Fluorescent Hydrogel Research Articles

A Fluorescent Hydrogel with AIE Emission for Dehydration-Visualizable Wearable Sensors.

Hydrogel-based wearable sensors eventually experience dehydration, which negatively impacts their function, leading to decreased sensitivity. Monitoring the real-time water retention rate and sensing performance of wearable flexible sensors without dismantling them remains a significant difficulty. In this study, a molecule having aggregation-induced emission (AIE) properties in an aqueous environment has been developed and produced, which can combine with anionic guar gum and acrylic acid to create an AIE hydrogel. Wearable sensing electronic devices have the capability to track motion signals at various joints of the human body. Additionally, they can effectively and visually monitor dehydration status during extended periods of operation. The fluorescence intensity of the hydrogel is primarily influenced by the level of aggregation of luminous monomers inside the network. This level of aggregation is predominantly governed by the hydrogel's water retention rate. Hence, the extended duration of hydrogel dehydration can be manifested through alterations in their fluorescence characteristics, which are employed for strain sensing. This approach enables users to assess the water retention of hydrogels with greater efficiency, eliminating the requirement for disassembling them from the completed electrical gadget. In summary, the use of AIE-based fluorescent hydrogels will advance the progress of intelligent wearable electronics.

Preparation of biomass carbon dots/carboxymethyl cellulose-based fluorescent hydrogel: Combines selective detection and visual adsorption for Copper(II)

Abstract In this study, we used nitrogen-doped carbon dots (NCDs), which were synthesized via the hydrothermal method of corn-stover biomass as raw material and polyethyleneimine (PEI) as the nitrogen source, introduced them into the carboxymethyl cellulose-based hydrogel to prepare an environmentally friendly fluorescent cellulose-based hydrogel (NCDs/CMC-PAM). NCDs/CMC-PAM was also used for simultaneous fluorescence monitoring and removal of Cu (II) in aqueous solution. The chemical and physical structures, adsorption behaviors and fluorescent properties of NCDs/CMC-PAM were investigated. The results showed that NCDs/CMC-PAM exhibited a well-linear response range of fluorescence response for Cu (II) (0∼100 μM, detection limit of 3.42 μM). NCDs/CMC-PAM showed maximum adsorption capacities of 237.71 mg/g for Cu (II), the adsorption process followed the Langmuir isotherm model and pseudo-second-order kinetic model, which is an exothermic spontaneous reaction with an increase in entropy. It can still maintain 79.03% of the original adsorption capacity after six cycles (pH=6). The adsorption mechanisms of NCDs/CMC-PAM for Cu (II) are intraparticle diffusion, electrostatic attraction, ion exchange, and ligand interaction. Hence, the present study provides a new green way to synthesize an adsorbent that can be applied for the adsorption and detection of heavy metal ions.

Enhancing Hydrogels with Quantum Dots

This manuscript explores the interdisciplinary integration of quantum dot–hydrogel composites and smart materials and their applications across a spectrum of fields, including biomedical engineering, environmental sensing, and energy harvesting. It covers the synthesis of novel materials like fluorescent hydrogel nanocomposites that display enhanced chemical stability, mechanical strength, and thermal resistance, highlighting their utility in environmental monitoring and catalysis. In the biomedical sector, innovations include hydrogel composites for targeted drug delivery and advanced therapies such as photothermal DNA hydrogels for tumor treatment. This review also discusses the application of these materials in imaging, diagnostics, and the development of smart sensors capable of detecting various biological and environmental changes. Its scope further extends to optoelectronics and the design of energy-efficient systems, underscoring the versatile functionalities of hydrogels in modern technological applications. Challenges remain in scaling up these technologies for commercial use and ensuring their long-term stability and safety, necessitating future research focused on sustainable, scalable solutions that can be integrated into existing systems.

Synthesis and Characterization of Multiple Stimuli-Responsive Fluorescent Polymer Hydrogels Based on Terpyridine and N-Isopropylacrylamide.

