We report a study of self-assembled beta-pleated sheets in B. mori silk fibroin films using thermal analysis and infrared spectroscopy. B. mori silk fibroin may stand as an exemplar of fibrous proteins containing crystalline beta-sheets. Materials were prepared from concentrated solutions (2−5 wt % fibroin in water) and then dried to achieve a less ordered state without beta-sheets. Crystallization of beta-pleated sheets was effected either by heating the films above the glass transition temperature (Tg) and holding isothermally or by exposure to methanol. The fractions of secondary structural components including random coils, alpha-helices, beta-pleated sheets, turns, and side chains were evaluated using Fourier self-deconvolution (FSD) of the infrared absorbance spectra. The silk fibroin films were studied thermally using temperature-modulated differential scanning calorimetry (TMDSC) to obtain the reversing heat capacity. The increment of the reversing heat capacity ΔCp0(Tg) at the glass transition fo...

/pdf/determining-beta-sheet-crystallinity-in-fibrous-proteins-by-2aov4wvj48.pdf

Determining Beta Sheet Crystallinity in Fibrous Proteins by Thermal Analysis and Infrared Spectroscopy

This article explores recent advances in the design and engineering of materials wholly or principally constructed from peptides. We focus on materials that are able to respond to changes in their environment (pH, ionic strength, temperature, light, oxidation/reduction state, presence of small molecules or the catalytic activity of enzymes) by altering their macromolecular structure. Such peptide-based responsive biomaterials have exciting prospects for a variety of biomedical and bionanotechnology applications in drug delivery, bio-sensing and regenerative medicine.

Peptide-based stimuli-responsive biomaterials

Tissue engineering holds great promise to develop functional constructs resembling the structural organization of native tissues to improve or replace biological functions, with the ultimate goal of avoiding organ transplantation. In tissue engineering, cells are often seeded into artificial structures capable of supporting three-dimensional (3D) tissue formation. An optimal scaffold for tissue-engineering applications should mimic the mechanical and functional properties of the extracellular matrix (ECM) of those tissues to be regenerated. Amongst the various scaffolding techniques, electrospinning is an outstanding one which is capable of producing non-woven fibrous structures with dimensional constituents similar to those of ECM fibres. In recent years, electrospinning has gained widespread interest as a potential tissue-engineering scaffolding technique and has been discussed in detail in many studies. So why this review? Apart from their clear advantages and extensive use, electrospun scaffolds encounter some practical limitations, such as scarce cell infiltration and inadequate mechanical strength for load-bearing applications. A number of solutions have been offered by different research groups to overcome the above-mentioned limitations. In this review, we provide an overview of the limitations of electrospinning as a tissue-engineered scaffolding technique, with emphasis on possible resolutions of those issues. Copyright © 2015 John Wiley & Sons, Ltd.

A review of key challenges of electrospun scaffolds for tissue-engineering applications.

Proteins and synthetic polymers that undergo aqueous phase transitions mediate self-assembly in nature and in man-made material systems. Yet little is known about how the phase behaviour of a protein is encoded in its amino acid sequence. Here, by synthesizing intrinsically disordered, repeat proteins to test motifs that we hypothesized would encode phase behaviour, we show that the proteins can be designed to exhibit tunable lower or upper critical solution temperature (LCST and UCST, respectively) transitions in physiological solutions. We also show that mutation of key residues at the repeat level abolishes phase behaviour or encodes an orthogonal transition. Furthermore, we provide heuristics to identify, at the proteome level, proteins that might exhibit phase behaviour and to design novel protein polymers consisting of biologically active peptide repeats that exhibit LCST or UCST transitions. These findings set the foundation for the prediction and encoding of phase behaviour at the sequence level.

Sequence heuristics to encode phase behaviour in intrinsically disordered protein polymers.

Photocatalysts formed from a single organic semiconductor typically suffer from inefficient intrinsic charge generation, which leads to low photocatalytic activities. We demonstrate that incorporating a heterojunction between a donor polymer (PTB7-Th) and non-fullerene acceptor (EH-IDTBR) in organic nanoparticles (NPs) can result in hydrogen evolution photocatalysts with greatly enhanced photocatalytic activity. Control of the nanomorphology of these NPs was achieved by varying the stabilizing surfactant employed during NP fabrication, converting it from a core–shell structure to an intermixed donor/acceptor blend and increasing H2 evolution by an order of magnitude. The resulting photocatalysts display an unprecedentedly high H2 evolution rate of over 60,000 µmol h−1 g−1 under 350 to 800 nm illumination, and external quantum efficiencies over 6% in the region of maximum solar photon flux. Photocatalysts formed from a single organic semiconductor can suffer from inefficient charge generation leading to low photocatalytic activities. Incorporating a heterojunction between a donor polymer and non-fullerene acceptor in organic nanoparticles leads to enhanced photocatalytic hydrogen evolution.

Enhanced photocatalytic hydrogen evolution from organic semiconductor heterojunction nanoparticles.

