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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

Highly selective and multicolor ultrasensitive assay of dipicolinic acid: The integration of terbium(III) and gold nanocluster

Ning Bi,Yin-Hong Zhang,Mei-Hua Hu,Jun Xu,Wei Song,Jian Gou,Yong-Xin Li,Lei Jia

A novel multicolor fluorescent nano-probe based on the hybridization of Tb 3+ ion with gold nanoclusters (Au NCs) was synthesized to monitor and on-site visual assay of 2,6-pyridinedicarboxylic acid (DPA), a biomarker of bacterial spores. DPA can replace the water molecule in the center of Tb 3+ and strongly coordinate with Tb 3+ based on the analyte-triggered antenna effect. Simultaneously, the red fluorescence of Au NCs is not influenced after addition of DPA and can be used as steady inside fluorescence reference channel to measure background noise. On this basis, the multicolor fluorescence nano-probe based on Tb 3+ -doped Au NCs for fast analysis of DPA was fabricated. The linear range of this method is 0 to 12.5 μM and the limit of detection is 3.4 nM, which is well below the quantity of DPA concentration of 60 μM released by the spore transmission dose of anthrax infection. The proposed multicolor fluorescence nano-probe was successfully detecting DPA in actual sample with good sensitivity and specificity. In addition, the visual paper-based nano-probe is designed to detect DPA by using the color scanning application of smart phone. This developed platform possesses abroad application prospects with advantages of effective, convenient carrying, simple operation, good selectivity and repeatability.

CAS / MDL: 16961-25-4
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Foods · 2022 ·Vol. 11 ·期 21 ·3388 · IF 5.561

Dipicolinic Acid-Tb3+/Eu3+ Lanthanide Fluorescence Sensor Array for Rapid and Visual Discrimination of Botanical Origin of Honey

Xijuan Tu,Yunmin Tao,Jiaxu Chen,Chunping Du,Qian Jin,Yuchang He,Ji Yang,Shaokang Huang,Wenbin Chen

In the present study, a lanthanide fluorescence sensor array was developed for the discrimination of honey’s botanical origin. Dipicolinic acid (DPA) was used as the antenna ligand for sensitizing the fluorescence of Tb3+and Eu3+to prepare the DPA-Tb3+/Eu3+complex. This lanthanide fluorescence sensor showed a cross-reactive response to the major constituents of honey, which led to the result that different classes of honey solution exhibited distinct quenching effects on the fluorescence of the DPA-Tb3+/Eu3+complex. Furthermore, a fluorescence sensor array composed of ten sensors was constructed by adjusting the pH and the component of the DPA-Tb3+/Eu3+complex to show multivariate responses towards honey. The visual fluorescence image of the sensor array was recorded by using a smartphone under excitation with portable UV lamp. Results indicated that the pattern of the visual image was related with the botanical origin. After extracting the RGB value of each sensor in 96-well plate, the ratio of R/G was used for principal component analysis (PCA). The results showed that three classes of honey (astragalus, logan, and litchi) were well distinguished. Moreover, the value of principal component 1 (PC1) showed good linearity with the composition of mixing honey and could be used for semi-quantitative analysis. The proposed lanthanide fluorescence sensor array presents a visual and portable method for the discrimination of a honey’s origin without the use of analytical instruments, and might provide a novel and simple strategy for the measurement of food origin.Keywords:honey;botanical origin;lanthanide complex;fluorescence;sensor array

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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
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Nanoscale · 2018 ·Vol. 10 ·期 15 ·7163-7170 · IF 7.233

A luminescent europium-dipicolinic acid nanohybrid for the rapid and selective sensing of pyrophosphate and alkaline phosphatase activity

Jiahui Zhao,Shuang Wang,Shasha Lu,Jian Sun,Xiurong Yang

As a ubiquitous hydrolysis enzyme in phosphate metabolism, alkaline phosphatase (ALP) is a significant biomarker in laboratory research and clinic diagnosis. Herein, we report a highly water-soluble Eu(DPA)3@Lap nanohybrid material for the rapid and selective assay of PPi and ALP through a luminescence off–on recognition process. Eu(DPA)3@Lap was successfully prepared in an aqueous solution, and it exhibited strong luminescence emission, high photostability, and long lifetime. More interestingly, the strong luminescence of Eu(DPA)3@Lap can be remarkably quenched by Cu2+ due to the high impetus of coordination between the DPA ligand and Cu2+ ion. Using Cu2+ as a signal transducer, the luminescence could be recovered upon the addition of PPi ion owing to the formation of a Cu2+–PPi complex; thus, a luminescence turn-on assay for PPi ions was realized. Utilizing the ability of Cu2+ to differentiate between PPi and Pi, a convenient and straightforward luminescence assay for ALP activity was accomplished based on the specific dephosphorylation of PPi to Pi. To the best of our knowledge, this elaborate luminescence sensing system constitutes the first luminescent nanohybrid material based on a europium organic complex for ALP activity assay. Furthermore, the recognition process of PPi and ALP was completed in a convenient and facile mix-and-readout manner, and it revealed significant potential in point of care testing.

