Copolymer Hydrogels Research Articles

Two Robust Strategies toward Hydrogels from Quenched Block Copolymer Nanofibrillar Micelles.

While the formation of (tri)block copolymer hydrogels has been extensively investigated, such studies mostly focused on equilibrium self-assembling whereas the use of preformed structures as building blocks such as out of equilibrium, quenched, nanofibrillar micelles is still a challenge. Here, we demonstrate that quenched, ultralong polystyrene-b-poly(ethylene oxide) (PS-b-PEO) micelles can be used as robust precursors of hydrogels. Two cross-linking strategies, (i) thermal fusion of micellar cores and (ii) chemical cross-linking of preformed micellar coronas were studied. The gelation process and the structure of the micellar networks were investigated by in situ rheological measurements, confocal microscopy and transmission electron microscopy. Direct observation of core fusion of preformed quenched micelles is provided validating this method as a robust gelation route. Using time sweep rheological experiments, it was found for both cross-linking methods that these 3D “mikado” gels are formed in three different stages, containing (1) initiation, (2) transition (growth), and (3) stabilization regimes.

Microwave assisted synthesis of xanthan gum-cl-poly (acrylic acid) based-reduced graphene oxide hydrogel composite for adsorption of methylene blue and methyl violet from aqueous solution

In the present study, facile and efficient method was adopted for the synthesis of graft copolymer hydrogel by graft copolymerization of acrylic acid (AA) onto xanthan gum (XG) biopolymer in the presence of N,N′-Methylenebisacrylamide (MBA), and ammonium persulfate (APS) as a cross-linking agent and initiator, respectively, under microwave irradiation. The optimization of hydrogel were selected based on the maximum swelling degree in water media and an optimum hydrogel was further impregnated with reduced graphene oxide (rGO) to form XG-cl-pAA/rGO hydrogel composite. The Fourier transform infrared (FT-IR), X-ray diffraction analysis (XRD), Thermogravimetric analysis (TGA), Scanning electron microscopy (SEM) were used to study the structure, thermal stability and morphology of XG-cl-pAA and XG-cl-pAA/rGO. The adsorption of methyl violet (MV) and methylene blue (MB) were study in batch mode and results shows adsorption highly dependent on solution pH, contact time, concentration and adsorbent loading. The XG-cl-pAA/rGO exhibited a very high adsorption potential, and the adsorption process followed the pseudo-second-order rate model and Langmuir adsorption isotherm with a maximum adsorption capacity (Qmax) of 1052.63 mg/g and 793.65 mg/g at 25 °C for MV and MB, respectively. We recommend XG-cl-pAA/rGO as environmentally benign, readily recoverable/recyclable material with excellent adsorption capacity for application in dyes removal.

Controlling injectability and in vivo stability of thermogelling copolymers for delivery of yttrium-90 through intra-tumoral injection for potential brachytherapy

Intra-tumoral injection of radiopharmaceuticals such as yttrium-90 (90Y) or phosphorus-32 (32P) is an important route for brachytherapy in unresectable solid tumors such as locally advanced hepatocellular carcinoma. However, the injected radiopharmaceuticals can potentially leak out from the tumor site due to high intra-tumoral pressure. In this study, we demonstrated the use of thermogelling copolymers that can be injected into tumor and subsequently solidify as hydrogels within the tumor that can potentially overcome the above problem. To this end, a series of thermogelling polyurethane copolymers with varying compositions were designed and synthesized from Pluronic F127, poly(3-hydroxylbutyrate), and poly(propylene glycol), which were characterized in terms of their molecular structures, compositions, phase diagrams, rheological properties, and injectability and body temperature stability in vitro and in vivo. The analyses of our data elucidated the injectability of the copolymer solutions at low temperatures, and the stability of the hydrogels at the body temperature. This provided the basis on which we could identify one copolymer with balanced composition as the most suitable candidate for intra-tumoral injection and for prevention of the leakage. Finally, the injectability and in vivo stability of the copolymer solution and hydrogel loaded with 90Y were further demonstrated in a mouse tumor model, and the in vivo biodistribution of 90Y showed that the radionuclide could be retained at the tumor site, indicating that the 90Y-loaded copolymer has a great potential for tumor radio-brachytherapy.

