Preparation and Characterisation of Cellulose Nanocrystal/Alginate/Polyethylene Glycol Diacrylate (CNC/Alg/PEGDA) Hydrogel Using Double Network Crosslinking Technique for Bioprinting Application

In this study, we aimed to prepare and characterise hydrogel formulations using cellulose nanocrystals (CNCs), alginate (Alg), and polyethylene glycol diacrylate (PEGDA). The CNC/Alg/PEGDA formulations were formed using a double network crosslinking approach. Firstly, CNC was extracted from oil palm trunk, and the size and morphology of the CNCs were characterised using TEM analysis. Secondly, different formulations were prepared using CNCs, Alg, and PEGDA. The mixtures were crosslinked with Ca2+ ions and manually extruded using a syringe before being subjected to UV irradiation at 365 nm. The shear-thinning properties of the formulations were tested prior to any crosslinking, while the determination of storage and loss modulus was conducted post extrusion after the Ca2+ ion crosslink using a rheometer. For the analysis of swelling behaviour, the constructs treated with UV were immersed in PBS solution (pH 7.4) for 48 h. The morphology of the UV crosslinked construct was analysed using SEM imaging. The extracted CNC exhibited rod-like structures with an average diameter and length of around 7 ± 2.4 and 113 ± 20.7 nm, respectively. Almost all CNC/Alg/PEGDA formulations (pre-gel formulation) displayed shear-thinning behaviour with the power-law index η < 1, and the behaviour was more prominent in the 1% [w/v] Alg formulations. The CNC/Alg/PEGDA with 2.5% and 4% [w/v] Alg displayed a storage modulus dominance over loss modulus (G′ > G″) which suggests good shape fidelity. After the hydrogel constructs were subjected to UV treatment at 365 nm, only the F8 construct [4% CNC: 4% Alg: 40% PEGDA] demonstrated tough and flexible characteristics that possibly mimic the native articular cartilage property due to a similar water content percentage (79.5%). In addition, the small swelling ratio of 4.877 might contribute to a minimal change of the 3D construct’s geometry. The hydrogel revealed a rough and wavy surface, and the pore size ranged from 3 to 20 µm. Overall, the presence of CNCs in the double network hydrogel demonstrated importance and showed positive effects towards the fabrication of a potentially ideal 3D bioprinted scaffold.

Broad-spectrum Antimicrobial ZnMintPc Encapsulated in Magnetic-nanocomposites with Graphene Oxide/MWCNTs Based on Bimodal Action of Photodynamic and Photothermal Effect

Microbial diseases have been declared one of the main threats to humanity, which is why, in recent years, great interest has been generated in the development of nanocomposites with antimicrobial capacity. In the present work, two magnetic nanocomposites, based on Graphene Oxide (GO) and Multiwall Carbon Nanotubes (MWCNTs) were studied. The synthesis of these magnetic nanocomposites consisted of three phases: first, the synthesis of Iron Magnetic Nanoparticles (MNPs) was carried out in the presence of MWCNTs and GO using the Co-precipitation method. The second phase consisted of the adsorption of photosensitizer menthol-Zinc phthalocyanine (ZnMintPc) into MWCNTs and GO, and the third phase was the encapsulation in poly (N-vinylcaprolactam-co-poly(ethylene glycol diacrylate)) poly (VCL-co-PEGDA) polymer VCL/PEGDA a biocompatible hydrogel, in order to obtain the magnetic nanocomposites: VCL/PEGDA-MNPs-MWCNTs-ZnMintPc and VCL/PEGDA-MNPs-GO-ZnMintPc. In vitro studies were carried out using Escherichia coli and Staphylococcus aureus bacteria and the Candida albicans yeast based on the PTT/PDT effect. This research describes the optical, morphological, magnetic and photophysical characterizations of nanocomposites and their application as antimicrobial agents. It was evaluated the antimicrobial effect of magnetics nanocomposites based on the Photodynamic/Photothermal (PDT/PTT) effect; for this purpose, doses of 65 mW cm-2 at 630 nm of light were used. The VCL/PEGDA-MNPs-GO-ZnMintPc nanocomposite was able to eliminate colonies of E. coli and S. aureus, while VCL/PEGDA-MNPs-MWCNTs-ZnMintPc nanocomposite was able to eliminate the three types of microorganisms; consequently, the latter is considered a broad-spectrum of antimicrobial agent in PDT and PTT.

