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Surface wrinkling structures based on a bilayer system are widely employed in storing and encrypting specific optical information. However, constructing a stable wrinkling structure with high-level security remains an extensive challenge due to the delamination issue between the skin layer and the substrate. Herein, a double cross-linking strategy is introduced between a hydrogel layer doped with fluorescent molecules and polydimethylsiloxane to establish a stable interfacial wrinkling structure with dual-mode functionality, in which the light reflection of the wrinkles and fluorescence intensity of fluorescent molecules can be simultaneously regulated by the modulus ratio between the two layers. The spontaneous wrinkling structures with a physically unclonable function can enhance the photoluminescence emission intensity of the wrinkling area under ultraviolet radiation. Meanwhile, the skin layer constructed of acrylamide and acrylic acid copolymer protects the interfacial wrinkling patterns from the loss of a detailed structure for authentication due to external damage. The stable interfacial wrinkling structures with fluorescence can find potential applications in the fields of information storage and encryption.

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In recent years, crosslinking technology has been found and widely used in food, textile, pharmaceutical, bioengineering and other fields. Crosslinking is a reaction in which two or more molecules bond to each other to form a stable three-dimensional network structure to improve the strength, heat resistance and other properties of substances. The researchers found that the cross-linking technology has a significant effect on improving the thermal stability of the colloidal delivery system. In this paper, crosslinking techniques that can be used to improve the thermal stability of colloidal delivery systems are reviewed, including enzyme-, ion-, chemical-, and combined cross-linking. Initially, the underlying mechanisms of these crosslinking technologies is reviewed. Then, the impacts of crosslinking on the heat-stability of colloidal delivery systems are discussed. Finally, the application of crosslinked delivery systems in improving the thermal stability of probiotics, polyphenols, pigments, and nutrients in foods and food packaging materials is introduced. The ability of proteins and polysaccharides to form heat-stable colloidal delivery systems can be improved by crosslinking. Nevertheless, more research is required to establish the impact of different crosslinking on the thermal stability of a broader range of different delivery systems, as well as to ensure their safety and efficacy.

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Hydrogel systems with strong fluorescence, as convenient tracers or bio-probes, have attracted much attention in biomedical engineering. Currently, most hydrogels endowed fluorescent properties due to modifying additional fluorophores. However, these fluorophores owing to photobleaching and toxicity limit the practical applications of hydrogels. Herein, we prepared a novel self-luminescence hydrogel through double crosslinking glutaraldehyde and hydrogen peroxide/horseradish peroxidase (H2O2/HRP) with sericin protein. The double cross-linked sericin hydrogel exhibits strong green and red intrinsic fluorescence which can be excited over a wide range of wavelengths. Moreover, this hydrogel with strong intrinsic fluorescence could penetrate thick pigskin tissue, which has potential application in implantable bio-tracer areas. In addition to the above unique properties, this sericin hydrogel possesses two types of micropore structures with high porosity, swelling properties, pH-responsive degradability, super elasticity, injectability, viscosity, and excellent biocompatibility. The investigation could significantly expand the scope of protein hydrogels in biomedical applications.

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The increasing number of petroleum-based plastics has caused severe environmental pollution, which has attracted great research interest in the development of low-cost, renewable, and degradable starch-based bioplastics. However, developing starch-based bioplastics with robust mechanical strength, excellent water resistance, and thermal resistance remains a great challenge. In this study, we presented a simple and efficient method for preparing high-performance novel starch-based bioplastics with chemical and physical double crosslinking network structures filled with 2,2,6,6-tetramethylpiperidine 1-oxy-oxidized cellulose nanofibers and zinc oxide nanoparticles. Compared with pure starch-based bioplastics, the tensile strength of the novel robust strength starch-based bioplastics increased by 431.2 %. The novel starch-based bioplastics exhibited excellent mechanical properties (tensile strength up to 24.54 MPa), water resistance, thermal resistance, and biodegradability. In addition, the novel starch-based bioplastics could be reused, crushed, dissolved, and re-poured after use. After recycling, the novel starch-based bioplastics could be discarded in the soil to achieve complete degradation within six weeks. Owing to these characteristics, the novel starch-based bioplastics are good alternatives used to replace traditional petroleum-based plastics and have great development prospects.

