Equilibrium and kinetic modeling of the adsorption of indigo carmine onto silk

Quantitative adsorption kinetic and equilibrium parameters for indigo carmine dyeing of silk were studied using UV-visible absorption spectroscopy. The effect of initial dye concentration, contact time, pH, material to liquor ratio (MLR), and temperature were determined to find the optimal conditions for adsorption. The mechanism of adsorption of indigo carmine dyeing onto silk was investigated using the pseudo first-order and pseudo second-order kinetic models. The adsorption kinetics was found to follow a pseudo-second-order kinetic model with an activation energy (E _a) of 51.06 kJ/mol. The equilibrium adsorption data of indigo carmine dye on silk were analyzed by the Langmuir and Freundlich models. The results indicate that the Langmuir model provides the best correlation. Adsorption isotherms were also used to obtain thermodynamic parameters such as free energy (ΔG ^o), enthalpy (ΔH ^o), and entropy (ΔS ^o) of adsorption. The negative values of ΔG ^o and Δ^{H o} indicate the overall adsorption process is a spontaneous and exothermic one.     

Dyeing properties and antimicrobial activity of silk fabric with extract of unripe Citrus Unshiu fruits

This study was carried out to optimize dyeing conditions of unripe Citrus Unshiu extract on silk fabric and to evaluate antimicrobial activity of the dyed fabric for its potential use as a functional natural dye. Unripe fruits of Citrus Unshiu in Jeju Island, Korea, extracted in 80 % Ethanol solution to final solid dye powder were dyed on silk fabric under a variety of conditions such as dye bath concentrations, temperature, and dyeing duration together with mordanting. Dyeing fastness properties to washing, rubbing, perspiration, and light were tested and the antimicrobial activities of the dyed fabric against Staphylococcus aureus and Klebsiella pneumoniae were investigated quantitatively. As results, the fabric showed the maximum dye uptake (K/S) under the conditions of 80 °C for temperature, 30 min for duration, and 600 % (o.w.f.) for dye concentration. Both pre- and post-mordanting seemed not to be effective on increasing K/S values of the dyed silk fabrics under the optimum dyeing conditions. Fastness ratings to washing, rubbing, and perspiration were all very good (4–5 grades) for both 300 and 600 % dyed silk fabrics. Excellent antimicrobial activities over 99 % reduction rate against two both bacteria were exhibited for all of dyed fabrics undergone more than 300 % of dye concentration. From these results, it was concluded that the dye concentration of 300 % of unripe Citrus Unshiu could be employed to produce antimicrobial silk fabric. Furthermore, to get more saturated shades on the fabric by the citrus, higher dye concentration such as 600 % was available as well.     

Thermodynamics of adsorption of laccaic acid onto chitosan and associated dye toxicity studies

The thermodynamics of adsorption of laccaic acid (lac dye) onto chitosan were investigated under acidic condition over various concentrations (20–293 mg/l). Langmuir, Freundlich, and Temkin isotherms were used to analyze the equilibrium data at different temperatures, with the Freundlich isotherm fitting the experimental data significantly better than the other isotherms. The effect of temperature on the adsorption isotherm was studied by carrying out a series of isotherms at 10, 20, 40, and 60 °C. It was found that more dye was strongly adsorbed by chitosan when the temperature of the dye solution increased. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) were also evaluated. The negative value of ΔG° and positive value of ΔH° indicated that the laccaic acid adsorption process is a spontaneous and an endothermic one. Attenuated total reflectance Fourier transform infrared spectroscopy confirmed the functional groups of chitosan that affected the laccaic acid adsorption. Therefore, laccaic acid molecules could interact with the chitosan via electrostatic forces, hydrogen bonding, and ion-dipole interactions under acidic condition. From the toxicity study, the dye solution with the initial dye concentrations of 40 and 120 mg/l before dye removal showed significant mortality to earthworm Diplocardia communis (P<0.01).     

