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MICROCHEMICAL JOURNAL · 2021 · IF 4.821

Dual-emission LaF3:Tb@DPA-Eu nanoparticles as a ratiometric fluorescence probe for the detection of marbofloxacin

Yuanyuan Duan,Yongli Yu,Limei Wang,Shuang Zhao

In this work, a facile method for the preparation of dual-emission lanthanide nanoparticles (NPs) was developed. Tb 3+ -doped LaF 3 NPs coated with 2,6-pyridinedicarboxylic acid (DPA) and Eu 3+ , namely LaF 3 :Tb@DPA-Eu NPs, could produce characteristic emissions of Tb 3+ and Eu 3+ under 272 nm excitation, which originated from the absorption of DPA. The LaF 3 :Tb@DPA-Eu NPs with tunable emission peaks and color could be synthesized by changing the concentration of Eu 3+ . Additionally, the obtained NPs were comprehensively characterized by various analytical methods. Transmission electron microscopy (TEM) images showed that the average size of the NPs was ~15 nm. Moreover, X-ray diffraction (XRD) analysis revealed that the products were single-phase LaF 3 , while the doped Tb 3+ entered the LaF 3 lattice to occupy the La 3+ sites. Owing to their excellent water solubility and good optical properties , the LaF 3 :Tb@DPA-Eu NPs were used as a fluorescence probe for the detection of marbofloxacin (MAR) based on the fluorescence quench. Notably, an effective ratiometric fluorescence method was established. The approach exhibited good sensitivity and selectivity with a linear range of 0.10 ~ 10.0 μM and detection limit of 85 nM. It was successfully employed for the determination of MAR in milk samples with recoveries of 98.1%–106%. Thus, the fluorescence method based on the LaF 3 :Tb@DPA-Eu NPs developed herein provides a convenient and fast platform for the detection of MAR.

研究领域: 分析化学 · 材料科学
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MICROCHEMICAL JOURNAL · 2026 · IF 5.1

Microplasma-fabricated CDs@Eu-DPA for ratiometric fluorescence and smartphone-mediated visual detection of oxytetracycline in food samples

Lanlan Wei,Yilan Zhao,Yaoye Chen,Ke Huang,Xiaoli Xiong,Qing Yang

A dual-emission CDs@Eu-DPA composite was rapidly synthesized via dielectric barrier discharge microplasma technology using carbon dots (CDs), 2,6-dipicolinic acid (DPA), and Eu 3+ as precursors. CDs@Eu-DPA was subsequently applied for ratiometric fluorescence and visual analysis of oxytetracycline (OTC) in food samples. When OTC was introduced, the blue fluorescence of CDs was quenched via the inner filter effect, while OTC coordinated with Eu 3+ in Eu-DPA to form a complex, leading to the enhancement of the red fluorescence of Eu 3+ at 615 nm through antenna effect. Additionally, principal component analysis was employed to distinguish four different antibiotics, including OTC, chlortetracycline, tetracycline, and doxycycline. Under optimized conditions, the ratiometric fluorescence analysis and smartphone-assisted RGB analysis exhibited linear detection ranges of 0.05–210.0 μM and 0.3–90.0 μM for OTC, respectively, with limits of detection of 0.02 μM and 0.08 μM, respectively. The satisfactory recoveries in food samples were ultimately achieved through the dual-mode sensing method.

CAS / MDL: 499-83-2 52-90-4
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AMB Express · 2018 ·Vol. 8 ·期 1 ·1-8 · IF 1.719

Rapid and simple detection of endospore counts in probiotic Bacillus cultures using dipicolinic acid (DPA) as a marker

