24September2017

Materials and Electronics Engineering

A Coumarin-based Ratiometric Fluorescent Probe for N2H4 and Its Application in Living Cells

Guang-Fu Wu a, Ming-Xin Li a, Yan Zhang b, Wen-Gang Ji a, Qiang-Bin Wang b, Qing-Xiao Tong a,*
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a Department of Chemistry, Shantou University, Guangdong, 515063, P. R. China

b Division of Nanobiomedicine and i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, 215123, P. R. China

Materials and Electronics Engineering 2014,1:3

Publication Date (Web): December 12, 2014 (Article)

DOI:10.11605/mee-1-3

*Corresponding author. E-mail: This email address is being protected from spambots. You need JavaScript enabled to view it.

 

Abstract

 


Figure 1 Absorption (a) and fluorescence (b) spectrum of 1 (10 μM) obtained upon titration with 3 equiv of hydrazine in CH3CN : HEPES (3:7, v/v, 20 mM, pH 7.4)  with λex = 460 nm. The time interval is 15 min in each scan. Inset: Fluorescent color changes of 1 upon addition of hydrazine with excitation at 365 nm using a handheld UV lamp.
      Hydrazine is of extraordinary interest given its reducibility and environmental toxicity. Thus rapid detection of hydrazine is of great importance. A coumarin-based ratiometric probe that enables rapid and visual detection of hydrazine was rational synthesized and the results of DFT calculations were in good agreement with experiments. It was successfully used to detect hydrazine in living cells.

 

Keywords

Fluorscent, Probe, Living cell

 

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      Fluorescent probes are widely used for biologically and environmentally important species detection due to their high sensitivity, rapid response and non-invasiveness. [1] Hydrazine (N2H4) is widely used as a fuel in rocket and missile propulsion systems due to its flammable and detonable characteristics. [2] It is a highly reactive base and a great reducing agent [3] and plays critical roles in many fields, such as chemistry, pharmaceutics and industry manufacture acting as reactant, precursor, corrosion inhibitor and so on. [4] Hydrazine and its water solutions, however, are highly poisonous to human, animals and environment. Long-range studies indicate that hydrazine is mutagenic and carcinogenic and could cause crucial damage to the liver, lungs, kidneys and the human central nervous system. Indeed, the U.S. Environmental Protection Agency (EPA) has set a low threshold limit value (TLV) of 10 ppb. [5] Although there is no endogenous hydrazine in living system, it is easily taken in by respiratory system or in contact with skin. Therefore, developing reliable and valid probes for hydrazine detection is of great importance and has attracted much attention.

      Thus far, there are only a few studies involving optical sensors for hydrazine detection. Chang et al designed a fluorescence turn-on type for hydrazine signaling by selective deprotection of the levulinate group. [6] Kim et al reported a naphthalimide-based sensor for hydrazine detection by introducing trifluoroacetyl acetone group. [7] Goswami et al developed a chemodosimeter by introducing a dicyano vinyl group that could react with hydrazine to produce a compound with strong fluorescence. [8] However, most of these probes worked in pure organic solvents or in acidic conditions that might limit their practical applications. What’s more, most of these reported fluorescent probes are fluorescence intensity-dependent probes, which means that hydrazine detection only depends on the changes of fluorescence intensity and could be affected by the excitation power and the detector sensitivity. The ratiometric approach [9] based on the intensity ratios at two wavelengths can avoid the effects of these factors to realize quantitative detection more effectively.

      In general, ratiometric fluorescent sensors could be divided into two types based on mechanisms. One is based on fluorescence resonance energy transfer (FRET) that requires two different conjugated chromophores. But the synthetic methods of FRET-based sensors are complex, generally they need spectral overlap between the absorption of acceptor and the emission of donor as well as proper distance (1-10 nm) between the two chromophores, which may limit the development of FRET-based sensors. The other is based on intramolecular charge transfer (ICT) mechanism containing only one fluorophore that is modified by electron-withdrawing group and electron-donating moiety. ICT-based ratiometric sensors are widely used in ionic sensing [10] and bioimaging [11] due to their easily-prepared, self-calibration and large stokes shifts etc.

