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A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (xxxx) xxx
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A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana Ya-Lin Qi a, 1, Jian Chen a, 1, Bo Zhang a, Hua Li a, Dong-Dong Li b, Bao-Zhong Wang a, **, Yu-Shun Yang a, ***, Hai-Liang Zhu a, * a b
State Key Laboratory of Pharmaceutical Biotechnology, School of Life Sciences, Nanjing University, Nanjing, 210023, China College of Chemical Engineering, Nanjing Forestry University, 159 Longpan Road, Nanjing, 210037, China
a r t i c l e i n f o
a b s t r a c t
Article history: Received 29 July 2019 Received in revised form 24 October 2019 Accepted 24 October 2019 Available online xxx
In this work, a primary method was constructed for detecting hydrazine in plant, thus accomplished the closed-loop monitoring of hydrazine circulation within manufacture, environment, plants, animals and human. From a series of sensors, QYL-1 was selected to present the hydrazine sensing properties. As a preliminary tool, QYL-1 suggested the ultra-wide linear range (0e20.0 equivalent) and high selectivity, which were extremely essential for linking the monitoring in various scale and field. For the first time, concentration-dependent tracking of hydrazine was successfully performed in Arabidopsis Thaliana root tips. Afterwards applications in water samples and living MCF-7 cells then fulfilled the demonstration of closing the loop by linking both the upstream and downstream nodes. More than raising a practical method, this work offered initial information for the closed-loop monitoring of hydrazine circulation, which might be significant for the ideal systematic managing in future. © 2019 Elsevier B.V. All rights reserved.
Keywords: Hydrazine detection Fluorescent sensor Biological imaging Plant tissue Closed-loop monitoring
1. Introduction All through the applications in extensive areas such as medicinal career, chemical engineering, material industy and environmental management, hydrazine (NH2NH2) acts as one of the most significant component with practical reductivity and basicity [1]. Despite the most widely known uses of military and astronautic propulsion [2], hydrazine can be applied in pharmaceutic synthesis of drugs such as isoniazid for tuberculosis [3], iproniazid for psychotic [4], and procarbazine for tumor [5]. However, as the reverse side of a coin, the high toxicity of hydrazine upon biological organism cannot be neglected [6]. It can cause dizziness, nausea, and even cancer, thus the US Environmental Protection Agency (EPA) has determined that hydrazine are a potential carcinogen with a minimum limit of 10 ppb [7]. To track back the enrichment process of hydrazine all through the route in manufacture, environment, plants, animals and human, exploiting selective and sensitive
* Corresponding author. ** Corresponding author. *** Corresponding author. E-mail addresses: [email protected] (B.-Z. (Y.-S. Yang), [email protected] (H.-L. Zhu). 1 Both authors contributed equally to the work.
Wang),
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methods to fulfill hydrazine monitoring at each key node was an urgent emergency [8,9]. Recent researches have raised practical methods for detecting trace hydrazine including electrochemistry [10], Raman spectroscopy [11], colorimetry [12], chemiluminescence [13], spectrophotometry [14], titrimetry [15], and so on. Since sophisticate preparation and strict technical requirements impeded convenient applications of these approaches, fluorescent sensors have caught the attentions of investigators due to high selectivity and good biocompatibility [16]. In reported cases, the recognizing moiety includes acetyl [17,18], levulinate [19], 4-bromo butyrate [20,21], phthalimide [22,23], aldehyde [24], cyanogroup [25,26], and the fluorescent moiety includes benzothiazole [27], 1,8-naphthalene imide [28], coumarin [29], rhodamine [30], phenothiazine [31], carbazole [32], cyanine dye [33], BODIPY [34]. With progressing selectivity and sensitivity, broadening and deepening the applications of hydrazine monitoring tools are facing new opportunities and challenges. In this work, we focused on the closed-loop monitoring of hydrazine circulation. Within the loop of manufacture [35], environment [36], plants, animals [37] and human [38], all nodes have been addressed except plant. Therefore we attempted to construct a primary method for detecting hydrazine in plant. For concise, we did not use complex tools of rare earth [39], aggregation-induced enhancement (AIE) [40], nanoparticles [41] or carbon dots [42].
https://doi.org/10.1016/j.saa.2019.117707 1386-1425/© 2019 Elsevier B.V. All rights reserved.
Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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Here the most important task was developing a fluorescent tool with simple structure and superior properties to initially complete the closed-loop monitoring of hydrazine circulation before the further improvement to generate more sophisticated sensors. We designed and synthesized three fluorescence probes QYL-1, QYL-2 and QYL-3 which only contain two steps and have a more than 80% yield. Among them, the probe QYL-1 display high sensitivity and selectivity for N2H4 both in vitro and in vivo as fluorescent chemodosimeter. To the best of our knowledge, there are some examples about the fluorescent probes based on excited state intramolecular proton transfer (ESIPT) mechanism using 2-(benzothiazol-2-yl)-phenol (HBT). For example, Sabyasachi Sarkar’s group designed a ratiometric probe HBT [43], whose excitation and emission wavelengths were 368 nm and 458 nm respectively, and the Stoke’s shift was 90 nm. Zhu’s group synthesized two probes 1 and 2 [44], and there was a methyl group or a benzene, respectively, connected to the phenol backbone. The sensing properties of probe 1 surpassed probe 2, with the emission wavelength of 479 nm and the detection limit of 0.37 mM. In this work, we developed a highly selective (>45-fold) probe QYL-1 with large Stoke’s shift (180 nm) for the detection of NH2NH2. A broader comparison with previous hydrazine sensors was provided in Tables S1 and SI. Typically recognizing and fluorescent moieties were employed with finetuned details to promote direct hydrazine monitoring in Arabidopsis thaliana (Fig. 1). 2. Experimental 2.1. Materials and methods All commercially available chemicals were directly used and no further purification was conducted. 1H NMR and 13C NMR spectra were recorded on Bruker DRX-600 spectrometer and analyzed with MestreNova software. Mass spectra were recorded on Agilent 6540 UHD Accurate Mass Q-TOF LC/MS and 1290 Infinity LC/6460 QQQ MS. UVevis spectra were recorded on Shimadzu UV-2550 spectrometer and fluorescence measurements were conducted on Hitachi F-7000 Fluorescence Spectrophotometer. The imaging experiments were performed using two-photon confocal fluorescent microscope Leica TCS SP8 MP. The probes was dissolved in MeCN to get the solution of 1.0 mM. Other concentrations were obtained by dilution. The excitation wavelength was set according to sensors (371 nm for QYL-1, 320 nm for QYL-2 and 310 nm for QYL-3). Both excitation and emission slit widths were 10 nm. The photomultiplier voltage was 500 V. In the selectivity evaluation, analytes except hydrazine were all set as 1.0 mM.
