Fluorescent Light-Up Detection of Amine Vapors Based on

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Fluorescent Light-Up Detection of Amine Vapors Based on Aggregation-Induced Emission Meng Gao,† Shiwu Li,† Yuhan Lin,† Yi Geng,† Xia Ling,† Luochao Wang,† Anjun Qin,*,† and Ben Zhong Tang*,†,‡ †

Guangdong Innovative Research Team, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China ‡ Department of Chemistry, Institute for Advanced Study, Institute of Molecular Functional Materials, State Key Laboratory of Molecular Neuroscience, and Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China S Supporting Information *

ABSTRACT: Amines play vital roles in agricultural, pharmaceutical, and food industries, but volatile amine vapors are serious threats to human health. Previously reported fluorescent sensors for amine vapor detection usually suffer from aggregation-caused quenching (ACQ) effect and need to be dispersed in solution or matrix materials. Herein, based on the fluorogen of 2-(2-hydroxyphenyl)quinazolin-4(3H)-one (HPQ) with aggregation-induced emission (AIE) properties, we have developed a fluorescent sensor HPQ-Ac for light-up detection of amine vapors through aminolysis reaction. The portable HPQ-Ac sensor can be easily prepared by directly depositing on filter paper, and it can only light up via exposure to amine vapors among various volatile organic compounds. Taking advantage of its portability and high sensitivity for amine vapors, HPQ-Ac sensor can also be used for food spoilage detection and fluorescent invisible ink. KEYWORDS: aggregation-induced emission, fluorescent sensor, amine vapors, light-up detection

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as portable sensors, which are highly emissive in aggregation state and do not need to be dispersed in solution or matrix materials.23,24 Herein, we have developed a fluorescent and portable sensor HPQ-Ac for light-up detection of amine vapors based on the fluorogen of 2-(2-hydroxyphenyl)quinazolin4(3H)-one (HPQ), which is highly emissive in the solid state (Scheme 1).25,26 HPQ has typical aggregation-induced emission (AIE) properties by virtue of excited state intramolecular proton transfer (ESIPT) and restriction of intramolecular motion (RIM) mechanisms.27 The protection of

ynthetic amines are produced in millions of tons each year and have broad applications in agricultural, pharmaceutical, and food industries.1,2 Biogenic and volatile amines are also widely generated by degradation of amino acids in biometabolism, and their abnormal high level can be used as an indicator for food spoilage3,4 or as biomarkers for various diseases, such as lung cancer,5 uremia,6 and hepatopathy.7 Despite the wide applications of amines, the volatile amine vapors are toxic, irritant, and corrosive to human skin, eyes, and respiratory system.1 It is thus critical to develop efficient methods for their detection. Conventional detection methods for amine vapors are based on GC−MS,8 HPLC,9 electrochemical systems,10,11 and colorimetric arrays,12,13 but they usually require large stationary instruments and complex components, which impede their applications in resourcelimited fields. Recently, fluorescent sensors for amines detection have shown great advantages with high sensitivity, low cost, and easy operation.14−22 However, most of them are based on fluorogens with aggregation-caused quenching (ACQ) properties and need to be diluted in solutions or dispersed in matrix materials, which will complicate the preparation processes and reduce the portability. It is thus highly desirable to develop easily fabricated and portable fluorescent sensors for amine vapors detection. Recently, fluorogens with aggregation-induced emission (AIE) properties have shown great potential to be developed © 2015 American Chemical Society

Scheme 1. Design Principle of Fluorescent Sensor HPQ-Ac for Light-Up Detection of Amine Vapors

Received: October 24, 2015 Accepted: November 30, 2015 Published: December 8, 2015 179

