A novel dual-function probe for recognition of Zn2+ and Al3+ and its application in real samples

SAA-117786; No of Pages 13 Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (xxxx) xxx

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A novel dual-function probe for recognition of Zn2+ and Al3+ and its application in real samples Xue-Jiao Sun, Ting-Ting Liu, Na-Na Li, Shuang Zeng, Zhi-Yong Xing ⁎ Department of Applied Chemistry, College of Science, Northeast Agricultural University, Harbin 150030, PR China

a r t i c l e

i n f o

Article history: Received 7 August 2019 Received in revised form 8 November 2019 Accepted 10 November 2019 Available online xxxx Keywords: Fluorescence Dual-function Al3+ Zn2+ Logic gate Plant imaging

a b s t r a c t A dual-function probe NAHH based on naphthalene was synthesized and characterized. Based on the combination effects derived from the inhabitation of photo-induced electron transfer (PET) and C_N isomerization, probe NAHH achieved in the recognition of Zn2+ and Al3+ both through obvious fluorescence enhancement and color changes detected by naked eye, respectively. Probe NAHH showed high sensitivity with the limit of detection as low as 3.02 × 10−7 M for Zn2+ and 7.55 × 10−8 M for Al3+, indicated the capability of probe NAHH in trace detection for Zn2+ and Al3+. The binding ratio of NAHH with Zn2+ and Al3+ were all 1:1 determined by Job plot, and the corresponding association constant was calculated as 8.48 × 104 M−1 and 4.45 × 105 M−1, respectively. The mechanism was further confirmed by FT-IR, 1H NMR titration and ESI-MS analysis. Furthermore, probe NAHH was successfully applied in logic gate construction and the detection of Zn2+ and Al3+ in Songhua River and test stripe. Fluorescence imaging experiments confirmed that NAHH could be used to monitor Zn2+ in plant root. © 2019 Elsevier B.V. All rights reserved.

1. Introduction Metal ions play a vital role in various fields such as life sciences, medical biotechnology and environmental chemistry [1–3]. Particularly, Zn2 + and Al3+ occupy a very vital position among most of metal ions in the living process. Aluminum (Al) which is considered as one of the most abundant metals in the Earth's crust, is widely dispersed in many regions closely associated with our daily lives such as water treatment, food additives and pharmaceutical packaging [4,5]. However, as an unnecessary element for human, excessive intake of Al3+ may affect the normal function of human organs and further cause various diseases such as Alzheimer's disease, dialysis encephalopathy, Parkinson's disease, and microcytic hypochromic anemia [6–11]. Moreover, high concentration of Al3+ in surroundings will inhibit plant growth and threaten fish survival [12,13]. Similarly, Zinc (Zn) as the second most abundant transition metal and one necessary element in the human body, plays a crucial role in physiological and pathological processes such as neural signal transmitters, immune function and cellular metabolism [14,15]. However, insufficient intake of Zn2+ is associated with unbalanced metabolism, thus leading to retarded growth in children and brain disorders. While excessive ingestion of Zn2+ can also cause various cerebropathia disorders, epilepsy, high blood cholesterol and ischemia [16–23]. Hence, it seems evident important for the development

⁎ Corresponding author. E-mail address: [email protected] (Z.-Y. Xing).

of an efficient method in trace monitoring of Al3+ and Zn2+ in vivo and surroundings as well. Development of fluorescent chemosensors for metal ions detection have been paid high attention due to their excellent sensitivity, simplicity, instantaneous response and low detection limit up to nanomolar scale [24]. Many excellent fluorescence sensors were developed for Al3 + [25–35] or Zn2+ [36–41] based on the design idea of single probe for one special metal ion, but the evolution of designing philosophy that one probe for multi-analyte with outstanding spectra and obvious color responses has received an intensive interest attributed to its distinct advantages of low cost, high efficiency and time saving. Up to date, various multi-function probes were reported for simultaneous recognition of different analytes base on different fluorophores [42–54], but few of them was for the simultaneous detection of Al3+ and Zn2+ [55–60], which might due to the weak coordination ability of Al3+ and the disturbance on Zn2+ by other transition metal ions like Cd2+. Therefore, it is still full of challenge to develop a multi-functional probe for selective response to Al3+ and Zn2+. Naphthalene is widely employed as an ideal fluorophore in the development of fluorescent probes due to its low fluorescence quantum yield and short fluorescence lifetime [61]. Especially, this kind structure of naphthalene that the 6-position with electron donating group (-OH) and the 2-position with electron withdrawing group (-C=O) can enhance its emission intensity based on ICT mechanism by increasing the push-pull effect [62]. Moreover, it is well known that Schiff base is a distinguished ligand, which usually display an fluorescence “off-on” through the inhabitation of –C=N isomerization or PET mechanism

https://doi.org/10.1016/j.saa.2019.117786 1386-1425/© 2019 Elsevier B.V. All rights reserved.

