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Nanomaterials · 2022 ·Vol. 12 ·期 11 ·1787 · IF 5.719

Novel Fluorescent Probe Based on Rare-Earth Doped Upconversion Nanomaterials and Its Applications in Early Cancer Detection

Zhou Ding,Yue He,Hongtao Rao,Le Zhang,William Nguyen,Jingjing Wang,Ying Wu,Caiqin Han,Christina Xing,Changchun Yan,Wei Chen,Ying Liu

In this paper, a novel rare-earth-doped upconverted nanomaterial NaYF4:Yb,Tm fluorescent probe is reported, which can detect cancer-related specific miRNAs in low abundance. The detection is based on an upconversion of nanomaterials NaYF4:Yb,Tm, with emissions at 345, 362, 450, 477, 646, and 802 nm, upon excitation at 980 nm. The optimal Yb3+:Tm3+doping ratio is 40:1, in which the NaYF4:Yb,Tm nanomaterials have the strongest fluorescence. The NaYF4:Yb, Tm nanoparticles were coated with carboxylation or carboxylated protein, in order to improve their water solubility and biocompatibility. The two commonly expressed proteins, miRNA-155 and miRNA-150, were detected by the designed fluorescent probe. The results showed that the probes can distinguish miRNA-155 well from partial and complete base mismatch miRNA-155, and can effectively distinguish miRNA-155 and miRNA-150. The preliminary results indicate that these upconverted nanomaterials have good potential for protein detection in disease diagnosis, including early cancer detection.Keywords:upconversion nanomaterials;novel fluorescent probe;miRNA-155;miRNA-150

研究领域: 生物医学 · 纳米技术 · 癌症诊断
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RSC Advances · 2024 ·Vol. 14 ·期 8 ·4990-5000 · IF 3.9

Morphology controlled synthesis of Fe3+-doped upconversion nanomaterials

Fuhua Huang,Cong Liu,Zhuoya Zhao,Li Wang,Jinglai Zhang,Hans Ågren,Jerker Widengren,Haichun Liu

This work details the synthesis of paramagnetic upconversion nanoparticles doped with Fe3+ in various morphologies via the thermal decomposition method, followed by comprehensive characterization of their structures, optical properties and magnetism using diverse analytical techniques. Our findings demonstrate that by precisely modulating the ratio of oleic acid to octadecene in the solvent, one can successfully obtain hexagonal nanodiscs with a consistent and well-defined morphology. Further adjustments in the oleic acid to octadecene ratio, coupled with fine-tuning of the Na+/F− ratio, led to the production of small-sized nanorods with uniform morphology. Significantly, all Fe3+-doped nanoparticles displayed pronounced paramagnetism, with magnetic susceptibility measurements at 1 T and room temperature of 0.15 emu g−1 and 0.14 emu g−1 for the nanodiscs and nanorods, respectively. To further enhance their magnetic properties, we replaced the Y-matrix with a Gd-matrix, and by fine-tuning the oleic acid/octadecene and Na+/F− ratios, we achieved nanoparticles with uniform morphology. The magnetic susceptibility was 0.82 emu g−1 at 1 T and room temperature. Simultaneously, we could control the nanoparticle size by altering the synthesis temperature. These upconversion nanostructures, characterized by both paramagnetic properties and regular morphology, represent promising dual-mode nanoprobe candidates for optical biological imaging and magnetic resonance imaging.

CAS / MDL: 112-80-1 112-88-9
研究领域: 纳米技术 · 材料科学 · 生物医学工程
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ANALYTICAL CHEMISTRY · 2017 · IF 6.32

Near-Infrared-to-Ultraviolet Light-Mediated Photoelectrochemical Aptasensing Platform for Cancer Biomarker Based on Core–Shell NaYF4:Yb,Tm@TiO2 Upconversion Microrods