Electrochromic cell with hydrogel-stabilized water-based electrolyte using electrodeposition as a fast color changing mechanism

A new type of electrochromic device that uses electrodeposition of lead(II) oxide in combination with hydrogel-stabilized water-based electrolyte has been investigated. Operation of selected devices was examined using a series of electrochemical techniques (cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy), along with UV–Vis transmittance spectroscopy. Presented devices with use of electrodeposited PbO from aqueous solution exhibited very short response time of 15 s. Data obtained from experiments showed high difference between bleached and tinted state while low potential required for color change (+1.7 V). All tested devices were unsealed and performed electrochromic effect for several cycles with unchanged repeatable cycling ability. Best characteristics, achieving good repeatability, high transmittance in bleached state and good coloration in tinted state, along with good stability, were obtained with device using a cross-linked random copolymer hydrogel N,N-dimethylacrylamide (DMAM) and N-isopropylacrylamide (NIPAM) with a 85:15 unit molar ratio (DMAM/NIPAM), in combination with water-based Pb2+/Ni2+ electrolyte and PbO as working electrode and NiO as counter electrode. Constructed devices showed stable color in tinted state and ability to self-bleach when short-circuited. This type of electrochromic cells could be used as a more time-stable and lower cost alternative for existing intercalation-type electrochromic devices.

Preparation of injectable hydrogels from temperature and pH responsive grafted chitosan with tuned gelation temperature suitable for tumor acidic environment

In this present work, stimuli responsive polymers that can respond to the temperature and pH of the environment were prepared. A series of temperature responsive diblock copolymers based on poly(ethylene glycol) methyl ether (mPEG) and ε-caprolactone (CL) were synthesized. Subsequently, the diblock copolymers were grafted onto chitosan, a pH responsive biopolymer. These chitosan-graft-(mPEG-block-PCL) (chitosan-g-(mPEG-b-PCL)) graft copolymers were structurally characterized by 1H NMR and FTIR and their sol-gel phase transitions were analyzed by the test tube inversion method as well as dynamic rheological measurements. These chitosan-g-(mPEG-b-PCL) graft copolymers demonstrated tunable temperature and pH responsive sol-gel phase transitions that correspond well with body temperature and pH of acidic tumor microenvironments. Gelation temperature (Tgel) decreased with increasing pH of the system, increasing PCL composition in the diblock copolymers, increasing solution concentration and decreasing grafting content of the diblock copolymers on chitosan. The graft copolymer hydrogels successfully showed the sustained release of both doxorubicin and curcumin for up to 2 weeks. The designed system was based on chitosan-g-(mPEG-b-PCL) graft copolymers, of which chitosan showed pH responsive properties and mPEG-b-PCL acted as a temperature sensitive moiety. In addition, mPEG and PCL are recognized as biocompatible polymers and chitosan has been engaged in various pharmaceutical research. Thus, this system could be considered an alternative choice for drug delivery applications.

Synthesis and Characterization of pH and Thermo Dual-Responsive Hydrogels with a Semi-IPN Structure Based on N-Isopropylacrylamide and Itaconamic Acid.