Please cite this article as: X.-J. Sun, T.-T. Liu, N.-N. Li, et al., A novel dual-function probe for recognition of Zn2+ and Al3+ and its application in real samples, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117786

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after coordination with some special analyte [31,57,58]. Taking above statements into consideration, a Schiff-based probe 6-hydroxy-N′-(2hydroxybenzylidene)-2-naphthohydrazide (NAHH) was synthesized by the condensation of 6-hydroxy-2-naphthohydrazide with 2hydroxybenzaldehyde. The probe NAHH exhibited simultaneously in the recognition of Zn2+ and Al3+ both through obvious fluorescence enhancement and significant color changes detected by naked eye. Furthermore, probe NAHH was successfully applied in logic gate construction and real sample detection. Fluorescence imaging experiments confirmed that NAHH could monitor Zn2+ in plant root. 2. Experiment 2.1. Materials and apparatus All analytical reagent grade chemicals and solvents employed for the synthesis and characterization were procured from commercial sources and used as received without any treatment. Nuclear magnetic resonance spectra (NMR) were recorded on a Bruker 600 MHz system, and the chemical shifts are reported in ppm with Me4Si as the internal standard. High resolution mass spectroscopy (HRMS) was carried out on a Waters Xevo UPLC/G2-SQ Tof MS spectrometer. The FT-IR spectra were recorded on a Bruker ALPHA-T by dispersing samples in KBr disks, in the range of 4000–400 cm−1. The UV–vis absorption and fluorescence spectra of the samples were measured on Pgeneral TU-2550 UV–vis Spectrophotometer and Perkin Elmer LS55 fluorescence spectrometer, respectively. 2.2. General method for the spectra experiments of NAHH Stock solutions of the metal ions (Al3+, Fe3+, Cr3+, Ca2+, Cd2+, Co2+, Cu , Fe2+, Mg2+, Mn2+, Ni2+, Pb2+, Zn2+, Hg2+, Na+, K+, Ag+) from the nitrate, chloride or perchlorate salts were prepared with ultrapure water. NAHH (0.1 mM) stock solution was prepared in C2H5OH, and then diluted to different concentration for the Al3+ (NAHH: 5 μM) and Zn2+ (NAHH: 10 μM) detection by fluorescence and UV–vis spectroscopy, respectively. The excitation wavelength was set at λ = 380 nm which was used for fluorescence experiments and the slits including excitation and the emission all were set to10 nm. According to the method provided in the literature [63,64], the quantum yield was calculated by following the formula: ΦF(X) = ΦF(S) (As Fx/Ax Fs) (ηx/ηs)2, using quinine sulfate (ΦF(S) = 0.55) as a reference. 2+

2.3. IR spectra measurement Al(NO3)3·9H2O (15.1 mg, 0.036 mmol) and Zn(ClO4)2·6H2O (13.4 mg, 0.036 mmol) was added to C2H5OH solution (10 mL) of NAHH (10 mg, 0.036 mmol), respectively. Then the mixture was stirred and refluxed for 2 h. The precipitate was filtered and dried, and IR spectra were obtained by KBr pallet method. 2.4. Imaging in plants The soybean roots were used to explore the application ability of the probe NAHH in biological systems. The soybeans obtained from the local market were immersed in deionized water at 30 °C for 4 h to expand. The beans were put into a petri dish with moist filter paper and placed in a constant temperature incubator (30 °C). When the roots length of the soybean reached 3–4 cm, the obtained seedlings were cultured in a solution of Zn2+ for 24 h, and then cultured in a probe solution for 2 h to obtain an imaged plant. The control plants were treated by three methods, one was treated with deionized water only, the other was treated with Zn2+ without probes, and the last one was incubated with probes but not Zn2+. All plants were treated with purified water prior to imaging.

