Biopolymer Hydrogels Research Articles

Metathesis in water conducted by tailor-made encapsulated Grubbs’ catalyst

Grubbs’ second-generation catalyst was encapsulated in alginate-based biopolymer hydrogel beads to conduct ring-closing metathesis in water.

Green bioprinting: extrusion-based fabrication of plant cell-laden biopolymer hydrogel scaffolds

Plant cell cultures produce active agents for pharmaceuticals, food and cosmetics. However, up to now process control for plant cell suspension cultures is challenging. A positive impact of cell immobilization, such as encapsulation in hydrogel beads, on secondary metabolites production has been reported for several plant species. The aim of this work was to develop a method for bioprinting of plant cells in order to allow fabrication of free-formed three-dimensional matrices with defined internal pore architecture for in depth characterization of immobilization conditions, cell agglomeration and interactions. By using extrusion-based 3D plotting of a basil cell-laden hydrogel blend consisting of alginate, agarose and methylcellulose (alg/aga/mc), we could demonstrate that bioprinting is applicable to plant cells. The majority of the cells survived plotting and crosslinking and the embedded cells showed high viability and metabolic activity during the investigated cultivation period of 20 d. Beside its compatibility with the plant cells, the novel alg/aga/mc blend allowed fabrication of defined 3D constructs with open macropores both in vertical and horizontal direction which were stable under culture conditions for several weeks. Thus, Green Bioprinting, an additive manufacturing technology processing live cells from the plant kingdom, is a promising new immobilization tool for plant cells that enables the development of new bioprocesses for secondary metabolites production as well as monitoring methods.

4D Biofabrication Using Shape-Morphing Hydrogels.

Despite the tremendous potential of bioprinting techniques toward the fabrication of highly complex biological structures and the flourishing progress in 3D bioprinting, the most critical challenge of the current approaches is the printing of hollow tubular structures. In this work, an advanced 4D biofabrication approach, based on printing of shape-morphing biopolymer hydrogels, is developed for the fabrication of hollow self-folding tubes with unprecedented control over their diameters and architectures at high resolution. The versatility of the approach is demonstrated by employing two different biopolymers (alginate and hyaluronic acid) and mouse bone marrow stromal cells. Harnessing the printing and postprinting parameters allows attaining average internal tube diameters as low as 20 µm, which is not yet achievable by other existing bioprinting/biofabrication approaches and is comparable to the diameters of the smallest blood vessels. The proposed 4D biofabrication process does not pose any negative effect on the viability of the printed cells, and the self-folded hydrogel-based tubes support cell survival for at least 7 d without any decrease in cell viability. Consequently, the presented 4D biofabrication strategy allows the production of dynamically reconfigurable architectures with tunable functionality and responsiveness, governed by the selection of suitable materials and cells.

Nitrogen efficiency in wheat yield through the biopolymer hydrogel

ABSTRACT Nitrogen use efficiency in wheat biomass and grain yields can be favored by the biopolymer hydrogel. The objective of the study was to analyze the use of the biopolymer hydrogel applied to the seed in the optimization of fertilizer-N on wheat biomass and grain yields, under different conditions of agricultural year and succession systems of high and reduced release of residual-N. In the study, two experiments were conducted, with different farming systems, soybean/wheat and maize/wheat, one to quantify the biomass yield rate and the other to determine grain yield. The experiments were conducted in the years 2014 and 2015, in a randomized block design with four replicates in a 4 x 4 factorial scheme, corresponding to hydrogel doses (0, 30, 60 and 120 kg ha-1) added in the groove along with the seed and N fertilizer rates (0, 30, 60 and 120 kg ha-1), applied as top-dressing. It is possible to improve the fertilizer-N efficiency by wheat using the biopolymer hydrogel for the production of biomass and grains. The highest wheat yield per kilogram of N supplied is obtained with 30 and 60 kg ha-1 of hydrogel, regardless of the year and succession system.