Zhenli Qiu,Jian Shu,Dianping Tang

Titanium dioxide (TiO2; as a potential photosensitizer) has good photocurrent performance and chemical stability but often exhibits low utilization efficiency under ultraviolet (UV) region excitation. Herein, we devised a near-infrared light-to-UV light-mediated photoelectrochemical (PEC) aptasensing platform for the sensitive detection of carcinoembryonic antigen (CEA) based on core–shell NaYF4:Yb,Tm@TiO2 upconversion microrods by coupling with target-triggered rolling circle amplification (RCA). The upconversion microrods synthesized through the hydrothermal reaction could act as a photosensing platform to convert the near-infrared (near-IR) excitation into UV emission for generation of photoinduced electrons. The target analyte was determined on a functional magnetic bead by using the corresponding aptamers with a sandwich-type assay format. Upon target CEA introduction, a complex was first formed between capture aptamer-1-conjugated magnetic bead (Apt1-MB) and aptamer-2-primer DNA (Apt2-pDNA). Thereafter, the carried primer DNA by the aptamer-2 paired with linear padlock DNA to trigger the RCA reaction. The guanine (G)-rich product by RCA reaction was cleaved by exonuclease I and exonuclease III (Exos I/III), thereby resulting in the formation of numerous individual guanine bases to enhance the photocurrent of core–shell NaYF4:Yb,Tm@TiO2 upconversion microrods under near-IR illumination (980 nm). Under optimal conditions, the near-IR light-mediated PEC aptasensing system could exhibit good photoelectrochemical response toward target CEA and allowed for the detection of target CEA as low as 3.6 pg mL–1. High reproducibility and good accuracy were achieved for analysis of human serum specimens. Importantly, the near-IR-activated PEC aptasensing scheme provides a promising platform for ultrasensitive detection of other biomolecules.

研究领域: 生物医学工程 · 分析化学 · 癌症诊断
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Nanomaterials · 2021 ·Vol. 11 ·期 12 ·3395 · IF 5.076

SiO2 Coated Up-Conversion Nanomaterial Doped with Ag Nanoparticles for Micro-CT Imaging

Wei Zhang,Yanli Lu,Yang Zang,Jinhui Han,Qingyun Xiong,Jinping Xiong

In this study, a new method for synthesizing Ag-NaYF4:Yb3+/Er3+@ SiO2nanocomposites was introduced. Using a hydrothermal method, the synthesized Yb3+- and Er3+-codoped NaYF4up-conversion luminescent materials and Ag nanoparticles were doped into up-conversion nanomaterials and coated with SiO2up-conversion nanomaterials. This material is known as Ag-UCNPs@SiO2, it improves both the luminous intensity because of the doped Ag nanoparticles and has low cytotoxicity because of the SiO2coating. The morphology of UCNPs was observed using scanning electron microscopy (SEM), and the mapping confirmed the successful doping of Ag nanoparticles. Successful coating of SiO2was confirmed using transmission electron microscopy (TEM). Fluorescence spectra were used to compare changes in luminescence intensity before and after doping Ag nanoparticles. The reason for the increase in luminescence intensity after doping with Ag nanoparticles was simulated using first-principles calculations. The cytotoxicity of Ag-UCNPs@SiO2was tested via the cell counting kit-8 (CCK-8) method, and its imaging ability was characterized using the micro-CT method.Keywords:up-conversion;nanomaterials;CT imaging

研究领域: 生物医学工程 · 纳米技术 · 医学影像学
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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

Ultrasensitive and reusable upconversion-luminescence nanofibrous indicator paper for in-situ dual detection of single droplet

Jun Zhang,Xin Li,Jun-Cheng Zhang,Jia-Shu Yan,Haotian Zhu,Jiang-Jun Liu,Ru Li,Seeram Ramakrishna,Yun-Ze Long

Traditional indicator paper is disposable after use, requires a large number of target solutions and can only detect one item. In this study, recyclable upconversion-fluorescence indicator papers consist of upconversion nanorods and plasmonic nanostructures are fabricated by electrospinning. Human-body fluids containing different riboflavin concentration and pH are used as target solution, because these two items are usually detected in clinic to distinguish ambiguous diseases but often performed by two different testing processes that inevitably need more target solutions. Significantly different from conventional detecting system, this recyclable indicator paper can simultaneously achieve riboflavin and pH detections by using only a single droplet of target solution. As low as 0.01 ppm riboflavin can be sensitively detected, which is superior to most reported detection limit of fluorescence sensor. Moreover, this indicator paper can detect a single droplet (~10 μl) rather than a large amount of target solution (>1 ml) needed by traditional detecting system, and the pH can also be simultaneously in-situ detected using the same indicator paper. After the detection, the target solution is easily removed so that it brings about excellent recyclability, which is another advantage over traditional detecting system.

