphthene was brominated and oxidised to prepare 4‐bromo‐1,8‐naphthalic anhydride and further reacted with butanethiol, 2‐aminoethanol and acryloyl chloride, in order to obtain a new polymerisable fluorescent dye. The synthesised dyes were characterised by differential scanning calorimetry, absorption spectroscopy (Fourier Transform–infrared, proton and carbon nuclear magnetic resonance, ultraviolet–visible spectroscopy) and fluorimetry. Molar extinction coefficients and wavelength maxima were obtained by examining the dye solution in ethanol. The solvatochromic effects of the prepared dyes have also been investigated. Finally, the dye was copolymerised with methyl methacrylate and an intrinsically coloured copolymer was obtained. The photophysical characteristics of the obtained copolymer have also been considered. It is assumed that 99% of the copolymerised dye is chemically bonded to polymer chains. The fluorescent characteristics of the copolymer in the solid state were determined by fluorometer and it was found that it has relatively high fluorescent intensity. The physical properties of the synthesised copolymer have been evaluated by differential scanning calorimetry and gel permeation chromatography.     

Synthesis,characterization and fluorescence performance of a waterborne polyurethane‐based fluorescent dye 4‐amino‐N‐cyclohexyl‐1,8‐naphthalimide,WPU‐ACN

A waterborne‐polyurethane‐based fluorescent dye 4‐amino‐N‐cyclohexyl‐1,8‐naphthalimide (WPU‐ACN) was synthesized by attaching 4‐amino‐N‐cyclohexyl‐1,8‐naphthalimide (ACN) into polyurethane chains according to a prepolymer?ionomer process. The structure of WPU‐ACN was confirmed by means of Fourier transform infrared spectroscopy and UV?visible absorption. The number‐average molecular weight, glass transition temperature and average emulsion particle size for WPU‐ACN were determined as 7.8 × 10⁵ g mol^?1, 60 °C and 60 nm, respectively. The improved thermal stability of WPU‐ACN could be attributed to the incorporation of naphthalimide units in the preformed urethane groups. The fluorescence intensity of WPU‐ACN was dramatically enhanced compared with that of ACN. It was found that the fluorescence intensity of WPU‐ACN increased with increasing temperature, and the fluorescence spectra of WPU‐ACN showed a positive solvatochromic effect. In addition, the fluorescence of WPU‐ACN emulsion was very stable not only for long‐term storage but also for fluorescence quenching. © 2013 Society of Chemical Industry     

A highly selective ratiometric fluorescent sensor for Hg2+ based on 1,8‐naphthalimide

A sulfur probe based on 1,8‐naphthalimide was designed and synthesised, and its sensing behaviour towards a mercury ion was investigated by fluorescence spectroscopy. The probe showed higher selective recognition towards Hg²⁺ than towards other metal ions in methanol solution. Compared with 4‐amino‐substituted naphthalimide derivatives, the probe exhibited different fluorescent characteristics for sensing Hg²⁺. The novel, reaction‐based probe is recommended for selective recognition of Hg²⁺ with significant fluorescence change.     

Synthesis and properties of novel rosin‐based water‐borne polyurethane

A series of novel rosin‐based water‐borne polyurethanes (RWPUs) was prepared from fumaropimaric acid polyester polyol (FAPP) synthesised from rosin acid. Emulsions of the prepared RWPUs were investigated by transmission electron microscopy, and dried films of the emulsions were characterised by Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction and differential scanning calorimetry. Other properties including water absorption, tensile strength, elongation at break, and antibacterial activity of the RWPUs were also determined. The results suggest that RWPU prepared with 35 wt% FAPP has good potential for applications, with improved mechanical properties, thermal stability and water resistance. The RWPU showed excellent antimicrobial properties in killing both Gram‐negative Escherichia coli and Gram‐positive Staphylococcus aureus. Copyright © 2011 Society of Chemical Industry     

A facile synthesis and tautomeric structure of novel 4‐arylhydrazono‐3‐(2‐hydroxyphenyl)‐2‐pyrazolin‐5‐ones and their application as disperse dyes

The main target of this paper was the synthesis of novel azo disperse dyes with better dyeing properties, together with a systematic investigation to determine their dominant tautomer(s) from 12 possible tautomeric structures. In this regard, novel azopyrazolin‐5‐one dyes were synthesised via the reaction of hydrazine hydrate with 2,3,4‐chromantrione‐3‐arylhydrazones. The acid dissociation constants both in the ground and in the excited state for the series prepared were determined and correlated by the Hammett equation. The results of this correlation, together with spectral data, indicated that the compounds under scrutiny exist predominantly in the keto‐hydrazo structure as a Z‐configuration, both in the ground and in the excited state. Finally, the synthesised dyes were applied as disperse dyes for dyeing polyester fabrics, and their fastness properties were evaluated. Also, the position of colour in CIELAB coordinates was estimated and discussed.     