Characterizing Viscoelastic Modulations in Biopolymer Hydrogels by Coherence-Gated Light Scattering.

pH-responsive hydrogels are of great interest for the controlled release of drugs. However, the changes in the structural and mechanical properties of hydrogels during the pH-responsive swelling/contraction process remains largely unknown. In this article, we demonstrate that coherence-gated dynamic light scattering can be used to in situ characterize the structural dynamics of chitosan (CS) hydrogels at different pH values and show that the CS hydrogels undergo viscoelastic modulations during the swelling/contraction/recovery process induced by pH changes. The conditions for the CS hydrogels to undergo these modulations are found by continuously monitoring the nonequilibrium, long-term dynamical process. Our findings are in a close correspondence to the macroscopic observations made at time points where the CS hydrogels are at equilibrium.

Non-uniform self-assembly: On the anisotropic architecture of \u03b1-synuclein supra-fibrillar aggregates

Although the function of biopolymer hydrogels in nature depends on structural anisotropy at mesoscopic length scales, the self-assembly of such anisotropic structures in vitro is challenging. Here we show that fibrils of the protein α-synuclein spontaneously self-assemble into structurally anisotropic hydrogel particles. While the fibrils in the interior of these supra-fibrillar aggregates (SFAs) are randomly oriented, the fibrils in the periphery prefer to cross neighboring fibrils at high angles. This difference in organization coincides with a significant difference in polarity of the environment in the central and peripheral parts of the SFA. We rationalize the structural anisotropy of SFAs in the light of the observation that αS fibrils bind a substantial amount of counterions. We propose that, with the progress of protein polymerization into fibrils, this binding of counterions changes the ionic environment which triggers a change in fibril organization resulting in anisotropy in the architecture of hydrogel particles.

Revealing the structure of high-water content biopolymer networks: Diminishing freezing artefacts in cryo-SEM images

High-water content biopolymer gels are widely used in diverse areas of research and in many commercial processes, including a significant proportion of importance to the food and pharmaceutical industries. The internal structures of these hydrogels are complex and span many length scales, the specifics of which are important in determining functionality. Elucidating these structures is critically important in extending and tailoring their use. Cryo-scanning electron microscopy (cryo-SEM) is a popular method for structural elucidation. A critical step in this imaging technique is cryo-fixation. However, consideration of the literature reveals that images of inefficiently cryo-fixed networks remain widely reported as being representative of the native structure of gels despite being significantly damaged by ice formation. Here, we show that the application of slow freezing methods, like the very commonly used slushy nitrogen method, indeed yield erroneous structures and produce singularly common structures for both protein and polysaccharide hydrogels. On the contrary, we demonstrate, by rapidly freezing thin samples of low concentration protein amyloid fibril hydrogels using a propane jet freezer, that cryo-SEM imaging of biopolymer hydrogels in their native state is feasible. In contrast, while the use of cryo-protectants is successful in reducing ice crystallisation, it can affect the bonding within hydrogels and hence, modify the structure under examination.

Dynamic Coordination Chemistry Enables Free Directional Printing of Biopolymer Hydrogel

Three-dimensional (3D) printing is a promising technology to develop customized biomaterials in regenerative medicine. However, for the majority of printable biomaterials (bioinks) there is always a compromise between excellent printability of fluids and good mechanical properties of solids. Three-dimensional printing of soft materials based on the transition from a fluid to gel state is challenging because of the difficulties to control such transition as well as to maintain uniform conditions three-dimensionally. To solve these challenges, a facile chemical strategy for the development of a novel hydrogel bioink with shear-thinning and self-healing properties based on dynamic metal–ligand coordination bonds is presented. The noncovalent cross-linking allows easy extrusion of the bioink from a reservoir without changing of its bulk mechanical properties. The soft hydrogel can avoid deformation and collapse using omnidirectional embedding of the printable hydrogel into a support gel bath sharing the same ...

A Bioinspired Alginate-Gum Arabic Hydrogel with Micro-/Nanoscale Structures for Controlled Drug Release in Chronic Wound Healing.

