Facile strategy of fabricating multifunctional hydrogel with high performance based on hybrid graphene oxide and carbon nanotube

Here we report a facile strategy of fabricating multifunctional polyacrylamide(PAM) hydrogels based on hybrid graphene oxide (GO) sheets and carbon nanotubes (CNTs). Compared to original PAM hydrogels cross-linked chemically with N,N-methylenebisacrylamide (BIS), the hybrid hydrogels exhibit high mechanical strength (strength > 90?kPa and broken strain > 2000%), well adhesion, environmental stability, dye-loading capacity, and excellent self-healing property. This study provides a new insight for the preparation of functionalized hydrogels with carbon nano-materials, and the resultant material shows very promising performance for a range of applications.     

Frontal polymerization as a new method for developing drug controlled release systems (DCRS) based on polyacrylamide

Stimuli-responsive polymers are macromolecular materials that undergo changes in response to small external stimuli in the environmental conditions. Among stimuli-responsive hydrogels are several polyacrylamides. Frontal polymerization is a fast, easy and inexpensive polymerization technique used for the synthesis of macromolecules.Aim of this work was the evaluation of the Frontal polymerization technique as new method for the preparation of controlled release dosage forms in which drug loading and polymer preparation occur together, as well as the possibility of obtaining more dosage units by a unique preparation. Hydrogels based on polyacrylamide containing diclofenac sodium salt were prepared using the Frontal polymerization and compared with similar systems obtained by the classic batch method. Polymers characterized by three different degree of cross-linking were prepared. The stability of the drug during the sample preparation was evaluated by IR analysis. The obtained samples were characterized in terms of drug content, morphology, in vitro drug release and swelling properties. Samples were studied also divided into disks. The results show that hydrogels based on polyacrylamide can be prepared by Frontal polymerization; these samples show similar properties to those obtained by batch polymerization. The drug is stable in the polymerization reaction conditions. Samples characterized by the lowest degree of cross-linking show drug loading values always higher than samples with the highest one regardless of the preparation method employed. The swelling ratio decreases as the degree of cross-linking increases. Loaded samples swell more than drug free ones. From a single preparation of hydrogel, three disks showing same drug content and in vitro release behaviour can be obtained and thus they can be used as three single dosage units.     

Characterization of the pore structure of aqueous three-dimensional polyacrylamide gels with a novel cross-linker

The properties of polyacrylamide hydrogels synthesized with a novel hexafunctional (three double bonds) cross-linker, hexahydro-1,3,5-triacryloyl-s-triazine (1a), was evaluated and compared to the currently used tetrafunctional (two double bonds) cross-linker N,N-methylenebisacrylamide (Bis). A variety of characterization techniques that require very little sample preparation and data handling were chosen and include polymerization temperature profiles and conversions, water swelling, differential scanning calorimetry (DSC), polyacrylamide gel electrophoresis (PAGE), Gradiflow electrophoretic separation process and scanning electron microscopy (SEM). The alternative use of 1a compared to Bis results in polyacrylamide gels with larger pore sizes and a broad pore size distribution.     

Morphological and mechanical properties of tannic acid/PAAm semi-IPN hydrogels for cell adhesion

A series of hydrogels were fabricated from tannic acid (TA), a typical plant polyphenol widely present in wood, and polyacrylamide (PAAm) by semi-IPN and cryogelation techniques. The introduction of TA into the PAAm network endows the system with enhanced cell adhesion properties. The cryogels with open interconnected macropores had a superfast swelling rate and a high swelling ratio, as well as high elasticity in response to compression. The degradation of the hydrogels can be tuned by modulating the content of cross-linker poly(ethylene glycol) diacrylate (PEGDA). Cytotoxicity results revealed that the hydrogels were non-toxic to COS-7 cells. All these results suggested that TA/PAAm semi-IPN hydrogels have great potential for applications in tissue engineering.     

Microstructured Polyacrylamide Hydrogels Prepared Via Inverse Microemulsion Polymerization

The synthesis by a two-stage polymerization process of microstructured polyacrylamide hydrogels with large swelling capacity and improved mechanical properties is reported. First, crosslinked polyacrylamide particles of nanosize scale are made by inverse microemulsion polymerization. These particles are then dried and redispersed in an aqueous solution of acrylamide and polymerized in the presence of a crosslinking agent. The microstructured hydrogels, in contrast to transparent conventional polyacrylamide hydrogels, are translucid due to the presence of the dispersed particles. The swelling capacity of these hydrogels increases as the particle content increases and their Young and elastic moduli (at equilibrium swelling) diminish only slightly. Mechanical tests disclose that the microstructured hydrogels have larger Young moduli than conventional hydrogels with an identical degree of swelling. Copyright 2001 Academic Press.     