2.5. Synthesis of NAHH The compound 6-hydroxy-2-naphthohydrazide was prepared by adopting the reported procedure [65]. As shown in Scheme 1, a solution (10 mL) of 2hydroxybenzaldehyde (234 mg, 1.92 mmol) in C2H5OH was added to a C2H5OH solution (10 mL) containing 6-hydroxy-2naphthohydrazide (293 mg, 1.47 mmol), and the reaction mixture was refluxed for 4 h. After cooling to room temperature, the solvent was removed and the solid was recrystallized from C2H5OH to achieve yellow powder solid (213 mg). Yield: 72.0%. m.p. 276–277. 1H NMR (Fig. S1) (600 MHz, DMSO-d6) δ (ppm) 12.18 (s, 1H), 11.38 (s, 1H), 10.13 (s, 1H), 8.68 (s, 1H), 8.46 (s, 1H), 7.93 (dd, J = 14.0, 8.9 Hz, 2H), 7.82 (d, J = 8.6 Hz, 1H), 7.61–7.52 (m, 1H), 7.35–7.29 (m, 1H), 7.24–7.17 (m, 2H), 6.99–6.91 (m, 2H). 13C NMR (Fig. S2) (151 MHz, DMSO-d6) δ 163.44, 157.96, 157.74, 148.43, 136.93, 131.77, 131.26, 130.05, 128.66, 127.26, 127.06, 126.76, 124.93, 120.13, 119.82, 119.23, 116.91, 109.21. HRMS: m/z (TOF MS ES−) (Fig. S3): Calcd. for C18H14N2O3: 305.0926 [NAHH-H+]−, found: 305.0932. 3. Results and discussion 3.1. Spectrum investigation Excellent selectivity is the essential factor for a fluorescent sensor. To estimate the selectivity of the probe NAHH, the fluorescence spectroscopy of NAHH toward different cations (Al3+, Fe3+, Cr3+, Ca2+, Cd2+, Co2+, Cu2+, Fe2+, Mg2+, Mn2+, Ni2+, Pb2+, Zn2+, Hg2+, Na+, K+, Ag+) were investigated in C2H5OH solution, respectively (Fig. 1). The free NAHH (λex = 380 nm) showing week emission with a poor fluorescence quantum yield (φ = 0.13%) was attributed to the mechanism of photo-induced electron transfer (PET) which was caused by electron transfer from nitrogen atom of imino (C=N) group to conjugated π system of naphthalene fluorophore [61,62], and the C_N isomerization which dissipated the excited state energy of NAHH, thus causing nonradiative emission [58]. Interestingly, the addition of Al3+ ion to the solution of NAHH (5 μM) induced not only a significant fluorescence enhancement (φ = 32.46%), but also an obvious blue-shift of emission peak from 503 nm to 456 nm (Fig. 1a) accompanied with the color change from dark gray to light blue. In contrast, the presence of other metal ions displayed acceptable fluorescence changes, which indicated a high selectivity of probe NAHH toward Al3+. Since the high fluorescence selectivity of NAHH toward Al3+, the UV–vis spectrum of NAHH in the absence and presence of Al3+ were further investigated (Fig. 1b), respectively. The result of NAHH itself displayed a maximum absorption band centered at 334 nm, which was caused by the π-π* transition of the imine units [31]. Upon the addition of Al3+, the maximum absorption band centered at 334 nm slightly shifted to 331 nm while a new band maximum at 384 nm emerged, indicated the occurrence of interaction between NAHH and Al3+. Similarly, the significant fluorescent change was detected upon the addition of Zn2+ to the solution of NAHH (10 μM). The fluorescence intensity centered at 503 nm was enhanced with higher fluorescence quantum yield (φ = 6.62%) compared with that of NAHH itself (φ = 0.13%) (Fig. 2a). Meanwhile, an obvious color change from colorless to green was observed (Fig. 2a, inset). Moreover, the UV–vis spectrum of NAHH also showed significant change upon the addition of Zn2+ (Fig. 2b) accompanied with color change from colorless to pale green under daylight (Fig. 2b, inset). This result could be ascribed to the formation of the NAHH-Zn2+ complexes which could inhibit the occurrence of C_N isomerization and PET process. In order to exclude the possibility that the enhancement of fluorescence intensity with increasing of Al3+ or Zn2+ concentration might be caused by the emission of pure Al3+ or Zn2+ in C2H5OH solution. The fluorescence spectra of C2H5OH solution containing different concentrations of Al3+ (10 μM, 50 μM and 100 μM) (Fig. S4) or Zn2+ (10

Please cite this article as: X.-J. Sun, T.-T. Liu, N.-N. Li, et al., A novel dual-function probe for recognition of Zn2+ and Al3+ and its application in real samples, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117786

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Scheme 1. Synthesis route of NAHH.