2.2. Synthesis of the sensors 2.2.1. Synthesis of the intermediates 3e1, 3e2 and 3e3 Compound 3e1, 2-(benzo[d]thiazol-2-yl)-6-methoxyphenol, was synthesized according to the following procedures. A solution of 2-aminothiophenol (0.9 mL, 12.6 mmol) and o-vanillin (1.44 g, 9.45 mmol) in ethanol (30 mL) was stirred for 10 min in an ice bath. Then aq H2O2 (30%, 56.8 mmol) and aq HCl (32% HCl, 28.35 mmol) were added slowly into the mixture, respectively. Then the resulting mixture was stirred at room temperature for 2 h. The solution was quenched by 35 mL cold water. The precipitate was filtered, dried and crystallized via ethanol to afford the title compound as a light yellow solid without further purification (2.20 g, 68%). 1H NMR (600 MHz, DMSO‑d6) d 11.21 (s, 1H), 8.15 (d, J ¼ 7.9 Hz, 1H), 8.07 (d, J ¼ 8.1 Hz, 1H), 7.75 (d, J ¼ 8.0 Hz, 1H), 7.55 (t, J ¼ 7.7 Hz, 1H), 7.46 (t, J ¼ 7.5 Hz, 1H), 7.16 (d, J ¼ 8.9 Hz, 1H), 6.98 (t, J ¼ 8.0 Hz, 1H), 3.88 (s, 3H). 13C NMR (151 MHz, DMSO‑d6) d 165.84, 151.82, 148.99, 146.76, 134.69, 126.99, 125.63, 122.60, 120.26, 119.94, 118.97, 114.60, 56.53. MS (ESI-TOF m/z): Calculated for [C14H12NO2S]þ: 258.0, Found: 258.0. Anal. Calcd. for C14H11NO2S: C 65.35, H 4.31, N 5.44, found: C 65.31, H 4.31, N 5.45. Compound 3e2, 2-(benzo[d]thiazol-2-yl)-5-methoxyphenol, was synthesized through the same approach of 3e1. White solid (2.00 g, 63%). 1H NMR (600 MHz, DMSO‑d6) d 8.13e8.09 (m, 1H), 8.06 (d, J ¼ 8.7 Hz, 1H), 8.01 (d, J ¼ 8.0 Hz, 1H), 7.53 (ddd, J ¼ 8.2, 7.2, 1.3 Hz, 1H), 7.42 (ddd, J ¼ 8.1, 7.2, 1.2 Hz, 1H), 6.67e6.62 (m, 2H). 13C NMR (151 MHz, DMSO‑d6) d 166.27, 163.34, 158.72, 133.82, 130.31, 126.93, 125.21, 122.42, 121.90, 111.76, 107.66, 101.63, 55.91. HRMS (ESI-TOF m/z): Calculated for [C14H12NO2S]þ: 258.0589, Found: 258.0587. Compound 3e3, 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol, synthesized through the same approach of 3e1. Yellow solid (2.26 g, 70%). 1H NMR (600 MHz, DMSO‑d6) d 10.34 (s, 1H), 8.47 (dd, J ¼ 8.8, 3.7 Hz, 1H), 7.95 (t, J ¼ 6.4 Hz, 1H), 7.77 (t, J ¼ 7.2 Hz, 1H), 7.59e7.50 (m, 1H), 7.40e7.33 (m, 2H), 3.96 (dd, J ¼ 4.7, 2.7 Hz, 3H). 13 C NMR (151 MHz, DMSO‑d6) d 169.15, 155.36, 155.33, 155.31, 137.36, 132.58, 129.56, 129.47, 129.45, 127.06, 126.37, 124.37, 124.35, 111.50, 53.05, 53.03. HRMS (ESI-TOF m/z): Calculated for [C14H12NO2S]þ: 258.0589, Found: 258.0583. 2.2.2. Synthesis of the sensors QYL-1, QYL-2 and QYL-3 For QYL-1, 2-(benzo[d]thiazol-2-yl)-6-methoxyphenyl acetate, compound 3e1 (114 mg, 0.5 mmol) was dissolved in acetic anhydride (5 mL) and stirred to reflux under nitrogen atmosphere for 4 h. The reaction process was monitored by TLC. After cooled down to 75 C, the solution was poured into ice water with fierce stirring.
Fig. 1. Illustration of the QYL series sensors for the closed-loop monitoring of hydrazine circulation.
Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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Then, the mixture was extracted with dichloromethane for 3 times. The organic layer was collected, evaporated and dried. The target product was obtained as a colorless solid without further purification (119 mg, 88%). 1H NMR (600 MHz, DMSO‑d6) d 8.17 (d, J ¼ 7.9 Hz, 1H), 8.11 (d, J ¼ 7.9 Hz, 1H), 7.90e7.87 (m, 1H), 7.58 (d, J ¼ 7.3 Hz, 1H), 7.51 (t, J ¼ 7.5 Hz, 1H), 7.45 (t, J ¼ 8.1 Hz, 1H), 7.36 (d, J ¼ 8.1 Hz, 1H), 3.87 (s, 3H), 2.47 (s, 3H). 13C NMR (151 MHz, DMSO‑d6) d 168.70, 162.14, 152.62, 152.26, 137.96, 135.24, 127.59, 127.19, 126.90, 126.22, 123.47, 122.63, 120.88, 115.46, 56.79, 39.98, 21.47. MS (ESI-TOF m/z): Calculated for [C16H13NO3SNa]þ ([MþNa]þ): 322.0, Found: 322.0. Anal. Calcd. for C16H13NO3S: C 64.20, H 4.38, N 4.68, found: C 64.28, H 4.38, N 4.67. For QYL-2, 2-(benzo[d]thiazol-2-yl)-5-methoxyphenyl acetate, it was synthesized through the same approach of QYL-1. Yellow solid (120 mg, 88%). 1H NMR (600 MHz, DMSO‑d6) d 8.26 (d, J ¼ 8.8 Hz, 1H), 8.13 (d, J ¼ 7.7 Hz, 1H), 8.06 (d, J ¼ 8.0 Hz, 1H), 7.55 (ddd, J ¼ 8.3, 7.2, 1.3 Hz, 1H), 7.46 (ddd, J ¼ 8.2, 7.2, 1.2 Hz, 1H), 7.08 (dd, J ¼ 8.9, 2.6 Hz, 1H), 7.01 (d, J ¼ 2.6 Hz, 1H), 3.87 (s, 3H), 2.49 (s, 3H). 13C NMR (151 MHz, DMSO‑d6) d 169.44, 162.44, 152.79, 149.91, 134.75, 131.06, 127.02, 125.74, 123.04, 122.47, 118.68, 113.46, 109.94, 56.36, 22.03. HRMS (ESI-TOF m/z): Calculated for [C16H14NO3S]þ: 300.0694, Found: 300.0681. For QYL-3, 2-(benzo[d]thiazol-2-yl)-4-methoxyphenyl acetate, it was synthesized through the same approach of QYL-1. White solid (115 mg, 84%). 1H NMR (600 MHz, DMSO‑d6) d 8.20e8.16 (m, 1H), 8.13 (d, J ¼ 8.1 Hz, 1H), 7.82 (d, J ¼ 3.1 Hz, 1H), 7.59 (ddd, J ¼ 8.3, 7.1, 1.3 Hz, 1H), 7.51 (ddd, J ¼ 8.2, 7.2, 1.2 Hz, 1H), 7.32 (d, J ¼ 8.9 Hz, 1H), 7.21 (dd, J ¼ 8.9, 3.1 Hz, 1H), 3.89 (s, 3H), 2.47 (s, 3H). 13C NMR (151 MHz, DMSO‑d6) d 169.90, 162.06, 157.50, 152.50, 142.14, 135.33, 127.21, 126.46, 126.22, 125.86, 123.48, 122.64, 118.60, 113.14, 56.19, 21.94. HRMS (ESI-TOF m/z): Calculated for [C16H14NO3S]þ: 300.0694, Found: 300.0692.
systems, with the addition of NH2NH2, the absorption peaks of three probes decreased at near 300 nm. QYL-1 was chosen for the following procedures due to the excitation wavelength (371 nm versus 320 nm or 310 nm), emission wavelength (480 nm versus 400 nm or 410 nm) and Stoke Shift (180 nm versus 90 nm or 110 nm). When the NH2NH2 concentration was increased to 40 equiv of the probe concentration, the fluorescence intensity of probe QYL-1 attained a 49-fold enhancement, while that of probe QYL-2 increased by 1.1-fold and QYL-3 increased by 1.4-fold. The fluorescence quantum yield was 0.19 for QYL-1, which was suitable for a turn-on system. Then the sensing system consisting of QYL-1 (10 mM) and hydrazine (400 mM) in PBS buffer (pH 7.4, 10 mM, 1 mM CTAB 1% MeCN v/v) at 37 C was performed to check the responses to different external conditions. Within the range of 7.0e11.0, the fluorescence signals of both QYL-1 and the detecting system remained relatively steady (Figs. S1 and SI), indicating a calibratingavailable wide window for application. Although the reaction reached complete saturation in 2 h, the enhancing rate of fluorescent signal was quite slow after 1 h, thus the reaction time was determined as 60 min (Figs. S2 and SI). Shown in Fig. 4, the fluorescence spectrum of QYL-1 (10 mM) with adding concentrations of hydrazine (0e500 mM) suggested a gradual turn-on change at 480 nm. The plateau was reached at 40.0 equivalent (400 mM) and the linear range was 0e20.0 equivalent (200 mM). The limit of detection (LOD) was then determined to be 0.12 mM (using formula 3s/k) and the limit of quantity (LOQ) was tested to be 0.45 mM by continuously diluting the concentration of hydrazine hydrate. One attractive advantage was the ultra-wide linear range, which was extremely essential for linking the monitoring in various scale and field through chemistry, environmental science, plant physiology and preclinical diagnostics.
3. Results and discussion
3.3. Selectivity of QYL-1
3.1. Synthesis of the sensors
The selectivity towards hydrazine was an important property, therefore the performance of QYL-1 was evaluated with a variety of analytes (Fig. 5a). Except for treating with hydrazine, no obvious enhancement in fluorescence intensity could be observed in the other groups. Furthermore, when the competitive experiment was conducted, the response of QYL-1 towards hydrazine was not interfered by the coexistence of other analytes (Fig. 5b). This probe did not show any color changes with the addition of different metals. Thus, in both independent and coexistence systems, the selectivity of QYL-1 for hydrazine was guaranteed, which also help built the feasibility of linking multi-field monitoring, especially in the now-missing plant part.
All the sensors were synthesized as shown in Fig. 2 and confirmed by satisfactory spectroscopic data (1H NMR, 13C NMR, MS or HRMS, Figs. S5e22, SI). 3.2. Quick screening of general fluorescent properties for sensing hydrazine We recruited and designed a series of sensors QYL-1~3 for hydrazine. After evaluating the absorption (Fig. 3aec) and fluorescence spectra (Fig. 3def) of the sensors as well as the detecting
Fig. 2. General synthesis route of the QYL series sensors.
Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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Fig. 3. The absorption (aec) and fluorescence spectra (def) of the sensors as well as the detecting systems. Slit widths 10 nm 10 nm, photomultiplier voltage 500 V.
Fig. 4. (a) The fluorescence spectra of QYL-1 (10 mM) in PBS buffer (10 mM, pH 7.4, 1 mM CTAB containing 1% MeCN) after treatment with hydrazine (0e400 mM) for 60 min; (b) The linear relationship between the fluorescence intensity and the concentration of hydrazine (0e200 mM) in PBS buffer (10 mM, pH 7.4, 1 mM CTAB containing 1% MeCN) for 60 min; (c) The curve between the fluorescence intensity and the concentration of hydrazine (0e500 mM).
