Rapid preparation of PAM/N-CNT nanocomposite hydrogels by DEM frontal polymerization and its performance study

In this study, a simple and eco-friendly method was proposed to efficiently prepare nanocomposite hydrogels with excellent mechanical properties and satisfactory pH response behaviour by frontal polymerization (FP) of DEM in close to 4 minutes. Acrylamide (AM) and choline chloride (ChCl) were used as raw materials to synthesize deep eutectic monomers (DEMs). Nitrogen-doped carbon nanotubes were dispersed in DEMs as fillers, and poly(acrylamide)/nitrogen-doped carbon nanotube (PAM/N-CNT) nanocomposite hydrogels were prepared by FP. The non-covalent interactions between PAM hydrogels and N-CNTs was verified by Fourier infrared spectroscopy. The mechanical properties of PAM/N-CNT nanocomposite hydrogels were investigated, as well as the swelling and pH response properties. The results showed that the compressive strength of PAM hydrogels was significantly enhanced by the addition of N-CNTs due to the hydrophobic interaction of N-CNTs, which also causes sensitive response properties of the PAM hydrogels in acid solution.

In this study, a simple and eco-friendly method was proposed to efficiently prepare nanocomposite hydrogels with excellent mechanical properties and satisfactory pH response behaviour by frontal polymerization of DEM in close to 4 minutes.     

A sodium alginate-based sustained-release IPN hydrogel and its applications

Interpenetrating polymer network (IPN) hydrogels are crosslinked by two or more polymer networks, providing free volume space in the three-dimensional network structure, and providing conditions for the sustained and controlled release of drugs. The IPN hydrogels based on the natural polymer sodium alginate can form a stable porous network structure. Due to its excellent biocompatibility, the loaded drug can be sustained to the maximum extent without affecting its pharmacological effect. Sodium alginate-based IPN hydrogels have broad application prospects in the field of sustained and controlled drug release. This paper begins with an overview of the formation of alginate-based IPN hydrogels; summarizes the types of alginate-based IPN hydrogels; and discusses the pharmaceutical applications of alginate-based IPN hydrogels. We aim to give an overview of the research on IPN hydrogels based on sodium alginate in sustained and controlled drug release systems.

Interpenetrating polymer network (IPN) hydrogels are crosslinked by two or more polymer networks, providing free volume space in the three-dimensional network structure, and providing conditions for the sustained and controlled release of drugs.     

Strong,tough and mechanically self-recoverable poly(vinyl alcohol)/alginate dual-physical double-network hydrogels with large cross-link density contrast

Strong and tough poly(vinyl alcohol) (PVA)/alginate hydrogen-bonded-ionic dual-physical double-network (DN) hydrogels have been successfully prepared by a facile route of a freeze–thaw (25–25–25 °C) cycle followed by concentrated (1.0 mol L⁻¹ of) aqueous-Ca²⁺ immersion of PVA/Na alginate (SA) mixed aqueous solutions. It was found that, at mole ratios of the PVA- to SA repeat units of 20/1 to 80/1, the DN gels likely evolved a semi-interpenetrating polymer network (IPN) morphology of rigid alginate networks dispersed in while interlocking with ductile PVA network to accomplish DN synergy that gave their high strength and toughness, where the high alginate rigidity originated probably from its dense cross-link induced syneresis and dispersion along crosslink-defective voids to result in little internal stress concentration. Tentatively mechanistically, as the 20/1–80/1 DN gels were stretched steadily, their mechanical response was gradually differentiated into distinct synergistic states: the sparsely hydrogen-bonded PVA served as a ductile matrix to bear small fractions of the established stresses at its large elongations; whereas the densely ionically (i.e. Ca²⁺) cross-linked alginate functioned as a rigid skeleton to sustain the remaining larger stresses upon its smaller local strains. Promisingly, this ductile-rigid matrix-skeleton synergistic mechanism of semi-IPN morphology may be universally extended to all A/B DN hydrogels of large A–B rigidity (or cross-link density) contrast, whether the cross-link nature of network(s) A or B is covalent, ionic, hydrogen bonded or van der Waals interacted. The strong and tough DN gels also displayed satisfactory self-recovery of viscoelastic behaviour, in that their Young''s modulus and dissipated energy in the uniaxial tensile mode and dynamic storage and loss moduli in the oscillatory shear mode all recovered significantly from non-linear viscoelastic regimes despite different degrees of failure to revert to (quasi)linear viscoelasticity.

