Size-matching Recognition of Biogenic Amines by Water-soluble Terphen[3]arene: Toward Visual Detection of Food Spoilage

Size-matching Recognition of Biogenic Amines by Water-soluble Terphen[3]arene: Toward Visual Detection of Food Spoilage | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 18 September 2025 V1 Latest version Share on Size-matching Recognition of Biogenic Amines by Water-soluble Terphen[3]arene: Toward Visual Detection of Food Spoilage Authors : Hong Yao 0000-0001-8868-3886 [email protected] , Baohong Yang , Jinwang Wang , Xiangting Sun , Wenyu Cao , Taibao Wei 0000-0001-6673-0602 , Qi Lin 0000-0002-3786-3593 , and Chunju Li Authors Info & Affiliations https://doi.org/10.22541/au.175819172.26878859/v1 166 views 132 downloads Contents Abstract Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract Convenient and efficient detection of biogenic amines (BAs) is crucial for ensuring food safety and quality, as well as for the diagnosis and treatment of diseases. In this study, terphen[3]arene macrocycle TP3 was designed and synthesized by skeleton extension, and further portal functionalized into the water-soluble derivative WTP3. Containing twelve carboxylation moieties and a medium-sized π-rich cavity, WTP3 showed good water solubility and host-guest performance with various aliphatic amines. Meanwhile, WTP3 exhibited excellent association affinities for aliphatic amines with large spatial sizes, such as 1,4-butanediamine (1,4-BDA), 1,5-pentanediamine (1,5-PDA), cyclohexylamine (CHA), di-n-butylamine (DBA) and tri-n-propylamine (TPA). Finally, a WTP3 -based smart label and portable detection device were constructed and successfully employed for the detection of aliphatic amines generated during food spoilage. With the help of AI technology, quantitative detection for aliphatic amines were expected to be further applied on intelligent packaging labels for food freshness. Cite this paper: Chin. J. Chem. 2024 , 42 , XXX—XXX. DOI: 10.1002/cjoc.202400XXX Size-matching Recognition of Biogenic Amines by Water-soluble Terphen[3]arene: Toward Visual Detection of Food Spoilage Hong Yao *a , Baohong Yang a , Jinwang Wang a , Xiangting Sun a , Wenyu Cao a , Tai-Bao Wei a , Qi Lin *a and Chunju Li b a Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, People’s Republic of China b Key Laboratory of Inorganic−Organic Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, Tianjin 300387, People’s Republic of China Terphenyl[3]arene | Aliphatic amine | Group substitution | Size-matching effect | Spoilage monitoring Comprehensive Summary Convenient and efficient detection of biogenic amines (BAs) is crucial for ensuring food safety and quality, as well as for the diagnosis and treatment of diseases. In this study, terphen[3]arene macrocycle TP3 was designed and synthesized by skeleton extension, and further portal functionalized into the water-soluble derivative WTP3. Containing twelve carboxylation moieties and a medium-sized π-rich cavity, WTP3 showed good water solubility and host-guest performance with various aliphatic amines. Meanwhile, WTP3 exhibited excellent association affinities for aliphatic amines with large spatial sizes, such as 1,4-butanediamine (1,4-BDA), 1,5-pentanediamine (1,5-PDA), cyclohexylamine (CHA), di-n-butylamine (DBA) and tri-n-propylamine (TPA). Finally, a WTP3 -based smart label and portable detection device were constructed and successfully employed for the detection of aliphatic amines generated during food spoilage. With the help of AI technology, quantitative detection for aliphatic amines were expected to be further applied on intelligent packaging labels for food freshness. Background and Originality Content In recent years, with the improvement of living standards and the explosive growth of food problems, food safety issues have attracted more and more attention [1-3] . Aquatic and meat product are a significant part of our diet as high-protein and high-fat food, and research has identified the presence of eight biogenic amines (BAs) exist in above foodstuffs including spermine, putrescine, cadaverine, tryptamine, phenylethylamine, spermidine, histamine and tyramine, which are prone to spoilage due to the activities of microorganisms [4] . Excessive intake of BAs especially simultaneous intake of multiple BAs can cause allergic reactions such as headache, nausea, palpitations, blood pressure changes and respiratory disorders, which can be life-threatening in severe cases [5-6] . Therefore, it is an urgent demand to develop timely and effective methods to detect the levels of biogenic amines, especially putrescine (1,4-butanediamine, 1,4-BDA) and cadaverine (1,5-pentanediamine, 1,5-PDA), to monitor the freshness of foodstuff. There have been many reports describing analytical methods for monitoring meat spoilage, including spectroscopy [7] , electropho- resis [8] , colorimetry [9] , mass balance [10] , electrochemistry [11] and fluorescence sensors [12] . However, traditional detection methods, such as fluorescent probe technology, often require expensive equipment and are dependent on highly trained operators [13] ). Currently, smartphone-assisted fluorescence analysis has been utilised for rapid detection of harmful and toxic substances. After capturing fluorescence images and extracting RGB values by smartphone, the conversion from light signals into digital signals was achieved and a linear relationship between concentration and RGB values was obtained. Compared with traditional visual analysis, colorimetric analysis based on smartphones can achieve higher sensitivity and accuracy, reducing errors of the naked eye. Therefore, developing an intelligent smartphone-assisted analysis and sensing system for real-time monitoring of meat quality remains highly significant. Macrocyclic compounds bearing unique pre-organized cavity structure and multiple noncovalent binding sites have attracted extensive attention since the birth of supramolecular chemistry [14-18] . In particular, methylene-linked macrocyclic arenes, such as calixarene [19,20] , resorcinarene [21] , pillararene [22-24] , hexnut[12]are ne [25] , geminiarene [26] , bowtiearene [27] , and prismarenes [28] , have been extensively studied over the past decade for their novel structures and excellent properties, showing great promise in supramolecular self-assembly, recognition and molecular machines [29] . Among the various factors influencing supramolecular recognition, the size-matching effect stands out as one of the most f undamental principles, playing a pivotal role in achieving efficient host–guest complexation and excellent selectivity [30-33] . To date, several supramolecular probes and sensing platforms have been designed based on host-guest interaction between cavities of host probes and specific target guest analytes [ 34,35] . However, the systematic exploration of size-matching-driven sensing platforms, especially those involving newly reported macrocyclic arenes, remains r elatively limited and warrants further investigation. Molecular recognition in aqueous environments is significantly important since most biological functions and processes occur in water. To address this challenge, water-soluble macrocyclic arenes have been selected as highly efficient assembly motifs for their inherent selectivity and excellent responsiveness [36] . Macrocyclic arenes provide well-defined hydrophobic cavities and tunable peripheral functionalities, making them particularly suitable for constructing efficient molecular recognition systems in aqueous media. Therefore, the development of synthetic approaches toward novel water-soluble macrocyclic molecule with larger, more rigid molecular skeletons and intrinsic fluorescence characteristics aim to expand the structural diversity of supramolecular building blocks and enable more effective sensing strategies in aqueous phase [37,38] . Inspired by previous work [39-43] , a water-soluble terphen[3]arene macrocycle compound WTP3 has been synthesized through skeleton extension and portal functionalization step by step (Fig. 1). Firstly, compared with previous reported smaller-size biphen[3]arenes, a skeleton extension strategy was employed by replacing biphenyl units with terphenyl units, thereby synthesizing an enlarged medium-sized terphen[3]arene macrocyclic compound TP3 . Subsequently, to enable biogenic amine recognition, a portal functionalization strategy was utilized, in which twelve carboxyl groups were rational introduced at the portals of WTP3 , enhancing its water solubility and binding affinity toward electropositive biogenic amines. To explore the feasibility of achieving controllable supramolecular self-assembly behaviours based on the size-matching effect, a series of aliphatic amine molecules with different structural sizes were used to evaluate the selectivity and responsiveness of WTP3 by testing the stability of the resulting host-guest complexes. The experiment