CN111088037B - Flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material and preparation method and application thereof - Google Patents
Flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of new chemical material preparation, and relates to a flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material, which has the chemical formula: k14H10[Eu4(H2O)4W6(H2glu)4O12(B‑α‑TeW9O33)4]·60H2O, in the formula, H6glu = gluconic acid. The compound belongs to a hexagonal crystal system,P6(1) space group with cell parameters ofa=44.9573(17)Å，b=44.9573(17)Å，c=25.3111(9)Å，α=90.00º，β=90.00º，γ=120.00º,V=44304(3)Å3,Z=6,R 1=0.0494,wR 2= 0.1191. The tellurium tungstate material is synthesized by a one-step self-assembly strategy regulated and controlled by an organic ligand. Researches show that the gluconic acid bridged tetranuclear europium-substituted tellurium tungstate fluorescent active material has good water solubility, is suitable for being used as a fluorescent sensor in water to detect copper ions, and has the detection limit of 8.82 multiplied by 10 to the copper ions−6 mM。
Description
Technical Field
The invention belongs to the technical field of preparation of new chemical materials, and particularly relates to a flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material, a preparation method thereof and application thereof in the field of fluorescence sensing.
Background
In recent years, the detection of trace substances by a fluorescent sensor has been a long-standing research subject, and particularly, the detection of metal ions and nutrients in daily-use water has attracted much attention. Among many fluorescence sensors, Metal Organic Frameworks (MOFs) have good fluorescence sensitivitySensitivity and selectivity are often used as fluorescent probes for the detection of metal ions (see z.m. Hao, x.z. Song, et al.J. Mater. Chem. A2013, 1, 11043-11050). However, these organic compounds have poor water solubility and are limited to tests conducted in organic solvents or organic-water mixed systems (see z.f. Wu, x.y. Huang,Chemistry Select 2018, 34884 and 4888), it is important to synthesize novel water-soluble fluorescent probe materials for detecting trace harmful substances in aqueous solution.
Polyoxometallate, as an inorganic metal ion oxygen cluster with remarkable structural characteristics, can provide abundant oxygen active sites to connect with rare earth metal ions to form a rare earth substituted polyoxometallate material with optical, magnetic, pharmaceutical, catalytic and other properties. Among them, rare earth substituted tellurium tungstates have attracted attention in recent years. For example, in 2013, Suzhongmin topic group reported that the first octapolytellulotungstate { (TeO) bridged by cerium ions3)W10O34}8{Ce8(H2O)20}(WO2)4(W4O12)]48−(see W.C. Chen, H.L. Li, et al.Chem. Eur. J. 2013, 19, 11007-11015). In 2015, Suzhou Zhongmin group reported an octa-polytellurotungstate [ Ce ] stabilized by trivalent cerium ions10Te8W88O298(OH)12(H2O)40]18−(see W.C. Chen, C. Qin, et al.Dalton Trans.2015, 44, 11290-11293). In 2018, a series of dimeric Dawson type tellurium tungstates [ H ]10(WO2){RE(H2O)5(TeW18O65)}2]14−（RE = EuIII, GdIII, TbIIIDMAH = dimethylamine hydrochloride) and the first containing a single defect [ TeW17O61]14−Building blocks [ H ]2Tb(H2O)4(TeW17O61)]9−Reported (see s.x. Shang, z.g. Lin, et al.Inorg. Chem. 2018, 57, 8831−8840）。However, the research on organic-inorganic hybrid rare earth substituted tellurium tungstates is still in the infancy stage. So far, only a few organic-inorganic hybrid rare earth-substituted tellurium tungstates have been reported. 2017-Buck 2018, Zhajun Wei et al reported isonicotinic acid coordinated rare earth substituted tetrapolytellurium tungstate [ RE2(H2O)4(pica)2W2O5][(RE(H2O)W2 (Hpica)2O4)(B-β-TeW8O30H2)2]2 4−（RE = LaIII、CeIII、NdIII、SmIII、EuIII) (see Q. Han, Y. Wen, et al.Inorg. Chem., 2017, 5613228-3)W2O4(IN)] [(B-α-TeW8O31)RE(H2O)(Ac)]2}2 20−（RE = CeIII、PrIII、NdIII、SmIII、EuIII GdIII、TbIII) (see Q. Han, J.C. Liu, et al.Inorg. Chem. 2017, 567257-7269) and organotin and rare earth coexisting tellurium tungstate [ RE-2(OH)(B-α-TeW7O28)Sn2(CH3)4(W5O18)]2 14−（RE = ErIII、YbIII、HoIII、YIII) (see J.L. Liu, M.T. Jin, et al.Inorg. Chem. 2018, 57, 12509-12520). Even so, there is still a very wide search space for organic-inorganic hybrid rare earth substituted tellurium tungstates, and particularly, rare earth substituted tellurium tungstates bridged by polyhydroxy ligands have not been reported so far.
Disclosure of Invention
The invention aims to provide a preparation method of a water-soluble flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material and application thereof in the field of fluorescence sensing.