Liang Xiao-Sheng,Liu Chun,Long Zhu,Guo Xiao-Hua

Spore counting in probiotic Bacillus cultures using dipicolinic acid (DPA) as a marker was studied for developing a rapid and simple detection method. The newly developed method is based on the fluorescence enhancement by a new chelating agent, which forms a complex with EuCl 3 and DPA. The results showed that 1,2-cyclohexanediamine-N,N,N′N′-tetraacetic acid (CyDTA) greatly enhanced the fluorescence intensity in all selected chelating agents. The optimal composition of the fluorescence complex DPA-Eu-CyDTA had a detection limit of 0.3 nM of DPA. Metal ions in high concentrations, including Cu 2+ , Fe 2+ , Fe 3+ , Al 3+ , and Zn 2+ , might lower the detection sensitivity, which could be eliminated by diluting the sample with the metal ions below 10 μM. The maximum release of DPA was achieved by heating treatments at 121 °C for at least 10 min for two types of Bacillus endospores. The spore concentrations and corresponding released DPA fluorescence intensities were linearly associated (coefficient R 2  = 0.9993 and 0.9995 for Bacillus subtilis MA139 and Bacillus licheniformis BL20386, respectively). The detection limit for both strains reached approximately 6800 spores/mL. The verification results showed that the DPA fluorimetry assay developed in the present study was fully consistent with the plate-counting assay. The study shows that the fluorescence complex DPA-Eu-CyDTA can be reliably used for the detection of endospores in Bacillus fermentation for the production of probiotics.

CAS / MDL: 499-83-2
研究领域: 微生物学 · 生物技术 · 食品科学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2024 · IF 4.3

Spatial confinement of styryl pyridine salt derivative in MCM-22 molecular sieve network for boosted fluorescence emission and stable ratiometric sensing of bacillus anthracis biomarkers

Rui Cao,Mengyu Zhang,Wen Tang,Jing Wu,Yang Luo,Yi Chen,Zhaodi Liu,Fuying Hao,Liangquan Sheng,Huajie Xu

In this work, a stable ratiometric nanofluorescent probe for the detection of 2,6-dipicolinic acid (DPA), a Bacillus anthracis biomarker, was developed based on confinement-induced emission enhancement of cationic styrylpyridine salt derivative L in MCM-22 molecular sieve pores. The cationic L and the lanthanide Tb 3+ were loaded into the pores of the molecular sieve by electrostatic interaction with the negatively charged AlO 4 tetrahedron unit, and L exhibited enhanced red fluorescence emission as a stable fluorescence reference mark in the nanoprobe platform due to the restricted molecular torsion of L in the pores of MCM-22. At the same time, the characteristic green fluorescence emission of Tb 3+ can be excited by energy transfer due to the “antenna effect” of DPA. The prepared Tb-L@MCM-22 nanoprobe showed specific selectivity and stable fluorescence ratiometric detection of DPA in tap water, lake water, bovine serum and actual bacterial spores. Benefiting from the confinement-induced fluorescence enhancement effect of L in the MCM-22 molecular sieve pores, the obtained Tb-L@MCM-22 can provide a stable reference signal for the fluorescence ratiometric detection of DPA with a limit of detection (LOD) of 78.6 nM and 1.310 × 10 4 spores per mL. More importantly, combining of the Tb-L@MCM-22 based DPA detection test strips with a smartphone app demonstrated a stable, convenient and rapid method for detecting of anthrax biomarkers.

研究领域: 分析化学 · 生物医学工程 · 材料科学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2018 · IF 2.88

Europium functionalized silicon quantum dots nanomaterials for ratiometric fluorescence detection of Bacillus anthrax biomarker

Zhan Zhou,Jiapei Gu,Yuze Chen,Xiaoxia Zhang,Haixia Wu,Xiaoguang Qiao

Bacillus anthracis spore causes anthrax to seriously threaten human health and even cause death. 2,6-Pyridinedicarboxylic acid (DPA) is a unique biomarker because it is a major component of Bacillus anthracis spore. Herein, we design europium functionalized silicon quantum dots as a ratiometric fluorescent nanoprobe to detect DPA with high sensitivity and selectivity. With the addition of DPA, the red emission peaks were observed at 618 nm. The novel probe enables ratiometric and sensitive DPA detection over nanomolar concentrations (as low as 1.02 μM). This work provided an efficient background-free and self-calibrating method for the recognition of DPA.

