Poly Ethylene Glycol Dimethacrylate Research Articles

Electrochemical Diffusion Study in Poly(Ethylene Glycol) Dimethacrylate-Based Hydrogels.

Hydrogels are of great importance for functionalizing sensors and microfluidics, and poly(ethylene glycol) dimethacrylate (PEG-DMA) is often used as a viscosifier for printable hydrogel precursor inks. In this study, 1-10 kDa PEG-DMA based hydrogels were characterized by gravimetric and electrochemical methods to investigate the diffusivity of small molecules and proteins. Swelling ratios (SRs) of 14.43-9.24, as well as mesh sizes ξ of 3.58-6.91 nm were calculated, and it was found that the SR correlates with the molar concentration of PEG-DMA in the ink (MCI) (SR = 0.1127 × MCI + 8.3256, R2 = 0.9692) and ξ correlates with the molecular weight (Mw) (ξ = 0.3382 × Mw + 3.638, R2 = 0.9451). To investigate the sensing properties, methylene blue (MB) and MB-conjugated proteins were measured on electrochemical sensors with and without hydrogel coating. It was found that on sensors with 10 kDa PEG-DMA hydrogel modification, the DPV peak currents were reduced to 92 % for MB, 73 % for MB-BSA, and 23 % for MB-IgG. To investigate the diffusion properties of MB(-conjugates) in hydrogels with 1-10 kDa PEG-DMA, diffusivity was calculated from the current equation. It was found that diffusivity increases with increasing ξ. Finally, the release of MB-BSA was detected after drying the MB-BSA-containing hydrogel, which is a promising result for the development of hydrogel-based reagent reservoirs for biosensing.

Tailoring of ionic imprinted polymer-based polyeugenol as a selective adsorbent of Fe(III) ions

ABSTRACT An imprinted polymer has been successfully synthesized using polyeugenol and polyethylene glycol dimethacrylate (PEGDMA) crosslinker for selective adsorption of Fe3+ ions. The synthesized imprinted polymer is milled to obtain a polymer with high adsorption performance. This work aims to determine the effect of milling on ionic imprinted polymer (IIP) and non-ionic imprinted polymer (NIP) as selective adsorbents of Fe3+ ion against competing metal ions. Adsorbent synthesis was carried out by adding polyeugenol with the crosslinking agent ethylene glycol dimethacrylate (EGDMA) in chloroform solvent and with the initiator 2,2’-Azobis(2-methyl propionitrile) (AIBN). IIP and NIP were used as adsorbents in the adsorption selectivity test of Fe3+ on the binary metals Fe3+/Cu2+, Fe3+/Zn2+, Fe3+/Ag+, and Fe3+/Cd2+. SEM (Scanning Electron Microscope) shows a more identical and smaller particle surface morphology in the milled IIP. Surface area analysis using the BET method (Brunauer-Emmett-Teller) showed an increase in the surface area of IIP after milling treatment. The adsorption capacity and selectivity of Fe3+ metal ions on milled IIP were greater than that of IIP. The selectivity of Fe3+ adsorption is greater in the binary metal ion mixture Fe3+/Cu2+ and Fe3+/Zn2+ than in the Fe3+/Cd2+ and Fe3+/Ag+ solutions.

Ion release mechanisms in composites containing CaP particles and hydrophilic monomers

