Composite Nanoprobe Research Articles

Construction of an upconversion luminescence composite nanoprobe for ratiometric single particle imaging detection of hydrogen peroxide in food

Hydrogen peroxide (H2O2) is associated with diseases and food safety. Thus, it is essential to achieve sensitive and efficient detection of H2O2. Herein, a ratiometric luminescence composite nanoprobe was designed for single particle imaging sensing of H2O2 by combining NaYbF4:Er@NaYbF4:Tm@NaGdF4:Yb upconversion nanoparticles (UCNPs) with cyanine dye IR-628. High brightness NaYbF4:Er@NaYbF4:Tm@NaGdF4:Yb UCNPs with double-peak emission (665 and 812 nm) were synthesised. Cyanine dye IR-628 with an absorption peak at 628 nm was synthesised and served as a recognition unit. More importantly, on the basis of the upconversion luminescence total internal reflection imaging technique, we developed a ratiometric single particle imaging quantitative analysis for sensing H2O2 with a limit of quantitation of 5 nM. This ratiometric single particle imaging method not only greatly eliminates the influence of the probe concentration and instrumental and environmental factors, but also reduces the dosage of the reagent used and improves the sensitivity of detection.

Dual-targeting lanthanide-ICG-MOF nanoplatform for cancer Theranostics: NIR II luminescence imaging guided sentinel lymph nodes surgical navigation.

Sentinel lymph node imaging is important for breast tumor staging and prediction of postoperative metastasis. However, clinical sentinel lymph node imaging has limitations such as low specificity, low contrast, and short retention time. The combination of bio-conjugates chemistry and luminescence technology may achieve the specific targeting effect. In this research, we designed a dual-targeting composite nanoprobe (∼50nm) using a metal-organic framework (MOF) as carrier, loaded with lanthanide and ICG, and combined with hyaluronic acid and folic acid to detect metastatic lymph nodes. The coupled hyaluronic acid and folic acid can target to the tumor cells and dentritic cells with a dual-targeting effect. The FA-HA/ZIF-8@ICG nanoprobes can accumulate rapidly in sentinel lymph node with a stronger luminescence intensity (1.6 times) than that of normal popliteal lymph nodes in vivo, thus distinguish metastatic sentinel lymph node from normal effectively. Furthermore, due to the MOF carrier, the integrated lanthanide and near-infrared dye by transferring the absorbed excitation energy from ICG to Nd3+ can enhance the signal-to-background ratio of NIR II imaging and have long retention time in vivo imaging. Finally, the FA-HA/ICG@Ln@ZIF-8 nanoplatform increased the penetration depth and contrast of imaging, prolonged the retention time, and achieved the sentinel lymph nodes surgical resection. This study has important implications for lymph node imaging and surgical navigation.

Construction of Aggregation-Induced Emission Molecule-MnO2 Composite Nanoprobe and Its Application in Alkaline Phosphatase Detection.

Alkaline phosphatase (ALP) is among the most studied enzymes by far, playing an important role in the metabolism of organisms and the regulation of protein activity. Herein, a label-free composite nanoprobe is constructed by combining inorganic nanomaterials and aggregation-induced emission (AIE) molecule to achieve highly sensitive and selective detection of ALP. Negatively charged 9,10-bis [2-(6-sulfonatopropoxyl) naphthylethenyl] anthracene (BSNVA) molecule is synthesized, which has the AIE performance and can be assembled on the surface of amino-SiO2 nanoparticles through electrostatic interaction for fluorescence enhancement. MnO2 nanosheets are rich in negative charges, enabling them to be wrapped on the surface of the amino-SiO2 nanosphere to shield the positive charge on its surface, making it impossible for BSNVA to accumulate on the surface and then weakening the bio-fluorescence of the system. Furthermore, with catalyzed substrates induced by ALP, generating ascorbic acid and the redox reaction between ascorbic acid and MnO2, the nanoprobe helps in realizing the high-sensitivity detection of ALP with a detection limit of 0.38 mU/mL. The proposed strategy requires no complex cleaning and modification processes and can overcome the quenching effect caused by the aggregation of traditional organic dyes, proving to be a simple, low-cost and "turn-on" fluorescent detection method for ALP.