Intermediate compositions enable synergised, strong-and-tough dual-physical double-network hydrogels of dispersion-induced rigid, ionic alginate-networks interlocking with global ductile, hydrogen-bonded poly(vinyl alcohol)-network.     

Design and performance of a poly(vinyl alcohol)/silk fibroin enzymatically crosslinked semi-interpenetrating hydrogel for a potential hydrophobic drug delivery

In this study, in order to obtain hydrogels with good properties for sustained release of hydrophobic drugs or for tissue engineering, poly(vinyl alcohol) (PVA)/silk fibroin (SF) semi-interpenetrating (semi-IPN) hydrogels with varied ratios of PVA/SF were enzymatically cross-linked using horseradish peroxidase. A vial inversion test determined approximate gelation times of PVA/SF hydrogels ranging from 5 to 10 min. The hydrogels with varied ratios showed differences in pore size and morphology. Mass loss rate of hydrogels increased from 15% to 58% with increasing PVA concentration. Stable hydrogels with PVA/SF at 0.5 : 1 w/w showed the best swelling ratio values in distilled water (7.36). FTIR analysis revealed that silk fibroin in these hydrogels exhibited the coexistence of amorphous and silk I crystalline structures and the SF and PVA molecules interacted with each other well. The mechanical properties of the composite hydrogels were controlled by the SF content. From the cell viability results, it was found that the hydrogels exerted very low cytotoxicity. Paeonol was chosen as the hydrophobic drug model for release studies from the hydrogels. Paeonol can be uniformly loaded into the composite hydrogels using the emulsifying property of PVA and paeonol release from the hydrogels was dependent on the PVA/SF ratio. This study applied a novel type of enzymatically crosslinked semi-IPN hydrogel that may have potential applications in drug delivery.

Enzymatically cross-linked PVA/SF semi-IPN hydrogels with tunable pore structure have potential applications in sustained release of hydrophobic drug.     

Synthesis of physically crosslinked PAM/CNT flakes nanocomposite hydrogel films via a destructive approach

Carbon nanotube (CNT)-based hydrogels have recently found a wide variety of applications due to the unique physical and chemical properties of CNTs. CNTs can be used as a nanofiller and/or crosslinker to produce nanocomposite hydrogels with good mechanical and structural properties. In this research, a novel method was reported for producing polyacrylamide (PAM)/oxidized-multiwalled carbon nanotube (O-MWCNT) flakes nanocomposite hydrogel films without using any organic cross-linker or surfactant. Through a mechanism dependent on the reactive oxygen species (ROS), some O-MWCNTs were broken down in situ into small flakes in the aqueous solutions containing acrylamide (AM) and sodium persulfate (NaPS) at the temperature range of 85–90 °C. Simultaneously, in situ polymerization of the AM monomers occurred using free radicals, which resulted in the formation of PAM chains. The flakes acted as crosslinkers by forming hydrogen bonds with PAM chains and formed a hydrogel network after 48 h at room temperature. The hydrogels were characterized by different techniques (FT-IR, Raman, FE-SEM, TEM, TGA, tensile test). The porous structure of the hydrogel films as well as micro-network structures with unique morphologies were observed by SEM. The O-MWCNT flakes and some undegraded O-MWCNTs in the hydrogel network were also observed by TEM. The results showed that PC₂I₂H hydrogel film, as an evolved hydrogel, has excellent swelling performance in aqueous solutions at different pH and temperatures. In addition, this hydrogel showed a tensile strength of 103 MPa in the dry state and an elongation of 703% in the swollen state.