Dyeing properties and colour fastness of cotton and silk fabrics dyed with<Emphasis Type="Italic">Cassia tora L.</Emphasis> extract

A natural colorant was extracted fromCassia tora L. using buffer solutions (pH: 2–11) as extractants. The dyeing solution (Cassia tora L. extract) extracted using pH 9 buffer solution was found to give the highest K/S values of dyed fabrics. Cotton and silk fabrics were dyed withCassia tora L. extract at 60°C for 60 min with pre-treatment of various metal salts as mordants. It was found thatCassia tora L. extract was polygenetic dyestuffs and its major components were anthraquinones. Studies have been made on the effects of the kind of mordant on dyeing properties and colour fastnesses of cotton and silk fabrics. The K/S of cotton fabrics increased in the order of the dyeing using FeSO₄>CuSO₄>ZnSO₄>MnSO₄≅Al₂(SO₄)₃>NiSO₄>none, however, the K/S of silk fabrics increased in the order of the dyeing using FeSO₄>CuSO₄>ZnSO₄≅Al₂(SO₄)₃>MnSO₄≅NiSO₄>none. It was found that the K/S values of dyed fabrics were largely affected by the colour difference (ΔE) between mordanted fabric and control fabric. However, they were not depended on the content of mordanted metal ion of the fabrics. Mordants FeSO₄ and CuSO₄ for cotton fabric, FeSO₄, CuSO₄, and Al₂(SO₄)₃ for silk fabric were found to give good light fastness (rating 4).     

Eco-friendly dyeing using natural mordant extracted from <Emphasis Type="Italic">Emblica officinalis G</Emphasis>. Fruit on cotton and silk fabrics with antibacterial activity

Emblica officinalis G. dried fruit tannin was extracted and applied as a natural mordant alone and in combination with metal mordant namely copper sulphate for dyeing on cotton and silk fabrics using natural dyes. The color strength, color-coordinates, wash and light fastness were also evaluated for cotton and silk fabrics with and without mordanting. The pre-mordanted cotton and silk fabrics on dyeing gave better color strength, wash and light fastness than those dyeing obtained without mordanting. The total phenolic content of the extract was calculated. Cotton and silk fabrics resulted in good antibacterial activity using the Emblica officinalis G. mordant. When mordant was used along with 0.5 and 1 % copper sulphate mordant and the activity enhanced and was active up to 20 washes.     

Synthesis, characterization and application of quinazolinone based reactive dyes for various fibers

Seven hot brand heterocyclic mono azo reactive dyes (7a–g) have been synthesized by coupling diazotized 2-phenyl-3{4′-[(4″-aminophenyl)sulphonyl]phenyl}-quinazoline-4(3H)-one-6-sulphonic acid (4) with various 2-chloro-4-nitro anilino cyanurated coupling components (6a–g) and their dyeing performance on silk, wool, and cotton has been assessed. The purity of dyes was checked by thin layer chromatography. These dyes were identified by recording IR and ¹H-NMR spectra. The λ _max, R _f value, %exhaustion, %fixation, light fastness, wash fastness, rubbing fastness, reflectance (%R) value, and K/S value have also been studied.     

Thermal degradation studies of poly(o-anisidine) doped with 5-sulfosalicylic acid

Thermal decomposition of the solid state of poly(o-anisidine) (POAN) base (POAN-EB) and salt [doped with 5-sulfosalicylic (SSA) acid] (SSA-doped POAN) forms has been studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) under non-isothermal conditions. The potential (PE) and optimum molecular geometric (OMG) energies of the repeating unit (tetramer form) of investigated matrix were calculated using molecular mechanics (MM+) calculations. These calculations (PE= −3.48×10⁹ and OMG=−122.72 kJ mol⁻¹) indicate that the optimum molecular geometric structure of this matrix is highly stable. The empirical formula of the doped polymer is best represented by [POAN-2SSA.n/6H₂O] and substantiate by elemental analysis and MM+ calculations. The full polymer decomposition and degradation were found to occur in three stages during the temperature increase. The decomposition activation energy (E _d) of both POAN base (POAN-EB) and its doped (SSA-doped POAN) were calculated by employing different approximations. The heating rate of decomposition and the frequency factor (k _o ) as well as kinetic parameters were calculated for doped or base form of this matrix. A remarkable heating rate dependence of the decomposition rate of the SSA-doped POAN matrix was observed.     

Influence of water hardness on acid dyeing with silk

In this paper, the effect of water hardness, expressed in CaCO₃ equivalent, on the dyeing silk with acid dye under acid, alkaline and isoelectric point dyeing conditions was studied by zeta potential method. Under acid condition and in the presence of calcium ion, the positive zeta potential of silk was found to decrease with a reduction in the dye adsorption. Such a phenomenon might be due to the presence of cation which increased the dyeing potential barrier at the interface between fibre and dye solution. This would result in a higher resistance of dye anions passing through the interface. Under alkaline condition, the zeta potential on silk was negative and resulted in a strong potential barrier for the dye anions. The presence of calcium ion would result in a decrease in the absolute value of zeta potential of silk fibre with an overall increase in dye absorption. Under isoelectric point, the zeta potential of silk fibre was found to be near zero and dye adsorption was not influenced by the cations. When studying the effect of calcium ion on the silk dyeing with acid dye under acid, alkaline and isoelectric point dyeing conditions, it was found that calcium ions influenced dye exhaustion and fixation greatly under acidic and alkaline dyeing conditions, which such influence became much smaller when the pH of dyebath was at the isoelectric point of the fibre. These results showed that calcium ion could produce strong electrolytic effect on dyeing even under very low concentrations.     