研究领域: 生物化学 · 纳米医学 · 分析化学
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DYES AND PIGMENTS · 2023 · IF 4.5

Luminescent properties of multi-stimuli-responsive Ln-BPDC-Phen Lanthanide complexes

Runze Jia,Xianju Zhou,Jian Wu,Li Li,Yongjie Wang,Guotao Xiang,Xiantong Tang,Zhiyu Yang,Huajing Gao

Stimuli-responsive smart luminescent materials have attracted more and more attention recently. A series of lanthanide organic complexes, [Ln 2 (BPDC) 3 (Phen) 2 (DMF) 2 ]·5H 2 O (Ln: lanthanide  = Eu, Tb, Eu x Tb 1−x , H 2 BPDC = 2,2′-Bipyridine-5,5′-dicarboxylic acid, H 2 Phen = 1,10-phenanthroline, DMF = N,N-dimethylformamide), were synthesized and characterized to be iso-structural. The complexes demonstrate selective and significant response to Fe 3+ ions, leading to fast and accurate measuring of Fe 3+ ions. Interestingly, the complexes exhibit diverse luminescent response to two isomers 2, 6-pyridine dicarboxylic acid (DPA) and 3, 5-pyridine dicarboxylic acid (H 2 PDC). The green emission due to Tb 3+ ions is enhanced by DPA upon excitation of 280 nm, which is ascribed to the absorption of DPA. Whilst it is quenched by DPA with the excitation of the ligands (339 nm). However, H 2 PDC quenches both the green and red emissions regardless of the excitation wavelength. The reason is that DPA provides more possibilities of the ligand exchange with the complex due to the suitable position of the carboxylic acid functional groups on the pyridine ring than H 2 PDC. Simultaneously, the luminescent response of the complex to DPA enables emission color tunability, which allows the complex to recognize and measure DPA/H 2 PDC isomers visually and easily. Moreover, the complex exhibits a wide-range (110–360 K) temperature sensing with high Sr = 3.92 %K −1 at 180 K. The multi-stimuli-response of the complexes makes them potential applicants for multi-functional sensing materials.

研究领域: 化学 · 材料科学
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NEW JOURNAL OF CHEMISTRY · 2025 · IF 2.5

A bismuth-based MOF proportional fluorescence sensor for the rapid and sensitive detection of an anthrax biomarker

Hao Guo,Dengke Zhuang,Zhiguo Yu,Liping Peng,Yanyan Ma,Zeyun Yang,Yu Yan,Yingfei Hui,Wu Yang

Bacillus anthracis is a highly dangerous zoonotic pathogen that poses a considerable threat to public health. Rapid and accurate detection of the biomarker 2,6-pyridinedicarboxylic acid (DPA) is necessary for the effective prevention and treatment of infections caused by this microorganism. Here, a new method for detecting DPA using a bi-emission ratio fluorescence sensor based on a bismuth organic skeleton (Bi-MOF) is developed. The dual-emission ratio fluorescent sensor (Eu@Bi-MOF) is prepared by Eu3+ functionalizing Bi-MOF, synthesized through using bismuth nitrate as the metal node and 1,3,5-phenyltricarboxylic acid as the ligand, with a post-synthetic modification method and exhibits a sensitive fluorescent response to DPA. In the presence of DPA, the fluorescence intensity of the Eu@Bi-MOF sensor at 438 nm remains unchanged, while the red fluorescence emission at 615 nm was significantly quenched due to the internal filtration effect (IFE). The fluorescence intensity ratio I438/I615 shows a good linear relationship with DPA concentration in the range of 0.5–60 μM, and the detection limit is as low as 0.36 μM. This method provides a sensitive and reliable alternative strategy for rapid DPA monitoring.