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DYES AND PIGMENTS · 2026 · IF 3.9

One-pot room temperature synthesis of Eu3+-functionalized COF and its application in ratiometric fluorescence detection of dipicolinic acid

Yanxin Li,Chunhong Wang,Jianhao Liu,Rang Li,Shijuan Zhang

Eu-COF was synthesized via a one-pot room-temperature method for the first time. • Dipicolinic acid triggered the emission of Eu 3+ and quench the fluorescence of COF, achieving its ratiometric detection. • The method is extendable to the fabrication of various Ln-COFs. A novel Eu 3+ -functionalized covalent organic framework (Eu-COF) was synthesized via a one-pot room-temperature Schiff base condensation between 2,5-diethoxybenzene-1,4-dicarbohydrazide (DEDH) and tetrakis(4-formylphenyl)ethylene (TFPE), breaking away from the traditional “synthesize first, modify later” strategy. The COF not only provided abundant anchoring sites for Eu 3+ ions, but also served as fluorescence reference. Dipicolinic acid (DPA) transferred energy to Eu 3+ via the antenna effect, triggering the characteristic emission of Eu 3+ at 619 nm, while the characteristic emission peak of COF at 556 nm was simultaneously reduced due to the photoinduced electron transfer and inner filter effect between COF and DPA, which led to the fluorescence quenching of COF, achieving the ratiometric detection of DPA. The synthesized Eu-COF exhibits a good linearity in the range of 0–100 μM, with a detection limit of 0.52 μM. This study pioneers the first one-pot room-temperature synthesis method for Eu 3+ -functionalized COFs. Download: Download high-res image (356KB) Download: Download full-size image

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CRYSTAL GROWTH & DESIGN · 2024 · IF 3.2

A Multifunctional MOF-on-MOF-Based Dual-Channel Luminescent Signal Readout Strategy for Classifying Phenylglyoxylic Acid and 2,6-Dipicolinic Acid

Danhua Guo,Huijun Li,Yiting Zhang,Yujie Nie,Xiaoqin Feng,Yingying Wu,Xiao-Lei Zhao,Zhouqing Xu,Yan Wang

A desirable MOF-on-MOF-based ratiometric fluorescent probe (denoted as HPU-26@ZIF-8@Cit@Eu) was designed through the seed-mediated method for classifying phenylglyoxylic acid (PGA, a real internal exposure level of styrene) and 2,6-dipicolinic acid (DPA, a unique bacterial endospore biomarker) with high selectivity and sensitivity. Characterization techniques were carried out with the PXRD pattern, XPS spectra, UV–vis absorption spectra, and DFT-calculated HOMO and LUMO energies for proven mechanisms. The results indicated that PGA could affect the LMCT-ET process in HPU-26 and be binded to Eu3+ in ZIF-8, thus resulting in a significant increase both in the blue fluorescence emission peak at 476 nm and the red fluorescence emission peak at 620 nm. According to the fluorescence intensity ratio (I620/I476), the limit of detection (LOD) reached as low as 0.63 μM within a wide concentration range from 0 to 100 μM, and a noticeable color change from blue to red could be observed. However, upon exposure to DPA, the energy transfer between Zn2+ and the ligand was influenced sharply, without prejudice to the fluorescent intensity of Eu3+ in ZIF-8. These phenomena made this probe with a stable reference signal have an ultralow LOD of 0.26 μM for DPA in the range of 0–175 μM, converting the fluorescence color from dark blue to bright blue. Meanwhile, the developed probe was applied to the construction of logic gates and hydrogel-based film for the determination of PGA and DPA in real samples with the help of a smartphone.

