Influence of polymerisation conditions on the properties of polymer/clay nanocomposite hydrogels

Free-radical polymerisation of acrylamide derivatives in the presence of exfoliated clay platelets has recently emerged as a new technique for the synthesis of strong and tough nanocomposite hydrogels (NCHs) with a unique hybrid organic/inorganic network structure. The central intent of many research studies in the field of NCHs conducted so far was to change hydrogel properties with the introduction of various clays and variation of the clay content. Here, we demonstrate that the properties of NCHs significantly vary depending on initiating conditions used for hydrogel synthesis via in situ polymerisation in solutions of high monomer concentrations (above 1 mol L-1 ). A unique, complementary combination of real-time dynamic rheology and pulsed NMR/MRI has been used to study the influence of the composition of a redox initiating system on the gelation process and hydrogel properties. The molar ratio of the persulphate initiator to tertiary amine activator affects the polymerisation kinetics, morphology and mechanical properties of the hydrogels. We further show that activator-dominated systems tend to produce hydrogels with higher storage modulus and lower water intake. This trend is attributed to the increase in the cross-linking degree. From the analysis of the water state in NCH and hydrogels prepared with and without an organic cross-linker, it was concluded that clay platelets did not form covalent bonds with polymer molecules but contributed to the formation of a physical network. There is evidence of self-crosslinking of polymer chains during acrylamide polymerisation at high monomer concentration. The composition of the initiating system influences the number of formed self-crosslinks

Structural reinforcement of cell-laden hydrogels with microfabricated three dimensional scaffolds

Hydrogels commonly used in tissue engineering are mechanically soft and thus often display structural weakness. Herein, we introduce a strategy for enhancing the structural integrity and fracture toughness of cell-laden hydrogels by incorporating a three-dimensional (3D) microfabricated scaffold as a structural element. Digital micromirror device projection printing (DMD-PP) system, a rapid prototyping technology which employs a layer-by-layer stereolithographic approach, was utilized to efficiently fabricate 3D scaffolds made from photocrosslinkable poly(ethylene glycol) diacrylate (PEGDA). The scaffold was incorporated into a photocrosslinkable gelatin hydrogel by placing it in a pre-gel solution, and inducing in situ hydrogel formation. The resulting scaffold-reinforced hydrogels demonstrated a significant increase in ultimate stress and provided structural support for mechanically weak hydrogels. In addition, the scaffold did not affect the rigidity of hydrogels, as it was not involved in the crosslinking reaction to form the hydrogel. Therefore, the presented approach could avoid inadvertent and undesired changes in the hydrogel rigidity which is a known regulator of cellular activities. Furthermore, the biocompatibility of scaffold-reinforced hydrogels was confirmed by evaluating the viability and proliferation of encapsulated fibroblasts. Overall, the strategy of incorporating 3D scaffolds into hydrogels as structural reinforcements presented in this study will be highly useful for enhancing the mechanical toughness of hydrogels for various tissue engineering applications.open3

Synergistic and competitive aspects of the adsorption of Poly(ethylene glycol) and Poly(vinyl alcohol) onto Na-Bentonite

Graph Presented) The competitive adsorption of poly(ethylene glycol) (PEG) and poly(vinyl alcohol) (PVOH) onto Na-bentonite has been assessed quantitatively. Particular emphasis was focused on the amount of organic located within the bentonite interlayer and any subsequent eff ects on the extent of layer expansion. The individual isotherms showed strong adsorption for both PVOH and PEG at amounts lower than the quantities required to produce a fully loaded bilayer (0.33 g of PVOH/g of clay) and single layered structures (0.10 g of PEG/g of clay), respectively. Above these concentrations, the incremental amounts adsorbed were smaller, and the concentration of adsorbates in solution gradually increased. Na-bentonite adsorbed more PVOH than PEG at any given concentration. In the competitive study, the amount of PVOH adsorbed was enhanced in the presence of PEG (0.10 and 0.30 g/g of clay), but less PEG was adsorbed. At low loadings of PVOH (0.02-0.10 g/g of clay), the amount of adsorbed PEG was increased but at higher PVOH levels PEG adsorption was reduced. The XRD data showed stepped changes in the d-spacing as the adsorbed amounts of both PEG and PVOH increased. The PEG-bentonite samples did not expand beyond a bilayer structure (18 A˚), but the XRD data for PVOH-treated samples indicated the formation of multilayer structures (d ≥ 44 A˚)