CAS / MDL: 10031-53-5 554-95-0
研究领域: 分析化学 · 生物传感器 · 材料科学 · 病原体检测 · 荧光光谱学
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MOLECULES · 2024 ·Vol. 29 ·期 12 ·2755 · IF 4.2

A Benzothiadiazole-Based Zn(II) Metal–Organic Framework with Visual Turn-On Sensing for Anthrax Biomarker and Theoretical Calculation

Jing Ru,Yi-Xuan Shi,Qing-Yun Yang,Teng Li,Hai-Ying Wang,Fan Cao,Qiang Guo,Yan-Lan Wang

2,6-pyridine dicarboxylic acid (DPA) is an exceptional biomarker of notorious anthrax spores. Therefore, the rapid, sensitive, and selective quantitative detection of DPA is extremely significant and urgent. This paper reports a Zn(II) metal–organic framework with the formula of {[Zn6(NDA)6(DPBT)3] 2H2O·3DMF}n(MOF-1), which consists of 2,6-naphthalenedicarboxylic acid (2,6-NDA), 4,7-di(4-pyridyl)-2,1,3-benzothiadiazole (DPBT), and Zn(II) ions. Structural analysis indicated that MOF-1 is a three-dimensional (3D) network which crystallized in the monoclinic system with theC2/c space group, revealing high pH, solvent, and thermal stability. Luminescence sensing studies demonstrated that MOF-1 had the potential to be a highly selective, sensitive, and recyclable fluorescence sensor for the identification of DPA. Furthermore, fluorescent test paper was made to detect DPA promptly with color changes. The enhancement mechanism was established by the hydrogen-bonding interaction and photoinduced electron transfer transition between MOF-1 and DPA molecules.

CAS / MDL: 10196-18-6
研究领域: 化学 · 生物学 · 材料科学
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MICROCHIMICA ACTA · 2020 ·Vol. 187 ·期 6 ·1-6 · IF 6.232

D-penicillamine modified copper nanoparticles for fluorometric determination of histamine based on aggregation-induced emission

Zhang Xiong,Liu Qiao,Wang Zong-Wen,Xu Hui,An Feng-Ping,Huang Qun,Song Hong-Bo,Wang Yi-Wei

A fluorometric method for the determination of histamine has been developed based on aggregation-induced emission (AIE) effect of D-penicillamine capped copper nanoparticles (DPA-CuNPs). The fluorescent DPA-CuNPs were synthesized by a one-pot method using D-penicillamine as both reducing agent and stabilizing ligand. The size, morphology and physical chemical properties of DPA-CuNPs were examined by transmission electron microscopy (TEM), fluorescence spectroscopy, fourier transform infrared spectroscopy (FTIR) and absorption spectroscopy. The DPA-CuNPs exhibit AIE effect and show intense red fluorescence (650 nm). In the presence of histamine, DPA-CuNPs are dispersed into small homogeneous particles, causing fluorescence quenching. Based on this reaction, a histamine sensor is constructed. The fluorescence of the CuNPs solution has a good linear relationship with histamine concentration in the range 0.05 μM to 5 μM and the determination limit (3σ/slope) is 30 nM. The estimated method was successfully applied to the determination of histamine in fish, pork and red wine. Schematic representation of copper nanoparticles for histamine analysis. In the presence of histamine, the strong red fluorescence of copper nanoparticles is obvious decreased through interaction of copper nanoparticles and histamine.

CAS / MDL: 462-94-2 52-67-5
研究领域: 分析化学 · 纳米技术 · 食品科学
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Frontiers in Microbiology · 2016 · IF 4.165

The Synergistic Effect of High Pressure CO2 and Nisin on Inactivation of Bacillus subtilis Spores in Aqueous Solutions

Rao Lei,Wang Yongtao,Chen Fang,Liao Xiaojun

The inactivation effects of high pressure CO2 + nisin (simultaneous treatment of HPCD and nisin, HPCD + nisin), HPCD→nisin (HPCD was followed by nisin), and nisin→HPCD (nisin was followed by HPCD) treatments on Bacillus subtilis spores in aqueous solutions were compared. The spores were treated by HPCD at 6.5 or 20 MPa, 84–86°C and 0–30 min, and the concentration of nisin was 0.02%. Treated spores were examined for the viability, the permeability of inner membrane (IM) using flow cytometry method and pyridine-2, 6-dicarboxylic acid (DPA) release, and structural damage by transmission electron microscopy. A synergistic effect of HPCD + nisin treatment on inactivation of the spores was found, and the inactivation efficiency of the spores was HPCD + nisin > HPCD→nisin or nisin→HPCD. Moreover, HPCD + nisin caused higher IM permeability and DPA release of the spores than HPCD. A possible action mode of nisin-enhanced inactivation of the spores was suggested as that HPCD firstly damaged the coat and cortex of spores, and nisin penetrated into and acted on the IM of spores, which increased the damage to the IM of spores, and resulted in higher inactivation of the spores.