A fluorescence sensor probe based on porous carbon, molecularly imprinted polymer and graphene quantum dots for the detection of trace sulfadimethoxine

A hierarchical composite nanoprobe was fabricated and utilized to detect sulfadimethoxine as a specific and sensitive fluorescent sensor. The hierarchical composite probe integrated graphene quantum dots and porous carbon in molecularly imprinted polymer (GQDs@PC@MIP). The quantitative analysis of sulfadimethoxine was obtained by measuring the quenching of the fluorescence response of the nanoprobe when sulfadimethoxine bound with the selective recognition sites. The fluorescence emission of the composite nanoprobe decreased linearly from 0.10 to 25.0 μg L−1 and the limit of detection was 0.03 μg L−1. The recognition sites were highly specific for the sulfadimethoxine molecule with an imprinting factor of 8.75. The developed hierarchical composite nanoprobe was used to determine sulfadimethoxine in milk. Recoveries between 86.8 and 98.9% were achieved with RSDs lower than 5%. The developed nano-optosensor showed good accuracy, providing results that were in good agreement with HPLC analysis. However, the developed assay showed better sensitivity, required simple and cost-effective instruments and was more convenient to operate.

Preparation of composite nanoprobe PB/CS by in-situ catalytic polymerization and study on its photothermal performance

Photothermal therapy (PTT) is a new treatment, and photoacoustic (PA) imaging-guided PTT has aroused extensive attention recently. Poly-2-phenyl-benzobisthiazole (PB) is a new type of conjugated polymer with good biocompatibility and excellent photothermal properties similar to single-walled CNT. However, the poor hydrophilicity of PB limits its application in biomaterials. In this work, chitosan-Cu(II) network structure was first constructed, and then the Cu(II) in-situ initiated the polymerization of aminobenzenedithiophenol and terephthalonitrile to obtain chitosan/PB composite. The excellent hydrophilicity of chitosan-based nanoparticle has successfully improved the water solubility of the obtained nanoprobe PB/CS. Additionally, PB/CS has an excellent PA signal. Thus, a simple and convenient nanosystem was fabricated and applied for PA imaging-guided PTT.

Fluorescence imaging of glutathione with aptasensor and monitoring deoxynivalenol-induced oxidative stress in living cells

Glutathione (GSH) is an important intracellular antioxidant. It is closely related to the homeostasis of the intracellular redox state which can be changed through deoxynivalenol (DON) exposure. More importantly, GSH deficiency can directly lead to apoptosis and cellular metabolic disorders mediated by intracellular redox homeostasis. Therefore, real-time monitoring of dynamic changes of GSH levels in living cells is urgently needed for the evaluation of intracellular oxidative stress. Herein, for the first time, an aptamer-based recognition composite nanoprobe (Apt-AuNCs-MoS2) was successfully constructed. The nanoprobe was employed for real-time and in situ imaging of DON-induced intracellular GSH changes and evaluation of oxidative stress status. The results indicated that the aptasensor revealed excellent specificity and high sensitivity to GSH in the solution system, and the limit of detection was as low as 35 nM. The results about DON-mediated oxidative stress indicated that the oxidative stress in living cells tends to be saturated with more than 20 ppm DON concentration. Thus, the strategy provides a novel aptasensor for the determination of GSH, offers a promising platform for fluorescence imaging of intracellular GSH in living cells, and further enriches in situ analysis of the in vitro toxicology.