ObjectiveTo investigate the effect of hydrophilic/permeable polymer matrices on water sorption/solubility (WS/SL), Ca2+ release, mechanical properties and hydrolytic degradation of composites containing dicalcium phosphate dihydrate (DCPD) particles. MethodsSix composites were tested, all with 10 vol% of glass particles and either 30 vol% or 40 vol% DCPD. Composites containing 1BisGMA:1TEGDMA in mols (at both inorganic levels) were considered controls. Four materials were formulated where 0.25 or 0.5 of the BisGMA/TEGDMA was replaced by pyromellitic dianhydride glycerol dimethacrylate (PMGDM)/ polyethylene glycol dimethacrylate (PEGDMA). Composites were tested for degree of conversion (FTIR spectroscopy), WS/SL (ISO 4049) and Ca2+ release (inductively coupled plasma optical emission spectroscopy). Fracture toughness (FT) and biaxial flexural strength/modulus (BFS/FM) were determined after 24 h and 60 days in water. The contributions of diffusional and relaxational mechanisms to Ca2+ release kinetics were analyzed using the semi-empirical Salim-Peppas model. Data were analysed by ANOVA/Tukey test (alpha: 0.05). ResultsWS/SL was higher for composites containing PMGDM/PEGDMA compared to the controls (p < 0.001). Only at 40% DCPD the 0.5 PMGDM/PEGDMA composite showed statistically higher Ca2+ release than the control. Relaxation diffusion was the main release mechanism. Initial FT was not negatively affected by matrix composition. BFS (both DCPD fractions) and FM (30% DCPD) were lower for composites with hydrophilic/permeable networks (p < 0.01). After 60 days in water, composites with PMGDM/PEGDMA presented significant reductions in FT, while all composites had reductions in BFS/FM. SignificanceIncreasing matrix hydrophilicity/permeability significantly increased Ca2+ release only at a high DCPD fraction.

Architectural differences in photopolymerized PEG-based thiol-acrylate hydrogels enable enhanced mechanical properties and 3D printability

Hydrogels have been widely investigated for applications in the human body due to their tunability and biocompatibility. Nevertheless, their application is still limited by their relatively low mechanical strength relative to load-bearing tissue scaffolds like articular cartilage. In this work, we synthesized hydrogels by combining linear poly(ethylene glycol) dimethacrylate (PEGDMA) with a 3-arm-PEG end-functionalized with thiol. We demonstrate that the combination of thiol-ene click chemistry with a multifunctional crosslinker reduces the crosslink and entanglement density in comparison with the otherwise statistically crosslinked/polymerized PEGDMA, whereby the only viable mode of gelation is through radical propagation or termination at the double bond. The corresponding minimization of topological heterogeneities that arises during thiol-ene crosslinking results in hydrogels with compressive strength in the range of tens of MPa. The molar mass of the linear PEGDMA precursor is readily tunable, unlocking access to a wider range of mechanical properties. We employed photo-mediated crosslinking protocol, which is amenable to advanced processing technologies such as light-based 3D printing techniques. Such advanced fabrication processes offer high precision and control during the generation of customizable macroscopic objects. Simple prototypes were generated using digital light processing (DLP) equipment. We demonstrate that integrating a simple co-macromonomer into a widely employed hydrogel platform can unlock new mechanical regimes and mitigate the inherent brittleness associated with these materials. The simplicity of this approach, coupled with its easy tunability and adaptability to light-based techniques, holds promise for broadening hydrogel applications in tissue engineering. Our findings contribute to advancing materials and methodologies, facilitating enhanced design and fabrication of functional constructs.

Improving the 3D Printability and Mechanical Performance of Biorenewable Soybean Oil-Based Photocurable Resins.

The general requirement of replacing petroleum-derived plastics with renewable resources is particularly challenging for new technologies such as the additive manufacturing of photocurable resins. In this work, the influence of mono- and bifunctional reactive diluents on the printability and performance of resins based on acrylated epoxidized soybean oil (AESO) was explored. Polyethylene glycol di(meth)acrylates of different molecular weights were selected as diluents based on the viscosity and mechanical properties of their binary mixtures with AESO. Ternary mixtures containing 60% AESO, polyethylene glycol diacrylate (PEGDA) and polyethyleneglycol dimethacrylate (PEG200DMA) further improved the mechanical properties, water resistance and printability of the resin. Specifically, the terpolymer AESO/PEG575/PEG200DMA 60/20/20 (wt.%) improved the modulus (16% increase), tensile strength (63% increase) and %deformation at the break (21% increase), with respect to pure AESO. The enhancement of the printability provided by the reactive diluents was proven by Jacobs working curves and the improved accuracy of printed patterns. The proposed formulation, with a biorenewable carbon content of 67%, can be used as the matrix of innovative resins with unrestricted applicability in the electronics and biomedical fields. However, much effort must be done to increase the array of bio-based raw materials.

