Enzyme-targeted near-infrared fluorescent probe for organophosphorus pesticide residue detection.

Pesticide residues significantly affect food safety and harm human health. In this work, a series of near-infrared fluorescent probes were designed and developed by acylating the hydroxyl group of the hemicyanine skeleton with a quenching moiety for monitoring the presence of organophosphorus pesticides in food and live cells. The carboxylic ester bond on the probe was hydrolyzed catalytically in the presence of carboxylesterase and thereby the fluorophore was released with near-infrared emission. Notably, the proposed probe 1 exhibited excellent sensitivity against organophosphorus based on the carboxylesterase inhibition mechanism and the detection limit for isocarbophos achieved 0.1734 µg/L in the fresh vegetable sample. More importantly, probe 1 allowed for situ visualization of organophosphorus in live cells and bacteria, meaning great potential for tracking the organophosphorus in biological systems. Consequently, this study presents a promising strategy for tracking pesticide residues in food and biological systems.

A fluorescent probe based on aptamer gold nanoclusters for rapid detection of mercury ions.

The mercuric ion (Hg2+) is a hazardous pollutant that is widely distributed in living organisms, foods, and environments with highly toxic and bio-accumulative properties. In the present study, a fluorescent probe based on aptamer gold nanoclusters (apt-AuNCs) was prepared for the ultrasensitive detection of Hg2+ in food. The principle underlying the prepared probe was the quenching of the fluorescence of apt-AuNCs in the presence of Hg2+ due to the strong metallophilic interactions between the 5d10 centers of Hg2+ and Au+. Under optimal conditions, the proposed fluorescent probe exhibited a linear relationship with Hg2+ concentration within the range of 2-200 nM (R2 = 0.9960). In addition, the limit of detection (LOD) was 0.0158 nM, which is below the Chinese standard value of 25 nM for Hg2+ in food. Furthermore, the apt-AuNCs were applied to detect Hg2+ in spinach and crawfish samples, with recovery percentages of 91.99%∼108.06%, meaning that apt-AuNCs could be used as a promising probe to detect Hg2+ in complex food samples.

Engineering sensitive gas sensor based on MOF-derived hollow metal-oxide semiconductor heterostructures.

Metal-organic frameworks (MOFs) derived hollow heterostructured metal oxide semiconductors (MOSs) are a class of functional porous materials exhibiting distinctive physiochemical properties. Owing to the unique advantages, including large specific surface, high intrinsic catalytic performance, abundant channels for facilitating electron transfer and mass transport, and strong synergistic effect between different components, MOF-derived hollow MOSs heterostructures can work as promising candidates for gas sensing, which have thus attracted increasing attention. Aiming to provide a deep understanding on the design strategy and MOSs heterostructure, this review presents a comprehensive overview on the advantages and applications of MOF-derived hollow MOSs heterostructures when they used n for the detection of toxic gases. In addition, a deep discussion about the perspective and challenge of this interesting field is also well organized, hoping to provide guidance for the future design and development of more accurate gas sensors.

An Adhesive Bioink toward Biofabrication under Wet Conditions.

Three-dimensional (3D) bioprinting is driving significant innovations in biomedicine over recent years. Under certain scenarios such as in intraoperative bioprinting, the bioinks used should exhibit not only cyto/biocompatibility but also adhesiveness in wet conditions. Herein, an adhesive bioink composed of gelatin methacryloyl, gelatin, methacrylated hyaluronic acid, and skin secretion of Andrias davidianus is designed. The bioink exhibits favorable cohesion to allow faithful extrusion bioprinting in wet conditions, while simultaneously showing good adhesion to a variety of surfaces of different chemical properties, possibly achieved through the diverse bonds presented in the bioink formulation. As such, this bioink is able to fabricate sophisticated planar and volumetric constructs using extrusion bioprinting, where the dexterity is further enhanced using ergonomic handheld bioprinters to realize in situ bioprinting. In vitro experiments reveal that cells maintain high viability; further in vivo studies demonstrate good integration and immediate injury sealing. The characteristics of the bioink indicate its potential widespread utility in extrusion bioprinting and will likely broaden the applications of bioprinting toward situations such as in situ dressing and minimally invasive tissue regeneration.

Micropore-Forming Gelatin Methacryloyl (GelMA) Bioink Toolbox 2.0: Designable Tunability and Adaptability for 3D Bioprinting Applications.