6‐Pyridinium benzo[a]phenazine‐5‐oxide derivatives as visible photosensitisers for polymerisation

Several 6‐pyridinium benzo[a]phenazine‐5‐oxide derivatives have been synthesised and characterised by proton nuclear magnetic resonance spectroscopy and mass spectrometry. The spectroscopic and electrochemical properties of these dyes were examined. The dyes were used as reducible sensitisers for selected electron donors (phenylthioacetic acid, phenoxyacetic acid, N‐phenylglycine, and ethyl 4‐N,N‐dimethylaminobenzoate) and as oxidisable sensitisers for electron acceptors (onium and N‐alkoxypyridinium salts). These photoredox pairs were found to be effective visible‐wavelength photoinitiators for the free radical polymerisation of trimethylolpropane triacrylate under visible light. The cationic photopolymerisation of cyclohexene oxide by the studied dyes and the onium salt photoredox pairs was ineffective. The obtained results are discussed on the basis of both free energy change for electron transfer to or from the benzo[a]phenazine dyes and the photochemical properties of the dyes, particularly their photobleaching. The proposed mechanism of dye fading is supported by density functional theory calculations and spectroscopic characterisation of the radical cation of the dye.     

Synthesis of temporarily solubilised azo disperse dyes containing a β‐sulphatoethylsulphonyl group and dispersant‐free dyeing of polyethylene terephthalate fabric

Disperse dyes containing a β‐sulphatoethylsulphonyl group have temporary solubility and can be applied for dispersant‐free dyeing of hydrophobic fibre. Six novel temporarily solubilised azo disperse dyes having a β‐sulphatoethylsulphonyl group in their structures were synthesised, and their dyeing properties on polyester were investigated. As a dye intermediate, a diazo component having dibromo groups was prepared, and 4‐diethylamino‐4′‐(2‐sulphatoethylsulphonyl‐4,6‐dibromo)azobenzene dyes were prepared by a diazo‐coupling reaction. Then, the dyes containing dicyano groups were prepared by cyanation of corresponding dyes with dibromo groups. The absorption maxima of the dyes were affected by the substituents in the diazo and coupling component rings and varied from 434 to 616 nm in dimethylformamide. Polyethylene terephthalate woven fabric could be dyed with the synthesised temporarily solubilised dyes without using any dispersants. Dyebath pH affected the K/S value at maximum absorption as well as percentage exhaustion on polyethylene terephthalate fabric, and the optimum pH was 5. The dyes gave brownish orange, red, purple, and greenish blue hues on polyethylene terephthalate fabrics, and colour build‐up was good. Wash fastness was good to excellent, rubbing fastness was moderate to excellent, and light fastness was poor to moderate.     

1,8‐Naphthalimides as Blue Emitting Fluorophores for Polymer Materials

The copolymerization of 1,8‐naphthalimide derivatives (as fluorophore) with acrylonitrile has been investigated. The photophysical characteristics of monomeric and polymeric fluorophores in N,N‐dimethylformamide solution have been determined and discussed. During copolymerization, no changes in the chromophoric systems of the fluorophore occur. The influence of the studied monomeric 1,8‐naphthalimide fluorophores upon the structurally bleached polyacrylonitrile has been determined. Infrared absorption characteristics of the polymerizable 4‐alkoxy‐ and 4‐allyloxy‐N‐substituted‐1,8‐naphthalimides have been measured and discussed. The effect of the substituents upon the vibration frequencies of the carbonyl and allylic groups has been established.

Blue fluorescent polyacrylonitrile copolymers with 1,8‐naphthalimides side‐group.     