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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2023 · IF 5.2

Fabrication of Eu3+-dipicolinic acid complex functionalized nanoSiO2 composites and their Langmuir-Blodgett films as visual fluorescence probe for tetracycline and oxytetracycline

Yue-Yang Ma,Ya Li,Hong-Xiang Huang,Dong-Jin Qian

Luminescent lanthanide complexes have attracted growing attention in the visual probe for detection of toxic and dangerous materials. Here, we report an interfacial self-assembly of Eu 3+ -dipicolinic acid complex functionalized nanoSiO 2 composites (nanoSiO 2 PyTAEu) and their Langmuir-Blodgett (LB) films as well as the luminescent probes to tetracycline (TC) and oxytetracycline (OTC). Organic linkers and Eu 3+ ions are anchored on the hydrophilic nanoSiO 2 particles’ surface via the surface silanization, substitution and coordination reactions, so they exhibit high stability and well distribution in the solutions and LB films. Both the nanocomposites of nanoSiO 2 PyTAEu and their LB films show strong and enhanced red fluorescence emissions of Eu 3+ ions when they are immersed in the aqueous TC solution, with the detection limit to 3.3 and 0.91 nmol/L, respectively. The present nanocomposites and LB films have the advantages of high sensitivity and stability.

CAS / MDL: 74124-79-1 25952-53-8
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2023 · IF 4.4

Dual-mode strategy for 2,6-dipicolinic acid detection based on the fluorescence property and peroxidase-like activity inhibition of Fe-MIL-88NH2

Donglian Deng,Jingyuan Xu,Tingting Li,Dongdong Tan,Yibing Ji,Ruijun Li

This work designed a fluorometric/colorimetric dual-mode sensor for detecting 2,6-dipicolinic acid (DPA) based on the blue emission property and peroxidase-like activity of Fe-MIL-88NH 2 . The fluorescence of Fe-MIL-88NH 2 was obviously turned off by Cu 2+ , but DPA was able to bring it back because it has a strong chelate bond with Cu 2+ . Fe-MIL-88NH 2 also displayed high peroxidase-like activity, which accelerated the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) to the blue oxidation product (oxTMB) when H 2 O 2 was present. When DPA was added, it efficiently inhibited the peroxidase-like activity of Fe-MIL-88NH 2 , causing less oxTMB and less absorbance at 652 nm. The fluorescence recovery of Fe-MIL-88NH 2 and the change in absorbance at 652 nm were used as analytical signals for dual-mode detection of DPA. The linear responses in the range of 10–60 μM and 60–160 μM were achieved for the fluorometric mode, and the limit of detection (LOD) was 1.46 μM. The respective values of linear range and LOD for the colorimetric mode were 5–25 μM and 3.00 μM, respectively. In summary, the dual-mode testing strategy successfully detected DPA in aqueous environmental samples, suggesting great potential in disease prevention and environmental analysis.

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POLYHEDRON · 2024 · IF 2.4

Germ must be found: The HNT@RhB@MOF-Tb polychromatic fluorescent nanoprobe is applied for the visual detection of 2,6-dipicolinic acid

Jian Gou,Luxin Xing,Yousong Hu,Lina Zhang,Yongxin Li,Ning Bi,Yuanyuan Huang,Jun Xu,Lei Jia

A polychromatic fluorescent nanoprobe based on natural halloysite nanotubes with fluorescent dyes and porous metal–organic frameworks co-loaded on the surface and inner wall of the nanotubes was constructed for the highly sensitive visual identification of the Bacillus anthracis biomarker 2,6-dichlorophenolic acid (DPA). The limit of detection for DPA was 11.27 nM, which is significantly lower than the spore-borne dose for anthrax infection (60 uM). The multi-color fluorescent probe showed potential for rapid, accurate, and highly selective detection of Bacillus anthracis markers in actual samples. Besides, a portable fluorescence detection platform was developed in combination with a smartphone color scanning APP to simplify the detection process and realize real-time semi-quantitative analysis.

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MICROCHIMICA ACTA · 2023 ·Vol. 190 ·期 8 ·1-8 · IF 5.7

Determination of 2, 6-dipicolinic acid as an Anthrax biomarker based on the enhancement of copper nanocluster fluorescence by reversible aggregation-induced emission

Ma Fanghui,Deng Lei,Wang Tingting,Zhang Aomei,Yang Minghui,Li Xiaoqing,Chen Xiang

The weak fluorescence efficiency of copper nanoclusters (Cu NCs) limits their wide applications in biosensing and bioimaging areas, while the aggregation-induced emission (AIE) effect is anticipated to increase their luminescence intensity. Herein, the weak red emission of Cu NCs is increased considerably by the addition of lanthanide Tb 3+ , ascribed to the AIE effect. Monitoring of spores contamination can be carried out by determining the level of 2, 6-dipicolinic acid (DPA), which is a marker of spores. Due to the stronger synergy between DPA and Tb 3+ for its clamped configuration of adjacent pyridine nitrogen group with the carboxylic acid group, the addition of DPA leads Tb 3+ to be taken away from Cu NCs through a stronger coordination effect, causing Cu NCs to return to the dispersed state and weakened fluorescence. Based on this, an "off–on-off" fluorescent probe for DPA sensing was built, in which Tb 3+ was used as a bridge to achieve AIE enhanced fluorescence effect on Cu NCs as well as a specific recognizer of DPA. The detection range for DPA was 0.1–60 μM and the detection limit was 0.06 μM, which was much lower than the infectious dose of anthrax spores. Since DPA is a unique biomarker for bacterial spores, the method was applied to the detection of actual bacterial spores and satisfactory results were obtained with a detection limit of 4.9*10 3  CFU mL −1 . Graphical Abstract