Novel PAM/CNT flakes nanocomposite hydrogel films were synthesized by in situ degradation of the oxidized-MWCNTs into flakes using persulfate activation. The flakes crosslinked the PAM chains via hydrogen bonding to form a hydrogel network.     

Highly stretchable,self-healing and conductive silk fibroin-based double network gels via a sonication-induced and self-emulsifying green procedure

Regenerated silk fibroin (RSF)-based hydrogels are promising biomedical materials due to their biocompatibility and biodegradability. However, the weak mechanical properties and lack of functionality limit their practical applications. Here, we developed a tough and conductive RSF-based double network (DN) gel, consisting of a sonication-induced β-sheet physically crosslinked RSF/S gel as the first network and a hydrophobically associated polyacrylamide/stearyl methacrylate (PAAm/C18) gel as the second network. In particular, the cross-linking points of the second network were micelles formed by emulsifying the hydrophobic monomer (C18M) with a natural SF- capryl glucoside co-surfactant. The reversible dynamic bonds in the DN provided good self-healing ability and an effective dissipative energy mechanism for the DN hydrogel, while the addition of calcium ions improved the self-healing ability and electrical conductivity of the hydrogel. Under optimal conditions, the RSF/S-PAAm/C18 DN gels exhibited large extensibility (1400%), high tensile strength (0.3 MPa), satisfactory self-healing capability (90%) and electrical conductivity (0.12 S·m⁻¹). The full physically interacted DN hydrogels are expected to be applied in various fields such as tissue engineering, biosensors and artificial electronic skin.

Silk fibroin-based double network gels, which were synthesized by the free radical polymerization via sonication-induced and self-emulsifying green procedure, exhibited highly stretchable, good self-healing and satisfactory conductive.     

Effect of size of latex particles on the mechanical properties of hydrogels reinforced by latex particles

Herein, cationic latex particles (CL) of different particle sizes were introduced as a cross-linking center to enhance the mechanical properties of the hydrophobically-associated hydrogels (P(AAm-co-HMA)-CL). Firstly, cationic polymethylmethacrylate (PMMA) latex particles were synthesized via soap-free emulsion polymerization. Subsequently, P(AAm-co-HMA)-CL hydrogels with outstanding mechanical properties were prepared using acrylamide as the monomer, hexadecyl methacrylate as the hydrophobic molecule, and CL as the cross-linking center. The size of CL had a significant effect on the mechanical properties and self-recovery properties of the P(AAm-co-HMA)-CL hydrogels. The hydrogel with larger CL size exhibited low mechanical properties due to weak hydrophobic interactions. In contrast, the hydrogel with small CL size displayed excellent mechanical properties due to an effective entanglement of the hydrophobic chains with the smaller size CL, which significantly affects the mechanical properties of the hydrogel. As a result, the maximum fracture stress and fracture strain of the hydrogel were up to 1.47 MPa and 2847%, respectively. This study can have a profound impact on the development of the technology of toughening hydrogels with latex particles.

Herein, cationic latex particles (CL) of different particle sizes were introduced as a cross-linking center to enhance the mechanical properties of the hydrophobically-associated hydrogels (P(AAm-co-HMA)-CL).     

Supramolecular polymer/peptide hybrid hydrogels with tunable stiffness mediated by interchain acid-amide hydrogen bonds