A series of stimuli-responsive fluorescent hydrogels were successfully synthesized via micelle radical copolymerization of hydrophilic acrylamide (AM), hydrophobic chromophore terpyridine-based monomer (TPY), and N-isopropylacrylamide (NIPAM). These hydrogels presented blue emissions (423-440 nm) under room temperature, which is caused by the π-π* transition of the conjugated structures. Once the ambient temperature was increased to 55 °C, the fluorescence color changed from blue (430 nm) to pink (575 nm) within 10 min, subsequently to yellow (535 nm), and eventually back to pink. The thermal-responsive properties are attributed to the transition of the TPY units from unimer to dimer aggregation via the intermolecular charge transfer complex at high temperatures. The hydrogels showed pH-responsive properties. The emission peak of the hydrogel exhibited a blue shift of ~54 nm from neuter conditions to acidic conditions, while a 6 nm red shift to an alkaline environment was observed. The hydrogels demonstrated an obvious change in fluorescence intensity and wavelength upon adding different metal ions, which is caused by the coordination between the terpyridine units incorporated on the backbones and the metal ions. As a consequence, the hydrogels presented a sharp quenching fluorescence interaction with Fe2+, Fe3+, Cu2+, Hg2+, Ni2+, and Co2+, while it exhibited an enhanced fluorescence intensity interaction with Sn2+, Cd2+, and Zn2+. The microstructural, mechanical, and rheological properties of these luminescent hydrogels have been systematically investigated.

Anchoring Au nanoclusters into coordination polymers: A novel approach toward ATP detection and its application

Adenosine triphosphate (ATP) is the main source of energy required for all life activities and is used as a biomarker for diseases such as cancer. It is of great significance to design a novel fluorescent probe with favorable performance for monitoring the changes of ATP concentration. Herein, a fluorescence probe named ZnCPs@AuNCs for ATP sensing was designed and fabricated by integrating AuNCs into ZnCPs. The emission intensity of AuNCs was greatly enhanced upon the formation of the ZnCPs@AuNCs nanocomposites, which may be attributed to ZnCPs restricting the molecular motion of AuNCs. Upon the introduction of ATP, the fluorescence intensity at 564 nm of ZnCPs@AuNCs is quenched. According to this phenomenon, a sensitive and reliable ATP sensing platform was established. Moreover, ZnCPs@AuNCs were incorporated into a poly (vinyl alcohol) matrix for the fabrication of fluorescent film, which exhibited solid-state fluorescence. Inspired by the remarkable fluorescent properties of ZnCPs@AuNCs, the fluorescent hydrogel was prepared by mixing ZnCPs@AuNCs with κ-carrageenan, which demonstrated a response to ATP and favorable self-healing ability. This work presents a perspective of ZnCPs@AuNCs in multiple applications such as biosensing, fluorescent film, and hydrogel construction.

A novel red fluorescent and dynamic nanocomposite hydrogel based on chitosan and alginate doped with inclusion complex of carbon dots

Red fluorescent hydrogels possessing injectable and self-healing properties have widespread potential in biomedical field. It is still a challenge to achieve a biomacromolecules based dynamic hydrogels simultaneously combining with excellent red fluorescence, good mechanical properties, and biocompatibility. Here we first explore hydrophilic inclusion complex of (R-CDs@α-CD) derived from hydrophobic red fluorescent carbon dots (R-CDs) and α-cyclodextrin (α-CD), and then achieved a red fluorescent and dynamic polysaccharide R-CDs@α-CD/CEC-l-OSA hydrogel. The nanocomposite hydrogel can be fabricated through controlled doping of red fluorescent R-CDs@α-CD into dynamic polymer networks, taking reversibly crosslinked N-carboxyethyl chitosan (CEC) and oxidized sodium alginate (OSA) as an example. The versatile red fluorescent hydrogel simultaneously combines the features of injection, biocompatibility, and augmented mechanical properties and self-healing behavior, especially in rapid self-recovery even after integration. The R-CDs@α-CD uniformly dispersed into dynamic hydrogel played the role of killing two birds with one stone, that is, endowing red emission of a hydrophilic fluorescent substance, and improving mechanical and self-healing properties as a dynamic nano-crosslinker, via forming hydrogen bonds as reversible crosslinkings. The novel red fluorescent and dynamic hydrogel based on polysaccharides is promising for using as biomaterials in biomedical field.