3.4. The reaction mechanism We used 2-(benzothiazol-2-yl)-phenol as the fluorescent reporting group based on excited state intramolecular proton transfer (ESIPT) mechanism (Figs. S3 and SI). To confirm this mechanism, IR spectra and mass spectrometry analysis were
carried out. As Shown in Fig. S4, a signal of the freshly formed eOHe group was also clearly observed in the IR spectrum after treatment with NH2NH2 (near 3300 cm1). Moreover, Job’s plot analysis for QYL-1 and NH2NH2 interaction (Figs. S4 and SI) inferred that the ratio of binding sites should be 1:1.
Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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Fig. 5. The intensity values at 480 nm in PBS buffer (10 mM, pH 7.4, 1 mM CTAB containing 1% MeCN) at 37 C indicated the selectivity of QYL-1 towards hydrazine (a) from other analytes and (b) in the coexistence systems. In (a): (1) Control; (2) Agþ; (3) Al3þ; (4) Fe2þ; (5) Pd2þ; (6) Zn2þ; (7) Ni2þ; (8) Mg2þ; (9) Mn2þ; (10) Kþ; (11) Cr3þ; (12) HSO 3 ; (13) SO4 ; þ 3þ 2þ 2þ 2þ 2þ þ (14) HPO 4 ; (15) SCN ; (16) CH3COO ; (17) ClO4 ; (18) Cl ; (19) Br ; (20) I ; (21) NO3 ; (22) Hydrazine; In (b): (1) Ag ; (2) Al ; (3) Pd ; (4) Ni ; (5) Mg ; (6) Mn ; (7) K ; (8) 2 Cr3þ; (9) SO 4 ; (10) HPO4 ; (11) SCN ; (12) CH3COO ; (13) ClO4 ; (14) Br ; (15) I ; (16) NO3 ; (17) CO3 ; (18) HCO3 ; (19) Hydrazine.
3.5. Application in Arabidopsis thaliana and closed-loop monitoring After all the in vitro preparation above, the confocal experiment in living Arabidopsis thaliana was subsequently performed (Fig. 6), as the major purpose of this work, to accomplish the closed-loop monitoring of hydrazine. Since it was the first trial of constructing a hydrazine monitoring model in plant, we attempted to set the parameters as general as possible. Therefore the growth period of the Arabidopsis thaliana root tissue was set as 5 days. After a preincubation with 100 mM QYL-1 for 30 min, the root tips were all
washed three times by cold PBS. Then the control (Fig. 6aec), low concentration (Fig. 6def) and high concentration (Fig. 6gei) groups were incubated with PBS, 1 mM hydrazine and 4 mM hydrazine for 1 h, respectively. Here remarkable enhancement of fluorescence intensity could be observed with a concentration-dependent tendency, which indicated the in situ imaging capability of our method in plant. Then we attempted to preliminarily achieve the closed-loop monitoring of hydrazine via associating in-plant detection with its upstream node environment and downstream node cells
Fig. 6. The confocol images of the Arabidopsis Thaliana root tips. Further incubations for 1 h with (aec) PBS, (def) 1 mM hydrazine, and (gei) 4 mM hydrazine were conducted respectively after a pre-incubation with 50 mM QYL-1 for 30 min lex ¼ 405 nm, green channel: 440e500 nm.
Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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Fig. 7. The confocol images of living MCF-7 cells. Further incubations for 1 h with (aec) PBS, (def) 200 mM hydrazine, and (gei) 400 mM hydrazine were conducted respectively after a pre-incubation with 10 mM QYL-1 for 30 min lex ¼ 405 nm, green channel: 440e500 nm.
(animal or human source). As seen in Fig. S5, in detecting systems with different water samples (Changjiang River water, rice water and tap water), the application of QYL-1 was almost not interfered. Meanwhile, when employed for imaging in living MCF-7 cells (Fig. 7), we found that almost no intracellular fluorescence was detected after MCF-7 cells were co-cultured only with QYL-1. By contrast, when cells incubated with N2H4 (200 mM and 400 mM) for 1 h, and then treated with QYL-1 for another 30 min, a green fluorescence enhancement could be observed. With the increase of hydrazine hydrate concentration, the enhancement of fluorescence intensity could be observed by naked eyes. The above results suggested that QYL-1 indicated a practical capability of monitoring hydrazine in both environmental and cellular samples. Herein, for the first time, we closed the loop of hydrazine monitoring at the insufficient gap of in-plant detection with a practical method linking both the upstream (environment) and downstream nodes (cells from animal or human source). Thus, we could track the hydrazine hydrate all through its circulation from human to environment, to plants, then back to animals and humans, realizing the closed-loop monitoring. 4. Conclusion In summary, we constructed a primary method for detecting hydrazine in plant, thus accomplished the closed-loop monitoring of hydrazine circulation within manufacture, environment, plants, animals and human. After a basic screening, we selected QYL-1 to conduct the hydrazine sensing procedures. Despite the improvable properties as a preliminary tool, QYL-1 suggested the ultra-wide linear range (0e20.0 equivalent) and high selectivity, which were extremely essential for linking the monitoring in various scale and
field. Subsequently, concentration-dependent tracking of hydrazine was successfully performed in Arabidopsis Thaliana root tips for the first time. Applications in water samples and living MCF-7 cells then fulfilled the demonstration of closing the loop by linking both the upstream and downstream nodes. Far more than raising a practical method for hydrazine detection, this work offered initial information for the closed-loop monitoring of hydrazine circulation, thus providing the ideal systematic managing in future. Declaration of competing interest All authors declare that there are no conflicts of interest. Acknowledgments This work is supported by the Major Science and Technology Program for Water Pollution Control and Treatment, China (No. 2017ZX07602-002), the Natural Science Foundation of Jiangsu Higher Education Institutions, China (No. 18KJB350004), and the Project for Young Teachers of Nanjing Forestry University, China (No. CX2017005). Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.saa.2019.117707. References [1] U. Engelhardt, Nonalternating inorganic heterocycles containing hydrazine as building block, Coord. Chem. Rev. 235 (2002) 53e91. [2] M.E. Ibele, Y. Wang, T.R. Kline, T.E. Mallouk, A. Sen, Hydrazine fuels for
Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana Ya-Lin Qi a, 1, Jian Chen a, 1, Bo Zhang a, Hua Li a, Dong-Dong Li b, Bao-Zhong Wang a, **, Yu-Shun Yang a, ***, Hai-Liang Zhu a, * a b
State Key Laboratory of Pharmaceutical Biotechnology, School of Life Sciences, Nanjing University, Nanjing, 210023, China College of Chemical Engineering, Nanjing Forestry University, 159 Longpan Road, Nanjing, 210037, China
a r t i c l e i n f o
a b s t r a c t
Article history: Received 29 July 2019 Received in revised form 24 October 2019 Accepted 24 October 2019 Available online xxx
In this work, a primary method was constructed for detecting hydrazine in plant, thus accomplished the closed-loop monitoring of hydrazine circulation within manufacture, environment, plants, animals and human. From a series of sensors, QYL-1 was selected to present the hydrazine sensing properties. As a preliminary tool, QYL-1 suggested the ultra-wide linear range (0e20.0 equivalent) and high selectivity, which were extremely essential for linking the monitoring in various scale and field. For the first time, concentration-dependent tracking of hydrazine was successfully performed in Arabidopsis Thaliana root tips. Afterwards applications in water samples and living MCF-7 cells then fulfilled the demonstration of closing the loop by linking both the upstream and downstream nodes. More than raising a practical method, this work offered initial information for the closed-loop monitoring of hydrazine circulation, which might be significant for the ideal systematic managing in future. © 2019 Elsevier B.V. All rights reserved.