A series of semi-interpenetrating polymer network (semi-IPN) hydrogels were synthesized and investigated in this study. Linear copolymer poly(N-isopropylacrylamide-co-itaconamic acid) p(NIPAM-co-IAM), which is formed by copolymerization of N-isopropylacrylamide (NIPAM) and itaconamic acid (IAM, 4-amino-2-ethylene-4-oxobutanoic acid), was introduced into a solution of NIPAM to form a series of pH and thermo dual-responsive p(NIPAM-co-IAM)/pNIPAM semi-IPN hydrogels by free radical polymerization. The structural, morphological, chemical, and physical properties of the linear copolymer and semi-IPN hydrogels were investigated. The semi-IPN hydrogel showed high thermal stability according to thermal gravimetric analyzer (TGA). Scanning electronic microscopy (SEM) images showed that the pore size was in the range of 119~297 µm and could be controlled by the addition ratio of the linear copolymer in the semi-IPN structure. The addition of linear copolymer increased the fracture strain from 57.5 ± 2.9% to 91.1 ± 4.9% depending on the added amount, while the compressive modulus decreased as the addition increased. Moreover, the pH and thermo dual-responsive properties were investigated using differential scanning calorimetry (DSC) and monitoring the swelling behavior of the hydrogels. In deionized (DI) water, the equilibrium swelling ratio of the hydrogels decreased as the temperature increased from 20 °C to 50 °C, while it varied in various pH buffer solutions. In addition, the swelling and deswelling rates of the hydrogels also significantly increased. The results indicate that the novel pH-thermo dual-responsive semi-IPN hydrogels were synthesized successfully and may be a potential material for biomedical, drug delivery, or absorption application.

Sustainable Hydrogels Based on Lignin-Methacrylate Copolymers with Enhanced Water Retention and Tunable Material Properties.

Synthesizing lignin-based copolymers would valorize a major coproduct stream from pulp and paper mills and biorefineries as well as reduce the dependence on petrochemical-based consumer goods. In this study, we used organosolv lignin isolated from hybrid poplar ( Populus trichocarpa × P. deltoides) to generate lignin-containing methacrylate hydrogels. The copolymer hydrogels were synthesized by first grafting 2-hydroxyethyl methacrylate (HEMA) onto lignin (OSLH) via esterification and then by free radical polymerization of OSLH with excess HEMA. The copolymer hydrogels were prepared with different stoichiometric ratios of OSLH (e.g., 0, 10, 20, and 40 wt %) with respect to HEMA. Copolymerization with OSLH led to an increase in cross-linking density, which in turn enhanced the hydrogel's material properties; we report up to 39% improvement in water retention, 20% increase in thermostability, and up to a 3 order increase in magnitude of the storage modulus ( G'). The copolymer's properties, such as water retention and glass transition temperature, could be tuned by altering the percent functionalization of lignin OH groups and the ratio of OSLH to HEMA.

Features of the Interaction of Alcian Blue with Gels Based on Copolymer of N-Vinylcaprolactam and Methacrylic Acid

The interaction of N-vinylcaprolactam–methacrylic acid copolymer hydrogel and N-vinylcaprolactam homopolymer hydrogel with alcian blue in aqueous solutions is studied. It is shown that copolymer gel are thermo- and pH-sensitive. Dye sorption by the copolymer gel and gel swelling degree depends on the pH of the solution. The features of the system behavior resulting from the pH sensitivity of both the gel and the dye are shown. The thermocollapse of gels incubated in aqueous solutions of alcian blue is studied. It is shown that the transition temperature of N-vinylcaprolactam–sodium methacrylate copolymer gel to the collapsed state decreases with the dye absorption. The temperature-induced collapse of homopolymer gels in dye solutions is reversible, while the copolymer gel mass restores incompletely during the return temperature decrease. The dye absorption by the copolymer gel leads to decreased hysteresis.

Carboxylic Terminated Thermo-Responsive Copolymer Hydrogel and Improvement in Peptide Release Profile.