Improvement of the dyeing and fastness properties of a naphthalimide fluorescent dye using poly(amidoamine) dendrimer

In this study, 4‐amino‐9‐methoxypropylnaphthalimide fluorescent dye (dye 1 ) was reacted with poly(amidoamine) dendrimer G = ?0.5 to prepare a naphthalimide–dendrimer hybrid dye (dye 2 ). The chemical structures of the synthesised dyes were confirmed by elemental analysis, Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance spectroscopy, and ultraviolet‐visible spectroscopy. The solvatochromism of the dyes was evaluated in various solvents with respect to visible absorption properties, and positive solvatochromism was observed by solvent polarity change from chloroform to ethanol. The dyeing ability of the synthesised dyes was investigated by their application onto nylon fabric, and nylon substrates dyed with dye 2 exhibited marked enhancement both in terms of colour strength and general fastness properties. The results of this study clearly demonstrated the high potential and performance of dye 2 as a novel promising fluorescent dye as compared with dye 1 . Overall, it was inferred that the modification of the naphthalimide fluorescent dye with poly(amidoamine) denderimer could markedly improve the dyeing and fastness properties of the naphthalimide fluorescent dye on nylon fabrics.     

Dyes derived from 3‐formyl‐2(1H)‐quinolone – synthesis,spectroscopic characterisation,and their behaviour in the presence of sulfhydryl and non‐sulfhydryl amino acids

Novel dyes based on a 3‐formyl‐2(1H)‐quinolone skeleton were synthesised and characterised using ¹H nuclear magnetic resonance spectroscopy and mass spectrometry. The spectroscopic properties of these dyes, such as their absorption spectra, emission spectra, and quantum fluorescence yields, were also examined. The behaviour of the obtained compounds at a pH of 7.4 in the absence and in the presence of thiol amino acids, such as l ‐cysteine, l ‐glutathione, and N‐acetyl‐l ‐cysteine, were studied. The spectroscopic responses of the tested dyes towards other amino acids were also investigated. A reference compound was synthesised to understand the reaction mechanism between the thiols and the obtained dyes. The experimental results show that the synthesised dyes have the potential to act as sensors for thiols.     

The synthesis of symmetrical and unsymmetrical alkylaminonaphthalic‐1,8‐N‐alkylimides

Symmetrical 4‐n‐alkylamino and 2‐(n‐alkylamino)naphthalic‐1,8‐N‐alkylimides are prepared with primary amines from 4‐ and 2‐halogenonaphthalic‐1,8‐anhydrides in N‐methylpyrrolidinone. 3‐Halogenonaphthalic‐1,8‐anhydrides only react at the anhydride. Unsymmetrical 4‐compounds result by reaction of primary amines with the anhydride in ethanol and then the 4‐halogeno‐N‐alkyl product in N‐methylpyrrolidinone with primary or secondary amines © 2000 Society of Chemical Industry     

Investigation of alkaline hydrolysis of phthalimide‐based azo dye and its application to after‐treatment optimisation for high‐fastness dyeing of polyesters

4‐Amino‐N‐methylphthalimide was prepared from phthalimide for use as a diazo component and was coupled with N,N‐Diethylaniline to produce a phthalimide‐derived monoazo disperse dye. The pseudo first‐order kinetics were confirmed by analyzing the dye hydrolysis under alkaline conditions using high performance liquid chromatography, and the optimal dyeing pH and alkali‐clearing conditions were proposed. The synthesised phthalimidyl disperse dyes exhibited excellent colour fastness with a mild alkaline after‐treatment instead of reduction clearing which results in a high biological oxygen demand and pH in conventional disperse dyeing wastewater.     

Preparation of thermally stable dyes derived from diketopyrrolopyrrole pigment by polymerisation with polyisocyanate binder

Four thermally stable and solvent soluble dyes were prepared from diketopyrrolopyrrole pigment via an N‐alkylation reaction. To improve the thermal stability of the dyes, a hydroxyl functional group that could react with blocked polyisocyanates was introduced into the dyes. The prepared dyes had absorption maxima near 500 nm, and the chromaticity diagrams of all synthesised dyes exhibited smaller x and y values than those of CI Pigment Red 254, indicating that the colour of the synthesised dyes was close to an orange shade. The dyes reacting with blocked polyisocyanates showed extremely high thermal stability compared with analogous dyes not reacting with polyisocyanates.     

Imparting insect repellency to nylon 6 fibers by means of a novel MCT reactive dye