Keywords: Hydrazine detection Fluorescent sensor Biological imaging Plant tissue Closed-loop monitoring
1. Introduction All through the applications in extensive areas such as medicinal career, chemical engineering, material industy and environmental management, hydrazine (NH2NH2) acts as one of the most significant component with practical reductivity and basicity [1]. Despite the most widely known uses of military and astronautic propulsion [2], hydrazine can be applied in pharmaceutic synthesis of drugs such as isoniazid for tuberculosis [3], iproniazid for psychotic [4], and procarbazine for tumor [5]. However, as the reverse side of a coin, the high toxicity of hydrazine upon biological organism cannot be neglected [6]. It can cause dizziness, nausea, and even cancer, thus the US Environmental Protection Agency (EPA) has determined that hydrazine are a potential carcinogen with a minimum limit of 10 ppb [7]. To track back the enrichment process of hydrazine all through the route in manufacture, environment, plants, animals and human, exploiting selective and sensitive
* Corresponding author. ** Corresponding author. *** Corresponding author. E-mail addresses: [email protected] (B.-Z. (Y.-S. Yang), [email protected] (H.-L. Zhu). 1 Both authors contributed equally to the work.
Wang),
[email protected]
methods to fulfill hydrazine monitoring at each key node was an urgent emergency [8,9]. Recent researches have raised practical methods for detecting trace hydrazine including electrochemistry [10], Raman spectroscopy [11], colorimetry [12], chemiluminescence [13], spectrophotometry [14], titrimetry [15], and so on. Since sophisticate preparation and strict technical requirements impeded convenient applications of these approaches, fluorescent sensors have caught the attentions of investigators due to high selectivity and good biocompatibility [16]. In reported cases, the recognizing moiety includes acetyl [17,18], levulinate [19], 4-bromo butyrate [20,21], phthalimide [22,23], aldehyde [24], cyanogroup [25,26], and the fluorescent moiety includes benzothiazole [27], 1,8-naphthalene imide [28], coumarin [29], rhodamine [30], phenothiazine [31], carbazole [32], cyanine dye [33], BODIPY [34]. With progressing selectivity and sensitivity, broadening and deepening the applications of hydrazine monitoring tools are facing new opportunities and challenges. In this work, we focused on the closed-loop monitoring of hydrazine circulation. Within the loop of manufacture [35], environment [36], plants, animals [37] and human [38], all nodes have been addressed except plant. Therefore we attempted to construct a primary method for detecting hydrazine in plant. For concise, we did not use complex tools of rare earth [39], aggregation-induced enhancement (AIE) [40], nanoparticles [41] or carbon dots [42].
https://doi.org/10.1016/j.saa.2019.117707 1386-1425/© 2019 Elsevier B.V. All rights reserved.
Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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Here the most important task was developing a fluorescent tool with simple structure and superior properties to initially complete the closed-loop monitoring of hydrazine circulation before the further improvement to generate more sophisticated sensors. We designed and synthesized three fluorescence probes QYL-1, QYL-2 and QYL-3 which only contain two steps and have a more than 80% yield. Among them, the probe QYL-1 display high sensitivity and selectivity for N2H4 both in vitro and in vivo as fluorescent chemodosimeter. To the best of our knowledge, there are some examples about the fluorescent probes based on excited state intramolecular proton transfer (ESIPT) mechanism using 2-(benzothiazol-2-yl)-phenol (HBT). For example, Sabyasachi Sarkar’s group designed a ratiometric probe HBT [43], whose excitation and emission wavelengths were 368 nm and 458 nm respectively, and the Stoke’s shift was 90 nm. Zhu’s group synthesized two probes 1 and 2 [44], and there was a methyl group or a benzene, respectively, connected to the phenol backbone. The sensing properties of probe 1 surpassed probe 2, with the emission wavelength of 479 nm and the detection limit of 0.37 mM. In this work, we developed a highly selective (>45-fold) probe QYL-1 with large Stoke’s shift (180 nm) for the detection of NH2NH2. A broader comparison with previous hydrazine sensors was provided in Tables S1 and SI. Typically recognizing and fluorescent moieties were employed with finetuned details to promote direct hydrazine monitoring in Arabidopsis thaliana (Fig. 1). 2. Experimental 2.1. Materials and methods All commercially available chemicals were directly used and no further purification was conducted. 1H NMR and 13C NMR spectra were recorded on Bruker DRX-600 spectrometer and analyzed with MestreNova software. Mass spectra were recorded on Agilent 6540 UHD Accurate Mass Q-TOF LC/MS and 1290 Infinity LC/6460 QQQ MS. UVevis spectra were recorded on Shimadzu UV-2550 spectrometer and fluorescence measurements were conducted on Hitachi F-7000 Fluorescence Spectrophotometer. The imaging experiments were performed using two-photon confocal fluorescent microscope Leica TCS SP8 MP. The probes was dissolved in MeCN to get the solution of 1.0 mM. Other concentrations were obtained by dilution. The excitation wavelength was set according to sensors (371 nm for QYL-1, 320 nm for QYL-2 and 310 nm for QYL-3). Both excitation and emission slit widths were 10 nm. The photomultiplier voltage was 500 V. In the selectivity evaluation, analytes except hydrazine were all set as 1.0 mM.
