Yellow pigment of Metarhizium anisopliae and its application to the dyeing of fabrics

Microbial dyes have received substantial attention because of their natural environmental protection, simple access, and reduced regional and seasonal restriction. In this work, a microbial dye, the yellow pigment produced by Metarhizium anisopliae, was first studied then applied. The strain produced by the culture was identified, and the conditions for producing yellow pigment were optimised. Further, the stability of M. anisopliae yellow pigment was examined, and the pigment was applied to the dyeing of silk and wool fabrics. The results showed that the homology of the strain with M. anisopliae was 99.98%. In liquid fermentation culture, the optimal carbon source was glucose, and the dosage was 30 g/l. The maximum pigment yield can be obtained by culturing with 4% v/v of inoculation quantity at pH 7 and 30 °C. In addition, the effects of pH, temperature and metal ions on the yellow pigment of M. anisopliae were significant. The optimum dyeing process conditions were dyeing temperatures of 80 °C for silk and 90 °C for wool, with a dyeing time of 60 min. This research developed a novel microbial dye and studied its application for the dyeing of protein fibres.     

Eco‐friendly pretreatment of silk fabric for dyeing with Delonix regia extract

The flowers of Delonix regia have been evaluated for the natural dyeing of silk using a biomordant and enzymes. This is an eco‐friendly textile pretreatment that does not utilise metal mordanting. The aqueous extract obtained from the dried red flowers was used for the dyeing of silk fabrics. A bright reddish‐brown hue colour was observed when 30% owf Delonix extract was used on the pretreated silk material. The silk fabric was treated with either an enzyme or biomordant. The resulting dyed fabric showed resistance to fading. Finally, all dyed specimens were tested for wash and light fastness properties, making Delonix a viable alternative to synthetic red dyes. Through desorption studies, the order of reactivity of enzymes towards dye uptake in the one‐step process was found to be lipase > diasterase > protease–amylase = Pyrus(biomordant). For the two‐step process, the order of reactivity of enzymes was found to be protease–amylase > lipase > Pyrus (biomordant) > diasterase. Overall, it can be concluded that, treatments, the two‐step process was better in terms of larger colour yield values, fastness properties and both dye adherence ability.     

Acylation of silk and wool with acid anhydrides and preparation of water-repellent fibers

Silk and wool fibers were acylated with two acid anhydrides, dodecenylsuccinic anhydride (DDSA) and octadecenylsuccinic anhydride (ODSA), at 75°C with N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) as the solvent, the latter of which allowed higher weight gains to be reached. The weight gain and acyl content of wool was always higher than that of silk. Tensile properties of silk remained unchanged regardless of weight gain, whereas wool displayed a noticeably higher extensibility at high weight gain. Fine structural changes of acylated wool were detected by DSC analysis. Moisture regain and water retention of acylated silk and wool decreased significantly, whereas water repellency increased. SEM analysis showed the presence of foreign material firmly adherent to the surface of both silk and wool, whose amount increased with increasing weight gain. These deposits were attributed to the presence of the modifying agents at the fiber surface on the basis of the characteristic IR bands. The possible application of silk and wool fibers acylated with DDSA or ODSA for the preparation of water-repellent textile materials is discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2832–2841, 2001     

Dyeing of natural and synthetic textiles in supercritical carbon dioxide with disperse reactive dyes

Polyester, nylon, silk and wool were dyed with disperse reactive dyes in supercritical carbon dioxide (scCO₂). The dyes were substituted with either vinylsulphone or dichlorotriazine reactive groups. Since earlier research showed that water, distributed over the scCO₂ and the textile, increased the colouration, experiments were done with the vinylsulphone dye with varying amounts of water in the dyeing vessel, to investigate if there is an optimum water concentration. The amounts were such, that no liquid water was present. The maximum colouration was obtained when both the scCO₂ and the textiles were saturated with water. At the saturation point, deep colours were obtained with the vinylsulphone dye for polyester, nylon, silk and wool, with fixation percentages between 70 and 92% when the dyeing time was 2 h. The positive effect of water was due to its ability to swell fibres or due to an effect of water on the reactivity of the dye–fibre system. Also the dichlorotriazine dye showed more colouration when the scCO₂ was moist. With this dye, experiments were conducted in water-saturated scCO₂, varying the pressure from 225 to 278 bar and the temperature from 100 to 116 °C. The colouration of polyester increased with pressure, the results for silk and wool were not sensitive to pressure. Increasing the temperature had no influence on the dyeing of polyester, silk and wool. The fixations on polyester, silk and wool, being between 71 and 97%, were also independent of pressure and temperature.     