Insect repellency of fiber is a property which makes the fiber to be of interest in the field of military and health. The insect‐repellent substrate could be prepared using either functional finishing or applying an insect‐repellent dye. In this article, insect‐repellent nylon 6 is obtained using a novel insect‐repellent reactive dye containing N,N‐diethyl‐m‐toluamide. To do this, N,N‐diethyl‐m‐toluamide (DEET) was first nitrated at the p‐position relative to amide functionality. The nitrated product was reduced in the presence of C₂H₅OH, SnCl₂, and HCl. The produced amine was then condensed with 2,4,6‐trichloro‐1,3,5‐triazine (cyanuric chloride) as a reactive group in below 5°C. The resultant adduct was finally reacted with an amino group present in 6‐amino‐1‐hydroxy naphthalene‐3‐sulfonic acid (J‐acid) to produce 7‐(4‐chloro‐6‐(4‐(diethylcarbamoyl)‐2‐methylphenylamino)‐1,3,5‐triazin‐2‐ylamino)‐4‐hydroxynaphthalene‐2‐sulfonic acid. To synthesis azo dye, sulfanilic acid was diazotized using HCl and NaNO₂ and then coupled to the above prepared component to produce insect‐repellent reactive dye. An analog dye was prepared via the same route without insect‐repellent group making stage. The chemical structures of the novel dyes were characterized using FTIR and ¹H‐NMR spectroscopy. The spectroscopic properties of the dyes were determined in terms of λ_max and ε_max in aqueous solution. The novel dyes were then reacted with nylon 6 and bonded to it covalently to provide permanent insect‐repellent substrate. The insect‐repellent efficacy of the reacted nylon 6 was studied using standard methods for Anophele mosquito repellent. The insect‐repellent dye reacted nylon 6 showed insect‐repellent activity. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis,spectral properties and application of novel disazo disperse dyes derived from polyester waste

Terephthalic dihydrazide was obtained through aminolytic depolymerisation of polyester bottle waste by using hydrazine hydrate. It was further reacted with 4‐aminobenzoic acid in the presence of polyphosphoric acid to obtain a cyclic compound, 4,4′‐[5,5′‐(1,4)‐phenylene)bis(1,3,4‐oxadiazole‐5,2‐diyl)dianiline, having a heterocyclic moiety. Diazotisation of this compound followed by coupling with various N,N‐disubstituted anilines afford a series of novel disazo disperse dyes. The structures of these synthesised dyes were confirmed by elemental analysis and Fourier Transform–infrared, proton nuclear magnetic resonance and mass spectroscopy. Ultraviolet–visible spectra of these azo dyes in different polar solvents showed considerable variation in the wavelength of maximum absorbance (λ_max). Application of these dyes on polyester and nylon fabrics using high‐temperature dyeing methods gave brilliant yellowish red hues with fair to moderate light fastness and very good to excellent wash fastness and sublimation fastness.     

Preparation,characterization, and properties of crosslinked hydroxylated poly(styrene‐b‐butadiene‐b‐styrene) triblock copolymer

Acrylic acid was crosslinked with N,N′‐methylenebisacrylamide and converted to bioactive hydrogels by neutralization with different amino containing compounds. Several amino containing compounds were used such as 2‐aminopyridine, triethanol amine, hexamethylenetetramine (HMTA), pyridine, and imidazole. The best crosslinker ratio was determined in addition to the maximum absorbed water in different mediums. The antibacterial activity of the prepared gels were examined against examples of Gram‐positive (Staphylococcus aureus) and Gram‐negative bacteria (Escherichia coli) using agar plate method. The study was extended by evaluating one of prepared gels in columns as models for water filters. All prepared gels showed antibacterial action in agar plate method against both bacterium and the column method using one of the prepared gels showed excellent filtration and biocidal action. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and application of KM‐type reactive dyes containing 2‐ethoxy‐4‐chloro‐s‐triazine

A new kind of hetero‐bifunctional reactive dye containing 2‐ethoxy‐4‐chloro‐s‐triazine, with better activity matching with β‐hydroxyethyl sulphone sulphate at a low fixation temperature, was successfully synthesised and characterised. An ethoxy group was designed to be introduced into triazine to increase the substantivity and the reactivity of the dyes. Thereby, the fixation of mono‐s‐chlorotriazine/hydroxyethyl sulphone sulphate (KM‐type) bifunctional reactive dyes on cotton was improved, and dyeing under mild conditions with high fixation was realised. Nineteen dyes with orange, red and blue colours were synthesised and characterised by UV‐Vis and infrared spectroscopy and mass spectrometry. Synthesised dyes were dyed at 60, 75 and 90°C, respectively. Exhaustion and reactivity for all of the ethoxy‐containing KM‐type dyes was over 90% at the optimal temperature, and fixation was over 87%, which was higher than the ethoxy‐free comparative dyes. The optimal fixation temperature of ethoxy‐containing dyes was initially reduced to 75°C, and then to 60°C. Compared with comparative dyes, the wash fastness and light fastness were basically unchanged, and the wet rub fastness of the H‐acid series was reduced by one grade.