Lanthanide Coordination Polymers Research Articles

A novel core–shell lanthanide coordination polymer ratiometric fluorescent probe for the ultrasensitive and visual detection of anthrax biomarker

A novel core–shell based lanthanide ratiometric fluorescent probe is designed for the rapid and sensitive detection of 2, 6-pyridine dicarboxylic acid (DPA), which is the biomarker of Bacillus anthracis. The fluorescent dye molecule 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) was encapsulated in silica nanoparticles as a reference signal and externally connected with guanine mononucleotide europium coordination polymers (Eu/GMP) as a response signal so as to construct a double-emission fluorescent sensor. The visual detection was enabled by the fluorescence color change from green to red under an UV lamp with the addition of DPA. In addition, the RGB auxiliary detection platform was built using color scanning software of smartphone. This work presents a novel and efficient method for detecting anthrax biomarkers.

Polymorphism and Its Influence on Catalytic Activities of Lanthanide-Glutamate-Oxalate Coordination Polymers.

To study the relationship between polymorphism and catalytic activities of lanthanide coordination polymers in the cycloaddition reactions of CO2 with epoxides, the monoclinic and triclinic polymorphs of [LnIII(NH3-Glu)(ox)]·2H2O, where LnIII = LaIII (I), PrIII (II), NdIII (III), SmIII (IV), EuIII (V), GdIII (VI), TbIII (VII), and DyIII (VIII), NH3-Glu- = NH3+ containing glutamate, and ox2- = oxalate, were synthesized and characterized. Factors determining polymorphic preference, the discrepancy between the two polymorphic framework structures, potential acidic and basic sites, thermal and chemical stabilities, active surface areas, void volumes, CO2 sorption/desorption isotherms, and temperature-programmed desorption of NH3 and CO2 are comparatively presented. Based on the cycloaddition of CO2 with epichlorohydrin in the presence of tetrabutylammonium bromide under solvent-free conditions and ambient pressure, catalytic activities of the two polymorphs were evaluated, and the relationship between polymorphism and catalytic performances has been established. Better performances of the monoclinic catalysts have been revealed and rationalized. In addition, the scope of monosubstituted epoxides was experimented and the outstanding performance of the monoclinic catalyst in the cycloaddition reaction of CO2 with allyl glycidyl ether under ambient pressure has been disclosed.

Highly Efficient and Thermally Durable Luminescence of 1D Eu3+ Coordination Polymers with Arsenic Bridging Ligands.

In this work, bisarsine oxides were evaluated as novel bridging ligands, aiming to develop practical and efficient luminescent lanthanide coordination polymers. We have synthesized one-dimensional (1D) Eu3+ coordination polymers that incorporate bisarsine oxide bridging ligands and hexafluoroacetylacetonate anions. These polymers exhibited a denser packing of chains compared to analogous polymers bridged with bisphosphine oxides. The coordination polymers demonstrated exceptional thermal stability and substantial emission quantum yields. Additionally, the bisarsine oxides induced a pronounced polarization effect, facilitating a sensitive electric dipole transition that yields considerably narrow band red emission. Remarkably, the Eu3+ coordination polymers with bisarsine oxides maintained intense emission even at 550 K. A distinctive feature of these polymers is their heating-induced emission enhancement observed when the temperature was increased from 300 K to 400 K.

Solvothermal self-assembly of seven lanthanide(III) coordination polymers using diphenic acid and 1,10-phenanthroline as co-ligands: Efficient detection of picric acid and Cu2+ ions in aqueous medium by europium based coordination polymer

Lanthanide based coordination polymers (Ln-CPs) act as efficient chemo-sensors on interaction with the target analyte and show a detectable variation in their optical properties. This work demonstrates interaction of metal ions and nitroaromatic compounds with Eu based CP resulting in quenching of luminescence emission intensity. Approaching towards this aim, seven iso-structural lanthanide coordination polymers having the formulae, [Ln(diphen)1.5(1,10-phen)(H2O)] where Ln = Sm (1), Gd (3), Dy (5), {[Ln(diphen)1.5(1,10-phen)(H2O)]·OH} Ln = Eu (2), Er (7) and {[Ln(diphen)1.5(1,10-phen)(H2O)]·CH3CN·H2O} Ln = Gd (4), Ho (6) (diphen = diphenic acid, 1,10-phen = 1,10 Phenanthroline), were assembled solvothermally by using diphenic acid and 1,10-Phenanthroline as ligands. These lanthanide coordination polymers were characterized by Single-crystal X-ray diffraction, FTIR, Powder X-ray diffraction, Thermogravimetric analysis, UV–visible spectroscopy and Photoluminescence. The CPs 1–7 possess one-dimensional (1D) infinite chain-like structures which crystallize in the monoclinic C2/c space group. The photoluminescence properties of CP 2 exhibit its sensing ability to detect some toxic nitroaromatic compounds and d-block metal ions. However, CP 2 shows highly sensitive behavior for the recognition of Cu2+ and picric acid as indicated by efficient luminescence quenching with the low limit of detection. Other metal ions (viz., Cr3+, Cu2+, Co2+, Zn2+, Mn2+, Ni2+, Cd2+, and Hg2+), and nitro compounds (viz., PA, m-DNB, p-NP, p-NA and NB) were also screened for sensing potential of CP 2.