Fabrication of chitosan-based fluorescent hydrogel membranes cross-linked with bisbenzaldehyde for efficient selective detection and adsorption of Fe2+

Chitosan, as a natural biomass material, is green, recyclable, sustainable and well biocompatible. The molecular chain is rich in active groups such as amino and hydroxyl groups, and its preparation of fluorescent probes has the advantages of biocompatibility and efficient detection performance. In this study, a bis(benzaldehyde) (BHD) fluorescent functional molecule was designed. Then a series of fluorescent chitosan-based hydrogel films (CSBHD) were prepared using chitosan as raw material and BHD as cross-linking agent. As a fluorescent probe for metal ions, CSBHD was able to efficiently detect Fe2+ with a linear correlation of fluorescence intensity in the range of 0–160 μM, and the limit of detection (LOD) was 0.55 μM. Moreover, it has excellent adsorption performance for Fe2+ ions, with a maximum adsorption capacity of 223.5 g/mg at 500 mg/L Fe2+ concentration. Finally, we characterised the structure and microscopic morphology of CSBHD films and found that CSBHD as a hydrogel film has a high cross-linking density, good water resistance, excellent thermal stability, strong resistance to swelling, and excellent stability in cycling tests. Hence, it has great potential for application in adsorption and detection of Fe2+ ions. It also provides a good strategy for the application of chitosan based fluorescent probe materials in environmental monitoring and heavy metal ion adsorption.

Fluorescent biopolymer hydrogels crosslinked with carbon quantum dots for selective detection of heavy iron (III) ions

In this study, carbon quantum dots (CQDs) were synthesized using glycerol and citric acid under microwave radiation, achieving an 83 % quantum yield (QY) and 1.59 nm particle size. These CQDs were employed as softeners and crosslinkers for the production of fluorescent granular and film hydrogels, in combination with biopolymers such as starch, chitosan (Ch), and gelatin (Ge). The resulting biopolymer-CQD composites were evaluated for their ability to selectively detect heavy metal ions, such as iron (III), as well as for their water vapor permeability (WVP), water solubility (WS), and swelling properties. Various analyses confirmed the formation of fluorescence bio-nanocomposites and improvements in their properties. Notably, a hydrogel film containing 50% wt CQDs exhibited the highest mechanical strength, with a tensile strength of 6.28 MPa and an elongation at fracture of 91.2%. Additionally, a strongly crosslinked fluorescent granular hydrogel with a ratio of Ge 25%: Ch 75% and a fixed amount of CQDs was able to absorb 136 times its own weight in water and exhibited increased water vapor permeability with higher CQD content. Overall, the fabricated materials show potential for the detection of iron (II), iron (III), and mercury (II) in aqueous media.

Multiple hydrogen-bonding induced nonconventional red fluorescence emission in hydrogels

The development of unconventional long-wavelength fluorescent polymer hydrogels without using polycyclic aromatic hydrocarbons or extended π-conjugation is a fundamental challenge in luminescent materials owing to a lack of understanding regarding the spatial interactions induced inherent clustering-triggered emission under water-rich conditions. Inspired by the color change of protein astaxanthin as a result of heat-induced denaturation, we propose a thermodynamically driven strategy to develop red fluorescence (~610 nm) by boiling multiple hydrogen-bonded poly(N-acryloylsemicarbazide) hydrogels in a water bath. We reveal that thermodynamically driven conformational changes of polymer chains from isolated hydrogen bonding donor-acceptor structures to through-space interaction structures induce intrinsic fluorescence shifts from blue to red during clustering-triggered emission. The proposed multiple hydrogen-bonding supramolecular hydrogel shows good fluorescence stability, mechanical robustness, and 3D printability for customizable shaping. We provide a viable method to prepare nonconventional long-wavelength fluorescent hydrogels towards soft fluorescent devices without initially introducing any fluorescent components.