results indicate that aliphatic amine guests with larger spatial structure consistently exhibit higher association affinities through constant value towards WTP3 . In addition, due to the good water solubility and outstanding response to amines guests, especially putrescine (1,4-BDA) and cadaverine (1,5-PDA), WTP3 was subsequently prepared into a durable and stable smart label, which was further applied to meat spoilage detection. Artificial intelligence (AI) [44] technology was used to evaluate the quality index values of spoiled shrimp by obtaining the fluorescence images of smart label, extracting colour change features and analysing the G/B value by line fitting method. This work demonstrates the potential application of water-soluble terphen[3]arene in food freshness detection. Fig. 1. Schematic illustration of the synthesis route of water-soluble terphen[3]arene WTP3 and its application in the visual detection of biogenic amines and food freshness, these small and triangular pyramids respectively represent small-sized and larger-sized aliphatic amine molecules. Results and Discussion A water-soluble terphen[3]arene WTP3 was successfully prepared by portal modification on macrocyclic skeleton endows WTP3 with excellent water solubility and lager cavity size (Fig. 1). The UV-vis absorption spectrum and fluorescence emission spectrum of WTP3 diluted solution (10 uM) were measured. The results show that the maximum absorption peak of WTP3 occurs at 310 nm and has a strong blue fluorescence emission at 380 nm which reaches the highest under 310 nm excitation (Fig. S6a and b†). Then the effect of pH on the fluorescence emission properties of WTP3 was investigated. As shown in Fig. S7†, in acidic media, WTP3 exhibits no fluorescence emission. With the increase of pH, the fluorescence emission intensity of WTP3 also increases, which might be applied in amines detection. Meanwhile the solid powder of WTP3 emits strong blue fluorescence under 310 nm irradiation. With the increase of pH, the fluorescence emission intensity of WTP3 also increases, which might be applied in amines detection. Meanwhile the solid powder of WTP3 emits strong blue fluorescence under 310 nm irradiation. Hence the recognition and adsorption performance of WTP3 for volatile aliphatic amine gases was carried out by exposing WTP3 powder under different volatile aliphatic amines including EDA, 1,4-BDA, CHA, ammonium hydroxide, TEA, DBA, TEOA and TPA (Fig. 5b). Results shown WTP3 can recognize 1,4-BDA, DBA and CHA obviously. After being fumigated by 1,4-BDA vapor, the fluorescence of WTP3 is enhanced with the color change from light blue to bright blue. Hence, WTP3 is an attractive nominee for sensing alkali compound in real applications with desirable fluorescence response peculiarities. It indicates that WTP3 could be regarded as a fluorescent sensing material to aliphatic amine compounds for further research. Inspired the influence of pH on the fluorescence intensity, the stimuli-responsive performances of WTP3 towards several aliphatic amine guests were studied in pure water, which include linear guests with different lengths n -Pro-A, n -Butyl-A, DEA, EDA, EOA, 1,4-BDA, 1,5-PDA, DBA, DMA and triangular pyramidal guests of different sizes TMA, TEA, TEOA, TPA and CHA (Fig. 2a). It can be clearly observed the fluorescent intensities of WTP3 increase with the addition of aliphatic amines, especially for DBA, TPA and CHA with bigger size. To verify that the fluorescence changes of WTP3 towards different aliphatic amines are caused by the entrance of guests into the cavity of WTP3 and the subsequent supramolecular assembly-induced emission enhancement (SAIEE) effect, control experiment was carried out by synthesizing the uncyclized water-soluble monomer compound WTP (Scheme S2†). As expected, monomer WTP shows negligible significant fluorescence response for above aliphatic amines (Fig. S8†). These results indicate that the macrocyclic structure of WTP3 is the key factor in the host-guest fluorescence response performance. Fig. 2. (a) Structural formulas of the aliphatic amines guests; (b) Fluorescence intensity of WTP3 at 310 nm in the presence of different aliphatic amines in water at room temperature. ([WTP3] = 10 μM，[amines] = 200 μM). The binding behaviours between WTP3 and eight typical guests in aqueous solution were investigated using fluorescence spectroscopy to evaluate the host-guest association affinity properties (Fig. 4, Fig. S9-14, S21†). Subsequently, the