Combined fabrication of zeolitic imidazolate framework-8 and lanthanide towards coordination polymers: A dual-signal fluorescent probe for sensing Cu2+ based on synergistic effect of aggregation-induced emission and antenna effect

Copper ion (Cu2+) detection remains an important task for monitoring water quality because of its specific toxicity. Herein, a new dual-signal fluorescent probe was developed by combining zeolitic imidazolate framework-8 (ZIF-8) and lanthanide for the detection of Cu2+ for the first time. The lanthanide coordination polymer (guanosine monophosphate and Eu3+, GMP/Eu) was initially incorporated into ZIF-8 to yield ZIF-8/GMP/Eu nanomaterials with extremely weak single emission fluorescence at 618 nm. It was found that the resulted nanomaterials could display a dual emission fluorescence at 515 nm and 618 nm after the introduction of tetracycline (TC) due to the synergistic effect of aggregation-induced emission effect (AIE, TC induced by ZIF-8) and antenna effect (AE, between TC and GMP/Eu). Interestingly, in the presence of Cu2+, the AIE of TC was destroyed because of the interaction of Cu2+ with ZIF-8 and TC. The AE between TC and GMP/Eu disappeared due to the formation of complex between TC and Cu2+. A dual-signal fluorescent probe of ZIF-8/GMP/Eu/TC was thereby established for sensing Cu2+ in the range of 0.5–100 μM. Such a dual-signal response strategy that intelligently utilized the “ON”/“OFF” of AIE and AE can not only eliminate the background interference, but also ensure the improved selectivity of Cu2+ sensing. Subsequently, the dual-signal fluorimetric strategy was applied for the detection of Cu2+ in environmental water samples, indicating the potential feasibility of applications for water quality monitoring.

Copper-doped Lanthanide Coordination Polymers as Luminescent Nanoenzyme for Ratiometric Sensing of H2O2 and Glutathione.

Design and fabrication of integrated multifunctional probes with intrinsic catalytic and detection abilities is of great importance to simplify the operation in biosensing application with high sensitivity. Herein, dual-emitting lanthanide coordination polymers (Ln-CPs) were facilely prepared by self-assembly of guanine diphosphate (GDP), terephthalic acid (TA), Tb3+ and Cu2+ designated as Tb/Cu-GDP/TA CPs. The doped Cu2+ endowed CPs with obviously enhanced peroxidase mimicking activity compared with free Cu2+. In the presence of H2O2, the probe catalyzed the oxidation of TA generating a new blue fluorescent product, while the fluorescence of Tb3+ decreased simultaneously. Therefore, a new sensitive ratiometric fluorescent sensor for H2O2 has been developed with a good linear range from 0.01 to 300μM and limit of 1.62nM. Moreover, the proposed platform could be extended to GSH ratiometric assay in the presence of H2O2, and interestingly, the detection performance could be easily adjusted by adding different concentration of H2O2. This work will facilitate the development of luminescent nanoenzymes based on Ln-CPs to construct the simple ratiomatric sensing platform.