Hydrogels are a class of biomaterials used in the field of tissue engineering and drug delivery. Many tissue engineering applications depend on the material properties of hydrogel scaffolds, such as mechanical stiffness, pore size, and interconnectivity. In this work, we describe the synthesis of peptide/polymer hybrid double-network (DN) hydrogels composed of supramolecular and covalent polymers. The DN hydrogels were prepared by combining the self-assembled pentafluorobenzyl diphenylalanyl aspartic acid (PFB-FFD) tripeptide for the first network and the polymeric PNIPAM-PEGDA copolymer for the second network. During this process, self-assembled peptide nanostructures are cross-linked to the polyacrylamide group in the polymer network through non-covalent interactions. The PNIPAM-PEGDA:PFB-FFD hydrogel exhibited higher mechanical stiffness (G′ ∼2 kPa) than the PNIPAM-PEGDA copolymer. Moreover, PNIPAM-PEGDA:PFB-FFD hydrogel shows a decrease in pore size (∼1.2 μm) compared to the original copolymer (∼5.2 μm), with the structural framework of highly interconnected fibrous peptide network. The mechanical stiffness of hydrogels was systematically investigated by rheological analysis in response to various variables, including UV exposure time, concentration of peptides, and amino acid functionalization. Modulating the time of UV irradiation resulted in PNIPAM-PEGDA:PFB-FFD hydrogels with a four-fold increase in stiffness. The influence of amino acid side chains and terminal charge of peptides on the strength of DN hydrogels was also investigated using pentafluorobenzyl diphenylalanyl lysine (PFB-FFK). Interestingly, PFB-FFK, which has an amine group on the side chain, does not exhibit the DN structures. The mechanical properties and pore sizes of PNIPAM-PEGDA:PFB-FFK hydrogel were very similar to those of the PNIPAM-PEGDA copolymer due to poor cross-linking. The biocompatibility of the hydrogel materials was tested with the hMSC cell line using the MTT method, and the results indicate that the materials are non-toxic and potentially useful for biological applications.

Adaptable, biocompatible hydrogels of peptide/polymer hybrid systems with double-network (DN) structures are developed with tunable mechanical stiffness.     

Polyacrylamide crosslinked by bis-vinylimidazolium bromide for high elastic and stable hydrogels

A series of ionic compounds 1,n-dialkyl-3,3′-bis-l-vinylimidazolium bromide (C_nVIM) are prepared and employed to crosslink acrylamide for polyacrylamide (PAAM) hydrogel preparation via in situ solution polymerization. The swelling behavior, mechanical properties and thermal stability of the prepared C_nVIM crosslinked PAAM hydrogels are investigated. C_nVIM effectively crosslink the PAAM networks to form porous structures in the hydrogel, which could stably absorb water as much as 75.9 fold in weight without structural degradation. The prepared hydrogels could endure compressive stress up to 1.95 MPa and compressive deformation more than 90%. Meanwhile, the C_nVIM crosslinked networks show superior thermal stability, and could retain the structural integrity under 150 °C for more than 240 h. The swelling degradation resistance, mechanical strength and thermal stability of C_nVIM crosslinked hydrogels are much better than those of a conventional N,N′-methylenebisacrylamide crosslinked PAAM hydrogel. Using bis-vinylimidazolium bromides as crosslinkers provides an optional strategy for constructing thermally and mechanically robust hydrogel networks.

Polyacrylamide hydrogels crosslinked by bis-vinylimidazolium bromides achieved robust mechanical stability under various conditions, such as equilibrium swelling, compression and high temperatures.     

Triple network hydrogels (TN gels) prepared by a one-pot,two-step method with high mechanical properties

In this work, poly(vinyl alcohol) (PVA) was incorporated into the networks of polyacrylamide/polyacrylic acid (PAM/PAA) to prepare novel PAM/PAA/PVA Triple-network (TN) hydrogels by an in situ polymerization and repeated freezing–thawing (F–T) process. The TN hydrogels have not only high mechanical strength, but also a moderate swelling ability by varying the weight ratio of calcium chloride (CaCl₂) and PVA and free shaping. The compressive stress of the as-prepared hydrogels could reach 11 MPa, and the highest stretching stress could reach 0.8 MPa. Upon mechanical loading, the coordination network between PAA and CaCl₂ served as sacrificial bonds to efficiently dissipate energy. However, they can reform when the mechanical load is released, resulting from the fast coordination between PAA and Ca²⁺. Therefore, TN hydrogels have potential application in biomaterials.

