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A novel fluorescence chemodosimeter for fluoride anions in aqueous solution based on siloxane-aurone moiety
Inorganic Chemistry Communications 78 (2017) 52–55
Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Short communication
A novel fluorescence chemodosimeter for fluoride anions in aqueous solution based on siloxane-aurone moiety Yongxiao Xu, Yibing Wang, Songfang Zhao, Ruifang Guan, Duxia Cao ⁎, Qianqian Wu, Xueying Yu, Yatong Sun School of Material Science and Engineering, University of Jinan, Jinan 250022, Shandong, China
a r t i c l e
i n f o
Article history: Received 31 January 2017 Received in revised form 2 March 2017 Accepted 3 March 2017 Available online 06 March 2017 Keywords: Aurone Fluoride anion Chemodosimeter Siloxane
a b s t r a c t A novel siloxane-aurone compound, 4′-cyano-4-tert-butyldiphenylsiloxane-aurone (named as TBDCN), was synthesized. The compound exhibits high sensitivity, fast response rate and high selectivity for fluoride anions recognition with obvious absorption and fluorescence response in aqueous solution, which is more sensitive than the traditionally type of chemodosimeters based on F−-triggered cleavage. The detection limits of TBDCN for F− are determined to be 1.9 μM and 0.0017 μM with absorption and fluorescence as detected signal, respectively, which satisfy the requirement from U.S. Environmental Protection Agency. The recognition mechanism is the F−-promoted dissociation of silicon-oxygen bond based on in situ mass spectra and 1H NMR spectra analysis. © 2017 Elsevier B.V. All rights reserved.
During the past years, fluorescence chemodosimeters, which are used to identify different ions and molecules, have been developed rapidly [1–4]. Many chemodosimeters are not able to detect ions in aqueous solution, especially fluoride anions (F−). Fluoride anions are very important to the organism, such as fluoride can be used in the treatment of dental caries and osteoporosis and excessive intake of fluoride can cause tooth or bone fluorosis [5,6]. As a very important anion, F− is a Lewis basic and has strong hydrolysis ability, which results in the recognition in aqueous solution being very difficult. Although the investigation on detection for F− has attracted many research interest for many years [7–9]. But the recognition in aqueous solution still cannot be solved completely. There are many types of chemodosimeters for F−, such as organoboron compound [10–14], hydrogen bonding receptor [15–17], organic silicon ether [18–23], and so on. F− promoted cleavage of silicon-oxygen bond in organic silicon ether is the best way to solve recognition in aqueous solution. But this reaction type of chemodosimeters normally has some shortcomings for F− recognition in aqueous solution, such as long response time (several tens of minutes or even hours) and low sensitivity [24,25]. Our group has devoted to fluoride recognition for many years [14,26,27]. Here a chemodosimeter for F− is reported, which exhibits fast response rate (about 5 min) and high sensitivity. The title compound, 4′-cyano-4-tert-butyldiphenylsiloxane-aurone (TBDCN) was synthesized with 4′-cyano-4-hydroxy-aurone [28] and
⁎ Corresponding author. E-mail address: [email protected] (D. Cao).
http://dx.doi.org/10.1016/j.inoche.2017.03.003 1387-7003/© 2017 Elsevier B.V. All rights reserved.