Biopolymeric hydrogels have drawn increasing research interest in biomaterials due to their tunable physical and chemical properties for both creating bioactive cellular microenvironment and serving as sustainable therapeutic reagents. Inspired by a naturally occurring hydrogel secreted from the carnivorous Sundew plant for trapping insects, here we have developed a bioinspired hydrogel to deliver mitsugumin 53 (MG53), an important protein in cell membrane repair, for chronic wound healing. Both chemical compositions and micro-/nanomorphological properties inherent from the natural Sundew hydrogel were mimicked using sodium alginate and gum arabic with calcium ion-mediated cross-linking. On the basis of atomic force microscopy (AFM) force measurements, an optimal sticky hydrogel scaffold was obtained through orthogonal experimental design. Imaging and mechanical analysis showed the distinct correlation between structural morphology, adhesion characteristics, and mechanical properties of the Sundew-inspired hydrogel. Combined characterization and biochemistry techniques were utilized to uncover the underlying molecular composition involved in the interactions between hydrogel and protein. In vitro drug release experiments confirmed that the Sundew-inspired hydrogel had a biphasic-kinetics release, which can facilitate both fast delivery of MG53 for improving the reepithelization process of the wounds and sustained release of the protein for treating chronic wounds. In vivo experiments showed that the Sundew-inspired hydrogel encapsulating with rhMG53 could facilitate dermal wound healing in mouse model. Together, these studies confirmed that the Sundew-inspired hydrogel has both tunable micro-/nanostructures and physicochemical properties, which enable it as a delivery vehicle for chronic wounding healing. The research may provide a new way to develop biocompatible and tunable biomaterials for sustainable drug release to meet the needs of biological activities.

In situ forming hydrogels with long-lasting miR-21 enhances the therapeutic potential of MSC by sustaining stimulation of target gene

Regulating stem cells by microRNA (miRNA) is promising in regenerative medicine. However, non-viral transfection is usually transient while stably lentiviral transfection is accompanied with oncogenic risk. In the study, we explored the feasibility to retain the microRNAs within biopolymer hydrogels for their long-lasting working and sustaining stimulation of target gene. miRNA-21 (MiR-21), a reported microRNA enhancing the therapeutic potential of mesenchymal stem cells (MSCs) was used. We demonstrated that miR-21 could be efficiently retained within collagen hydrogel after forming complex with cationic polymer polyethylenimine (PEI). Due to the electronic interaction with positively charged PEI, the release of miR-21 was largely prevented during 2 week incubation (<20%), while free miR-21 encapsulated in hydrogels was largely released (>50%). When MSCs were cultivated in the PEI/miR-21-incorporated hydrogels, the sustained activation of targeted gene HIF-1α was observed, resulting in the sustaining up-regulation of several downstream therapeutic cytokines. Then, the hydrogels encapsulating miR-21/PEI were coated onto tissue plate for MSC cultivation, which further confirmed the long-lasting retention and efficacy of miR-21 on the plate surface. In addition, under H2O2-simulated stress condition, we also demonstrated that the anti-apoptotic capacity of MSCs was significantly improved when growing on miR-21-retained hydrogels. Our study provided a safe and promising method for long-lasting stem cell regulation with miRNAs.

Nitrogen efficiency in oat yield through the biopolymer hydrogel

ABSTRACT The retainers of water in the soil can favor nitrogen (N) use efficiency in oat yield. The aim of the study was to determine if the conditions of use of the biopolymer hydrogel increase the fertilizer-N use efficiency in oat yield in succession systems of high and low residual-N release. In each succession system (soybean/oat, corn/oat), two experiments were conducted in 2014 and 2015, one to quantify biomass yield and the other to estimate grain yield and lodging. The design was randomized blocks with four replicates in a 4 x 4 factorial scheme for hydrogel doses (0, 30, 60 and 120 kg ha-1), added in the furrow with the seed, and N fertilizer doses (0, 30, 60 and 120 kg ha-1) applied in the fourth-expanded-leaf stage. The use of hydrogel increases N use efficiency in oat yield, especially under the conditions of 30 to 60 kg ha-1 of biopolymer; however, this effect is dependent on the succession system and on weather conditions.

Anti-Microbial Biopolymer Hydrogel Scaffolds for Stem Cell Encapsulation.

Biopolymer hydrogels are an attractive class of materials for wound dressings and other biomedical applications because of their ease of use and availability from biomass. Here, we present a hydrogel formation approach based on alginate and chitosan. Alginate is conventionally cross-linked using multivalent ions such as Ca2+ but in principle any polycationic species can be used such as polyelectrolytes. Exchanging the cross-linking Ca2+ ions partially with chitosan, which at pH 7 has available positive charges as well as good interactions with Ca2+, leads to an improved Young’s modulus. This gel is non-toxic to mammalian cells and hence allows conveniently for stem cell encapsulation since it is based on two-component mixing and gel formation. Additionally, the chitosan is known to have a bactericidal effect which is retained when using it in the alginate–chitosan gel formation and the formed hydrogels displayed bactericidal effects against P. aeruginosa and S. aureus. The combination of anti-bacterial properties, inclusion of stem cells, and the hydrogel nature would provide an ideal environment for complex wound healing.