Novel materials for radiation sensing in radiotherapy treatments: Development of luminescent YVO4:Eu3+ polymer-based nanocomposites

This scientific work explores the development of luminescent nanocomposite materials for radiation sensors in Fiber Optic Dosimetry (FOD). The study emphasizes the use of YVO4:Eu3+ as a scintillator material due to its high luminescent efficiency. However, the challenge arises from its higher effective atomic number compared to soft tissue. To address this issue, the work explores the dispersion of YVO4:Eu3+ as nanoparticles (NPs) in a biocompatible polymeric matrix, specifically considering poly(methyl methacrylate) (PMMA) and poly(ethylene glycol) dimethacrylate (PEGDMA). Both PMMA/YVO4:Eu3+@TMSPM and PEGDMA/YVO4:Eu3+@TMSPM formulations were synthesized with minimal impact on the glass transition temperatures of the polymers. Under UV and beta particle excitation, these formulations exhibit emission spectra characteristic of Eu3+ f-f transitions. The decay times of the main emission peak at 620 nm were 615 μs, 584 μs, and 567 μs for the NPs, PEGDMA- and PMMA-based polymeric nanocomposites (PNCs), respectively. These decay times fall within the range suitable for scintillators in LINAC pulsed radiation facilities. Also, PEGDMA- and PMMA-based PNCs with varying contents of YVO4:Eu3+ NPs showed radioluminescence spectra under beta particle irradiation. This work demonstrates the feasibility of developing PEGDMA- and PMMA-based PNCs containing dispersed YVO4:Eu3+ NPs for their application as scintillators in radiotherapy dosimetry.

The Effects of Incorporating Nanoclay in NVCL-NIPAm Hydrogels on Swelling Behaviours and Mechanical Properties.

Following the formulation development from a previous study utilising N-vinylcaprolactam (NVCL) and N-isopropylacrylamide (NIPAm) as monomers, poly(ethylene glycol) dimethacrylate (PEGDMA) as a chemical crosslinker, and Irgacure 2959 as photoinitiator, nanoclay (NC) is now incorporated into the selected formulation for enhanced mechanical performance and swelling ability. In this research, two types of NC, hydrophilic bentonite nanoclay (NCB) and surface-modified nanoclay (NCSM) of several percentages, were included in the formulation. The prepared mixtures were photopolymerised, and the fabricated gels were characterised through Fourier transform infrared spectroscopy (FTIR), cloud-point measurements, ultraviolet (UV) spectroscopy, pulsatile swelling, rheological analysis, and scanning electron microscopy (SEM). Furthermore, the effect of swelling temperature, NC types, and NC concentration on the hydrogels' swelling ratio was studied through a full-factorial design of experiment (DOE). The successful photopolymerised NC-incorporated NVCL-NIPAm hydrogels retained the same lower critical solution temperature (LCST) as previously. Rheological analysis and SEM described the improved mechanical strength and polymer orientation of gels with any NCB percentage and low NCSM percentage. Finally, the temperature displayed the most significant effect on the hydrogels' swelling ability, followed by the NC types and NC concentration. Introducing NC to hydrogels could potentially make them suitable for applications that require good mechanical performance.