Preparation of cyanine dye sensitized upconversion luminescent nanoprobe and hypochlorous acid detection by light-emitting energy transfer

A novel light-emitting energy transfer (ET) system was designed to detect hypochlorous acid. NaGdF4:Yb,Er@NaGdF4:Yb, Nd upconversion nanoparticles (UCNPs) were sensitized by cyanine dye and formed micelles with the amphiphilic polymer DSPE-PEG-COOH to produce a hydrophilic UCNPs-Dye@DSPE-PEG-COOH nanoprobe. In the presence of hypochlorous acid, the structure of cyanine dyes was destroyed, thus the energy transfer from cyanine dye to UCNPs was inhibited, which results in the luminescent intensity of the composite nanoprobe decreased. Under the optimal conditions, the linear detection range for determination of hypochlorous acid is 0.040–20 μM, and the detection limitation is 0.010 μM. In addition, the method can be utilized to detect hypochlorous acid in serum samples with satisfactory results.

Au nanostars@PDA@Fe3O4-based multifunctional nanoprobe for integrated tumor diagnosis and photothermal therapy

A multifunctional nanoprobe (based on Au nanostars@PDA@Fe3O4) is developed for tumor targeted imaging and targeted photothermal therapy. Au nanostars and Fe3O4 are connected with polydopamine, and combined with antibody-FITC or antibody-quantum dots for in vitro or in vivo fluorescence labeling (FL), respectively, to form the composite nanoprobe. The shape and lattice structure of Au nanostars and Fe3O4 were confirmed with TEM, HRTEM and XRD experiments. Compared with other Au nanoparticles@Fe3O4 composite probes, the Au nanostars@PDA@Fe3O4 structure has a low photothermal conversion threshold. Compared with the corresponding pure Au nanostars, the photothermal efficiency of the probe has increased by 50%, while maintaining 171% and 32% fluorescence enhancement in vitro and in vivo, respectively. Due to the charge transfer channel, the phonon emission of Au can go on in Fe3O4 via the PDA linking. Under the precise guidance of multimodal imaging, the nanoprobe conducts homogeneous photothermal ablation of bulky solid tumors (~ 400 mm3) in a xenograft mouse model. Animal model magnetic resonance imaging (MRI) results found that the MRI T2 signal intensity of the probe was 65% stronger than that of pure Fe3O4 nanoparticles. These results suggest that this nanoplatform is promising for integrated tumor diagnosis and targeted cancer therapy.

A nanoprobe based on molybdenum disulfide nanosheets and silver nanoclusters for imaging and quantification of intracellular adenosine triphosphate

Adenosine triphosphate (ATP), as a high-energy phosphate compound that stores and releases energy in living cells, has an irreplaceable role in many physiological processes and maintenance of biological functions, and can be used as an indicator of many diseases. In this work, a composite nanoprobe, silver nanocluster (AgNC) @ molybdenum disulfide (MoS2), was designed to achieve in situ fluorescence imaging and quantitative analysis of intracellular ATP in HeLa cells by fluorescence spectrometry and inductively coupled plasma mass spectrometry (ICP-MS). The probe was constructed based on the adsorption of DNA-AgNCs by MoS2 nanosheets, and the DNA-AgNCs were prepared with the ATP aptamer as a template, whose fluorescence was initially quenched by MoS2. When the probe was incubated into the cells, intracellular ATP recognized the aptamer sequence and caused the DNA-AgNCs to fall off the MoS2 nanosheets, resulting in fluorescence recovery. Here, AgNCs not only acted as a fluorescence label for imaging, but also as an element tag for quantitative analysis of intracellular ATP with the detection of 107Ag by ICP-MS. The ATP in HeLa cells detected by this method was 24.6 ± 1.7 nmol L−1, which was in good agreement with the test result of the ATP test kit (20.4 ± 0.8 nmol L−1). The proposed method has potential application in medical clinical diagnosis and evaluation of the body’s metabolic level via fluorescence imaging and ICP-MS detection of intracellular ATP.

Dual-Emission Reverse Change Ratio Photoluminescence Sensor Based on a Probe of Nitrogen-Doped Ti3C2 Quantum Dots@DAP to Detect H2O2 and Xanthine.