2.2. Synthesis of the sensors 2.2.1. Synthesis of the intermediates 3e1, 3e2 and 3e3 Compound 3e1, 2-(benzo[d]thiazol-2-yl)-6-methoxyphenol, was synthesized according to the following procedures. A solution of 2-aminothiophenol (0.9 mL, 12.6 mmol) and o-vanillin (1.44 g, 9.45 mmol) in ethanol (30 mL) was stirred for 10 min in an ice bath. Then aq H2O2 (30%, 56.8 mmol) and aq HCl (32% HCl, 28.35 mmol) were added slowly into the mixture, respectively. Then the resulting mixture was stirred at room temperature for 2 h. The solution was quenched by 35 mL cold water. The precipitate was filtered, dried and crystallized via ethanol to afford the title compound as a light yellow solid without further purification (2.20 g, 68%). 1H NMR (600 MHz, DMSO‑d6) d 11.21 (s, 1H), 8.15 (d, J ¼ 7.9 Hz, 1H), 8.07 (d, J ¼ 8.1 Hz, 1H), 7.75 (d, J ¼ 8.0 Hz, 1H), 7.55 (t, J ¼ 7.7 Hz, 1H), 7.46 (t, J ¼ 7.5 Hz, 1H), 7.16 (d, J ¼ 8.9 Hz, 1H), 6.98 (t, J ¼ 8.0 Hz, 1H), 3.88 (s, 3H). 13C NMR (151 MHz, DMSO‑d6) d 165.84, 151.82, 148.99, 146.76, 134.69, 126.99, 125.63, 122.60, 120.26, 119.94, 118.97, 114.60, 56.53. MS (ESI-TOF m/z): Calculated for [C14H12NO2S]þ: 258.0, Found: 258.0. Anal. Calcd. for C14H11NO2S: C 65.35, H 4.31, N 5.44, found: C 65.31, H 4.31, N 5.45. Compound 3e2, 2-(benzo[d]thiazol-2-yl)-5-methoxyphenol, was synthesized through the same approach of 3e1. White solid (2.00 g, 63%). 1H NMR (600 MHz, DMSO‑d6) d 8.13e8.09 (m, 1H), 8.06 (d, J ¼ 8.7 Hz, 1H), 8.01 (d, J ¼ 8.0 Hz, 1H), 7.53 (ddd, J ¼ 8.2, 7.2, 1.3 Hz, 1H), 7.42 (ddd, J ¼ 8.1, 7.2, 1.2 Hz, 1H), 6.67e6.62 (m, 2H). 13C NMR (151 MHz, DMSO‑d6) d 166.27, 163.34, 158.72, 133.82, 130.31, 126.93, 125.21, 122.42, 121.90, 111.76, 107.66, 101.63, 55.91. HRMS (ESI-TOF m/z): Calculated for [C14H12NO2S]þ: 258.0589, Found: 258.0587. Compound 3e3, 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol, synthesized through the same approach of 3e1. Yellow solid (2.26 g, 70%). 1H NMR (600 MHz, DMSO‑d6) d 10.34 (s, 1H), 8.47 (dd, J ¼ 8.8, 3.7 Hz, 1H), 7.95 (t, J ¼ 6.4 Hz, 1H), 7.77 (t, J ¼ 7.2 Hz, 1H), 7.59e7.50 (m, 1H), 7.40e7.33 (m, 2H), 3.96 (dd, J ¼ 4.7, 2.7 Hz, 3H). 13 C NMR (151 MHz, DMSO‑d6) d 169.15, 155.36, 155.33, 155.31, 137.36, 132.58, 129.56, 129.47, 129.45, 127.06, 126.37, 124.37, 124.35, 111.50, 53.05, 53.03. HRMS (ESI-TOF m/z): Calculated for [C14H12NO2S]þ: 258.0589, Found: 258.0583. 2.2.2. Synthesis of the sensors QYL-1, QYL-2 and QYL-3 For QYL-1, 2-(benzo[d]thiazol-2-yl)-6-methoxyphenyl acetate, compound 3e1 (114 mg, 0.5 mmol) was dissolved in acetic anhydride (5 mL) and stirred to reflux under nitrogen atmosphere for 4 h. The reaction process was monitored by TLC. After cooled down to 75 C, the solution was poured into ice water with fierce stirring.
Fig. 1. Illustration of the QYL series sensors for the closed-loop monitoring of hydrazine circulation.
Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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Then, the mixture was extracted with dichloromethane for 3 times. The organic layer was collected, evaporated and dried. The target product was obtained as a colorless solid without further purification (119 mg, 88%). 1H NMR (600 MHz, DMSO‑d6) d 8.17 (d, J ¼ 7.9 Hz, 1H), 8.11 (d, J ¼ 7.9 Hz, 1H), 7.90e7.87 (m, 1H), 7.58 (d, J ¼ 7.3 Hz, 1H), 7.51 (t, J ¼ 7.5 Hz, 1H), 7.45 (t, J ¼ 8.1 Hz, 1H), 7.36 (d, J ¼ 8.1 Hz, 1H), 3.87 (s, 3H), 2.47 (s, 3H). 13C NMR (151 MHz, DMSO‑d6) d 168.70, 162.14, 152.62, 152.26, 137.96, 135.24, 127.59, 127.19, 126.90, 126.22, 123.47, 122.63, 120.88, 115.46, 56.79, 39.98, 21.47. MS (ESI-TOF m/z): Calculated for [C16H13NO3SNa]þ ([MþNa]þ): 322.0, Found: 322.0. Anal. Calcd. for C16H13NO3S: C 64.20, H 4.38, N 4.68, found: C 64.28, H 4.38, N 4.67. For QYL-2, 2-(benzo[d]thiazol-2-yl)-5-methoxyphenyl acetate, it was synthesized through the same approach of QYL-1. Yellow solid (120 mg, 88%). 1H NMR (600 MHz, DMSO‑d6) d 8.26 (d, J ¼ 8.8 Hz, 1H), 8.13 (d, J ¼ 7.7 Hz, 1H), 8.06 (d, J ¼ 8.0 Hz, 1H), 7.55 (ddd, J ¼ 8.3, 7.2, 1.3 Hz, 1H), 7.46 (ddd, J ¼ 8.2, 7.2, 1.2 Hz, 1H), 7.08 (dd, J ¼ 8.9, 2.6 Hz, 1H), 7.01 (d, J ¼ 2.6 Hz, 1H), 3.87 (s, 3H), 2.49 (s, 3H). 13C NMR (151 MHz, DMSO‑d6) d 169.44, 162.44, 152.79, 149.91, 134.75, 131.06, 127.02, 125.74, 123.04, 122.47, 118.68, 113.46, 109.94, 56.36, 22.03. HRMS (ESI-TOF m/z): Calculated for [C16H14NO3S]þ: 300.0694, Found: 300.0681. For QYL-3, 2-(benzo[d]thiazol-2-yl)-4-methoxyphenyl acetate, it was synthesized through the same approach of QYL-1. White solid (115 mg, 84%). 1H NMR (600 MHz, DMSO‑d6) d 8.20e8.16 (m, 1H), 8.13 (d, J ¼ 8.1 Hz, 1H), 7.82 (d, J ¼ 3.1 Hz, 1H), 7.59 (ddd, J ¼ 8.3, 7.1, 1.3 Hz, 1H), 7.51 (ddd, J ¼ 8.2, 7.2, 1.2 Hz, 1H), 7.32 (d, J ¼ 8.9 Hz, 1H), 7.21 (dd, J ¼ 8.9, 3.1 Hz, 1H), 3.89 (s, 3H), 2.47 (s, 3H). 13C NMR (151 MHz, DMSO‑d6) d 169.90, 162.06, 157.50, 152.50, 142.14, 135.33, 127.21, 126.46, 126.22, 125.86, 123.48, 122.64, 118.60, 113.14, 56.19, 21.94. HRMS (ESI-TOF m/z): Calculated for [C16H14NO3S]þ: 300.0694, Found: 300.0692.
systems, with the addition of NH2NH2, the absorption peaks of three probes decreased at near 300 nm. QYL-1 was chosen for the following procedures due to the excitation wavelength (371 nm versus 320 nm or 310 nm), emission wavelength (480 nm versus 400 nm or 410 nm) and Stoke Shift (180 nm versus 90 nm or 110 nm). When the NH2NH2 concentration was increased to 40 equiv of the probe concentration, the fluorescence intensity of probe QYL-1 attained a 49-fold enhancement, while that of probe QYL-2 increased by 1.1-fold and QYL-3 increased by 1.4-fold. The fluorescence quantum yield was 0.19 for QYL-1, which was suitable for a turn-on system. Then the sensing system consisting of QYL-1 (10 mM) and hydrazine (400 mM) in PBS buffer (pH 7.4, 10 mM, 1 mM CTAB 1% MeCN v/v) at 37 C was performed to check the responses to different external conditions. Within the range of 7.0e11.0, the fluorescence signals of both QYL-1 and the detecting system remained relatively steady (Figs. S1 and SI), indicating a calibratingavailable wide window for application. Although the reaction reached complete saturation in 2 h, the enhancing rate of fluorescent signal was quite slow after 1 h, thus the reaction time was determined as 60 min (Figs. S2 and SI). Shown in Fig. 4, the fluorescence spectrum of QYL-1 (10 mM) with adding concentrations of hydrazine (0e500 mM) suggested a gradual turn-on change at 480 nm. The plateau was reached at 40.0 equivalent (400 mM) and the linear range was 0e20.0 equivalent (200 mM). The limit of detection (LOD) was then determined to be 0.12 mM (using formula 3s/k) and the limit of quantity (LOQ) was tested to be 0.45 mM by continuously diluting the concentration of hydrazine hydrate. One attractive advantage was the ultra-wide linear range, which was extremely essential for linking the monitoring in various scale and field through chemistry, environmental science, plant physiology and preclinical diagnostics.
3. Results and discussion
3.3. Selectivity of QYL-1
3.1. Synthesis of the sensors
The selectivity towards hydrazine was an important property, therefore the performance of QYL-1 was evaluated with a variety of analytes (Fig. 5a). Except for treating with hydrazine, no obvious enhancement in fluorescence intensity could be observed in the other groups. Furthermore, when the competitive experiment was conducted, the response of QYL-1 towards hydrazine was not interfered by the coexistence of other analytes (Fig. 5b). This probe did not show any color changes with the addition of different metals. Thus, in both independent and coexistence systems, the selectivity of QYL-1 for hydrazine was guaranteed, which also help built the feasibility of linking multi-field monitoring, especially in the now-missing plant part.
All the sensors were synthesized as shown in Fig. 2 and confirmed by satisfactory spectroscopic data (1H NMR, 13C NMR, MS or HRMS, Figs. S5e22, SI). 3.2. Quick screening of general fluorescent properties for sensing hydrazine We recruited and designed a series of sensors QYL-1~3 for hydrazine. After evaluating the absorption (Fig. 3aec) and fluorescence spectra (Fig. 3def) of the sensors as well as the detecting
Fig. 2. General synthesis route of the QYL series sensors.
Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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Fig. 3. The absorption (aec) and fluorescence spectra (def) of the sensors as well as the detecting systems. Slit widths 10 nm 10 nm, photomultiplier voltage 500 V.
Fig. 4. (a) The fluorescence spectra of QYL-1 (10 mM) in PBS buffer (10 mM, pH 7.4, 1 mM CTAB containing 1% MeCN) after treatment with hydrazine (0e400 mM) for 60 min; (b) The linear relationship between the fluorescence intensity and the concentration of hydrazine (0e200 mM) in PBS buffer (10 mM, pH 7.4, 1 mM CTAB containing 1% MeCN) for 60 min; (c) The curve between the fluorescence intensity and the concentration of hydrazine (0e500 mM).