Preparation of metal‐containing protein fibers and their antimicrobial properties

Bombyx mori silk, Antheraea pernyi silk, and wool fibers were chemically modified by treatment with tannic acid (TA) or by acylation with ethylenediaminetetraacetic (EDTA) dianhydride. Kinetics of TA loading or acylation with EDTA‐dianhydride varied from fiber to fiber. B. mori silk and wool displayed the highest weight gains with TA and EDTA‐dianhydride, respectively. The uptake of different metal ions (Ag⁺, Cu²⁺, Co²⁺) by protein fibers, either untreated or chemically modified, was studied as a function of weight gain and pH of the aqueous metal solution. Below pH 7, absorption of metal ions by untreated and TA‐treated fibers was negligible. Acylation with EDTA‐dianhydride enabled protein fibers to absorb and bind significant amounts of metal ions in the acidic and neutral pH range. The levels of metal desorption at acidic pH depended on the fiber‐metal combination. Untreated protein fibers usually displayed the lowest stability of the metal complex. Metal complexes with protein fibers exhibited prominent antimicrobial activity against the plant pathogen Cornebacterium. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 638–644, 2003     

Structure and dyeability of Bombyx mori silk fibers with different filament sizes

This study deals with the analysis of structure, physical properties, and dyeing behavior of silk fibers with different filament sizes. Fine and coarse silk fibers were obtained from Akebono and Ariake cocoon varieties, respectively. Both samples exhibited a fairly similar x-ray crystallinity, while the degree of molecular orientation increased with decreasing the fiber size. Tensile strength and energy of fine silk fibers were significantly higher, while elongation at break did not change in relation to the fiber size. Fine silk fibers exhibited a slightly higher thermal stability, as shown by the upward shift of both the DSC decomposition temperature and the TMA final extension step at above 300°C. The TGA and DMA (E″) patterns remained unchanged regardless of fiber size. The amino acid analysis confirmed the absence of any difference of chemical structure between fine and coarse silk fibers, the content of acidic, basic, and other characteristic amino acid residues being exactly the same. Accordingly, both samples adsorbed the same amount of hydrochloric acid. Ex-haustion dyeing tests with various direct, acid, and reactive dyes showed the occurrence of appreciable differences in the perceived color between fine and coarse silk fibers. The size of color difference was quantitatively evaluated by reflectance measurements and discussed in relation to silk fiber morphology, structure, as well as dyeing conditions. The kinetics of diffusion of two model dyes was not significantly affected by the different fiber size and structure. © 1996 John Wiley & Sons, Inc.     

Multifunctional wool fiber treated with <Emphasis Type="Italic">ɛ</Emphasis>-polylysine

A creative method for fabricating environmentally-benign multifunctional wool fibers was established and reported. Through coating the wool fibers with ɛ-polylysine, the surface morphology and biochemical properties of the fibers were altered, enhancing their antimicrobial, hygroscopic and finished properties. The process of ɛ-polylysine coating was dependent on the solution environment, which influenced the electrostatic interactions between ɛ-polylysine molecules and wool fibers. The results showed that a maximum ɛ-polylysine coating (23.60 mg/g) on the surface of wool fibers was reached when wool fibers were soaked at 50 °C for 2 h in the solution with 10% on weight of fabric (owf) ɛ-polylysine and pH 8.0. The coated wool fiber showed promising antimicrobial rates of 96.98% and 97.93% against Escherichia coli and Micrococcus luteus, respectively. The wool fiber coated with the ɛ-polylysine was more hydrophilic than the uncoated wool fabrics. The functional wool fibers after water scrubbing for two times still have good antibacterial efficiency against Escherichia coli and Micrococcus luteus, and antimicrobial rates were 96.77% and 97.33%, respectively. This study shows that wool fibers modified by the nontoxic ɛ-polylysine have a great potential to be used in constructing multifunctional textiles.     