The acid doping behavior of polybenzimidazole membranes in phosphoric acid for proton exchange membrane fuel cells

The acid doping behavior of poly(2,2′-(m-phenylene)-5,5′-bibenzimidazole) (PBI) membranes in aqueous phosphoric acid was studied at room temperature. It was found that doping phosphoric acid in the membrane obeyed a multimolecular layer absorption mechanism proposed in this work. Equation, i.e., 1/[L ^T ] _B =(1 − C ₀/17.5)/2.1, was presented to describe the relationship of the acid doping level of membranes and the concentration of the doping acid in a range of 2–14 mol L⁻¹. The acid doping kinetics as well as the influence of the doped acids on the conductivity and mechanical strength of the PBI membranes was investigated.     

Extraction, identification and dyeing studies of Isosalipurposide, a natural chalcone dye from Acacia cyanophylla flowers on wool

A chalcone compound Isosalipurposide 1 was qualitatively isolated from Acacia cyanophylla yellow flowers. The dyeing of wool fabrics with this chalcone compound as a natural dye has been studied. The effect of dye bath pH and dyeing temperature were investigated. The obtained shades were bright with generally a good fastness. A post-mordanting method was used in the dyeing of wool with this chalcone dye. It was found that, generally, mordanting improved light fastness especially in the case of zinc sulphate.     

Synthesis of thermotropic polyurethanes containing imide units and their mesophase behavior

Thermotropic polyurethanes were synthesized from 1,6-hexane diisocyanate (HDI) as a diisocyanate, 1,6-hexane diol (HD), and rigid diols containing imide unit such as N,N′-bis(4-hydroxyphenyl)-3,4,3′,4′-biphenyl-dicarboxyimide (BPDI) or bis-N-(4-hydroxyphenyl)-4,4′-oxydiphthalimide (ODPI). The effects of structure difference between BPDI and ODPI and composition of HD/BPDI (ODPI) on the thermal and liquid crystalline behavior were studied. Thermotropic polyurethanes with an inherent viscosity of 0.59–0.70 were obtained. The melting temperature of BPDI-based polyurethanes were in the range of 150–290°C, however, those of ODPI-based polyurethanes were in the range of 150–190°C. All the polyurethanes based on ODPI (25–100 mole %) clearly exhibited a stable liquid crystalline phase, and BPDI-based polyurethane having 5–25% of BPDI showed a mesophase. The melting and isotropization temperatures (T _m , T _i ) andΔT(T _i −T _m ) increased with increasing BPDI and ODPI content. The polyurethanes based on BPDI has higher melting points and thermal stability compared to ODPI-based polyurethanes.     

Application of acacia natural dyes on cotton by pad dyeing

Coloration of textiles, traditionally achieved using natural dyes, commonly employs synthetic dyes at the industrial level. A revival of commercial interest in natural dyes has opened several research avenues. This paper investigates the application by padding of cotton fabric with 10 g/l of two natural dyes derived from the Acacia plant family. Three mordanting techniques were studied; of which post-mordanting produced the most even shade. Among the two mordants investigated, the use of copper sulfate resulted in a level beige shade at 15 g/l concentration while ferrous sulfate performed best at 5 g/l yielding a yellow-grey shade. An optimum process-sequence for the copper sulfate mordant was “pad (dye)→dry→steam followed by pad (mordant)→steam→dry”, and for ferrous sulfte it was “pad (dye)→steam→dry followed by pad (mordant)→steam→dry”. Typically a change in mordant resulted in a different shade with the same dye. The study concluded that padding is a readily adaptable process for the dyeing of cotton using natural dyes and acceptable fastness in shades can be obtained.     

