Preparation and characterisation of controlled porosity alginate hydrogels made via a simultaneous micelle templating and internal gelation process

Controlled porosity alginate hydrogel monoliths were synthesised by simultaneous micelle templating (MT) and an internal gelation reaction. In water, the self assembling surfactant, cetyltrimethylammonium bromide (CTAB) formed non-spherical micelles that were used as a template for pore formation. The porous microstructure was assessed by mercury intrusion porosimetry (MIP), helium pycnometry, X-ray microtomography (XMT) and scanning electron microscopy (SEM), respectively. The MT hydrogels displayed relatively monodisperse pore size distributions (with pore sizes ranging from 32.5 μm to 164.0 μm), high total pore volumes (4.5–20.3 cm³/g) and high degrees of porosity (83–97%). Some control over pore size distributions was achieved by varying the surfactant concentration; higher surfactant concentrations, led to smaller pores with lower total pore volumes. Uniaxial compression testing revealed that hydrogels made via MT are stable in cell culture media for 28 days. Fourier transform infrared (FTIR) spectroscopy data, suggested that all surfactant could be removed from the final product by washing with ethanol and water, making these hydrogels potentially suitable for tissue engineering (TE) applications.     

Swelling behavior of polyacrylamide/laponite clay nanocomposite hydrogels: pH-sensitive property

In this study, an investigation is carried out on the influence of varying clay contents (25–43%), pH values (2–11 buffer solutions), heat treatment, temperatures (25–60 °C) and ionic strengths (saline solution, 10^?7–0.1 M) on the water absorbency of polyacrylamide (PAAm)/laponite nanocomposite (NC) hydrogels in the absence of polyelectrolyte. For the influence of pH value on swelling behaviors, a maximum swelling ratio occurs at pH 11. Heat treatment of the hydrogels significantly improved the swelling capacity and created an obvious pH sensitive area (pH 3–4). The swelling capacity of the hydrogels was enhanced by increasing the temperature of the absorbing media. The results of swelling at different ionic strengths also indicate that the ionic strength can considerably weaken the swelling abilities of the NC hydrogels.     

Release of BSA from porous matrices constituted of alginate–Ca and PNIPAAm-interpenetrated networks

The synthesis of thermosensitive Interpenetrating Polymer Network (IPN) hydrogels and the release of Bovine Serum Albumin (BSA) from the hydrogels were reported. The hydrogels, constituted of poly(N-isopropyl acrylamide) PNIPAAm network interpenetrated in alginate–Ca²⁺ network, were synthesized in a two-stepped process. In the first step, PNIPAAm network was synthesized from an aqueous solution containing N-isopropyl acrylamide (NIPAAm) monomers and N,N′-methylene-bis-acrylamide (MBAAm) co-monomers, and sodium alginate (SA) (1 or 2% w/v). The concentration of NIPAAm monomers in the hydrogel-forming solution was always 2.5, 5.0 or 10.0% (w/v). In the second step, alginate–Ca²⁺ networks were formed by immersion of the membrane, obtained on the first step, in a 1.0% (w/v) aqueous calcium chloride. The IPN hydrogels were characterized as a function of temperature (from 25 to 45 °C) through the following measurements: drop water contact angle (DWCA), compression elastic modulus (E) and cross-linking density (ν_e). The morphology was investigated using scanning electronic microscopy (SEM). In vitro release of BSA from the hydrogels was monitored by UV–Vis spectroscopy at 22 °C and 37 °C. DWCA results showed a decrease in the hydrogel hydrophilicity when the temperature and/or the PNIPAAm amount on hydrogels were increased. PNIPAAm-loader hydrogels are more compacted and presented elevated rigidity, mainly above 35 °C. This trend was attributed to the collapsing of PNIPAAm chains as the hydrogels were warmed above its Lower Critical Solution Temperature (LCST), which in aqueous solution is ca. 32–33 °C. The amount of BSA released from the alginate–Ca²⁺/PNIPAAm hydrogels changes inversely to both amount of PNIPAAm and temperature. The transport of BSA from the hydrogels was evaluated through a conventional model. In the lesser-compacted hydrogels the release occurs mostly by diffusion. In the more compacted ones the chain relaxation contributes to the BSA release. Thus, the alginate–Ca²⁺/PNIPAAm IPN-typed matrixes may be considered as smart hydrogels for the release of BSA, because the amount and rate of BSA released may be tailored by both the NIPAAm concentration in the hydrogel-forming solution and the control of temperature of hydrogel.     