Softness evaluation of keratin fibers based on single‐fiber bending test

The evaluation of single‐fiber softness by bending is an ingenious and vital approach for the basic investigation of both the fiber bending properties and the textile softness. The bending behavior and bending modulus of wool, alpaca and silk fibers have been measured by an axial‐buckling method developed by the authors, which uses the fiber compression bending analyzer (FICBA). The bending properties of single fibers were quantified by calculating the equivalent bending modulus and the flexural rigidity by measuring the protruding length and diameter of fiber needles and the critical force, P_cr, obtained from the peak point of the force‐displacement curve. The measured data showed that the equivalent bending modulus of the alpaca fiber is higher than that of wool fiber, and even the rigidity is 10 times as high as wool, but its friction coefficient is lower than that of wool, which means that the soft handle of alpaca fabrics is mainly due to the smooth surface and low friction coefficient of alpaca fibers in contrast to that of wool fiber. For the silk fiber, despite high equivalent bending modulus, the smoother handle of silk should be mainly due to the thin fiber diameter in contrast to that of keratin fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 701–707, 2006     

Dyeing,fastness, and deodorizing properties of cotton,silk, and wool fabrics dyed with coffee sludge (Coffea arabica L.) extract

A natural colorant was extracted from Coffea arabica L., using water as extractant at 90°C for 90 min. Studies have been made on the dyeing, color fastness, and deodorization properties of cotton, silk, and wool fabrics dyed with Coffea arabica L. extract solutions. The best mordants were found to be FeSO_4, CuSO₄, and SnSO₄ for improving the color strength (K/S) of cotton, silk, and wool fabrics. Mordants MnSO₄, ZnSO₄, and NiSO₄ for cotton (Rating 3), and all mordants except MnSO₄ for silk (Rating 3), mordants CuSO₄, FeSO₄, CoSO₄, Al₂(SO₄)₃, and MnSO₄ for wool (Rating 4) were the best mordants to improve the light fastness. It was found that FeSO₄ and CuSO₄ were the best mordants for the improvements of color strength (K/S) and light fastness for silk and wool fabrics. In addition, it was found that cotton, silk, and wool fabrics dyed with the Coffea arabica L. extract showed good deodorization performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 251–257, 2007     

Production of antimicrobially active silk proteins by use of metal‐containing dyestuffs

The work presented here discusses a new technique for preparing silk fibers and films with persistent antimicrobial activity through use of metallic dyestuffs during the fiber dyeing process. The length of the silk fibers investigated contracted when the fibers were immersed in concentrated neutral salt solutions, such as calcium or potassium nitrate, at elevated temperature levels. The birefringence and molecular orientation of the silk fibroin molecules became less ordered by the action of the neutral salt solutions, resulting in increased dyestuff absorption. Subsequently, contracted silk fibers were dyed with metallic dyestuffs containing Cr or Cu for the purpose of obtaining silk fibers with antimicrobial activity. Silk fibers dyed with metallic dyestuffs showed significant antimicrobial activity against the plant pathogen Cornebacterium and the human pathogen Coli bacillus. Tensile strength of the silk fibers after the salt shrinking and dyeing processes did not show a significant change, whereas the elongation at break was increased slightly. The techniques described here for preparing significantly active antimicrobial silk fibers are effective and economic ways of providing new materials for industrial and biomedical applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1181–1188, 2002     