In order to achieve the purpose, the invention adopts the following technical scheme:
a flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material has a chemical formula: k14H10[Eu4(H2O)4W6(H2glu)4O12(B-α-TeW9O33)4]·60H2O, wherein H6glu = gluconic acid.
The preparation method of the flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material can be prepared by a one-step self-assembly reaction strategy of organic ligand regulation, and specifically comprises the following steps:
mixing Na2WO4·2H2O and K2TeO3Completely dissolved in distilled water, adjusting the pH of the reaction system to 1.0-3.5 by hydrochloric acid, and adding Eu (NO)3)3·6H2O、H6glu and KCl, regulating the pH value to 1.0-3.5 again, stirring for 10-40 min, heating to react at 80-100 ℃ for 0.5-2.5 h, cooling, filtering, standing and volatilizing for 2-5 days, and separating out a transparent rod-shaped crystalline material, namely the target material flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material. In the above-mentioned preparation process, Na is used although2WO4·2H2O as a reaction raw material but due to Na+Ion and K+The ions have a smaller ionic radius than the ions and are therefore not present in the target material.
Further, the above-mentioned Na2WO4·2H2O、K2TeO3、Eu(NO3)3·6H2O、H6The molar ratio of glu to KCl is 13.2-15.0: 1.3-1.8: 1.0-3.0: 2.0-3.0: 25.2-27.2.
the invention provides an application of the flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material as a fluorescent sensor.
The invention also provides an application of the flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material as a water-soluble fluorescent probe.
The application of the flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material as a water-soluble fluorescent probe is further preferable, and the flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material can be used for detecting copper ions or cysteine in a water system.
The invention utilizes a one-step self-assembly strategy of organic ligand regulation and control to synthesize a flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material. In the reaction, TeO with lone pair electron effect3 2-The precursor can be used as a template to synthesize vacancy polyacid, expose vacancy active sites and further react with rare earth ions. In addition, oxygen atoms in the polyhydroxy gluconic acid bridging ligand and the tellurium tungstate vacancy oxygen active sites can be coordinated with rare earth ions, so that the structural stability of the target material is enhanced. The added polyhydroxy gluconic acid bridging ligand increases the competition of the reaction of the tellurium tungstate building blocks and the organic ligand with europium ions, avoids the precipitation generated by the too fast reaction of the tellurium tungstate and the europium ions, and is beneficial to the generation of the target crystalline material.
The invention provides a flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material, which is used as a water system fluorescent probe for detecting the content of copper ions and cysteine in water, and provides possibility for the polyoxometallate material serving as a fluorescent sensing probe and being applied to environment and clinical detection. Compared with the prior art, the invention has the following advantages:
1) the crystal structure of the flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material can be accurately determined through X-ray single crystal diffraction;
2) the flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material is prepared by adopting a one-step self-assembly strategy of organic ligand regulation, and has the advantages of simple operation method, easy operation and potential application value;
3) the flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material provided by the invention shows excellent water solubility and fluorescence luminescence characteristics, and provides conditions for the material to be used as a water system fluorescent probe;
4) the flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material is used as a fluorescent probe, so that sensitive detection of copper ions and cysteine in water is realized, and good selectivity is achieved;
5) the invention provides a detection mechanism of a flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material as a fluorescent probe, provides experimental basis for further development of a polyoxometallate-based fluorescent probe, and widens the potential application field of the polyoxometallate material.
Drawings
In fig. 1, a) a molecular building block of a target material; b) keggin type vacancy building block and [ Eu ]4(H2O)4W6(H6glu)4O12]24+The connection mode of the clusters; c) center [ Eu ]4(H2O)4W6(H6glu)4O12]24+A cluster structure diagram; d) [ Eu1 (H)2O)W3(H6glu)O2]5+Building block connection mode; e) simplified [ Eu ]4(H2O)4W6(H6glu)4O12]24+A schematic diagram of a cluster structure; f) eu (Eu)3+Ion distorted single capped quadrangular geometry; g) polyhydroxy Flexible ligands H6glu and [ Eu ]2(H2O)2W3O6(B-α-TeW9O33)2]4−A subunit connection mode; h) a molecular structural side view of a target material; i) dimeric [ Eu2(H2O)2W3O6(B-α-TeW9O33)2]4−A subunit structure; j) dimeric [ Te ]2W19O68]8−A unit structure diagram; k) [ Eu ] as a source of electric potential2(H2O)2W2O4]10+A metal cluster structure diagram; l) simplified [ Eu2(H2O)2W2O4]10+Metal cluster knotPatterning; m) reduced [ Eu ]2(H2O)2W2O4]10+A metal cluster side view;