Bioprinting the Tumor Microenvironment with an Upgraded Consumer Stereolithographic 3D Printer

A widespread application of three-dimensional (3D) bioprinting in basic and translational research requires the accessibility to affordable printers able to produce physiologically relevant tissue models. To facilitate the use of bioprinting as a standard technique in biology, an open-source device based on a consumer-grade 3D stereolithographic (SL) printer was developed. This SL bioprinter can produce complex constructs that preserve cell viability and recapitulate the physiology of tissues. The detailed documentation of the modifications apported to the printer as well as a throughout performance analysis allow for a straightforward adoption of the device in other labs and its customization for specific applications. Given the low cost, several modified bioprinters could be simultaneously operated for a highly parallelized tissue production. To showcase the capability of the bioprinter, we produced constructs consisting of patient-derived cholangiocarcinoma organoids encapsulated in a gelatin methacrylate (GelMA)/polyethylene glycol diacrylate (PEGDA) hydrogel. A thorough characterization of different GelMA/PEGDA ratios revealed that the mechanical properties of the bioprinted tumor model can be accurately fine-tuned to mimic a specific tumor micro-environment. Immunofluorescence and gene expression analyses of tumor markers confirmed that the bioprinted synthetic hydrogel provides a flexible and adequate replacement of animal-derived reconstituted extracellular matrix.

Poly(ethylene glycol) Diacrylate Iongel Membranes Reinforced with Nanoclays for CO2 Separation

Despite the fact that iongels are very attractive materials for gas separation membranes, they often show mechanical stability issues mainly due to the high ionic liquid (IL) content (≥60 wt%) needed to achieve high gas separation performances. This work investigates a strategy to improve the mechanical properties of iongel membranes, which consists in the incorporation of montmorillonite (MMT) nanoclay, from 0.2 to 7.5 wt%, into a cross-linked poly(ethylene glycol) diacrylate (PEGDA) network containing 60 wt% of the IL 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][TFSI]). The iongels were prepared by a simple one-pot method using ultraviolet (UV) initiated polymerization of poly(ethylene glycol) diacrylate (PEGDA) and characterized by several techniques to assess their physico-chemical properties. The thermal stability of the iongels was influenced by the addition of higher MMT contents (>5 wt%). It was possible to improve both puncture strength and elongation at break with MMT contents up to 1 wt%. Furthermore, the highest ideal gas selectivities were achieved for iongels containing 0.5 wt% MMT, while the highest CO2 permeability was observed at 7.5 wt% MMT content, due to an increase in diffusivity. Remarkably, this strategy allowed for the preparation and gas permeation of self-standing iongel containing 80 wt% IL, which had not been possible up until now.

Electrostatic loading and photoredox-based release of molecular cargo from oligoviologen-crosslinked microparticles

Although on-demand cargo release has been demonstrated in a wide range of microparticle platforms, many existing methods lack specific loading interactions and/or undergo permanent damage to the microparticle to release the cargo. Here, we report a novel method for electrostatically loading negatively charged molecular cargo in oligoviologen-crosslinked microparticles, wherein the cargo can be released upon activation by visible light. A water-in-oil (W/O) emulsion polymerization method was used to fabricate narrowly dispersed microparticles crosslinked by a dicationic viologen-based dimer and a poly(ethylene glycol) diacrylate. A zinc-tetraphenyl porphyrin photocatalyst was also polymerized into the microparticle and used to photochemically reduce the viologen subunits to their monoradical cations through a visible-light-mediated photoredox mechanism with triethanolamine (TEOA) as a sacrificial reductant. The microparticles were characterized by microscopy methods revealing uniform, spherical microparticles 481 ± 20.9 nm in diameter. Negatively charged molecular cargo (methyl orange, MO) was electrostatically loaded into the microparticles through counteranion metathesis. Upon irradiation with blue (450 nm) light, the photo-reduced viologen crosslinker subunits lose positive charges, resulting in release of the anionic MO cargo. Controlled release of the dye, as tracked by absorption spectroscopy, was observed over time, yielding release of up to 40% of the cargo in 2d and 60% in 5d in single dynamic dialysis experiment. However, full release of cargo was achieved upon transferring the microparticles to a fresh TEOA solution after the initial 5d period.