3D-Printed Fluorescent Hydrogel Consisting of Conjugated Polymer and Biomacromolecule for Fast and Sensitive Detection of Cr(VI) in Vegetables.

Portable fluorescent film sensors offer a solution to the contamination issue in homogeneous sensor detection systems. However, their special structure leads to low sensitivity and a long response time, resulting in a significant scientific challenge limiting their development and application. In this work, we propose a dual design strategy to prepare highly sensitive film sensors for rapidly detecting Cr2O72-. Specifically, P(Fmoc-Osu)-SA hydrogel films were developed by integrating the biological macromolecule sodium alginate (SA) with the conjugated polymer poly(N-(9-Fluorenylmethoxycarbonyloxy)succinimide) (P(Fmoc-Osu)), using both mold and inkjet 3D printing methods. The "molecular wire effect" of the sensing unit P(Fmoc-Osu) and the water channel within the film substrate are responsible for the improved sensitivity and the reduced response time of this thin film sensor. P(Fmoc-Osu)-SA hydrogel films prepared by these two methods can rapidly detect Cr2O72- with limits of detection of 1.18 and 0.078 nM, respectively. Considering that 3D-printed hydrogel films can be tailored to different shapes according to detection needs, the P(Fmoc-Osu)-SA hydrogel films produced from this method were effectively applied in vegetable samples. This study provides an innovative and effective strategy for the development of biocompatible hydrogel sensors that offer the potential for determining trace amounts of Cr2O72- in agriculture.

Enzymatic fluorescent supramolecular hydrogel with aggregation-induced emission characteristics for sensing alkaline phosphatase

Alkaline phosphatase is an important biomarker for medical diagnosis. An enzymatic fluorescence supramolecular hydrogel with AIE properties was developed and used for sensing alkaline phosphatase in vitro and in living cells. In the presence of ALP, K(TPE)EFYp was partially converted to the hydrogelator K(TPE)EFY and self-assembled into nanofibers to form Hydrogel. With the sol–gel transition and the AIE effect, the fluorescence emission was turned on. The linear concentration range of ALP activity in vitro quantified by this method was determined as 0–3 U/L with aLODat 0.02 U/L. In addition, cell imaging and serum experiment showed that K(TPE)EFYp could also be used to detect ALP activity in living cells and biological samples.

Development of fluorescent sensing platform with degradable hydrogel for rapid and ultratrace detection of Cr(VI) in vegetables

Degradable fluorescent film sensors are highly ideal for real-time outdoor detection of heavy metal ions and offer the advantage of preventing secondary contamination, aligning with the principle of sustainable development. In this work, we constructed a degradable fluorescent hydrogel for the specific detection of Cr(VI) ions, utilizing poly(1-pyrene butyric acid) (PPBA) as the sensing moiety and sodium alginate (SA) as the cross-linking substrate. The porous network structure of the PPBA-SA film provided enhanced ion transport channels and active sites, thereby reducing fluorescence response time and augmenting detection sensitivity. The PPBA-SA film exhibited rapid and selective recognition of Cr(VI) ions among a panel of 16 anions and 22 cations, achieving an impressive limit of detection of 1.99 nM. Moreover, we successfully applied this platform to detect Cr(VI) ions in four different vegetable samples. Notably, the PPBA bound with Cr(VI) ions could be effortlessly removed from the film, and the substrate underwent rapid degradation within 24 h, attaining a degradation rate of 72.4 %. This work provides an innovative and effective strategy for fabricating green and sustainable fluorescent sensors.