Statement of Retraction: Two lanthanide coordination polymers: treatment activity on the endometrial carcinoma by inhibiting the VEGF signaling pathway

Statement of Retraction: Two lanthanide coordination polymers: treatment activity on the endometrial carcinoma by inhibiting the VEGF signaling pathway

Ratiometric luminescence detection of H2O2 in food samples using a terbium coordination polymer sensitized with 3-carboxyphenylboronic acid

A ratiometric luminescent probe was fabricated using adenosine monophosphate (AMP) as a bridging ligand and 3-carboxyphenylboronic acid (3-CPBA) as the sensitizer and functional ligand that allowed the probe to recognize hydrogen peroxide (H2O2). The probe was labeled AMP-Tb/3-CPBA. Adding H2O2 caused the nonluminescent 3-CPBA to be converted into 3-hydroxybenzoic acid, which strongly luminesces at 401 nm. This meant that adding H2O2 decreased the AMP-Tb/3-CPBA luminescence intensity at 544 nm and caused luminescence at 401 nm. The 401 and 544 nm luminescence intensity ratio (I401/I544) was strongly associated with the H2O2 concentration between 0.1 and 60.0 μM, and the detection limit was 0.23 μM. Dual emission reverse-change ratio luminescence sensing using the probe allowed environmental effects to be excluded and the assay to be very selective. We believe that the results pave the way for the development of new functionalized lanthanide coordination polymers for use in luminescence assays.

Crystal structure and characterization of a new lanthanide coordination polymer, [Pr2(pydc)(phth)2(H2O)3]·H2O

A new lanthanide coordination polymer, poly[[triaquabis(μ4-phthalato)(μ3-pyridine-2,5-dicarboxylato)dipraseodymium] monohydrate], {[Pr2(C7H3NO4)2(C8H4O4)(H2O)3]·H2O} n or {[Pr2(phth)2(pydc)(H2O)3]·H2O} n , (pydc2− = pyridine-2,5-dicarboxylate and phth2− = phthalate) was synthesized and characterized, revealing the structure to be an assembly of di-periodic {Pr2(pydc)(phth)2(H2O)3} n layers. Each layer is built up by edge-sharing {Pr2N2O14} and {Pr2O16} dimers, which are connected through a new coordination mode of pydc2− and phth2−. These layers are stabilized by internal hydrogen bonds and π–π interactions. In addition, a three-dimensional supramolecular framework is built by interlayer hydrogen-bonding interactions involving the non-coordinated water molecule. Thermogravimetric analysis shows that the title compound is thermally stable up to 400°C.

Statement of Retraction: Lanthanide coordination polymers: prevention activity on the hypotension after anesthesia by regulating the α receptor expression on the peripheral blood vessels

Statement of Retraction: Lanthanide coordination polymers: prevention activity on the hypotension after anesthesia by regulating the α receptor expression on the peripheral blood vessels

A multi-color fluorescent sensing system integrated with color recognition, liquid crystal display, and voice output module for intelligent detection of two targets

Both tetracycline antibiotics (TC) and Bacillus anthracis are highly resistant to extreme environments. However, there are few studies on the intelligence detection of these two substances by establishing different detection channels. In this research, dual rare-earth coordination polymers were prepared for the detection of Bacillus anthracis and tetracycline. As a unique biomarker of B. anthracis, 2,6-pyridine dicarboxylic acid (DPA) can enhance the green fluorescence emission of Tb3+, achieving a fluorescence change from red to yellowish-green under 282 nm excitation light. Under the excitation light of 395 nm, the TC can coordinate to Eu3+ and sensitize Eu3+ to emit light through the “antenna effect,” thus achieving the fluorescence change from colorless to red. To validate the protocol's applicability in environmental samples, we detected tetracycline and Bacillus anthracis in milk, honey, and tap water. In addition, quick sensing of Bacillus anthracis in soil and tetracycline on the surface of fruits was also achieved by glove-based portable sensors. Furthermore, combined with the color recognition, liquid crystal display, and intelligent voice output system in 51 microcontrollers, it can realize the intelligent and instantaneous detection of various target molecules in real life, which had a wide range of application value and prospects.

Portable and Recyclable Luminescent Lanthanide Coordination Polymer Film Sensors for Adenosine Triphosphate in Urine.

Adenosine triphosphate (ATP) is a small molecule that is released to the urine from bladder urothelial cells and the bladder mucosal band of the human body. In certain cases, ATP can serve as a biomarker in bladder disease. For the practical applicability of luminescent sensors for ATP in urine, it is significant to find a new strategy for making the detection progress simple and available for in-field urine analysis. Here, a novel luminescent lanthanide coordination polymer (Tb-BPA) was designed and synthesized for quick and sensitive detection of ATP through luminescence quenching with a quenching constant of 4.90 × 103 M-1 and a detection limit of 0.55 × 10-6 M. Besides, Tb-BPA has excellent anti-interference ability and can detect ATP in simulated urine with a small relative standard deviation (<4%). Moreover, the luminescent polyacrylonitrile nanofiber films modified by Tb-BPA were prepared by electrospinning and were used for ATP visual detection. Notably, this film is easy to recover and reuse, and maintains good detection performance after at least 7 cycles.