Proton-conducting Organic-inorganic Sulfo-containing Membranes for Fuel Cell

Cross-linked organiс-inorganic sulfo-containing membranes of various compositions based on acrylic monomers (acrylonitrile, acrylic acid, 3-sulfopropylacrylate potassium salt, ethylene glycol diacrylate) and sol-gel systems of tetraethoxysilane have been developed. Synthesis of the polymer matrix was carried out by UV-initiated polymerization of the monomer mixture and the inorganic component was formed in situ while conducting the sol-gel process of the precursor. FTIR, SEM, EDS, DMA, impedance spectroscopy were used to characterize the synthesized materials. The influence of inorganic component content on the properties of the membranes was investigated. DMA results show that an increase in silica content leads to a decrease in packing density and an increase in structural heterogeneity in sulfo-containing polyacrylate/silica membranes. The highest values of proton conductivity 1.12 ꞏ 10−2 Sm/cm at 60 °C were found in membranes containing 3 wt.%. of the added sol-gel system. Further increase of silica content does not increase the proton conductivity of the membranes. The proton transfer activation energies in the membranes were calculated from the temperature dependence of proton conductivity. The obtained cross-linked sulfo-containing organic-inorganic materials can be used for the development of proton-conducting membranes for fuel cells.

Microwave-assisted oxidative coupling of thiols using polystyrene supported bromoderivatives of 2-oxazolidone

Polymer-supported reagents have become popular in synthetic organic chemistry over the past decades. But the kinetics of polymer-supported reactions is slow compared to solution phase synthesis because of the poor diffusion of the reactants through the macromolecular polymer matrix. This difficulty can be reduced to a great extent by performing polymer-supported reactions under microwave (MW) conditions. The present work is focussed on the design and development of an innovative, powerful, MW stable and recyclable polymeric reagent prepared by attaching bromoderivative of 2-oxazolidone into the macromolecular matrix of polystyrene. 3% cross-linked polystyrene was prepared by free radical aqueous suspension polymerization technique using tetra ethylene glycol diacrylate as the cross-linking agent and the resulting beads were functionalized by chloromethylation followed by reaction with 2-oxazolidone. Bromine functionality is introduced into the polymer by treating with bromine in carbon tetrachloride. The synthetic utility of the prepared polymeric reagent was demonstrated by the oxidative coupling of thiols to disulfides under MW irradiation. No over oxidation was observed in this protocol and the utilization of polystyrene support simplifies work up and product isolation. The synthesised polymeric reagent displayed good cyclic stability up to five cycles without any substantial decrease in bromine content and satisfactory storage stability under normal laboratory condition. Moreover this may be the first report that uses MW energy for the oxidation of thiols to disulfides using polymer-supported reagents. [Formula: see text]

Delamination-Free In-Air and Underwater Oil-Repellent Filters for Oil-Water Separation: Gravity-Driven and Cross-Flow Operations

Separating oil-water mixtures is critical in a variety of practical applications, including the treatment of industrial wastewater, oil spill cleanups, as well as the purification of petroleum products. Among various methodologies that have been utilized, membranes are the most attractive technology for separating oil-water emulsions. In recent years, selective wettability membranes have attracted particular attention for oil-water separations. The membrane surfaces with hydrophilic and in-air oleophobic wettability have demonstrated enhanced effectiveness for oil-water separations in comparison with underwater oleophobic membranes. However, developing a hydrophilic and in-air oleophobic surface for a membrane is not a trivial task. The coating delamination process is a critical challenge when applying these membranes for separations. Inspired by the above, in this study we utilize poly(ethylene glycol)diacrylate (PEGDA) and 1H,1H,2H,2H-heptadecafluorodecyl acrylate (F-acrylate) to fabricate a hydrophilic and in-air oleophobic coating on a filter. We utilize methacryloxypropyl trimethoxysilane (MEMO) as an adhesion promoter to enhance the adhesion of the coating to the filter. The filter demonstrates robust oil repellency preventing oil adhesion and oil fouling. Utilizing the filter, gravity-driven and continuous separations of surfactant-stabilized oil-water emulsions are demonstrated. Finally, we demonstrate that the filter can be reused multiple times upon rinsing for further oil-water separations.

3D Printing Polymeric Materials for Robots with Embedded Systems

The fabrication of robots and their embedded systems is challenging due to the complexity of the interacting components. The integration of additive manufacturing (AM) to robotics has made advancements in robotics manufacturing through sophisticated and state-of-the-art AM technologies and materials. With the emergence of 3D printing, 3D printing materials are also being considered and engineered for specific applications. This study reviews different 3D printing materials for 3D printing embedded robotics. Materials such as polyethylene glycol diacrylate (PEGDA), acrylonitrile butadiene styrene (ABS), flexible photopolymers, silicone, and elastomer-based materials were found to be the most used 3D printing materials due to their suitability for robotic applications. This review paper revealed that the key areas requiring more research are material formulations for improved mechanical properties, cost, and the inclusion of materials for specific applications. Future perspectives are also provided.