Preparation and characterization of amidated pectin based hydrogels for drug delivery system

In the current studies attempts were made to prepare hydrogels by chemical modification of pectin with ethanolamine (EA) in different proportions. Chemically modified pectin products were crosslinked with glutaraldehyde reagent for preparing hydrogels. The hydrogels were characterized by Fourier transform infrared spectroscopy (FTIR), organic elemental analysis, X-ray diffraction studies (XRD), swelling studies, biocompatibility and hemocompatibility studies. Mechanical properties of the prepared hydrogels were evaluated by tensile test. The hydrogels were loaded with salicylic acid (used as a model drug) and drug release studies were done in a modified Franz’s diffusion cell. FTIR spectroscopy indicated the presence of primary and secondary amide absorption bands. XRD studies indicated increase in crystallinity in the hydrogels as compared to unmodified pectin. The degree of amidation (D _A) and molar and mass reaction yields (Y _M and Y _N) was calculated based on the results of organic elemental analysis. The hydrogels showed good water holding properties and were found to be compatible with B-16 melanoma cells & human blood.     

Intelligent poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide)-carboxymethyl cellulose full interpenetrating polymeric networks for protein adsorption studies

Poly(N-isopropyl acrylamide) (PNIPAm)–carboxymethyl cellulose (CMC) full interpenetrating polymeric networks (IPNs), based on PNIPAm and CMC, were prepared and investigated for adsorption of biomolecules utilizing a model protein, bovine serum albumin (BSA). N-isopropyl acrylamide monomers were polymerized in the presence of a natural polymer, e.g., carboxymethyl cellulose sodium salt. N,N′-methylenebisacrylamide (CL) was used to crosslink PNIPAm and CMC chains and IPN formed simultaneously. Spectroscopic and thermal characterization of the hydrogels were done with IR spectroscopy and thermogravimetric analysis. The swelling properties of PNIPAm and PNIPAm–CMC hydrogels were investigated as functions of the medium pH, temperature, ionic strength, and BSA. It was observed that the adsorption of protein molecules onto the hydrogels was mainly dependent on temperature and pH of the environment during the experiments. The maximum adsorption capacity (X) was observed at pH 4.7 which is the isoelectric point of BSA and at 40 °C for both hydrogels; and introducing CMC to PNIPAm increased the protein adsorption of the hydrogel. Adsorbed amounts of BSA were 26.70 mg g⁻¹ (4 °C) and 38.70 mg g⁻¹ (40 °C) for PNIPAm–CMC full IPN hydrogels. Adsorbed BSA (up to 80%) was eluted in the elution medium containing 0.1 mol dm⁻³ NaSCN at pH 8.0. Synthesized cylindrically shaped PNIPAm–CMC full IPN hydrogels can be used for adsorption studies related to the removal of proteins in pH- and temperature-sensitive biotechnological areas.     

Slow release of ciprofloxacin from double potential drug delivery system

Psyllium polysaccharide is a bulk laxative and has been used for the treatment of constipation which is responsible for the diverticulitis. Ciprofloxacin is an antibiotic used for the microorganism infested in the diverticula. Hence, the functionalization of psyllium with polyvinyl alcohol (PVA) and poly(acrylamide) [poly(AAm)] will develop the drug delivery system (DDS) with potential for dual action for the treatment of diverticulitis, that is, by treating the constipation due to laxative action of psyllium and release of ciprofloxacin from DDS in controlled manner. The optimum conditions for the synthesis of hydrogels have been obtained as 42.21 × 10⁻² mol/L of AAm, 3% (w/v) of PVA, 32.43 × 10⁻³ mol/L of N,N′-methylenebisacrylamide (NN-MBA), 17.53 × 10⁻³ mol/L ammonium persulfate, and 1 g of psyllium. The characterization of the hydrogels has been carried out by SEMs, EDAX, FTIR, and swelling studies. Swelling and drug release studies have also been carried out to determine the mechanism of swelling of hydrogels and drug release from the drug loaded hydrogels. The release of the drug from the hydrogels occurred through Fickian diffusion mechanism in pH 2.2 and pH 7.4 buffer.     