Chemical modification of silk with aromatic acid anhydrides

Bombyx mori silk fibers were chemically modified by acylation with aromatic acid anhydrides, such as phthalic and o-sulfobenzoic anhydrides. We examined the reactivity of these modifying agents toward silk fibers, the physical and thermal properties, and the dyeing behavior with acid and cationic dyes. The o-sulfobenzoic anhydride was more reactive toward silk fibroin than phthalic anhydride. The amount of both basic and acidic amino acid residues decreased after modification with aromatic acid anhydrides. The moisture regain of silk treated with phthalic anhydride remained almost unchanged, while that of the samples modified with o-sulfobenzoic anhydride increased linearly as the weight gain increased. Chemically modified silk fabrics showed improved crease recovery behavior, even though phthalic anhydride seemed more effective at comparatively low weight gain. The modification of silk with o-sulfobenzoic anhydride caused a drastic a reduction of acid dye uptake and enhanced the affinity of silk for cationic dye. Silk fibers did not show any significant change in thermal behavior, regardless of the modification with o-sulfobenzoic anhydride. Silk fibers modified with phthalic anhydride showed on differential scanning calorimetry (DSC) curves a minor and broad endothermic peak at around 210°C, attributed probably to the breaking of the crosslinks formed between adjacent fibroin molecules.     

Physical properties and dyeability of silk fibers modified with ethoxyethylmethacrylate polymer

The structural characteristics, physical properties, and dyeing behavior of Bombyx mori silk fibers containing ethoxyethylmethacrylate (ETMA) polymer are reported in relation to the add-on. The add-on value increased with the reaction time and attained a maximum after 60 min at 80°C. The surface of silk fibers with an add-on value of 40% showed the presence of several irregular granules, consisting of ETMA oligomers. The infrared spectrum of the silk fibers containing the ETMA polymer showed overlapped absorption bands due to the molecular conformation of untreated silk and ETMA polymer, giving evidence that the ETMA polymerization occurred inside the fiber matrix. The DSC results suggested that the thermal decomposition behavior of the silk fiber remained almost unchanged, except that the decomposition temperature shifted slightly to higher temperature. The tensile properties of the silk fiber remained unchanged regardless of the ETMA polymerization. The rate and extent of acid dye uptake was greatly increased by the polymerization of ETMA into the silk fibers as well as the transfer printing properties.     

Dyeing of silk fabric with phenazine from Pseudomonas species

Phenazines, namely oxychlororaphin and pyorubin, were extracted from Pseudomonas sp., purified and their dyeing potential as colorants for silk dyeing were examined. The effects of the process variables, such as phenazine concentration, pH, temperature, time, type of mordant, relative colour strength and fastness properties have been studied. The results showed that the optimum condition for dyeing was 90 °C at pH 3 and dyeing time 90 min for oxychlororaphin, and 70 °C at pH 3 and dyeing time 60 min for pyorubin. The K/S value of a pre‐mordanted silk fabric with oxychlororaphin was high when compared to that with the pyorubin. The antimicrobial activity of a dyed silk fabric was tested against Salomonella paratyphi, Escherichia coli and Shigella flexneri.     

Development of Environmentally Friendly Wool Shrink-Proof Finishing Technology Based on L-Cysteine/Protease Treatment Solution System

The particular scale structure and mechanical properties of wool fiber make its associated fabrics prone to felting, seriously affecting the service life of wool products. Although the existing Chlorine–Hercosett treatment has a remarkable effect, it can lead to environmental pollution. Therefore, it is of great significance to develop an environmentally friendly and effective shrink-proof finishing technology. For this study, L-cysteine was mixed with protease to form a treatment solution system for shrink-proof finishing of wool fibers. The reduction performance of L-cysteine and its effect on wool were compared with those of other reagents, demonstrating that L-cysteine has an obvious reduction and destruction effect on the wool scale layer. Based on this, L-cysteine and protease 16L were mixed in a certain proportion to prepare an L-cysteine/protease treatment solution system (L/PTSS). The shrink-proof finishing of a wool top was carried out by the continuous multiple-padding method, and the processing parameters were optimized using the response surface method. The results indicated that when the concentrations of L-cysteine and protease 16L were 9 g/L and 1 g/L, respectively, the wool was padded five times at 50 °C, and each immersion time was 30 s, the felt ball density of the treated wool reduced from 135.86 kg/m³ to 48.65 kg/m³. The structure and properties of the treated wool were also characterized using SEM, TG, and tensile strength tests, which indicated that the fiber scale structure was stripped evenly. Meanwhile, the treated fibers still retained adequate thermal and mechanical properties, indicating suitable application value. XPS, FT-IR, Raman, UV absorbance, and other test results revealed the reaction mechanism of L/PTSS with the wool fibers. After L-cysteine rapidly reduced the disulfide bonds in wool, protease can hydrolyze peptide chains more effectively, causing the scale layer to gradually peel off. Compared with the chlorination method and other protease shrink-proof technologies, L/PTSS can achieve the finishing effect on wool rapidly and effectively, without causing excessive pollution to the environment. The conclusions of this study provide a foundation for the development and industrial application of biological enzyme shrink-proof finishing technology.     