Current strategies for treatment of intervertebral disc degeneration: substitution and regeneration possibilities

Background: Intervertebral disc degeneration has an annual worldwide socioeconomic impact masked as low back pain of over 70 billion euros. This disease has a high prevalence over the working age class, which raises the socioeconomic impact over the years. Acute physical trauma or prolonged intervertebral disc mistreatment triggers a biochemical negative tendency of catabolic-anabolic balance that progress to a chronic degeneration disease. Current biomedical treatments are not only ineffective in the long-run, but can also cause degeneration to spread to adjacent intervertebral discs. Regenerative strategies are desperately needed in the clinics, such as: minimal invasive nucleus pulposus or annulus fibrosus treatments, total disc replacement, and cartilaginous endplates decalcification. Main Body: Herein, it is reviewed the state-of-the-art of intervertebral disc regeneration strategies from the perspective of cells, scaffolds, or constructs, including both popular and unique tissue engineering approaches. The premises for cell type and origin selection or even absence of cells is being explored. Choice of several raw materials and scaffold fabrication methods are evaluated. Extensive studies have been developed for fully regeneration of the annulus fibrosus and nucleus pulposus, together or separately, with a long set of different rationales already reported. Recent works show promising biomaterials and processing methods applied to intervertebral disc substitutive or regenerative strategies. Facing the abundance of studies presented in the literature aiming intervertebral disc regeneration it is interesting to observe how cartilaginous endplates have been extensively neglected, being this a major source of nutrients and water supply for the whole disc. Conclusion: Severalinnovative avenues for tackling intervertebral disc degeneration are being reported â from acellular to cellular approaches, but the cartilaginous endplates regeneration strategies remain unaddressed. Interestingly, patient-specific approaches show great promise in respecting patient anatomy and thus allow quicker translation to the clinics in the near future.The authors would like to acknowledge the support provided by the Portuguese Foundation for Science and Technology (FCT) through the project EPIDisc (UTAP-EXPL/BBBECT/0050/2014), funded in the Framework of the “International Collaboratory for Emerging Technologies, CoLab”, UT Austin|Portugal Program. The FCT distinctions attributed to J. Miguel Oliveira (IF/00423/2012 and IF/01285/ 2015) and J. Silva-Correia (IF/00115/2015) under the Investigator FCT program are also greatly acknowledged.info:eu-repo/semantics/publishedVersio

Human-based fibrillar nanocomposite hydrogels as bioinstructive matrices to tune stem cell behavior