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from 0 to 90 vol %, it increased rapidly with further increasing water fractions from 90 to 99 vol %. The fluorescence quantum yields of HPQ also increased from 0.3% in THF to 32.4% in H2O/THF (99:1, v/v) and further to 59.4% in the solid state. The large Stokes shift (159 nm) of HPQ exhibited in H2O/ THF (99:1, v/v) indicates that the ESIPT process can smoothly proceed in aggregation state by avoiding the disruption on intramolecular hydrogen bond from polar solvents. The strong fluorescence emission and large Stokes shift of HPQ in aggregation state is due to the synergistic effect of excited state intramolecular proton transfer (ESIPT) and restriction of intramolecular motion (RIM) mechanisms. A theoretical calculation was carried out to help understand the photophysical properties of HPQ, and the energy gap between the LUMO and HOMO levels was found to be equal to 4.23 eV (Figure S4). To demonstrate that HPQ-Ac can be used as a light-up senor in aggregation state, we further measured the UV and photoluminescence (PL) spectra of HPQ-Ac and HPQ in H2O/THF (99:1, v/v) (Figure 2). HPQ-Ac shows a maximum absorption wavelength at 285 nm and negligible fluorescence, while HPQ shows a red-shifted absorption and an intense fluorescence with maximum emission at 492 nm. This experiment shows that HPQ-Ac is potential to be used as a fluorescent light-up sensor in aggregation state through cleavage of the O-acetyl bond to yield highly emissive HPQ product. HPQ-Ac as a portable sensor for amine vapors detection was then illustrated by using ammonia vapor as an example. A 20 μL CH2Cl2 solution of HPQ-Ac (10 mM) was dropped on filter paper and dried by evaporation to easily provide a portable sensor. As shown in Figure 3, HPQ-Ac on filter paper itself was almost nonemissive under UV irradiation, but its fluorescence intensity increased rapidly after exposure to increasing ammonia vapor concentration. For example, when ammonia vapor concentration was higher than 20 ppm (maximum allowed concentration at working place),2 the strong fluorescence can be directly observed by naked eye with the assistance of a portable UV lamp. Based on the signal-tonoise ratio method, the detection limit (3δ/S) for ammonia vapor was calculated to be 8.4 ppm (Figure S5). The fluorescence spectra of HPQ-Ac were also measured with

phenoxyl group with acetyl group in HPQ-Ac can efficiently quench its fluorescence by disrupting the intramolecular hydrogen bond and blocking the ESIPT process.28 After reaction with amine vapors to cleave the O-acetyl bond through aminolysis reaction, the generated HPQ will recover its fluorescence by restoring intramolecular hydrogen bond and restriction of intramolecular motion in aggregation or solid state.

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RESULTS AND DISCCUSION The synthetic route to HPQ-Ac is shown in Scheme 2. The reaction of 2-aminobenzamide 1 and salicylaldehyde 2 in the Scheme 2. Synthetic route to HPQ and HPQ-Ac

presence of iodine as oxidant can efficiently afford compound 2-(2-hydroxyphenyl)quinazolin-4(3H)-one (HPQ) in 82% yield. Further reaction of HPQ with sodium methoxide and acetyl anhydride can afford HPQ-Ac in 95% yield. Their structures were confirmed with NMR and mass spectroscopies (Figures S1 and S2). We first investigated the AIE properties of HPQ by measuring its UV and photoluminescence (PL) spectra in THF/water mixture with different water fractions (Figure 1). The increasing water fractions in THF/water mixture can reduce the solubility of HPQ and induce the formation of nanoaggregates (Figure S3). Although the fluorescence intensity of HPQ remained low with water fractions ranging

Figure 1. (A) Normalized UV−vis absorption spectra of HPQ in THF (dashed line); PL spectra of HPQ in THF and THF/water mixtures with different water fractions ( f w); [HPQ] = 10 μM; λex = 333 nm. (B) Plot of relative PL intensity (I/I0) of HPQ at 492 nm versus the solvent composition of THF/water mixture. Inset: Photographs of HPQ in THF and H2O/THF (99:1, v/v) taken under UV light (365 nm). 180

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Figure 4. Normalized UV−vis absorption spectra in THF of HPQ, HPQ-Ac, and the reaction product of HPQ-Ac with ammonia vapor; [HPQ] = [HPQ-Ac] = 10 μM.

Figure 2. UV−vis absorption (dashed line) and PL (solid line) spectra of HPQ-Ac (red) and HPQ (black) in H2O/THF (99:1, v/v). Inset: Photographs of HPQ-Ac (left) and HPQ (right) in H2O/THF (99:1, v/v) taken under UV light. [HPQ-Ac] = [HPQ] = 10 μM.

Figure 3. Fluorescent emission spectra of HPQ-Ac loaded filter paper after exposure to ammonia vapor (0, 10, 22, 37, 50, 144, 331, 360 ppm) for 5 min. Excitation wavelength: 333 nm. Inset: Photographs of HPQ-Ac treated with ammonia vapor taken under UV light (365 nm).

Figure 5. Light-up ratio (I/I0) for amine vapors detection, where I0 and I are the PL intensities of HPQ-Ac at 492 nm and that upon exposure with various amine vapors generated from their corresponding aqueous or methanolic solutions (0.08 M). Excitation wavelength: 333 nm.

increased exposure time to ammonia vapor at 360 ppm, and a fast light-up process to full brightness was observed in minutes (Figure S6). These experiments clearly demonstrate that HPQAc loaded on filter paper can be used as a portable sensor for ammonia vapor detection with advantages of excellent portability and simple operation. To verify that ammonia vapor could cleave the O-acetyl bond in HPQ-Ac to yield HPQ product, the UV−vis absorption spectrum for the reaction product of HPQ-Ac with ammonia vapor was measured, and it overlapped very well with that of HPQ. This experiment demonstrates that the reaction of ammonia vapor with HPQ-Ac is efficient enough to completely cleave the O-acetyl bond (Figure 4). The detection ability of HPQ-Ac sensor toward various amine vapors was then investigated (Figure 5). The excellent light-up ratios (I/I0) for ammonia, hydrazine, and alkyl amines

