Detection of biogenic amine histamine using a triboelectric nanogenerator integrated biodegradable sensor

Abstract

Improperly preserved fish, like tuna or mackerel, can cause Scombroid food poisoning due to the presence of excess histamine, which triggers an allergic reaction in the human body. Although there are several sensitive and reliable histamine detection techniques, it remains challenging to develop portable, lightweight devices that enable rapid detection of histamine at any point in the fish production chain. Herein, we have demonstrated a self-powered biodegradable sensor using a triboelectric nanogenerator (TENG) to detect histamine. The TENG consists of two triboelectric layers: polycaprolactone (PCL) and wool fabric. The PCL TENG generates the highest output of 213 V, 640 nA, 70 μW power, and also demonstrates long-term stability. The biosensor was prepared using the PCL substrate with an interdigitated (IDT) patterned gold electrode, which was further functionalized with diamine oxidase (DAO) by a simple self-assembled monolayer (SAM) technique for the specific detection of histamine. Upon addition of histamine onto the sensor, DAO degrades the histamine and produces various byproducts, which leads to a change in resistance, further leading to a huge increment in the current output. The selectivity of the sensor by using various other biogenic amines, such as L-tyrosine and tyramine, was also demonstrated. The sensor indicated a good sensitivity of 0.07961 μA ppm⁻¹ with R² = 0.98 and a limit of detection (LOD) of 43.34 ppm. In addition, the biodegradable test of PCL has shown 42.4% degradability for up to 60 days. This work proposes an entirely novel approach for TENG-based biodegradable biosensor systems as well as a quick and efficient way to detect histamine.

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1. Introduction

Contaminated food can cause foodborne illnesses that affect millions of people worldwide every year.^1–3 Food safety is essential to protect public health and to ensure that the food we eat is free of harmful contaminants.^4,5 The decarboxylation process of alpha amino acids, which is the result of protein hydrolysis, forms most of the chemical structures that make up biogenic amines, which are organic molecules with relatively low molecular weight and basic characteristics.⁶ Each of these structures has at least one nitrogen atom. Biogenic amines are often recognized as key agents in the microbiological degradation of seafood and fish, as well as various other foods and beverages such as cheese, wine, meat, and fermented foods.^7,8

Histamine is a strong, biologically active molecule that is one of the most significant biogenic amines, which can cause a variety of responses, such as allergic reactions and food poisoning.^9,10 An amino acid known as histidine, present in some fish (like tuna and mackerel), is decarboxylated by microorganisms to form histamine. While foods containing low amounts of histamine are not generally considered to pose a health risk, eating foods high in histamine can lead to Scombroid food poisoning.^11,12 Because it is mostly associated with the ingestion of poisonous fish, this condition is also known as histamine fish poisoning.

The rapid increase in histamine levels in fish is mostly due to the presence of large amounts of histidine and inappropriate storage conditions (temperature >4 °C and/or long storage time) that promote bacterial activity. Additionally, freezing, heating, sterilization, and canning do not affect histamine levels.^13,14 Histamine detection not only ensures freshness and quality but also prevents food poisoning.^15,16 The most common analytical techniques for the analysis of histamine are mass spectrometric detection, fluorescence, gas/liquid chromatography coupled with UV-vis, and separation techniques.^17,18 These techniques are very reliable and selective but have several disadvantages, such as long analysis time, non-portable and expensive instruments, highly qualified instructors, laborious experiments, large amounts of chemicals and solvents, and waste.^19–21 Additionally, the device requires power to operate and is not portable, so on-site analysis is not viable. A comparison of the conventional method and the TENG-based self-powered sensing platforms for biogenic amines detection is provided in Table S1. Since histamine concentrations rise when fish are stored under inappropriate conditions, the development of portable devices that allow monitoring of histamine levels from fishing to consumption is essential.

Self-powered biosensors are increasingly popular due to their rapid analysis, reliable results, adaptability, compactness, portability, and elimination of the requirement to operate a power source. These self-powered systems use triboelectric nanogenerators (TENGs) to convert waste mechanical energy into electrical energy without the use of a battery.²² Furthermore, TENGs can generate electrical energy from low mechanical stimuli, and it has a cost-effective fabrication process.²³ The self-powered sensor fabricated in this study is outstanding for its simplicity, biodegradability, easy functionalization, rapid detection, and greater selectivity.^24,25

