Fluorescent Hydrogel Research Articles

Bio-friendly fluorescent polyvinyl alcohol/gelatin/chitosan hydrogel membranes strengthened by g-C3N4/CQDs nanocomposite: Preparation, investigation of UV-absorption, mechanical and rheological properties

This study’s purpose is to synthesize fluorescent hydrogel membranes using polyvinyl alcohol, chitosan and gelatin as bio-friendly substances, and to analyze the strengthening effect of graphitic carbon nitride/carbon quantum dots nanocomposite (g-C3N4/CQDs) on optical, mechanical and rheological properties of the synthesized hydrogel membranes (HMs). A two-step pyrolysis of the mixture of starch as a natural resource and urea as a nitrogen resource with 1:10 weight proportion was utilized to synthesize g-C3N4/CQDs nanocomposite via microwave-assisted system. Water absorption value in the synthesized samples was calculated 237–275%. UV absorbance and fluorescence features were investigated by UV–visible and photoluminescence spectroscopy. Results indicated that adding 0.5 wt% and 1 wt% g-C3N4/CQDs to HMs matrix led to UV absorption in 225, 275 and 395 nm wavelengths and strong fluorescence emission in 515 nm (green region). Samples flexibility was figured 22–56% by tensile test results so that by an increase in filler content, flexibility was driven down but tensile strength was driven up. Rheometry test findings confirmed that g-C3N4/CQDs adding resulted in improvement of rheological properties of the HMs like storage modulus and loss modulus, and growth of complex viscosity.

Stimuli‐responsive fluorescent hydrogels: Strategies and applications

AbstractStimuli‐responsive fluorescent hydrogels are three‐dimensional networked polymeric materials with tunable luminescence and dynamic properties, which play an important role as a water‐rich soft material in the fields of information encryption, bionic actuation, bioimaging, environmental monitoring, and luminescent materials. Compared with conventional hydrogels, their unique luminescent properties allow the visualization of microscopic dynamics within the polymer network. By rational inclusion of dynamic motifs, such as photoswitches, AIEgens, lanthanide complexes, and host–guest complexes, these materials are endowed with tunability of emission, shape, and phase in time and space in response to environmental effectors. In this review, we summarize the fabrication strategies that are mainly used by recently reported stimuli‐responsive fluorescent hydrogels and the applications of these materials.

Nature-inspired recycling of a protein mixture into a green fluorescent protein-based hydrogel.

Protein-based materials are biocompatible and have a variety of remarkable properties; consequently, they are finding more and more applications. Nature recycles proteins in multiple ways, ranging from bio-degradation (a slow approach) to fast recycling of protein metabolism. The latter is a wonderful example because a random mixture of proteins gets digested into amino acids (AAs), the fundamental building blocks of proteins. These AAs are then used by cells to produce whichever protein is needed at the time of synthesis. Seen through the lens of recycling, this process transforms a random mixture into something not necessarily present at the start but needed at the moment of recycling. We have recently shown that the process of protein recycling can be performed in vitro and called it NaCRe (Nature Inspired Circular Recycling). In a previous NaCRe proof-of-concept experiment, we started with various protein mixtures but were able to produce only small quantities of recycled protein, in the microgram scale. Here, we show that NaCRe can be used to convert milligrams of a protein mixture containing one of the most common protein materials (silk) into a milligram of an hydrogel made of green fluorescent protein (GFP). We show that in order for NaCRe to be efficient the starting protein mixture must contain a good balance of all AAs and discuss the challenges encountered when scaling up NaCRe.

A facile strategy for the large-scale preparation of starch-based AIE luminescent nanoaggregates via host-guest interactions and their versatile applications.