研究领域: 生物医学工程 · 分析化学
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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

Development of a highly sensitive immuno-type fluorescence sensor utilising rare earth element-doped upconversion nanomaterials and graphene oxide for the detection of fenitrothion residues in food

Konghao Peng,Anqi Bai,Yue Wu,Shihan Wang,Heran Gao,Shurong Li,Lingyan Zhang,Min Jin,Wei Peng,Peijun Meng

Fenitrothion is an organophosphorus insecticide, and its residues in agricultural goods pose significant risks to human health. Therefore, prompt and precise identification of fenitrothion residues in agricultural commodities is of significant importance. This study employed rare earth element-doped upconversion nanomaterials (REEs-UCNPs) and graphene oxide (GO) to develop an immune-based fluorescence sensor for fenitrothion detection. The nanomaterials NaYF 4 :Yb,Er@NaYF 4 were synthesised via the solvothermal method, with polyacrylic acid modified on their surface through ligand exchange. NaYF 4 :Yb,Er@NaYF 4 was conjugated with a monoclonal antibody using a glutaraldehyde cross-linking method, while GO was conjugated with the fenitrothion antigen. The precise interaction between the antigen and the antibody resulted in the binding of NaYF 4 :Yb,Er@NaYF 4 to GO. When exposed to an excitation wavelength of 980 nm, GO could absorb the fluorescence emitted by NaYF 4 :Yb,Er@NaYF 4 at 542 nm through the fluorescence resonance energy transfer mechanism. The fenitrothion pesticide could competitively bind to the monoclonal antibody with the antigen, thereby restoring the system’s fluorescence. Under ideal conditions, the sensor’s detection limit for fenitrothion was 0.081 ng/mL, with a linear range of 0.1–100 ng/mL. The spiking recoveries of fenitrothion in seven real samples varied from 91.79 % to 105.43 %, with relative standard deviations of 1.81–10.63 %. This study effectively developed a sensitive, accurate and specific immuno-type fluorescence sensor for the efficient and precise quantitative detection of fenitrothion in agricultural materials.

研究领域: 食品科学 · 分析化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2018 · IF 5.667

Shape-controllable synthesis of silica coated core/shell upconversion nanomaterials and rapid imaging of latent fingerprints

Lijia Wang,Wenhong Gu,Zhengbin An,Qingyun Cai

Upconversion nanomaterials with complex morphologies have attracted considerable interests due to morphology-dependent properties. In this work, silica coated-NaYF 4 upconversion nanomaterials (NaYF 4 @SiO 2 ) of various shapes – nanorods, nanodumbbell and nanowire – were synthesized through controlling the ratio of NaYF 4 nanorods to silica. The nanodumbbell and nanowire morphologies showed much higher fluorescence efficiency than that of nanorod. These upconversion nanoparticles (UCNPs) exhibited a high signal-to-noise ratio, effectively circumvent luminescence quenching and excellent photo-stability under 980 nm excitation. In particular, the as-prepared nanodumbbells were successfully applied to rapid latent fingerprint imaging, showing advantages over commercial fluorescence reagents. Such nanoparticles with further modification are expected to have a great potential in forensic and biological sciences.