complete association constants (Ka) by linear least-squares fitting and the limit of detection (LOD) were determined and calculated by fluorescence titration based on 3σ/S method (Table 1). Table 1. Association Constant ( K a ) and Limit of detection (LOD) of WTP3 for eight amine guests in H 2 O at 25 °C. TMA 1.49 × 10 3 1.02 × 10 -6 TEA 8.93 × 10 4 5.13 × 10 -7 TPA 1.17 × 10 5 2.75 × 10 -7 TEOA 1.33 × 10 4 1.50 × 10 -7 DBA 1.67 × 10 6 2.94 × 10 -7 CHA 1.09 × 10 5 2.40 × 10 -7 1,4-BDA 1.30 × 10 5 1.88 × 10 -7 1,5-PDA 1.61 × 10 5 2.45× 10 -7 Comparison of the association constants ( K a ) revealed that WTP3 exhibited stronger binding with DBA, 1,5-PDA , 1,4-BDA, TPA and CHA, with K a values of 1.67 × 10 6 M -1 , 1.61 × 10 5 M -1 , 1.30 × 10 5 M -1 , 1.17 × 10 5 M -1 and 1.09 × 10 5 M -1 respectively, which are higher than those observed for TMA, TEA and TEOA, as expected. The lengths of the alkyl chain and the sizes of triangular pyramidal guests will significantly influence the stability for the macrocyclic-amine complex. It is speculated the size-matching effect should be the dominant factor of stability for the present host-guest complex. The stoichiometry ratios were verified to be 1:1 between WTP3 and the amine guests by the Job’s plot method ( Fig. 4d, Fig. S9-11d†). Fig. 3. (a) Chemical structure of 1,4-BDA, 1,5-PDA, WTP3 ; 1H NMR spectra (400 MHz, D 2 O, 298 K) of (b) 1,4-BDA and (c) 1,5-PDA in the presence of WTP3 ([G] = [H] = 12.0 mM，[H@G] = 12.0 mM). In addition, the 1 H NMR spectra also confirmed the strong host-guest interaction between WTP3 and aliphatic amines. As shown in Fig. 3b, the characteristic proton signals of methylene group (H4) and phenyl group (H1) on WTP3 are shifted to the downfield obviously when 1 equiv. of DBA was added. On the contrary, the protons located on the alkyl chain (Ha, Hb, Hc) of 1,4-BDA and 1,5-PDA were observed upfield shift due to the shielding effect of the electron-rich cavity of WTP3 accompanying with a significant broadening effect. The results showed 1,4-BDA and 1,5-PDA were successfully encapsulated in the cavity of WTP3 . Moreover, 1 H NMR titration experiments were performed in D 2 O with a constant concentration of WTP3 (6.0 mM) and variable concentrations of DBA and TPA to further investigate the host-guest self-assembly behaviours. Interestingly, the protons Ha~d of DBA moves rapidly to the high field at the beginning of 1 H-NMR titration (Fig. S15†) and then slowly tends to a constant value, indicating that the oligomer might be gradually transforming into a supramolecular polymer. Non-linear fitting method was used to analyse the data of 1 H NMR titration (Eq. S1, in Supporting Information), giving K a values of WTP3 with DBA and TPA were 8.40 × 10 2 M -1 and 1.42 × 10 2 M -1 respectively (Fig. S17a and b†). Fig. 4. Fluorescence titration spectra (a) and K a calculation (b) of WTP3 (10μM) in the presence of different concentrations of 1,4-BDA in water; (c) Limit of detection (LOD) for the WTP3 with DBA; (d) Job ’s plot method for the interaction between WTP3 and DBA constructed by fluorescence spectroscopy. (λex = 310 nm, slit width = 3 ~ 5 nm). Observed the above K a values calculated from different methods, it seemed that aliphatic amine guests owning larger spatial structure always show higher association constant. This may still be attributed to the size-matching effects between the aliphatic amine guests and macrocyclic host WTP3 . For instance, TPA, the largest among the tested triangular pyramidal guests, fits well into the cavity of WTP3 , whereas the much smaller TMA leads to size mismatch and an unstable host–guest complex (Scheme 1). Meanwhile, density functional theory (DFT) calculations are performed at the B3LYP/6-31G* basis level with the Gaussian 09 program [45] to better understand the relationship between molecular structures of guests and the luminescence properties of the induced macrocycle complexes. The molecular configurations, frontier molecular orbitals (Fig. S18†), weak interactions and energy gaps (Δ) between the HOMO and LUMO (Fig. S19†) of DBA, TPA, WTP3 , WTP3@DBA , WTP3@TPA were optimized and calculated. The independent gradient model (IGM) was employed to visualize the interaction isosurfaces between WTP3 and the guest molecules DBA and TPA, highlighting distinct interaction characteristics for each complex. [46,47] There are weak intermolecular interactions such as C-H‧‧‧O, N-H‧‧‧O and C-H‧‧‧π in host-guest