研究领域: 食品科学 · 微生物学
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BIOSENSORS & BIOELECTRONICS · 2025 · IF 10.5

Ratiometric fluorescence sensor based on bimetallic organic frameworks for anthrax biomarker detection

Limin Zheng,Jiarong Zhang,Jie Gao,Fusheng He,Siqian Yang,Hua He,Pierre Dramou,Deli Xiao

It is of great significance to construct ratiometric fluorescence sensors with simple operation and desirable anti-interference ability. In this study, a bimetallic organic framework was prepared for the first time by a one-pot solvothermal method, using 4,4’-biphenyl dicarboxylic acid as ligand, lanthanide metal Terbium ions (Tb 3+ ) and transition metal Zirconium ions (Zr 4+ ) as central metal ions. This preparation method was easy to carry out. On this basis, a novel ratiometric fluorescence sensor Tb-Zr-MOF was constructed successfully for the detection of anthrax biomarker 2,6-pyridinedicarboxylic acid (DPA). When DPA was added into the detection system, the fluorescence of Tb 3+ was enhanced due to the energy transfer from DPA to Tb 3+ . Therefore, under the single excitation at 285 nm, the fluorescence emission intensity of Tb-Zr-MOF at 402 nm remained unchanged and the fluorescence emission intensity at 546 nm increased. As a ratiometric fluorescence sensor, Tb-Zr-MOF showed good linear response to DPA in the range of 5∼100 μM and the limit of detection was 1.72 μM. This sensor reduces the interference of environmental factors and achieves high sensitivity detection, which is superior to the traditional single emission peak fluorescence sensor. In addition, the developed Tb-Zr-MOF sensor was used to detect DPA in Bauhinia bark samples successfully. The recovery rate was 98.80%∼104.8%, which proved the practical application of Tb-Zr-MOF in complex environment. It is expected to provide a reliable method for the detection of biomarkers of Bacillus anthracis .

研究领域: 分析化学 · 生物医学检测
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RSC Advances · 2020 ·Vol. 10 ·期 71 ·43523-43532 · IF 3.119

Preparation of antistatic epoxy resin coatings based on double comb-like quaternary ammonium salt polymers

Wei Gao,Zeng-chao Dang,Fu-sheng Liu,Sheng Wang,Duan-wei Zhang,Meng-xi Yan

Two kinds of double comb-like quaternary ammonium salt polymers P(DPA-EPI) and P(DBA-EPI) with lower polarity were designed and synthesized using epichlorohydrin (EPI), di-n-propylamine (DPA) and di-n-butylamine (DBA) as raw materials. The transparent antistatic epoxy resin coatings were obtained using the two polymers as antistatic agents, respectively. Because P(DPA-EPI) and P(DBA-EPI) with good hygroscopic performance are easily dissolved in epoxy resin paints and are nearly linearly arranged in the epoxy resin paints, the obtained transparent antistatic epoxy resin coatings achieve good antistatic properties. The values of ρs of the coatings reach 5.13 × 108 Ω sq−1 and 2.69 × 108 Ω sq−1, respectively, with a lower addition amount of polymers of only 1.0 wt%. The two antistatic epoxy resin coatings also have good durability. Compared to the epoxy resin coating, with the introduction of P(DPA-EPI) and P(DBA-EPI), the thermal stability and adhesion of the antistatic epoxy resin coatings do not change obviously, but the Rockwell hardness values slightly reduce.

研究领域: 材料科学 · 化学工程
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