Investigation and feed-forward neural network-based estimation of dyeing properties of air plasma treated wool fabric dyed with natural dye obtained from Hibiscus sabdariffa

In the colouring processes of textile products, more environmentally friendly chemicals and finishing methods should be used instead of conventional ones that harm the environment every day, so that alternative realistic ways to protect nature, both academically and industrially, could be possible. Due to some inconveniences caused by synthetic dyes that are widely used today, in this study, ultrasonic dyeing of wool fabric with Hibiscus sabdariffa was carried out after environmental-friendly air vacuum plasma application which increased the absorption of the dyes into the textile material. According to the performance results, colour strengths of the wool fabrics were increased significantly. Surface morphology analysis was carried out and etching effects of air vacuum plasma treatment were clearly seen on the micrographs of the treated wool fabrics. An environmental-friendly green process was achieved through this study and it was concluded that vacuum air plasma treatment could be an alternative green-process as a pretreatment to increase the dye up-take of natural dyeing treatment. Moreover, in this study, a feed-forward neural network (FFNN) model was presented and used for predicting the dyeing properties (L, a, b and K/S) of samples. The experimental results showed that the presented model achieves the regression values greater than 0.9 for all dyeing properties. Consequently, it was considered that the proposed FFNN was successfully modelled and could be efficiently utilised for dyeing characteristics of wool fabrics dyed with natural dye extracted from Hibiscus sabdariffa.     

Electrochemical formation of some conducting fibers

A study on the electrochemical grafting of polyaniline onto cotton, silk, and wool fibers was made. These insulating natural fibers became moderately conducting when they were subjected to electrical treatment in the polymerizing solution of aniline in aqueous HBF₄ medium. The weight gain of the fibers increased linearly and electrical resistance decreased with the time of electrolysis. The multiple cycled voltammograms of the solution of aniline in the aqueous solution of HBF₄ at the tip of conducting silk and wool fibers, which functioned as a microelectrode, were successfully recorded. The deep green polyaniline film was deposited on the fiber microelectrodes during electrolysis at +0.85 V vs. an Ag/Ag⁺ electrode. The IR spectra suggest the coordination between the polyaniline and fibers. © 1996 John Wiley & Sons, Inc.     

Infrared spectroscopy of graft polymers separated from graft copolymers of wool and silk with methyl methacrylate

The HCl- or papain-decomposition residues obtained from reduced wool fibers grafted with 1.5–3.0% methyl methacrylate were extractively fractionated successively with cold acetone, hot acetone, and benzene. Each fraction was examined by infrared spectroscopy. Generally, the 715 cm^?1 spectral band considered to be due to vc-s-c was found in the hot acetone-soluble fraction. It was concluded that the thiol groups on wool keratin provide the main sites of grafting, as might be expected. A similar result was obtained for grafted silk fibroin fibers, the methionine residue being presumed to be related to some of the grafting sites at least. Furthermore, a sort of stereoregularity was observed in some of the graft polymer fractions, isotactic-rich material being obtained in the case of silk fibers. In the range of very low grafting, a stereoregulating effect on the structure of the polymer formed within fibers appears to be present in relation to the grafting or adsorption sites of monomers and the fine structure of fibers.     