complexes, which is consistent with our previous 1 H NMR titration. Comparing individual amines guests and macrocyclic host, the energy gaps of host-guest complex were changed obviously indicating the host-guest self-assembly behaviors. Compared with the individual guest, the decreased energy gap upon complexation contributes to the fluorescence enhancement observed in the self-assembly system. However, compared to the macrocyclic host, the increased energy gap contributes to the stability of host-guest assembly. Subsequently, SEM was employed to investigate the nanostructures of macrocyclic host WTP3 and its corresponding host-guest assemblies. As shown in Fig. S20†, it can be clearly observed that the free WTP3 exhibits irregularly morphology with a wrinkled and rough surface texture. However, the host-guest assemblies WTP3@G exhibit regular spherical cluster structure and coral-like structure. The distinctly different morphologies indicate a transformation in molecular organization upon guest inclusion. Fig. 5. (a) Fluorescence images of shrimp stored at different temperatures and times; (b) Fumigation experiments; (c) The change of fluorescence intensity of WTP3 with different time at 20℃ and -16℃. Notably, WTP3 is also capable of recognizing two typical biogenic anime (1,4-BDA and 1,5-PDA) as evidenced by the fluorescent spectra. The K a values were calculated to be 1.30 × 10 5 M -1 and 1.61× 10 5 M -1 respectively, with LOD determined to be 1.88 × 10 −7 M and 2.45 × 10 −7 M (Fig. 4, Fig. S21† ). To evaluate the gas-phase sensing performance of WTP3, small vials containing WTP3 solution were placed inside larger sealed containers filled with 1,4-BDA or CHA, and the fluorescence response of WTP3 to the amines was monitored over time. The results showed that obvious fluorescence enhancement was connected with the exposed time in volatile amines (Fig. S22†). Since both putrescine (1,4-BDA) and cadaverine (1,5-PDA) are typical volatile amines generated during the microbial decomposition of proteins in meats, the high sensitivity of WTP3 towards these analytes makes it a promising candidate for evaluating meat freshness. To this end, WTP3 -based smart label was prepared for more convenient and efficient on-site detection of meat corruption. Smart label and solution of WTP3 were simultaneously sealed in a glass box containing fresh shrimp sample and stored under both ambient and refrigerated conditions. As shown in Fig. 5, with the increase of storage time, the blue fluorescence of both the smart label and the detective solution became progressively stronger, indicating the shrimp spoilage and a corresponding increase in the concentration of volatile biogenic amines. The accelerated spoilage of shrimp at room temperature, in accordance with real-world conditions, confirmed the reliability and stability of the smart label under both ambient and refrigerated environments. Subsequently, a portable detection device was constructed (Fig. 1), featuring a compact and lightweight design suitable for on-site detection. The fluorescence images of the smart label under 310 nm UV light were then recorded and the corresponding RGB values were extracted using a mobile application (Color Picker). The G/B ratios were plotted against exposed time to generate a calibration curve achieving the improvement from the common qualitative test to accurate quantitative detection. Conclusions In summary, we have successfully developed an amine-responsive terphen[3]arene ( WTP3 ) through skeleton extension and carboxylic acid portal functionalization. Upon the addition of various aliphatic amines, WTP3 shows selective recognition toward guest molecules through host–guest interactions, accompanied by supramolecular aggregation induced emission enhancement (SAIEE) effects. The properties of these host–guest assemblies were systematically investigated using UV-vis spectroscopy, fluorescence spectroscopy, 1 H NMR, SEM and DFT theory calculation. The results revealed that the chain length and molecular size of the aliphatic amines significantly affect the stability of the macrocyclic-amine complexes, showing excellent consistency with size-matching effect. Benefiting from its high sensitivity to volatile amines in both solid and solution states, WTP3 was further applied in the fabrication of a smart label for monitoring meat spoilage through fluorescence colour changes. To enhance the accuracy and practicality of detection in real samples, a portable