Herein, we have developed a biodegradable self-powered portable sensor for detecting histamine by using a TENG device. Polycaprolactone (PCL) substrate with IDT patterned gold sputtered electrode was used to obtain a portable and robust sensor that allows analysis of the target molecule. The diamine oxidase (DAO) enzyme was functionalized by cross-linking using glutaraldehyde for better stabilization of the sensor using the self-assembled monolayer technique. The TENG was prepared using PCL and wool fabric as two triboelectric layers with the aluminum electrode, and a 3D printed eye-shaped structure was used in contact-separation mode for stable electrical output. The PCL TENG generates an output of 213 V, 640 nA, 70 μW power, with long-term stability. Upon the addition of histamine onto the sensor, it degrades the histamine and produces several byproducts, and the resistance of the TENG decreases, leading to an increase in the current output. Using a variety of additional biogenic amines, including tyramine and L-tyrosine, the selectivity of the sensor was also confirmed. With a limit of detection (LOD) of 43.34 ppm and an R² = 0.98, the sensor showed a good sensitivity of 0.07961 μA ppm⁻¹. Furthermore, the biodegradability test revealed 42.4% degradability of the PCL substrate over 60 days. This work provides a rapid and effective method for histamine detection as well as an altogether novel approach for TENG-based biodegradable biosensor systems.

2. Materials and methods

2.1. Chemicals and materials

Polycaprolactone (PCL), chloroform 99%, and L-tyrosine were purchased from Alfa Aesar Korea. Diamine oxidase from porcine kidney (≥0.05 unit per mg solid), phosphate buffer saline (PBS, pH 7.2) was purchased from Sigma Aldrich, Korea. Histamine, L-histidine 98%, tyramine, and 3-mercaptopropionic acid (MPA) were purchased from Alfa Aesar, Korea. Polylactic acid (PLA) wires for 3D printing were purchased from Sigma Aldrich, Korea. Wool fabrics were purchased from Daiso, Korea. Copper wire and aluminum tape were purchased from Alibaba, China.

2.2. Fabrication of biosensor

The PCL polymer substrate was prepared using 1 gram of PCL powder with 20 ml of chloroform, mixed for 1 hour at 30 °C using a magnetic stirrer. After the solution became clear, it was poured into a glass Petri plate, spread evenly, and stored in the oven at 35 °C for 24 hours. After drying, the free-standing PCL film was obtained and stored for further use. A 3D-printed IDT-patterned mask was used for sputtering gold as an electrode. The biosensor was now fabricated for functionalization and sensing purposes.

2.3. Fabrication of TENG

TENG was made up using a 3D printed eye-shaped substrate using PLA wires and operated in vertical contact separation mode. PCL and wool fabrics were used as two triboelectric layers, whereas the adhesive aluminum (Al) tape was used as the electrode. Kapton tape was used to paste the copper wires drawn from both sides of the electrode. The PCL and wool fabric were uniformly pasted onto the adhesive conductive Al tape. The active area of the TENG was 3 cm × 3 cm.

2.4. Biosensor functionalization

The PCL-gold-based sensor substrate was thoroughly cleaned to remove any contaminants and dirt, followed by a drying step using a stream of N₂ gas. Firstly, 0.1 mM of 3-MPA solution was drop-casted onto the gold electrode and left for 15 minutes. 1 ml of DAO solution having a concentration of 10 mg ml⁻¹ was prepared using PBS buffer, deposited on the electrode of the PCL sensor using the drop casting method, and left to dry for 30 minutes at room temperature. The biosensor was ready to use and stored in the refrigerator (4 °C) to avoid enzyme degradation for further use.

2.5. Experimental techniques

The vertical-contact separation of the TENG was done using a linear motor (M/S LINMOT, USA). The electrical output of the TENG was measured using an electrometer (M/S Keithley 6514). The TENG substrate and the IDT patterned mask were 3D printed using an FFT-based 3D printer (M/S Ultimaker, Netherlands). The polymer solution was prepared using a magnetic hot plate and stirrer (HS15, Misung Scientific Co., Ltd, Korea). The electrode was sputtered by the Sputtering system (DAEKI HI-TECH, Korea). The surface morphology of the sensor was taken using a scanning electron microscope (M/S Hitachi, SU-8020) and elemental mapping using OXFORD EDS. The X-ray spectra were recorded using an X-ray diffractometer (M/S Bruker, Germany) with Cu-Kα radiation. The UV-vis spectrum was measured using a UV-vis spectrophotometer (M/S Edinburgh Instruments, UK). The surface chemistry was investigated employing an X-ray photoelectron spectrometer (XPS, Thermo Scientific, Escalab 250 Xi). The surface roughness of the PCL polymer was investigated using atomic force microscopy (AFM, Park Systems, XE7).