Luminescent nanomaterials with outstanding optical properties have attracted growing interest due to their widespread applications. However, large-scale fabrication of luminescent nanomaterials with desired properties through a simple and economical process remains challenging. As a renewable natural resource, starch is non-toxic, easily accessible, and inexpensive, making it a popular choice for uses in various biomedical fields. In this work, we present a facile assembly strategy for the fabrication of starch-based luminescent nanoaggregates using starch as the host material and aggregation-induced emission luminogens (AIEgens) as guest molecules. By employing simple procedures under mild conditions, highly luminescent nanoparticles with small sizes, high water dispersibility, and low cytotoxicity are prepared on a large scale. The resulting nano-assemblies demonstrate significantly enhanced fluorescence intensities, reduced susceptibility to photobleaching and low cytotoxicity. These fluorescent supramolecular aggregates can be employed in various application fields, including the fabrication of fluorescent hydrogels, fingerprint detection, cell imaging and in vivo lymphatic system imaging. The methodology developed in this work has immense potential to greatly promote the production of high-quality nanoparticles on the industrial scale, offering a cost-effective solution that can meet the needs of various applications and pave the way for wider implementation of nanotechnology.

Transient cucurbit[7]uril-mediated host-guest complexes for time-dependent fluorescence and information-self-erasing hydrogel.

A non-equilibrium cucurbit[7]uril-mediated supramolecular host-guest system is fabricated by using urea/urease to control aqueous solution pH on time dimension, showing transient assembly behavior and time-dependent fluorescence. The dynamic assembly can be also achieved in hydrogel network, resulting in a time-dependent fluorescent hydrogel for information encryption.

Fabrication of a porous Urea@MIL-100(Fe)/CI-MCC/SA hydrogel for All-In-One adsorption, removal and fluorescence monitoring of nitrite

In this paper, a novel All-In-One Urea@MIL-100(Fe)/CI-MCC/SA hydrogel platform was generated by microcrystalline cellulose (MCC) functionalized with pH-response probe (CI), MIL-100 (Fe) and sodium alginate (SA), which was as a carrier of urea to adsorb, remove and monitor NO2-. Under acidic condition, the fluorescent hydrogel platform could produce N2, CO2 and H2O through the diazotization and redox reaction between urea and NO2- with a removal efficiency up to 99.8%, and could also character a good adsorption property for NO2- due to the positive charges of protonation (the maximum adsorption capacity was 21.67 mg g−1), and the adsorption kinetics conformed to pseudo-second-order model. By carried out the NO2- removal step in fluorescent hydrogel platform, NO2- could also be detected indirectly by sensing the changes of pH within 15 min. The linear response range was 0–0.005 M, and the detection limit (LOD) was 74 μM. These results demonstrated that this All-In-One Urea@MIL-100(Fe)/CI-MCC/SA hydrogel platform had great potential in environment. This strategy for the removal and monitoring of NO2- could be employed to related applications in water purification and environmental protection. Environmental implicationNitrite is one of the important indicators of water monitoring, which is harmful to human and environment. The removal and monitoring of nitrite in industrial wastewater and surface water is very important, but there are no studies about it at present. Based on the fact that urea can react with nitrite to produce green products, we synthesized a novel functional hydrogel to achieve adsorption, removal and fluorescence monitoring of nitrite for the first time. Besides, the practicability of the material in environmental water samples was verified through the detection of nitrite in simulated wastewater.

Enhancing diabetic wound healing with a pH-responsive nanozyme hydrogel featuring multi-enzyme-like activities and oxygen self-supply

Diabetic wound treating remains a challenging due to bacterial infections, oxidative stress, tissue hypoxia, and high glucose levels. Herein, a multi-enzyme-like activities nanocomposite (Mo,Fe/Cu,I-Ag@GOx) was designed and anchored to a multifunctional fluorescence hydrogel. The nanozyme gel, loaded with glucose-oxidase (GOx), exhibits intrinsic GOx, peroxidase (POD)-, oxidase (OXD)-, catalase (CAT)- and superoxide dismutase (SOD)-like activities with pH-switchable glucose-initiated cascade reaction for diabetic wound healing. In the first cascade-reaction, initiated by GOx, the nanozyme gel catalyzes glucose and O2 into gluconic acid and H2O2 to further generate superoxide anion radical (O2·-) and hydroxyl radicals (·OH) to eradicate bacteria. In the second cascade-reaction, as the wound pH changes alkalescent microenvironment, the nanozyme gel simulates SOD to transform O2·- into O2 and H2O2, and then decomposes endogenous and exogenous H2O2 into O2 via CAT-like activity to reduce oxidative stress and alleviate hypoxia. The gel by calcium ion (Ca2+) cross-linked sodium alginate (SA) and chitosan (CS) containing nanozyme was constructed with injectability, adhesion and fluorescence properties, as well as beneficial biocompatible. Importantly, the water/alcohol solubility of the nanozyme gel allows it to be used as a dressing without causing secondary injury to the wound. The multifunctional fluorescence hydrogel exhibits efficiently promote pro-angiogenesis and bacteria-infected wound healing.

