Key Characteristics of a Novel Silk Yarn from Fresh Cocoons

We studied the key characteristics of a novel silk yarn reeled from fresh cocoons. Compared with traditional silk yarn, this novel silk yarn displayed better mechanical properties, especially in terms of a higher breaking stress and toughness, and exhibited a different surface morphology. A cross-sectional observation and the sericin content results illustrated that different sericin coatings on the silk yarn reeled from fresh cocoons surface did not improve the mechanical properties. The degumming and tensile testing analysis indicated that degummed silk fibroin of novel silk yarn is able to resist deformation and fracture better than silk fibroin of traditional silk yarn. The FTIR results revealed that the selected techniques is an important contributor to the silk fibroin mechanical properties, because novel technique brought higher percentage beta-sheet structures in novel silk yarn fibroin than traditional silk yarn. The new technique that using novel silk yarn has improved its mechanical properties and it is expected that the silk yarn with superior mechanical properties could be used in fabrics transistors, electrodes and reinforced biomaterials.     

Relationships between antithrombogenicity and surface free energy of regenerated silk fibroin films

Silk fibroin (SF) was dissolved in calcium chloride/ethanol/water mixture (1/2/8 in mole ratio) at 70°C for 4 h. The dissolved silk fibroin was regenerated by casting the dialyzed solution into the films. The films were treated with 50% aqueous solution of methanol for different times, and their antithrombogenicity was evaluated byin vitro andin vivo tests.In vivo blood tests were made by a method of peripheral vein indwelling suture. It was found that the silk fibroin had a good anti-thrombogenicity and an absorbability even though the polymer showed foreign body reaction. Finally, the blood compatibilty of silk fibroin films which were subjected to structural change by the methanol treatment, was examined in connection with their interfacial surface energy, and a correlation between these properties was found to be present.     

A new consolidation system for aged silk fabrics: Interaction between ethylene glycol diglycidyl ether,silk Fibroin and Artificial Aged Silk Fabrics

Consolidation of fragile historic silks is of great importance for further displays and researches. An effective and convenient method to consolidate aged silk fabric has been proposed by using a silk fibroin (SF)/ethylene glycol diglycidyl ether (EGDE) consolidation system. Artificial aged silk fabrics treated with SF/EGDE show great improvement in mechanical properties. The chemical reaction between EGDE and silk fabrics has been proved in previous paper. And in this paper, mechanical test, field emission scanning electron microscopy (FESEM), Fourier transform infrared spectrum (FTIR) test and amino acid analysis (AAA) were applied to illustrate the interactions between SF and silk fabric, EGDE and SF. Results show that SF takes part in the consolidation in the form of adhesions on the surface of silk fibers. The chemical reactions and film adhesion are both responsible for the improvements of mechanical properties in the consolidation.     

Antibacterial properties of silk fibroin/chitosan blend films loaded with plant extract

The silk fibroin (SF)/chitosan (CHI) blend films were prepared by dissolving them in formic acid. The morphology of the films was examined by scanning electron microscopy (SEM). The roughness of the membranes was determined by atomic force microscopy (AFM). These films were treated with the extracts of Pistacia terebinthus, Pistacia lentiscus, and Hypericum empetrifolium. Folin-Ciocalteu assay was used to determine the amount of total phenols adsorbed on these blend films. The antibacterial properties of films were tested using disc diffusion and turbidity measurement methods against Escherichia coli and Staphylococcus epidermidis. The release of adsorbed phenolics from the film surface resulted in antibacterial properties.     

Grafting of tyrosine-containing peptide onto silk fibroin membrane for improving enzymatic reactivity

During enzymatic modifications of silk fibroins, the accessibility of tyrosinases to the reactive sites was limited owing to the steric hindrance of tyrosine residues in the fibroin proteins. To improve the reactivity of silk fibroin, a tyrosine-containing peptide (TyrP) was covalently grafted onto the fibroin surfaces using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC). Enzymatic oxidation of the modified fibroins was subsequently carried out with a mushroom tyrosinase, followed by coupling of ε-polylysine (ε-PL) with the generated o-quinone residues of silk fibroins. The efficacy of grafting reaction was examined by means of SDS-PAGE and amine acid analysis. The results indicated EDC treatment might cause the direct self-crosslinks of silk fibroins and TyrP-bridged cross-links of fibroin molecules as well, which led to a noticeable increase in the molecular weight of fibroin proteins. TyrP-grafted fibroins displayed higher reactivity compared to the untreated, and more ε-PL was bonded to the fibroin surfaces when incubating with tyrosinase, resulting in improved wettability and mechanical property. The presented work offers an efficient alternative for the enzymatic modification of the fibroin-based materials with tyrosinase.     

