Silk sericin-polylactide protein-polymer conjugates as biodegradable amphiphilic material and its application in drug release systems

Silk sericin (SS) is a byproduct of silk production. In order to transform it into value-added products, sericin can be used as a biodegradable and pH-responsive building block in drug delivery materials. To this end, amphiphilic substances were synthesized via the conjugation of hydrophobic polylactide (PLA) to the hydrophilic sericin using a bis-aryl hydrazone linker. PLA was esterified with a terephthalaldehydic acid to obtain aromatic aldehyde terminated PLA (PLA-CHO). In addition, lysine groups of SS were modified with the linker succinimidyl-6-hydrazino-nicotinamide (S-HyNic). Then, both macromolecules were mixed to form the amphipilic protein-polymer conjugate in buffer-DMF solution. The formation of bis-aryl hydrazone linkages was confirmed and quantified by UV-vis spectroscopy. SS-PLA conjugates self-assembled in water into spherical multicompartment micelles with a diameter of around 100 nm. Doxorubicin (DOX) was selected as a model drug for studying the pH-dependent drug release from SS-PLA nanoparticles. The release rate of the encapsulated drug was slower than that of the free drug and dependent on pH, faster at pH 5.0, and it resulted in a larger cumulative amount of drug released than at physiological pH of 7.4. The SS-PLA conjugate of high PLA branches showed smaller particle size and lower loading capacity than the one with low PLA branches. Both SS-PLA conjugates had negligible cytotoxicity, whereas after loading with DOX, the SS-PLA micelles were highly toxic for the human liver carcinoma immortalized cell line HepG2. Therefore, the SS-based biodegradable amphiphilic material showed great potential as a drug carrier for cancer therapy

Self-reporting fiber-reinforced composites that mimic the ability of biological materials to sense and report damage

Sensing of damage, deformation, and mechanical forces is of vital importance in many applications of fiber-reinforced polymer composites, as it allows the structural health and integrity of composite components to be monitored and microdamage to be detected before it leads to catastrophic material failure. Bioinspired and biomimetic approaches to self-sensing and self-reporting materials are reviewed. Examples include bruising coatings and bleeding composites based on dye-filled microcapsules, hollow fibers, and vascular networks. Force-induced changes in color, fluorescence, or luminescence are achieved by mechanochromic epoxy resins, or by mechanophores and force-responsive proteins located at the interface of glass/carbon fibers and polymers. Composites can also feel strain, stress, and damage through embedded optical and electrical sensors, such as fiber Bragg grating sensors, or by resistance measurements of dispersed carbon fibers and carbon nanotubes. Bioinspired composites with the ability to show autonomously if and where they have been damaged lead to a multitude of opportunities for aerospace, automotive, civil engineering, and wind-turbine applications. They range from safety features for the detection of barely visible impact damage, to the real-time monitoring of deformation of load-bearing components

Effects of silk degumming process on physicochemical, tensile, and optical properties of regenerated silk fibroin

Sericin removal from silk (degumming) affects material characteristics of silk fibroin (SF). Sodium carbonate is most commonly used for degumming, but numerous alternative methods are available. Herein, a systematic comparison of degumming methods is provided. Sodium carbonate, sodium oleate, trypsin, and ionic liquid are used, and materials are characterized regarding mass loss, SF content, molecular integrity of SF, refractive index, and tensile properties. Complete degumming is achieved within 30 min of using sodium carbonate, but results in significant reduction of molecular weight, shift toward less acidic charge variants, and reduction of yield- and rupture force. Sodium oleate and trypsin are inefficient and negatively affect tensile properties, while ionic liquid shows good efficiency and marginal degradation of SF but also reduced yield- and rupture force. Refractive index is not affected by degumming. These results allow rational selection of the degumming method and tuning of SF properties for biomedical applications

Rendering polyurethane hydrophilic for efficient cellulose reinforcement in melt-spun nanocomposite fibers

Many commodity plastics, such as thermoplastic polyurethanes (PUs), require reinforcement for use as commercial products. Cellulose nanocrystals (CNCs) offer a “green” and scalable approach to polymer reinforcement as they are exceptionally stiff, recyclable, and abundant. Unfortunately, achieving efficient CNC reinforcement of PUs with industrial melt processing techniques is difficult, mostly due to the incompatibility of the hydrophobic PU with hydrophilic CNCs, limiting their dispersion. Here, a hydrophilic PU is synthesized to achieve strong reinforcement in melt‐processed nanocomposite fibers using filter paper‐sourced CNCs. The melt‐spun fibers, exhibiting smooth surfaces even at high CNC loading (up to 25 wt%) indicating good CNC dispersion, are bench‐marked against solvent‐cast films—solvent processing is not scalable but disperses CNCs well and produces strong CNC reinforcement. Mechanical analysis shows the CNC addition stiffens both nanocomposite films and fibers. The stress and strain at break, however, are not significantly affected in films, whereas adding CNCs to fibers increases the stress‐at‐break while reducing the strain‐at‐break. Compared to earlier studies employing a hydrophobic (and stiffer) PU, CNC addition to a hydrophilic PU substantially increases the fiber stiffness and strength. This work therefore suggests that rendering thermoplastics more hydrophilic might pave the way for “greener” polymer composite products using CNCs

Infiltration of Proteins in Cholesteric Cellulose Structures

| openaire: EC/H2020/788489/EU//BioELCell The authors received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie Grant Agreement no. 722842 (ITN Plant-inspired Materials and Surfaces—PlaMatSu), the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (Grant Agreement no. 788489), the FinnCERES bioeconomy flagship funded by the Academy of Finland, and the Canada Excellence Research Chair initiative and the Canada Foundation for Innovation (CFI). This work moreover benefitted from support from the Swiss National Science Foundation through the National Center of Competence in Research Bio-Inspired Materials. L.G.G. acknowledges funding by the Aalto University School of Chemical Engineering doctoral program. L.K.B. and N.B. would like to thank Alexandre Redondo and Chris Rader for lab assistance. The authors also thank Sara Roldan Velasquez for all scientific discussions on mechanical properties andDr. Bodo Wilts for proofreading the manuscript and giving scientific advice and having constructive discussions.Cellulose nanocrystals (CNCs) can spontaneously self-assemble into chiral nematic (cn) structures, similar to natural cholesteric organizations. The latter display highly dissipative fracture propagation mechanisms given their "brick" (particles) and "mortar" (soft matrix) architecture. Unfortunately, CNCs in liquid media have strong supramolecular interactions with most macromolecules, leading to aggregated suspensions. Herein, we describe a method to prepare nanocomposite materials from chiral nematic CNCs (cn-CNCs) with strongly interacting secondary components. Films of cn-CNCs were infiltrated at various loadings with strongly interacting silk proteins and bovine serum albumin. For comparison and to determine the molecular weight range of macromolecules that can infiltrate cn-CNC films, they were also infiltrated with a range of poly(ethylene glycol) polymers that do not interact strongly with CNCs. The extent and impact of infiltration were evaluated by studying the optical reflection properties of the resulting hybrid materials (UV-vis spectroscopy), while fracture dissipation mechanisms were observed via electron microscopy. We propose that infiltration of cn-CNCs enables the introduction of virtually any secondary phase for nanocomposite formation that is otherwise not possible using simple mixing or other conventional approaches.Peer reviewe

Erratum to: Guidelines for the use and interpretation of assays for monitoring autophagy (3rd edition) (Autophagy, 12, 1, 1-222, 10.1080/15548627.2015.1100356

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