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Stimulus-responsive hydrogels have been widely used in the field of drug delivery because of their three-dimensional pore size and the ability to change the drug release rate with the change in external environment. In this paper, the temperature-sensitive monomer 2-methyl-2-acrylate-2-(2-methoxyethoxy-ethyl) ethyl ester (MEO2MA) and oligoethylene glycol methyl ether methacrylate (OEGMA) as well as the pH-sensitive monomer N,N-Diethylaminoethyl methacrylate (DEAEMA) were used to make the gel with temperature and pH response. Four kinds of physicochemical double-crosslinked amphiphilic co-network gels with different polymerization degrees were prepared by the one-pot method using the stereocomplex between polylactic acid as physical crosslinking and click chemistry as chemical crosslinking. By testing morphology, swelling, thermal stability and mechanical properties, the properties of the four hydrogels were compared. Finally, the drug release rate of the four gels was tested by UV-Vis spectrophotometer. It was found that the synthetic hydrogels had a good drug release rate and targeting, and had great application prospect in drug delivery.

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The increasing accumulation of plastic waste has brought serious environmental issues. Biodegradable plastics are promising candidates to solve the problem but still remain a scientific challenge. Here, xylan plastic (XP) was fabricated by a strategy of double cross-linking through etherification combined with hot pressing. The mechanical properties, particularly the toughness of XP, were significantly enhanced by the incorporation of chemical and physical cross-linking domains. The tensile strength, toughness, and modulus of XP can reach up to 55 MPa, 2.2 MJ/m3, and 1.7 GPa, respectively, which are superior to most traditional plastics. Dynamic mechanical analysis (DMA) characterizations confirmed that XP is thermoplastic and can be hot formed. Additionally, the reversible hydrogen bond interaction between xylan chains could be simply regulated by water molecules, rendering XP readily transformed and repeatedly reprogrammed into versatile 2D/3D shapes. Moreover, XP showed a low thermal expansion coefficient and excellent optical properties. Cytotoxicity and degradability tests demonstrated that XP had excellent nontoxicity and can be biodegraded in 60 days. This work thus suggests an avenue for the scalable production of high-performance xylan-based plastics, in which the raw material comes from industrial wastes and exhibits great potential in response to plastic pollution.

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An ideal wound dressing should have excellent antimicrobial properties and provide a suitable microenvironment for regenerating damaged skin tissue. In this study, we utilized sericin to biosynthesize silver nanoparticles in situ and introduced curcumin to obtain Sericin-AgNPs/Curcumin (Se-Ag/Cur) antimicrobial agent. The hybrid antimicrobial agent was then encapsulated in a physically double cross-linking 3D structure network (Sodium alginate-Chitosan, SC) to obtain the SC/Se-Ag/Cur composite sponge. The 3D structural networks were constructed through electrostatic interactions between sodium alginate and chitosan and ionic interactions between sodium alginate and calcium ions. The prepared composite sponges have excellent hygroscopicity (contact angle 51.3° ± 5.6°), moisture retention ability, porosity (67.32 % ± 3.37 %), and mechanical properties (>0.7 MPa) and exhibit good antibacterial ability against Pseudomonas aeruginosa (P. aeruginosa) and Staphylococcus aureus (S. aureus). In addition, in vivo experiments have shown that the composite sponge promotes epithelial regeneration and collagen deposition in wounds infected with S. aureus or P. aeruginosa. Tissue immunofluorescence staining analysis confirmed that the SC/Se-Ag/Cur complex sponge stimulated upregulated expression of CD31 to promote angiogenesis while downregulating TNF-α expression to reduce inflammation. These advantages make it an ideal candidate for infectious wound repair materials, providing an effective repair strategy for clinical skin trauma infections.