in FIG. 2, a) fromcWhen viewed in the axial direction, the target material has a unique three-dimensional topological structure; b) a simplified diagram of a three-dimensional topological structure; c) the right-handed spiral duct A is shown schematically when viewed from the b-axis direction; d) a simplified diagram of the duct A; e) a simplified diagram of a left-handed spiral duct B; f) a simplified diagram of a right-handed helical tunnel C;
in FIG. 3, a) is an infrared spectrum of a target material; b) is a thermogram of the target material;
in FIG. 4, a) is a graph of the emission spectrum of a target material at an excitation wavelength of 394 nm; b) is an excitation spectrum diagram of a target material at an emission wavelength of 614 nm; c) detecting a life decay curve of a 614 nm characteristic emission peak of a target material at an excitation wavelength of 394 nm;
in fig. 5, a) is the time-resolved spectrum of the target material; b) emission spectra of the target material at decay times of 80.00 and 91.61 μ s; c) the energy transfer schematic diagram of tellurium-tungsten-oxygen fragments and europium ions in the target material;
in FIG. 6, a) is the fluorescence emission spectrum of the target material in the pH range of 0.01-4.63; b) the fluorescence emission spectrum of the target material in a pH range of 4.63-13.67 shows that the pH stability range of the material in aqueous solution is 3.00-10.00; c) is an ultraviolet spectrogram of a target material with the pH range of 0.01-5.25; d) the ultraviolet spectrogram of a target material in a pH range of 5.25-13.99 shows that the pH stability range of the material in aqueous solution is 3.00-10.00;
in fig. 7, a) is a fluorescence emission spectrum of a target material at different times; b) the ultraviolet spectrograms of target materials at different times;
in FIG. 8, a) is an electrospray mass spectrum of the target material aqueous solution at different times within the mass-to-charge ratio range of 1400-4000; b) is an electrospray mass spectrogram of a target material in the mass-to-charge ratio range of 1600-3500 at different times; c) is an electrospray mass spectrogram of a target material aqueous solution in the mass-to-charge ratio range of 1400-4000 under different pH values; d) is an electrospray mass spectrogram of a target material aqueous solution in the mass-to-charge ratio range of 1600-3500 under different pH values;
in FIG. 9, a) is a comparison graph of fluorescence emission spectra of an aqueous solution of a target material in the presence of different metal ions; b) is a comparison graph of the intensity of a fluorescence emission peak of a target material aqueous solution at 614 nm in the presence of different metal ions; c) a comparison graph of fluorescence emission spectra of a target material aqueous solution containing 0.50 mM copper ions and 0.50 mM other metal ions; d) the target material aqueous solution contains 0.50 mM copper ions+And a comparison plot of the intensity of the fluorescence emission peak at 614 nm with 0.50 mM of other metal ions; e) fluorescence emission spectrum of target material water solution in the presence of anion; f) is a comparison graph of the intensity of a fluorescence emission peak at 614 nm of a target material aqueous solution in the presence of different anions;
in FIG. 10, a) is a comparison graph of fluorescence emission spectra of target materials in different concentrations of aqueous solutions of copper ions; b) the intensity of a fluorescence emission peak at 614 nm in a fluorescence emission spectrum of a target material is determined according to the concentration of copper ions (1.00 multiplied by 10)−5-1.0 mM) curve of change; c) the intensity of a fluorescence emission peak at 614 nm in a fluorescence emission spectrum of a target material is determined according to the concentration of copper ions (1.00 multiplied by 10)−5– 8.00×10−2mM);
FIG. 11, a) is a graph showing the comparison of the fluorescence intensity recovery of the fluorescence sensing system for different kinds of amino acids; b) the fluorescence intensity of the fluorescence sensing system is gradually recovered along with the increase of the concentration of cysteine; c) the fluorescence emission main peak intensity contrast diagram of the sensing system under different cysteine concentrations; d) the detection effect of the fluorescence sensing system on cysteine and a linear fitting graph are obtained;
FIG. 12, a) is the fluorescence emission spectrum of the fluorescence sensing system when it contains two different amino acids simultaneously; b) the fluorescence emission main peak intensity of the fluorescence sensing system is compared with that of the fluorescence emission main peak intensity of the fluorescence sensing system containing two amino acids.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.
In the examples described below, K is used2TeO3Purchased from Zhengzhou Xipek chemical Co., Ltd, Na2WO4·2H2O is purchased from Tianjin Kemi Euro reagent, Inc., Eu (NO)3)3·6H2O from chemical Co., Ltd of Hua Weiruike, Beijing6glu was purchased from Shanghai Aladdin Biotechnology Ltd (C)4H9)2Sn(OOCCH3)2Purchased from Zhengzhou Xipek chemical Co., Ltd, and KCl purchased from Zhengzhou Xipek chemical Co., Ltd.
Example 1:
a flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material has a chemical formula: k14H10[Eu4(H2O)4W6(H2glu)4O12(B-α-TeW9O33)4]·60H2O, wherein H6glu = gluconic acid.
The flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material is synthesized by adopting a one-step self-assembly reaction strategy, and the preparation method specifically comprises the following steps:
will K2TeO3 (0.400 g, 1.576 mmol)、Na2WO4·2H2O (4.684 g, 14.201 mmol) was added to 20 mL of distilled water and dissolved sufficiently in 6 mol. L –1The pH was adjusted to 2.0 with HCl. Subsequently, Eu (NO) is added in sequence3)3·6H2O (0.900 g, 2.018 mmol)、H6glu (810. mu.L, 2.560 mmol) and KCl (2.000 g, 26.828 mmol) in 4 mol. L –1The pH was adjusted to 2.0 with NaOH and stirred for 30 min. Then reacting for 2h in water bath at 90 ℃, cooling, filtering, standing and volatilizing for 5 days, and separating out colorless transparent rod-shaped crystals, namely the target material. Yield: 0.87 g (as Na)2WO4·2H2Calculated yield of O is 18.87%).
Example 2:
a flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material has a chemical formulaComprises the following steps: k14H10[Eu4(H2O)4W6(H2glu)4O12(B-α-TeW9O33)4]·60H2O, wherein H6glu = gluconic acid.
The flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material is synthesized by adopting a one-step self-assembly reaction strategy, and the preparation method specifically comprises the following steps:
will K2TeO3 (0.398 g, 1.568 mmol)、Na2WO4·2H2O (4.686 g, 14.207 mmol) was added to 20 mL of distilled water and dissolved sufficiently in 6 mol. L –1The pH was adjusted to 2.0 with HCl. Subsequently, Eu (NO) is added in sequence3)3·6H2O (0.899 g, 2.015 mmol)、H6glu (810. mu.L, 2.560 mmol) and KCl (1.998 g, 26.800 mmol) in 4 mol. L –1The pH was adjusted to 2.0 with NaOH and stirred for 30 min. Then reacting for 2h in water bath at 90 ℃, cooling, filtering, standing and volatilizing for 5 days, and separating out colorless transparent rod-shaped crystals, namely the target material. Yield: 0.76 g (as Na)2WO4·2H2Calculated yield of O is 13.78%).
Example 3:
a flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material has a chemical formula: k14H10[Eu4(H2O)4W6(H2glu)4O12(B-α-TeW9O33)4]·60H2O, wherein H6glu = gluconic acid.
The flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material is synthesized by adopting a one-step self-assembly reaction strategy, and the preparation method specifically comprises the following steps:
will K2TeO3 (0.400 g, 1.576 mmol)、Na2WO4·2H2O (4.686 g, 14.207 mmol) was added to 20 mL of distilled water and dissolved sufficiently in 6 mol. L –1Of HClThe pH was adjusted to 3.0. Subsequently, Eu (NO) is added in sequence3)3·6H2O (0.900 g, 2.018 mmol)、H6glu (810. mu.L, 2.560 mmol) and KCl (2.000 g, 26.828 mmol) in 4 mol. L –1The pH was adjusted to 3.0 with NaOH and stirred for 30 min. Then reacting for 2h in water bath at 90 ℃, cooling, filtering, standing and volatilizing for 5 days, and separating out colorless transparent rod-shaped crystals, namely the target material. Yield: 0.68 g (as Na)2WO4·2H2Calculated yield of O is 14.75%).
The crystal structure of the target material prepared in the above examples 1 to 3 was determined and characterized by the present invention, and the unit cell parameters thereof were as follows:
target Material K14H10[Eu4(H2O)4W6(H2glu)4O12(B-α-TeW9O33)4]·60H2O, in the formula, H6glu = gluconic acid. The compound belongs to a hexagonal crystal system,P6(1) space group with cell parameters ofa = 44.9573(17) Å，b = 44.9573(17) Å，c = 25.3111(9) Å，α = 90.00º，β = 90.00º，γ = 120.00º, V = 44304(3) Å3, Z = 6, R 1 = 0.0494, wR 2= 0.1191. The molecular structural unit is shown in figure 1a, and the tetrameric polyanion can be regarded as Keggin type [ B-alpha-TeW ] with 4 three-vacancy positions9O33]8−Fragment and a hetero-metal cluster [ Eu ]4(H2O)4W6(H6glu)4O12]24+ (FIG. 1b) composition. Hetero metal cluster [ Eu ]4(H2O)4W6(H6glu)4O12]24+Can be further split into 1 [ Eu ]4(H2O)4W4(H6glu)4O8]20+Units and 2 bridging WO6Octahedron (fig. 1 c). Wherein [ Eu ]4(H2O)4W4(H6glu)4O8]20+The ion is composed of 4 identical ionsEu(H2O)W(H6glu)O2]5+Fragment composition. In [ Eu (H)2O)W(H6glu)O2]5+In fragment, { WO6The octahedron is bridged with Eu through gluconic acid3+The ions are connected. [ Eu1 (H) formed centering around Eu1 and W32O)W3(H6glu)O2]5+For example (FIG. 1d), the terminal carboxyl and vicinal hydroxyl groups of the gluconic acid ligand are linked to W3, the hydroxyl groups on the C3, C4, C5 atoms are linked to Eu13+And (4) cation combination. The other three [ Eu (H)2O)W(H6glu)O2]5+Chemical coordination of the fragment to [ Eu1 (H)2O)W3(H6glu)O2]5+Similarly, gluconic acid is centrally linked to Eu2 and W4, Eu3 and W2, Eu4 and W6, respectively. Furthermore, Eu1 and W6, Eu2 and W2, Eu3 and W4, and Eu4 and W3 atoms are bridged by [ WO 3 ]6]6-Double bridge oxygen [ mu ] in octahedron2-O is interconnected to form [ Eu ] of a distorted quadrangular structure4(H2O)4W6(H6glu)4O12]24+A heterometal cluster. In addition, W18 and W1 centers are bridged by { WO6The double bridge oxygen in the octahedron is respectively reacted with Eu13+And Eu23+Ion, Eu33+And Eu43+The ions are bridged and distributed at both ends of the distorted quadrangular prism to form a double-cap quadrangular prism configuration (fig. 1 e). From the crystallographic point of view, 4 crystallographically independent Eu3+The ions adopt a similar distorted single-cap square antiprism configuration (fig. 1 f). Therefore, only Eu13+The ions are taken as examples to describe the coordination configuration of the rare earth ions. At Eu13+Of the coordinating oxygen atoms of the ion, 5 oxygen atoms are derived from { WO6Double bridge oxygen of octahedronμ 2–O [Eu–O: 2.384(1)–2.517(1) Å]The 3 oxygen atoms are derived from the organic ligand gluconic acid [ Eu-O: 2.463(1) -2.520 (1) A]1 oxygen atom from a coordinated water [ Eu-O: 2.452(0) A](FIG. 1 f). Wherein, 5 and { WO6Octahedron connected double bridge oxygenμ 2in-O, the O136 and O141 atoms originate from a triple-vacancy [ B-alpha-TeW9O33]8−Fragment [ Eu 1-O136: 2.437(1) A, Eu 1-O141: 2.444(1) A]The O104 atom comes from [ WO ] which acts as a bridge6Octahedral [ Eu 1-O104: 2.384(1) A }]O73 and O83 atoms are linked to the terminal carboxyl group of gluconic acid { WO6Octahedral [ Eu 1-O73: 2.517(1) A, Eu 1-O83: 2.428(1) A]. In the distorted, single-cap, square, inverted prism, the atoms O73, O104, O136, and O141 constitute the lower base of the inverted prism, and the atoms O83, O94, O1W, and O165 constitute the upper base of the inverted prism. Notably, the O166 atom from the gluconic acid ligand occupies the apical position of the tetragonal antiprism. Viewed from another aspect, the tetrameric polyanion of this material can also be viewed as a dimeric subunit [ Eu ] bridged by 4 gluconic acids2(H2O)2W3O6(B-α-TeW9O33)2]4−And (4) forming. Two [ Eu ]2(H2O)2W3O6(B- α-TeW9O33)2]4−The subunits are staggered to form dihedral angles of about 41.5 ° (fig. 1g, h). This distorted spatial arrangement may be associated with the gluconic acid ligand and two [ Eu ]2(H2O)2W3O6(B-α-TeW9O33)2]4−Steric hindrance between subunits is involved. Wherein [ Eu ] is of an open type2(H2O)2W3O6(B-α-TeW9O33)2]4−The subunits can be viewed as being composed of two [ B-alpha-TeW ]9O33]8−Fragments sharing a bridge { WO6Octahedral composition, 2 [ Te ]2W19O68]8−The included angle of the segments is 65.9o (FIG. 1i, j). And the open coordination mode provides good opportunity for encapsulating the metal center. Thus, 2 tungsten and 2 europium centers are encapsulated in the open region to form [ Eu2(H2O)2W3O6(B-α-TeW9O33)2]4−A subunit. In a four-core metal oxygen cluster [ Eu ]2(H2O)2W2O4]10+The centers of Eu1, W2, Eu2, and W6 are connected to each other via O atoms to form a distorted quadrangle (see FIG. 1 l). The distances between Eu 1-W2, Eu 1-W6, Eu 2-W2 and Eu 2-W6 are 4.118(7), 4.236(8), 4.259(2) and 4.101(2) a, respectively. The bridged W18 center is located on one side of the distorted quadrilateral plane, and the distances of W18-Eu 1 and W18-Eu 2 are 4.109(6) and 4.125(7) A, respectively (FIG. 1 m).
In addition, each tetrameric polyanion was linked to 3 bridging potassium ions, respectively, and each potassium ion was linked to 3 tetrameric polyanions, respectively, to form a unique three-dimensional (3, 3) -linked supramolecular framework (fig. 2a, b). FromcViewed in the axial direction, the tetrameric polyanion and potassium ion are along 61The spiral channels are arranged to form 1 channel having a cross-sectional dimension of about 9.0X 9.0A2(iii) left-handed helical channels (see fig. 2c, d). And 2 adjacent spiral channels a are further connected by 2 potassium ions and 2 tetrameric polyanions, forming 1 right-handed spiral channel B between 2 spiral channels a (fig. 2 e). Meanwhile, 3 spiral channels A are connected with 1 left-handed spiral channel C (figure 2 f). Such a rimcThe hexagonal arrangement mode in the axial direction greatly increases the contact area of the tetrameric polyanion and water, and is very favorable for detecting trace substances in water by the tetrameric polyanion.