Synthesis of acid dyes containing polyetheramine moieties and their low‐temperature dyeing properties on wool fiber

To realize the low‐temperature dyeing of wool fibers, the use of auxiliaries and wool modification are common methods. Low‐temperature auxiliaries may cause water‐pollution problems, and wool modification is a costly and uncontrollable process. In this study, new acid dyes, named D1–D3, containing polyetheramine groups were synthesized and applied to wool fiber by conventional and low‐temperature exhaust dyeing procedures. The results indicate that the new acid dyes could interact with wool‐fiber‐like auxiliaries and render a high exhaustion rate to the wool fiber at a dyeing temperature of 80 °C. In comparison with Acid Blue 25, the D1–D3 dyes showed an increased dyeing rate, especially under a dyeing temperature of 80 °C. Despite the bigger relative molecular masses of D1–D3, the exhaustion rates of D1–D3 were still higher, and the times of half‐dyeing were shorter than that of Acid Blue 25. The color differences between the wool fabrics dyed with the four dyes at 80 and 98 °C, respectively, were compared. We found that the color differences of D1–D3 between 80 and 98 °C were smaller than that of Acid Blue 25. The interactions between the dyes and wool fiber were analyzed and manifested by the measurement of the ζ potential of the dyes and wool fiber. The leveling and transfer properties of the D1–D3 dyes were also investigated, and the color differences of the wool fabrics dyed with Acid Blue 25, D1, and D2 were very low at all measured pH values and temperatures. The fastnesses of D1–D3 on wool fabric were almost the same as that of Acid Blue 25. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45793.     

BmSuc1 Affects Silk Properties by Acting on Sericin1 in Bombyx mori

BmSuc1, a novel animal-type β-fructofuranosidase (β-FFase, EC 3.2.1.26) encoding gene, was cloned and identified for the first time in the silkworm, Bombyx mori. BmSuc1 was specifically and highly expressed in the midgut and silk gland of Bombyx mori. Until now, the function of BmSuc1 in the silk gland was unclear. In this study, it was found that the expression changes of BmSuc1 in the fifth instar silk gland were consistent with the growth rate of the silk gland. Next, with the aid of the CRISPR/Cas9 system, the BmSuc1 locus was genetically mutated, and homozygous mutant silkworm strains with truncated β-FFase (BmSUC1) proteins were established. BmSuc1 mutant larvae exhibited stunted growth and decreased body weight. Interestingly, the molecular weight of part of Sericin1 (Ser1) in the silk gland of the mutant silkworms was reduced. The knockout of BmSuc1 reduced the sericin content in the silkworm cocoon shell, and the mechanical properties of the mutant line silk fibers were also negatively affected. These results reveal that BmSUC1 is involved in the synthesis of Ser1 protein in silk glands and helps to maintain the homeostasis of silk protein content in silk fibers and the mechanical properties of silk fibers, laying a foundation for the study of BmSUC1 regulation of silk protein synthesis in silk glands.     

Structural changes and dyeability of silk fibroin fiber following shrinkage in neutral salt solution

The fine structural changes of Bombyx mori silk fibroin fibers, induced by shrinking with concentrated calcium chloride aqueous solution at elevated temperature were investigated as a function of shrinking rate. Tensile strength decreased and elongation at break increased in the shrinkage range 13–67%, the shape of the stress–strain curve changing from rubberlike to brittle at high shrinkage values (70–90%). The birefringence gradually decreased over the entire shrinking range examined, the curve becoming steep as the shrinkage exceeded about 67%. The behavior of isotropic refractive index (n_iso) closely resembled that of birefringence (Δn) in the shrinking range 13–67%. Beyond shrinkage of 67%, the n_iso showed a tendency to increase, especially for the sample with 80% shrinkage. Dichroism measurements showed that the molecular orientation within the amorphous regions decreased sharply at the beginning of the shrinking treatment, within the range 0–13%, then attained a saturation at about 55%. The position and intensity of the major X-ray diffraction peak at 20.5° remained essentially unchanged regardless of the shrinking treatment. The results of dyeing behavior showed that the saturation value attained by shrunk silk fibers was significantly larger than that of the untreated control sample. Both standard affinity and the heat of dyeing increased slightly for the shrunk silk fibroin fiber, suggesting that a larger number of reactive sites became available for the interaction between dye molecules and fibroin chains. A schematic model is proposed for explaining the relation between structural changes and enhanced dyeability of the silk fibers following shrinkage in neutral salt solution. © 1994 John Wiley & Sons, Inc.