CAS / MDL: 1310-73-2
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PEST MANAGEMENT SCIENCE · 2026 · IF 4.2

Roles of spoVF operon subunits A and B (dipicolinic acid synthase) in regulating cell morphology and biofilm formation in the biocontrol agent Bacillus subtilis

Yang Yang,Yu-Xin Zhou,Le-Yao Jia,Xin-Yang Song,Ya-Jie Lai,Si-Yuan Liu,Su-Yan Wang,Pedro Laborda,Xin-Chi Shi

BACKGROUND The spoVF operon, encoding the dipicolinic acid (DPA) synthase, is critical for sporulation in Bacillus subtilis . A recent study suggested that spoVF expression in vegetative cells promotes biofilm formation, yet the detailed regulatory pathways and the underlying metabolic connections remain to be fully elucidated. RESULTS In this study, deletion of spoVF subunits spoVFA and spoVFB severely reduced DPA synthesis, downregulated mreB gene expression, and impaired biofilm formation, with mutant ΔA showing stronger effects than mutant ΔB. Although wild type B. subtilis 168 cells exhibited rod shape, double mutant ΔAΔB cells were spherical. In the MT strain, engineered for enhanced spoVF expression during vegetative growth, the upregulation of key TCA cycle genes (e.g., citC ) and glutamate synthesis genes (e.g., gltA ) was observed. This metabolic reprogramming was accompanied by the promotion of Spo0A phosphorylation. The activated Spo0A~P then inhibited the SinR and AbrB repressors, which led to the activation of the eps and tasA biofilm operons. The MT strain showed superior stress tolerance to high temperature (42 °C), salt, acidic and alkaline pH, and UV-A and UV-B radiation. Additionally, the MT strain exhibited higher nutrient competition ability, and in vitro and in vivo antifungal activities against the sweet potato ( Ipomoea batatas L. Lam) storage root pathogen Ceratocystis fimbriata compared to mutant ΔA, ΔB, and ΔAΔB strains. CONCLUSIONS This study elucidates how the spoVF operon links the central metabolic pathways with B. subtilis cell morphology and biofilm formation, offering a novel target for engineering advanced Bacillus -based biocontrol agents. © 2026 Society of Chemical Industry.

CAS / MDL: 314-13-6
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ACS Applied Nano Materials · 2021 · IF 5.097

Europium(III)-Modified Silver Nanoparticles as Ratiometric Colorimetric and Fluorescent Dual-Mode Probes for Selective Detection of Dipicolinic Acid in Bacterial Spores and Lake Waters

Shengnan Yin,Changlun Tong

Detection of Bacillus anthracis spores is of great importance for biosecurity and prevention of disease outbreaks. In this paper, a ratiometric colorimetric and fluorescent dual-mode platform for rapid, sensitive, and visual detection of dipicolinic acid (DPA), a biomarker of anthrax spores, was developed based on Eu3+-modified silver nanoparticles (AgNPs). Eu3+-modified AgNPs can induce the aggregation of AgNPs, its localized surface plasmon resonance (LSPR) absorption at 392 nm is decreased, and a new absorption peak at 524 nm emerged. Interestingly, upon the addition of DPA, it can effectively inhibit the aggregation of AgNPs–Eu3+, and the solution color changes from pink to yellow, while the red characteristic fluorescence of Eu3+ is turned on owing to the energy transfer from DPA to Eu3+ by the antenna effect. A new insight that AgNPs can also enhance the fluorescence of Eu3+ was found. Eu3+-modified AgNPs as a dual-mode platform for ratiometric colorimetric and fluorescence detection of DPA were thus fabricated. The good linearity is in the range of 1.0–25 μM with a LOD of 0.31 μM for the ratiometric colorimetric assay and 0.25–45 μM with a LOD of 17 nM for the fluorescent assay, which is greatly lower than the dose of DPA (60 μM) released by the contagious number of spores to cause anthrax. The ratiometric colorimetric and fluorescent probes were successfully applied for the detection of DPA in lake waters and Bacillus subtilis, and as low as 1.8 × 104 spores were detected.

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