TN hydrogels with high mechanical properties are prepared and they have potential application in biomaterials.     

Fabrication of stable superabsorbent hydrogels for successful removal of crystal violet from waste water

Smart superabsorbent hydrogels consisting of acrylamide/sodium alginate (AS), acrylamide/sodium alginate/2-acrylamido-2-methylpropane sulphonic acid (ASA_x, x = amount of AMPS) were synthesized via free radical polymerization. The swelling behavior of the hydrogels was studied in distilled and tap water. It was found that by increasing the amount of 2-acrylamido-2-methylpropanesulphonic (AMPS) in the hydrogel composition, the hydrogel swelling capability was enhanced from 3685% for AS to 4797% for ASA₁ and 21 175% for ASA₂ in distilled water, while in tap water this property varied from 915% for AS to 988% and 1588% for ASA₁ and ASA₂, respectively. All the samples were found to be efficient for the removal of crystal violet from aqueous solution. The absorption efficiency and % removal increased from 1.78 mg g⁻¹ and 62.6% for AS to 3.31 mg g⁻¹ and 75% for ASA₁ and 3.34 mg g⁻¹ and 82.1% for ASA₂. The effects of pH, contact time, initial dye concentration and hydrogel dosage on the removal process were studied in detail. The mechanism of CV removal occurs according to the Freundlich isotherm following pseudo second order kinetics. The thermodynamic parameters showed that the sorption process is spontaneous and endothermic in nature. The superabsorbent hydrogels were regenerated and reused in six consecutive cycles with 5% decrease in efficiency.

Smart superabsorbent hydrogels consisting of acrylamide/sodium alginate (AS), acrylamide/sodium alginate/2-acrylamido-2-methylpropane sulphonic acid (ASA_x, x = amount of AMPS) were synthesized via free radical polymerization.     

Effects of amphiphilic monomers and their hydrophilic spacers on polyacrylamide hydrogels

Hydrogels based on physical interactions have been extensively studied due to their special network structure and excellent mechanical properties. In this paper, a series of hydrogels based on hydrophobic interactions were prepared via the free-radical copolymerization of acrylamide and polymerizable amphiphilic monomers dodecanol polyoxyethylene (n) acrylates (AEO-n-AC, n = 3, 7, 9, 15, 23) by a simple and facile method. The prepared single-network hydrogels cross-linked by the self-assemble AEO-n-AC micelles acting as cross-linkers exhibited great tensile strength of 0.45 MPa and excellent compression strength of 4.5 MPa. Transmission electron microscopy tests reflected that the morphologies of the self-associated micelles were determined by the hydrophilic segment of the amphiphilic monomers, which further affected the mechanical properties of the hydrogel. Amphiphilic monomer with appropriate length of hydrophilic spacers could significantly enhance the tensile strength of the hydrogel. Meanwhile, amphiphilic monomers with long hydrophilic segment were advantageous for the compression properties of the hydrogel. Furthermore, the hydrogels exhibited excellent micro self-repair ability during the cycling tensile and loading-unloading test even at the strain and compression were 400%, 0.95, respectively. This discover of hydrophilic spacer effect is of great significance for the design of physical interaction-based hydrogels with high strength and compression properties.

HA-gels with different hydrophilic spacers were synthesized. These hydrophilic spacers endow the gel with good tensile properties, excellent compression properties and self-recovery. We believe it is a meaningful discovery.     