Construction of Highly Luminescent Lanthanide Coordination Polymers and Their Visualization for Luminescence Sensing.

NaH2SIP was selected as an organic ligand (NaH2SIP = 5-sulfoisophthalic acid monosodium salt). We successfully constructed a new class of lanthanide coordination polymers Ln-HS ([Ln(SIP)(DMF)(H2O)4]DMF·H2O; Ln = Eu, Tb, Sm, and Dy) by a simple solvothermal synthesis method. They exhibited excellent photoluminescence properties for Ln3+ ions, where Eu-HS and Tb-HS exhibited high quantum yields of 13.70 and 42.38%, respectively. The codoped lanthanide coordination polymers obtained by doping with different ratios of Eu3+/Tb3+ serve as excellent ratiometric thermometers with high sensitivities in the physiological temperature range, with values of 16.8, 7.0, and 14.5%·K-1, respectively. The luminescent colors of Tb0.95Eu0.05-HS and Tb0.94Eu0.06-HS exhibit variations from green to yellow to orange, achieving visualized luminescence in a narrow temperature range. The composite film material Tb0.94Eu0.06-HS@PMMA demonstrates this color variation. Next, Tb0.5Sm0.5-HS obtained by Tb3+/Sm3+ codoping was investigated. The difference in the luminescence colors visible to the naked eye at different excitation wavelengths and the change in luminescence colors occur in a very narrow temperature range. All of them show the great value of the visualized luminescence in practical anticounterfeiting, with double anticounterfeiting function and high security.

A highly efficient lanthanide coordination polymer luminescent material for the multi-task detection of environmental pollutants.

It is challenging to explore novel-structure lanthanide coordination polymers (Ln-CPs) for sensing environmental pollutants. Herein, we designed and synthesized an organic bridging linker 3-(carboxymethoxy)-1-(carboxymethyl) pyrazole-4-carboxylic acid (H3ccpc), and then successfully prepared and characterized a novel Ln-CP, namely [Tb2(ccpc)2(H2O)6]·1.5H2O (ccpcTb). Structural analysis indicates that ccpcTb exhibits a two-dimensional structure, in which Tb ions are in an eight-coordinated environment. The photoluminescence performance of ccpcTb was discussed in detail. The ccpcTb displays bright green luminescence and behaves as a multi-responsive luminescent sensor toward Fe3+ ions, Cr2O72- ions and 2,4,6-trinitrophenol with high selectivity and low detection limits. Furthermore, the possible luminescence sensing mechanisms have been addressed in detail. The luminescence quenching mechanism of sensing Fe3+ and Cr2O72- is attributed to the energy competitive absorption, while that of sensing TNP is due to the synergistic effect of energy competitive absorption and photo-induced electron transfer.

Luminescent lanthanide-based molecular materials: applications in photodynamic therapy.

Luminescent lanthanide molecular compounds have recently attracted attention as potential photosensitizers (PSs) for photodynamic therapy (PDT) against malignant cancer tumours because of their predictable systemic toxicity, temporospatial specificity, and minimal invasiveness. A photosensitizer exhibits no toxicity by itself, but in the presence of light and oxygen molecules, it can generate reactive oxygen species (ROS) to cause damage to proteins, nucleic acids, lipids, membranes, and organelles, which can induce cell apoptosis. This review focuses on the latest developments in luminescent lanthanide-based molecular materials as photosensitizers and their applications in photodynamic therapy. These molecular materials include lanthanide coordination complexes, nanoscale lanthanide coordination polymers, and lanthanide-based nanoscale metal-organic frameworks. In the end, the future challenges in the development of robust luminescent lanthanide molecular materials-based photosensitisers are outlined and emphasized to inspire the design of a new generation of phototheranostic agents.

Portable visual assay for anthrax biomarker based on lanthanide coordination polymer nanoparticles and smartphone-integrated mini-device

A novel portable sensor based on LML-Tb3+-AMP NPs and a custom-built device was fabricated for real-time and visual detection of anthracis biomarker.