Macroporous hydrogels based on 2-hydroxyethyl methacrylate. Part 4: Growth of rat bone marrow stromal cells in three-dimensional hydrogels with positive and negative surface charges and in polyelectrolyte complexes

The growth of bone marrow stromal cells was assessed in vitro in macroporous hydrogels based on 2-hydro- xyethyl methacrylate (HEMA) copolymers with different electric charges. Copolymers of HEMA with sodium methacrylate (MA⁻) carried a negative electric charge, copolymers of HEMA with [2-(methacryloyloxy)ethyl] trimethylammonium chloride (MOETA⁻) carried a positive electric charge and terpolymers of HEMA, MA⁻ and MOETA⁺ carried both, positive and negative electric charges. The charges in the polyelectrolyte complexes were shielded by counter-ions. The hydrogels had similar porosities, based on a comparison of their diffusion parameters for small cations as measured by the real-time tetramethylammonium iontophoretic method of diffusion analysis. The cell growth was studied in the peripheral and central regions of the hydrogels at 2 hours and 2, 7, 14 and 28 days after cell seeding. Image analysis revealed the highest cellular density in the HEMA-MOETA⁺ copolymers; most of the cells were present in the peripheral region of the hydrogels. A lower density of cells but no difference between the peripheral and central regions was observed in the HEMA-MA⁻ copolymers and in polyelectrolyte complexes. This study showed that positively charged functional groups promote the adhesion of cells.     

Study on swelling of hydrogels (PAAm) at various temperatures by using fluorescence technique

Steady-state fluorescence (SSF) technique was employed for studying swelling of polyacrylamide (PAAm) hydrogels. Disc-shaped gels were prepared by free-radical crosslinking copolymerization of acrylamide (AAm) with N, N′- methylenebis (acrylamide) (BIS) as crosslinker in the presence of ammonium persulfate (APS) as an initiator. Pyranine was introduced as a fluorescence probe. Fluorescence intensity of pyranine was measured during in situ swelling process at various temperatures and it was observed that fluorescence intensity values decreased as swelling is proceeded. Li–Tanaka equation was used to determine the swelling time constants, τ_c and cooperative diffusion coefficients, D _c from intensity, weight and volume variations during the swelling processes. It is observed that swelling time constants, τ_c decreased and diffusion coefficients, D _c increased as the swelling temperature is increased. The swelling activation energies, ΔE were measured from the intensity, weight and volume variations and found to be 10.7, 32.2 and 64.1 kJ mol⁻¹, respectively.     

Polyaniline and polypyrrole modified conductive nanocomposites of polyfuran and polythiophene with montmorillonite clay

Nanocomposites of polyfuran (PF) and polythiophene (PTP) with montmorillonite clay (MMT) were prepared and modified by loading of polyaniline (PANI) and polypyrrole (PPY) moieties via polymerization of aniline (ANI) and pyrrole (PY) in aqueous dispersions of PF-MMT and PTP-MMT nanocomposites. Formation of PANI and PPY and their subsequent incorporation in the PF-MMT and PTP-MMT composites was confirmed by FTIR absorption studies. X-ray diffraction (XRD) patterns of PANI and PPY modified PF-MMT and PTP-MMT composites showed that PF-MMT and PTP-MMT intercalates were still present in the modified composites. Scanning electron microscopic analysis revealed distinctive morphological patterns of the various composite particles. The dc conductivity values of PANI and PPY modified PF-MMT and PTP-MMT composites were in the order of 10⁻² S/cm in either system – a value much improved compared to the same for both of the unmodified PF-MMT (10⁻⁷ S/cm) and PTP-MMT (10⁻⁵ S/cm) nanocomposites respectively.     