The present invention characterizes the infrared spectra (FIG. 3a) and the thermograms (FIG. 3b) of the target material. Its infrared spectrum is 963, 860, 788 and 710 cm–1The characteristic peak is attributed to the three-vacancy Keggin type [ B-alpha-TeW ]9O33]8–In the unitν(W–Ot)、ν(W–Ob)、ν(W–Oc) Andν(Te-O) stretching vibration. At 1361 and 1633 cm–1The absorption peaks correspond to the symmetric and asymmetric stretching vibration of the carboxyl respectively, and prove that H6glu ligands are present in the material. In addition, at 3390 cm–1The strong and wide absorption peak shows that the target material contains crystal water or coordinated water. As can be seen from the thermogravimetric analysis chart, the thermogravimetric process of the target material can be divided into two steps. The first step weight loss occurred between 25 ℃ and 250 ℃ and was 8.07% (theoretical: 7.92%) corresponding to the targetLoss of 60 crystal waters in the material. The first step weight loss occurs at 250oC-700 oBetween C, the weight loss is 13.56% (theory: 13.67%), which is attributed to the loss of 4 coordinated waters in the target material, the decomposition of 4 gluconic acid organic ligands, 4 WO3The weight loss analysis is matched with the calculated value.
The preparation method of the fluorescence sensor comprises the following steps:
1.0 mg of the target material prepared in example 1 was dissolved in 1 mL of an aqueous solution to obtain a target material aqueous fluorescent sensor.
The detection method of the fluorescence sensor comprises the following steps:
all fluorescence measurements were performed on an Edinburgh (FLS 980) steady state transient fluorescence spectrometer, England. To contain 1 mg mL –1The water solution of the target material is used as a fluorescence sensor, and the objects to be detected with different masses are dissolved in the fluorescence sensor for detection.
To apply the target material to a fluorescence sensor, its fluorescence properties were first tested. Under 394 nm light excitation, the emission spectrum of the target material has 5 characteristic peaks at 579, 594, 614, 650 and 701 nm, which respectively correspond to the europium ions5D0→7F0、5D0→7F1、5D0→7F2、5D0→7F3And5D0→7F4the transition (fig. 4 a). Wherein, the characteristic peak with the strongest emission intensity at 614 nm can be used as a detection signal for detecting trace substances in water. When the strongest emission peak at 614 nm was monitored, the excitation spectra obtained showed 5 characteristic excitation peaks at 362, 379, 394, 415 and 465 nm, corresponding to europium ions, respectively7F0→5D4、7F0→5G2、7F0→5L6、7F0→5D3And7D0→5D2transition (fig. 4 b). When monitoring at 614 nmeasuring the fluorescence attenuation curve of the material (FIG. 4c) with the strongest emission peak at m, fitting the fluorescence attenuation curve to a second-order exponential functionτ 1= 100.00 μ s (0.03%) andτ 2= 404.06 μ s (99.97%) and an average lifetime of 339.81 μ s.
The energy transfer of tungsten oxygen cluster fragments to europium ions (fig. 5a) in the target material was investigated by means of time resolved spectroscopy (TRES). Within 80-200 μ s, the emission intensity of the characteristic emission band of the tungsten-oxygen cluster fragment at 470 nm shows a rapid decay tendency, while the emission intensity of the characteristic emission peak of europium ion changes less significantly (FIG. 5 a). As can be seen from the comparison of the emission spectra of the target material at decay times of 80.00 and 91.61 μ s (FIG. 5 b), the emission peak of the tungsten oxygen cluster fragment decays rapidly, while the emission peak of the europium ion increases in intensity, which directly demonstrates the energy transfer from the tungsten oxygen cluster fragment to the europium ion. Thus we propose a mechanism for luminescence of the target material (FIG. 5c) when excited with 394 nm excitation light, a portion of the light is absorbed by the tungsten oxygen cluster fragments and electrons are taken from the ground state1A1gExcited to triplet state1T1u. Due to the spin coupling effect, the electrons relax to3T1uEnergy level. When electrons return to tungsten-oxygen cluster fragment1A1gIn the ground state, part of electrons are captured by europium ions, and europium ion emission is further excited, so that energy transfer from tungsten oxygen clusters to rare earth ions is generated. The energy transfer from the tungsten oxygen cluster to the rare earth ions sensitizes the fluorescence emission intensity of the rare earth ions to a certain extent and provides a foundation for applying the target compound to fluorescence detection.
In addition, the stability of the fluorescent probe in aqueous solution is an important index for exploring the performance of a subsequent fluorescent sensor. Therefore, the stability of the fluorescent probe in aqueous solution was tested by means of fluorescence spectroscopy. The test shows that: in the case of aqueous solution pH 3-10, there was little change in the intensity and shape of the fluorescence emission spectra, while in the case of pH less than 3 or greater than 10, there was a significant change in the fluorescence emission spectra, indicating decomposition of the material (FIGS. 6 a-b). At the same time, ultraviolet light is usedSpectroscopy the stability of the target material in aqueous solution was tested. The test shows that the material is O at 192 nm under the condition of pH of 3-10tAbsorption peak of absorption band → W and O at 250 nmb(c)No change in absorption peaks of the → W absorption band occurred, indicating that the aqueous material solution can exist stably at a pH of 3 to 10 (fig. 6 c-d).
