Synthesis and application to cellulose of reactive dye precursor of anti‐bacterial N‐halamine

To achieve textile dyeing and functional finishing in one process, a bleach‐resistant reactive dye precursor to anti‐bacterial N‐halamine was synthesised by reacting a type of dichlorotriazine reactive dye with 4‐amino‐2,2,6,6‐tetramethylpiperidine. The synthesised compound, which can be transformed to an N‐halamine molecule by exposure to dilute bleach solution, was used to dye cotton fabrics. After exposure to a dilute sodium hypochlorite solution, dyed cotton fabrics showed excellent anti‐bacterial properties against Staphylococcus aureus and Escherichia coli O157:H7, facilitating a ca. 6‐log reduction in bacteria within a short period of contact. Compared with the dichlorotriazine reactive dye, the reactive dye precursor demonstrated comparable dyeing properties including exhaustion and fixation values. No differences in rub fastness, wash fastness or bleach fastness were detected between fabrics dyed with, respectively, dichlorotriazine reactive dye and the reactive dye precursor to N‐halamine.     

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.     

Design,Synthesis, and Biological Evaluation of Shikonin and Alkannin Derivatives as Potential Anticancer Agents via a Prodrug Approach

To minimize the cytotoxicity of shikonin and alkannin that arises through the generation of reactive oxygen species (ROS) and alkylation of the naphthazarin ring, two series of novel core‐scaffold‐modified shikonin and alkannin derivatives were designed. These derivatives, which differ in their configurational and positional isomerism (R‐, S‐, and 2‐ and 6‐isomers) were synthesized in high enantiomeric excess (>99 % ee). The selectivity of the dimethylated derivatives was significantly higher than the parent shikonin in vitro, but some side effects were still observed in vivo. Surprisingly, the dimethylated diacetyl derivatives with poor anticancer activity in vitro showed tumor‐inhibiting effects similar to paclitaxel without any toxicity in vivo. The anticancer activity of these derivatives is in agreement with their low ROS generation and alkylating capacity, emphasizing their potential as prodrugs. This strategy provides means to address the nonspecific cytotoxicity of naphthazarin analogues toward normal cells.     

5,8‐Dihydroxy‐9,12,15(Z,Z,Z)‐Octadecatrienoic Acid Production by Recombinant Cells Expressing Aspergillus nidulans Diol Synthase

Whole cells of recombinant Escherichia coli expressing diol synthase from Aspergillus nidulans produced 5,8‐dihydroxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid from α‐linolenic acid via 8‐hydroperoxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid as an intermediate. The optimal conditions for 5,8‐dihydroxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid production using whole recombinant cells were exhibited at pH 7.0, 40 °C, and 250 rpm with 40 g/L cells, 12 g/L, α‐linolenic acid, and 5 % (v/v) dimethyl sulfoxide in a 250‐mL baffled flask containing 50 mL reaction solution. Under these conditions, whole recombinant cells produced 9.1 g/L 5,8‐dihydroxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid for 100 min, with a conversion yield of 75 % (w/w), a volumetric productivity of 5.5 g/L/h, and specific productivity of 137 mg/g‐cells/h. As an intermediate, 8‐hydroperoxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid was observed at approximately 1.4 g/L after 100 min. With regard to dihydroxy fatty acid production, this is the highest reported volumetric and specific productivities thus far. This is the first report on the biotechnological production of 5,8‐dihydroxy‐9,12,15(Z,Z,Z)‐octadecatrienoic acid.     

Synthesis of sulfated β‐cyclodextrin/cotton/ZnO nano composite for improve the antibacterial activity and dyeability with Azadirachta indica

The sulfated β‐cyclodextrin (sb‐cd) was prepared from β‐cyclodextrin and the sb‐cd was crosslinked with cotton fabric using ethylenediaminetetraacetic acid (EDTA) as crosslinker. After crosslinking, the synthesized ZnO nanoparticles were padded on this fabric surface. Then, the treated fabrics were dyed with neem extract. The synthesized polymer, crosslinked and nanoparticle‐treated cotton fabrics were characterized using fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), particle sized analyzer, and transmission electron microscopy (TEM) studies. The antibacterial test was done against Staphylococcus aureus and Escherichia coli bacterium. The composite coated with neem dyed cotton fabric has exhibited 71% of dye uptake with 2–3 fastness grade and it has 99% of antibacterial efficiency for S. aureus and 97% for E. coli bacterium. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Direct coloration of textiles with photochromic dyes. Part 1: Application of spiroindolinonaphthoxazines as disperse dyes to polyester,nylon and acrylic fabrics†