      Herein, in view of the above problems, we constructed an ICT system based on a coumarin derivate as ratiometric probe (Scheme 1) to realize highly selective detection of N2H4 in aqueous solution. Coumarin and its derivatives, especially 7-diethylaminocoumarin [12], were widely used as fluorochrome in sensing for high quantum yield, large stokes shift and good photostability. As intramolecular conjugated charge transfer compounds, the electron donor and acceptor should be located in the 3- and 7-position of coumarin ring for efficient ICT. Diethylin group is one kind of important electron donor while cyanoacrylate moiety is a strong electron acceptor. Upon excitation ICT will occur with electron from the donor to acceptor. Moreover, the specific reaction between 2-cyanoacrylate and hydrazine yield the compound hydrazone which is similar to the reaction between arylidenemalononitrile and hydrazine. [13] Due to the hydrazone formation, the change of intramolecular electron density distribution will result in ratiometric responses in both the absorption and emission in aqueous solution. In a preliminary study, Peng’s group first reported a fluorescent probe [11c] based on aza-coumarin for hydrazine detection (Scheme 1). But this probe only can work in organic solution (90 % DMSO) with an acidic pH (pH = 3.7), and this will obviously confine its practical application. Here, we designed a new fluorescent probe 1 based on coumarin for hydrazine detection. Compared to Peng’s work, unsaturated N and one cyanogroup of azo-coumarin were replaced by C and an ester group. This minor structural modification make the probe possess greater advantages, i.e., better water solubility and lower toxicity. The rational designed probe worked in aqueous solution with proper pH (pH = 7.4), then we conducted cell imaging and test paper experiment, which indicate the potential applications of probe 1 in living cells and in vitro.

      The probe 1 was synthesized on the basis of the route outlined in Scheme S1. Probe 1 reacted with hydrazine giving the product 1-NH2. The product 1 and 1-NH2 were characterized by 1H-NMR and TOF-MS (Fig. S1, S2, S9, S11).

scheme1

Scheme 1 The probes structure for hydrazine detection of Peng’s group and this work.

      Fig. 1 shows changes of UV-Vis and fluorescence spectra of probe 1 with different concentration of hydrazine in aqueous HEPES buffer (20 mM, pH 7.4) containing 30% acetonitrile at room temperature. With increasing amounts of hydrazine, the absorption bands centered at 325 and 525 nm diminished gradually, and two distinct absorption bands at 275 and 425 nm emerged. The former is attributed to a π-π* transition and the latter an ICT transition. [14] The presence of well-defined isobestic point at 460 nm indicates the formation of a new species. Meanwhile, the colour of the solution changes from red to yellow which can be observed by the naked eye. When excitated at the isobestic point of 460 nm, the emission at 510 nm increased significantly and the emission band of 575 nm disappeared gradually, showing a clear ratiometric fluorescence response. The large blue-shift of 65 nm in the emission behaviour changed the color of the solution fluorescence from orange to green. Furthermore, we explored the changes of spectra upon addition of other amines and representative anions, namely Et3N, Et2NH, NH4OH, Cl-, I-, AcO-, SO42- and CO32-, only the solution containing hydrazine displayed a remarkable change (Fig. S3, S4). 

Figure 1 Absorption (a) and fluorescence (b) spectrum of 1 (10 μM) obtained upon titration with 3 equiv of hydrazine in CH3CN : HEPES (3:7, v/v, 20 mM, pH 7.4)  with λex = 460 nm. The time interval is 15 min in each scan. Inset: Fluorescent color changes of 1 upon addition of hydrazine with excitation at 365 nm using a handheld UV lamp.

Figure 1 Absorption (a) and fluorescence (b) spectrum of 1 (10 μM) obtained upon titration with 3 equiv of hydrazine in CH3CN : HEPES (3:7, v/v, 20 mM, pH 7.4) with λex = 460 nm. The time interval is 15 min in each scan. Inset: Fluorescent color changes of 1 upon addition of hydrazine with excitation at 365 nm using a handheld UV lamp.

       Moreover, the ratio of fluorescence intensities at 510 nm and 575 nm (I510/I575) exhibited a 2240 fold enhancement, i.e., from 0.002 to 4.48 before and after the addition (3 equiv.) of hydrazine. A linear relationship was observed between the fluorescence intensity and the quantity intensity in the range of 2-12 μM (Fig. 2a). The detection limit [15] (S/N = 3) was determined to be 0.13 μM in aqueous solution (Fig. S5). The kinetic study about the probe for hydrazine detection was also examined for that the changes of absorption spectrum was in a linear relationship with time (Fig. S6). The reaction was monitored at 525 nm at room temperature. The value of negative slope was -0.223 min-1 indicates that the reaction could be regarded as a pseudo-first-order reaction.