Aldehyde modified nanocellulose-based fluorescent hydrogel toward multistage data security encryption

In view of the insecurity of encode information storage based on fluorescence switch single-stage encryption, a fluorescent hydrogel for multistage data security encryption were proposed, named as polyvinyl alcohol/dialdehyde cellulose nanofibrils/carbon quantum dots hydrogel. Herein, the interpenetrating network was formed by chemically crosslinking between polyvinyl alcohol (PVA) and dialdehyde cellulose nanofibrils (DACNF). Additionally, nitrogen-doped carbon quantum dots (CDs) synthesized by one-step hydrothermal method were introduced into the above hydrogel system by hydrogen bonds. The resultant fluorescent hydrogels possessed high stretchability up to 530 %, good strength of 0.96 MPa, Fe3+-responsive fluorescence quenching, fluorescence recovery triggered by ascorbic acid and borax-triggered shape memory. Moreover, various complex 3D hydrogel geometries were fabricated by folding/assembling 2D fluorescent hydrogel sheets, extending data encryption capability from 2D plane to 3D space. More remarkably, the 3D data encryption-erasing process of fluorescent hydrogel was realized by the strategy of alternating treatment of Fe3+ solution and ascorbic acid solution. This work provided a facile and general strategy for constructing high security important information encryption and protection.

Bioinspired Multistimuli-Induced Synergistic Changes in Color and Shape of Hydrogel and Actuator Based on Fluorescent Microgels.

Fluorescent hydrogels have emerged as one of the most promising candidates for developing biomimetic materials and artificial intelligence owing to their unique fluorescence and responsive properties. However, it is still challenging to fabricate hydrogel that exhibits synergistic changes in fluorescence color and shape in response to multistimulus via a simple method. Herein, blue- and orange-emitting fluorescent microgels (MGs) both are designed and synthesized with pH-, thermal-, and cationic-sensitivity via one-step polymerization, respectively. The two fluorescent MGs are incorporated into transparent doubly crosslinked microgel (DX MG) hydrogels with a preset ratio. The DX MG hydrogels can tune the fluorescent color accompanied by size variation via subjecting to external multistimulus. Thus, DX MG hydrogels can be exploited for multiresponsive fluorescent bilayer actuators. The actuators can undergo complex shape deformation and color changes. Inspired by natural organisms, an artificial morning glory with color and size changes are showcased in response to buffer solutions of different pH values. Besides, an intelligent skin hydrogel, imitating natural calotes versicolor, by assembling four layers of DX MG with different ratios of MGs, is tailored. This work serves as an inspiration for the design and fabrication of novel biomimetic smart materials with synergistic functions.

Principles and approaches in the development of fluorescent hydrogels for cancer diagnosis

Principles and approaches in the development of fluorescent hydrogels for cancer diagnosis

Continuous monitoring of temperature and freshness in cold chain transport based on the dual-responsive fluorescent hydrogel

Comprehensive attention should be paid to the potential food spoilage in food transport. However, there is a problem of freshness destruction by repeated freezing and thawing during the cold chain transport. Herein, a fluorescent hydrogel with N-doped green-emitting carbon dots (N-GCDs), bovine serum albumin-gold nanoclusters (BSA-AuNCs) as fluorescent probes and polyvinyl alcohol-sodium alginate hydrogel as carrier matrix was developed to continuously detect temperature and freshness. Due to the solvatochromic effect of N-GCDs, when the temperature surpassed the threshold, the mixture of water and dimethyl sulfoxide underwent a phase transition and melted into the gel, changing the fluorescence color to realize the temperature monitoring. Then, due to the pH effect of BSA-AuNCs, the gel could respond to pH changes in food deterioration to monitor the food freshness. Thus, the changes of both fluorescence color and intensity of the hydrogel provides a new method for visual and portable authenticity of food freshness.