3. Results and discussion

Fig. 1(a) shows a schematic diagram of the PCL-wave TENG, consisting of two tribo-layers of PCL film and wool fabric, along with an Al electrode and 3D printed PLA substrate. Fig. 1(b) shows the operation mechanism of the contact separation mode of the TENG. In the initial state (i), as both layers are in fully pressed position the equal and opposite charges are generated on the triboelectric layers. As wool is a positive layer than PCL, the negative charges appear on the PCL layer. As the two triboelectric layers separate (ii), potential difference is created and electrons flow from the top to the bottom electrode. When the two triboelectric layers are completely separated from each other (iii), there is no flow of electrons, and the device is in an equilibrium state. Again, while the two opposite layers are in contact (iv), the electrons move from the bottom to the top electrode. This periodic separation of the contacts results in an electrical output from the TENG.

Fig. 1 (a) Schematic diagram of the PCL-wool TENG and layers, (b) schematic diagram of the working mechanism of TENG.

The schematic diagram of the biosensor functionalization is shown in Fig. 2. An IDT-patterned gold electrode (100 nm) was prepared using the sputtering system, as shown in Fig. 2(a). Functionalization of the gold electrode was done using a self-assembled monolayer (SAM) technique, as shown in Fig. 2(b). For the formation of SAM on the gold electrode surface, a linker molecule called 3-MPA was used. MPA contains a thiol (–SH) group that has a strong affinity for gold surfaces. When MPA is introduced to a gold electrode, the thiol group interacts with the gold atoms, forming a stable covalent bond. This results in the formation of a densely packed SAM on the gold surface, with the carboxylic acid (–COOH) groups of the MPA exposed to the solution. This MPA plays a key role in helping the diamine oxidase (DAO) bind to the gold surface for further sensing. After the –COOH groups were activated, DAO was introduced to the system. The DAO's amino groups react with the activated –COOH groups on the MPA-SAM surface, leading to the covalent attachment of DAO to the gold electrode surface, Fig. 2(c). This immobilization is important for the enzyme to retain its activity and for the biosensor to function effectively. The SAM of MPA not only anchors DAO to the gold surface but also provides a stable, biocompatible environment, preserving the enzyme's activity. In the presence of histamine, DAO catalyzes the oxidative deamination of histamine to form imidazole acetaldehyde Fig. 2(d).

Fig. 2 (a–d) Schematic diagram of the step-by-step process of the biosensor functionalization method.

Fig. 3(a) shows the SEM image of the biosensor substrate marked for the gold electrode and bare PCL substrate. Supplementary Fig. 1 (Fig. S1) shows the SEM, at% of bare PCL and PCL-gold electrode surface. The elemental color mapping of the PCL-gold electrode surface is shown in Fig. S2, providing evidence of no impurities are present. The surface roughness (R_q) of the PCL substrate was 33.227 nm from the atomic force microscopy image data, as shown in Fig. 3(b).

Fig. 3 (a) SEM image of PCL-gold substrate, (b) AFM image of the PCL substrate, (c) XRD patterns of pure PCL and PCL-gold substrate, (d) FT-IR spectra of PCL-gold substrate, (e) and (f) XPS spectra results of functionalized sensor substrate with DAO.

The XRD spectrum of pure PCL and PCL with gold electrode is shown in Fig. 3(c). The X-ray diffraction (XRD) pattern of PCL shows distinct peaks at 2θ = 21.5° and 23.85°, corresponding to the (110) and (200) planes, respectively.²⁶ A weaker peak at 2θ = 15.7° is also observed. These peaks are characteristic of PCL's semi-crystalline structure.^27,28 For the PCL-gold substrate, the intensity of these PCL peaks is reduced, suggesting decreased crystallinity due to the incorporation of gold ions. This reduced crystallinity may contribute to the accelerated degradation of the polymer. After gold deposition, a distinct peak at 38.2° appears, indexed to the (111) plane of sputtered gold, confirming successful sputtering. The absence of other Au peaks (44.3°, 64.5°) can be attributed to the thin film nature.

Fig. 3(d) shows the FT-IR spectra of the PCL-gold substrate. The characteristic peaks of PCL are asymmetric CH₂ bonds, symmetric CH₂ bonds, and carbonyl bonds (C=O). The spectrum of PCL shows a sharp signal at 1715 cm⁻¹, which corresponds to (C=O, carbonyl bond).^29,30 The IR bands at 2937 cm⁻¹ and 2860 cm⁻¹ correspond to asymmetric CH₂ stretching and symmetric CH₂ stretching, respectively.^31,32 The IR band at 1157 cm⁻¹ (C–O & C–C stretching in amorphous phase), 1240 cm⁻¹ (asymmetric C–O–C stretching), and 1470 cm⁻¹, 1366 cm⁻¹, 1294 cm⁻¹ (C–O & C–C stretching in crystalline phase), respectively.^33,34 Gold does not produce FT-IR bands because it lacks the molecular structure that would allow it to absorb infrared light and undergo vibrational transitions.