      To further explore the selectivity of reaction, the competitive experiment was also conducted in the presence of the following species, i.e., Zn2+, Cd2+, Hg2+, Pb2+, Ag+, Fe2+, Co2+, Ni2+, Cu2+, Et3N, Et2NH, NH4OH, Cl-, I-, AcO-, SO42- and CO32- (Fig. 2b). The results showed that the emission spectra were not interfered in significant amount. What’s more, probe 1 was selective for hydrazine over other amines, including Et3N, Et2NH and NH4OH. And it was not perturbed by environmentally abundant metal ions. These findings indicate that probe 1 could be used to detect hydrazine in complicated systems with high selectivity.

Figure 2 (a) Ratio of fluorescent intensities at 510 and 575 nm as function of hydrazine concentration in CH3CN: HEPES (3:7, v/v, 20 mM, pH 7.4). (b) Fluorescence intensity ratio (I510/I575) responses of 1 (10 μM) to hydrazine (30 μM) and other analytes (50 μM) in CH3CN: HEPES (3:7, v/v, 20 mM, pH 7.4). Black bars represent the addition of other analytes and hydrazine to the solution of probe 1. Red bars represent the addition of hydrazine to the solution containing 1 and other analytes. 1 Zn2+, 2 Cd2+, 3 Hg2+, 4 Pb2+, 5 Ag+, 6 Fe2+, 7 Co2+, 8 Ni2+, 9 Cu2+, 10 other amines and anions (Et3N, Et2NH, NH4OH, Cl-, I-, AcO-, SO42- and CO32-), 11 hydrazine. The time interval is 15 min in each scan with λex = 460 nm.

Figure 2 (a) Ratio of fluorescent intensities at 510 and 575 nm as function of hydrazine concentration in CH3CN: HEPES (3:7, v/v, 20 mM, pH 7.4). (b) Fluorescence intensity ratio (I510/I575) responses of 1 (10 μM) to hydrazine (30 μM) and other analytes (50 μM) in CH3CN: HEPES (3:7, v/v, 20 mM, pH 7.4). Black bars represent the addition of other analytes and hydrazine to the solution of probe 1. Red bars represent the addition of hydrazine to the solution containing 1 and other analytes. 1 Zn2+, 2 Cd2+, 3 Hg2+, 4 Pb2+, 5 Ag+, 6 Fe2+, 7 Co2+, 8 Ni2+, 9 Cu2+, 10 other amines and anions (Et3N, Et2NH, NH4OH, Cl-, I-, AcO-, SO42- and CO32-), 11 hydrazine. The time interval is 15 min in each scan with λex = 460 nm.

      The very proposed mechanism is that 1 reacts with hydrazine giving hydrazine. 1H-NMR, IR and TOF-MS further confirmed our prediction (Fig. S8-S10). Moreover, to better understand the optical responses of probe 1 reacting with hydrazine, theoretical calculations were explored. We employed density function theory (DFT) with the TD-DFT/B3LYP/6-31g** of the Gaussian 09 program. Optimized ground-state geometries (Fig. S7) and the electron distributions in the frontier molecular orbitals of 1 and 1-NH2 are both examined. As shown in Fig 3, for 1 and 1-NH2, the S0→S1 transitions were electron density redistributions from the coumarin ring to the cyanoacrylate group (probe 1) or hydrazone (1-NH2), namely an ICT progress. The dihedral angle between coumarin ring and C=N in probe 1 is 2.87° that provides an efficient π-conjugation and favors efficient ICT transition between the donor and acceptor (Fig. S8). Moreover, the emission wavelength of 1 is larger than that of 1-NH2 for that cyanoacrylate moiety of 1 is a stronger electron acceptor than hydrazone. For 1-NH2, the energy gap between the HOMO and LUMO was larger than that of probe 1, which was in agreement with the blue-shift in the absorption and emission spectra.

Figure 3 HOMO and LUMO energy levels of 1 and 1-NH2.

Figure 3 HOMO and LUMO energy levels of 1 and 1-NH2.

      To demonstrate the practical ability of the probe 1 for hydrazine detection in biological samples located in an aqueous environment, confocal microscopy experiments were performed. The double-channel fluorescence images at 500-550 nm and 570-620 nm are shown in Fig. 4. When HeLa cells were incubated with probe 1 (10 μM) at 37℃ for 1 h, the cells displayed very weak green intracellular fluorescence at 500-550 nm and orange-red intracellular fluorescence at 570-620 nm, indicating that 1 was cell membrane permeable. A strong fluorescence in the green channel was detected obviously and fluorescence intensity decreased in the red channel when hydrazine (30 μM) was added and then incubated for 30 min. These results were consistent with the observations in aqueous solution, implying that probe 1 could be exploited for ratiometric fluorescence imaging of hydrazine in living cells. Finally, we also prepared the test paper of probe 1. The colour of the test paper changed from red to yellow while the fluorescence from orange-red to green, which could be both observed by naked eyes (Fig. S11) upon inserting the prepared test paper into the hydrazine aqueous solution.