A simple route to interpenetrating network hydrogel with high mechanical strength

A simple two-step method was introduced to improve the hydrogel mechanical strength by forming an interpenetrating network (IPN). For this purpose, we synthesized polyacrylate/polyacrylate (PAC/PAC), polyacrylate/polyacrylamide (PAC/PAM), polyacrylamide/polyacrylamide (PAM/PAM) and polyacrylamide/poly(vinyl alcohol) (PAM/PVA) IPN hydrogels. The PAC/PAC IPN and PAC/PAM IPN hydrogels showed compressive strength of 70 and 160 kPa, respectively. For the PAM/PAM IPN and PAM/PVA IPN hydrogels, they exhibited excellent tensile strength of 1.2 and 2.8 MPa, and elongations at break of 1750% and 3300%, respectively. A strain relaxation was also observed in the case of PAM series IPN hydrogels. From FTIR, TGA and SEM measurements, we confirmed that physical entanglement, hydrogen bonds and chemical crosslinking played major roles in improving hydrogel strength and toughening. The two-step technique contributes to the understanding of ideal networks, provides a universal strategy for designing high mechanical strength hydrogels, and opening up the biomedical application of hydrogels.     

Composite hydrogels with temperature sensitive heterogeneities: influence of gel matrix on the volume phase transition of embedded poly-(N-isopropylacrylamide) microgels

The thermo-responsive behaviour of poly-(N-isopropylacrylamide) (PNiPAM) microgels embedded in covalently cross-linked non-temperature-sensitive polyacrylamide (PAam) hydrogel matrixes with different compositions was investigated by using small angle neutron scattering (SANS). The composition of the composite hydrogel was varied by (a) increasing the cross-linker and acrylamide concentration leading to strong hydrogel matrixes and (b) by increasing the microgel concentration to obtain composite gels with an internal structure. Additionally we synthesized composite hydrogels by using γ-irradiation as initiation for the polymerisation. This leads to the formation of chemical bonds between the PNiPAM microgels and the surrounding polyacrylamide matrix. Thus it is possible to synthesize hydrogels without an additional cross-linker, as well as pure particle networks. Some samples were prepared at two different temperatures, below and above the volume phase transition temperature of PNiPAM, resulting in highly swollen or totally collapsed microgels during the incorporation step. The volume phase transition of microgels is not influenced by a hydrogel matrix with high acrylamide concentration independent of the preparation temperature. However, an increased cross-linker concentration leads to a corset like constraint on microgel swelling. Microgels, which are embedded in the collapsed state (at 50 °C), are not able to swell upon cooling, whereas microgels embedded in the swollen state can collapse upon heating. For samples with an increased microgel concentration, the close microgel packing was disturbed by the formation of the polyacrylamide matrix. The hydrogel matrix squeezes the microgels together and leads to partial aggregation. The experiments demonstrate how composite hydrogels with stimuli-sensitive heterogeneities can be prepared such that the full responsiveness of the embedded microgels is retained while the macroscopic dimensions of the gel are not affected by the volume phase transition of the microgels.     

Synthesis,structure and mechanical properties of nanocomposites based on exfoliated nano magnesium silicate crystal and poly(acrylamide)

In this study, hydrolyzed polyacrylamide based nanocomposite (HPAM-NC) hydrogels crosslinked by chromium (III) acetate, was synthesized using free radical polymerization. The introduction of magnesium silicate nanocrystals (MSNCs) into the hydrolyzed polyacrylamide (HPAM) network endows the system with enhanced mechanical properties. The successful formation and crystalline behavior of HPAM-NC hydrogels was verified by Fourier Transform Infrared (FTIR) spectroscopy and X-Ray Diffraction (XRD) analyses. Field-Emission Scanning Electron Microscopy (FESEM) and rheology tests showed that the morphology and mechanical properties of HPAM-NC hydrogels were strongly influenced by different content of parameters including concentration of copolymer, nanoparticle and cross-linker. The results showed that this nanocomposite hydrogel is a moldable material so it can expand its application as value-added product.     

Property and Application of BACy‐Based Functional Hydrogels

Conventional polyacrylamide hydrogels prepared from the free radical polymerization between acrylamide and N,N′‐methylenebisacrylamide (NMBA) have been frequently used in the biochemical technique like the sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS‐PAGE) to resolve protein mixtures. In this study, we have prepared an alternative polyacrylamide hydrogel from the cross‐linking of acrylamide and N,N′‐bisacrylylcystamine (BACy). In addition, we have compared the BACy‐based hydrogel with the NMBA‐based polyacrylamide hydrogel for their physical properties such as swelling ratio, shear modulus, crosslink density and morphology. Moreover, we further determined whether BACy‐based polyacrylamide hydrogel could be applied to SDS‐PAGE and proteomics research. The results showed that this type of hydrogel is capable of separating proteins and facilitates further in‐gel protein digestion and the following protein identifications by mass spectrometry. In summary, our study provides a basis for the putative application of BACy‐based hydrogels.     