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Flexible hydrogels have emerged as highly-desirable materials for wearable strain sensors. However, pristine biomass hydrogel systems are limited by their lack of stretchability, self-adhesion, and sensitivity. Here, a novel CA/MWCNT/PAAm double-network conductive hydrogel was developed through integrating casein (CA) micelles and multi-walled carbon nanotubes (MWCNT) into the polyacrylamide (PAAm) network. The resulting hydrogel displayed desired properties such as adhesiveness, toughness, self-healing, and near-infrared photothermal response. In this hybrid system, MWCNT were uniformly dispersed in the presence of casein micelles through hydrogen bonding and electrostatic interactions, favoring its role of nano reinforcement. Moreover, based on the "casein micelle-nanoparticle double cross-linking" mechanism and its double network structure, the prepared hydrogel showed high extensibility (2288 % ± 63 %), fast responsiveness (273 ± 5.13 ms), high sensitivity (GF = 12.46 ± 0.35), and a wide strain range (1-1000 %). Through consistent and repeated electrical inputs, this hydrogel was able to detect including large and small human movements, such as hand, leg, and swallowing motions. The results from this study provide a new way to fabricate bio-based hydrogel sensors with excellent mechanical and electrical properties.

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This study was carried out to develop soy protein isolate (SPI)/sodium carboxymethyl cellulose (NaCMC) synbiotic microgels by applying a double-crosslinking technique using transglutaminase and different concentrations of AlCl3 (0 %, 6 %, 7 %, 8 %) and also by adding Lactobacillus acidophilus (L. acidophilus) and pectic oligosaccharide. Synbiotic microgels crosslinked using 8 % AlCl3 (SPI/NaCMC-Al3+8 microgels) showed the highest encapsulation efficiency (92 %). The double-crosslinked microgels exhibited a smooth surface as proved by SEM. FT-IR, XRD, and DSC analyses showed the possible interaction within matrices and demonstrated the higher thermal stability of synbiotic microgels prepared using a higher concentration of AlCl3. All in all, after exposure to simulated digestion fluid, heat treatment (72 °C, 15 s), and refrigerated storage, more cells in double-crosslinked microgels survived compared to single-crosslinked microgels. In particular, probiotic viability was highest in SPI/NaCMC-Al3+8 microgels. These results indicate that the SPI/NaCMC-Al3+8 microgels developed in this study can effectively protect L. acidophilus against the external environment.

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The aim of this study was to develop ι-carrageenan (ιC)/sodium caseinate (NaCas) synbiotic microgels loading Lacticasebacillus paracasei produced by double-crosslinking with calcium ions and different concentrations (0, 5, 10, and 15 U/g protein) of transglutaminase (TGase). The synbiotic microgels were coated/filled with pectic oligosaccharide (POS). Field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD) analyses indicated that L. paracasei was successfully microencapsulated in synbiotic microgels. In Fourier transform infrared (FT-IR) analysis, the new formation of covalent and ionic crosslinking was observed in double-crosslinked synbiotic microgels. The encapsulation efficiency of L. paracasei was significantly increased from 87.82 to 97.68 % by increasing the concentration of TGase from 0 to 15 U/g protein, respectively. After exposure to simulated gastric fluid for 2 h and simulated intestinal fluid for 4 h, the survival rate of L. paracasei was significantly increased as the concentration of TGase increased.