Natural dyeing with black cowpea seed coat. I. Dyeing properties of cotton and silk fabrics

A new trial to determine the dyeing properties of cotton and silk fabrics with a black cowpea seed coat as crop waste was investigated. The natural dye anthocyanins were extracted from a black cowpea seed coat in an aqueous solution and used to dye silk and cotton. The optimal conditions for colorant extraction were an aqueous solution of a dried seed coat of black cowpea in a 1:10 liquor ratio at 70 °C for 4 hours with pH of 4. The best dye-uptake of silk and cotton fabric were obtained when the pH was 3.5 and 3.0 respectively, the temperature was 80 °C for 1 hour and the liquor ratio of black cowpea was 1:20. Different colors as dusky brown, brown, faint yellow, light green, reddish brown, cyan and green could be obtained using a various kind of mordants. The depth and brightness of color tones were affected by different dyeing and mordanting pH conditions. The colors of the fabrics were examined using a computer color matching system in terms of the K/S values and CIELAB color-difference values. The dyeing was evaluated using standard light, wash and heat fastness tests. Good wash and heat fastness were obtained but the poor light fastness indicated the need for improvement to fulfill the requirement for textile applications.     

Sonicator dyeing of natural polymers with <Emphasis Type="Italic">Symplocos spicata</Emphasis> by metal chelation

Symplocos spicata (local name: Dom sheng) belonging to Family Symplococeae produces yellowish brown natural dye which has been used for dyeing textiles since ancient times by the Monpas tribe of Arunachal Pradesh. Symplocos spicata (Dom Sheng) was found in the Lumla area of Tawang district. Leaves of the plant are used by the Monpas and Tibetans for extraction of dye. Innovative sonicator dyeing with S. spicata showed that pretreatment with 2–4% metal mordant of the weight of the fabric is optimum showing very good fastness properties for dyed natural polymers such as cotton, wool, and silk. CIELab and K/S of the dyed fabrics were also evaluated. The superiority of sonicator dyeing over conventional dyeing has been established through this study.     

Application of <Emphasis Type="Italic">Sterculia Foetida</Emphasis> Fruit Shell Waste Biomolecules on Silk for Aesthetic and Wellness Properties

There has been growing interest in the use of bioresource waste for natural dyeing and finishing. This paper discusses dye extraction from the novel source fruit shell waste of Sterculia foetida and its application on mulberry silk fabric to confer aesthetic coloration and wellness properties such as ultra-violet (UV) protection and antibacterial properties. Treated fabrics showed a substantial increase in color depth and adequate wash, light, and rubbing fastness properties for dyed silk fabrics with and without mordanting. Pre-and post-mordanting of silk fabrics were carried out using mordants such as alum, harda (myrobalan), and copper sulfate. UV-visible spectrophotometric analysis of fruit shell extract (FSE) at different pHs and FSE with three different mordants at neutral pH was used to understand the phenomena of dye-fiber interaction. The treated fabrics characterised by ATR-FTIR, SEM-EDS, and XRD analysis indicate the nature of dye fiber interaction justifying the multifunctional properties. The treated fabric also showed very good ultraviolet protection property and antibacterial properties both against S. aureus and E. coli bacteria even after ten washes. The results indicate that Sterculia foetida fruit shell extract offers an excellent potential as coloration, antibacterial, and ultraviolet protective agent for mulberry silk fabric.     

Dyeing of cotton and silk yarn with the extracted dye from the fruit hulls of mangosteen,<Emphasis Type="Italic">Garcinia mangostana</Emphasis> linn

The extracted dye from the dried fruit hulls of mangosteen was used as a natural dye for the dyeing of cotton and silk yarn. The optimal conditions for dye extraction were to extract the dried fruit hulls of mangosteen at 80°C for 1 hour with a 15 % w/v citric acid solution in a 1:4 ratio of mangosteen powder to solvent. Cotton dyeing with the extracted dye from the dried fruit hulls of mangosteen was carried out at 60°C for 60 minutes with a material to liquor ratio of 1:25. The effect on dyeing of mordant type with different mordanting methods was studied. The results showed that the dyeing of cotton using the post-mordanting method with ferrous sulfate and calcium hydroxide not only provided better depth of shade but also provided better wash fastness and light fastness than with other mordants (alum; zinc tetrafluoroborate) or without a mordant. Good fastness properties were also obtained using a post-mordanted silk with calcium hydroxide.     