Titanium carbide quantum dots (Ti3C2 QDs) derived from two-dimensional (2D) Ti3C2Tx (MXene) are the rising-star material recently. Herein, nitrogen-doped Ti3C2 QDs (N-Ti3C2 QDs) were synthesized via a solvothermal method. The obtained N-Ti3C2 QDs exhibited excitation-dependent photoluminescence, antiphotobleaching, and dispersion stability. Furthermore, by combining the N-Ti3C2 QDs and DAP (2,3-diaminophenazine, the oxidative product of o-phenylenediamine) as a composite nanoprobe (N-Ti3C2 QDs@DAP), we developed a dual-emission reverse change ratiometric sensor to quantitatively monitor H2O2 based on photoinduced electron-transfer effects, where N-Ti3C2 QDs acted as the donor and DAP as the acceptor. On the basis of the xanthine converting into H2O2 through the catalysis of xanthine oxidase, the N-Ti3C2 QDs@DAP nanoprobe was also exploited for xanthine sensing. As a result, the proposed assay was demonstrated to be highly sensitive for H2O2 and xanthine with detection limits of 0.57 and 0.34 μM, respectively. In a word, we have investigated the application of N-Ti3C2 QDs in H2O2 and xanthine sensing and opened a new and exciting avenue for the N-Ti3C2 QDs in biosensing.

Construction of a novel GQD based ratiometric fluorescent composite probe for viscosity detection.

Herein, a novel ratiometric fluorescent composite nanoprobe RV-1@GQDs-OH was developed based on OH-functionalized GQDs (GQDs-OH) and molecular probe (RV-1) viaπ-π stacking. Compared with the conventional "on-off" viscosity probes, RV-1@GQDs-OH can be successfully applied in living systems for the ratiometric detection of viscosity changes in the viscosity range of 0-600 cP.

A single-particle enumeration method for the detection of Fe2+ based on a near-infrared core-shell upconversion nanoparticle and IR-808 dye composite nanoprobe.

Ferrous ion (Fe2+) is an important component of hemoglobin and plays a role in transporting O2 to human tissues. If iron deficiency is present, iron deficiency anemia may occur, so it is critical to develop sensitive and accurate methods to detect Fe2+. Herein, a novel luminescence energy transfer (ET) system has been designed for the sensitive detection of Fe2+ by a single-particle enumeration (SPE) method in the near-infrared (NIR) region through combining NIR-to-NIR β-NaGdF4:Yb,Tm@NaYF4 upconversion nanoparticles (UCNPs) and IR-808 dye. IR-808 dye can quench the luminescence of the UCNPs because of the efficient overlap between the absorption spectrum of IR-808 and the emission spectrum of the UCNPs. When Fe2+ and H2O2 are added to the system, the Fenton reaction produces hydroxyl radicals (˙OH). The generated ˙OH reacts with IR-808 and the structure of IR-808 is destroyed. As a result, the ET process is suppressed, causing recovery of the luminescence of the UCNPs, which is reflected as an increase in the number of luminescent particles. Accurate quantification of Fe2+ is achieved by statistically counting the target concentration-dependent luminescent particles. Under the optimal conditions, the linear detection range of Fe2+ is 5-10 000 nM, which is much wider than the ensemble luminescence spectra measurements in bulk solution. Moreover, this strategy can be applied to detection in serum samples with satisfactory results.

A Unique Approach to Development of a Multiratiometric Fluorescent Composite Probe for Multichannel Bioimaging.

Ratiometric fluorescent probes have shown great potential for optical sensing and have been widely used for bioimaging. However, due to extremely stringent molecular design, most conventional organic ratiometric fluorescent probes can only achieve one single ratio. Currently, the detection of a target in living systems in a multiratiometric manner is prominently challenging. Therefore, it is of great significance to develop a method to construct the multiratiometric fluorescent probes for accurate quantitative detection of specific small molecules. To address this challenge, we developed a unique multiratiometric composite fluorescent probe. Herein, a new triple-ratiometric fluorescent composite nanoprobe CP@GQDs-OH based on OH-functionalized GQDs (GQDs-OH) and red emission ratiometric fluorescent molecular probe (CP) was prepared through π-π stacking. The novel nanoprobe showed high selectivity for SO2 with three linear ratio changes. Significantly, CP@GQDs-OH was successfully applied for the detection of SO2 in the living cells and zebrafishes by the unprecedented triple-ratiometric fashion.