Oil/water interfaces of guar gum-based biopolymer hydrogels and application to their separation

Oily wastewater treatment has become a significant research subject due to potential environmental related applications, e.g., oil spill remedy process. In this paper, a natural polymer based hydrogel, prepared from guar gum (GG) and metaborate, was coated onto a stainless steel mesh, and the as-prepared hydrogel-coated material was applied for oil/water separation. The strong hydrophilic GG hydrogel imparted excellent underwater oleophobicity and ultra-low oil adhesion. The results proved that the as-prepared GG hydrogel-coated material possessed excellent self-cleaning property and high oil/water separation efficiency

Release behavior and bioefficacy of imazethapyr formulations based on biopolymeric hydrogels

ABSTRACTControlled release formulations of imazethapyr herbicide have been developed employing guar gum-g-cl-polyacrylate/bentonite clay hydrogel composite (GG-HG) and guar gum-g-cl-PNIPAm nano hydrogel (GG-NHG) as carriers, to assess the suitability of biopolymeric hydrogels as controlled herbicide release devices. The kinetics of imazethapyr release from the developed formulations was studied in water and it revealed that the developed formulations of imazethapyr behaved as slow release formulations as compared to commercial formulation. The calculated diffusion exponent (n) values showed that Fickian diffusion was the predominant mechanism of imazethapyr release from the developed formulations. Time for release of half of the loaded imazethapyr (t1/2) ranged between 0.06 and 4.8 days in case of GG-NHG and 4.4 and 12.6 days for the GG-HG formulations. Weed control index (WCI) of GG-HG and GG-NHG formulations was similar to that of the commercial formulation and the herbicidal effect was observed for relatively longer period. Guar gum-based biopolymeric hydrogels in both macro and nano particle size range can serve as potential carriers in developing slow release herbicide formulations.

Evaluation of fibrin-gelatin hydrogel as biopaper for application in skin bioprinting: An in-vitro study.

Recent advances in tissue engineering have led to the development of the concept of bioprinting as an interesting alternative to traditional tissue engineering approaches. Biopaper, a biomimetic hydrogel, is an essential component of the bioprinting process. The aim of this work was to synthesize a biopaper made of fibrin-gelatin hybrid hydrogel for application in skin bioprinting. Different composition percentages of the two biopolymer hydrogels, fibrin-gelatin, have been studied for the construction of the biopaper and were examined in terms of water absorption, biodegradability, glucose absorption, mechanical properties and water vapor transmission. Subsequently, tissue fusion study was performed on prepared 3T3 fibroblast cell line pellets embedded into the hydrogel. Based on the obtained results, fibrin-gelatin blend hydrogel with the same proportion of two components provides a natural scaffold for fibroblast-based bioink embedding and culture. The suggested optimized hydrogel was a suitable candidate as a biopaper for skin bioprinting technology.

Investigation on Au-nano incorporated pH-sensitive (itaconic acid/acrylic acid/triethylene glycol) based polymeric biocompatible hydrogels

The pH-sensitive gold nano hydrogel based on itaconic acid, acrylic acid and triethylene glycol (GIAT) has been prepared by free radical polymerization viz. organic solventless approach with different monomer ratios. The nature of bonding and structural identification of GIAT hydrogels were characterized by FT-IR spectroscopy. The surface morphology of gold gel was examined using scanning electron microscopy (SEM). In addition, transmission electron microscopy (TEM) was used to identify the size of gold nano particles. The in vitro biocompatibility of GIAT hydrogel has been evaluated in 3T3 fibroblast cell lines. The obtained results show that gold nano particle incorporated hydrogel possess ~99% of cell proliferation. Followed by, the impact of gold nano particles on swelling, surface morphology was studied. The consecutive preparation of hydrogel, effect of different pH conditions, and stoichiometry of monomeric units have also been discussed. The degree of swelling was measured in carbonate buffer solutions for 24h period with varying pH such as 1.2, 6.0, 7.4 and 10.0. The obtained results showed that the stoichiometry of itaconic acid and gold nano particles plays an essential role in modifying the nature of GIAT polymeric hydrogels. In conclusion, promising Au-nano incorporated pH-sensitive bio polymeric hydrogels were prepared and characterized. The unique properties of these Au-nano hydrogel make them attractive use in biomedical applications.