Thermosensitive alginate–gelatin–nitrogen-doped carbon dots scaffolds as potential injectable hydrogels for cartilage tissue engineering applications

Hybrid injectable and biodegradable hydrogels based on oxidized alginate/gelatin and containing nitrogen-doped carbon dots (NCDs) as a reinforcement have been fabricated and crosslinked by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)/N-hydroxysuccinimide (NHS) as the chemical crosslinking agents in the hydrogel system. The idea of composite hydrogels relies on the assumption that they supply a microenvironment that is convenient for the exchange of nutrients via a porous structure and cell proliferation and have mechanical characteristics that approximately match natural tissue. The effect of the NCD content on the morphology structure, mechanical strength, swelling ratio, and biodegradation has been investigated. The results indicate that nanocomposite hydrogels containing a higher content of NCDs have smaller pore sizes and higher mechanical properties. The in vitro biodegradation and swelling behavior demonstrated that increasing the amount of NCDs up to 0.06% decreased the swelling ratio and weight loss of the hydrogels. The composite hydrogels are biocompatible, as verified by the MTT assay of MG-63 cells. The N-doped graphene quantum dots considerably affect degradation and interaction within the cells and hydrogels.

The low gelation time (120 s) and gelation temperature at body temperature (37 °C) make oxidized alginate/gelatin/NCDs hydrogels suitable as temperature-sensitive injectable hydrogels for cartilage tissue engineering.     

Bi-functional silica nanoparticles for simultaneous enhancement of mechanical strength and swelling capacity of hydrogels

A combination of strong load-bearing capacity and high swelling degree is desired in hydrogels for many applications including drug delivery, tissue engineering, and biomedical engineering. However, a compromising relationship exists between these two most important characteristics of hydrogels. Improving both of these important properties simultaneously in a single hydrogel material is still beyond the satisfactory limit. Herein, we report a novel approach to address this problem by introducing a silica-based bi-functional 3D crosslinker. Our bi-functional silica nanoparticles (BF-Si NPs) possess amine groups that are able to offer pseudo-crosslinking effects induced by inter-cohesive bonding, and acrylate groups that can form conventional covalent crosslinking in the same hydrogel. We fabricated polyacrylic acid (PAc-Si) and polyacrylamide (PAm-Si) hydrogels using our BF-Si NPs via free radical polymerization to demonstrate this concept. Incorporation of the BF-Si crosslinkers into the hydrogels has resulted in a large enhancement in the mechanical properties compared to conventional hydrogel crosslinked with N,N′-methylene bisacrylamide (MBA). For instance, tensile strength and the toughness increased by more than 6 times and 10 times, respectively, upon replacing MBA with BF-Si in polyacrylamide hydrogel. Moreover, the hydrogels crosslinked with BF-Si exhibited a remarkably elevated level of swelling capacity in the aqueous medium. Our facile yet smart strategy of employing the 3D bi-functional crosslinker for combining high swelling degree and strong mechanical properties in the same hydrogels can be extended to the fabrication of many similar acrylate or vinyl polymer hydrogels.

Bi-functional silica crosslinkers simultaneously enhance the mechanical strength and swelling capacity of the polyacrylic acid and polyacrylamide hydrogels.     

Poly(N,N-dimethylacrylamide-octadecyl acrylate)-clay hydrogels with high mechanical properties and shape memory ability

As a type of important intelligent materials, shape memory hydrogels (SMHs) have gathered a lot of interest due to their promising applications. However, preparing SMHs with excellent mechanical properties still remains a big challenge. In this study, a new type of SMHs with excellent mechanical strength is created. The SMHs were prepared by free radical micellar polymerization of hydrophobic monomer (octadecyl acrylate) with gelatin as emulsifier in a aqueous system containing hydrophilic monomer (N,N-dimethylacrylamide, DMA) and clay as reinforcing filler. The polymerization provided physically cross-linked network structures constructed by two non-covalent interactions, i.e. hydrophobic association formed by monomer units and multiple H-bonds among inorganic clay, gelatin and DMA. A judicious combination of the two physically cross-linked networks significantly improved the mechanical strength of hydrogels. More interestingly, the hydrogels demonstrated shape memory behavior due to the hydrophobic poly(octadecyl acrylate) domains. The novel SMHs are expected to find practical applications as biomaterials.

As a type of important intelligent materials, shape memory hydrogels (SMHs) have gathered a lot of interest due to their promising applications.     