Isolation of Cellulose Nanosphere from Corn Husk as a Filler for UV-Cured PEGDMA Nanocomposite Hydrogels

Cellulose nanosphere (CNS) was isolated from corn husk by delignification, bleaching, acid hydrolysis, dialysis, and sonication. Successful isolation of CNS was confirmed by FTIR Analysis. The isolated CNS was found to have an average diameter of 18 nm and crystallinity index of 70% using TEM and XRD Analysis, respectively. A decrease in onset degradation temperature (Tonset) and an increase in residual mass were also observed in the TG analysis of cellulose fiber and CNS. Nanocomposite hydrogels using poly (ethylene glycol) dimethacrylate (PEGDMA) as matrix and CNS as nanofiller was prepared by UV-curing. FTIR Analysis revealed similar transmittance patterns among all the treatments. Thermal characterization showed that the addition of CNS lowers the Tonset and Tmax while increasing the temperature required for the total degradation of the UV-cured nanocomposite hydrogels.

A three-dimensional co-continuous network structure polymer electrolyte with efficient ion transport channels enabling ultralong-life all solid-state lithium metal batteries

Solid polymer electrolytes (SPEs) have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility, scalability, and interface compatibility with electrodes. Herein, a novel all-solid polymer electrolyte (PPLCE) was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol) dimethacrylate (PEGDMA) acts as a structural frame, combined with poly(ethylene glycol) diglycidyl ether short chain interspersed serving as mobile ion transport entities. The preparaed PPLCEs exhibit excellent mechanical property and outstanding electrochemical performances, which is attributed to their unique three-dimensional co-continuous structure, characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase, resulting in a distinctive nanostructure with short-range order and long-range disorder. Remarkably, the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs, which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte. When used in a lithium-ion symmetrical battery configuration, the 6 wt%-PPLCE exhibites super stability, sustaining operation for over 2000 h at 30 °C, with minimal and consistent overpotential of 50 mV. The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g−1 at current densities of 0.2 and 1 C, respectively. Even after more than 300 cycles at a current density of 0.2 C, it retaines an impressive 73.5% capacity. Moreover, it displayes stable cycling for over 180 cycles at a high current density of 0.5 C. The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.

Novel Approach for the Immobilization of Cellobiose Dehydrogenase in PEDOT:PSS Conductive Layer on Planar Gold Electrodes

Third-generation biosensors use enzymes capable of direct electron transfer (DET) to the sensor surface. They are of interest for continuous glucose monitoring in blood or interstitial fluid, but they are rarely investigated. One reason is the hindered DET of the enzymes to the metallic electrodes. In this publication, a novel method for the immobilization of cellobiose dehydrogenase (CDH) DET enzymes employing conductive poly(3,4-ethylenedioxythiophene)-poly (styrene sulfonate) (PEDOT:PSS) inks and a protective polyethylene glycol dimethacrylate (PEG-DMA) hydrogel layer on gold electrodes is reported. This layer stack showed a glucose-specific current response for voltages between −0.2 and 0.4 V in physiological PBS buffer, and enabled interference-less sensing in a solution of acetaminophen, ascorbic acid, dopamine, and uric acid at 0 V. A Michaelis–Menten fit led to a maximum current density (Imax) of 257 ± 7.9 nA/mm2 and a Michaelis–Menten constant (Km) of 28.4 ± 2.2 mM, with a dynamic range of 0.1–20 mM glucose and a limit of detection of 0.1 mM. After 16 h of continuous measurement of 20 mM glucose, the signal decreased to 60% of its initial value. Storage stability was successfully verified until up to 10 days. In summary, this paper shows a simplified approach for the fabrication of third-generation biosensors using CDH-PEDOT:PSS and PEG-DMA hydrogel inks.