External stimuli response on a novel chitosan hydrogel crosslinked with formaldehyde

Keeping in mind the significance of hydrogels as an external stimuli sensitive super absorbing material, some transparent covalent hydrogels of chitosan were prepared by crosslinking with varying amounts of formaldehyde solution used as crosslinking agent. The characteristics of hydrogels were investigated by Fourier transform infrared (FT-IR) spectroscopy and swelling experiments. The effect of crosslinking agent on water absorbency has been investigated. The hydrogels exhibited a relatively higher swelling ratio in the range of 2066–3306% and equilibrium water content (EWC) in the range of 95-38–97 06% at pH 7 and 35°C temperature. The influence of external stimuli such as pH, temperature, and ionic strength of the swelling media on equilibrium swelling properties has been observed. Hydrogels showed a typical pH and temperature responsive behaviour such as low pH and high temperature has maximum swelling while high pH and low temperature show minimum swelling. An increase in the ionic strength of swelling media caused a continuous decrease in the swelling of hydrogels at both acidic and basic pH.     

Polyacrylamide and methylcellulose hydrogel as delivery vehicle for the controlled release of paraquat pesticide

PAAm–MC hydrogels as a potential delivery vehicle for the controlled release of paraquat pesticide was investigated, as they play an essential role to use hydrogels in controlled release technology. The release kinetics of paraquat was determined using UV–Vis measurements. The release mechanism of paraquat from PAAm–MC hydrogels was investigated through a semi-empirical model proposed by Ritger and Peppas. In general, the initial rate of paraquat release was fast, decreasing after several days, hence indicating that paraquat on the surface (or close to) of hydrogels diffused rapidly after the initial swelling of the gel. Later, the cumulative release occurred in a very controlled and sustained manner, with the paraquat concentration maintaining constant from 15 to 46 days. The paraquat release capacity was dependent on the swelling of the matrix and the density of the network chains. The curves obtained from Peppas’s model presented good linearity (R ² ≥ 0.999), indicating that such model can be applicable to analyze the systems. The n values for the pesticide release from hydrogels indicate that paraquat release has Fickian and non-Fickian diffusion, depending of hydrogel formulation. The values of k showed that the release of paraquat becomes slower when the MC and AAm concentration increases. Finally, to the best of our knowledge, we report a hydrogel-based vehicle (first carrier) that is able to prolong the sustained release of paraquat pesticide up to 45 days, which is essential for its application in controlled release systems.     

Cationic poly(VCL–AETA) hydrogels and ovalbumin (OVA) release in vitro

The objective of this research is to explore the synthesis of a new family of water soluble polycationic copolymeric precursors that could be photo-crosslinked into hydrogels. The in vitro control release of ovalbumin protein (OVA) from this family of hydrogels was also studied to assess the biomedical potential of this new family polycationic hydrogels. A series of novel poly(VCL–AETA) copolymer hydrogels was fabricated in an aqueous medium via photo-induced polymerization and crosslinking of hydrophobic N-vinylcaprolactam (VCL) and hydrophilic [2-(acryloxy)ethyl]trimethylammonium chloride (AETA) monomers over a wide range of VCL to AETA feed molar ratios of 2:1, 1:1, 1:2, 1:5. N,N′-methylene bisacrylamide (MBA) was used as a crosslinker. Ovalbumin (OVA), a model antigen, was preloaded into poly(VCL–AETA) hydrogel precursors and its release profiles in pH 7.4 PBS at 37°C were investigated as a function of VCL to AETA monomer feed ratios over a period of 4 weeks. The in vitro results showed that OVA initial burst and subsequent sustained releases could be controlled by 3 material parameters: the hydrophobic VCL to hydrophilic AETA monomer feed ratios, crosslinking density and hydrogel degradation rate. Thus, the hydrophobic-hydrophilic VCL–AETA hydrogel network for controlled OVA release could offer advantages over organic solvent-based single component polymer system. However, these in vitro OVA release profiles may change in an in vivo environment.     

Synthesis and characterization of HDA/NaMMT organoclay

In this study, the rheologic and colloidal characterizations of sodium montmorillonite (NaMMT) were examined. Hexadecylamine (CH₃(CH₂)₁₅NH₂, HDA) was added to the bentonite water dispersion (2%, w/w) in different concentrations in the range 5.6 × 10⁻⁴−9.4 × 10⁻³ mmol/l. The rheological and electrokinetic behaviour of aqueous montmorillonite dispersions was investigated as a function of solid content and HDA concentration. The basal spacings of the HDA/NaMMT composites were studied by X-ray diffraction. The FTIR spectra were obtained from the modified bentonite products, which revealed the characteristic absorbances after treatment with HDA.     