tert-butyldiphenylsilyl chloride as the starting materials, imidazo as catalyzer and dichloromethane as solvent. The synthetic route is shown in Scheme 1. Yellow solid with a yield of 56% was obtained. The compound was fully characterized by nuclear magnetic resonance and high-resolution mass spectra [29]. Density functional theory (DFT) quantum chemical calculation on the compound was carried out. The frontier molecular orbitals (HOMO and LUMO) of the compound were shown in Fig. 1. The calculation results indicate that the molecule possesses weak polarity with dipolar moment being 5.13D and charge slightly transfers from benzofuranone group to cyano group upon the excitation. The titration was carried out in aqueous solution (VHEPES:Vethanol = 1:1). TBDCN was dissolved in the aq.-HEPES buffer-ethanol mixed solution and fluoride anions in HEPES buffer solution was progressively added. TBDCN can recognize F− in aqueous solution with high sensitivity. As shown in Fig. 2a, TBDCN exhibits two absorption bands in blueviolet region with main absorption peaks at 307 nm (ε = 3.76 × 104 M− 1 cm− 1) and 391 nm (ε = 3.43 × 104 M−1 cm− 1) in aq.-HEPES buffer-ethanol solution (1:1, v/v). Upon the addition of F−, the original absorption peak at 391 nm gradually decreases with a little bathochromic shift, which indicates that there is some reaction between the chemodosimeter and cyanide anions. Absorption spectra would remain stable after 24 equiv. F− was added. The fluorescence spectra of TBDCN also exhibit obvious response change. TBDCN emits yellow fluorescence at 527 nm. After the addition of fluoride anions, the original fluorescence gradually decreases, at last fluorescence decreases to about 10% of the original intensity. Time-dependent fluorescence spectral changes upon addition of 24 equiv. F− to TBDCN were also
Y. Xu et al. / Inorganic Chemistry Communications 78 (2017) 52–55
53
Scheme 1. Synthetic route to the title compound TBDCN.
Fig. 1. The electron density distribution of the frontier molecular orbitals HOMO (a) and LUMO (b) of the compound.
measured (Fig. S1). As shown in Fig. S1, we can see that TBDCN can response F− with fast response rate (about 5 min). The detection limits [30,31] of the compound to F− with absorption and fluorescence spectra as detected signal (Fig. S2) are 1.9 μM and 0.0017 μM, respectively. U.S. Environmental Protection Agency limits
the fluoride anions in drinking water being 37.1–63.6 μM [25]. Then the detection limits satisfy the requirement from U.S. Environmental Protection Agency. Furthermore, the response time is short and response rate is fast. Every titration point will remain stable after about 5 min.
Fig. 2. UV–vis absorption (a) and fluorescence (b) spectral changes of TBDCN upon titration with KF in aq.-HEPES buffer-ethanol solution (VHEPES:Vethanol = 1:1).
Fig. 3. UV–vis absorption (a) and fluorescence (b) spectral changes of TBDCN in HEPES buffer-ethanol solution (VHEPES:Vethanol = 1:1) upon the addition of various anions. Insert: Changes in UV–vis absorption (391 nm) and fluorescence (527 nm) spectra of the compound in the presence of various anions in response to F−.
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Y. Xu et al. / Inorganic Chemistry Communications 78 (2017) 52–55
Fig. 4. The reaction mechanism of TBDCN to detect F−.