Effect of sericin blending on molecular orientation of regenerated silk fiber

The use of regenerated silk fiber is limited due to its inferior mechanical properties in spite of high potential in a wide variety of applications. Many studies have been conducted in order to improve the mechanical properties of the regenerated silk materials, but no one has so far suggested an obvious solution. Meanwhile, some reports showed evidence that structural development of silk protein can be manipulated by physical interactions between silk fibroin (SF) and silk sericin (SS) during the regeneration process, especially in recrystallization process of SF. Such a hypothesis suggests a promising clue to enhance the mechanical properties of silk-based materials. Therefore, in this study, we tried to elucidate how SS can promote developing the molecular chain orientation of SF, resulting in an improvement of mechanical properties of regenerated silk fiber during spinning process. The tensile properties of the regenerated silk fiber were significantly improved compared to those of pure SF fiber when a proper amount of SS was blend with SF; both tenacity and breaking elongation increased by approximately 30 % and 70 % at three fold draw ratio, respectively. Quantitative analysis of X-ray diffraction and Herman’s orientation coefficient confirmed that such an improvement of tensile property was mainly caused by an increase of molecular orientation induced by sericin during the drawing process.     

Enhanced mechanical properties of silk fibroin-based composite plates for fractured bone healing

We successfully fabricated bacterial cellulose/silk fibroin (BC/SF) composite plates having similar strength to that of human cortical bone (12.8–17.7 GPa). The mechanical properties of the BC/SF composite plates were investigated at various BC nanofiber contents. The BC nanofibers acted as good reinforcements for the stress transfer produced by the interactions between the BC nanofibers and the SF matrix, as confirmed by the molecular deformation of the BC nanofibers. The BC/SF composite plates have a promising potential as a replacement material for existing metal bone plate.     

1-Aminoanthraquinone Diazonium Salt on the Coupling Modification Dyeing of Silk Fibroin with Enhanced Color Fastness

Chromophore incorporated into the protein chains through residue modification on silk fibroin will be an important way to get new dyeing technology with improved color fastness. Herein, 1-aminoanthraquinone diazonium salt was prepared and used for the modified dyeing on tyrosine of silk fibroin. The silk after modified dyeing was measured by UV-Vis, FTIR, MS, ¹H-NMR, Data color, and other testing techniques. Interestingly, the resulting silk showed excellent rub and wash fastness. The enhanced color fastness is contributed by an electrophilic substitution reaction between 1- aminoanthraquinone diazonium salt and the ortho position of phenolic hydroxyl in tyrosine molecular. Moreover, the mechanical property of silk was protected effectively by the mild coupling modified dyeing, better than the traditional acid dyeing under high temperature for a long time. This facile strategy provides an alternative approach to silk dyeing and benefits the silk applications.     

Chitosan–starch composite film: preparation and characterization

Chitosan film has potential applications in agriculture, food, and pharmacy. However, films made only from chitosan lack water resistance and have poor mechanical properties. Forming miscible, biodegradable composite film from chitosan with other hydrophilic biopolymers is an alternative. The objective of this study was to prepare chitosan/starch composite films by combining chitosan (deacetylated degree, 90%) solution and two thermally gelatinized cornstarches (waxy starch and regular starch with 25% amylose). The film’s tensile strength (TS), elongation-at-break (E), and water vapor transmission rate (WVTR) were investigated. The possible interactions between the two major components were evaluated by X-ray diffraction and Fourier-transform infrared spectroscopy (FTIR). Regardless of starch type, both the TS and E of the composite films first increased and then decreased with starch addition. Composite film made with regular starch showed higher TS and E than those with waxy starch. The addition of starch decreased WVTRs of the composite films. The introduction of gelatinized starch suppressed the crystalline peaks of chitosan film. The amino group band of chitosan molecule in the FTIR spectrum shifted from 1578 cm⁻¹ in the chitosan film to 1584 cm⁻¹ in composite films. These results indicated that there was a molecular miscibility between these two components.     

