Jiugang Yuan

Modification of Bombyx mori silk fabrics by tyrosinase‐catalyzed grafting of chitosan

Tyrosinase could oxidize tyrosyl residues in silk fibroin and result in the production of activated o‐quinone residues, which could facilitate the grafting of the functional amino‐compounds onto silk fibers. In this study, the enzymatic modifications of Bombyx mori silk fibroin with tyrosinase and chitosan were investigated, aiming at improving the properties of silk fabrics, including dyeability, crinkling resistance, and antibacterial activity. The grafting grades of chitosan were evaluated by a color‐development method using bromocresol green. The result indicated that chitosan molecules were not only adsorbed on silk fibers via electrostatic interactions, they also could react with the oxidized silk fibers with tyrosinase. For the silk fabric combinedly treated with tyrosinase and chitosan, tensile strength and crinkling resistance were noticeably increased as compared to that of the chitosan‐treated. The antibacterial activity and its durability measurements revealed the actions of the tyrosinase‐catalyzed grafting of chitosan. The efficacy of the graft reaction might be further enhanced by increasing the accessibility of reactive sites in silk fibers.

Synthesis and characterization of starch-poly(methyl acrylate) graft copolymers using horseradish peroxidase

Horseradish peroxidase (HRP)-mediated graft polymerization in the presence of hydrogen peroxide (H2O2) and acetylacetone (Acac) has been successfully applied to the synthesis of starch-poly(methyl acrylate) (PMA). The graft copolymer was characterized by Fourier transform infrared (FT-IR), elemental analysis, nuclear magnetic resonance ((1)H NMR and (13)C NMR), and differential scanning calorimetry (DSC). FT-IR, elemental analysis and NMR confirmed that methyl acrylate (MA) was grafted onto starch successfully. DSC results showed the graft reaction had changed the crystalline regions of the gelatinized starch. The effects of pH, MA content, HRP dosage, incubation temperature and time on grafting percentage (GP) and grafting efficiency (GE) were also investigated. The GP and GE under optimal conditions reached 30.21% and 45.13%, respectively.

Cellulase immobilization onto the reversibly soluble methacrylate copolymer for denim washing

Cellulase treatment of denim fabrics is an environmentally friendly way for producing desired worn look. In this work, the enzymatic treatments of the denim fabrics, i.e., bio-washing, using native cellulase and cellulase immobilized with reversibly soluble copolymer (Eudragit S-100), immobilized-cellulase, have been investigated. According to the analyses of the lightness (CIE L value), color strength (K/S value) and color variations, at a cellulase concentration level of 6% o.w.f., the denim fabrics treated with the immobilized cellulase showed decoloration and color effect close to the native cellulase. However, the immobilized cellulase treatment of the denim fabrics showed lower weight loss and considerably higher tensile strength than those treated with the native cellulase. Both the native and immobilized cellulases improved the crystalline indice and the apparent crystallite size of the fiber sample compared with the control ones. The amorphous portion of the cellulose suffered more hydrolysis by the native cellulase than the immobilized cellulase. Scanning electron microscope pictures (SEM) and digital pictures further indicated that the immobilized cellulase can efficiently remove indigo dyestuffs on the surfaces of the denim fabrics without the problem of excessive damage to the fibers.

Hydrophobic modification of cotton fabric with octadecylamine via laccase/TEMPO mediated grafting.

Hydrophobic cotton fabrics were prepared by grafting octadecylamine (ODA) onto cotton fiber surfaces via the laccase/2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) treatment. The cotton fibers were oxidized by laccase/TEMPO to introduce aldehyde groups, which reacted with the amino groups of ODA to form Schiff base. First, ODA was coupled to glucan, used as a model compound of cellulose. The results of FT-IR and MALDI-TOF mass spectroscopy prove the formation of a Schiff base between ODA and glucan. Moreover, the existence of ODA in the grafted cotton fibers was verified by ATR-FTIR, elemental analysis, X-ray photoelectron spectroscopy. Finally, the hydrophobicity of the ODA-grafted cotton fabrics was estimated. The surface hydrophobicity of the cotton fabrics increased after the enzymatic grafting reaction.

Covalent Immobilization of Catalase onto Regenerated Silk Fibroins via Tyrosinase-Catalyzed Cross-Linking

Regenerated silk fibroins could be used as medical scaffolds and carrier materials for enzyme immobilization. In the present work, tyrosinase enzyme was used for enzymatic oxidation of silk fibroins, followed by immobilization of catalase onto the fibroin surfaces through physical adsorption and covalent cross-linking as well. Spectrophotometry, SDS-PAGE, and Fourier transform infrared spectroscopy (FTIR) were used to examine the efficiency of enzymatic oxidation and catalase immobilization, respectively. The results indicate that tyrosine residues in silk fibroins could be oxidized and converted to the active o-quinones. Incubating silk fibroins with catalase and tyrosinase led to a noticeable change of molecular weight distribution, indicating the occurrence of the cross-links between silk fibroins and catalase molecules. Two different pathways were proposed for the catalase immobilizations, and the method based on grafting of catalase onto the freeze-dried fibroin membrane is more acceptable. The residual enzyme activity for the immobilized catalase exhibited higher than that of the control after repeated washing cycles. Meanwhile, the thermal stability and alkali resistance were also slightly improved as compared to free catalase. The mechanisms of enzymatic immobilization are also concerned.