The selectivity of the compound for other anions was also investigat− ed. As shown in Fig. 3, other anions such as SCN−, SO24 −, HSO− 3 , Cl , − CO2– 3 and Br , did not affect absorption and fluorescence spectra obviously. Different from other anions, the absorption and fluorescence peaks of TBDCN upon the addition of F− changed clearly. The competitive binding experiment of the anions to F− was also measured. Results indicate that these competing anions can neither lead to obvious spectral changes of TBDCN nor interfere the recognition reaction between the compound and F−. The recognition mechanism is investigated based on in situ mass spectra (Fig. S3) and 1H NMR spectra (Fig. S4), which is shown in Fig. 4. The mass spectra peak of the compound is 524.1621 ((M + H)+). After the addition of F−, the peak at 524.1621 disappears and a new peak at 264.8421 appears, which is attributed to the removement of tert-butyldiphenylsilane group. As shown in Fig. S3, both hydrogen proton signals of TBDCN at 6.99 ppm (C5, d, J = 8.0 Hz) and 6.84 (Cα, s) are up shifted to 6.26 ppm (C5, d, J = 8.0 Hz) and 6.53 ppm (Cα, s), respectively. No obvious change in 1H NMR spectrum of other hydrogen proton signals was observed. Si\\F bond (ESi\\F = 141 kcal/mol) has higher dissociation energy than Si\\O bond (ESi\\O = 103 kcal/mol). Then after the addition of F−, F− will promote the dissociation of Si\\O bond and combine with O. No obvious absorption peak change is observed during the titration, which is because the molecular backbone dose not change obviously and charge transfer is similar. The quench of fluorescence is from quenching of oxygen ion. In summary, a novel siloxane-aurone compound as fluorescence chemodosimeter for F− has been synthesized. This compound can recognize F− with high sensitivity, fast response rate and obvious absorption and fluorescence change. The recognition mechanism is F−-promoted the dissociation of Si\\O bond. The compound has good practical application potential in fluoride recognition. Acknowledgements This work was supported by the National Natural Science Foundation of China (21672130, 51373069, 21601065), the Natural Science Foundation of Shandong Province (ZR2015BL011), Key Research and Development Plan of Shandong Province (2016GSF117004), Colleges and Universities Science and Technology Foundation of Shandong Province (J16LA08) and the Fund of Graduate Innovation Foundation of University of Jinan, GIFUJN (S1504). Appendix A. Supplementary material Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.inoche.2017.03.003. References [1] Y. Zhou, J.F. Zhang, J. Yoon, Fluorescence and colorimetric chemosensors for fluoride-ion detection, Chem. Rev. 114 (2014) 5511–5571. [2] F. Wang, L. Wang, X.Q. Chen, J. Yoon, Recent progress in the development of fluorometric and colorimetric chemosensors for detection of cyanide ions, Chem. Soc. Rev. 43 (2014) 4312–4324.
[3] L. Chen, S.Y. Yin, M. Pan, K. Wu, H.P. Wang, Y.N. Fan, C.Y. Su, A naked eye colorimetric sensor for alcohol vapor discrimination and amplified spontaneous emission (ASE) from a highly fluorescent excited-state intramolecular proton transfer (ESIPT) molecule, J. Mater. Chem. C 4 (2016) 6962–6966. [4] Y.M. Yang, Q. Zhao, W. Feng, F.Y. Li, Luminescent chemodosimeters for bioimaging, Chem. Rev. 113 (2013) 192–270. [5] S.Y. Yin, Y.X. Zhu, M. Pan, Z.W. Wei, H.P. Wang, Y.N. Fan, C.Y. Su, Nanosized NIR-luminescent Ln metal-organic cage for picric acid sensing, Eur. J. Inorg. Chem. (2017) 646–650. [6] K.N. Wang, W.J. Feng, Y.B. Wang, D.X. Cao, R.F. Guan, X.Y. Yu, Q.Q. Wu, A coumarin derivative with benzothiazole Schiff's base structure as chemosensor for cyanide and copper ions, Inorg. Chem. Commun. 