Preparation and characterization of cellulose nanofiber reinforced thermoplastic starch composites

In the present study, cellulose nanofibers composite films were manufactured based on thermoplastic starch. Nanofibers were extracted from rice straw employing a developed chemo-mechanical method. In the chemical step, almost all of non-cellulosic components were removed and a white pulp of cellulose microfibers was obtained. Then, a diluted suspension of fibers was ultrasonicated to destruct intermolecular hydrogen bonds achieving nanofibers networks. Afterward, bio-nanocomposites were prepared by film casting. In order to study the effect of nanofibers content on the composite properties, the mechanical and dynamic mechanical properties, morphology, humidity absorption, and transparency of films were investigated. The yield strength and Young modulus of nanocomposites were satisfactorily enhanced compared to the pure thermoplastic starch film. The glass transition temperature of films was shifted to higher temperatures by increasing nanofibers contents. The uniform dispersion of the nanofibers was investigated using SEM images. The humidity absorption resistance of films was significantly enhanced by using 10 wt% cellulose nanofibers. The transparency of the nanocomposites was reduced compared to the pure starch films.     

The effect of multi-walled carbon nanotubes on the molecular orientation of poly(vinyl alcohol) in drawn composite films

Poly(vinyl alcohol) (PVA)/multi-walled carbon nanotube (MWNT) composite films were prepared by casting a DMSO solution of PVA and MWNTs, whereby the MWNTs were dispersed by sonication. A significant improvement in the mechanical properties of the PVA drawn films was achieved by the addition of a small amount of MWNTs. The initial modulus and the tensile strength of the PVA drawn film increased by 30% and 45% respectively, with the addition of 1 wt% MWNTs, which are close to those calculated from the rule of mixtures, and were strongly dependent upon the orientation of the PVA matrix. The mechanical properties, however, were not improved with a further increase in the MWNT content. The orientation of MWNTs in the composite was not well developed compared to that of the PVA matrix. This result suggests that the improvement of the molecular orientation of the PVA matrix plays a major role in the increase of the mechanical properties of the drawn PVA/MWNT composite films.     

Structure,electrical and mechanical properties of polyamide 66/acid-treated MWCNT composite films prepared by solution mixing in the presence of nonionic surfactant

Two different sets of polyamide 66(PA66)-based composite films containing 2.0-10.0 wt% acid-treated multiwalled carbon nanotubes (MWCNT) were manufactured by solution mixing and casting method in the presence or absence of a nonionic surfactant. For the improved dispersion and interfacial interaction of MWCNTs in the PA66 matrix, carboxylic acid-functionalized MWCNTs were prepared by the acid-treatment of pristine MWCNTs. The uniform dispersion of the acidtreated MWCNTs in the PA66 matrix was confirmed from FE-SEM images of the fractured composite film surfaces. DSC thermograms supported that the acid-treated MWCNTs served as nucleating agents for the melt-crystallization of PA66 in both composite films prepared with/without the addition of the surfactant. The electrical and tensile mechanical properties of the composite films prepared with the surfactant were ~20 % higher than those of the composite films manufactured without the surfactant. For both composite films, sheet resistivity and tensile mechanical properties were found to be highly decreased and increased, respectively, with the increment of the acid-treated MWCNT content.     

Effects of environment parameters on sol-gel transition and dry-spinnability of regenerated silk fibroin aqueous solution

Protein concentration, pH, the types and concentrations of metallic ions, and extensional flow are thought to be important environment parameters affecting the natural spinning process. In this study, we investigate the effects of the types and concentrations of metallic ions (Ca²⁺, Mg²⁺, and K⁺ ions), pH, and silk fibroin concentration on the sol-gel transition and the rheological behavior of a regenerated silk fibroin (RSF) aqueous solution. The results show that with an increase in the silk fibroin concentration, the weak acidic RSF aqueous solutions containing Mg²⁺ or Ca²⁺ ions undergo a phase transition to a weak gel state. Moreover, the rheological characterization of RSF aqueous solutions shows a dramatic change, and their apparent viscosities increase by almost three orders of magnitude and approach the apparent viscosity of the native dope in the silkworm gland. By using conventional pressure equipment, we investigate the dry-spinnability of weak gels. Further, we observe that the as-spun fibers exhibit a smooth surface and have inferior mechanical properties. The structure of the as-spun fibers is predominantly in a random coil or Silk I conformation.     