Enzymatic grafting of lactoferrin onto silk fibroins for antibacterial functionalization

Enzymatic oxidation of tyrosine side-chains in proteins could produce reactive o-quinones that might subsequently react with the primary amino groups of functional compounds, which provided a worthwhile reference for functionalization of fibrion materials. In the present work the potential for using tyrosinase to graft the bovine lactoferrin onto Bombyx mori silk fibroin was examined. Lactoferrin could adsorb onto silk fibers and covalently bind to the previous enzymatically oxidized fibroin surface. The enzyme-generated quinones in silk fibers also might cause self-crosslinking of fibroin peptides, which led to beneficial changes of silk properties. For the fabric treated with tyrosinase and lactoferrin slight improvements of dyeability and strength were obtained in comparison to the control. The combinedly treated fabric showed encouraging resistance to S. aureus and E. coli, the antibacterial activities reached to 87.0 % and 76.4 %, respectively. The durability of the antibacterial silk was noticeably higher than that of the sample treated with lactoferrin alone.

Immobilization of cellulases on the reversibly soluble polymer Eudragit S-100 for cotton treatment

Cellulases can penetrate into the fiber, causing tensile strength loss of the cellulosic fibers or fabrics. To minimize the tensile strength loss, we have immobilized cellulases on Eudragit S‐100. The characteristics of covalent Eudragit cellulase were evaluated using gel filtration analysis and UV spectra. Gel filtration analysis revealed that the cellulases were covalently bound to the polymer. Covalent Eudragit cellulase was loaded with the enzyme of about 40% and had a relative activity about 80% at a Eudragit S‐100 concentration of 15 g/L. When cellulase is bound to the polymer, the solubility profile becomes similar to the one of Eudragit. In addition, the effects of the enzyme on the cotton yarns and fabric using cellulases have been investigated. Native and immobilized cellulases caused improvements in whiteness and wrinkle recovery angle of the fabric in comparison to the control samples. The bending stiffness results show that native and immobilized cellulase treated cotton fabric has an improved softness than the control samples. It was found that using the immobilized cellulase reduced the weight and tensile strength, because the hydrolytic attack is only limited to the surfaces of cotton fibers.

A novel approach for grafting of β-cyclodextrin onto wool via laccase/TEMPO oxidation

This study demonstrated a new enzymatic methodology to graft β-cyclodextrin onto wool. The primary hydroxyl groups in β-cyclodextrin were oxidized to aldehyde groups using laccase/2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), which reacted with the amino groups of wool to form Schiff bases. The effects of treatment conditions (treatment temperature, laccase dosage, TEMPO dosage, treatment time) on the aldehyde and carboxyl contents in β-cyclodextrin were studied. FTIR spectrum of oxidized β-cyclodextrin showed the presence of aldehyde and carboxyl groups. Results of MALDI-TOF mass spectroscopy confirmed the coupling of β-cyclodextrin to tyrosine, which was used as a model compound for wool. ATR-FTIR spectroscopy of the grafted wool confirmed the presence of β-cyclodextrin in grafted wool and the formation of a Schiff base between β-cyclodextrin and wool.

A study of surface morphology and structure of cotton fibres with soluble immobilized-cellulase treatment

Our previous studies have demonstrated that cotton fabrics treated with soluble immobilized-cellulase showed considerably lower degradation and higher retention of tensile strength than those treated with free cellulase. It is important to investigate the surface morphology and structure of cotton fibres for understanding the enzymatic degradation. In this study, the effects of the soluble immobilized-cellulase on the surface morphology and structure of cotton fibres were investigated. The ultrastructural changes in the fibre surfaces were inspected using Tapping-Mode Atomic Force Microscopy (TM-AFM) and scanning electron microscopy (SEM), and the results showed that the smooth surfaces could be obtained after the immobilized-cellulase treatment, and no obvious damage was observed on the fibre surfaces. The hydrogen bonds in the certain depth area beneath the fibre surface were investigated using Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy (ATR-FTIR) after the cellulase treatments. Furthermore, the result of fibre accessibility indicated that the hydrolysis occurring in the interior of the cotton fibres was limited during the immobilized-cellulase treatment. Crystalline index (CI) of the cotton fibres treated with free cellulase was slightly higher than that of fibres treated with immobilized cellulase.

Modification of ramie with 1-butyl-3-methylimidazolium chloride ionic liquid

For a long time, alkali is the main modification reagent for ramie modification due to its good effect and low cost. However, the large consumption of alkali in the processing leads to a serious pollution to the environment. To develop a new eco-friendly modification method, a mixed green solvent composed of 95 wt% 1-butyl-3-methylimidazolium chloride ionic liquid and 5 wt% water was employed in the paper. The swelling ratio, surface composition and crystal index was studied in detail with video microscope, FTIR and XRD analysis. Results showed that the solvent system had a distinct swelling effect on ramie. The crystal index of ramie fiber decreased from 74.2 % to 54.5 % after the treatment. Otherwise, the modification also removed some gummy substances including 75 % content of pectin in ramie. These changes improved the wetability and dyeing properties of ramie. However, the treatment also did much harm to the tensile strength.