Slippery Core‐Sheath Hydrogel Optical Fiber Built by Catalytically Triggered Interface Radical Polymerization

AbstractHydrogel‐based optical waveguides have attracted extensive attention in optogenetics, implantable photomedicine, and biosensors due to their excellent biocompatibility and tissue‐like modulus in compared with traditional SiO2‐based rigid optical fibers. However, the existing ion‐induced supramolecular assembly of alginate‐based hydrogel optical fibers commonly lack of long‐term stability due to poor mechanical property accompanied with swollen. In this paper, a novel catalytic surface polymerization method is developed based on a redox reaction mechanism to in situ grow robust and slippery cladding layer on a core poly(ethylene glycol) dimethacrylate (PEGDA) hydrogel fiber by using the alternative H‐bonding poly(N ‐acryloyl glycinamide) (PNAGA) hydrogels. The resultant hydrogel optical fiber with core‐cladding heterogeneous structure can achieve the desirable total reflection condition, leading to good light transmission and low light loss. The PNAGA cladding with robust H‐bonding network endows the hydrogel optical fiber with high stability and outstanding lubrication in humid environment. More importantly, the hydrogel optical fiber possesses good tissue‐like mechanical performance together with excellent biocompatibility, which shows the great advantages for biomedical applications in compared with traditional glass optical fibers. This work will broaden implantable hydrogel optical fibers in material design and structure processibility, promoting the use of hydrogel‐based optical fibers in various applications.

The critical role of in-situ lithium fluoride in gel polymer electrolyte for high-performance rechargeable batteries

Lithium-ion (Li-ion) batteries are continuously being developed to enhance safety and energy density. One promising approach involves combining high nickel cathode material (NCM811) with Gel Polymer Electrolyte (GPE). However, achieving compatibility between these components remains a challenge. In this study, we investigate the use of Ethyl difluoroacetate (DFEA) to enhance the mechanical stability, ionic conductivity, and heat-resisting of polyethylene glycol dimethacrylate (PEGDMA) based GPE, thereby improving battery performance. The modified GPE/DFEA exhibits a smoother surface, increased Young's modulus (2.2 GPa), and high ionic conductivity (7.10 mS cm−1). Additionally, it enables the in-situ formation of a LiF-rich interface film on the electrode/electrolyte surfaces. Moreover, the Li||Li symmetrical cell with GPE/DFEA demonstrates stable cycling for 500 h without dendrite growth. Furthermore, Li|Cu asymmetrical cells using GPE/DFEA achieve an average Coulombic efficiency (CE) of 99.0% over 200 cycles at 1 mA cm−2, compared to only 62.2% for liquid electrolyte (LE). Importantly, the GPE/DFEA allows for operation beyond the conventional voltage limit of 4.25 V, reaching 4.38 V. It is successfully implemented in an Ah-level NCM811/graphite pouch cell, resulting in an energy density of 250 Wh/kg and improved cycle stability at 45 °C compared to standard electrolytes. Moreover, the GPE/DFEA-based batteries exhibit enhanced safety performance under conditions such as needle puncture and overcharge. The developed GPE can meet the practical requirements for battery applications.

Microbe-cellulose hydrogels as a model system for particulate carbon degradation in soil aggregates.

Particulate carbon (C) degradation in soils is a critical process in the global C cycle governing greenhouse gas fluxes and C storage. Millimeter-scale soil aggregates impose strong controls on particulate C degradation by inducing chemical gradients of e.g. oxygen, as well as limiting microbial mobility in pore structures. To date, experimental models of soil aggregates have incorporated porosity and chemical gradients but not particulate C. Here, we demonstrate a proof-of-concept encapsulating microbial cells and particulate C substrates in hydrogel matrices as a novel experimental model for soil aggregates. Ruminiclostridium cellulolyticum was co-encapsulated with cellulose in millimeter-scale polyethyleneglycol-dimethacrylate (PEGDMA) hydrogel beads. Microbial activity was delayed in hydrogel-encapsulated conditions, with cellulose degradation and fermentation activity being observed after 13days of incubation. Unexpectedly, hydrogel encapsulation shifted product formation of R. cellulolyticum from an ethanol-lactate-acetate mixture to an acetate-dominated product profile. Fluorescence microscopy enabled simultaneous visualization of the PEGDMA matrix, cellulose particles, and individual cells in the matrix, demonstrating growth on cellulose particles during incubation. Together, these microbe-cellulose-PEGDMA hydrogels present a novel, reproducible experimental soil surrogate to connect single cells to process outcomes at the scale of soil aggregates and ecosystems.

