Facile and versatile solid state surface modification of silk fibroin membranes using click chemistry

Raynal, Laetitia; Allardyce, Benjamin J.; Wang, Xungai; Dilley, Rodney J.; Rajkhowa, Rangam; Henderson, Luke C.

doi:10.1039/c8tb02508h

Cited by 13 publications

(12 citation statements)

References 26 publications

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“…The phenol groups from the tyrosines (∼5%) of silk chains were chosen for chemical modifications through diazonium coupling , and oxidative coupling strategies , in ASS, NS, and BLS solutions (Schemes S1 and S2), respectively. The grafting processes were carried out under same conditions (silk and reagent concentrations, temperature, and time).…”

Section: Resultsmentioning

confidence: 99%

Structure–Chemical Modification Relationships with Silk Materials

Liu

Zhang

et al. 2019

ACS Biomater. Sci. Eng.

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Chemical modifications used with silk materials can be challenging due to heterogeneous reactions, in part due to the assembly state of the protein chains. Here, we assess factors that determine the efficiency of chemical modifications with silk materials. Unlike other natural macromolecules, silk presents changeable self-assembled or aggregation states in aqueous solution, which affect the chemical reactions based on reactive group distribution or accessibility. To confirm this hypothesis, silk nanofibers in various conformation and aggregation states in solution were exposed to the same reaction conditions. Amorphous silk nanofibers provided improved control for consistent chemical modification outcomes, while silk nanofibers with control of structure could be utilized to generate bifunctional materials through multiple chemical modifications. The results of the chemical modifications demonstrated that control of the conformational transitions of silk nanofibers provided a feasible strategy for developing multifunctional silk materials with improved chemical outcomes.

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Section: Resultsmentioning

confidence: 99%

Structure–Chemical Modification Relationships with Silk Materials

Liu

Zhang

et al. 2019

ACS Biomater. Sci. Eng.

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“…29 Furthermore, the diazonium salt-based modification approach was adopted to impart reactivity to the silk fibroin substrates, which were further exploited for postmodification following catalyst-aided azide−alkyne click chemistry. 25,26 However, the utility of amine residues present in silk fibroin is rare for chemical modification due to its poor availability. Recently, Sun et al exploited the amine and hydroxyl residues of a silk fibroinderived nanofibrous membrane for modification with pyro-mellitic dianhydride following the acid-catalyzed anhydride ring-opening reaction.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…20,24−27 For example, Raynal et al controlled the water wettability of a silk fibroin-derived membrane from ∼34 to ∼85°through the strategic use of catalyst-assisted click chemistry between azide and alkyne, where the silk membrane was functionalized with alkyne groups following the coupling reaction of diazonium with the tyrosine residues of the protein. 26 In another approach, Zheng et al performed the targeted oxidation of the serine residues of silk fibroin using sodium hypochlorite in a basic environment to investigate the impact of human bone marrow-derived mesenchymal stem cell proliferation and differentiation on the oxidized silk scaffolds. 28 But a catalyst-free, facile approach to optimize the chemistry of silk protein-derived materials is a concern in the literature reported till date.…”

Section: ■ Introductionmentioning

confidence: 99%

Unconventional and Facile Fabrication of Chemically Reactive Silk Fibroin Sponges for Environmental Remediation

Shome

Moses

Rather

et al. 2021

ACS Appl. Mater. Interfaces

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Silk fibroin and silk microfibers, both derived from silk cocoon, have been widely used for prospective biomedical, energy, and environmental applications. However, various complex and catalyst-based approaches have been adopted for chemical modification and integration of different functionalities in silk fibroin-based materials. Here, both tailored water wettability and mechanical property have been associated with silk microfiber reinforced silk fibroin sponges (SMFRSFSs) through the strategic introduction of β-sheets and a facile and catalyst-free chemical reaction at ambient conditions. While the controlled tailoring of β-sheets in the silk fibroin skeletal framework of the sponges allowed us to modulate the compressive modulus, the 1,4-conjugate addition reaction between amine residues of silk (fiber and fibroin) and acrylate groups of a multifunctional cross-linker provided residual chemical reactivity. Further, the chemically “reactive” sponge was postmodified with the selected alkylamines to introduce a wide range of water wettability (from 36 to 161°) without affecting the mechanical property. Thereafter, the silk cocoon-derived and extremely water-repellent sponge was used for environment-friendly cleaning of oil spillages through selective absorption-based and filtration-based oil/water separation at different and severe aqueous conditions. This silk cocoon-derived mechanically tailorable and chemically reactive sponge could also be useful for various biomedical and energy-related applications.