A novel pH-sensitive hydrogel composed of N,O-carboxymethyl chitosan and alginate cross-linked by genipin for protein drug delivery.

A novel pH-sensitive hydrogel system composed of a water-soluble chitosan derivative (N,O-carboxymethyl chitosan, NOCC) and alginate blended with genipin was developed for controlling protein drug delivery. Genipin, a naturally occurring cross-linking agent, is significantly less cytotoxic than glutaraldehyde and may provide a less extent of cross-linking to form a semiinterpenetrating polymeric network (semi-IPN) within the developed hydrogel system. The drug-loading process used in the study was simple and mild. All procedures used were performed in aqueous medium at neutral environment. In the study, preparation of the NOCC/alginate-based hydrogels was reported. Swelling characteristics of these hydrogels as a function of pH values were investigated. Additionally, release profiles of a model protein drug (bovine serum albumin, BSA) from test hydrogels were studied in simulated gastric and intestinal media. The semi-IPN formation of the genipin-cross-linked NOCC/alginate hydrogel was confirmed by means of the scanning electron microscopy-energy dispersive X-ray spectrometer (SEM-EDS) and the ninhydrin assays. The percentage of decrease of free amino groups and cross-linking density for the NOCC/alginate hydrogel cross-linked with 0.75 mM genipin were 18% and 26 mol/m(3), respectively. At pH 1.2, the swelling ratio of the genipin-cross-linked NOCC/alginate hydrogel was limited (2.5) due to formation of hydrogen bonds between NOCC and alginate. At pH 7.4, the carboxylic acid groups on the genipin-cross-linked NOCC/alginate hydrogel became progressively ionized. In this case, the hydrogel swelled more significantly (6.5) due to a large swelling force created by the electrostatic repulsion between the ionized acid groups. The amount of BSA released at pH 1.2 was relatively low (20%), while that released at pH 7.4 increased significantly (80%). The results clearly suggested that the genipin-cross-linked NOCC/alginate hydrogel could be a suitable polymeric carrier for site-specific protein drug delivery in the intestine.     

Transformation of theranostic alginate-based microbubbles from raspberry-like to core–shell-like microbubbles and in vitro studies

In this study alginate-based microbubbles with a raspberry-like or core–shell-like morphology and with an average particle size of 553.6 ± 69.6 μm were synthesized; this was done through a novel procedure of transforming the structure with a 40 kHz ultrasonication which also stimulated the release of the components inside. Through the use of the electrospray technique in conjunction with agitation processes, components such as shikonin (SHK) and indocyanine green (ICG) were simultaneously encapsulated in alginate microbubbles to produce SHK–ICG alginate microbubbles; these microbubbles had half-maximal inhibitory concentrations of approximately 2.08 and 4.43 μM toward CP70 and SKOV3 ovarian cancer-cell lines, respectively, in an in vitro cell model. Moreover, these SHK–ICG alginate microbubbles enhanced brightness by 2.5 fold in ultrasound imaging relative to CaCl₂ medium only. In conclusion, SHK–ICG alginate microbubbles have promise for use in theranostics.

In this study alginate-based microbubbles with a raspberry-like or core–shell-like morphology and with an average particle size of 553.6 ± 69.6 μm were synthesized; this was done through a transformation of the structure with applying a 40 kHz ultrasonication.     

Synthesis of nanomedicine hydrogel microcapsules by droplet microfluidic process and their pH and temperature dependent release