1,3,3‐Trimethylspiroindoline‐2,3′‐3H‐naphth[2,1‐b][1,4]oxazine ( 1a ) and 6′‐piperidino‐1,3,3‐trimethylspiroindoline‐2,3′‐3H‐naphth[2,1‐b][1,4]oxazine ( 1b ) were applied as disperse dyes to polyester, nylon and acrylic fabrics. Under optimised dyeing conditions, photochromic fabrics were produced which, on irradiation with ultraviolet or exposure to sunlight, turned blue ( 1a) or blueish‐purple ( 1b ). Dye 1a showed enhanced photochromic colour change performance compared with dye 1b . The photochromic colour build was highest on nylon and lowest on acrylic fabric. The colour change properties and the technical performance (wash fastness and photostability) of the photochromic fabrics were evaluated using specifically adapted colour measurement methods. The data were analysed in terms of variation of lightness, a*, b*, chroma, hue angle and ΔE, colour difference before and after exposure, and K/S curves as a function of irradiation time. The fabrics generally showed good wash fastness. Although the colour build‐up decreased with exposure to the Xenotest fadeometer, some residual photochromism remained after prolonged exposure.     

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.     

Modified polyurethane with improvement of acid dye dyeability

This article concerns the modification of polyurethane using polyamide 6,6 prepolymer to improve the dyeability properties of the polyurethane copolymer with acid dye. First, the carboxyl‐terminated polyamide 6,6 prepolymer was synthesized from adipic acid and 1,6‐diaminohexane. The isocyanate‐terminated polyurethane prepolymer was also synthesized from polytetramethylene glycol and 4,4′‐diphenylmethane diisocyanate in N,N‐dimethylformamide. The polyurethane prepolymer was then extended with a mixture of 1,4‐butanediol and the polyamide 6,6 prepolymer (molar ratios of 1,4‐butanediol to prepolymer being 100%, 75%, 50%, and 25%, respectively). Finally, the poly(urethane–amide) copolymers were dyed with acid dyes. The chemical, physical, and the dyeing properties of the poly(urethane–amide) coploymers are discussed. From the experimental results, it is found that the inherent viscosity of poly(urethane–amide) coploymers is increased with the increasing amount of polyamide content. The structure is proven by infrared spectra, which exhibits the absorption peaks of urethane and amide groups as we expected. From the differential scanning calorimetry measurements, it is found that the poly(urethane–amide) coploymers have two‐phase structures and good phase separation. There are four transition temperatures (T_gs, T_gh, T_ms, and T_mh), but only those copolymers in PTMG 2,000 series possess T_ms. Moreover, the T_gs is found to change with the length of soft segment, and the T_gh is increased with the increasing amount of polyamide content. Also, the dyed copolymers exhibit higher T_gh than those without dyeing of dye molecule, but the T_gs is not obviously changed. For mechanical properties, it is indicated that both the modulus and the strength of the coploymers are higher than those of unmodified polyurethane, but they are lowered after being dyed with dye molecule due to further separation of intermolecular distance of the dyed polyurethanes. For dye uptake in dyeing properties, it is found to increase with increasing amount of polyamide content. For dye fastness, the dyed copolymers exhibit higher grade of water fastness than that of unmodified polyurethane. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1397–1404, 2003     

Direct coloration of textiles with photochromic dyes. Part 2: The effect of solvents on the colour change of photochromic textiles†

Polyester, acrylic and nylon textile substrates dyed with two spirooxazine dyes, 1,3,3‐trimethyl‐spiroindoline‐2,3′‐3H‐naphth[2,1‐b][1,4]oxazine ( 1a ) and 6′‐piperidino‐1,3,3‐trimethyl spiroindoline‐2,3′‐3H‐naphth[2,1‐b][1,4]oxazine ( 1b ), exhibit significantly higher photochromic colour build‐up when wet compared with after drying. A study of this phenomenon, extended beyond water to the influence of a series of selected organic solvents on photochromic behaviour, using colour measurement of the photochromic textiles under controlled ultraviolet irradiation conditions, is reported. The results of molecular modelling calculations (AM1 in water and PM5 in water) have been used as a means of interpreting the observed effects, in conjunction with qualitative arguments based on solvation and fibre swelling.     