detection device and smartphone-relied RGB analysis were integrated. These findings are expected to provide valuable insights for the design and development of intelligent packaging labels for real-time food freshness monitoring. Experimental Synthesis of WTP3 Firstly, terphenyl monomer ( TP ) were synthesized according to a previous report [48] , then it was used as functional templates dissolved in 1,2-dichloroethane and 0.6 mL boron trifluoride diethyl etherate to afford terphen[3]arene ( TP3 ). Secondly, the perhydroxylated terphen[3]arene ( OH-TP3 ) can be conveniently prepared by the cleavage of the ether groups of TP3 through the reaction with an excess of BBr3 (4.52 mL), with a yield of 80%. Subsequently, OH-TP3 (0.36 g) was dissolved in 90 mL acetonitrile through the nucleophilic substitution reaction with ethyl bromoacetate (1.67 g) in the presence of an excess of K₂CO₃ to prepare the ethoxycarbonyl substituted terphen[3]arene ( COOEt-TP3 ) with a yield of 62%. COOEt-TP3 (0.7 g) is hydrolyzed in an aqueous solution of NaOH and then acidified with HCl to obtain the carboxylic acid substituted terphen[3]arene ( COOH-TP3 ), with a yield of 85%, and it is insoluble in water. Then, the water-soluble carboxylato-terphen[3]arene ( WTP3 ), a white solid powder, is obtained with a high yield (98%) by the reaction of COOH-TP3 (0.3 g) with ammonium hydroxide (25% - 28%) (120 mL), and it exhibits good solubility in an aqueous medium. For detailed synthesis, please refer to the supporting information Scheme S1. Host-guest binding affinity of WTP3 toward aliphatic amines In a 2 mL system of WTP3 (10 μM) measured in a UV-vis cuvette and a fluorescence cuvette, the absorption intensity at 310 nm and the optimal excitation and maximum emission wavelengths were identified at 300 nm and 370 nm, respectively. The prepare a solution containing the WTP3 substance with a pH ranging from 1 to 14 by using acidic and alkaline buffer solutions. Take photos and record the fluorescence emission properties of WTP3 at different pH values. Inspired the influence of pH on the fluorescence intensity of WTP3 , the host-guest binding abilities were studied by fluorescence spectrometer through measuring 2 mL of WTP3 (10 μM) solution and adding 20 equivalent amounts of several aliphatic amine guests in pure water, which include linear guests with different lengths n-propylamine (n-ProA), n-butylamine (n-Butyl-A), diethylamine (DEA), ethanolamine (EDA), ethanolamine (EOA), 1,4-butanediamine (1,4-BDA), 1,5-pentanediamine (1,5-PDA), di-n-butylamine (DBA), dimethylamine (DMA) and triangular pyramidal guests of different sizes trimethylamine (TMA), triethylamine (TEA), triethanolamine (TEOA), tri-n-propylamine (TPA) and cyclohexyl amine (CHA). Then perform fluorescence titration by continuously adding guest molecules to 2 mL of WTP3 (10 μM) in pure water to evaluate the host-guest association affinity. The association constants (Ka) were calculated by linear least-squares fitting and the limit of detection (LOD) were determined using fluorescence titration data based on 3σ/S method. As well the stoichiometry ratios were verified to be 1:1 between WTP3 and the amine guests by the Job’s plot method. Results revealed the lengths of the alkyl chain and the sizes of triangular pyramidal guests will significantly influence the stability for the macrocyclic-amine complex. It is speculated the size-matching effect should be the dominant factor of stability for the present host-guest complex. Control experiment According to the above method of synthesizing WTP3 , then we synthesized uncyclized water-soluble monomer compound WTP . Fluorescence measurements were carried out to examine its response toward the selected aliphatic amines (Fig. S8†). Sensing mechanism of WTP3 To explore the mechanism of strong host-guest interaction between WTP3 and aliphatic amines, WTP3 dissolved in a 0.5 mL D2O system (6.0 mM and 12.0 mM), variable concentrations guests of 1,4-BDA, 1,5-PDA, DBA and TPA were added respectively, then they were determined by 1H NMR. Meanwhile the optimized molecular structures in the ground and excited states were obtained at the B3LYP /6-31G level of density functional theory (DFT) and the B3LYP /6-31G level of time-dependent density functional theory (TDDFT). Fumigation experiments of WTP3 WTP3 was selected as amine-responsive macrocyclic. 