Cost-efficient and ultrasensitive hydrogel-based visual point-of-care sensor integrated with surface patterning and strongly emissive carbon dots directly from Prunus mume Carbonisatus

Point-of-care (POC) sensors possess significant potential for various applications such as environmental monitoring and clinical diagnosis. However, POC sensors often encounter challenges regarding accuracy and sensitivity. Herein, we present a facile, cost-efficient and high-yield synthesis strategy of strongly blue-emitting carbon dots (CDs) from Prunus mume Carbonisatus (PMC) for fabricating surface patterned fluorescent hydrogel POC sensors with ultra-high sensitivity and accuracy. By rationally integrating Fe3+-responsive PMC-CDs with surface patterning enhanced visualization (SPEV) strategy, we achieve accurate POC detection of Fe3+ ions with a visual detection limit of 0.1 μM using the pseudo-color-assisted patterned POC sensors. Benefiting from more diverse and well-controlled visual information provided by the pseudo-color images of patterned hydrogels, the ultrasensitive and accurate visual POC detection of Fe3+ in iron supplements and human serum samples could be easily achieved without using any expensive instruments. This single emitting fluorophore-based surface patterned hydrogel sensing platform exhibits exceptional visual quantitative capability and remarkable convenience, thus holding great promise for visual POC testing.

Green and sustainable preparation of functionalized carbon quantum dots and fluorescent hydrogel from exopolysaccharides for multiple fluorescence applications

Xanthan gum (XG) and oxidized xanthan gum (OXG) were used as raw materials to prepare two fluorescent carbon quantum dots (CQDs), XG-CQDs and OXG-CQDs, by hydrothermal method. Their microstructure, optical properties and the selectivity and accuracy in Cr6+ ion detection and fluorescent anti-counterfeiting applications were investigated. They indicated stable fluorescence in high concentration of salt (4 mol/L NaCl) and wide pH range, and had single selectivity to Cr6+ ion, good information encryption and anti-counterfeiting effect. OXG-PEI (polyetherimide) hydrogel was further built based on the cross-linking action of aldehyde groups in OXG-CQDs with amino groups of PEI. OXG-PEI hydrogel displayed the same photoluminescence properties as OXG-CQDs, and could be combined with a smartphone to build an RGB-based detection platform with lower limit of detection (3.67 mg/L) for Cr6+ ion detection. Based on its down-conversion luminescence properties, OXG-PEI hydrogel could absorb more than 99.0 % UV light (200–400 nm) for UV shielding application, and it as light conversion material layer could be coated in light emitting diode (LED) chip to construct a pure green LED device. This research provides a new insight into the preparation of multifunctional XG-derived CQDs materials with dazzling applications in environmental detection, UV shielding, LEDs construction and fluorescent anti-counterfeiting.

Multifunctional hydrogels simultaneously featuring ultrahigh stretchability, remarkable tearing resistance, and reusable fluorescence for information encoding–decoding and smart anticounterfeiting

Fluorescent hydrogels with fluorescent dyes are widely used for anti-counterfeiting encryption. However, developing highly stretchable and remarkable tear-resistant hydrogels with reusable fluorescence for anti-counterfeiting purposes remains challenging. In this study, we fabricated and characterized double network (DN) hydrogels comprising polyvinyl alcohol-borax (PVA-borax) as the first network and poly(methacrylamide-co-polyethylene glycol-co-pyrenylmethyl acrylate) (P(MAM-co-PEGMA-co-PyMA)) as the second network with varying MAM to PEGMA ratios. SEM images showed the hydrogels had 3D porous structures. FT-IR and thermal properties analysis (DSC and TGA) indicated the presence of hydrogen bonds between PVA-borax and P(MAM-co-PEGMA-co-PyMA) without any chemical bonds. The red shift in characteristic absorption bands at 841 and 710 cm−1 further confirmed the presence of π-π* interactions between pyrene moieties. XRD analysis revealed no significant changes in crystalline phase of the hydrogels, which facilitated the formation of a 3D network due to abundant hydrogen bond presence. When the MAM to PEGMA ratio was adjusted to 9:2, the resulting hydrogels exhibited remarkable properties such as ultra-high stretchability (strain over 3300 %), excellent notch-insensitivity, and exceptional tear resistance (tearing energy over 3.25 × 105 J/m2). Importantly, the hydrogel's fluorescence intensity could be reversibly changed by alternatively adding Fe3+ and EDTA-2Na. It could be reused more than 10 times while maintaining a fluorescence intensity of around 80 %, demonstrating its reliability as a versatile hydrogel probe for Fe3+ detection with “ON-OFF-ON” fluorescence behavior. Furthermore, the hydrogels demonstrated exceptional 2D encryption and decryption capabilities, highlighting their potential applications in information storage and data security. To improve the level of anti-counterfeiting, multiple encryption approaches such as QR codes and ASCII binary codes were rationally designed. Overall, this study successfully developed a universal DN hydrogel platform with ultra-high stretchability and remarkable tear resistance, capable of rapid encoding and decoding of complex information for smart anti-counterfeiting.