71 (2016) 102–104. [7] W.J. Xu, S.J. Liu, H.B. Sun, X.Y. Zhao, Q. Zhao, S. Sun, S. Cheng, T.C. Ma, L.X. Zhou, W. Huang, FRET-based probe for fluoride based on a phosphorescent iridium(III) complex containing triarylboron groups, J. Mater. Chem. 21 (2011) 7572–7581. [8] H.Y. Zhao, F.P. Gabbaï, Nucleophilic fluorination reactions starting from aqueous fluoride ion solutions, Org. Lett. 13 (2011) 1444–1446. [9] S. Vishwakarma, A. Kumar, A. Pandey, K.K. Upadhyay, A multi writable thiophenebased selective and reversible chromogenic fluoride probe with dual –NH functionality, Spectrochim. Acta A 170 (2017) 191–197. [10] E.J. Jun, Z. Xu, M. Lee, J. Yoon, A ratiometric fluorescent probe for fluoride ions with a tridentate receptor of boronic acid and imidazolium, Tetrahedron Lett. 54 (2013) 2755–2758. [11] M.S. Yuan, Q. Wang, W.J. Wang, D.E. Wang, J.R. Wang, J.Y. Wang, Truxene-cored πexpanded triarylborane dyes as single- and two-photon fluorescent probes for fluoride, Analyst 139 (2014) 1541–1549. [12] Z.Q. Guo, I. Shin, J. Yoon, Recognition and sensing of various species using boronic acid derivatives, Chem. Commun. 48 (2012) 5956–5967. [13] D.K. You, S.H. Lee, J.H. Lee, S.W. Kwak, H. Hwang, J. Lee, Y. Chung, M.H. Park, K.M. Lee, Synthesis and photophysical properties of phenanthroimidazole-triarylborane dyads: intriguing ‘turn-on’ sensing mediated by fluoride anions, RSC Adv. 7 (2017) 10345–10352. [14] D.X. Cao, H.Y. Zhao, F.P. Gabbaï, A sandwich complex of trimesitylborane Mes3B: synthesis,characterization and anion binding properties of Mes2B[(η6-Mes)FeCp]+, New J. Chem. 35 (2011) 2299–2305. [15] D. Thongkum, T. Tuntulani, Fluoride-induced intermolecular excimer formation of bispyrenylthioureas linked by polyethylene glycol chains, Tetrahedron 67 (2011) 8102–8109. [16] Y.C. Wu, J.P. Huo, L. Cao, S. Ding, L.Y. Wang, D. Cao, Z.Y. Wang, Design and application of tri-benzimidazolyl star-shape molecules as fluorescent chemosensors for the fast-response detection of fluoride ion, Sensors Actuators B Chem. 237 (2016) 865–875. [17] Y.P. Zhang, S.M. Jiang, Fluoride-responsive gelator and colorimetric sensor based on simple and easy-to-prepare cyano-substituted amide, Org. Biomol. Chem. 10 (2012) 6973–6979. [18] H.J. Ben, X.K. Ren, B. Song, X.P. Li, Y.K. Feng, W. Jiang, E.Q. Chen, Z.H. Wang, S.C. Jiang, Synthesis, crystal structure, enhanced photoluminescence properties and fluoride detection ability of S-heterocyclic annulated perylenediimide-polyhedral oligosilsesquioxane dye, J. Mater. Chem. C (2017)http://dx.doi.org/10.1039/ C6TC05171E. [19] R. Hu, J. Feng, D.H. Hu, S.Q. Wang, S.Y. Li, Y. Li, G.Q. Yang, A rapid aqueous fluoride ion sensor with dual output modes, Angew. Chem. Int. Ed. 49 (2010) 4915–4918. [20] B. Zhu, F. Yuan, R. Li, Y. Li, Q. Wei, Z. Ma, B. Du, X. Zhang, A highly selective colorimetric and ratiometric fluorescent chemodosimeter for imaging fluoride ions in living cells, Chem. Commun. 47 (2011) 7098–7100. [21] M. Dong, Y. Peng, Y.-M. Dong, N. Tang, Y.-W. Wang, A selective, colorimetric, and fluorescent chemodosimeter for relay recognition of fluoride and cyanide anions based on 1,1′-binaphthyl scaffold, Org. Lett. 14 (2012) 130–133. [22] K. Dhanunjayarao, V. Mukundam, K. Venkatasubbaiah, Ratiometric sensing of fluoride anion through selective cleavage of Si\ \O bond, Sensors Actuators B Chem. 232 (2016) 175–180. [23] X.J. Zheng, W.C. Zhu, H. Ai, Y. Huang, Z.Y. Lu, A rapid response colorimetric and ratiometric fluorescent sensor for detecting fluoride ion, and its application in real sample analysis, Tetrahedron Lett. 57 (2016) 5846–5849. [24] F.F. Du, Y.Y. Bao, B. Liu, J. Tian, Q.B. Li, R.K. Bai, POSS-containing red fluorescent nanoparticles for rapid detection of aqueous fluoride ions, Chem. Commun. 49 (2013) 4631–4633. [25] C.Y. Wang, S. Yang, M. Yi, C.H. Liu, Y.J. Wang, J.H. Li, Y.H. Li, R.H. Yang, Graphene oxide assisted fluorescent chemodosimeter for high-performance sensing and bioimaging of fluoride ions, ACS Appl. Mater. Interfaces 6 (2014) 9768–9775.