It is well-known that tissue engineering scaffolds that feature highly interconnected and size-adjustable micropores are oftentimes desired to promote cellular viability, motility, and functions. Unfortunately, the ability of precise control over the microporous structures within bioinks in a cytocompatible manner for applications in 3D bioprinting is generally lacking, until a method of micropore-forming bioink based on gelatin methacryloyl (GelMA) was reported recently. This bioink took advantage of the unique aqueous two-phase emulsion (ATPE) system, where poly(ethylene oxide) (PEO) droplets are utilized as the porogen. Considering the limitations associated with this very initial demonstration, this article has furthered the understanding of the micropore-forming GelMA bioinks by conducting a systematic investigation into the additional GelMA types (porcine and fish, different methacryloyl-modification degrees) and porogen types (PEO, poly(vinyl alcohol), and dextran), as well as the effects of the porogen concentrations and molecular weights on the properties of the GelMA-based ATPE bioink system. This article exemplifies not only the significantly wider range of micropore sizes achievable and better emulsion stability, but also the improved suitability for both extrusion and digital light processing bioprinting with favorable cellular responses.

Vertical Extrusion Cryo(bio)printing for Anisotropic Tissue Manufacturing.

Due to the poor mechanical properties of many hydrogel bioinks, conventional 3D extrusion bioprinting is usually conducted based on the X-Y plane, where the deposited layers are stacked in the Z-direction with or without the support of prior layers. Herein, a technique is reported, taking advantage of a cryoprotective bioink to enable direct extrusion bioprinting in the vertical direction in the presence of cells, using a freezing plate with precise temperature control. Of interest, vertical 3D cryo-bioprinting concurrently allows the user to create freestanding filamentous constructs containing interconnected, anisotropic microchannels featuring gradient sizes aligned in the vertical direction, also associated with enhanced mechanical performances. Skeletal myoblasts within the 3D-cryo-bioprinted hydrogel constructs show enhanced cell viability, spreading, and alignment, compared to the same cells in the standard hydrogel constructs. This method is further extended to a multimaterial format, finding potential applications in interface tissue engineering, such as creation of the muscle-tendon unit and the muscle-microvascular unit. The unique vertical 3D cryo-bioprinting technique presented here suggests improvements in robustness and versatility to engineer certain tissue types especially those anisotropic in nature, and may extend broad utilities in tissue engineering, regenerative medicine, drug discovery, and personalized therapeutics.

Terminal protection of peptides by interactions with proteins: A "signal-on" peptide-templated gold nanocluster beacon for label-free protein detection.

Characterization of the protein-peptide interactions are a critical for understanding the functions and signal pathways of proteins. Herein, a new finding of universal terminal protection that protein bind specifically with peptide and provide a protective coating to prevent peptide hydrolysis in the presence of peptidase. On the basis of this mechanism, we first reported a novel label-free fluorescence biosensor strategy that utilizes the protection of specific terminal protein on peptide-templated gold nanocluster (AuNCs) beacon for the detection of proteins. The fluorescence quenching of peptide-templated AuNCs can be effectively inhibited with increasing concentration of the specific protein, exhibiting a satisfactory sensitivity and selectivity toward protein with the detection limit of MDM2 and gp120 are 0.0019 U/mL and 0.0012 U/mL, respectively. The developed label-free fluorescence biosensor strategy provides new ideas to detect and screen protein for analyzing protein-peptide interaction in biomedical applications.

A sensitive "Switch-on" phosphorescent probe for ferrous iron quantification in drug and In vitro imaging of living cells.

Iron plays an important role in various physiological processes. However, the detailed biological functions of iron have not been sufficiently explored because of a lack of effective methods to monitoring iron, especially the labile ferrous ion (Fe2+). In the current study, a novel turn-on phosphorescent probe for Fe2+ quantification and visualization has been proposed based on the hybrid nanocomposite of manganese dioxide and gemini iridium complex (MnO2-GM-Ir). The surfactant-like GM-Ir with positive charges was beneficial to combine with the negatively charged manganese dioxide (MnO2) nanosheets, and thus endowing the MnO2-GM-Ir nanocomposite excellent dispersion ability in the water as well as efficiently avoiding the interference to the detection caused by the agglomeration of nanocomposite. Phosphorescence of GM-Ir was effectively quenched by MnO2 nanosheets through fluorescence resonance energy transfer (FRET) and the inner filter effect (IFE), while the phosphorescence could be significantly recovered in the presence of Fe2+via a selective Fe2+-mediated reduction of MnO2 nanosheets, indicating a highly-specific selectivity towards Fe2+ with a low detection limit (80 nM). The drug test assay and in vitro imaging studies further proved that the MnO2-GM-Ir nanocomposite could be employed as a promising probe for the quantitative detection of exogenous Fe2+ in drug and in vitro imaging of living cells.