Removal of methylene blue with hemicellulose/clay hybrid hydrogels

In this study, we chose corn stover hemicellulose for the preparation of hydrogels with admirable adsorption properties under mild alkaline conditions. Clay nanosheets were introduced to this system and hemicellulose/clay hybrid hydrogels were prepared. Morphological, mechanical properties and the methylene blue adsorption behaviors of the prepared hydrogels were studied. Results suggested that the addition of clay not only improved the mechanical strength of hemicellulose-based hydrogels, but also increased the adsorption capacity on methylene blue. Moreover, the adsorptions were confirmed to follow pseudo-second order equation for both gels with and without clay. The maximum adsorption capacities on methylene blue for hemicellulose-based hydrogels with or without clay reached 148.8 and 95.6 mg/g, respectively. These results implied that hemicellulose-based hydrogels could be used as promising adsorbents for the removal of methylene blue from waste water.     

Rheological behavior and reversible swelling of pH sensitive poly(acrylamide-<Emphasis Type="Italic">co</Emphasis>-itaconic acid) hydrogels

The study involved preparation of poly(acrylamide-co-itaconic acid) hydrogels by radical cross-linking copolymerization. The copolymer hydrogels were characterized through infrared spectroscopy, thermal analysis, swelling measurements and in oscillatory and steady shear rheology. Results showed that more stable copolymers were formed due to the strong interaction in the hydrogels. These hydrogels have shown substantial percent swelling in water and shrinking in saline solution and acidic buffers. The rheological properties were described by the Herschel-Bulkley and power-law models to explore their non-Newtonian behavior. The results showed that higher itaconic acid content raised the polymer viscosity; the degree of shear-thinning and polymer elasticity (G′) were also increased. The transition from the viscous (G′ < G″) to the predominant viscoelastic behavior (G′ > G″) occurs at a crossover frequency ranged from 17.8 rad/s for polyacrylamide to 15.7, 12.8 and 12.5 rad/s for copolymers.     

Birefringent hydrogels based on PAAm and lyotropic liquid crystal: Optical, morphological and hydrophilic characterization

In this work, hydrogels of polyacrylamide (or PAAm) with confined lyotropic liquid crystal (potassium laurate-decanol-water, KL-DeOH-H₂O) (or LLC) were synthesized. The hydrogels were characterized by polarized optical microscopy (POM), refractometry, optical transmission, scanning electron microscopy (SEM) and small angle X-ray scattering (SAXS). Besides these techniques, the hydrophilicity of hydrogels was characterized by the degree of swelling. Based on POM, it was observed that the texture of the birefringent hydrogels obtained depends on their cross-linking density, and that it is formed soon after hydrogel synthesis. Refractometry results indicated an behavior antagonist to that obtained for the system constituted by thermotropic liquid crystal inserted into the PAAm lattice in relation to the dependence of Δn on the AAm concentration and the optical transmittance. SEM micrographs show that birefringent hydrogels present rougher surface when compared to the surface of PAAm hydrogels. For the same AAm concentrations, it was observed that the hydrogels with confined LLC present larger swelling values (Q) when compared to those of PAAm hydrogels. The loss of water by birefringent hydrogels is twofold slower than that of PAAm hydrogels. Hydrogels formed by PAAm and lyotropic liquid crystal synthesized in this work can be potentially used in optical devices.     

Composite hydrogels based on polyacrylamide and cellulose: Synthesis and functional properties

Biocompatible composite hydrogels based on polyacrylamide and reinforced with bacterial or vegetable cellulose were synthesized. In the mechanical characteristics and water content, these hydrogels are similar to knee joint cartilages with average rigidity level. The structure and chemical composition of the hydrogels after their residence for 45 days in laboratory animal joints were studied by scanning electron microscopy and energydispersive X-ray microanalysis. Prolonged contact of the hydrogels with bones results in formation of calcium phosphate spherulites similar in composition to hydroxyapatite.     

Preparation and characterization of biodegradable gelatin-PAAm-based IPN hydrogels for controlled release of maleic acid to improve the solubility of phosphate fertilizers

In this study, interpenetrating polymer network (IPN) hydrogel systems including maleic acid (MA) were constituted to improve the solubility of phosphate fertilizers. A series of full and semi-IPN hydrogels were prepared from various gelatin/polyacrylamide mixtures by using two different cross-linkers. The effects of polymer composition on the morphological structures and swelling behaviors of the hydrogels were investigated. The swelling values of all hydrogels were found to be in between 435% and 830%. MA release from load0ed hydrogels was followed and it was determined that MA-loaded hydrogels efficiently decreased pH and improved the solubility of Ca₃(PO₄)₂ in releasing medium.     