Y. Xu et al. / Inorganic Chemistry Communications 78 (2017) 52–55 [26] Y.L. Deng, Y. Chen, D.X. Cao, Z.Q. Liu, G.Z. Li, A cationic triarylborane as water-tolerant fluorescent chemosensor for fluoride anions, Sensors Actuators B Chem. 149 (2010) 165–169. [27] D.X. Cao, Z.Q. Liu, G.Z. Li, A trivalent organoboron compound as one and two-photon fluorescent chemosensor for fluoride anion, Sensors Actuators B Chem. 133 (2008) 489–492. [28] H.H. Chen, Y.H. Sun, C.J. Zhou, D.X. Cao, Z.Q. Liu, L. Ma, Three hydroxyaurone compounds as chemosensors for cyanide anions, Spectrochim. Acta A 116 (2013) 389–393. 1 [29] H NMR (400 MHz, CDCl3) δ: 1.19 (s, 9H), 6.15 (d, J = 8.0 Hz, 1H), 6.77 (s, 1H), 6.79 (d, J = 8.0 Hz, 1H), 7.20 (t, J = 8.0 Hz, 1H), 7.35–7.43 (m, 3H), 7.43–7.49 (m, 2H),
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7.69–7.74 (m, 3H), 7.75–7.80 (m, 4H), 7.97 (d, J = 8.0 Hz, 2H). 13C NMR (100 MHz, CDCl3), δ: 19.88, 26.47, 104.94, 108.55, 112.32, 114.79, 128.12, 130.42, 131.42, 132.06, 132.59, 135.64, 138.24, 148.65, 155.07, 166.91, 182.32. MS for (M + H)+: Calcd exact mass 524.1658; found 524.1621. [30] J. Isaad, A.E. Achari, Biosourced 3-formyl chromenyl-azo dye as Michael acceptor type of chemodosimeter for cyanide in aqueous environment, Tetrahedron 67 (2011) 5678–5685. [31] S. Park, H.-J. Kim, Highly activated Michael acceptor by an intramolecular hydrogen bond as a fluorescence turn-on probe for cyanide, Chem. Commun. 46 (2010) 9197–9199.
Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Short communication
A novel fluorescence chemodosimeter for fluoride anions in aqueous solution based on siloxane-aurone moiety Yongxiao Xu, Yibing Wang, Songfang Zhao, Ruifang Guan, Duxia Cao ⁎, Qianqian Wu, Xueying Yu, Yatong Sun School of Material Science and Engineering, University of Jinan, Jinan 250022, Shandong, China
a r t i c l e
i n f o
Article history: Received 31 January 2017 Received in revised form 2 March 2017 Accepted 3 March 2017 Available online 06 March 2017 Keywords: Aurone Fluoride anion Chemodosimeter Siloxane
a b s t r a c t A novel siloxane-aurone compound, 4′-cyano-4-tert-butyldiphenylsiloxane-aurone (named as TBDCN), was synthesized. The compound exhibits high sensitivity, fast response rate and high selectivity for fluoride anions recognition with obvious absorption and fluorescence response in aqueous solution, which is more sensitive than the traditionally type of chemodosimeters based on F−-triggered cleavage. The detection limits of TBDCN for F− are determined to be 1.9 μM and 0.0017 μM with absorption and fluorescence as detected signal, respectively, which satisfy the requirement from U.S. Environmental Protection Agency. The recognition mechanism is the F−-promoted dissociation of silicon-oxygen bond based on in situ mass spectra and 1H NMR spectra analysis. © 2017 Elsevier B.V. All rights reserved.