Swelling and diffusion characteristics of modified poly (N-isopropylacrylamide) hydrogels

Thermo-responsive hydrogels are capable of swelling changes to external temperature. A series of modified poly (N-isopropylacrylamide) (PNIPA) hydrogels was synthesized by free radical polymerization in aqueous solution. Acrylamide (AAm) was used to increase the lower critical solution temperature (LCST), while sodium alginate (SA) was used to improve the swelling performance of the hydrogels. Experiments show that 5.5% mass ratio of AAm increased the LCST by about 9 °C above that of conventional PNIPA. Also, SA significantly improved the equilibrium swelling ratio associate with temperature change. Trypan blue diffusion revealed significant differences in the fluid release obtained from hydrogels with modified LCST and swelling properties. The implications of the modified fluid release and swelling characteristics are also discussed for the device design of thermo-sensitive hydrogels for localized drug delivery.     

Preparation of highly concentrated aqueous hydroxyapatite suspensions for slip casting

This paper reports the preparation of highly concentrated aqueous hydroxyapatite (HA) suspensions for slip casting of dense bone implants. The dispersing behaviour of HA powders in aqueous media was monitored by viscosity and zeta potential analyses as a function of pH of the slurry. The rheological properties of concentrated aqueous hydroxyapatite suspensions have been characterized with varying pH, NH₄PAA concentration and solids loading. The intrinsic pH of the suspension was found suitable for slip casting. The optimum dispersant concentration is 0.75 wt.% for 75 wt.% solid loading. A stable suspension with 75 wt.% solid was suitable for slip casting with viscosity of 0.36 Pa s at 100 s⁻¹. Finally, crack-free and dense microstructures have been obtained successfully with a grain size of 2–5 μm.     

Carboxymethyl derivative of scleroglucan: a novel thermosensitive hydrogel forming polysaccharide for drug delivery applications

A carboxymethyl derivative of scleroglucan (Scl-CM) with a derivatization degree of 65 ± 5% was synthesized. The rheological behaviour of this novel polymer was studied and compared with that of the starting polymer. We observed that the charged moieties carried on the chains could prevent the triple helix formation of Scl. Scl-CM aqueous solutions behave like true polymer solutions up to 1% w/v, whereas above this concentration a weak gel behaviour was observed. CaCl₂ addition to aqueous Scl-CM solutions led to a physical gel formation; the hydrogel strength was related to polymer and CaCl₂ concentrations. Temperature sweeps, registered at 1 Hz on hydrogels differing in CaCl₂ concentration, evidenced a gel → sol transition in the range of 30–40°C, depending on the molar ratio between carboxylic groups and Ca⁺². In order to verify a possible use of these hydrogels as drug delivery systems, acyclovir was loaded into the network. Rheological analysis evidenced that the loaded drug can affect the hydrogel elastic modulus. The release of acyclovir in phosphate buffer was evaluated at different temperatures in order to assess the suitability of this novel drug delivery system in topical applications.     

Highly Stretchable and Tough Hydrogels below Water Freezing Temperature

Hydrogels consist of hydrophilic polymer networks dispersed in water. Many applications of hydrogels rely on their unique combination of solid‐like mechanical behavior and water‐like transport properties. If the temperature is lowered below 0 °C, however, hydrogels freeze and become rigid, brittle, and non‐conductive. Here, a general class of hydrogels that do not freeze at temperatures far below 0 °C, while retaining high stretchability and fracture toughness, is demonstrated. These hydrogels are synthesized by adding a suitable amount of an ionic compound to the hydrogel. The present study focuses on tough polyacrylamide‐alginate double network hydrogels equilibrated with aqueous solutions of calcium chloride. The resulting hydrogels can be cooled to temperatures as low as ?57 °C without freezing. In this temperature range, the hydrogels can still be stretched more than four times their initial length and have a fracture toughness of 5000 J m^?2. It is anticipated that this new class of hydrogels will prove useful in developing new applications operating under a broad range of environmental and atmospheric conditions.     