μM, 50 μM and 100 μM) (Fig. S5) were measured, respectively. The results showed that the pure Al3+/Zn2+ of C2H5OH solution had almost no fluorescence emission, which further confirmed that the enhancement of fluorescence intensity was caused by the interaction between NAHH and Al3+/Zn2+. In addition, the fluorescence responses of NAHH to Al3+/Zn2+ in various solvents (including C2H5OH, CH3OH, DMF, DMSO, acetone, acetonitrile, CH3Cl and THF) were also examined. The results showed that the most remarkable enhancement in fluorescence intensity of NAHH in the presence of Al3+ (Fig. S6) or Zn2+ (Fig. S7) were all in C2H5OH solution. Hence, C2H5OH was chosen as the solvent for the detection of Al3 + and Zn2+. In order to conduct quantity analysis for the Al3+ and Zn2+, the sensitivities of NAHH for Al3+ and Zn2+ were performed by concentrations titration through fluorescence (Fig. 3) and UV–vis absorbance (Fig. 4) signals in C2H5OH solution, respectively. The fluorescence intensity increased gradually with the increasing concentration of Al3+ (Fig. 3a), and a good linear relationship in the concentration range from 3 μM to 6.5 μM was observed (Fig. S8). When the concentration of Al3+ reached 10 μM, the maximum intensity was achieved a platform (Fig. 3a, insert). As for the gradual addition of Zn2+ into the solution of NAHH (Fig. 3b), the fluorescence intensity of NAHH centered at 503 nm was also enhanced linearly with the Zn2+ concentration ranging from 2.5 μM to 7.5 μM (Fig. S9). The saturation concentration of Zn2+ was found at about 10 μM when the fluorescence intensity of NAHH remained constant (Fig. 3b, insert), which was similar to that of Al3+ concentrations titration. However, the fluorescence intensity of NAHH decreases a bit when Zn2+ concentration was more than 10 μM, which might be caused by the side effect of water came from the addition of the Zn(ClO4) aqueous solution during the titration experiment. Hence, verified experiments were carried out by gradual increasing the fraction of water from 1‰ to 50‰ in C2H5OH solution (containing 10 μM NAHH and 10 μM Zn2 + ) (Fig. S10). The result showed that the fluorescence intensity (λem = 503 nm) was decreased gradually with the enhancement of the

fraction of water in C2H5OH solution, and which could be significantly decreased to one third of the maximum when the fraction of water was 50‰, indicated that the probe NAHH in sensing Zn2+ was easily disturbed by the water and the acceptable volume fraction in C2H5OH solution was no more than 5‰. The titration results mentioned above indicated that the binding ratio of NAHH to Al3+/Zn2+ were all 1:1. Moreover, based on the reported method [32], the detection limits (calculated using 3σ/k, where σ is the standard deviation of the blank measurements, and k is the slope of the intensity ratio versus sample concentration plot) of NAHH to Al3+ and Zn2+ was determined as 7.55 × 10−8 M and 3.02 × 10−7 M, respectively. On the other hand, the coordinating potentiality of NAHH to Al3+/ 2+ Zn was further investigated by UV–vis titration experiments, respectively (Fig. 4). Upon successive addition of Al3+ ion, the band centered at 334 nm of NAHH was gradually decreased with a slightly 3 nm blue-shift, and a new peak at 383 nm emerged with the isosbestic point at 354 nm at the same time (Fig. 4a), indicating the complex formation between NAHH and Al3+. The absorbance of NAHH at 383 nm reached the platform when the addition of Al3+ was 10 μM, and a good linear relationship between the absorbance of NAHH and Al3+ was in the range of 0–8 μM (Fig. S11). Analogously, the sequential addition of Zn2+ to the NAHH solution displayed a gradually increased peak at 398 nm while the peak at 334 nm gradually decreased with a 9 nm blue-shift, indicated the occurrence of NAHH binding with Zn2+ (Fig. 4b). The absorbance of NAHH at 398 nm remained constant when the addition of Zn2+ was 10 μM, and a good linear relationship was observed between the absorbance of NAHH and Zn2+ ranging from 0 to 8 μM (Fig. S12). According to the results of UV–vis titration experiments of NAHH with Al3+ and Zn2+, the absorbance of NAHH almost reached a platform when the addition of Al3+ and Zn2+ were all 10 μM, which was similar to the result of fluorescence titration and further confirmed the binding ratio of NAHH to Al3+/Zn2+ mentioned above. Furthermore, the detection limit of NAHH for Al3+ and Zn2+ was calculated to be 1.36 × 10−7 M and 2.05 × 10−7 M, respectively.

Fig. 1. (a) Fluorescence selectivity spectrum of NAHH (5 μM) with various metal ions (25 μM) in C2H5OH solution (λex = 380 nm). Inset: Visual of the fluorescence change of the solution of NAHH (5 μM) and NAHH + Al3+ (25 μM) under UV light of 365 nm; (b) UV–vis absorption spectral of NAHH (5 μM) itself and in the presence of five equivalent amount of Al3+ in C2H5OH solution. (For interpretation of the references to color in this figure, the reader is referred to the web version of this article.)

