On the routines of wild-type silk fibroin processing toward silk-inspired materials: a review

For years, silk fibroin of a domestic silkworm, Bombyx mori, has been recognized as a valuable material and extensively used. In the last decades, new application fields are emerging for this versatile material. Those final, specific applications of silk dictate the way it has been processed in industry and research. This review focuses on the description of various approaches for silk downstream processing in a laboratory scale, that fall within several categories. The detailed description of workflow possibilities from the naturally found material to a finally formulated product is presented. Considerable attention is given to (bio-) chemical approaches of silk fibroin transformation, particularly, to its enzyme-driven modifications. The focus of the current literature survey is exclusively on the methods applied in research and not industry.

Exploring the properties of genetically engineered silk-elastin-like protein films

Free standing films of a genetically engineered silk-elastin-like protein (SELP) were prepared using water and formic acid as solvents. Exposure to methanol-saturated air promoted the formation of aggregated β-strands rendering aqueous insolubility and improved the mechanical properties leading to a 10-fold increase in strain-to-failure. The films were optically clear with resistivity values similar to natural rubber and thermally stable up to 180 °C. Addition of glycerol showed to enhance the flexibility of SELP/glycerol films by interacting with SELP molecules through hydrogen bonding, interpenetrating between the polymer chains and granting more conformational freedom. This detailed characterization provides cues for future and unique applications using SELP based biopolymers.

Bombyx mori Silk Fibers: An outstanding family of materials

Designing novel multifunctional materials from natural resources is a challenging goal that has increasingly attracted researchers. Recently, the great potential of silk fibers has been recognized. The target readers for this review are researchers from different backgrounds (i.e., non-specialists in silk research) with special interests on the physical–chemical characterization of silk fibers, since their knowledge is crucial for the improvement of existent silk-based biomaterials and the basis for the development of new products. Examples of usual applications of Bombyx mori silk fibers are given and some of the most recent and exciting progress in new technological fields, is presented.

Silk fibroin based multifunctional materials

Silk fibroin is a commonly available natural biopolymer produced in specialized glands of arthropods, such as silkworms or spiders, scorpions, mites, bees and flies. This biopolymer has a long history of use in textile production and also as sutures or treatment of skin wounds. Silk fibroin has been increasingly explored in other areas of biomedical science where we can find a higher morphological diversification of silk biomaterials like films, electrospun fibers, 3D porous scaffolds or nanoparticles. In recent years it has been demonstrated that fibroin is an excellent material for active components in optical devices. This new application opens the way towards the development of multifunctional optoelectronic devices, which in perspective can be made fully biocompatible and eventually bioresorbable. Moreover, fibroin can be added to other biocomponents in order to modify the biomaterial properties leading to optimized and total different functions. These improvements can go from higher cell adhesion in tissue engineering or enhanced optical transparency, smoothness or flexibility in optoelectronic devices. The tuning and completely understanding of silk fibers physicochemical properties and interaction with other elements are of crucial importance for the improvement of already existent silk-based materials and the basis for the development of new products.

Lithium-doped silk fibroin films for application in electrochromic devices

Silk fibroin (SF) is a commonly available natural biopolymer produced in specialized glands of arthropods, with a long history of use in textile production and also in health cares. The exceptional intrinsic properties of these fibers, such as self-assembly, machinability, biocompatibility, biodegradation or non-toxicity, offer a wide range of exciting opportunities [1]. It has long been recognized that silk can be a rich source of inspiration for designing new materials with tailored properties, enhanced performance and high added value for targeted applications, opening exciting new prospects in the domain of materials science and related technological fields, including bio-friendly integration, miniaturization and multifunctionalization. In recent years it has been demonstrated that fibroin is an excellent material for active components in optics and photonics devices. Progress in new technological fields such as optics, photonics and electronics are emerging [2,3]. The incorporation of polymer electrolytes as components of various devices (advanced batteries, smart windows, displays and supercapacitors) offers significant advantages with respect to traditional electrolytes, including enhanced reliability and improved safety. SF films are particularly attractive in this context. They have near-perfect transparency across the VIS range, surface flatness (together with outstanding mechanical robustness), ability to replicate patterned substrates and their thickness may be easily tailored from a few nanometers to hundreds of micrometers through spin-casting of a silk solution into subtract. Moreover, fibroin can be added to other biocomponents or salts in order to modify the biomaterial properties leading to optimized and total different functions. Preliminary tests performed with a prototype electrochromic device (ECD) incorporating SF films doped with lithium triflate and lithium tetrafluoroborate (LiTFSI and LiBF4, respectively) as electrolyte and WO3 as cathodic electrochromic layer, are extremely encouraging. Aiming to evaluate the performance of the ion conducting SF membranes doped with LiTFSI and LiBF4 (SF-Li), small ECDs with glass/ITO/WO3/SF-Li/CeO2-TiO2/ITO/glass configuration were assembled and characterized. The device exhibited, after 4500 cycles, the insertion of charge at -3.0 V reached –1.1 mC.cm-2 in 15 s. After 4500 cycles the window glass-staining, glass/ITO/WO3/Fibrin-Li salts electrolyte/CeO2-TiO2/ITO/glass configuration was reversible and featured a T  8 % at λ = 686 nm