To improve the release profile of peptide drugs, thermos-responsive triblock copolymer poly (ε-caprolactone-co-p-dioxanone)-b-poly (ethylene glycol)-b-poly (ε-caprolactone-co-p-dioxanone) (PECP) was prepared and end capped by succinic anhydride to give its carboxylic terminated derivative. Both PCEP block copolymer and its end group modified derivative showed temperature-dependent reversible sol-gel transition in water. The carboxylic end group could significantly decrease the sol-gel transition temperature by nearly 10 °C and strengthen the gel due to enhanced intermolecular force among triblock copolymer chains. Furthermore, compared with the original PECP triblock copolymer, HOOC–PECP–COOH copolymer displayed a retarded and sustained release profile for leuprorelin acetate over one month while effectively avoiding the initial burst. The controlled release was believed to be related to the formation of conjugated copolymer-peptide pair by ionic interaction and enhanced solubility of drug molecules into the hydrophobic domains of the hydrogel. Therefore, carboxyl terminated HOOC–PECP–COOH hydrogel was a promising and well-exhibited sustained release carrier for peptide drugs with the advantage of being able to develop injectable formulation by simple mixing.

Direct 3D Printing of High Strength Biohybrid Gradient Hydrogel Scaffolds for Efficient Repair of Osteochondral Defect

AbstractThe emerging 3D printing technique allows for tailoring hydrogel‐based soft structure tissue scaffolds for individualized therapy of osteochondral defects. However, the weak mechanical strength and uncontrollable swelling intrinsic to conventional hydrogels restrain their use as bioinks. Here, a high‐strength thermoresponsive supramolecular copolymer hydrogel is synthesized by one‐step copolymerization of dual hydrogen bonding monomers, N‐acryloyl glycinamide, and N‐[tris(hydroxymethyl)methyl] acrylamide. The obtained copolymer hydrogels demonstrate excellent mechanical properties—robust tensile strength (up to 0.41 MPa), large stretchability (up to 860%), and high compressive strength (up to 8.4 MPa). The rapid thermoreversible gel ⇔ sol transition behavior makes this copolymer hydrogel suitable for direct 3D printing. Successful preparation of 3D‐printed biohybrid gradient hydrogel scaffolds is demonstrated with controllable 3D architecture, owing to shear thinning property which allows continuous extrusion through a needle and also immediate gelation of fluid upon deposition on the cooled substrate. Furthermore, this biohybrid gradient hydrogel scaffold printed with transforming growth factor beta 1 and β‐tricalciumphosphate on distinct layers facilitates the attachment, spreading, and chondrogenic and osteogenic differentiation of human bone marrow stem cells (hBMSCs) in vitro. The in vivo experiments reveal that the 3D‐printed biohybrid gradient hydrogel scaffolds significantly accelerate simultaneous regeneration of cartilage and subchondral bone in a rat model.

Swelling or deswelling? Composition-dependent CO2-responsive swelling behaviors of poly(acrylamide-co-2-dimethylaminoethyl methacrylate) hydrogels

Use of CO2 to realize both swelling and deswelling in a same type of copolymer is a challenging topic. Herein, we synthesized poly(acrylamide-co-2-dimethylaminoethyl methacrylate) (P(AM-co-DMAEMA)) copolymer hydrogels by easy solution copolymerization that showed both swelling and deswelling when exposed to CO2. Interestingly, the copolymer hydrogels were found to show a convincing CO2-induced “composition-dependent” swelling behaviors. The as-prepared hydrogels with 4.1 to 23.3 mol% DMAEMA showed a decreased swelling ratio when CO2 was purged. In contrast, further raising DMAEMA molar ratio from 23.3 to 67.8%, the copolymer hydrogels showed CO2-induced increased swelling. Insights from NMR and XPS results revealed different characteristics of poly(N,N-dimethylaminoethyl methacrylate in the hydrogel samples with varying monomer compositions, which were considered to be responsible for the composition-dependent swelling behavior. By discovering a simple method to synthesize a copolymer hydrogel which showed CO2-induced composition-dependent swelling behaviors, this study is conducive to developing CO2-tunable smart materials.

Engineering Elastin-Like Polypeptide-Poly(ethylene glycol) Multiblock Physical Networks.