Photodetachable Adhesion

Peeling from strong adhesion is hard, and sometimes painful. Herein, an approach is described to achieve both strong adhesion and easy detachment. The latter is triggered, on‐demand, through an exposure to light of a certain frequency range. The principle of photodetachable adhesion is first demonstrated using two hydrogels as adherends. Each hydrogel has a covalent polymer network, but does not have functional groups for bonding, so that the two hydrogels by themselves adhere poorly. The two hydrogels, however, adhere strongly when an aqueous solution of polymer chains is spread on the surfaces of the hydrogels and is triggered to form a stitching polymer network in situ, in topological entanglement with the pre‐existing polymer networks of the two hydrogels. The two hydrogels detach easily when the stitching polymer network is so functionalized that it undergoes a gel–sol transition in response to a UV light. For example, two pieces of alginate–polyacrylamide hydrogels achieve adhesion energies about 1400 and 10 J m^?2, respectively, before and after the UV radiation. Experiments are conducted to study the physics and chemistry of this strong and photodetachable adhesion, and to adhere and detach various materials, including hydrogels, elastomers, and inorganic solids.     

Synthesis,characterization, and application of modified silica in the removal and preconcentration of lead ions from natural river water

This paper describes the synthesis, modification, and application of modified silica for the removal of lead ions from aqueous medium. The modification reaction provided a reduction in surface are from 737 to 399 m² g⁻¹, which was attributed to the 4-amine-2-mercaptopyrimidine molecule attachment onto its surface. The characterization through FTIR spectra demonstrated bands at 3347 cm⁻¹ assigned to N–H stretching vibrations and the absence of thiol bands at 2600 e 2547 cm⁻¹ at Si-mod spectrum is an indicative that the attachment occurred via SH groups. The linearization of adsorption isotherm data through the modified Langmuir equation resulted in a maximum adsorption capacity of 2.9 μmol g⁻¹. The material was applied in a continuous flow system in the preconcentration of water samples from Paraná River and the results were in agreement with metal concentration determined directly through atomic absorption spectrometry with graphite furnace. The method validation was performed through analysis of water standard reference material (1643e), which also presented a 7.2-fold enrichment factor.     

Accelerated ageing experiments with crosslinked and conventional ultra-high molecular weight polyethylene (UHMW-PE) stabilised with α-tocopherol for total joint arthroplasty

Samples of untreated ultra-high molecular weight polyethylene (UHMW-PE), UHMW-PE sterilized with γ-rays in nitrogen atmosphere (conventional UHMW-PE, widely used for articulating surfaces in endoprostheses) and UHMW-PE, which has been crosslinked by electron beam irradiation and annealed subsequently, were stabilized with α-tocopherol and aged in air at 120^∘C as well as in 10% aqueous hydrogenperoxide with 0.04 mg/ml FeCl₃ as catalyst at 50^∘C. The oxidative degradation was monitored with the help of infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), solubility measurements and size exclusion chromatography (SEC) and were compared to unstabilized samples. When aged in air at 120^∘C, the crosslinked UHMW-PE showed a slightly slower increase of the carbonyl (CO)-number (according to DIN 53383) in FTIR than conventional UHMW-PE. A stabilisation with 0.4% w/w α-tocopherol resulted in an increase of lifetime by a factor of approx. 40 for all samples. Ageing in 10% aqueous H₂O₂ at 50^∘C yielded similar results for all three unstabilised samples. The addition of the natural antioxidant α-tocopherol led to a prolongation of lifetime by a factor of approx. 2.5. A linear loss of α-tocopherol was detected during ageing. An increase of crystallinity as well as lamella thickness during ageing was observed with the help of DSC. The two-phase structure of crosslinked UHMW-PE with two melting endotherms at 114^∘C and 137^∘C was replaced very quickly by a single melting point at 130^∘C. This effect was delayed with the stabilized samples. In the solubility and SEC measurements, a severe molecular degradation and drop of molar mass of all materials could be observed after ageing in H₂O₂, leading to a complete destruction and, in case of crosslinked UHMW-PE, to a serious damage of the molecular network, respectively. in partial fulfilment of a Ph.D. (Dr.mont.) thesis at the University of Leoben