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Normally, hydrogel electrolytes widely used in flexible energy storage devices have limited tolerance to different pHs. Most gel electrolytes will lose their compressible capability when the adaptable pH is changed. Herein, a poly(acrylamide3 -co-(sulfobetaine methacrylate)1 )@polyacrylamide (P(A3 -co-S1 )@PAM) hydrogel electrolyte equipped with a dual crosslinking network (DN) is successfully fabricated, which exhibits excellent tolerance to any pHs, endowing various energy storage devices including batteries and supercapacitors with superior mechanical durability. The batteries with mild and alkaline P(A3 -co-S1 )@PAM electrolytes display superior stability (over 3000 cycles). Additionally, a Zn||MnO2 battery based on the P(A3 -co-S1 )@PAM hydrogel electrolyte (mild) under 50% compression strain also shows excellent charge-discharge stability and high capacity at 152.4 mAh g-1 after 600 cycles. The strong reversible hydrogen bonds and electrostatic forces originating from zwitterionic structures of poly(sulfobetaine methacrylate) play an important role in dissipating and dispersing energy imposed abruptly. Meanwhile, the zwitterionic structure and intermolecular NH⋯OC hydrogen bonds of the hydrogel lead to the property of acid resistance and alkali resistance. The tough and robust covalent crosslinking bonds and the tight arrangement of DN polymer chains enable the hydrogel electrolytes to recover their initial shape fast once unloading.

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Nowadays, the Magnetically Targeted Drug Delivery System (MTDDS) is among the most attractive and promising strategies for delivering drugs to the target site. The present study aimed to obtain a biopolymer-magnetite-drug nanosystem via a double crosslinking (ionic and covalent) technique in reverse emulsion, which ensures the mechanical stability of the polymer support in the form of original hybrid nanospheres (NSMs) loaded with biologically active principles (the 5-Fluorouracil (5-FU)) as a potential treatment for cancer. Obtained NSMs were characterized in terms of structure (FT-IR), size (DLS), morphology (SEM), swelling, and 5-FU entrapment/release properties, which were dependent on the synthesis parameters (polymer concentration, dispersion speed, and amount of ionic crosslinking agent). SEM analysis results revealed that NSMs presented a spherical shape and are homogeneous and separated. Moreover, NSMs' ability to load/release 5-FU was tested in vitro, the results confirming, as expected, their dependence on the varied synthesis process and NSM swelling ability in physiological liquids. The drug transport mechanism through the polymer matrix of its release is the Fickian type. The morphological, bio-material characteristics and the ability to include and release an antitumor drug highlight the utility of the NSMs obtained for targeting and treating some tumor diseases.

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Chitosan (CS) crosslinking has been thoroughly investigated, but the chemical reactions leading to submicronic hydrogel formulations pose problems due to various physical/chemical interactions that limit chitosan processability. The current study employs the chemical modification of chitosan by Michael addition of poly (ethylene glycol) methyl ether acrylate (PEGA) to the amine groups to further prepare chitosan particulate hydrogels (CPH). Thus, modified CS is subjected to a double crosslinking, ionic and covalent, in water/oil emulsion. The studied process parameters are polymer concentration, stirring speed, and quantity of ionic crosslinker. The CPH were structurally and morphologically characterized through infrared spectroscopy, scanning electron microscopy, light scattering granulometry, and zeta potential, showing that modified CS allows better control of dimensional properties and morphology as compared with neat CS. Swelling properties were studied in acidic and neutral pH conditions, showing that pH-dependent behavior was maintained after grafting and double crosslinking. The applicability of the prepared materials was further tested for drug loading and in vitro delivery of levofloxacin (LEV), showing excellent capacity. CPH were found to be cyto- and hemocompatible demonstrating their potential for effective use as a controlled release system for different biomedical applications.

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Antibacterial hydrogels, particularly antibiotic-loaded hydrogels, are promising wound dressing materials for treatment of bacteria-infected wound. However, it is challenging to achieve sustained release of antibiotics from hydrogels through physical encapsulation of the antibiotics. Herein, an interpenetrating polymer network P(AA-co-HEMA)Gen hydrogel is reported with double crosslinking formed by free radical polymerization of 2-hydroxyethyl methacrylate (HEMA) and acrylic acid (AA), while using the antibiotic gentamicin (Gen) as the dynamic physical crosslinker. Gentamicin is incorporated into the hydrogel networks via electrostatic interaction between the carboxyl groups of poly(acrylic acid) and the amino groups of gentamicin, which leads to pH-responsive drug release and a significant increase in mechanical strength (i.e., elastic modulus, viscous modulus, and compressive modulus). More importantly, the hydrogels with optimal compositions demonstrate long-lasting antibacterial activity against both Gram-positive bacteria (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli) over 28 d. The in vivo studies that are conducted in an S. aureus-infected full-thickness skin wound model demonstrate that the double crosslinking hydrogels loaded with gentamicin eliminate bacteria in the wounds more effectively and significantly accelerate wound healing as compared to 3M dressing and the control without any treatment. Taken together, this antibiotic-loaded interpenetrating polymer network hydrogel is potentially a promising wound dressing material for the treatment of bacteria-infected wound.