During the past years, fluorescence chemodosimeters, which are used to identify different ions and molecules, have been developed rapidly [1–4]. Many chemodosimeters are not able to detect ions in aqueous solution, especially fluoride anions (F−). Fluoride anions are very important to the organism, such as fluoride can be used in the treatment of dental caries and osteoporosis and excessive intake of fluoride can cause tooth or bone fluorosis [5,6]. As a very important anion, F− is a Lewis basic and has strong hydrolysis ability, which results in the recognition in aqueous solution being very difficult. Although the investigation on detection for F− has attracted many research interest for many years [7–9]. But the recognition in aqueous solution still cannot be solved completely. There are many types of chemodosimeters for F−, such as organoboron compound [10–14], hydrogen bonding receptor [15–17], organic silicon ether [18–23], and so on. F− promoted cleavage of silicon-oxygen bond in organic silicon ether is the best way to solve recognition in aqueous solution. But this reaction type of chemodosimeters normally has some shortcomings for F− recognition in aqueous solution, such as long response time (several tens of minutes or even hours) and low sensitivity [24,25]. Our group has devoted to fluoride recognition for many years [14,26,27]. Here a chemodosimeter for F− is reported, which exhibits fast response rate (about 5 min) and high sensitivity. The title compound, 4′-cyano-4-tert-butyldiphenylsiloxane-aurone (TBDCN) was synthesized with 4′-cyano-4-hydroxy-aurone [28] and
⁎ Corresponding author. E-mail address: [email protected] (D. Cao).
http://dx.doi.org/10.1016/j.inoche.2017.03.003 1387-7003/© 2017 Elsevier B.V. All rights reserved.
tert-butyldiphenylsilyl chloride as the starting materials, imidazo as catalyzer and dichloromethane as solvent. The synthetic route is shown in Scheme 1. Yellow solid with a yield of 56% was obtained. The compound was fully characterized by nuclear magnetic resonance and high-resolution mass spectra [29]. Density functional theory (DFT) quantum chemical calculation on the compound was carried out. The frontier molecular orbitals (HOMO and LUMO) of the compound were shown in Fig. 1. The calculation results indicate that the molecule possesses weak polarity with dipolar moment being 5.13D and charge slightly transfers from benzofuranone group to cyano group upon the excitation. The titration was carried out in aqueous solution (VHEPES:Vethanol = 1:1). TBDCN was dissolved in the aq.-HEPES buffer-ethanol mixed solution and fluoride anions in HEPES buffer solution was progressively added. TBDCN can recognize F− in aqueous solution with high sensitivity. As shown in Fig. 2a, TBDCN exhibits two absorption bands in blueviolet region with main absorption peaks at 307 nm (ε = 3.76 × 104 M− 1 cm− 1) and 391 nm (ε = 3.43 × 104 M−1 cm− 1) in aq.-HEPES buffer-ethanol solution (1:1, v/v). Upon the addition of F−, the original absorption peak at 391 nm gradually decreases with a little bathochromic shift, which indicates that there is some reaction between the chemodosimeter and cyanide anions. Absorption spectra would remain stable after 24 equiv. F− was added. The fluorescence spectra of TBDCN also exhibit obvious response change. TBDCN emits yellow fluorescence at 527 nm. After the addition of fluoride anions, the original fluorescence gradually decreases, at last fluorescence decreases to about 10% of the original intensity. Time-dependent fluorescence spectral changes upon addition of 24 equiv. F− to TBDCN were also
Y. Xu et al. / Inorganic Chemistry Communications 78 (2017) 52–55
53
Scheme 1. Synthetic route to the title compound TBDCN.
Fig. 1. The electron density distribution of the frontier molecular orbitals HOMO (a) and LUMO (b) of the compound.
measured (Fig. S1). As shown in Fig. S1, we can see that TBDCN can response F− with fast response rate (about 5 min). The detection limits [30,31] of the compound to F− with absorption and fluorescence spectra as detected signal (Fig. S2) are 1.9 μM and 0.0017 μM, respectively. U.S. Environmental Protection Agency limits
the fluoride anions in drinking water being 37.1–63.6 μM [25]. Then the detection limits satisfy the requirement from U.S. Environmental Protection Agency. Furthermore, the response time is short and response rate is fast. Every titration point will remain stable after about 5 min.