A strong nucleophilic fluorination agent to achieve highly stable in-situ 3D cross-linked gel polymer electrolyte for lithium-ion batteries

The Gel Polymer Electrolyte (GPE) is recognized as a promising alternative to conventional electrolytes, aiming to enhance the longevity and energy density of lithium-ion batteries (LIBs). However, several challenges persist, particularly concerning the conductivity and voltage window of GPE in battery systems. In this study, we introduce an in-situ 3D crosslinked GPE, using polymethyl methacrylate (PMMA) as the monomer and polyethylene glycol dimethacrylate (PEGDMA) as the crosslinking agent, to ensure structural stability and optimized ion conductivity. We also incorporate a potent nucleophilic fluorination agent, Tetrabutylammonium fluoride (TBAF), to augment the compatibility and oxidation resistance of the formulated FGPPE. The recurring (–CH2CH2O-) units of PEGDMA, coupled with in-situ lithium fluoride (LiF) and C-F groups introduced by TBAF, endow the FGPPE with a remarkable ionic conductivity of 7.8 mS cm−1 and a distinctly electrochemical stability of 4.65 V. Notably, the Li metal anode, featuring an F-rich solid-state interface (SEI), demonstrates uniform Li+ deposition, sustaining a cycling life of 1000 h and maintaining a commendable average coulomb efficiency of 98.5 % over 300 cycles. Additionally, the NCM811/SiC pouch cell integrated with FGPPE showcases superior cycling stability, retaining 99.4 % of its capacity after 600 cycles at an elevated voltage of 4.45 V. Such advancements in gel polymer electrolyte design can significantly expedite the commercial deployment of gel polymer Li-ion batteries.

Preparation and application of the thermo-/pH−/ ion-sensitive semi-IPN hydrogel based on chitosan

Chitosan based hydrogels with multiple stimulus responses have broad application prospects in many fields. Considering the advantages of semi interpenetrating network (IPN) technology and the special temperature and ion responsiveness of polymers containing zwitterionic groups, a semi-IPN hydrogel was prepared through in situ free radical polymerization of N,N-dimethyl acrylamide and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide with polyethylene glycol dimethacrylate as a crosslinker and carboxymethyl chitosan as filler. The gel mass fraction and swelling ratio were measured, and the preparation conditions were optimized. The result indicated that the hydrogel possessed a unique thermo-/pH−/ ion-sensitive behavior. The swelling ratio increased with the increase of temperature and ion concentration, and showed a decreasing trend with the increase in pH. In addition, the hydrogel was stable when the stimuli changed. Adsorption behavior of the hydrogel to Eosin Y (EY) was systematically investigated. The adsorption process can be described well by the pseudo-second-order kinetic model and Langmuir isotherm model, indicating that it was a chemical adsorption. The experiments indicated that the hydrogel exhibited good antifouling and reusability features. Therefore, the semi-IPN hydrogel with antifouling properties and thermo-/pH−/ion-sensitivity can be easily manufactured is expected to find applications in water treatment fields.

In Vitro Characterizations of Poly(Ethylene Glycol) Dimethacrylate)-Nanofibrillated Cellulose as an Injectable Biomaterial Substitute for Herniated Nucleus Pulposus