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Ion-exchange membranes (IEMs) are a core component that greatly affects the performance of electrochemical energy conversion processes such as reverse electrodialysis (RED) and all-vanadium redox flow battery (VRFB). The IEMs used in electrochemical energy conversion processes require low mass transfer resistance, high permselectivity, excellent durability, and also need to be inexpensive to manufacture. Therefore, in this study, thin-reinforced anion-exchange membranes with excellent physical and chemical stabilities were developed by filling a polyethylene porous substrate with functional monomers, and through in situ polymerization and post-treatments. In particular, the thin-reinforced membranes were made to have a high ion-exchange capacity and a limited degree of swelling at the same time through a double cross-linking reaction. The prepared membranes were shown to possess both strong tensile strength (>120 MPa) and low electrical resistance (<1 Ohm cm2). As a result of applying them to RED and VRFB, the performances were shown to be superior to those of the commercial membrane (AMX, Astom Corp., Japan) in the optimal composition. In addition, the prepared membranes were found to have high oxidation stability, enough for practical applications.

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Lycopene is claimed to have numerous physiological benefits, but its poor water solubility, chemical instability, and low bioavailability limit its application in functional foods and health care products. In this study, lycopene-loaded emulsions containing oil droplets with different interfacial structures were prepared and then cross-linked using transglutaminase (TG) and/or calcium ions (Ca2+) to form emulsion gels. The oil droplets were first coated by interfacial layers comprised of whey protein isolate (WPI) and sodium alginate (SA). During emulsion preparation, the SA was added either before or after homogenization to create complex or layer-by-layer coatings, respectively. Subsequently, TG and Ca2+ were used to cross-link WPI and SA to form emulsion gels. The results show that double-crosslinking increased the gel strength and viscosity of the emulsion gels. The layer-by-layer emulsion gels were stronger and more viscous than the complex ones. The photochemical and gastrointestinal stability of lycopene encapsulated within the emulsion gels was higher than that of free lycopene. An MTT toxicity test showed that the emulsion gels exhibited no cytotoxicity to Caco-2 cells. The lycopene-loaded emulsion gels exhibited stronger anti-inflammatory activity on the Caco-2 cells than the control. In addition, the absorption of lycopene by the Caco-2 cells increased after encapsulation. This study provides a new approach of preparing edible soft materials to enhance the application of hydrophobic bioactives (like lycopene) in functional foods.

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Collagen scaffolds, one of the most used biomaterials in corneal tissue engineering, are frequently crosslinked to improve mechanical properties, enzyme tolerance, and thermal stability. Crosslinkers such as 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) are compatible with tissues but provide low crosslinking density and reduced mechanical properties. Conversely, crosslinkers such as glutaraldehyde (GTA) can generate mechanically more robust scaffolds; however, they can also induce greater toxicity. Herein, we evaluated the effectivity of double-crosslinking with both EDC and GTA together with the capability of sodium metabisulfite (SM) and sodium borohydride (SB) to neutralize the toxicity and restore biocompatibility after crosslinking. The EDC-crosslinked collagen scaffolds were treated with different concentrations of GTA. To neutralize the free unreacted aldehyde groups, scaffolds were treated with SM or SB. The chemistry involved in these reactions together with the mechanical and functional properties of the collagen scaffolds was evaluated. The viability of the cells grown on the scaffolds was studied using different corneal cell types. The effect of each type of scaffold treatment on human monocyte differentiation was evaluated. One-way ANOVA was used for statistical analysis. The addition of GTA as a double-crosslinking agent significantly improved the mechanical properties and enzymatic stability of the EDC crosslinked collagen scaffold. GTA decreased cell biocompatibility but this effect was reversed by treatment with SB or SM. These agents did not affect the mechanical properties, enzymatic stability, or transparency of the double-crosslinked scaffold. Contact of monocytes with the different scaffolds did not trigger their differentiation into activated macrophages. Our results demonstrate that GTA improves the mechanical properties of EDC crosslinked scaffolds in a dose-dependent manner, and that subsequent treatment with SB or SM partially restores biocompatibility. This novel manufacturing approach would facilitate the translation of collagen-based artificial corneas to the clinical setting.