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“…5.3% of the amino acids composing silk fibroin are tyrosine, which is distributed through the silk fibroin protein sequence, and this azobenzene postmodified silk fibroin is then referred to as “azosilk” or “optosilk.” This diazonium coupling method, developed by Murphy and Kaplan, can be performed in mild conditions and results in a relatively high conversion of tyrosine residues to azobenzene residues (≈40%) . It is now the typical method used for synthesizing azosilk, and the modification is usually completed on silk fibroin dissolved in an aqueous solution before it is cast into its final structure, though Raynal et al have developed an approach for modifying silk fibroin that has already been cast on a surface …”

Section: Interfacing Azo To Bio: An Eye Toward Influencing Living Sysmentioning

confidence: 99%

Photoreversible Soft Azo Dye Materials: Toward Optical Control of Bio‐Interfaces

Chang

Fedele

Priimägi

et al. 2019

Advanced Optical Materials

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systems interact with artificial materials, researchers have now assembled a versatile toolkit of materials and processes that allows one to fine-tune interactions at the interface, tailoring specific biological responses on demand. These strategies for biocontrol can be broadly categorized as chemical (charge, ligand presence, surface groups), material changes (moisture content, stiffness), or morphological changes (molecular orientation, surface topography, or mechanical actuation). Rational design of materials for biological interface applications has a unique set of challenges due to the unique requirements of a wide range of biological systems, since different tissues present specific compositions, with their own elasticity, structural organization, and triggering mechanisms. Even within a single organ or tissue, mechanical properties can vary widely depending on the region. A recent study of viscoelasticity in live mouse brain tissue for example found a tenfold difference within the brain depending on the region and morphological structure studied. [2] However, most biological tissues are far less stiff, and far more viscoelastic than typical artificial materials employed at their interface, especially early artificial cell culture materials, which can be much stiffer than in vivo extracellular matrix by many orders of magnitude. [3] In vivo, cells interface with a surrounding microenvironment consisting of an intricate macromolecular network of proteins and sugars swollen in an aqueous media gel. Therefore, the interaction between cells and the extracellular matrix (ECM) in the body is complex and involves a variety of cues related to topography, chemical markers, protein composition, solubility factors, and mechanical properties such as stiffness and elasticity (Figure 1a). [4] Yet much research over the past decades was focused on studying in vitro the effects of each of these signals on cell behavior, with a particular interest on the chemical factors, whereas only recently more advanced biomaterials with controlled physicomechanical properties have been developed, such as those with tunable and variable stiffness, alignment and orientation of key functional groups, and mechanical actuation. There is a large range of stiffness in human tissue, where bone (≈100 GPa) is nine orders of magnitude harder than brain tissue (≈0.1 kPa). [4] Therefore, biomaterial researchers assume a complex task of providing materials and processing technologies for controlling stiffness and micro-and nanostructures in Photoreversible optically switchable azo dye molecules in polymer-based materials can be harnessed to control a wide range of physical, chemical, and mechanical material properties in response to light, that can be exploited for optical control over the bio-interface. As a stimulus for reversibly influencing adjacent biological cells or tissue, light is an ideal triggering mechanism, since it can be highly localized (in time and space) for precise and dynamic control over a biosystem, and low-power visible light...

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Facile and versatile solid state surface modification of silk fibroin membranes using click chemistry

Abstract: Reported is a fast and versatile protocol to surface modify pre-cast silk membranes targeting tyrosine residues.

Cited by 13 publications

References 26 publications

Structure–Chemical Modification Relationships with Silk Materials

Structure–Chemical Modification Relationships with Silk Materials

Unconventional and Facile Fabrication of Chemically Reactive Silk Fibroin Sponges for Environmental Remediation

Photoreversible Soft Azo Dye Materials: Toward Optical Control of Bio‐Interfaces

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