Tough, self-healing, adhesive double network conductive hydrogel based on gelatin-polyacrylamide covalently bridged by oxidized sodium alginate for durable wearable sensors.

Pursuing high-performance conductive hydrogels is still hot topic in development of advanced flexible wearable devices. Herein, a tough, self-healing, adhesive double network (DN) conductive hydrogel (named as OSA-(Gelatin/PAM)-Ca, O-(G/P)-Ca) was prepared by bridging gelatin and polyacrylamide network with functionalized polysaccharide (oxidized sodium alginate, OSA) through Schiff base reaction. Thanks to the presence of multiple interactions (Schiff base bond, hydrogen bond, and metal coordination) within the network, the prepared hydrogel showed outstanding mechanical properties (tensile strain of 2800 % and stress of 630 kPa), high conductivity (0.72 S/m), repeatable adhesion performance and excellent self-healing ability (83.6 %/79.0 % of the original tensile strain/stress after self-healing). Moreover, the hydrogel-based sensor exhibited high strain sensitivity (GF = 3.66) and fast response time (<0.5 s), which can be used to monitor a wide range of human physiological signals. Based on this, excellent compression sensitivity (GF = 0.41 kPa-1 in the range of 90-120 kPa), a three-dimensional (3D) array of flexible sensor was designed to monitor the intensity of pressure and spatial force distribution. In addition, a gel-based wearable sensor was accurately classified and recognized ten types of gestures, achieving an accuracy rate of >96.33 % both before and after self-healing under three machine learning models (the decision tree, SVM, and KNN). This paper provides a simple method to prepare tough and self-healing conductive hydrogel as flexible multifunctional sensor devices for versatile applications in fields such as healthcare monitoring, human-computer interaction, and artificial intelligence.

Fully physical crosslinked BSA-based conductive hydrogels with high strength and fast self-recovery for human motion and wireless electrocardiogram sensing.

The emergence of protein hydrogel sensors has attracted intensive attention because of their biocompatibility and biodegradability, and potential application in wearable electronics. However, natural protein hydrogel sensors commonly exhibited low conductivity, weak mechanical strength, and unsatisfactory self-recovery performance. Herein, a fully physical crosslinked conductive BSA-MA-PPy/P(AM-co-AA)/Fe3+ hydrogel based on methacrylic anhydride (MA)-modified and polypyrrole (PPy)-functionalized bovine serum albumin (BSA) introduced into poly(acrylamide-co-acrylic acid) (P(AM-co-AA)) matrix was constructed. Due to the presence of the hydrogen bond complexation and the metal-ligand coordination between ferric ion (Fe3+) and the polymer chain, the as-prepared hydrogel showed outstanding mechanical strength (5.36 MPa tensile stress, 17.66 MJ/m3 toughness, and 1.61 MPa elastic modulus) and fast self-recovery performance (99.89 %/96.18 %/93.57 % stress/elastic modulus/dissipated energy within 10 min at room temperature). Meanwhile, the hydrogel exhibited outstanding conductivity (1.13 S/m) due to the presence of PPy and Fe3+ moieties, high strain sensitivity (GF = 4.98) and good biocompatibility without causing skin allergic reactions. Thus, the hydrogel can be fabricated into strain sensor to monitor the joint motion of the human body. Moreover, it can be used as soft electrode in electrocardiogram device to realize wireless heart-rate monitoring in the real-time conditions (relaxation and post-exercising), which exhibited excellent reusability, stability, and reliability simultaneously.

Highly Fluorescent N-Doped Carbon Quantum Dots Derived from Bamboo Stems for Selective Detection of Fe3+ Ions in Biological Systems.

The establishment of sensing platform for trace analysis of Fe3+ in biological systems is meaningful for health monitoring. Herein, a Fe3+ sensitive fluorescent nanoprobe was constructed based on highly fluorescent N-doped carbon quantum dots (NCQDs) derived from bamboo stems through a hydrothermal method employing ethylenediamine as the nitrogen dopant. The prepared NCQDs had a uniformly distributed size and their mean size was around 2.43 nm. Abundant functional groups (C=N, N-H, C=O, and carboxyl) anchored on NCQDs demonstrated successful doping of N in CQDs. The obtained NCQDs possessed a high fluorescence quantum yield of 20.02% and outstanding fluorescence stability over a wide pH range and at high ionic strengths. Moreover, Fe3+ ions presented a specific fluorescent quenching effect to the as-prepared NCQDs. The calibration curve for fluorescence quenching degree corresponding to Fe3+ concentration showed a linear response in a range of 0.01-10 µM, and detection limit was 0.486 µM, which indicated that the NCQDs had high sensitivity to Fe3+ ions. Ascribed to these unique properties, the NCQDs were selected as luminescent probes for trace amount of Fe3+ ions in human serum. These results demonstrated their promising use in clinical diagnostics and other biologically relevant studies.

Hexadecylpyridinium Chloride Mediated Hydrothermal Synthesis of NaYF4:Yb, Er Nanocrystal and Their Luminescent Properties.