Photocatalytic degradation of formaldehyde by silk mask paper loading nanometer titanium dioxide

Silk mask paper with different adsorbability was prepared by changing the beating degree of silk pulp and the basis weight of silk paper, and photocatalytic silk mask paper was prepared by loading nanometer titanium dioxide (nano-TiO₂) on the silk mask paper, then degradation of formaldehyde by silk mask paper loading nano-TiO₂ under daylight lamps and ultraviolet lamps were investigated, respectively. Results showed that silk mask paper could adsorb formaldehyde and had higher adsorption efficiency in the initial stage, and the adsorption/desorption equilibrium could be basically achieved in 60 minutes. The adsorption capacity of silk mask paper made from silk pulp with beating degree of 45 ^oSR was relatively low, and it increased with the increase of beating degree, but there was little change in adsorption when the beating degree of silk pulp exceeded 65 ^oSR. Under daylight lamps, 26.61 %, 31.42 % and 38.21 % of formaldehyde could be degraded in 180 minutes by silk mask paper loading 1 wt%, 3 wt% and 5 wt% nano-TiO₂, respectively. However, under ultraviolet (UV) lamps, 46.23 %, 55.47 % and 66.38 % of formaldehyde could be degraded within the same time, respectively. More formaldehyde could be degraded by photocatalytic silk mask paper under UV lamps than under daylight lamps, and the more the load of nano-TiO₂ on the silk mask paper, the higher the degradation rate of formaldehyde within the same time.     

A Comparative study of redox parameters and electrochemical impedance spectroscopy of polycarbazole derivatives on carbon fiber microelectrode

In this study, N-Carbazole and its derivatives (N-Vinylcarbazole, N-Ethylcarbazole, N-Vinylbenzylcarbazole, and N-Benzylcarbazole) were electrochemically polymerized on carbon fiber microelectrodes (diameter ∼7 μm) by cyclic voltammetry within a potential range from 0.0 to 1.4 V. Redox parameters, Scanning electron microscopic (SEM) images were determined and also capacitance behaviors of polymers were examined via electrochemical impedance spectroscopy (EIS). EIS measurements of polycarbazole derivatives were given comparatively. The existence of a capacitance behavior is shown by Nyquist, Bode magnitude, Bode-phase, Admittance plots relationship. Although the highest low frequency capacitance (C_LF=12901 μA cm⁻²) and maximum phase angle of 81.9 ° at a frequency of 1 Hz were obtained for N-Vinylbenzylcarbazole, the lowest anodic and cathodic potential difference (ΔE=0.04 V) and double layer capacitance (C _dl =0.11 μA cm⁻²) were indicated in 0.1 M LiClO₄/PC.     

Removal of benzidine-based azo dye from aqueous solution using amide and amine-functionalized poly(ethylene terephthalate) fibers

In this study, amide and amine groups bound to poly(ethylene terephthalate) fibers are used to remove the colored toxic Congo red dye from aqueous solution. The effects of process variables like pH, contact time, graft yield, and initial dye concentration on the adsorption were investigated. The maximum adsorption of Congo red to amide and amine groups was observed at pH 3 and 5 respectively. Equilibrium was attained at approximately 60 min for the amine group. The adsorption capacity of amine group on the poly(ethylene terephthalate) fiber was 46.5 mg g⁻¹ at 25 °C, which was higher than that of the amide group on the poly(ethylene terephthalate) fiber. Desorption was done using 0.1 M NH₃, and recovery was measured at 58.2 %. The used adsorbent was regenerated and recycled six times. The results showed that the amine-functionalized fiber could be considered as potential adsorbents for removal of Congo red from aqueous solution.     

Total Phenolics Level,Antioxidant Activities and Cytotoxicity of Young Sprouts of Some Traditional Korean Salad Plants

The aim of this investigation was to study the antioxidant and anticancer activities of young sprouts of some traditional Korean salad plants. Total phenolics, antioxidant and anticancer activities of the methanol extracts from young sprouts of 11 salad plants were determined. The highest amount of phenolics was found in methanol extracts of Euonymus alatus (235.7 mg kg⁻¹), followed by Hypericum ascyron (197.1 mg kg⁻¹), Zanthoxylum piperitum (194.1 mg kg⁻¹) and Zanthoxylum schinifolium (142.5 mg kg⁻¹). Methanol extracts of E. alatus, H. ascyron, and Z. piperitum at 63 mg kg⁻¹ exhibited the highest dose-depend DPPH radical scavenging activity by 91.2, 91.2 and 83.9%, respectively. According to the MTT results, the methanol extracts from Stellaria aquatica, Eleutherococcus sessilifolrus and Z. schinifolium showed the highest anticancer activities against Calu-6 (IC50 < 25.0 μgml⁻¹) and from S. aquatica—the highest anticancer activities against SNU-601 (153.3 μgml⁻¹), following by E. sessilifolrus (196.7 μg ml⁻¹) and Amaranthus mangostanus (303.1 μgml⁻¹). Total phenolics were highly correlated with the DPPH, suggesting that they contribute to the antioxidant properties of the studied plants. In conclusion: young sprouts of Korean salad possess antioxidant and anticancer properties and could be used as a supplement to proper drugs.