Figure 4 Confocal fluorescence images of HeLa cells incubated with 10 μM probe 1. (a–d) Cells incubated with 1 for 1 h. (e–h) 1 stained cells exposed to 30 μM hydrazine. (a and e) Brightfield images; (b and f) fluorescence images with emission collected at 500–550 nm; (c and g) fluorescence images with emission collected at 570–620 nm; (d and h) Overlap of (a, b and c), (e, f and g). λex = 488 nm.

Figure 4 Confocal fluorescence images of HeLa cells incubated with 10 μM probe 1. (a–d) Cells incubated with 1 for 1 h. (e–h) 1 stained cells exposed to 30 μM hydrazine. (a and e) Brightfield images; (b and f) fluorescence images with emission collected at 500–550 nm; (c and g) fluorescence images with emission collected at 570–620 nm; (d and h) Overlap of (a, b and c), (e, f and g). λex = 488 nm.

      In summary, the novel coumarin-based ratiometric probe was successfully designed. The probe can work in aqueous solution and could detect hydrazine in situ by preparing the test paper. It displayed distinct changes in the intensity ratio of both absorption and emission spectrum upon addition of hydrazine and the remarkable color changes could be observed by naked eyes. The sensing mechanism was elucidated by absorption and emission spectra, 1H-NMR, MS and IR, and was well rationalized by DFT calculations. Confocal fluorescence experiments further demonstrate its potential application in living cells.

References

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Acknowledgements

This work was financially supported by National Natural Science Foundation of China (No. 91027041 and 51273108) and the National Basic Research Program of China (No. 2013CB834803).