研究领域: 材料科学 · 生物医学工程
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IEEE SENSORS JOURNAL · 2024 · IF 4.3

Ratiometric Design of Optical Fiber Sensor with Temperature Correction for Detection of Hydroxyl Radicals

Lei Li,Xiaoyu Sun,Zeman Shao,Yanchun Wei,Sen Liu,Zhongmei Yang,Qiuyang Zhang,Changjiang Pan

Detection of hydroxyl radicals (·OH) is often required in environmental governance and biomedicine. To enhance the sensing accuracy and stability, this study constructed a temperature-corrected and ratio-calibrated sensor for sensitive hydroxyl radical detection by loading upconversion nanomaterials and dye molecules methylene blue (MB) on optical fibers. Based on the multi-color emission of upconversion materials and the ·OH trapping of MB molecules, the ·OH detection and real-time temperature correction are achieved. The results show that the MB molecules can react sensitively and specifically with ·OH. Under near-infrared excitation, precise information on temperature and MB absorption is obtained by detecting the ratio of multiple characteristic wavelengths of light, thus enabling the quantitative detection of ·OH. The limit of detection (LOD) of ·OH can be reach as low as 0.26 μM. The method shows the advantages of high sensitivity, low cost, and ease of miniaturization and is expected to be applied in environmental and biomedical fields.

研究领域: 环境科学 · 生物医学工程
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SENSORS AND ACTUATORS B-CHEMICAL · 2023 · IF 8.4

SDR-assisted multi-primers triggering functional signal hairpin probe for miRNA detection with enzyme-free and high sensitivity

Weihua Zhao,Jun Xu,Hongbo Li,Shengliang Zhong,Ruqin Yu

MiRNA can exist in body fluids and its changes directly affect human life and health, which has been a research hotspot in recent years. In this work, we designed an enzyme-free sensing system for highly sensitive detection of miRNA-21 based on strand displacement reaction (SDR) that can recycle the target and functional hairpin probes (HP) that modified on upconversion nanomaterials (UCNPs). The target gene circulates through the SDR process and completes the initial signal amplification process. Then, the C2 sequences and targets released by the SDR process can continue to be combined with functional hairpin probes modified with fluorophore and quenching groups. After infrared irradiation, HP is broken, and C2 or the target can take the fluorophores away from the quenching group, so that the fluorescence signal can be detected to achieve highly sensitive detection of the target. In sensing system, the use of magnetic beads can reduce the background signal during the reaction process, and the functional hairpin probe can accurately turn the signal on and off. The sensor system not only shows excellent detection performance (detection limit of 30.3 fM) in buffer and actual detection, but also has excellent selectivity, which can provide a new detection method for miRNA-21 detection.

CAS / MDL: 9048-46-8
研究领域: 生物化学 · 分子生物学 · 纳米医学
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JOURNAL OF ELECTRONIC MATERIALS · 2024 ·Vol. 53 ·期 5 ·2514-2523 · IF 2.2

Upconversion Spectral Modulation and Temperature Sensing of NaYF4:Yb3+/Ho3+/Tm3+/Gd3+ Nanorods with Resistance to Thermal Quenching

Zhou Wei,Yang Jian,Jin Xiangliang

Upconversion (UC) nanomaterials are of interest to researchers because of their excellent photostability, effective quantum efficiency and optical temperature dependence. However, most UC nanomaterials are thermally quenched, which causes optical nanothermometers to be susceptible to their own thermal effects, reducing the accuracy of temperature measurements. In this paper, NaYF 4 :Yb 3+ /Ho 3+ /Tm 3+ /Gd 3+ nanorods with UC luminescence and resistance to thermal quenching are prepared through a simple hydrothermal method. The UC luminescence intensity of NaYF 4 :Yb 3+ /Ho 3+ /Tm 3+ /Gd 3+ nanorods is adjusted by doping with Tm 3+ ions. The luminescence intensity at each location shows different temperature dependence as the temperature increases. When the temperature reaches 573 K, the integrated luminescence intensity is three times that at 293 K. At the same time, the intensity at all temperature points in the range of 293–573 K is greater than the intensity at 293 K, which shows that the nanorods have excellent resistance to thermal quenching. In addition, the relative sensitivity ( S r ) of LIR( I 696 / I 476 ), LIR( I 696 / I 541 ), LIR( I 696 /I 646 ), LIR( I 696 / I 802 ), and LIR( I 541 / I 476 ) is investigated based on the luminescence intensity ratio (LIR) technique. The S r of LIR( I 696 / I 802 ) is found to have larger values in the low-temperature range, while S r of LIR( I 696 / I 476 ) has larger values in the high-temperature range. The use of LIR( I 696 / I 802 ) and LIR( I 696 / I 476 ) in separate temperature bands allows S r to reach 0.93–1.67 %K −1 in the range of 293–573 K, confirming that the nanorods have high S r over a wide temperature interval. This study indicates that the NaYF 4 :Yb 3+ /Ho 3+ /Tm 3+ /Gd 3+ nanorods are promising candidates for optical thermometers with high sensitivity, wide temperature range, and resistance to thermal quenching.