Enhancement biocompatibility of bacterial cellulose membrane via laccase/TEMPO mediated grafting of silk fibroins

Silk fibroin (SF) has the characteristic of moisture penetrability and biocompatibility. To enhance the biocompatibility of bacterial cellulose (BC), silk fibroin is grafted onto BC membrane using laccase and 2,2′,6,6′-tetramethylpiperidine-N-oxyl (TEMPO). As the model compound of BC, cellobiose is incubated with laccase/TEMPO for disclosing the mechanism of enzymatic oxidation. The structure and property of the composite membranes of SF/BC are investigated by means of FTIR, XPS, DSC, and biocompatibility analysis. The results indicate that cellobiose might react with hexamethylenediamine and form Schiff bases. The concentration of amino group in SF solution noticeably decreased after laccase/TEMPO oxidation, indicating the occurrence of self-crosslinking of SF. After enzymatic grafting of SF, the content of atomic nitrogen on BC surface was increased compared to that of the control. Meanwhile, the composite membrane of SF/BC exhibits more satisfactory biocompatibility compared to BC, and it has potential applications in biomedical fields.     

Influence of noncellulosic contents on nano scale refinement of waste jute fibers for reinforcement in polylactic acid films

In the present study, nanofibrils of cellulose are extracted from waste jute fibers using high energy planetary ball milling process in wet condition. The rate of refinement of untreated fibers having non-cellulosic contents was found slower than treated fibers due to strong holding of fiber bundles by non-cellulosic contents. At the end of three hours of wet milling, untreated fibers were refined to the size of 850 nm and treated fibers were refined to the size of 443 nm. In the subsequent stage, composite films of poly lactic acid (PLA) were prepared by solvent casting with 3 wt% loading of untreated jute nanofibrils, treated jute nanofibrils and microcrystalline cellulose. The influence of non-cellulosic contents on mechanical properties of PLA films are investigated based on results of tensile test, dynamic mechanical analysis and differential scanning calorimetry. The maximum improvement was observed in case of treated jute nanofibril/PLA composite film where initial modulus and tensile strength increased by 207.69 % and 168.67 %, respectively as compared to neat PLA film. These improvements are attributed to the increased interaction of treated jute nanofibrils with PLA matrix due to their higher precentage of cellulosic contents and mechanically activated surface.     

茶多酚-壳聚糖复合膜的制备及保鲜效果研究

本研究以聚乙烯醇（PVA）和壳聚糖（CTS）为基材,甘油作为增塑剂,以茶多酚（TP）为功能性添加剂制备无污染、可降解且具有抗氧化功能的活性包装材料TP-CTS/PVA复合膜,分析TP浓度对复合膜机械性能、抗氧化能力、抑菌能力等理化性质的影响,研究复合膜与包装相关性能的影响,以期提高复合膜的综合性能。将其应用于圣女果的保鲜,测定其在贮存期间理化指标及微生物指标,进一步将不同TP浓度的复合膜涂抹于新鲜圣女果表面,分析圣女果在贮存期间的感官品质、腐烂率、失重率、可溶性糖、可滴定酸等指标的变化,系统研究复合膜对圣女果的保鲜效果。结果表明：以TP为功能性添加剂共混CTS和PVA制备的复合膜兼具抗氧化和抑菌效果;随着TP浓度增加,复合膜的颜色逐渐变深,TP浓度为1.5%时,复合膜的水溶性最低(19.85±0.64)%,此时复合膜的抗张强度呈最大值(13.19±0.77)MPa;当TP浓度增大,其对Escherichia coli和Staphylococcus aureus的抑菌能力也不断增强,能有效抑制细菌生长; TP浓度为2.0%时,复合膜对DPPH自由基清除率达到最大值(38.53±0.91)%;采用复合膜涂覆对圣女果能减少水分蒸腾、延缓果蔬机体衰老从而起到良好的保鲜效果,涂膜能有效延缓圣女果的腐烂和失水变质的现象,表明TP-CTS/PVA复合膜能改善果蔬的保鲜货架期和商品价值;在相同贮存时间内,当用TP浓度为1.50%复合膜涂抹圣女果时,圣女果的感官评价得分、失重率、腐烂率、可滴定酸含量、可溶性糖含量等各项指标较其他TP浓度试验组效果更好。研究表明,当TP浓度为1.5%~2.0%时制备的TP-CTS/PVA复合膜其抑菌性、耐水性、抗氧化性、以及保鲜性能等各项指标较为均衡,将其实际应用于生产中可根据需求调整TP浓度。本研究目的为探索开发抗菌抗氧化功能型复合膜和功能型包装材料替代塑料包装材料的可能性,为同时解决食品保鲜与环境污染问题提供依据。     