Upconversion nanocrystals with uniform size and hydrophilic surface have potential applications in biological medical engineering. In this study, hydrophilic NaYF4:Yb, Er nanospheres were synthesized via hexadecylpyridinium chloride (CPC) mediated hydrothermal process. The synthesized NaYF4:Yb, Er upconversion nanospheres (UCNSs) were characterized by various characterization methods. Results showed that the synthesized UCNSs exhibited a uniform sphere-like structure with average diameter of ~250 nm. The surface of UCNSs was captured by CPC molecule indicating hydrophilic properties of UCNSs. The spherical UCNSs composed of mixed phase (α+ß) NaYF4 nanocrystals. This is the novel study for synthesis of NaYF4:Ln3+ crystal employing CPC as ligand. Moreover, the effect of CPC concentration on synthesis of UCNSs was investigated by comparatively studying morphology, crystal phase and luminescent properties of desired sample prepared under different experimental conditions. It was found that high concentrations of CPC ligands were more favorable for forming NaYF4 crystal nanospheres with morphology that is more regular, have smoother surface, with higher crystallinity and better upconversion fluorescent properties. The possible growing mechanism was proposed and growing of NaYF4:Yb, Er nanospheres followed the classical Ostwald ripening process.

Upconversion Nanoparticles@Carbon Dots@Meso-SiO2 Sandwiched Core-Shell Nanohybrids with Tunable Dual-Mode Luminescence for 3D Anti-Counterfeiting Barcodes.

Development of advanced fluorescent materials for constructing a secure and unclonable encryption is urgently required; however, their application in anti-counterfeiting applications is a great challenge. In this work, we proposed and synthesized a new type of upconversion nanoparticles@carbon dots@meso-SiO2 nanohybrids by integrating two fluorescent materials of lanthanide-doped NaYF4 upconversion nanoparticles (UCNPs) and carbon dots (CDs) into mesoporous silica (mSiO2) to produce a novel sandwichlike core-shell structure and a dual-mode fluorescence from UCNPs and CDs. By tailoring the UCNP core of different upconversion luminescence, all three kinds of dual-mode luminescent UCNPs@CDs@mSiO2 nanohybrids exhibited typical RGB upconversion luminescence under a 980 nm laser and blue downconversion luminescence under a 365 nm UV light. Due to strong the hydrophilic nature of the nanohybrids, they can be further fabricated into environmentally benign luminescent inks for creating highly secured, fluorescent-based, three-dimensional anti-counterfeiting barcodes via inkjet printing. The resultant UCNPs@CDs@mSiO2 inks with a dual-mode and tunable luminescence nature endow the inkjet-printing barcodes with an extremely high encoding capacity and high security. Such dual-mode fluorescent inks and barcodes are simple to fabricate, easy to view, efficient for coding, and difficult to clone, thus making them promising nanomaterials for anti-counterfeiting applications.

Design of novel lanthanide-doped core-shell nanocrystals with dual up-conversion and down-conversion luminescence for anti-counterfeiting printing.

Development of advanced luminescent nanomaterials and technologies is of great significance for anti-counterfeiting applications in global economy, security, and human health, but has proved to be a great challenge. In this work, we design, synthesize, and characterize mono-disperse, dumbbell-shaped lanthanide-doped NaYF4@NaGdF4 core-shell nanoparticles (CSNPs) with dual-mode fluorescence by coating the NaGdF4:Ln'3+ shell onto NaYF4:Ln3+ core nanospheres via a two-step oleic acid mediated thermal decomposition process. Different from the conventional synthesis method to produce spherical nanoparticles, the epitaxial growth of the NaGdF4:Ln'3+ shell onto the nanosphere cores and the lattice mismatch between ß-NaGdF4 and ß-NaYF4 nanocrystals enable the formation of dumbbell-shaped CSNPs, as evidenced by the morphological evolution of CSNPs and as explained by the Ostwald ripening growth mechanism. By tailoring different doped lanthanide ions in the core and the shell, the resultant CSNPs exhibit tunable but different up-/down-conversion luminescence under the irradiation of a 980 nm laser and 254 nm UV light, respectively. Finally, these hydrophilic CSNPs are further fabricated into environmentally benign luminescent inks for inkjet printing to create a variety of dual-mode fluorescent patterns (peacock, temple, and a logo of "Hunan University of Technology") on different paper-based substrates (A4 paper, envelope, and postcard). Our dual-mode light-responsive CSNPs, along with an easy fabrication method, provide a simple and promising material and technique for anti-counterfeiting applications.

Synthesis of Lanthanide-Ion-Doped NaYF4 RGB Up-Conversion Nanoparticles for Anti-Counterfeiting Application.

Well-defined and mono-dispersed lanthanide-ion-doped NaYF4 up-conversion nanoparticles (UCNPs) were synthesized via thermal decomposition using lanthanide oleate as the precursor. By rational selecting the dopant pairs of the doped lanthanide ions (Y3+, Yb3+, Er3+ and Tm3+) with accurate molar ratios, three-primary-color (RGB) UCNPs which exhibited green (UCNPs-G), blue (UCNPs-B) and red (UCNPs-R) fluorescence, respectively, were prepared. The X-ray diffraction (XRD) patterns showed that the three UCNPs were purely hexagonal-phase NaYF4 crystals. Transmission electron microscopy (TEM) images revealed that the synthesized UCNPs exhibited well-defined nanosphere morphology with uniform size distribution. The average diameters were 23.95±3.35 nm for UCNPs-G, 20.63±2.59 nm for UCNPs-B, and 19.24±2.37 nm for UCNPs-R, respectively. After surface modification employing polyacrylic acid (PAA) as modifier, the obtained UCNPs were converted to be hydrophilic, which can be used as fillers to construct luminescent polymer films and luminescent ink in anti-counterfeiting application.