Exploring silk based biomaterials functionalized with antimicrobial peptides to prevent surgical site infections

Surgical site infections (SSI) often occur after invasive surgery, which is as a serious health problem, making it important to develop new biomaterials to prevent infections. Spider silk is a natural biomaterial with excellent biocompatibility, low immunogenicity and controllable biodegradability. Through recombinant DNA technology, spider silk-based materials can be bioengineered and functionalized with antimicrobial (AM) peptides 1. The aim of this study is to develop new materials by combining spider silk chimeric proteins with AM properties and silk fibroin extracted from Bombyx mori cocoons to prevent microbial infection. Here, spider silk domains derived from the dragline sequence of the spider Nephila clavipes (6 mer and 15 mer) were fused with the AM peptides Hepcidin and Human Neutrophil peptide 1 (HNP1). The spider silk domain maintained its self-assembly features allowing the formation of beta-sheets to lock in structures without any chemical cross-linking. The AM properties of the developed chimeric proteins showed that 6 mer + HNP1 protein had a broad microbicidal activity against pathogens. The 6 mer + HNP-1 protein was then assembled with different percentages of silk fibroin into multifunctional films. In vitro cell studies with a human fibroblasts cell line (MRC5) showed nontoxic and cytocompatible behavior of the films. The positive cellular response, together with structural properties, suggests that this new fusion protein plus silk fibroin may be good candidates as multifunctional materials to prevent SSI.

In vitro phosphorylation as tool for modification of silk and keratin fibrous materials

An overview is given of the recent work on in vitro enzymatic phosphorylation of silk fibroin and human hair keratin. Opposing to many chemical "conventional" approaches, enzymatic phosphorylation is in fact a mild reaction and the treatment falls within "green chemistry" approach. Silk and keratin are not phosphorylated in vivo, but in vitro. This enzyme-driven modification is a major technological breakthrough. Harsh chemical chemicals are avoided, and mild conditions make enzymatic phosphorylation a real "green chemistry" approach. The current communication presents a novel approach stating that enzyme phosphorylation may be used as a tool to modify the surface charge of biocompatible materials such as keratin and silk.

Enzymatic processing of protein-based fibers

Wool and silk are major protein fiber materials used by the textile industry. Fiber protein structure-function relationships are briefly described here, and the major enzymatic processing routes for textiles and other novel applications are deeply reviewed. Fiber biomodification is described here with various classes of enzymes such as protease, transglutaminase, tyrosinase, and laccase. It is expected that the reader will get a perspective on the research done as a basis for new applications in other areas such as cosmetics and pharma.

Cutinase promotes dry esterification of cotton cellulose

Cutinase from Thermobifida fusca was used to esterify the hydroxyl groups of cellulose with the fatty acids from triolein. Cutinase and triolein were pre-adsorbed on cotton and the reaction proceeded in a dry state during 48 hours at 35ºC. The cutinase-catalyzed esterification of the surface of cotton fabric resulted in the linkage of the oleate groups to the glycoside units of cotton cellulose. The superficial modification was confirmed by performing ATR-FTIR on treated cotton samples and by MALDI-TOF analysis of the liquors from the treatment of the esterified cotton with a crude cellulase mixture. Modified cotton fabric also showed a significant increase of hydrophobicity. This work proposes a novel bio-based approach to obtain hydrophobic cotton. This article is protected by copyright. All rights reserved.

Effect of hormonal changes on corneal biomechanical properties and anterior segment ocular perameters

Dissertação de mestrado em Optometria Avançada