Fig. 2. UV–vis absorption (a) and fluorescence (b) spectral changes of TBDCN upon titration with KF in aq.-HEPES buffer-ethanol solution (VHEPES:Vethanol = 1:1).
Fig. 3. UV–vis absorption (a) and fluorescence (b) spectral changes of TBDCN in HEPES buffer-ethanol solution (VHEPES:Vethanol = 1:1) upon the addition of various anions. Insert: Changes in UV–vis absorption (391 nm) and fluorescence (527 nm) spectra of the compound in the presence of various anions in response to F−.
54
Y. Xu et al. / Inorganic Chemistry Communications 78 (2017) 52–55
Fig. 4. The reaction mechanism of TBDCN to detect F−.
The selectivity of the compound for other anions was also investigat− ed. As shown in Fig. 3, other anions such as SCN−, SO24 −, HSO− 3 , Cl , − CO2– 3 and Br , did not affect absorption and fluorescence spectra obviously. Different from other anions, the absorption and fluorescence peaks of TBDCN upon the addition of F− changed clearly. The competitive binding experiment of the anions to F− was also measured. Results indicate that these competing anions can neither lead to obvious spectral changes of TBDCN nor interfere the recognition reaction between the compound and F−. The recognition mechanism is investigated based on in situ mass spectra (Fig. S3) and 1H NMR spectra (Fig. S4), which is shown in Fig. 4. The mass spectra peak of the compound is 524.1621 ((M + H)+). After the addition of F−, the peak at 524.1621 disappears and a new peak at 264.8421 appears, which is attributed to the removement of tert-butyldiphenylsilane group. As shown in Fig. S3, both hydrogen proton signals of TBDCN at 6.99 ppm (C5, d, J = 8.0 Hz) and 6.84 (Cα, s) are up shifted to 6.26 ppm (C5, d, J = 8.0 Hz) and 6.53 ppm (Cα, s), respectively. No obvious change in 1H NMR spectrum of other hydrogen proton signals was observed. Si\\F bond (ESi\\F = 141 kcal/mol) has higher dissociation energy than Si\\O bond (ESi\\O = 103 kcal/mol). Then after the addition of F−, F− will promote the dissociation of Si\\O bond and combine with O. No obvious absorption peak change is observed during the titration, which is because the molecular backbone dose not change obviously and charge transfer is similar. The quench of fluorescence is from quenching of oxygen ion. In summary, a novel siloxane-aurone compound as fluorescence chemodosimeter for F− has been synthesized. This compound can recognize F− with high sensitivity, fast response rate and obvious absorption and fluorescence change. The recognition mechanism is F−-promoted the dissociation of Si\\O bond. The compound has good practical application potential in fluoride recognition. Acknowledgements This work was supported by the National Natural Science Foundation of China (21672130, 51373069, 21601065), the Natural Science Foundation of Shandong Province (ZR2015BL011), Key Research and Development Plan of Shandong Province (2016GSF117004), Colleges and Universities Science and Technology Foundation of Shandong Province (J16LA08) and the Fund of Graduate Innovation Foundation of University of Jinan, GIFUJN (S1504). Appendix A. Supplementary material Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.inoche.2017.03.003. References [1] Y. Zhou, J.F. Zhang, J. Yoon, Fluorescence and colorimetric chemosensors for fluoride-ion detection, Chem. Rev. 114 (2014) 5511–5571. [2] F. Wang, L. Wang, X.Q. Chen, J. Yoon, Recent progress in the development of fluorometric and colorimetric chemosensors for detection of cyanide ions, Chem. Soc. Rev. 43 (2014) 4312–4324.
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