Thermodynamics of Swelling of Polyacrylamide and Poly(methacrylic acid) Lyophilized Xerogels in Water

The structure and thermodynamic functions of water mixing with polyacrylamide and poly(methacrylic acid) xerogels prepared via drying of chemically crosslinked hydrogels equilibrium swollen in water are studied by methods of scanning electron microscopy, low-temperature nitrogen adsorption, differential scanning calorimetry, isothermal interval sorption of water vapor, and microcalorimetry. The liquid-phase drying in air at 70°C and solid-phase lyophilic drying under vacuum are used. Samples dried by different methods have dissimilar structures, which significantly affects the thermodynamics of the interaction of xerogels with water. The Flory–Huggins parameter of interaction of polyacrylamide and poly(methacrylic acid) with water and also its enthalpy and entropy components are independent of the procedure of xerogel preparation. The influence of the latter component manifests itself only in the thermodynamics of the relaxation of the nonequilibrium glassy structure of polymer.     

Mechanical, thermal and surface properties of polyacrylamide/dextran semi-interpenetrating network hydrogels tuned by the synthesis temperature

The mechanical, rheological, thermal, and surface behaviors of three polyacrylamide/dextran (PAAm/Dx) semi-interpenetrating polymer network (semi-IPN) hydrogels, prepared at 22°C, 5°C and ?18°C, were investigated. The results were compared with those obtained on cross-linked PAAm without Dx synthesized under the same conditions. Hydrogels prepared at the lowest temperature were the most mechanically stable. The thermal stability of the semi-IPN hydrogels is slightly lower than the corresponding PAAm gels, irrespective of preparation temperature. The water vapor sorption capacity depended on the presence of Dx as well as preparation temperature, which determines the network morphology.      

Electrically induced gel-sol transition of polyvinyl alcohol/polyacrylamide semi-interpenetrated hydrogels

Polyvinyl alcohol/polyacrylamide semi-interpenetrated hydrogels were prepared via freeze-thaw process. When a 20 V of DC was applied across the gels, the gels with lower polyacrylamide content underwent a contraction or partly turned into solution, while for the gels with higher polyacrylamide concentration, a complete gel-sol transition was observed in a short time.     

Synthesis of Polyacrylamide Gels for Restricting the Water Inflow in Development of Oil Fields

Thermally stable hydrogels resistant to highly mineralized stratal water were synthesized from the nonionogenic polyacrylamide, paraform, resorcinol, sulfosalycilic acid, and Atren Fibre structuring additive. It was shown that the hydrogels are promising for development of gel screens in the borehole zone of oil-producing wells to restrict the water inflow and raise the oil recovery factor.     

Studies of sodium humate/polyacrylamide/clay hybrid hydrogels. I. Swelling and rheological properties of hydrogels

A type of novel hybrid hydrogels from sodium humate (SH), polyacrylamide (PAM), and hydrophilic Laponite clay were prepared using potassium persulfate (KPS) as the initiator and N,N′-methylenebisacrylamide (MBA) as the cross-linker. The structures of the hydrogels were characterized by field emission scanning electron microscope and FTIR. Their swelling properties, swelling mechanism and rheological properties were also investigated. Experiments show that the composite is heterogeneous in the PAM/SH hydrogel system, while the clay collaborates with SH and improves the network structure of PAM/SH/clay hydrogel. High water-absorbing capability is shown for both hydrogel systems. Han plot proves that clay and SH are compatible with PAM for PAM/SH/clay hydrogels.     

New hydrogels based on the interpenetration of physical gels of agarose and chemical gels of polyacrylamide

In this paper we report a novel method for preparing interpenetrating polymer hydrogels of agarose and polyacrylamide (PAAm) in three steps. The procedure consists in (i) formation of physical hydrogels of agarose, (ii) diffusion of acrylamide, N,N′-methylene-bis-acrylamide and potassium persulfate (the initiator) from aqueous solutions inside the gel of agarose, and (iii) cross-linking copolymerization reaction of the aforementioned reactants to produce PAAm chemical gels interpenetrated with the agarose physical gels. Viscoelasticity measurements and thermal analysis have been performed in order to follow the kinetics of copolymerization. The viscoelastic, swelling and thermal properties of the resulting hydrogels confirm the formation of an interpenetrated system. Further evidence of interpenetration is obtained from inspection with atomic force microscopy. The improvement of the agarose and PAAm gel properties in the resulting interpenetrated hydrogel is analyzed in view of the results.