9.2 mg of WTP3 powder was dissolved in 5 mL water in a beaker. An appropriate amount of sodium carboxymethyl cellulose and silica gel were added, and the mixture was stirred constantly to ensure the formation of a homogeneous solution. This mixture was evenly spread onto a glass plate and dried, then placed horizontally in a petri dish pre-infused with an appropriate amount of volatile organic amine solvent including EDA, 1,4-BDA, CHA, ammonium hydroxide, TPA, DBA, TEOA and TEA, and stored tightly at room temperature for 24 hours. Exposure of WTP3 powder to different volatile aliphatic amines was recorded. Smart label for visual food spoilage detection Non-fluorescent filter paper was cut into pieces with dimensions of 1.0 × 1.0 cm and circular pieces with a radius of 1.0 cm, then immersed in an aqueous solution of WTP3 (1 mM) for 30 minutes, romoved and air-dried. The filter paper showed uniform blue fluorescence under 310 nm UV light and was subsequently used in food spoilage detection experiments. Meat freshness detection device To evaluate the effectiveness of the WTP3-based smart label for monitoring food spoilage, an experimental device was designed using two transparent plastic packaging boxes of identical specifications, serving as experimental and control groups. Each box was configured with one smart label, a gel bottle containing 3 mL of WTP3 solution, and 25~30 g of fresh shrimp. The experimental group was stored at 20 °C to simulate room-temperature conditions, while the control group was kept at –16 °C to represent a frozen storage environment. Both boxes were sealed to maintain a consistent atmosphere, with the transparent packaging allowing for direct observation of the label. Dynamic monitoring was conducted at 12-hour intervals. At each time point, two key parameters were recorded: (1) fluorescence intensity using a standard fluorescence spectrometer, and (2) visual changes in the smart label under 310 nm UV light. The color changes were documented with reference to a predefined color comparison chart. To quantitatively analyze the color response of the smart label, images were captured at different time points using a smartphone. A color picker tool was used to extract the RGB values from each image. These values, particularly the green-to-blue (G/B) ratio, were plotted to construct a calibration curve correlating label color change with the degree of shrimp spoilage over time. Supporting Information The supporting information for this article is available on the WWW under https://doi.org/10.1002/cjoc.202500xxx. Acknowledgement This work was supported by the National Natural Science Foundation of China (NSFC) (No. 22061039，22165027, 22001214), the Top Leading Talents Project of Gansu Province, the Key R & D program of Gansu Province (21YF5GA066), Gansu Province College Industry Support Plan Project (No. 2022CYZC-18) References 1. Zhuang, Q.; Peng, Y.; Yang, D.; Nie, S.; Guo, Q.; Wang, Y.; Zhao. 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Manuscript received: XXXX, 2025 Manuscript revised: XXXX, 2025 Manuscript accepted: XXXX, 2025 Version of record online: XXXX, 2025 Left to Right: Hong Yao, Baohong Yang, Jinwang Wang, Wenyu Cao, Xiangting Sun, Tai-Bao Wei, Qi Lin, Chunju Li Entry for the Table of Contents Text for Table of Contents to summarize the article is required in 1‒3 lines. (The height of this row is fixed at 6.2 cm. Please adjust the image and text to fit this height.) Information & Authors Information Version history V1 Version 1 18 September 2025 Copyright This work is licensed under a Non Exclusive No Reuse License. Keywords aliphatic amine group substitution size-matching effect spoilage monitoring terphenyl[3]arene Authors Affiliations Hong Yao 0000-0001-8868-3886 [email protected] Northwest Normal University View all articles by this author Baohong Yang Northwest Normal University View all articles by this author Jinwang Wang Northwest Normal University View all articles by this author Xiangting Sun Northwest Normal University View all articles by this author Wenyu Cao Northwest Normal University View all articles by this author Taibao Wei 0000-0001-6673-0602 Northwest Normal University View all articles by this author Qi Lin 0000-0002-3786-3593 Northwest Normal University View all articles by this author Chunju Li Tianjin Normal University View all articles by this author Metrics & Citations Metrics Article Usage 166 views 132 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Hong Yao, Baohong Yang, Jinwang Wang, et al. 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