In addition to pH, the effect of the stability of the material in aqueous solution over time is also of critical importance. The target material was tested for up to 96 hours by fluorescence spectroscopy (fig. 7a) and uv spectroscopy (fig. 7b), and the results showed that the structure remained.
FIG. 8 shows electrospray mass spectra of aqueous solutions of target materials at different times and pH. Electrospray high resolution mass spectrometry analysis shows that the ion peaks { [ Eu ]4(H2O)8W6(H6glu)4O12(B-α-TeW9O33)4]}8– (m/z = 1510.32)、{Na[Eu4(H2O)10W6(H6glu)4O12(B-α-TeW9O33)4]}7– (m/z = 1734.27)、{K2[Eu4(H2O)4 W6(H6glu)4O12(B-α-TeW9O33)4]}6– (m/z = 20170.87)、{K2[Eu4(H2O)12W6(H6glu)4O12(B-α- TeW9O33)4]}6– (m/z = 2040.52)、{K2Na[Eu4(H2O)14W6(H6glu)4O12(B-α-TeW9O33)4]}5–(m/z = 2460.27) remained in the 4 day test (fig. 8a and b) with essentially no change in intensity, indicating that the structure remained. To further demonstrate the stability of the material at different pH, electrospray mass spectrometry was performed on aqueous solutions of the material at different pH ranges. Tests have shown that the material has characteristic molecular ion peaks (m/z = 1510.32, 1734.27, 20170.87, 2040) in the pH range 3-1052, 2460.27) and when the pH of the aqueous solution is lower than 3 or higher than 10, the ion peak intensity in the aqueous solution is reduced or even not detected, indicating that the target material is stable in the pH range of 3-10 (fig. 8c, d), and this excellent stability provides important conditions for the fluorescent probe to be used for detecting metal ions and biomolecules.
Fluorescence measurements were performed by dissolving 1.00 mg of material in 1.00 mL of an aqueous solution containing 1.00 mM of different metal ions. The test showed alkali metal ion (Li)+、Na+、K+、Cs+) Alkaline earth metal ion (Mg)2+、Ba2+) And Al3+And Cd2+The ions do not influence the luminescence property of the fluorescent probe, and then the fluorescent probe contains Cu which is not filled with d orbits2+The ion generates a remarkable quenching effect on the luminescence of the fluorescent probe, which shows that the fluorescent sensing system based on the material as the fluorescent probe generates a remarkable quenching effect on Cu2+Ions have significant recognition properties (fig. 9 a-b). Based on the material, the material has good selectivity for a fluorescent probe, and simultaneously contains 0.50 mM CuCl2And 0.50 mM of other metal ions, and the results show that the fluorescent probe emits light with the intensity corresponding to that of the other metal ions and only contains 0.50 mM of CuCl2The fluorescence probe emission spectrum intensity of the aqueous solution hardly changed from that of the aqueous solution (FIGS. 9 c-d). In addition, the copper-containing alloy contained 1.00 mM of a different copper source (CuSO)4、CuCl2、CuBr2、Cu(Ac)2、CuNO3) The test results show that different anions have no significant effect on the fluorescence probe emission spectrum intensity (fig. 9 e-f). Therefore, the fluorescence sensing system taking the material as the fluorescent probe has higher selectivity and anti-interference property for detecting copper ions.
Next, in order to find the sensitivity of the sensor to the detection of copper ion concentration, the sensitivity to copper ion concentration was 1.00X 10−5Fluorescence emission measurements were performed to 1.00 mM aqueous solutions of the target material (FIGS. 10a-b), and it can be seen that the intensity of the emission peak at 614 nm is seenIGradually decreases with the increase of the concentration of copper ions, and accordingly, the blank emission peak intensity of the sensorI 0Intensity of emission peak in the presence of copper ionIRatio of (I 0 /I) Gradually increases with the increasing of the concentration of the copper ions, and the concentration of the copper ions is 1.00 multiplied by 10−5–8.00×10−2The range of mM increases linearly. Cu2+The ion is 1.00X 10−5 – 8.00×10−2The linear fit equation over the mM concentration range is:I 0/I = 122.6591C+1.0782 (FIGS. 10 b-c). Calculating a formula according to the detection limit:LOD = 3s / k (s is the standard deviation of 3 measurements of fluorescence emission spectrum intensity in the absence of copper ions,kslope of linear fit), the detection limit of the fluorescence sensor to copper ions is 8.82 x 10−6And mM shows that the fluorescence sensor has higher sensitivity.