Shade darkening effect of polyorganosiloxane modified with amino and hydroxy groups on dyed polyester microfiber fabric

The novel polyorganosiloxane material S‐101 modified with amino and hydroxy groups is synthesized. Shade darkening effect of modified polyorganosiloxane on dyed polyester microfiber fabric is investigated by reflectance spectrum, color yield (K/S), and the color differences (ΔE). The colorimetric data of CIELAB is discussed. The results show that the novel material of silicone polymer modified with amino and hydroxy groups has excellent shade darkening effect on dyed polyester microfiber fabric. The rates of the color yield increase (I%) of all dyed fabric with four dyes (Disperse Yellow S‐4RL, Red GS, Blue 2BLN, and Black SF‐R) exceed 10%. The shapes of the reflectance spectra curves of the dyed fabrics before and after treated with S‐101 are not noticeable change. The dyed fabrics with the polymer have not significant effect on the wash fastness and wet rubbing fastness. The low reflectance thin film on dyed fabrics is formed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Simultaneous antimicrobial and dyeing of wool: A facial method

This study is carried out to examine the effects of simultaneous dyeing and antimicrobial finishing of wool yarns. Wool yarns were dyed with acid dye along with colloidal silver nanoparticles through the exhaustion method in a one‐bath. Different concentrations of nanosilver were examined to evaluate its influences on the color and the antibacterial properties of the yarns. The antibacterial property of the sample has been tested by a Gram‐negative bacterium Escherichia coli and a Gram‐positive bacterium Staphylococcus aureus. Also, the tenacity of wool yarns, color, and rubbing fastness of the dyed yarns has been measured. The color fastness against washing and antibacterial property of the dyed yarns after 10 laundering cycles was also considered. The fiber morphology was studied by SEM pattern, EDX, and X‐ray diffractometer. The results showed that the wool yarns dyed with acid dye along with 25 ppm of silver nanoparticles exhibited a very good antimicrobial effect even after 10 laundering cycles on S. aureus while the rubbing fastness remained unchanged, and the color fastness and tenacity were even improved. © 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.     

Pretreatment of cotton fabrics with polyamino carboxylic acids for salt‐free dyeing of cotton with reactive dyes

In this study, polyamino carboxylic acids have been used to improve the dyeability of cotton in a salt‐free reactive dyeing process. These polyamino carboxylic acids were prepared by partial carboxylation of polyvinylamine. Cotton fabric was pretreated with polyamino carboxylic acids and dyed with reactive dyes. The colour strengths of the dyed fabrics were evaluated by measuring the K/S values. The fastness properties (washing, rubbing and light fastness) of the dyed cotton fabrics were also measured. The pretreatment of cotton with polyamino carboxylic acids creates positive charges on the fabric surface. In this way, salt‐free reactive dyeing of cotton or dyeing with only a small amount of electrolyte is possible.     

Microwave‐assisted polycondensation of 4,4′‐(hexafluoroisopropylidene)‐N,N′‐bis(phthaloyl‐L‐leucine) diacid chloride with aromatic diols

A new facile and rapid polycondensation reaction of 4,4′‐(hexafluoroisopropylidene)‐N,N′‐bis(phthaloyl‐L ‐leucine) diacid chloride (1) with several aromatic diols such as phenol phthalein (2a), bis phenol‐A (2b), 4,4′‐hydroquinone (2c), 1,4‐dihydroxyanthraquinone (2d), 1,8‐dihydroxyanthraquinone (2e), 1,5‐dihydroxy naphthalene (2f), dihydroxy biphenyl (2g), and 2,4‐dihydroxyacetophenone (2h) was performed by using a domestic microwave oven in the presence of a small amount of a polar organic medium such as o‐cresol. The polymerization reactions proceeded rapidly, compared with the conventional solution polycondensation, and was completed within 10 min, producing a series of optically active poly(ester‐imide)s with quantitative yield and high inherent viscosity of 0.50–1.12 dL/g. All of the above polymers were fully characterized by IR, elemental analyses, and specific rotation. Some structural characterization and physical properties of this optically active poly(ester‐imide)s are reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3003–3009, 2000     

Improving the UV resistance of aromatic poly(1,3,4‐oxadiazole) fiber using the disperse dye modified with octavinyl POSS. Part 2: Fixing form of dye and UV resistance ability

Disperse Red 60 modified with octavinyl polyhedral oligomeric silsesquioxanes (POSS) was used to color poly(p‐phenylene‐1,3,4‐oxadiazoles) (p‐POD) fiber. The dyed p‐POD fiber was given high UV resistance and excellent color strength (K/S value) simultaneously. And the effects of the UV irradiation time on the K/S values and the strength retention of dyed fiber were investigated. The results indicated that the modified dye (1:3) molecules can easily be adsorbed on fiber surface and diffuse into fiber, whose fixing form on the fiber surface is a semiembedded type. Meanwhile, the surface morphology, the aggregation structure, the thermal property, the color fastness, and anti‐UV durability of the dyed p‐POD fiber were characterized. After UV accelerated aging, the macroscopic and microscopic structures of the dyed p‐POD fiber can well be maintained and the color fastness is also satisfactory. Meanwhile, this method also solves the problem of poor anti‐UV durability of the modified fiber with the previous processes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44928.     