Electrochemical immunosensor detection of tumor markers based on a GO composite nanoprobe for signal amplification

A novel strategy based on nanoprobes for signal amplification was introduced in an electrochemical immunoassay platform.

Surface Complexation-Based Biocompatible Magnetofluorescent Nanoprobe for Targeted Cellular Imaging

We report the synthesis of a magnetofluorescent biocompatible nanoprobe-following room temperature complexation reaction between Fe3O4-ZnS nanocomposite and 8-hydroxyquinoline (HQ). The composite nanoprobe exhibited high luminescence quantum yield, low rate of photobleaching, reasonable excited-state lifetime, luminescence stability especially in human blood serum, superparamagnetism and no apparent cytotoxicity. Moreover, the nanoprobe could be used for spatio-controlled cell labeling in the presence of an external magnetic field. The ease of synthesis and cell labeling in vitro make it a suitable candidate for targeted bioimaging applications.

A dual mode targeting probe for distinguishing HER2-positive breast cancer cells using silica-coated fluorescent magnetic nanoparticles

We report a composite nanoprobe based on silica-coated magnetic nanoparticles (NPs) for distinguishing breast cancers at different HER2 statuses. The nanoprobe has a core–shell structure, with Fe3O4 NPs as the magnetic core and dye-embedded silica as the fluorescent shell, whose average size is about 150 nm. Besides, the outmost surfaces of the probes were modified with specific antibodies to endow the probe with a targeting ability. With such a structure, the nanoprobe can accomplish dual mode targeting of human breast cancer cells based on fluorescence and magnetic resonance imaging (MRI). In the experiments, three human breast cancer cell lines were used to test the targeting ability of the nanoprobe. Specifically, SKBR3 cells with a high HER2 expression level were used as the model target cells, while MCF7 cells with a lower HER2 expression levels and HER2-negative MDA-MB-231 cells were used as the controls. Both the fluorescence and MRI imaging results confirmed that the nanoprobe can distinguish three cancer cell lines with different HER2 expression levels. With the dual mode imaging and specific targeting properties, we anticipate that the presented nanoprobe may have a great potential in the diagnosis and treatment of cancerous diseases.

Robust one pot synthesis of colloidal silver nanoparticles by simple redox method and absorbance recovered sensing

Conventional synthesis of silver nanoparticles employs a reducing agent and a capping agent. In this report water-soluble silver nanoparticles (AgNPs) were prepared facilely by chemical reduction of Ag(I) ions. 4-Amino-3-(d-gluco-pentitol-1-yl)-4,5-dihydro-1,2,4-triazole-5-thione (AGTT) was used both as reducing and stabilizing agent. Direct heating methodology was found to be more suitable for achieving particles with a hydrodynamic diameter of ∼20nm. AGTT exists as tautomer in solution form and our studies indicate that –NH2 group is involved in the reduction and stabilization of Ag+ and thione (Δ=S) group of AGTT is possibly involved in stabilizing the nanoparticles via coordinate covalent linkage. Characterization of synthesized silver nanoparticles was performed by UV–vis, FT-IR and by FESEM. Based on the absorption properties of synthesized AgNPs, we used AgNPs to detect bovine serum albumin (BSA) and AgNPs-BSA composite nanoprobe was further applied to detect Cu2+ based on absorbance recovery. The proposed method has advantages over existing methods in terms of rapid synthesis and stability of AgNPs and their applications. Analysis is reproducible, cost effective and highly sensitive. The lowest detectable concentration of BSA in this approach is 3nM, and for Cu2+ it can detect upto 200pM.