Anthrapyrazolone functionalized Oligo(ethylene glycol)methyl ether methacrylates based fluorescent polymeric hydrogel for selective detection of Tetracycline drug

Tetracycline (TC) antibiotics are essential for treating bacterial infections; however, overuse and improper disposal place the environment in danger and promote the growth of drug-resistant microorganisms. Monitoring their impact on living organisms is vital. Polymeric-based hydrogels offer promise in antibiotic detection due to their versatility and biocompatibility, despite their uncommon use for this purpose. In this study, we have synthesized a fluorescent polymeric hydrogel, P(OEGMA-co-DIMA) utilizing oligo(ethylene glycol)methyl ether methacrylates (OEGMA) and laboratory-synthesized fluorescent anthrapyrazolone containing monomer, 2-(benzo[1,2,3-cd:4,5,6-c’d]bis(indazole)-2(7H)-yl)ethyl methacrylate (DIMA) for the fluorometric detection of TC in the aqueous medium. The P(OEGMA-co-DIMA) hydrogel exhibited exceptional affinity towards TC while exhibiting high selectivity. The chemosensing behavior of the hydrogel was also compared with the DIMA monomer. Upon adding TC, emission analysis revealed a notable quenching in the emission intensity of the P(OEGMA-co-DIMA) hydrogel as well as the DIMA monomer. The Stern Volmer rate constants (Ksv) of the hydrogel (Ksv = 9.99 x 103 M−1) in water and DIMA (Ksv = 25.63 x 103 M−1) in acetonitrile showed a higher quenching rate constant with a limit of detections (LODs) of 1.3 nM and 0.11 nM. Turn-off fluorescence behavior occurs via a static quenching mechanism through a photoinduced electron transfer process and intermolecular hydrogen bonding. To validate the selectivity, the interference analyses in an aqueous medium with different antibiotics are provided. To rationalize the real-time applicability of the hydrogel, studies were extended to water samples obtained from deionized water, tap water, lake water, and also in milk samples. The recovery rate and LOD for real samples ranged from 83.8% to 111% and 0.83 to 3.6 nM, respectively.

Fluorescent hydrogel with high toughness response based on lanthanide Metals: Material Adhesion, multicolor Modulation, information encryption

Natural polymer-based luminescent materials (NPLMs) are widely used in various fields of science and technology during the high-tech era. This study describes the formation of polyacrylamide (PAM) by thermally initiated free radical in situ polymerization of acrylamide monomer. The resulting hydrogel is physically entangled and chemically crosslinked with hypromellose (HPMC) to create a three-dimensional network structure. Lanthanide organic compatibilizers (Ln-L) are then introduced as luminescent units to produce fluorescent hydrogel materials. The study found that the tensile strength of PAM/HPMC/Ln (0/6 Eu/Tb) hydrogel increased by 230.53 % from 11.76 to 27.11 MPa. Similarly, the compressive strength increased by 208.30 % from 16.14 to 33.62 MPa. Additionally, by adjusting the molar ratio of lanthanide metals, hydrogels can achieve colorful fluorescence modulation. Moreover, an information encryption function was implemented using a Python design program in combination with the fluorescent properties of hydrogels.

Fluorescent Double Network Hydrogels with Ionic Responsiveness and High Mechanical Properties for Visual Detection

Fluorescent Double Network Hydrogels with Ionic Responsiveness and High Mechanical Properties for Visual Detection

Smart fluorescent PVA/CS/AV/g-C3N4QDs hydrogel nanocomposites: synthesis and study of UV absorbance, rheological and self-healing properties