Indole-3-acetic acid based tunable hydrogels for antibacterial, antifungal and antioxidant applications

ABSTRACTIndole-3-acetic acid (IAA) based biopolymeric hydrogels with tunable anti-oxidant and anti-fungal character has been synthesized via condensation polymerization as pH-sensitive hydrophilic material.The present study focused on the synthesis of antifungal heterocyclic hydrogel using citric acid (CA), indole-3-acetic acid (IAA) and ethylene glycol (EG) by condensation polymerization. The hydrogels revealed a pH-sensitive swelling behavior, with increased swelling in acidic media, which in turn has decreased the swelling in the basic media.The hydrogel samples were tested for antifungal activity against Aspergillus fumigates, Rhizopusoryzae and Candida albicans at different concentrations (500, 1000, 1500, 2000 μg/well). Ketoconazole was used as positive control and DMSO as negative control for antifungal activity. Fungi were increasingly identified as major pathogens in various infections. Hydrogels with antifungal properties may constitute an important restriction to fungal infections. The biopolymeric hydrogels were characterized by Fourier transform infrared (FT-IR) spectroscopy, 1H-NMR,13C-NMR, TGA, DSC followed by scanning electron microscopy (SEM). The increased antifungal activity was monitored in equimolar composition more than that of other compositions. The antioxidant activity of ICE with DPPH and NO radicals has been compared with rutin. Such antifungal hydrogels with antioxidant properties is recommended for medical applications such as bandages, catheters, drains and tubes to prevent infection.

Antioxidant Properties of Indole-3-Acetic Acid based Biopolymeric Hydrogels

Antioxidant Properties of Indole-3-Acetic Acid based Biopolymeric Hydrogels

Indole-3-acetic acid/diol based pH-sensitive biological macromolecule for antibacterial, antifungal and antioxidant applications

Indole-3-acetic acid (IAA)/diol based pH-sensitive biopolymeric hydrogels with tunable biological properties (cytotoxicity, anti-oxidant and anti-fungal) have been synthesized via condensation polymerization. The present study focused on the synthesis of heterocyclic hydrogel using citric acid (CA), indole-3-acetic acid (IAA) and diethylene glycol (DEG) by condensation polymerization. The hydrogels revealed a pH-sensitive swelling behaviour, with increased swelling in acidic media, then turns to decreased the swelling in the basic media. The hydrogel samples were tested for antifungal activity against Aspergillus fumigates, Rhizopusoryzae and Candida albicans at different concentrations using ketoconazole as positive control and DMSO as negative control for antifungal activity. Antioxidant activity increasing nature in DPPH than NO radical compared with rutin and confirmed non toxic property using cytotoxicity analysis. The biopolymeric hydrogels were characterized by Fourier transform infrared (FT-IR) spectroscopy, 1H NMR,13C NMR, TGA, DSC followed by scanning electron microscopy (SEM). Such hydrogels with antioxidant properties is recommended for medical applications such as bandages, catheters, drains and tubes to prevent infection.

Alginate- and gelatin-based bioactive photocross-linkable hybrid materials for bone tissue engineering

The paper presents the synthesis, the physico-chemical and the biological properties of novel hybrid materials prepared from photo-crosslinked gelatin/alginate-based hydrogels and silica particles exhibiting potential for the regeneration of bone tissue. Both alginate and gelatin were functionalized with methacrylate and methacrylamide moieties, respectively to render them photo-crosslinkable. Submicron silica particles of two sizes were dispersed within three types of polymeric sols including alginate, gelatin, and gelatin/alginate blends, which were subsequently photo-crosslinked. The swelling ratio, the gel fraction and the mechanical properties of the hybrid materials developed were examined and compared to these determined for reference hydrogel matrices. The in vitro cell culture studies have shown that the prepared materials exhibited biocompatibility as they supported both MEFs and MG-63 mitochondrial activity. Finally, the in vitro experiments performed under simulated body fluid conditions have revealed that due to inclusion of silica particles into the biopolymeric hydrogel matrices the mineralization was successfully induced.