Hybrids of protein biopolymers and synthetic polymers are a promising new class of soft materials, as the advantages of each component can be complementary. A recombinant elastin-like polypeptide (ELP) was conjugated to poly(ethylene glycol) (PEG) by macromolecular coupling in solution to form multiblock ELP-PEG copolymers. The hydrated copolymer preserved the thermoresponsive properties from the ELP block and formed hydrogels with different transition temperatures depending on salt concentration. Small angle scattering indicates that the copolymer hydrogels form sphere-like aggregates with a "fuzzy" interface, while the films form a fractal network of nanoscale aggregates. The use of solutions with different salt concentrations to prepare the hydrogels was found to influence the transition temperature, the mechanical properties, and the size of the nanoscale structure of the hydrogel without changing the secondary structure of the ELP. The salt variation and the addition of a plasticizer also affected the nanoscale structure and the mechanical characteristics of the films.

UV and blue-light anti-reflective structurally colored contact lenses based on a copolymer hydrogel with amorphous array nanostructures

Novel anti-reflective structurally colored contact lenses not only block UV- and blue-light but also avoid the risk of chemical dyes.

Elastomeric and pH-responsive hydrogels based on direct crosslinking of the poly(glycerol sebacate) pre-polymer and gelatin

The synthesis and biomedical applications of novel elastomeric, pH-responsive, biocompatible and biodegradable copolymer hydrogels based on poly(glycerol sebacate) and gelatin.

Synthesis and characterizations of various polyvinyl pyrrolidon/hydroxyl ethyl methacrylate nanocomposite hydrogels as drug delivery systems

ABSTRACTUsing polymer hydrogels and nanocomposites hydrogels still promising materials for many applications. Polyvinyl pyrrolidone (PVP) has been used with various polymers synthetic and natural for different applications. In this study PVP and hydroxyl ethyl methacrylate (HEMA) copolymer hydrogels were prepared by the aid of gamma radiation and the PVP/HEMA nanocomposite hydrogels were obtained by in situ adsorption and reduction method of iron salts and silver nitrates (AgNO3) to form PVP/HEMA-Fe3O4 and PVP/HEMA-Ag nanocomposites. The prepared hydrogels and the formed nanoparticles were studied by various techniques; FTIR, TEM, SEM and also the gel content and swelling behavior were evaluated. The prepared hydrogels and nanocomposites hydrogels were examined as drug delivery systems for Ciprofloxacin HCl as model drug. The PVP/HEMA-Fe3O4 nanocomposite gave the suitable load and release behavior towards Ciprofloxacin HCl.

Anti-Adherent Biomaterials for Prevention of Catheter Biofouling

Medical device-associated infections present a leading global healthcare challenge, and effective strategies to prevent infections are urgently required. Herein, we present an innovative anti-adherent hydrogel copolymer as a candidate catheter coating with complementary hydrophobic drug-carrying and eluting capacities. The amphiphilic block copolymer, Poloxamer 188, was chemically-derivatized with methacryloyl moieties and copolymerized with the hydrogel monomer, 2-hydroxyethyl methacrylate. Performance of the synthesized copolymers was evaluated in terms of equilibrium swelling, surface water wettability, mechanical integrity, resistance to encrustation and bacterial adherence, and ability to control release of the loaded fluoroquinolone antibiotic, ofloxacin. The developed matrices were able to provide significant protection from fouling, with observed reductions of over 90% in both adherence of the common urinary pathogen Escherichia coli and encrusting crystalline deposits of calcium and magnesium salts relative to the commonly employed hydrogel, poly (hydroxyethyl methacrylate). Additionally, the release kinetics of a loaded hydrophobic drug could be readily tuned through facile manipulation of polymer composition. This combinatorial approach shows significant promise in the development of suitable systems for prevention of catheter-associated infections.