Carbon Quantum Dot (CQD)-Based Composite Fluorescent Hydrogel for the Isolation and Determination of Iron (III)

Carbon quantum dots (CQDs) were derived from saponin and introduced into polyacrylamide hydrogel to prepare a novel bifunctional material (CQDs@HG). This hydrogel emitted strong blue fluorescence under ultraviolet light (365 nm) and exhibited stable adsorption and detection of iron(III) in water samples. The morphological characteristics, chemical composition, Fe3+ adsorption performance, and optical properties of CQDs@HG were characterized. Depending upon the Fe3+ concentration, CQDs@HG exhibited different quenching effects to allow Fe3+ determination. The limit of detection was 0.115 μM, and the adsorption was as high as 12.13 mg/g. The mechanism was due to both static and dynamic quenching. Notably, the sensor based on CQDs@HG successfully determined Fe3+ in water samples, with spiked recoveries between 95.32% and 103.11%. When combined with software image analysis, the sensor semi-quantitatively determined Fe3+ in the field. This fluorescent hydrogel provides a reference for constructing portable sensors for monitoring hazardous substances in water.

Fabrication of 1,8-naphthalimide modified cellulose derivative composite fluorescent hydrogel probes and their application in the detection of Cr(VI)

The design and development of a rapid and quantitative method for the detection of heavy metal ions is of great importance for environmental protection. We have prepared a 1,8-Naphthalimide modified cellulose composite fluorescent hydrogel (CENAEA/PAA) with a stereo double network structure. Characterized by excellent hydrogel functional structure and fluorescence detection performance, it can efficiently and selectively identify and detect Cr(VI) with linear quenching in the range of 0–400 μmol/L and detection limit of 0.58 μmol/L for Cr(VI). The results show that the CENAEA/PAA can effectively adsorb Cr(VI) with a maximum adsorption capacity of 189.04 mg/g. Finally, the morphological characteristics, chemical structure, fluorescence properties and adsorption behavior of CENAEA/PAA were analyzed and fitted well with the pseudo-second-order model and Freundlich model. Thus, the present work provides a green and sustainable approach for the synthesis of a functional material that can be used for the detection and adsorption of heavy metal ions.

Fluorescent starch-based hydrogel with cellulose nanofibrils and carbon dots for simultaneous adsorption and detection of Pb(II)

The adsorption removal of lead (Pb) ions has become a crucial area of research due to the potential health hazards associated with Pb contamination. Developing cost-effective adsorbents for the removal of Pb(II) ions is significantly important. Hence, a novel fluorescent starch-based hydrogel (FSH) using starch (ST), cellulose nanofibrils (CN), and carbon dots (CD) was fabricated for simultaneous adsorption and detection of Pb(II). A comprehensive characterization of FSH, including its morphological features, chemical composition, and fluorescence characteristics, was conducted. Notably, FSH exhibited a maximum theoretical adsorption capacity of 265.9 mg/g, which was 13.0 times higher than that of pure ST. Moreover, FSH was employed as a fluorescent sensor for Pb(II) determination, achieving a limit of detection (LOD) of 0.06 μg/L. An analysis was further performed to investigate the adsorption and detection mechanisms of Pb(II) utilizing FSH. This study provides valuable insights into the production of a novel cost-effective ST-based adsorbent for the removal of Pb(II) ions.