Amino acid is a biological small molecule which is very beneficial to human bodies, but does not carry a luminescent group, so that the aim of detection cannot be achieved by using a traditional fluorescence quenching method. However, chelation between the amino acid and the copper ions can occur, so that quenching of the copper ions to the emission spectrum intensity of the fluorescent probe is reduced, and the quenched fluorescent signal is gradually recovered. By utilizing the principle, the invention further develops an off-on type fluorescence sensor based on a copper ion fluorescence quenching system to realize the detection of the content of the amino acid in the water.
1.00 mL of the mixture contained 1.00 mg of the target material and 4.00X 10−2In the fluorescent sensing system of the mM copper ion aqueous solution, when 0.10 mM glycine, threonine, lysine or glutamic acid respectively exists, the fluorescence emission intensity of the fluorescent probe is not changed significantly, however, when 0.10 mM cysteine exists, the fluorescence emission intensity of the fluorescent probe is obviously enhanced (FIG. 11a), which shows that the copper ion based fluorescence quenching system has obvious recognition effect on cysteine. 1.00 mL of the mixture contained 1.00 mg of the target material and 4.00X 10−2In the mM copper ion aqueous solution fluorescence sensing system, the fluorescence emission intensity based on the copper ion fluorescence quenching system is linearly increased along the process that the cysteine concentration is gradually increased from 0.02 mM to 0.14 mM, and when the cysteine concentration reaches 0.14 mM, the fluorescence emission intensity is linearly increasedThe fluorescence emission intensity of the copper ion fluorescence quenching system is substantially restored to the initial state (FIG. 11b-c), and when the cysteine concentration is further increased, the fluorescence emission intensity is substantially maintained. From this it can be derived that the linear fit equation for cysteine in the 0.02-0.14 mM concentration range is:I 0/I = 33.8079C+ 0.3778 (FIG. 11d), the detection limit was calculated to be 1.75X 10−4mM shows that the phosphor system based on quenching of copper ions has a good detection effect on cysteine.
In addition, the interference rejection of this "off-on" type fluorescence sensor was also tested, and the fluorescence emission signal based on the copper ion fluorescence quenching system was detected in the presence of 0.10 mM cysteine and 0.10 mM other amino acids (FIG. 12). The test result shows that: when the fluorescent sensor contains two kinds of amino acid, the fluorescent signal of the fluorescent sensor is still the same as the emission signal only containing cysteine, which shows that the sensor constructed based on the copper ion fluorescence quenching system has good anti-interference capability on the detection of the cysteine.
In conclusion, the invention synthesizes and reports a flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material K14H10[Eu4(H2O)4W6(H2glu)4O12(B-α-TeW9O33)4]·60H2And O, by utilizing the excellent water solubility and the stable fluorescence luminescence characteristic of the POMs, the POMs are used as a water system fluorescence probe to realize the detection of copper ions and cysteine, so that the potential application of the POMs in environmental monitoring and clinical medicine detection is widened, and the POMs can be used as candidate materials with excellent application value in the preparation of fluorescence sensing devices. The test result shows that: the material has very good sensitivity and selectivity to copper ions and cysteine. The rare earth-substituted tellurium tungstate material is used as a water system fluorescent probe to realize the detection of metal ions and cysteine, and a foundation is laid for widening the potential application of the polyoxometallate material in the aspects of environment and clinical detection.
Claims (6)
1. A flexible polyhydroxy gluconic acid ligand bridged tetranuclear europium substituted tellurium tungstate material has a chemical formula: k14H10[Eu4(H2O)4W6(H2glu)4O12(B-α-TeW9O33)4]·60H2O, wherein H6glu = gluconic acid.
2. The method of preparing a flexible polyhydroxygluconate ligand bridged tetranuclear europium-substituted tellurium tungstate material as claimed in claim 1, which comprises the following steps:
mixing Na2WO4·2H2O and K2TeO3Dissolving completely in distilled water, adjusting pH to 1.0-3.5, and adding Eu (NO)3)3·6H2O、H6glu and KCl, regulating pH to 1.0-3.5, stirring for 10-40 min, heating at 80-100 deg.C for 0.5-2.5 hr, cooling, filtering, standing for volatilizing for 2-5 days to obtain a transparent rod-like crystalline material, i.e. the tetranuclear europium-substituted tellurium tungstate material.
3. The method of claim 2, wherein the flexible polyhydroxygluconate ligand bridged tetranuclear europium substituted tellurium tungstate material is Na2WO4·2H2O、K2TeO3、Eu(NO3)3·6H2O、H6The molar ratio of glu to KCl is 13.2-15.0: 1.3-1.8: 1.0-3.0: 2.0-3.0: 25.2-27.2.
4. the use of the flexible polyhydroxygluconate ligand bridged tetranuclear europium-substituted tellurium tungstate material as claimed in claim 1 as a fluorescent sensor.
5. The use of the flexible polyhydroxygluconate ligand bridged tetranuclear europium-substituted tellurium tungstate material as claimed in claim 1 as a water-soluble fluorescent probe.
6. The use of the flexible polyhydroxygluconate ligand-bridged tetranuclear europium-substituted tellurium tungstate material as claimed in claim 5, which is used as a water-soluble fluorescent probe for detecting copper ions or cysteine in an aqueous system.
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