(benzylamine, EtNH2, Et2NH, NMe3, Et3N) indicate that these amine vapors can efficiently cleave the O-acetyl bond to generate highly emissive HPQ product through aminolysis reaction.29,30 However, for aromatic amines (aniline, 2methylaniline), significantly decreased light-up ratios were observed due to their much lower basicity and nucleophilicity caused by delocalization of electrons on nitrogen into the aromatic ring. 31 Biogenic amines, such as putrescine, cadaverine, and histamine, cannot efficiently light-up the HPQ-Ac sensor due to their low volatile property.32 For various organic solvent vapors screened, such as hexane, CH2Cl2, EtOAc, THF, MeCN, MeOH, and EtOH, almost no light-up response was observed (Figures S7). These experiments demonstrate that HPQ-Ac sensor can be used for 181

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active HPQ product. The portable HPQ-Ac sensor can be easily prepared by directly depositing on filter paper and the light-up fluorescence can be observed even by naked eye with the assistance of a UV lamp. The HPQ-Ac sensor has significant advantages in excellent light-up ratio and high selectivity toward amine vapors than other volatile organic compounds. Taking advantage of its portability and high sensitivity for amine vapors, the HPQ-Ac sensor can be used for food spoilage monitoring by detection of volatile amines generated by microbial growth. Moreover, it can be used as fluorescent invisible ink revealed only by treatment with both ammonia vapor and UV light. Thus, HPQ-Ac sensor with AIE characteristics is promising for broad applications in various fields.

selective light-up detection of amine vapors among various volatile organic compounds. As biogenic volatile amine vapors (e.g., NH3 and NMe3) generated by microbial growth are an important indicator for food spoilage,3,4 we then tested whether HPQ-Ac can be used as a food spoilage sensor using saury fish as an example. When saury fish was sealed in a plastic bag and stored at −20 °C for 2 days, only a very weak fluorescence was observed for HPQ-Ac loaded filter paper after placing it in the plastic bag for 5 min (Figure 6A). However, it showed a strong fluorescence when

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EXPERIMENTAL SECTION

Materials and Chemicals. THF was distilled from sodium under dry nitrogen prior to use. All chemicals and reagents were purchased from commercial sources and used as received without further purification. Equipment and Methods. UV−vis absorption spectra were measured on a Shimadzu UV-2600 spectrophotometer. Photoluminescence spectra were recorded on a Horiba Fluoromax-4 spectrofluorometer. Fluorescence quantum yields were measured using a Hamamatsu absolute PL quantum yield spectrometer C11347 Quantaurus_QY. Dynamic light scattering was measured using an ALV (Germany) apparatus. Theoretical calculations were performed using the Gaussian 09 program. 1H NMR and 13C NMR spectra were measured on a Bruker AV 500 NMR spectrometer. High resolution mass spectra (HRMS) were recorded on a GCT Premier CAB 048 mass spectrometer operated in MALDI-TOF model. Synthesis of 2-(2-Hydroxyphenyl)quinazolin-4(3H)-one (HPQ). A mixture of 2-aminobenzamide (272 mg, 2 mmol), salicylaldehyde (244 mg, 2 mmol), and iodine (508 mg, 2 mmol) in 15 mL of ethanol was stirred at reflux for 6 h. After the reaction completed, the excessive iodine was removed by adding Na2S2O3 aqueous solution (5 wt %). The generated precipitation was filtered and further washed by water (10 mL × 2) and ethanol (10 mL × 2), the resulting white solid was then dried under vacuum to afford HPQ as a white solid (390 mg, 82% yield). 1H NMR (d6-DMSO, 500 MHz): δ 13.78 (br s, 1H), 12.48 (br s, 1H), 8.23 (dd, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H), 8.16 (dd, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H), 7.86 (td, J1 = 8.5 Hz, J2 = 1.5 Hz, 1H), 7.77 (d, J = 8.0 Hz, 2H), 7.56 (td, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H), 7.46 (td, J1 = 8.0 Hz, J2 = 1.5 Hz, 1H), 7.02 (dd, J1 = 8.5 Hz, J2 = 1.0 Hz, 1H), 6.97 (td, J1 = 8.0 Hz, J2 = 1.0 Hz, 1H). 13C NMR (d6-DMSO, 125 MHz): 161.4, 160.0, 153.7, 146.1, 135.0, 133.7, 127.7, 127.0, 126.0, 120.7, 118.8, 117.9, 113.7. HRMS (ESI): m/z [M]+ calcd for C14H10N2O2, 238.0742; found, 238.0757. Synthesis of 2-(4-Oxo-3,4-dihydroquinazolin-2-yl)phenyl Acetate (HPQ-Ac). HPQ (238 mg, 1.0 mmol) was added into a methanol (5 mL) solution of MeONa (108 mg, 2.0 mmol), and the mixture was stirred at room temperature for 5 min. After the mixture became a clear solution, the solvent was removed under evaporation. Anhydrous THF (10 mL) and acetic anhydride (408 mg, 4.0 mmol) were then added under N2 atmosphere, and the mixture was stirred at room temperature for 2 h. The solvent was removed under evaporation, and the residue was washed with water and further dried under vacuum to afford HPQ-Ac as a white solid (266 mg, 95% yield). 1H NMR (CDCl3, 500 MHz): δ 10.42 (br s, 1H), 8.29 (dd, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 8.02 (dd, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 7.81− 7.79 (m, 2H), 7.59−7.56 (m, 1H), 7.54−7.50 (m, 1H), 7.44 (td, J1 = 7.5 Hz, J2 = 1.0 Hz, 1H), 7.28−7.26 (m, 1H), 2.32 (s, 3H). 13C NMR (CDCl3, 125 MHz): 168.9, 162.6, 149.7, 149.1, 148.4, 134.9, 132.3, 130.4, 127.9, 127.2, 126.7, 126.5, 126.0, 123.8, 120.9, 21.1. HRMS (ESI): m/z [M + H]+ calcd for C16H13N2O3, 281.0926; found, 281.0936. Preparation and Determination of Ammonia Vapor Concentration. A volume of 5 mL of ammonia solution with various