References

1. (a) J. Han, K. Burges, Fluorescent indicators for intracellular pH. Chem. Rev. 110, 2709 (2010). doi:10.1021/cr900249z (b) J. Du, M. Hu, J. Fan, X. Peng, Fluorescent chemodosimeters using “mild” chemical events for the detection of small anions and cations in biological and environmental media. Chem. Soc. Rev. 41, 4511 (2012). doi:10.1039/C2CS00004K (c) X. Chen, T. Pradhan, F. Wang, J.S. Kim, J. Yoon, Fluorescent chemosensors based on spiroring-opening of xanthenes and related derivatives. Chem. Rev. 112, 1910 (2012). doi:10.1021/cr200201z 
2. (a) Hydrazine and Its Derivatives, In kirk-othmer encyclopedia of chemical technology 5th ed.; J.I. Kroschwitz, A. Seidel, Eds., Wiley: New York 13, 562 (2005). (b) J.-W. Mo, B. Ogorevc, X.J. Zhang, B. Pihlar, Cobalt and copper hexacyanoferrate modified carbon fiber microelectrode as an all-solid potentiometric microsensor for hydrazine. Electroanal. 12, 48 (2000). doi:10.1002/(SICI)1521-4109(20000101)12:13.0.CO;2-H (c) S.D. Zelnick, D.R. Mattie, P.C. Stepaniak, Occupational exposure to hydrazines: Treatment of acute central nervous system toxicity. Aviat. Space Envir. Md. 74, 1285 (2003). 
3. H.W. Schiessl, Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, Inc. 562 (2000).
4. I.C. Vieira, K.O. Lupetti, O. Fatibello-Filho, Sweet potato (ipomoea batatas (l.) lam.) tissue as a biocatalyst in a paraffin/graphite biosensor for hydrazine determination in boiler feed water. Anal. Lett. 35, 2221 (2002). doi:10.1081/AL-120016097 
5. A. Umar, M.M. Rahman, S.H. Kim, Y.-B. Hahn, Zinc oxide nanonail based chemical sensor for hydrazine detection. Chem. Commun. 44, 166 (2008). doi:10.1039/B711215G
6. M.G. Choi, J. Hwang, J.O. Moon, J. Sung, S.-K. Chang, Hydrazine-selective chromogenic and fluorogenic probe based on levulinated coumarin. Org. Lett. 13, 5260 (2011). doi:10.1021/ol202136q
7. M.H. Lee, B. Yoon, J.S. Kim, J.L. Sessler, Naphthalimide trifluoroacetyl acetonate: a hydrazine-selective chemodosimetric sensor. Chem. Sci. 4, 4121 (2013). doi:10.1039/C3SC51813B 
8. S. Goswami, S. Paul, A. Manna, A highly reactive (1 min) ratiometric chemodosimeter for selective “nked eye” and fluorogenic detection of hydrazine. RSC Adv. 3, 18872 (2013). doi:10.1039/C3RA42771D
9. (a) X.J. Peng, Y.Q. Xu, S.G. Sun, Y.K. Wu, J.L. Fan, A ratiometric fluorescent sensor for phosphates: Zn2+-enhanced ICT and ligand competition. Org. Biomol Chem. 5, 226 (2007). doi:10.1039/B614786K (b) L.K. Zhang, G.F. Wu, Y. Zhang, Y.C. Tian, Q.X. Tong, D. Li, A two-in-one fluorescent sensor with dual channels to detect Zn2+ and Cd2+. RSC Adv. 3, 21409 (2013). doi:10.1039/C3RA44591G (c) L.K. Zhang, Q.X. Tong, L.J. Shi, A highly selective ratiometric fluorescent chemosensor for Cd2+ ions. Dalton T. 42, 8567 (2013). doi:10.1039/C3DT50640A (d) L.Y. Niu, Y.S. Guan, Y.Z. Chen, L.Z. Wu, C.H. Tung, Q.Z. Yang, BODIPY-based ratiometric fluorescent sensor for highly selective detection of glutathione over cysteine and homocysteine. J. Am. Chem. Soc. 134, 18928 (2012). doi:10.1021/ja309079f (e) X.Z. Wang, J. Cao, C.C. Zhao, Design of a ratiometric fluorescent probe for benzenethiols based on athiol–sulfoxide reaction. Org. Biomol. Chem. 10, 4689 (2012). doi:10.1039/C2OB25633A (f) L.L. Long, L.P. Zhou, L. Wang, S.C. Meng, A.H. Gong, C. Zhang, A ratiometric fluorescent probe for iron (III) and its application for detection of iron (III) in human blood serum. Anal. Chim. Acta. 812, 145 (2014). doi:10.1016/j.aca.2013.12.024
10. (a) X.J. Peng, Y.Q. Xu, S.G. Sun, Y.K. Wu, J.L. Fan, A ratiometric fluorescent sensor for phosphates: Zn2+-enhanced ICT and ligand competition. Org. Biomol. Chem. 5, 226 (2007). doi:10.1039/B614786K (b) Z.C. Xu, Y. Xiao, X.H. Qian, J.N. Cui, D.W. Cui, Ratiometric and Selective Fluorescent Sensor for CuII Based on Internal Charge Transfer (ICT). Org. Lett. 7, 889 (2005). doi:10.1021/ol0473445 
11. (a) D. Srikun, E.W. Miller, D.W. Domaille, C.J. Chang, An ICT-based approach to ratiometric fluorescence imaging of hydrogen peroxide produced in living cells. J. Am. Chem. Soc. 130, 4596 (2008). doi:10.1021/ja711480f (b) F.B. Yu, P. Li, P. Song, B.S. Wang, J.Z. Zhao, K.L. Han, An ICT-based strategy to a colorimetric and ratiometric fluorescence probe for hydrogen sulfide in living cells. Chem. Commun. 48, 2852 (2012). doi: 10.1039/C2CC17658K (c) J.L. Fan, W. Sun, M.M. Hu, J.F. Cao, G.H. Cheng, H.J. Dong, K.D. Song, Y.C. Liu, S.G. Sun, X.J. Peng, An ICT-based ratiometric probe for hydrazine and its application in live cells. Chem. Commun. 48, 8117 (2012). doi:10.1039/C2CC34168A
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Additional Info

  • Type of Publishing: JOUR - Journal
  • Title:

    A Coumarin-based Ratiometric Fluorescent Probe for N2H4 and Its Application in Living Cells

  • Author: Guang-Fu Wu, Ming-Xin Li, Yan Zhang, Wen-Gang Ji, Qiang-Bin Wang, Qing-Xiao Tong
  • Year: 2014
  • Volume: 1
  • Issue: 1
  • Journal Name: Materials and Electronics Engineering
  • Publisher: Nicety Press Company Limited
  • ISSN: 2410-1648
  • URL: http://www.meej.org/volume-1/december-2014/item/364-a-coumarin-based-ratiometric-fluorescent-probe-for-n2h4-and-its-application-in-living-cells
  • Abstract:

    Hydrazine is of extraordinary interest given its reducibility and environmental toxicity. Thus rapid detection of hydrazine is of great importance. A coumarin-based ratiometric probe that enables rapid and visual detection of hydrazine was rational synthesized and the results of DFT calculations were in good agreement with experiments. It was successfully used to detect hydrazine in living cells.

  • Publish Date: Friday, 12 December 2014
  • Start Page: 3
  • DOI: 10.11605/mee-1-3