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. 2017 Feb 1;8(2):1535-1546.
doi: 10.1039/c6sc04367d. Epub 2016 Oct 25.

A supramolecular Tröger's base derived coordination zinc polymer for fluorescent sensing of phenolic-nitroaromatic explosives in water

Sankarasekaran Shanmugaraju  1 , Charlyne Dabadie  1 , Kevin Byrne  2 , Aramballi J Savyasachi  1 , Deivasigamani Umadevi  1 , Wolfgang Schmitt  2 , Jonathan A Kitchen  3 , Thorfinnur Gunnlaugsson  1
Affiliations

A supramolecular Tröger's base derived coordination zinc polymer for fluorescent sensing of phenolic-nitroaromatic explosives in water

Sankarasekaran Shanmugaraju et al. Chem Sci. .

Abstract

A V-Shaped 4-amino-1,8-napthalimide derived tetracarboxylic acid linker (L; bis-[N-(1,3-benzenedicarboxylic acid)]-9,18-methano-1,8-naphthalimide-[b,f][1,5]diazocine) comprising the Tröger's base (TB) structural motif was rationally designed and synthesised to access a nitrogen-rich fluorescent supramolecular coordination polymer. By adopting the straight forward precipitation method, a new luminescent nanoscale Zn(ii) coordination polymer (TB-Zn-CP) was synthesized in quantitative yield using Zn(OAc)2·2H2O and tetraacid linker L (1 : 0.5) in DMF at room temperature. The phase-purity of as-synthesised TB-Zn-CP was confirmed by X-ray powder diffraction analysis, infra-red spectroscopy, and elemental analysis. Thermogravimetric analysis suggests that TB-Zn-CP is thermally stable up to 330 °C and the morphological features of TB-Zn-CP was analysed by SEM and AFM techniques. The N2 adsorption isotherm of thermally activated TB-Zn-CP at 77 K revealed a type-II reversible adsorption isotherm and the calculated Brunauer-Emmett-Teller (BET) surface area was found to be 72 m2 g-1. Furthermore, TB-Zn-CP displayed an excellent CO2 uptake capacity of 76 mg g-1 at 273 K and good adsorption selectivity for CO2 over N2 and H2. The aqueous suspension of as-synthesized TB-Zn-CP showed strong green fluorescence (λmax = 520 nm) characteristics due to the internal-charge transfer (ICT) transition and was used as a fluorescent sensor for the discriminative sensing of nitroaromatic explosives. The aqueous suspension of TB-Zn-CP showed the largest quenching responses with high selectivity for phenolic-nitroaromatics (4-NP, 2,4-DNP and PA) even in the concurrent presence of other potentially competing nitroaromatic analytes. The fluorescence titration studies also provide evidence that TB-Zn-CP detects picric acid as low as the parts per billion (26.3 ppb) range. Furthermore, the observed fluorescence quenching responses of TB-Zn-CP towards picric acid were highly reversible. The highly selective fluorescence quenching responses including the reversible detection efficiency make the nanoscale coordination polymer TB-Zn-CP a potential material for the discriminative fluorescent sensing of nitroaromatic explosives.