Thiol‐ene photofunctionalization of 1,4‐polymyrcene

1,4‐Polymyrcene was synthesized by anionic polymerization of β‐myrcene and was subjected to photochemical functionalization with various thiols (i.e. methyl thioglycolate, methyl 3‐mercaptopropionate, butyl 3‐mercaptopropionate, ethyl 2‐mercaptopropionate and 2‐methyl‐2‐propanethiol) using benzophenone/UV light as the radical source. The yield of thiol addition to the trisubstituted double bonds of 1,4‐polymyrcene decreased in the order 1° thiol (ca 95%) > 2° thiol (ca 80%) > 3° thiol (<5%), due to the reversibility of the thiol‐ene reaction. Remarkably, thiol addition to the side‐chain double bonds was 8 ? 10 times (1° thiol) or 24 times (2° thiol) faster than to the main‐chain double bonds, which can be explained by the different accessibility of the double bonds and steric hindrance. Despite the use of a 10‐fold excess of thiol with respect to myrcene units, the thiol‐ene addition was accompanied by chain coupling reactions, which in the extreme case of 3° thiol (or in the absence of thiol) resulted in the formation of insoluble crosslinked material. As an example, a methyl‐thioglycolate‐functionalized 1,4‐polymyrcene was saponified/crosslinked to give submicron polyelectrolyte particles in dilute alkaline solution. © 2018 Society of Chemical Industry     

Natural colorant from the bark of Macaranga peltata: kinetic and adsorption studies on silk

The colour component from the bark of Macaranga peltata has been extracted and, using spectral techniques, the main colouring ingredient has been identified as ellagic acid. The dyeing properties of the extract on silk have been studied. The colour coordinates of the dyed samples were found to be in the yellow–red quadrant of the colour space diagram and the dyed samples exhibited acceptable fastness properties. The effect of temperature and dye concentration on the rate of dyeing has been studied. Adsorption studies revealed that the process fits well with the Langmuir isotherm model. The thermodynamic parameters of the dyeing process have been evaluated using an Arrhenius plot. The experimental results revealed that the adsorption was exothermic and spontaneous in nature, and exhibited first‐order kinetics. Further, the effect of electrolyte on rate of dyeing has also been recorded. The rate of adsorption increases as the disrupting effect of the added electrolyte cation increases and follows the order: Al³⁺ > Ca²⁺ > Na⁺.     

Optimising by response surface methodology the dyeing of polyester with a liposome‐encapsulated disperse dye

Optimisation of conditions for dyeing polyester with liposome‐encapsulated CI Disperse Red 50 was performed using response surface methodology. The effects of temperature, time, and lecithin:dye ratio on the colour strength of dyed fabrics were investigated by a central composite design. The coefficient of determination, the probability value in analysis of variance, and the normality plot of residuals demonstrated sufficient significance of the proposed fitness function. It was found that the temperature and time of the dyeing cycle were effective factors in the dyeing of polyester fabrics with encapsulated dye. It was also established that the colour yield of dyed fabrics was above 25 in the case of a dyeing time of >80 min, a lecithin:dye ratio of ≤2, and a temperature of ca. 128 °C. Comparison of colour strengths produced by liposome‐encapsulated dye and commercial dye revealed that there was approximately the same build‐up on polyester. Dyeings from encapsulated CI Disperse Red 50 exhibited very similar fastness to dyeings from conventional CI Disperse Red 50.     

Investigation on colour,fastness properties and HPLC‐DAD analysis of silk fibres dyed with Rubia tinctorium L. and Quercus ithaburensis Decaisne

Silk fabric samples were dyed according to the various procedures using madder (Rubia tinctorium L.) and walloon oak (Quercus ithaburensis Decaisne) extracts. The colour coordinates, K/S, as well as wash, light, rub and perspiration fastness values were determined. A reversed‐phase high‐performance liquid chromatography with diode‐array detection was utilised for the identification of the components of dyes present in the dyed fabrics and in the plant extracts.     

Assessment of the dyeing properties of pigments from five fungi and anti‐bacterial activity of dyed cotton fabric and leather

The present study was aimed to assess the anti‐bacterial activity and dyeing property of the pigments obtained from five fungal species. Cotton fabric and leather samples were dyed with the purified pigments and their anti‐bacterial activity was assayed under in‐vitro conditions. Post‐mordant cotton fabric and leather samples exhibited maximum bacterial reduction when compared with the pre‐mordant and dyed samples. Pigment exhaustion, colour coordinates and fastness properties of the dyed cotton fabric and leather samples were also assessed. The toxicity of the pigments was evaluated by seed germination assay.