Fly ash/polyurethane thin film for the adsorption of volatile organic compounds (VOCs) from air

Polyurethane (PU) films containing different amounts of fly ash particles (FAPs) were prepared by simple solution casting method. The morphological, thermal, and mechanical properties of the composite films were investigated by several characterization methods. Results show that sufficient amounts (up to 40 wt%) of FAPs can be incorporated throughout the film. The presence of FAPs within PU film not only acts as filler to increase the mechanical strength of the film but also increases its volatile organic compounds (VOCs) adsorption capacity. The VOCs adsorption capacity of FAPs/PU composite films were investigated on three different compounds (chloroform, toluene, and benzene). It showed consistent trend in the order of toluene > benzene > chloroform for all the samples. The VOCs adsorption capacity of PU film was found to be increased by two fold when 20 wt% of FA was incorporated through it. The present results suggest the potential use of FAPs as filler materials for PU films with improved VOCs adsorption from outdoor and indoor air.     

Soy protein films with the hydrophobic surface created through non-covalent interactions

Different plasticizers (P) such as glycerol, 1,2 propanediol, trimethylol propane, thiodiglycol, and formamide (30% by weight w.r.t. soy protein) were used to prepare soy protein films (coded as SP) by compression molding at 140 °C and 20 MPa. The SP films were immersed in 0.5% (w/v) benzilic acid solution for 26 h to get arylated soy protein films (SP-B) with the evolution of CO₂, leading to the formation of diphenylhydroxymethane (DPHM) on the surface. Lotus leaf like structure, on the surface of SP-B film, with high hydrophobicity has been created, supported by the existence of nano/micro spheres. The SP-B and SP films were characterized by Fourier transformed infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, tensile testing, optical transmittance, contact angle, and biodegradation experiments. The mechanical properties, transmittance, and contact angle of SP-B films increased significantly, compared with SP. The SP-B films exhibited high water resistance in the range of 67–82%. These results indicated attractive interactions (often termed as π-interactions) of DPHM aromatic groups took place in the SP-B films resulting in the formation of nanospheres or microspheres. This work provided a good way for increasing the surface hydrophobicity and the mechanical properties of the protein materials through non-covalent interactions.     

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.     

Preparation and characterization of blended <Emphasis Type="Italic">Bombyx mori</Emphasis> silk fibroin scaffolds

The aim of this study was to compare physical, mechanical and biological properties of 3-dimensional scaffolds prepared from Bombyx mori silk fibroin (SF), fibroin blended with collagen (SF/C), and fibroin blended with gelatin (SF/G) using a freeze-drying technique. The prepared scaffolds were sponge-like structure that exhibited homogeneous porosity with highly interconnected pores. Average pore size of these scaffolds ranged from 65–147 μm. All biodegradable scaffolds were capable of water absorption of 90 %. The degradation behavior of these scaffolds could be controlled by varying the amount of blended polymer. The SF/C and SF/G scaffolds showed higher compressive modulus than that of SF scaffolds which could be attributed to the thicker pore wall observed in the blended constructs. The less crystalline SF structure was observed in SF/G scaffolds as compared to SF/C scaffolds. Thus, the highest compressive modulus was observed on SF/C matrix. To investigate the feasibility of the scaffolds for cartilage tissue engineering application, rat articular chondrocytes were seeded onto the scaffolds. The MTT assay demonstrated that blending collagen or gelatin into SF sponge facilitated cell attachment and proliferation better than SF scaffolds. The blended SF scaffolds possessed superior physical, mechanical and biological properties in comparison to SF scaffolds and showed high potential for application in cartilage tissue engineering.