Response to exterior stimulants, such as light and pH and also self-healing behavior are the major specifications of smart nanocomposites. This project aims to synthesise various weight percentages of smart fluorescent hydrogel nanocomposites using natural and bio-friendly materials including polyvinyl alcohol (PVA), corn starch (CS), aloe vera (AV) and g-C3N4QDs (PSA/CN). Graphitic carbon nitride quantum dots (g-C3N4QDs or CN) were synthesised by way of pyrolysis of the urea and citric acid (CA) blend with 18:1 weight proportion employing microwave-supported procedure. Next, synthesis and properties of the prepared nanocomposites were verified by means of microscopic and electroscopic methods. The strong absorption peaks registered at 230, 290 and 390 nm confirmed UV absorption ability of the synthesised PSA/CN nanocomposites. In response to 390 nm exciting wavelength, these nanocomposites emitted green fluorescence (FL) at 505–510 nm. Adding CN (0.25 wt% and 0.5 wt%) to the hydrogel matrix bred a growth in thermal stability of the resultant nanocomposites. Loading diverse weight percentages of CN into hydrogel matrix led the rheological features of the hydrogel nanocomposites to improve. Studies on pH-responsive and rheological analyses approved self-healing behavior of the PSA/CN nanocomposites against damages.

On-Off Ratiometric Fluorescence Europium(III) Metal-Organic Framework for Quantitative Detection of the Inflammatory Marker Neopterin.

Benefiting from the unique photoluminescence behavior of the lanthanide(III) ions and organic ligands, a lanthanide(III) metal-organic framework (Ln-MOF) material can simultaneously demonstrate photoluminescence of lanthanide(III) cations and organic molecules and endow its superior applications of fluorescence sensing behaviors. Herein, we present a europium(III) MOF material {[Eu2(BPTA)·(CH3COO)2·3DMA]·0.5DMA·3H2O}n (1) (where H4BPTA is 3,3',5,5'-biphenyltetracarboxylic acid) for photoluminescence performance of quantitatively sensing the inflammatory marker neopterin (Neo). The obtained 1 comprises Eu2(COO)4 paddlewheel secondary building units, which could be bridged by BPTA4- ligands to extend a 2D framework. The fluorescence titration indicates 1 can achieve simultaneous fluorescence behavior of Eu3+ ions and Neo via on-off ratiometric effects and thus could be exploited as the ratiometric fluorescence sensor matrix. Such a fluorescence phenomenon of 1 as a ratiometric sensor for quantitative detection of Neo via an on-off ratiometric effect is never observed in MOF chemistry. Moreover, naked-eye visible color variations of the fluorescence for 1 could be observed from red to blue with increasing concentrations of Neo, confirmed by fluorescent test strips as well as portable fluorescent hydrogels. And 1 also shows a low detection limit of 15.11 nM. A synergetic contribution of the competitive absorption, fluorescence resonance energy-transfer, and photoinduced electron-transfer mechanisms between Neo and the framework of 1 realizes the on-off ratiometric fluorescence behavior for Neo detection, supported by the UV-vis spectral overlap experiment and DFT calculations.

Conjugated Polymer-Based Hydrogel Film for a Fast and Sensitive Detection of Fe(Ⅲ) in Vegetables.

Fluorescent film sensors are ideal for the real-time outdoor detection of heavy metal ions of Fe3+, but they are limited because of their low sensitivity and long response time due to their special structure. In this work, we constructed a fluorescent hydrogel for the specific detection of Fe3+, utilizing poly(9-fluorenecarboxylic acid) (PFCA) as the sensing moiety and sodium alginate (SA) as the cross-linking substrate, which exhibited a rapid and selective recognition of Fe3+ among a panel of 16 anions and 21 cations. It can sense Fe3+ at 0.1 nM immediately owing to the porous network structure of the PFCA-SA film that provided enhanced ion transport channels and active sites, and the "molecular line effect" of polymer PFCA. Moreover, we successfully applied this platform to detect Fe3+ in four different vegetable samples. This work provides an innovative and effective strategy for fabricating green and sustainable fluorescent sensors.

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.