Chitosan and alginate hydrogels are attractive because they are highly biocompatible and suitable for developing nanomedicine microcapsules. Here we fabricated a polydimethylsiloxane-based droplet microfluidic reactor to synthesize nanomedicine hydrogel microcapsules using Au@CoFeB–Rg3 as a nanomedicine model and a mixture of sodium alginate and PEG-g-chitosan crosslinked by genipin as a hydrogel model. The release kinetics of nanomedicines from the hydrogel were evaluated by simulating the pH and temperature of the digestive tract during drug transport and those of the target pathological cell microenvironment. Their pH and temperature-dependent release kinetics were studied by measuring the mass loss of small pieces of thin films formed by the nanomedicine-encapsulating hydrogels in buffers of pH 1.2, 7.4, and 5.5, which replicate the pH of the stomach, gut and blood, and cancer microenvironment, respectively, at 20 °C and 37 °C, corresponding to the storage temperature of hydrogels before use and normal body temperature. Interestingly, nanomedicine-encapsulating hydrogels can undergo rapid decomposition at pH 5.5 and are relatively stable at pH 7.4 at 37 °C, which are desirable qualities for drug delivery, controlled release, and residue elimination after achieving target effects. These results indicate that the designed nanomedicine hydrogel microcapsule system is suitable for oral administration.

A kind of pH and temperature dependent interpenetrating hydrogel was designed and synthesized via crosslinking of alginate and polyethylene-glycol grafting chitosan by genipin for encapsulated nanomedicine with controlled release.     

Graphene oxide based crosslinker for simultaneous enhancement of mechanical toughness and self-healing capability of conventional hydrogels

Extraordinary self-healing efficiency is rarely observed in mechanically strong hydrogels, which often limits the applications of hydrogels in biomedical engineering. We have presented an approach to utilize a special type of graphene oxide-based crosslinker (GOBC) for the simultaneous improvement of toughness and self-healing properties of conventional hydrogels. The GOBC has been prepared from graphene oxide (GO) by surface oxidation and further introduction of vinyl groups. It has been designed in such a way that the crosslinker is able to form both covalent bonds and noncovalent interactions with the polymer chains of hydrogels. To demonstrate the efficacy of GOBC, it was incorporated in a conventional polyacrylamide (PAM) and polyacrylic acid (PAA) hydrogel matrix, and the mechanical and self-healing properties of the prepared hydrogels were investigated. In PAM-GOBC hydrogels, it has been observed that the mechanical properties such as tensile strength, Young''s modulus, and toughness are significantly improved by the incorporation of GOBC without compromising the self-healing efficiency. The PAM-GOBC hydrogel with a modulus of about 0.446 MPa exhibited about 70% stress healing efficiency after 40 h. Whereas, under the same conditions a PAM hydrogel with commonly used crosslinker N,N′-methylene-bis(acrylamide) of approximately the same modulus demonstrated no self-healing at all. Similar improvement of self-healing properties and toughness in PAA-GOBC hydrogel has also been observed which demonstrated the universality of the crosslinker. This crosslinker-based approach to improve the self-healing properties is expected to offer the possibility of the application of commonly used hydrogels in many different sectors, particularly in developing artificial tissues.

Introduction of a two-dimensional graphene oxide-based crosslinker simultaneously improve the mechanical and self-healing properties of hydrogels by offering an interesting combination of covalent and reversible hydrogen bonds to polymer backbones.     

Self-assembled functional components-doped conductive polypyrrole composite hydrogels with enhanced electrochemical performances

A conductive hydrogel is a composite conductive material formed by combining a conductive polymer with a nanogel structure of a hydrogel. Conductive hydrogels not only have potential applications in supercapacitors, sensors, and modulators, they can also be synthesized by many methods, such as copolymerization, crosslinking, and grafting. In this work, we successfully prepared three conductive composite hydrogels by in situ polymerization, namely polypyrrole sodium alginate conductive hydrogel, ferric chloride-doped polypyrrole sodium alginate hydrogel and doped polypyrrole sodium alginate hydrogel with sodium dodecylbenzene sulfonate. In addition, a series of characterizations were performed for the three conductive hydrogels described above. The results show that the polypyrrole sodium alginate hydrogel doped with ferric chloride forms a nanofiber network with a more stable structure and better electrochemical performance.

New functional components-doped conductive polypyrrole composite hydrogels are prepared via a self-assembled process, demonstrating potential applications in catalysis as well as electrochemical materials.