Multiresponsive Self-Healing Lanthanide Fluorescent Hydrogel for Smart Textiles.

Lanthanide organometallic complexes exhibit strong luminescence characteristics, owing to their antenna effects. The f-d energy level transition causes this phenomenon, which occurs when ligands and the external electrons of lanthanide metals coordinate. Based on this phenomenon, we used two lanthanide metals, europium (Eu) and terbium (Tb), in the present study as the metal center for iminodiacetic acid ligands. Further, we developed the resulting fluorescent organometallic complex as a smart material. The ligand-metal bond in the material functioned as a metal chelating agent and a cross-linking agent in a dynamically coordinated form, thereby prompting the material to self-heal. Temperature-sensitive poly-N-isopropylacrylamide was incorporated into the material as the polymer backbone. Afterward, we combined it with water-soluble poly(vinyl alcohol) and an additional ligand from poly(acrylic acid) to fabricate a high-performance hydrogel composite material. The shrinkage and expansion of the polymer form a grid between the materials. Because of the different coordination stabilities of Eu3+ and Tb3+, the corresponding material exhibits environmental responses toward excitation wavelength, temperature, and pH, thus generating different colors. When used in fabrics, the cross-linking mechanism of the material effectively looped the material between fabric fibers; furthermore, the temperature sensitivity of the polymer adjusted the size of pores between fabric fibers. At relatively higher temperatures (>32 °C), the polymer structure shrank, fiber pores expanded, and air permeability improved. Thus, this material appears to be promising for use in smart textiles.

Fluorescent imidazolium hydrogels for tracing and recovering platinum with highest purity from spent auto catalyst

In this study, fluorescent polymeric hydrogels were synthesized and engineered to trace and recover platinum with maximum purity from spent auto catalysts by selective coordination. These three-dimensional hydrogels were prepared using a water-soluble polymeric probe [p(DMAA-co-M1), P1, where DMAA = N,N′-dimethylacrylamide, M1 = quaternized imidazole with anthracene unit] in the presence of N,N′-methylenebisacrylamide as a crosslinker. P1 was extremely selective and sensitive toward platinum ions by fluorescence quenching, with a limit of detection of 0.03 mM. Owing to the high sensitivity and selectivity of P1, the hydrogels derived from P1 exhibited the effective platinum ion detection, followed by the selective recovery from the mixtures of excess amounts of various metal ions. The platinum absorption capacity of the hydrogels from a used auto catalyst leach liquid was 0.2 g platinum/1.0 g hydrogel. Inductively coupled plasma measurements indicated that the purity of the recovered platinum was 95.76%, and the palladium composition was 4.14%. These hydrogels were recycled by thiourea and reused for multiple cycles, indicating that they are a promising candidate for platinum recovery with a contribution to the circular economy.

Photo-induced multi-color fluorescent hydrogels for optical information coding and encryption

In this study, we proposed a method to prepare multi-color fluorescent hydrogels with polyvinyl alcohol (PVA) as the cross-linking network and 7-(6-carboxylpentoxy)-4-methylcoumarin (CPMC), N-ethoxyhexanoate-3,3-dimethyl-6-nitro-indolinspiropyran (SPCOOH) and 2′,7′-dichlorofluorescein (DCF) were introduced to the system. Due to the hydroxyl group in PVA can form a reversible borate bond with borax, the hydrogel could be combined with each other through this chemical bond, thus hydrogels possess reversible cross-linking property and programmable property. The introduction of CPMC, SPCOOH and DCF into the hydrogel could give the hydrogel different photo-response properties. Under UV light irradiation, PVA-CPMC, PVA-CPMC/DCF, PVA-SPCOOH and PVA/DCF hydrogels could emit blue, cyan, pink purple and green fluorescence respectively. In addition, PVA/DCF and PVA-CPMC/DCF hydrogels could emit green fluorescence under 505 nm light irradiation. Based on the various properties of hydrogels, we respectively demonstrated the application of hydrogels in the fields of two-dimensional information encryption, three-dimensional information encryption, three-dimensional information coding and anti-counterfeiting, which can achieve the expected results. Therefore, multi-color fluorescent hydrogels may have potential applications in information encryption, information coding, flexible display and other fields.