Please cite this article as: X.-J. Sun, T.-T. Liu, N.-N. Li, et al., A novel dual-function probe for recognition of Zn2+ and Al3+ and its application in real samples, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117786

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Fig. 2. (a) Fluorescence selectivity spectrum of NAHH (10 μM) with various metal ions (50 μM) in C2H5OH solution (λex = 380 nm). Inset: Visual of the fluorescence change of the solution of (100 μM) and NAHH + Zn2+ (500 μM) under UV light of 365 nm. (b) UV–vis absorption spectral change of NAHH (10 μM) in presence of five equivalent amount of Zn2+ in C2H5OH solution; Inset: Visual of color change of the NAHH (100 μM) in C2H5OH solution of before and after addition of Zn2+ (500 μM) under daylight. (For interpretation of the references to color in this figure, the reader is referred to the web version of this article.)

3.2. Metal ions competition investigation To further explore the utility of probe NAHH for Al3+ and Zn2+ ions, competition experiments were carried out in presence of various competing metal ions by measuring the maximum fluorescence intensity centered at 503 nm under the same condition (Fig. 5). NAHH was treated with Al3+ and Zn2+ in the presence of other competitive metal ions with same concentration, respectively. The result showed other competitive cations had insignificant interference for the Al3+/ Zn2+ sensing, indicating the high selectivity of probe NAHH in the sensing of Al3+ and Zn2+ ions.

and kept stable for probe NAHH in sensing Al3+ (Fig. 6a) compared with that of in sensing Zn2+ which fluorescence intensity of probe NAHH (λem = 503 nm) showed saturated instantaneously and remained almost unchanged more than 100 s (Fig. 6b). Interestingly, the NAHH solution color was changed from light green to light blue in the case of co-existence of Al3+ and Zn2+ after a certain time (Video S1). The above result suggested that the binding process of NAHH toward Zn2+ was faster than that of Al3+, and it could be used to judge whether the co-existence of Al3+ and Zn2+ was exist or not in a pending tested sample. Especially, this property might be used as calculating time through color change illustrated in Fig. S13. 3.4. Sensing mechanism

3.3. Time response To evaluate the sensitivity and stability of probe NAHH, the timedependent fluorescence response of NAHH in the presence of Al3+ and Zn2+ were recorded in C2H5OH solution illustrated in Fig. 6, respectively. The result showed that the response signal almost could be received immediately whatever in sensing Al3+ or Zn2+ but it took a relatively long response time to reach the maximum (λem = 456 nm)

The stoichiometry of NAHH with metal ions (Al3+ and Zn2+) was firstly determined by Job's plot analysis (Fig. 7), respectively. The total concentration of NAHH and Al3+ was kept constant at 10 μM during this experimental process, and the variable molar fraction of guest [Al3 + ]/([NAHH] + [Al3+]) was varied from 0.1 to 0.9 (Fig. 7a). On the other hand, the total concentration of NAHH and Zn2+ was kept constant at 50 μM while the mole fraction of Zn2+ was the same as that of

Fig. 3. (a) Fluorescence titration of probe (5 μM) with Al3+ (0–2.5 eq) in C2H5OH solution. Inset: plot of the emission intensities of NAHH (5 μM) as a function of externally added Al3+ at 456 nm (λex = 380 nm). (b) Fluorescence titration of probe (10 μM) with Zn2+ (0–2 eq) in C2H5OH solution. Inset: plot of the emission intensities of NAHH (10 μM) as a function of externally added Zn2+ at 503 nm (λex = 380 nm). (Error bar was represented as mean ± standard deviation, n = 3).

Please cite this article as: X.-J. Sun, T.-T. Liu, N.-N. Li, et al., A novel dual-function probe for recognition of Zn2+ and Al3+ and its application in real samples, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117786

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Fig. 4. (a) Absorption titration spectra of probe NAHH (5 μM) toward different concentrations of Al3+ in C2H5OH solution. (b) Absorption titration spectra of probe NAHH (10 μM) toward different concentrations of Zn2+ in C2H5OH solution. (Error bar was represented as mean ± standard deviation, n = 3).

Al3+ (Fig. 7b). The result showed that when the molar fraction was 0.5, the fluorescence intensity recorded at 456 nm for Al3+ and 503 nm for Zn2+ were all reached maximum, respectively. This indicated the stoichiometry complex between probe NAHH and Al3+/Zn2+ was all 1:1, which further confirmed the conclusion drew by the concentration titration experiments mentioned above. Furthermore, the association constant (K) was determined by using modified Benesi-Hildebrand plot equation [33] as followed.

n h io 3þ þ 1=ð F max − F min Þ 1=ð F−F min Þ ¼ 1= K ð F max −F min Þ Al

where, Fmax, F and Fmin are the fluorescence intensities of NAHH in the presence of Al3+/Zn2+ at saturation, at an intermediate Al3+ concentration, and absence of Al3+, respectively. K is the stability constant. Hence, according to the result of fluorescence titration of NAHH with Al3+ and Zn2+, the Benesi–Hildebrand plot all demonstrated good linearity with the corresponding correlation coefficient (R) of 0.98977 (Fig. S14) and 0.98944 (Fig. S15), respectively. The association constants of NAHH to Al3+ and Zn2+ were 4.45 × 105 M−1 and 8.48 × 104 M−1, respectively.