Two isomorphic rare earth coordination polymer based on 1-imidazol-1-yl-2,4,6-phenyltricarboxylic acid ligand: Synthesis, structure, fluorescence sensing and practical applications

Two three-dimensional metal organic framework {[Ln2 (ttc)3]∙1.5 DMF}n{Ln3+=Tb3+(1), Sm3+(2)} was synthesized by solvothermal reaction of rare earth metal Ln3+ ions and 1-imidazol-1-yl-2,4,6-benzene-tricarboxylic acid (H3ttc). The crystal characteristics and composition of the two compounds were confirmed by powder X-ray diffraction (PXRD) and thermogravimetric analysis (TG), and the single crystal X-ray diffraction confirmed that they are isomorphic. The luminescence and sensing properties of the two compounds were investigated in detail, the Tb-MOF exhibits characteristic emission of Tb3+ through effective sensitization by antenna effect and emits bright green fluorescence under excitation light of 254 nm. Fluorescence experiments show that Tb-MOF has high selectivity and sensitivity for the detection of TNP, Cr2O72−, and Al3+ with the limit of detection of 2.89×10−8 mol·L−1, 2.35×10−8 mol·L−1 and 2.69×10−8 mol·L−1, respectively. In addition, possible luminescence quenching mechanisms are discussed. As a result, such a Tb-MOF will be a promising candidate and applies to the field of fluorescent ink and fingerprint retrieval.

Lanthanide coordination polymers based on an aromatic dicarboxylic acid and 1,10-phenanthroline ligands: synthesis, structure and luminescence properties

A novel series of lanthanide coordination polymers (Ln-CPs) have been obtained based on mixed ligands, 2-[(4-carboxyphenyl)methoxy]benzoic acid (H2cob) and 1,10-phenanthroline (phen), namely {Ln[(Hcob)(cob)(phen)]n, Ln = La (1), Pr (2), Sm (3), Eu (4)}. Complexes 1–4 were characterized by single crystal X-ray diffraction, elemental analysis, powder X-ray diffraction, infrared spectroscopy and thermogravimetric analysis. Single crystal X-ray diffraction revealed that complexes 1–4 show two-dimensional layer structures. The luminescence properties of complexes 3 and 4 were thoroughly investigated.

Four orotate-based lanthanide coordination polymers with rhomboid [Ln4(μ3-OH)2]-based 1D chainlike structure exhibiting luminescence and large magnetocaloric effect

Four isostructural lanthanide coordination polymers with orotic acid (H3OA) as building ligand, {[Ln(HOA)(μ3-OH)(H2O)2]·H2O}n (Ln = Eu (1); Gd (2); Tb (3); Dy (4)), were synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analyses demonstrate that complexes 1–4 have an one-dimensional (1D) chainlike structure consisting of rhomboid [Ln4(μ3-OH)2] unit and HOA2- linker. Magnetic studies indicate that 2 displays a large magnetocaloric effect with magnetic entropy value of 37.11 J kg−1 K−1 at 2.0 K for ΔH = 7.0 T. This is a considerable value among the reported molecular magnetic coolants, and has a great application potential in the field of ultra-low temperature refrigeration. In addition, the solid-state photophysical properties of 1 and 3 exhibit obvious characteristic Eu(III) and Tb(III) photoluminescence emission in the visible region, suggesting that Eu- and Tb-based luminescence were sensitized effectively by the energy transfer from the ligand to the metal centers.

Crystal structure and thermally enhanced photoluminescence in Eu(III) coordination polymers self-assembled from p-nitrobenzoic acid

Luminescent thermal quenching is a very troublesome thing for the practical application of luminescent materials, but also is a very common phenomenon. In theory, artificially reducing the number of quenching group around the luminescent lanthanide ion can effectively enhance the luminescence of lanthanide luminescent materials. In this paper, {[Eu2(NBA)6(H2O)4]∙H2O}n [Eu-NBA, NBA = p-nitrobenzoic acid] coordination polymers containing abundant coordination and interstitial water molecules were synthesized via hydrothermal methods. The chemical composition, crystal structures, and thermal stability of Eu-NBA coordination polymers were systemically investigated by Frontier-transfer infrared (FTIR) spectra, single-crystal X-ray diffraction and thermogravimetric analysis. X-ray diffraction analysis results revealed that Eu-NBA coordination polymers were crystallized into one-dimensional (1D) chain structures, where the adjacent Eu3+ ions were linked together by bidentate and/or tetradentate bridging carboxylate groups of the NBA ligands. The temperature-dependent photoluminescence spectra revealed that the shape and intensity of the luminescence spectra strongly depended on the coordination environment around Eu3+, and significant luminescent thermal enhancement was observed. These experimental results provided useful theoretical support for further understanding of the luminescence enhancement mechanism of lanthanide coordination polymers.