A novel mitochondria-targeted phosphorescence probe for hypochlorite ions detection in living cells.

Monitoring hypochlorite anion (ClO-) in living cells is particularly meaningful and valuable, because over-exposure of the ClO- may cause a potential health hazard towards animals and humans. Considering the special structure and properties of the gemini surfactant, a novel amphiphilic gemini-iridium complex Ir[(ppy-iso)2(bpy-tma2Br2)] (Ir-iso) with isoniazide as a recognition site for ClO- was designed. The Ir-iso possessed an excellent water-solubility as well as a strong ClO- binding capacity, as revealed from the rapid response of emission signal towards ClO-. It was worth noting that such probe had a highly-specific selectivity with a low detection limit (20.5 nM) and was suitable in physiological environment. The cell viability assay, cell imaging, and co-location studies further proved that the Ir-iso had little cytotoxicity and was specifically localized in the mitochondria of breast cancer cells, being a promising candidate of chemo-sensor to detect the endogenous ClO- in living cells.

Amphiphilic gemini-iridium (III) complex for rapid and selective detection of picric acid in water and intracellular.

Inspired by the structure and properties of gemini surfactant, a novel amphiphilic gemini-iridium complex (GIC-Ir) has been developed, which can spontaneously form vesicles by self-assembly and exhibit excellent dispersibility and high emission intensity in water. The emission of GIC-Ir can be rapidly and selectively quenched by picric acid (PA) due to the aromatic groups and two long-chain quaternary ammonium (QA) groups with positive charge, which endow GIC-Ir vesicles outstanding capability to capture negatively charged PA, and greatly promote the interaction between GIC-Ir and PA. Theoretical calculations and spectral studied indicated that the photoinduced electron transfer and resonance energy transfer may be responsible to the emission quenching. Furthermore, the real water samples and in vitro studies further prove that GIC-Ir can be used as a promising chemosensor for the detection of PA both in water and intracellular.

Amphiphilic Gemini Iridium(III) Complex as a Mitochondria-Targeted Theranostic Agent for Tumor Imaging and Photodynamic Therapy.

Clinical diagnostics and therapeutics of tumors are significantly benefitted by the development of multifunctional theranostic agents, which integrate tumor targeting, imaging, and therapeutics. However, the integration of imaging and therapy functionalities to a unimolecular framework remains a great challenge. Herein, a family of amphiphilic gemini iridium(III) complexes (GIC), Ir1-Ir6, are synthesized and characterized. The presence of quaternary ammonium (QA) groups endows GIC with adjustable water solubility and excellent self-assembly properties. Spectroscopic and computational results reveal that introducing QA groups into cyclometalating ligands (CN ligands) can overcome the drawback of aggregation-caused emission quenching and ensure Ir1-Ir3 with high emission intensity and excellent singlet oxygen (1O2) generation ability in aqueous media. Cell-based assays indicate that Ir3 shows higher cellular uptake efficiency and localizes specifically in the mitochondria, as well as exhibits outstanding photostability and an impressive phototoxicity index with satisfactory performance in mitochondria-targeted imaging and photodynamic therapy (PDT) of tumor cells. Furthermore, in vivo studies further prove that Ir3 possesses excellent antitumor activity and remarkably inhibits the growth of the HepG2 cells under PDT treatment. Consequently, this study presents a promising strategy for designing clinical application potential multifunctional iridium complex theranostic agents for mitochondria-targeted imaging and PDT in a single molecular framework.

A cyclometalated iridium(III) complex-based fluorescence probe for hypochlorite detection and its application by test strips.

A new cyclometalated iridium(III) complex-based fluorescence probe (IrCN) for hypochlorite (ClO-) has been synthesized and characterized. The probe displayed nonfluorescent around 577 nm, while a 54-fold enhancement in fluorescence emission intensity was observed after the addition of ClO- due to the removal of C=N isomerization effect. Such "turn-on" fluorescence probe worked excellently in wide pH range (5-12) with short response time (<20 s) and the detection limit was as low as 0.11 µM. In addition, IrCN exhibited high selectivity towards ClO- even in the presence of other competing species. Furthermore, IrCN was successfully integrated in fluorescent test strips for real-time detection of ClO-.