In order to accurate grasp the interaction between NAHH and Al3+/ Zn , the binding detail of NAHH with Al3+/Zn2+ was firstly reflected by FT-IR spectra compared with that of NAHH itself (Fig. 8). As for the IR spectrum of free NAHH, the stretching frequency of phenolic hydroxyl groups (-OH) and amide (-NH) were located at 3060 cm−1 and 3283 cm−1, respectively. However, all of them were disappeared in that of NAHH-Al3+, indicated the deprotonation of phenolic hydroxyl group and amide of NAHH during the binding process with Al3+. Moreover, the stretching bands of C_N of NAHH shifted from 1553 cm−1 to 1544 cm−1, indicating the enhancement of conjugate after the coordination of C_N group with Al3+. While the FT-IR spectra of NAHH-Zn2 + , the characteristic frequency of phenolic hydroxyl groups (-OH) was similar to that of NAHH-Al3+. Moreover, the stretching bands of C_O and C_N were all obviously shifted to 1612 cm−1 and 1545 cm−1, respectively. This revealed that the coordination NAHH might to chelate with Zn2+ via N atom of imine group, and O atoms from phenolic hydroxyl and carbonyl, respectively. 1 HNMR titration experiments were measured in DMSO-d6 to further confirm the binding sites of the NAHH with Al3+ and Zn2+ (Fig. 9), respectively. The proton signals at 11.38 ppm and 10.13 ppm were assigned to the phenolic hydroxyl (Hc) and amide (Hb) groups of NAHH, respectively. After the addition of Al3+, all of them were all disappeared (Fig. 9a), suggesting the deprotonation on hydroxyl and 2+

Fig. 5. (a) Competition selectivity of NAHH (5 μM) toward Al3+ (5 equiv.) in the presence of other metal ions (5 equiv.) with emission at 456 nm. (b) Competition selectivity of NAHH (10 μM) toward Zn2+ (5 equiv.) in the presence of other metal ions (5 equiv.) with emission at 503 nm.

Please cite this article as: X.-J. Sun, T.-T. Liu, N.-N. Li, et al., A novel dual-function probe for recognition of Zn2+ and Al3+ and its application in real samples, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117786

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Fig. 6. (a) Time-dependent fluorescence profile of NAHH (5 μM) after treatment with Al3+ ions (25 μM) in C2H5OH solution at 456 nm. λex = 380 nm (b) Time-dependent fluorescence profile of NAHH (10 μM) after treatment with Zn2+ ions (50 μM) in C2H5OH solution at 503 nm (λex = 380 nm).

amide groups during the combination of NAHH with Al3+, which further confirmed the result obtained by FT-IR analysis. While the addition of Zn2+ to the solution of NAHH (Fig. 9b), the proton signal of the phenolic hydroxyl (Hc) and amide (Hb) were all weakened gradually, indicating the deprotonation of the phenolic hydroxyl (Hc) on probe NAHH. ESI-MS analyses were measured to explore the coordination of NAHH with Al3+ and Zn2+ in C2H5OH solution (Fig. 10), respectively. Peaks at m/z 395.1190 was attributed to [NAHH-2H++Al3++H2O + C2H5OH]+ (Calcd: 395.1188) generated in the spectra of NAHH + Al3+ (Fig. 10a). While in the spectra of NAHH + Zn2+ (Fig. 10b), peak at 401.0483 was attributed to [NAHH-H++Zn2++CH3OH]+ (Calcd: 401.0480). These results indicated the formation of stable complexes between probe NAHH and Al3+/Zn2+, respectively. Basing on the above results, the probable binding mechanism of both NAHH-Al3+ and NAHH-Zn2+ was illustrated in Scheme 2. 3.5. Reversibility investigation The reversibility was one of the most significant factors in the development of sensors for practical application. For better insight into the regeneration property of NAHH toward Al3+ and Zn2+ ions, the corresponding metal ions (3 equiv.) and EDTA (3 equiv.) were alternately added to NAHH solution to assess fluorescence reversibility of the NAHH (Fig. S16). The result indicated that the chelation process was reversible by adding appropriate agent such as EDTA. However, on the