Figure 6. HPQ-Ac sensor for detection of amine vapors generated from saury fish stored at (A) −20 °C and (B) 25 °C for 2 days.

saury fish was kept at room temperature for 2 days, indicating fish spoilage and it being unsuitable for consumption (Figure 6B). This experiment demonstrates that HPQ-Ac can be used as a food spoilage sensor by efficient detection of amine vapors generated in food spoilage. Amine vapors have long been used for revealing invisible ink by inducing color formation.33 Due to the high brightness and photostability of HPQ,26 it is highly attractive to develop HPQAc into fluorescent invisible ink which can only be revealed by treatment with both amine vapors and UV light. To illustrate that HPQ-Ac can be used for fluorescent invisible ink, “AIE” letters were first written on filter paper with its CH2Cl2 solution (10 mM), which was invisible under daylight or UV light. After exposure to ammonia vapor, the highly emissive “AIE” letters can be clearly observed under UV light (Figure 7). It is

Figure 7. Photos of HPQ-Ac written “AIE” letters on filter paper before and after exposure to ammonia vapor under daylight and UV light.

noteworthy that, without UV light, “AIE” letters were still invisible. This experiment demonstrates that HPQ-Ac as fluorescent invisible ink has great potential in secret communications and anticounterfeiting labels.

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CONCLUSIONS We have developed a fluorescent sensor HPQ-Ac for light-up detection of amine vapors via aminolysis reaction to yield AIE182

DOI: 10.1021/acssensors.5b00182 ACS Sens. 2016, 1, 179−184

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ACS Sensors concentrations was placed at the bottoms of sealed 100 mL bottles. After ammonia vapor reached equilibrium with its aqueous solution by standing overnight at room temperature, the ammonia vapor concentration was determined by using Gastec ammonia detector tubes with a pump. Detection of Amine Vapors Based on HPQ-Ac Loaded Filter Paper. A volume of 20 μL of CH2Cl2 stock solution of the HPQ-Ac (10 mM) was drop-casted onto the Whatman filter paper followed by evaporation to dry. The HPQ-Ac loaded filter paper was exposed to different amine vapors generated from their corresponding 0.08 M aqueous (ammonia, hydrazine, alkyl amines) or methanolic (aromatic amines) solutions for 5 min, and then the light-up fluorescence was measured with a fluorimeter (excitation wavelength: 333 nm).

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssensors.5b00182. NMR spectra, dynamic light scattering spectra, molecular orbital amplitude plots of HOMO and LUMO of HPQ, the light-up ratio (I/I0) for ammonia vapor detection, time-dependent fluorescence spectra for ammonia vapor detection, and selectivity study of the sensor for various organic solvent vapors (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The work was financially supported by the Key Project of the Ministry of Science and Technology of China (2013CB834702); National Science Foundation of China (21490571, 21222402, and 21174120); the Fundamental Research Funds for the Central Universities (2015ZY013 and 2015ZZ104); the Research Grants Council of Hong Kong (604711, 602212, and HKUST2/CRF/10); Guangdong Innovative Research Team Program (201101C0105067115); China Postdoctoral Science Foundation Grant (2015M580716).

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