3.4. The reaction mechanism We used 2-(benzothiazol-2-yl)-phenol as the fluorescent reporting group based on excited state intramolecular proton transfer (ESIPT) mechanism (Figs. S3 and SI). To confirm this mechanism, IR spectra and mass spectrometry analysis were
carried out. As Shown in Fig. S4, a signal of the freshly formed eOHe group was also clearly observed in the IR spectrum after treatment with NH2NH2 (near 3300 cm1). Moreover, Job’s plot analysis for QYL-1 and NH2NH2 interaction (Figs. S4 and SI) inferred that the ratio of binding sites should be 1:1.
Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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Fig. 5. The intensity values at 480 nm in PBS buffer (10 mM, pH 7.4, 1 mM CTAB containing 1% MeCN) at 37 C indicated the selectivity of QYL-1 towards hydrazine (a) from other analytes and (b) in the coexistence systems. In (a): (1) Control; (2) Agþ; (3) Al3þ; (4) Fe2þ; (5) Pd2þ; (6) Zn2þ; (7) Ni2þ; (8) Mg2þ; (9) Mn2þ; (10) Kþ; (11) Cr3þ; (12) HSO 3 ; (13) SO4 ; þ 3þ 2þ 2þ 2þ 2þ þ (14) HPO 4 ; (15) SCN ; (16) CH3COO ; (17) ClO4 ; (18) Cl ; (19) Br ; (20) I ; (21) NO3 ; (22) Hydrazine; In (b): (1) Ag ; (2) Al ; (3) Pd ; (4) Ni ; (5) Mg ; (6) Mn ; (7) K ; (8) 2 Cr3þ; (9) SO 4 ; (10) HPO4 ; (11) SCN ; (12) CH3COO ; (13) ClO4 ; (14) Br ; (15) I ; (16) NO3 ; (17) CO3 ; (18) HCO3 ; (19) Hydrazine.
3.5. Application in Arabidopsis thaliana and closed-loop monitoring After all the in vitro preparation above, the confocal experiment in living Arabidopsis thaliana was subsequently performed (Fig. 6), as the major purpose of this work, to accomplish the closed-loop monitoring of hydrazine. Since it was the first trial of constructing a hydrazine monitoring model in plant, we attempted to set the parameters as general as possible. Therefore the growth period of the Arabidopsis thaliana root tissue was set as 5 days. After a preincubation with 100 mM QYL-1 for 30 min, the root tips were all
washed three times by cold PBS. Then the control (Fig. 6aec), low concentration (Fig. 6def) and high concentration (Fig. 6gei) groups were incubated with PBS, 1 mM hydrazine and 4 mM hydrazine for 1 h, respectively. Here remarkable enhancement of fluorescence intensity could be observed with a concentration-dependent tendency, which indicated the in situ imaging capability of our method in plant. Then we attempted to preliminarily achieve the closed-loop monitoring of hydrazine via associating in-plant detection with its upstream node environment and downstream node cells
Fig. 6. The confocol images of the Arabidopsis Thaliana root tips. Further incubations for 1 h with (aec) PBS, (def) 1 mM hydrazine, and (gei) 4 mM hydrazine were conducted respectively after a pre-incubation with 50 mM QYL-1 for 30 min lex ¼ 405 nm, green channel: 440e500 nm.
Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707
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Y.-L. Qi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (xxxx) xxx
Fig. 7. The confocol images of living MCF-7 cells. Further incubations for 1 h with (aec) PBS, (def) 200 mM hydrazine, and (gei) 400 mM hydrazine were conducted respectively after a pre-incubation with 10 mM QYL-1 for 30 min lex ¼ 405 nm, green channel: 440e500 nm.
(animal or human source). As seen in Fig. S5, in detecting systems with different water samples (Changjiang River water, rice water and tap water), the application of QYL-1 was almost not interfered. Meanwhile, when employed for imaging in living MCF-7 cells (Fig. 7), we found that almost no intracellular fluorescence was detected after MCF-7 cells were co-cultured only with QYL-1. By contrast, when cells incubated with N2H4 (200 mM and 400 mM) for 1 h, and then treated with QYL-1 for another 30 min, a green fluorescence enhancement could be observed. With the increase of hydrazine hydrate concentration, the enhancement of fluorescence intensity could be observed by naked eyes. The above results suggested that QYL-1 indicated a practical capability of monitoring hydrazine in both environmental and cellular samples. Herein, for the first time, we closed the loop of hydrazine monitoring at the insufficient gap of in-plant detection with a practical method linking both the upstream (environment) and downstream nodes (cells from animal or human source). Thus, we could track the hydrazine hydrate all through its circulation from human to environment, to plants, then back to animals and humans, realizing the closed-loop monitoring. 4. Conclusion In summary, we constructed a primary method for detecting hydrazine in plant, thus accomplished the closed-loop monitoring of hydrazine circulation within manufacture, environment, plants, animals and human. After a basic screening, we selected QYL-1 to conduct the hydrazine sensing procedures. Despite the improvable properties as a preliminary tool, QYL-1 suggested the ultra-wide linear range (0e20.0 equivalent) and high selectivity, which were extremely essential for linking the monitoring in various scale and
field. Subsequently, concentration-dependent tracking of hydrazine was successfully performed in Arabidopsis Thaliana root tips for the first time. Applications in water samples and living MCF-7 cells then fulfilled the demonstration of closing the loop by linking both the upstream and downstream nodes. Far more than raising a practical method for hydrazine detection, this work offered initial information for the closed-loop monitoring of hydrazine circulation, thus providing the ideal systematic managing in future. Declaration of competing interest All authors declare that there are no conflicts of interest. Acknowledgments This work is supported by the Major Science and Technology Program for Water Pollution Control and Treatment, China (No. 2017ZX07602-002), the Natural Science Foundation of Jiangsu Higher Education Institutions, China (No. 18KJB350004), and the Project for Young Teachers of Nanjing Forestry University, China (No. CX2017005). Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.saa.2019.117707. References [1] U. Engelhardt, Nonalternating inorganic heterocycles containing hydrazine as building block, Coord. Chem. Rev. 235 (2002) 53e91. [2] M.E. Ibele, Y. Wang, T.R. Kline, T.E. Mallouk, A. Sen, Hydrazine fuels for
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Please cite this article as: Y.-L. Qi et al., A turn-on fluorescent sensor for selective detection of hydrazine and its application in Arabidopsis thaliana, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117707