研究领域: 材料科学 · 光学 · 纳米技术
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FOOD CHEMISTRY · 2024 · IF 8.5

Rapid determination for tyrosine isomers in food based on N-acetyl-L-cysteine/Upconversion nanomaterials target-induced quench by chiral Electrochemiluminescence sensor

Zhe Wang,Yongjiao Ren,Boxi Zhou,Zhen Chen,Zixiao Wang,Junying Wang,Junping Wang

Rapid determination of amino acid isomer is very important for the evaluation of the amino acid nutrition in different foods, so a fast and sensitive electrochemiluminescence (ECL) sensor was innovatively fabricated for the determination of tyrosine isomers in foods based on N-Acetyl-L-cysteine/upconversion nanomaterials possessed a good particular selectivity to L-tyrosine. Under the optimal conditions, for L-tyrosine, the limit of detection (LOD) of the sensor for L-tyrosine was 2.87 × 10 −6  M, detection range of 5.5 × 10 −5 –5.5 × 10 −3  M, for D-tyrosine, LOD was 2.56 × 10 −5  M, detection range was from 5.5 × 10 −4 to 5.5 × 10 −3  M. The developed chiral sensor was used to determinate the tyrosine isomers in foods successfully, which provided a convenient method to quickly evaluate the nutritional value of amino acids in food.

CAS / MDL: 616-91-1
研究领域: 分析化学 · 食品科学 · 生物医学
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Pharmaceutics · 2020 ·Vol. 12 ·期 7 ·680 · IF 4.421

Oleic Acid Copolymer as A Novel Upconversion Nanomaterial to Make Doxorubicin-Loaded Nanomicelles with Dual Responsiveness to pH and NIR

Jin Zhang,Xiaoyue Tang,Chuanqing Huang,Zeyu Liu,Yong Ye

Oleic acid (OA) as main component of plant oil is an important solvent but seldom used in the nanocarrier of anticancer drugs because of strong hydrophobicity and little drug release. In order to develop a new type of OA nanomaterial with dual responses to pH and near infrared light (NIR) to achieve the intelligent delivery of anticancer drugs. The novel OA copolymer (mPEG-PEI-(NBS, OA)) was synthesized by grafting OA ando-nitrobenzyl succinate (NBS) onto mPEGylated polyethyleneimine (mPEG-PEI) by amidation reaction. It was further conjugated with NaYF4:Yb3+/Er3+nanoparticles, and encapsulated doxorubicin (DOX) through self-assembly to make upconversion nanomicelles with dual response to pH and NIR. Drug release behavior of DOX, physicochemical characteristics of the nanomicelles were evaluated, along with its cytotoxic profile, as well as the degree of cellular uptake in A549 cells. The encapsulation efficiency and drug loading capacity of DOX in the nanomicelles were 73.84% ± 0.58% and 4.62% ± 0.28%, respectively, and the encapsulated DOX was quickly released in an acidic environment exposed to irradiation at 980 nm. The blank nanomicelles exhibited low cytotoxicity and excellent biocompatibility by MTT assay against A549 cells. The DOX-loaded nanomicelles showed remarkable cytotoxicity to A549 cells under NIR, and promoted the cellular uptake of DOX into the cytoplasm and nucleus of cancer cells. OA copolymer can effectively deliver DOX to cancer cells and achieve tumor targeting through a dual response to pH and NIR.

研究领域: 纳米技术 · 药学 · 癌症研究 · 材料科学
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