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Figures

Scheme 1
Scheme 1. Synthesis of the bis-naphthalimide derived Tröger’s base tetracarboxylic acid linker (L) from commercially available 4-nitro-1,8-naphthalic anhydride, that was then used to generate the Zn(ii) coordination polymer (TB-Zn-CP).
Fig. 1
Fig. 1. (A) Scanning electron microscopy and atomic force microscopy images (B) of as-synthesized TB-Zn-CP. (C) Dynamic light scattering (DLS) measurements of TB-Zn-CP dispersed in water.
Fig. 2
Fig. 2. The N2 adsorption–desorption isotherm measured at 77 K (inset: corresponding pore-size distribution curve) of TB-Zn-CP (left). The uptake capacitates of TB-Zn-CP for CO2, N2 and H2 at 273 K (right).
Fig. 3
Fig. 3. Fluorescence emission spectra of TB-Zn-CP (λ max = 520 nm) and L (λ max = 532 nm) dispersed in water (inset: visual color of TB-Zn-CP taken under UV lamp).
Fig. 4
Fig. 4. Observed fluorescence quenching (left) of TB-Zn-CP upon addition of PA (μM) in water and its corresponding Stern–Volmer plot (right).
Fig. 5
Fig. 5. Extent of fluorescence quenching of TB-Zn-CP observed upon the addition of various analytes. Inset: the colour changes observed.
Fig. 6
Fig. 6. Competitive selective binding affinity of TB-Zn-CP towards different NACs in the presence of PA in aqueous medium.
Fig. 7
Fig. 7. Fluorescence decay profile (left) of the aqueous suspension of TB-Zn-CP upon the addition of PA in different concentrations (0–90.9 μM) (left) and extent of fluorescence quenching (right) observed after the addition of PA (47.6 μM) at different temperatures (25–45 °C).
Fig. 8
Fig. 8. Plot of quenching efficiency as a function of exposure time (0 → 8 min) monitored at different concentrations of PA (47.6 → 130.4 μM).
Fig. 9
Fig. 9. Change in fluorescence intensity of TB-Zn-CP at different concentrations of PA.
Fig. 10
Fig. 10. Reproducibility of the quenching ability of TB-Zn-CP for PA dispersed in water. The material was recovered by centrifugation after each experiment and washed several times with water.
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References

    1. Banerjee D., Hu Z., Li J. Dalton Trans. 2014;43:10668–10685. - PubMed
    2. Shanmugaraju S., Mukherjee P. S. Chem. Commun. 2015;51:16014–16032. - PubMed
    3. Barry D. E., Caffrey D. F., Gunnlaugsson T. Chem. Soc. Rev. 2016;45:3244–3274. - PubMed
    4. Ayme J.-F., Beves J. E., Leigh D. A., McBurney R. T., Rissanen K., Schultz D. Nat. Chem. 2012;4:15–20. - PubMed
    5. You L., Zha D., Anslyn E. V. Chem. Rev. 2015;115:7840–7892. - PubMed
    6. Diehl K. L., Anslyn E. V. Chem. Soc. Rev. 2013;42:8596–8611. - PubMed
    7. Lloyd G. O., Steed J. W. Nat. Chem. 2009;1:437. - PubMed
    1. Sun X., Wang Y., Lei Y. Chem. Soc. Rev. 2015;44:8019–8061. - PubMed
    2. Salinas Y., Martinez-Manez R., Marcos M. D., Sancenon F., Costero A. M., Parra M., Gil S. Chem. Soc. Rev. 2012;41:1261–1296. - PubMed
    3. Zyryanov G. V., Kopchuk D. S., Kovalev I. S., Nosova E. V., Rusinov V. L., Chupakhin O. N. Russ. Chem. Rev. 2014;83:783.
    1. Shanmugaraju S., Jadhav H., Karthik R., Mukherjee P. S. RSC Adv. 2013;3:4940–4950.
    2. Shanmugaraju S., Mukherjee P. S. Chem.–Eur. J. 2015;21:6656–6666. - PubMed
    3. Ghosh S., Mukherjee P. S. Organometallics. 2008;27:316–319.
    4. Ghosh S., Gole B., Bar A. K., Mukherjee P. S. Organometallics. 2009;28:4288–4296.
    1. Hu Z., Deibert B. J., Li J. Chem. Soc. Rev. 2014;43:5815–5840. - PubMed
    2. Nagarkar S. S., Desai A. V., Ghosh S. K. CrystEngComm. 2016;18:2994–3007.
    3. Venkatramaiah N., Kumar S., Patil S. Chem. Commun. 2012;48:5007–5009. - PubMed
    4. Chahal M. K., Sankar M. Anal. Methods. 2015;7:10272–10279.
    1. Mukherjee P. S., Sunipa P. and Shanmugaraju S., in Molecular Self-Assembly, Pan Stanford Publishing, 2012, pp. 259–299.
    2. Ivy M. A., Gallagher L. T., Ellington A. D., Anslyn E. V. Chem. Sci. 2012;3:1773–1779.
    3. Pramanik S., Hu Z., Zhang X., Zheng C., Kelly S., Li J. Chem.–Eur. J. 2013;19:15964–15971. - PubMed

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