The extracellular matrix (ECM)-biomimetic fibrillar structure of platelet lysate (PL) gels along with its enriched milieu of biomolecules has drawn significant interest in regenerative medicine applications. However, PL-based gels have poor structural stability which severely limits its performance as a bioinstructive biomaterial. Here, rod-shaped cellulose nanocrystals (CNC) are used as a novel approach to modulate the physical and biochemical microenvironment of PL gels enabling their effective use as injectable human-based cell scaffolds with a level of biomimicry that is difficult to recreate with synthetic biomaterials. The incorporation of CNC (0 to 0.61 wt.%) into the PL fibrillar network during the coagulation cascade leads to decreased fiber branching, increased interfiber porosity (from 66 to 83%) and modulate fiber (from 1.4 ± 0.7 to 27 ± 12 kPa) and bulk hydrogel (from 18 ± 4 to 1256 ± 82 Pa) mechanical properties. As result of these physicochemical alterations, nanocomposite PL hydrogels resist to the typical extensive clot retraction (from 76 ± 1 to 24 ± 3 at Day 7) and show favored retention of PL bioactive molecules. The feedback of these cues on the fate of human adipose-derived stem cells is evaluated, showing how it can be explored to modulate the commitment of encapsulated stem cells toward different genetic phenotypes without the need for additional external biological stimuli. These fibrillar nanocomposite hydrogels allow therefore to explore the outstanding biological properties of human-based PL as an efficient engineered ECM which can be tailored to trigger specific regenerative pathways in minimal invasive strategies.The authors thank the Hospital da Prelada (Porto, Portugal) for providing adipose tissue samples. The authors acknowledge the financial support from project Recognize (UTAP-ICDT/CTM-BIO/0023/2014), project NORTE-01-0145FEDER-000021 supported by the Norte Portugal Regional Operational Programme (NORTE 2020), under the PORTUGAL 2020 Partnership Agreement, through the European Regional Development Fund (ERDF), the European Union Framework Programme for Research and Innovation HORIZON 2020, under the TEAMING Grant agreement No. 739572 – The Discoveries CTR EU, Forecast 668983, Marie Skłodowska-Curie grant agreement No. 706996 (PrinTendon) and CHEM2NATURE 692333; FCT/MCTES (Fundação para a Ciência e a Tecnologia/ Ministério da Ciência, Tecnologia, e Ensino Superior) and the Fundo Social Europeu através do Programa Operacional do Capital Humano (FSE/POCH) in the framework of PhD grant PD/59/2013 – PD/BD/113807/2015 for BBM, Post-Doc grant SFRH/BPD/112459/2015 for R.D.info:eu-repo/semantics/publishedVersio

Polymeric Nanohybrids as a New Class of Therapeutic Biotransporters

This is the peer reviewed version of the following article: Macromol Chem Phys. 2016 Jun; 217(11): 1245–1259., which has been published in final form at http://doi.org/10.1002/macp.201500464. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.A possible solution to enhance existing drug and gene therapies is to develop hybrid nanocarriers capable of delivering therapeutic agents in a controlled and targeted manner. This goal can be achieved by designing nanohybrid systems, which combine organic or inorganic nanomaterials with biomacromolecules into a single composite. The unique combination of properties along with their facile fabrication enables the design of smart carriers for both drug and gene delivery. These hybrids can be further modified with cell targeting motifs to enhance their biological interactivity. In this Talents and Trends article, an overview of emerging nanohybrid-based technologies will be provided to highlight their potential use as innovative platforms for improved cancer therapies and new strategies in regenerative medicine. The clinical relevance of these systems will be reviewed to define the current challenges which still need to be addressed to allow these therapies to move from bench to bedside

Hydrogel beads bio-nanocomposite based on Kappa-Carrageenan and green synthesized silver nanoparticles for biomedical applications

This paper describes the fabrication and characterization of bio-nanocomposite hydrogel beads based on Kappa-Carrageenan (κ-Carrageenan) and bio-synthesized silver nanoparticles (Ag-NPs). The silver nanoparticles were prepared in aqueous Citrullus colocynthis seed extract as both reducing and capping agent. Cross-linked κ-Carrageenan/Ag-NPs hydrogel beads were prepared using potassium chloride as the cross-linker. The hydrogel beads were characterized using XRD and FESEM. Moreover, swelling property of the hydrogel beads was investigated. The Ag release profile of the hydrogels was obtained by fitting the experimental data to power law equation. The direct visualization of the green synthesized Ag-NPs using TEM shows particle size in the range of 23 ± 2 nm. The bio-nanocomposite hydrogels showed lesser swelling behavior in comparison with pure κ-Carrageenan hydrogel. Regardless the slow Ag release, κ-Carrageenan/Ag-NPs presented good antibacterial activities against Staphylococcus aureus, Methicilin Resistant Staphylococcus aurous, Peseudomonas aeruginosa and Escherichia coli with maximum zones of inhibition 11 ± 2 mm. Cytotoxicity study showed that the bio-nanocomposite hydrogels with non-toxic effect of concentration below 1000 μg/mL have great pharmacological potential and a suitable level of safety for use in the biological systems