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In this study, we introduced a novel double crosslinked chitin aerogel via etherification with EGDE for mechanical reinforcement. Samples with different EGDE: chitin weight ratios from 0 to 1.5:1 were fabricated through chitin dissolution in KOH/urea aqueous solution, ethanol neutralization and washing, and supercritical CO2 drying. Both the physical and chemical crosslinking maintained the high porosity and light weight of chitin aerogels. The morphology under SEM has shown the close-ended and denser fibrils alignment for EGDE crosslinked aerogels and the mesoporous and macroporous structure induced by emulsion effect from excessive EGDE. FTIR characterization was conducted for chemical structure analysis. Compressive testing showed an increase of 247 % compressive strength at 10 % strain and 243 % modulus could be achieved at 1.0 EGDE samples. TGA results revealed a delayed thermal degradation for the chemically crosslinked samples. This study demonstrates EGDE an effective chemical crosslinker for reinforced chitin aerogels.

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Chitosan (CS) hydrogels have been widely used throughout basic tissue engineering and regenerative medicine research and it is very desirable to develop advanced CS materials with superior mechanical and topographical properties for more extensive applications. Herein, we present the design of a double crosslinking pure CS hydrogel material via the synergic effect of the chemical covalent network, hydrophobic interactions, enhanced intermolecular hydrogen bonding and the formation of the CS crystallite. The resultant pure CS hydrogel possesses increases in strength and toughness by two orders of magnitude (fracture energy ∼7.733 J m-2; maximal compression stress ∼10.81 MPa, elastic modulus ∼1.33 MPa). We utilize1H NMR and FT-IR to prove the success of chemical modification. The results of Raman spectra and WXRD have proved the existence of physical interaction between CS hydrogels and microcrystals, thus explaining the enhancement mechanism of mechanical strength of CS hydrogel. The live and death results also show that MSCs can grow well on CS hydrogels, and the results of CCK-8 indicate low cytotoxicity of CS hydrogels. This CS hydrogel shows great potential applications in tissue engineering and regenerative medicine.

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Cell fate and morphologies are influenced by the mechanical property of matrix. However, the relevant works about the dynamic adjustable of matrix mechanical property is rare and most of them need extra stimulation, such as the controllable of the degradation. In this study, double crosslinking (DC) hydrogels are fabricated by sequential covalent crosslinking and electrostatic interactions between hyaluronic acid and poly-lysine. Without any extra stimulation or treatment, the compressive stress of DC-hydrogels increases from 22.4 ± 9.4 kPa to 320.1 ± 6.6 kPa with the elongation of incubation time in DMEM solution. The change of compressive stress of matrix induced the morphology of L929 fibroblast cells adjusted from the distributed round shape to spheroid cell clusters and finally to spread shape. RNA sequence analysis also demonstrated that the differentially gene expression and GO enrichment between the cells seeded on the DC-hydrogel with different incubation time. In addition, by increasing the electrostatic interactions ratio of the hydrogel, the biodegradation, compressive stress and energy dissipation of the DC-hydrogels were also significantly improved. Therefore, our study provides new and critical insights into the design strategy to achieve DC-hydrogels which can in situ alter cells morphology and open up a new avenue for the application of disease therapy.

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