Strontium-substituted apatites have provoked increased interest in recent years for their beneficial effects on osteoporotic bone treatment and replacement. In this study, rod- and acicular-shaped, strontium-substituted calcium deficient hydroxyapatite (CDHA) nanoparticles with (Ca + Sr)/P ratio of 1.61 were synthesized via accelerated microwave processing. The X-ray powder diffraction analysis indicates the synthesized nanoparticles as apatite phase with diffraction patterns similar to those of hydroxyapatite. The hydrodynamic diameter of the particles were observed to be ~200–500 nm and found to increase with strontium substitution along with an increase in the negative zeta potential by dynamic light scattering method, suggesting the particles to be agglomerates in water. The morphology of the nanoparticles was studied using transmission electron microscopy (TEM), where, pure CDHA showed globular and strontium substituted CDHAs showed rod and acicular shape for 5% and 10% Sr substitution, respectively. The average size of the particles in TEM was measured to be 33 nm × 5 nm, 40 nm × 6 nm, and 55 nm × 8 nm (L × W) for pure and strontium-substituted CDHAs, respectively. Inductively coupled plasma spectroscopy, energy dispersive X-ray analysis, and Fourier transform infrared spectroscopy further confirm the substitution of strontium and deficiency of calcium in the synthesized nanoparticles. Thermal stability and in vitro solubility of CDHA nanoparticles were observed to increase with strontium substitution. The MTT [3-(4, 5-Dimethylthiazole-2-yl)-2, 5-diphenyl tetrazolium bromide] assay indicate that the substituted nanoparticles are non-toxic to human periodontal ligament fibroblast (HPDLF) cells. Cell uptake study by fluorescence microscopy using rhodamine-123 and actin/DAPI stained HPDLF cells show cellular localization of the nCDHA, nSr5CDHA, nSr10CDHA nanoparticles without any adverse effects. The strontium-substituted CDHAs showed significant antimicrobial activity against Escherichia coli and Staphylococcus aureus bacteria by colony count method. The 10% Sr substituted CDHA show the maximum microbial reduction of around 56% for E. coli and 35% for S. aureus with 1 × 105 cells/mL of respective bacterial culture.

Strontium-Substituted Calcium Deficient Hydroxyapatite Nanoparticles: Synthesis, Characterization, and Antibacterial Properties

Nanocellulosic materials, such as cellulose nanocrystals, cellulose nanofibers, and bacterial nanocellulose, that display high surface area, mechanical strength, biodegradability, and tunable surface chemistry have attracted great attention over the last decade for biomedical applications. Simultaneously, 3D printing is revolutionizing the field of biomedical engineering, which enables the fast and on-demand printing of customizable scaffolds, tissues, and organs. Nanocellulosic materials hold tremendous potential for 3D bioprinting due to their printability, their shear thinning behavior, their ability to live cell support and owing to their excellent biocompatibility. The amalgamation of nanocellulose-based feedstocks and 3D bioprinting is therefore of critical interest for the development of advanced functional 3D hydrogels. In this context, this review briefly discusses the most recent key developments and challenges in 3D bioprinting nanocellulose-based hydrogel constructs that have been successfully tested for mammalian cell viability and used in tissue engineering applications.

https://www.mdpi.com/2073-4360/11/5/898/pdf

3D Bioprinted Nanocellulose-Based Hydrogels for Tissue Engineering Applications: A Brief Review.

Biomimetic hydrogels offer a new platform for hierarchical structure-controlled, tough, biocompatible, mechanically tunable, and printable gels for regenerative medicine. Herein, we report for the ...

Tunable Biomimetic Hydrogels from Silk Fibroin and Nanocellulose

Electrically conductive hydrogels (ECHs), an emerging class of biomaterials, have garnered tremendous attention due to their potential for a wide variety of biomedical applications, from tissue-engineered scaffolds to smart bioelectronics. Along with the development of new hydrogel systems, 3D printing of such ECHs is one of the most advanced approaches towards rapid fabrication of future biomedical implants and devices with versatile designs and tuneable functionalities. In this review, an overview of the state-of-the-art 3D printed ECHs comprising conductive polymers (polythiophene, polyaniline and polypyrrole) and/or conductive fillers (graphene, MXenes and liquid metals) is provided, with an insight into mechanisms of electrical conductivity and design considerations for tuneable physiochemical properties and biocompatibility. Recent advances in the formulation of 3D printable bioinks and their practical applications are discussed; current challenges and limitations of 3D printing of ECHs are identified; new 3D printing-based hybrid methods for selective deposition and fabrication of controlled nanostructures are highlighted; and finally, future directions are proposed.

3D Printable Electrically Conductive Hydrogel Scaffolds for Biomedical Applications: A Review.

Glass ionomer cements (GICs) are clinically attractive filling materials often employed in the field of dentistry as restorative and luting materials. The present work aims to formulate bioactive nanocrystalline calcium deficient hydroxyapatite (nCDHA)-GIC composite cements with improved mechanical and resorption properties of the set cement than GICs. The nCDHA was synthesized via an accelerated microwave process and characterized by X-ray powder diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) methods. The synthesized nCDHA was mixed with GIC in different compositions (5, 10 and 15 wt%) maintaining the powder to liquid ratio. Cylinders of dimensions 8 mm height and 4 mm diameter were formed using a Teflon mold following a conventional cement forming technique. The XRD and FT-IR of the cylinders showed increased intensity and characteristic bands of CDHA with increase in nCDHA content. The surface cracks and the elemental composition of the set cements were analyzed by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). Decreased surface hardness was observed for composite cements with increase in nCDHA addition. The cement cylinders were tested for ionic release in Millipore water (pH=7) via inductive coupled plasma (ICP) spectroscopy and in demineralization solution of pH=5 to find out the weight loss in an acidic environment at 37 °C performed periodically for 5 weeks. The ionic release percentage, weight loss and compressive strength were observed to increase with an increase in nCDHA addition.

Rajkamal Balu

Papers

Strontium-Substituted Calcium Deficient Hydroxyapatite Nanoparticles: Synthesis, Characterization, and Antibacterial Properties

3D Bioprinted Nanocellulose-Based Hydrogels for Tissue Engineering Applications: A Brief Review.

Tunable Biomimetic Hydrogels from Silk Fibroin and Nanocellulose

3D Printable Electrically Conductive Hydrogel Scaffolds for Biomedical Applications: A Review.

Effects of nanocrystalline calcium deficient hydroxyapatite incorporation in glass ionomer cements