Removal of some cationic dyes from aqueous solution by acrylamide- or 2-hydroxyethyl methacrylate-based copolymeric hydrogels

In this study, anionic hydrogels were prepared using a crosslinker (N,N′-methylenebisacrylamide) through a free radical addition reaction in aqueous solutions of neutral acrylamide or 2-hydroxyethyl methacrylate monomer and anionic monomers, mesaconic acid or aconitic acid. Cationic dyes along with safranine (azine-), nile blue (oxazine-) and methylene blue (thiazine-) were selected as models of pollutants, and adsorption of these dyes onto the hydrogels was investigated. To examine the effect of concentration on adsorption, dye solutions prepared with a concentration range of 5–50 mg l−1 and 0.1 g hydrogel at 25 °C were exposed to the hydrogels until equilibrium was established. Dye adsorption onto the hydrogels was found to be an L type Giles adsorption isotherm. Monolayer sorption capacity and adsorption constant values were calculated from the Langmuir plots. To calculate RL values, a non-dimensional analysis was used and they were always found to be 0 azine > thiazine. Furthermore, the higher the number of carboxyl groups in the hydrogel composition, the higher the adsorbed amount of substance.

Conducting Polymeric Hydrogel Electrolyte Based on Carboxymethylcellulose and Polyacrylamide/Polyaniline for Supercapacitor Applications

Conducting polymer hydrogels represent a unique class of materials that possess enormous application in flexible electronic devices. In the present work, conducting carboxymethylcellulose (CMC)-co-polyacrylamide (PAAm)/polyaniline was synthesized by a two-step interpenetrating network solution polymerization technique. The synthesized CMC-co-PAAm/polyaniline with interpenetrating network structure was prepared by in situ polymerization of aniline to enhance conductivity. The molecular structure and morphology of the copolymer hydrogels were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The novel conducting polymer hydrogels show good electrical and electrochemical behavior, which makes them potentially useful in electronic devices such as supercapacitors, biosensors, bioelectronics, solar cells and memory devices.

A Novel Triblock Copolymer Hydrogel Foam Delivery System to Improve Talc Pleurodesis Efficacy

A Novel Triblock Copolymer Hydrogel Foam Delivery System to Improve Talc Pleurodesis Efficacy

Synthesis, characterization and physiochemical investigation of chitosan-based multi-responsive Copolymeric hydrogels

This paper describes the synthesis and physicochemical characterization of Poly(N-isopropylacrylamide)-Chitosan-Poly(Acrylic acid) [PNIPAAm-CS-PAA] based polymeric microgels. Three different samples of multi-responsive (PNIPAAM-CS-PA) microgels were synthesized using various amounts of N Nˡ- Methylene bis-acrylamide (MBA) and Acrylic acid (AA) by free radical emulsion polymerization. The redox initiator Ammonium per sulfate (APS) was used to initiate the reactions while MBA was used as a crosslinking agent. The purified polymeric microgels were then characterized using UV-Visible spectroscopy, Fourier transform infrared spectroscopy (FT-IR), Laser light scattering (LLS), Ostwald viscometry, dynamic Rheology and swelling/de-swelling measurements. From the spectroscopic result it was observed that all the reactions have been completed and the resultant microgels were successfully synthesized. The influence of various parameters such as, chemical composition and some external stimuli like temperature and pH on the physicochemical behavior of polymeric microgels was investigated through visual stability test, laser light scattering, viscometry and rheological measurement. The LLS analysis was performed to deduce the size, in the terms of hydrodynamic radius (Rh), of the microgel samples in aqueous media at different pH and temperature. From LLS analysis the microgels were found to be stable at all pH values above the pKa values (4.2) of AA in temperature ranges from 20 °C to 50 °C. With rising in temperature and pH causes aggregation of particles and decrease in stability of microgels due to the decrease in hydrophobicity. From the Rheological measurements, various physiochemical properties such as, elasticity, viscosity, shear stress, storage modulus, loss modulus, phase angle and complex viscosity of the microgels were gathered. The Ostowald viscometry was used to measure the flow viscosity of microgels at different pH and temperatures. The present observations reflect that the prepared samples are multi-responsive and their physicochemical behavior can be tuned very easily by changing their composition and/or varying the external stimuli.