premise of higher sensitivity of NAHH using the fluorescence intensity as response signal, the renewable performance only could be repeated three times, which limited its application in the development of logic device. In addition, several reported probes which could simultaneously recognize Al3+ and Zn2+ were outlined in Table 1 for comparative analysis [55–60]. 4. Applications 4.1. Application in real water samples analysis To explore potential feasibility of Probe NAHH for the determination of Al3+ and Zn2+ in real water sample [66,67]. The water samples were collected from the Songhua River and local region of campus in Heilongjiang Province. Al3+ and Zn2+ at different levels (3–8 μM) were spiked by water samples, and the fluorescence responses of Probe NAHH at 456 nm for Al3+ and 503 nm for Zn2+ in real water samples were determined, respectively. As shown in Fig. 11, with the increase of concentration of Al3+ in tested samples including tap water and Songhua water, the fluorescence intensity were all increased gradually (Fig. 11a), and which was similar to that of Zn2+ (Fig. 11b). Moreover, a good linearity was found between fluorescence intensity and Al3+/Zn2+ over the concentration range of 3–8 μM, which were illustrated in Figs. S17 and S18, respectively. The desirable recovery and relative standard deviations (R.S.D) values (Tables S1 and S2) indicated that Probe NAHH could be

Fig. 7. (a) Job's plot of NAHH (456 nm) with Al3+. (b) Job's plot of NAHH (503 nm) with Zn2+.

Please cite this article as: X.-J. Sun, T.-T. Liu, N.-N. Li, et al., A novel dual-function probe for recognition of Zn2+ and Al3+ and its application in real samples, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117786

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4.4. Imaging in plant Up to now, the detection of some analyte which can be imaged in cell is widely investigated by many researches for the application in biological systems. However, imaging in plant tissue is scarcely reported [57,71]. Hence, probe NAHH was employed to investigate its practical bioimaging of Zn2+ in the soybean roots. Freshly sprouted soybeans were used as a model and further processed in solutions of Zn2+ ions and the probe NAHH, respectively. As shown in the Fig. 14, only the plants treated with the solution of probe NAHH and Zn2+ showed strong green fluorescence which confirmed that the fluorescence enhancement of the plants was indeed caused by complexation of probe NAHH with Zn2+. The control plants showed blue fluorescence, which may be due to the spontaneous fluorescence of the vascular tissue of the soybean root itself, and so the application of Al3+ imaging could not be achieved in that condition. These results showed that NAHH was cell-permeable and capable of imaging of Zn2+ in plant tissue.

5. Conclusion Fig. 8. The FT-IR spectrum for the probe NAHH and Al3+/Zn2+ complex.

applied in quantitative analysis in real water sample for the detection of Al3+ and Zn2+. 4.2. Application in test paper To evaluate the application property of a probe, the development of application in test strips for one analyte detection is one of the most important factors due to its simple and cost-effective for fast and portable detection. Consideration the selectivity of probe NAHH to Al3+ and Zn2 + through the significant fluorescence color change, the test paper experiments for Al3+ and Zn2+ were investigated, respectively. Test papers were firstly immersed in NAHH solution containing different concentrations of Al3+ (10, 20, 30, 40 and 50 μM) and Zn2+ (100, 200, 300, 400 and 500 μM), respectively. After dried in air, as depicted in Fig. 12, the color of the test paper changed from indigo to light blue with the increasing of Al3+ concentration under 365 nm ultraviolet light (Fig. 12a, bottom). While for the increasing concentration of Zn2 + , the color of the test paper was gradually changed from lake blue to light blue under 365 nm ultraviolet light (Fig. 12b, bottom). These results indicated that the probe NAHH can detect Al3+ or Zn2+ conveniently in the actual sample through the test paper.

In summary, a simple Schiff-based dual-functional probe NAHH was designed and synthesized which displayed fluorescence turn-on to Al3+ and Zn2+ with different emission wavelength. Job's plot confirmed the complex of NAHH-Al3+ and NAHH-Zn2+ were all 1:1 stoichiometry. Especially, NAHH achieved in discrimination Zn2+ from Al3+ by color change through “naked-eye” detection. Moreover, probe NAHH had been successfully applied in the detection Al3+ and Zn2+ in real water samples, fast and portable detection by test strips, logic gate construction and imaging of Zn2+ in plant. Supplementary data to this article can be found online at https://doi. org/10.1016/j.saa.2019.117786.

Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgements This work was supported by the Postdoctoral Scientific Research Developmental Fund of Heilongjiang Province (No. LBH-Q14023). References

4.3. Logic gates representation Recently, molecular logic has received much more attention [68–70] in supramolecular systems. The feature of sensor NAHH persuaded us to exploit a logic gate base on given binary system. And then, a system consisting of chemically coded information (Al3+ and Zn2+) as input (X and Y) and fluorescent signals from two emission (456 nm and 503 nm) bands as output (1 and 2) was designed (Fig. 13a). For input, the present of Al3+/Zn2+ and absence of Al3+/Zn2+ are assigned as the “1” state and the “0” state, respectively. In the absence of chemical input, NAHH showed no emission band. However, the addition of Al3+ (5 equiv.) to the solution of NAHH produced an emission band at 456 nm, and the addition of Zn2+ (5 equiv.) to NAHH produced a fluorescence peak at 503 nm (Fig. 13b). Due to the above behavior, the molecular system NAAH provides a potential structure for simulating an INHIBIT logic gate with a YES logic function. For the YES logic gate, Output1 is in the state “1” only if Al3+ is present. In addition, Output 2 results in an INHIBIT logic gate which is the combine of AND and NOT gates. Hence, a logic circuit with logic gates above was constructed to detect Zn2+ ions and Al3+ ions (Fig. 13c), respectively.

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Please cite this article as: X.-J. Sun, T.-T. Liu, N.-N. Li, et al., A novel dual-function probe for recognition of Zn2+ and Al3+ and its application in real samples, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117786

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Scheme 2. Proposed mechanism of NAHH in sensing Al3+ and Zn2+.

t1:1 t1:2

Table 1 Comparison of the characteristics with previously reported sensors for Al3+/Zn2+.

t1:3

Ref.

Analyte

Methods of detection

LOD

Binding Constants

Application

t1:4

[55]

Al3+ Zn2+

Fluorescent

10.04 × 10−8 M 4.98 × 10−8 M

2.13 × 103 M−1 1.62 × 104 M−1

Logic gate

t1:5

[56]

Al3+ Zn2+

Fluorescent

3.7 × 10−9 M 3.0 × 10−8 M

1.16 × 104 M−1 2.08 × 104 M−1

Real sample Test strips Cell imaging

t1:6

[57]

Al3+ Zn2+

Fluorescent

8.04 × 10−7 M 7.95 × 10−7 M

1.66 × 104 M−1 0.60 × 104 M−1

Real sample Cell imaging

t1:7

[58]

Al3+ Zn2+

Fluorescent

8.30 × 10−8 M 1.24 × 10−7 M

1.30 × 106 M−1 7.90 × 104 M−1

Logic gate Cell imaging

t1:8

[59]

Al3+ Zn2+

Fluorescent

1.27 × 10−7 M 5.50 × 10−8 M

3.50 × 109 M−1 4.27 × 104 M−1

Logic gate Cell imaging

t1:9

[60]

Al3+ Zn2+

Fluorescent

5.22 × 10−8 M 7.88 × 10−8 M

6.45 × 102 M-1/2 1.73 × 106 M−1

Real sample

t1:10

This work

Al3+ Zn2+

Fluorescent Absorbance

7.55 × 10−8 M 1.36 × 10−7 M 3.02 × 10−7 M 2.05 × 10−7 M

4.45 × 105 M−1/ 1.59 × 105 M−1 8.48 × 104 M−1/ 3.53 × 104 M−1

Real sample Test strips Logic gate Plant imaging

Probes

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Fig. 11. (a) Fluorescent response of Probe NAHH (5 μM) in “tap water” and “the Songhua River water” in C2H5OH solution upon addition of different concentration of Al3+ (λex = 380 nm, λem = 456 nm); (b) Fluorescent response of Probe NAHH (5 μM) in “tap water” and “the Songhua River water” in C2H5OH solution upon addition of different concentration of Zn2+ (λex = 380 nm, λem = 456 nm).

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Fig. 12. (a) Test strip of probe NAHH (10 μM) for different concentrations of Al3+ under daylight (top) and UV lamp at 365 nm (bottom); (b) test strip of probe NAHH (100 μM) for different concentrations of Zn2+ under daylight (top) and UV lamp at 365 nm (bottom). (For interpretation of the references to color in this figure, the reader is referred to the web version of this article.)

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X.-J. Sun et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy xxx (xxxx) xxx

Fig. 13. (a) Truth table of NAHH/Al3+/Zn2+ for pictorial representation of molecular logic gate; (b) output response figure; (c) respective logic gates histogram.

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Fig. 14. Images of the soybean root (a) under the daylight and (b) under the UV lamp 365 nm. From left to right: plants was only incubated with deionized water; plants was treated with Zn2+ (100 μM) for 24 h; plants was only incubated with probe (100 μM) for 2 h; and plants was incubated with Zn2+ (100 μM) for 24 h and then with probe (100 μM) for 2 h.

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Please cite this article as: X.-J. Sun, T.-T. Liu, N.-N. Li, et al., A novel dual-function probe for recognition of Zn2+ and Al3+ and its application in real samples, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, https://doi.org/10.1016/j.saa.2019.117786