Highlights: Novel synthetic biopolymer hydrogels were successfully prepared using photopolymerization method based on pristine PEGDMA and pristine NFC. Biocomposite hydrogel based on pristine PEGDMA: pristine NFC can be developed as a substitute biomaterial for the nucleus pulposus in cases of herniated nucleus pulposus which can afford for clinical application standards Abstract As many as 30-80% of cases low back pain (LBP) is frequently attributed to herniated nucleus pulposus (HNP) with 18-29% of instances reported in Indonesia. HNP can cause in motor weakness, sensory disturbances and decreased physiological reflexes. HNP occurs due to protrusion of the intervertebral disc through the annulus fibrosus which can be caused by the rupture of the annulus fibrosus or decreased proteoglycans (PGs). Hydrogel implant material is injected into the disc space, which can restore disc thickness caused by disc degeneration with minimal invasive. This study utilizes poly(ethylene glycol) dimethacrylate (PEGDMA):nanofibrillated cellulose (NFC) used to treat first-degree HNP using photopolymerization method. PEGDMA is very hydrophilic and is able to produce hydrogel. The addition of NFC to the PEGDMA precursor that forms a hydrogel was able to show mechanical properties as a hydrogel biocomposite candidate. This research to characterize of PEGDMA:NFC for biomaterial substitute of HNP. Characterizations involves Fourier Transform Infrared (FTIR) test, viscosity assessment and in vitro injection model test. PEGDMA:NFC concentrations explored include 1:0 (control), 1:0.5 (K1 sample), 1:0.75 (K2 sample) and 1:1 (K3 sample). FTIR test can indicating each functional group for hydrogel biomaterial of PEGDMA:NFC. Based on characterization results, the K3 sample has the best results with a concentration of 1:1. The viscosity value was 74,67 dPa.s and in vitro injection model test showed the addition of NFC indicates the hydrogel state when released from the mold will be not ruptured. Hydrogels can be injected with syringe 18 gauge. Consequently, the study concludes that the PEGDMA:NFC biocomposite hydrogel can be effectively applied in cases of herniated nucleus pulposus.

In Vitro and In Vivo Evaluation of 3D Printed Poly(Ethylene Glycol) Dimethacrylate-Based Photocurable Hydrogel Platform for Bone Tissue Engineering.

This study focuses to develop a unique hybrid hydrogel bioink formulation that incorporates poly(ethylene glycol) dimethacrylate (PEGDMA), gelatin (Gel), and methylcellulose (MC). This formulation achieves the necessary viscosity for extrusion-based three-dimensional (3D) printing of scaffolds intended for bone regeneration. After thorough optimization of the hybrid bioink system with Gel, three distinct scaffold groups are investigated in vitro: 0%, 3%, and 6% (w/v) Gel. These scaffold groups are examined for their morphology, mechanical strength, biodegradation, in vitro cell proliferation and differentiation, and in vivo bone formation using a rat cranial defect model. Among these scaffold compositions, the 3% Gel scaffold exhibits the most favorable characteristics, prompting further evaluation as a rat mesenchymal stem cell (rMSC) carrier in a critical-size cranial defect within a Lewis rat model. The compressive strength of all three scaffold groups range between 1 and 2MPa. Notably, the inclusion of Gel in the scaffolds leads to enhanced bioactivity and cell adhesion. The Gel-containing scaffolds notably amplify osteogenic differentiation, as evidenced by alkaline phosphatase (ALP) and Western blot analyses. The in vivo results, as depicted by microcomputed tomography, showcase augmented osteogenesis within cell-seeded scaffolds, thus validating this innovative PEGDMA-based scaffold system as a promising candidate for cranial bone defect healing.

Poly(ethylene Glycol) Methyl Ether Methacrylate-Based Injectable Hydrogels: Swelling, Rheological, and In Vitro Biocompatibility Properties with ATDC5 Chondrogenic Lineage.

Here, we present the synthesis of a series of chemical homopolymeric and copolymeric injectable hydrogels based on polyethylene glycol methyl ether methacrylate (PEGMEM) alone or with 2-dimethylamino ethyl methacrylate (DMAEM). The objective of this study was to investigate how the modification of hydrogel components influences the swelling, rheological attributes, and in vitro biocompatibility of the hydrogels. The hydrogels' networks were formed via free radical polymerization, as assured by 1H nuclear magnetic resonance spectroscopy (1H NMR). The swelling of the hydrogels directly correlated with the monomer and the catalyst amounts, in addition to the molecular weight of the monomer. Rheological analysis revealed that most of the synthesized hydrogels had viscoelastic and shear-thinning properties. The storage modulus and the viscosity increased by increasing the monomer and the crosslinker fraction but decreased by increasing the catalyst. MTT analysis showed no potential toxicity of the homopolymeric hydrogels, whereas the copolymeric hydrogels were toxic only at high DMEAM concentrations. The crosslinker polyethylene glycol dimethacrylate (PEGDMA) induced inflammation in ATDC5 cells, as detected by the significant increase in nitric oxide synthase type II activity. The results suggest a range of highly tunable homopolymeric and copolymeric hydrogels as candidates for cartilage regeneration.

Biocompatibility and Bioactivity of a Dual-Cured Resin-Based Calcium Silicate Cement: In Vitro and in vivo Evaluation

IntroductionThis study aimed to assess the biocompatibility and bioactivity of a dual-cured resin-based calcium silicate cement in vitro and in vivo. MethodsFor in vitro analyses, standardized samples were prepared using TheraCal LC, TheraCal PT, and ProRoot MTA. The amount of residual monomer released from TheraCal LC and TheraCal PT was assessed using liquid chromatography/mass spectrometry. Calcium ion release from the materials was evaluated using inductively coupled plasma-optical emission spectroscopy. Scanning electron microscopy and energy-dispersive X-ray spectroscopy were used to determine the calcium weight volume in the materials. For in vivo analysis, a rat direct pulp capping model with TheraCal LC, TheraCal PT, and ProRoot MTA groups (n = 16 per group) was used. The rats were euthanized after 7 or 28 days, and histological and immunohistochemical analyses (CD68 and DSPP) were performed. ResultsBisphenol A-glycidyl methacrylate and polyethylene glycol dimethacrylate release from TheraCal PT was lower than that from TheraCal LC (P < .05). Similar results were obtained for calcium-ion release and calcium weight volume, with ProRoot MTA showing the highest values. In the in vivo evaluation, TheraCal PT showed significantly greater hard tissue formation than TheraCal LC (P < .017). TheraCal PT showed lower CD68 expression and greater DSPP expression than TheraCal LC (P < .017). There were no significant differences in the expression of CD68 or DSPP between the TheraCal PT and ProRoot MTA groups. ConclusionsWithin the limitations of this study, the biocompatibility and bioactivity of TheraCal PT could be comparable to those of ProRoot MTA.

Polymeric Hydrogels for Intervertebral Disc Replacement/Integration: Playing with the Chemical Composition for Tuning Shear Behavior and Hydrophilicity.

Damages to the intervertebral disc (IVD) due to improper loading or degeneration result in back pain, which is a common disease affecting an increasing number of patients. Different strategies for IVD remediation have been developed, from surgical treatment to disc replacement, by using both metallic and non-metallic materials. Hydrogels are very attractive materials due to their ability to simulate the properties of many soft tissues; moreover, their chemical composition can be varied in order to assure performances similar to the natural disc. In particular, for the replacement of the IVD outer ring, namely, the anulus fibrosus, the shear properties are of paramount importance. In this work, we produced hydrogels through the photo-induced crosslinking of different mixtures composed of two hydrophilic monofunctional and difunctional polymers, namely, poly(ethyleneglycol) methyl ether methacrylate (PEGMEMA) and poly(ethyleneglycol) dimethacrylate (PEGDMA), together with a hydrophobic molecule, i.e., tert-butyl acrylate (tBA). By changing the ratio among the precursors, we demonstrated the tunability of both the shear properties and hydrophilicity. The structural properties of hydrogels were studied by solid-state nuclear magnetic resonance (NMR). These experiments provided insights on both the structure and molecular dynamics of polymeric networks and, together with information obtained by differential scanning calorimetry (DSC), allowed for correlating the physical properties of the hydrogels with their chemical composition.