The XPS studies illustrated that DAO molecules were chemisorbed on the gold electrode surface. A high-resolution spectrum of the Au4f core level, shown in Fig. 3(e), can be characterized by two prominent pairs of peaks due to Au 4f_7/2 and Au_5/2 spin–orbit coupling. In comparison, the positions of the first and most important pair (BEs of 82.8 and 86.5 eV) are related to gold. The experimental XPS spectra (Fig. 3f) for N_1s show a nice peak at 399.2 eV, which is attributed to the amine functionalization (–NH₂) of DAO on the gold electrode,³⁵ indicating that the protonated DAO is chemisorbed to the electrode surface successfully. The presence of functionalized DAO enhances the interaction with a specific target which is histamine.

The electrical characterization of the PCL TENG is shown in Fig. 4. As shown in Fig. 4(a) and (b), three different opposite layers of paper, aluminum, and wool were taken for the voltage and current. The highest voltage and current of 213 V, 640 nA were achieved using the PCL-wool-based TENG and were further chosen for future experiments. A long-term stability of up to 2000 seconds was tested using the PCL-wool TENG, as shown in Fig. 4(c). The voltage output across different load resistors was tested, as shown in Fig. 4(d). The voltage output increases by increasing the load resistance as per Ohm's law (V = IR). The power of the PCL-wool TENG device was calculated using the formula P = V²/R. The highest output power achieved was 70 μW, Fig. 4(e). The voltage and current output across different resistors are shown in Fig. S3. Various capacitors (including 0.1 μF, 0.22 μF, 0.47 μF, and 1 μF) were charged using the PCL-wool TENG for up to 100 seconds, which is shown in Fig. 4(f).

Fig. 4 (a) and (b) Voltage and current of PCL-based TENG using different opposite layers (paper, aluminum, wool), (c) long-term stability test of the PCL-wool TENG, (d) and (e) voltage, and power across various load resistances, (f) charging of various capacitors (0.1, 0.22, 0.47, 1 μF) using the PCL-wool TENG.

The charge–discharge behavior of the 0.1 μF capacitor was tested using the TENG, as depicted in Fig. 5(a). Voltage and current output of the PCL-wool TENG were tested using different frequencies, as shown in Fig. 5(b) and (c). As the result shows, the voltage output of the TENG with increasing frequency remains almost constant. The flow of charges through the electrode increases due to the higher frequency, making the current output increase and the voltage constant. Fig. 5(d) shows the powering of the LED light using the PCL-wool TENG by converting the AC output to DC output using a bridge rectifier in the circuit connection. Fig. 5(e) and (f) shows biomechanical energy harvesting from finger pressing and palm pressing upon the PCL-wool TENG. The results show the slow, normal, and fast pressing of the finger and palm and the corresponding voltage output. This demonstration makes the PCL-wool TENG a portable, lightweight, and low-cost device that can be used in any circumstance using biomechanical energy.

Fig. 5 (a) Charging–discharging curve of a 0.1 μF capacitor using PCL-wool TENG, (b) and (c) voltage and current of the PCL-wool TENG with different frequencies, (d) powering of LED using the PCL-wool TENG, (e) and (f) biomechanical energy harvesting by finger pressing and palm pressing using PCL-wool TENG.

The sensing and detection of various histamine concentrations using the biosensor is shown in Fig. 6. The DAO-functionalized histamine sensor was externally connected to the PCL-wool TENG circuit instead of the load resistor, so the DAO-functionalized sensor acted as the load resistor of the setup. The schematic diagram of the mechanism of infection and the symptoms of Scombroid food poisoning are illustrated in Fig. 6(a). Various concentrations of the histamine solutions were prepared (50 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm), and 200 μl of each ppm solution was dropped in the functionalized sensor after a washing step with PBS buffer. After the histamine solution was dropped into the functionalized sensor, the current output was recorded after 60 seconds. As shown in Fig. 6(b), the current output immensely increased with increasing concentrations of ppm and reached up to 40 μA. The drop in resistance of the sensor was cross-checked using an impedance analyzer, which confirms the drop in resistance up to the Ohms (Ω) range by functionalizing another sensor (Fig. S4).

Fig. 6 (a) Schematic representation of the Scombroid food poisoning, (figure created by the author, with elements from Vecteezy (dead fish) and PNGTree (food-poisoned man)). (b) Current output of the PCL-wool TENG-based biosensor with different concentrations (ppm) of histamine, (c) regression coefficient value of the sensor by linear fitting of current output value, (d) selectivity test by measuring the current output of different biogenic amines and amino acids.

The current output of the PCL-wool TENG was also tested using 100–1000 Ω resistors to confirm the current output range in μA, as shown in Fig. S5. This experiment proves that the resistance of the biosensor significantly drops to the Ohm range after adding the analyte, which results in the current output being increased significantly. While the current outputs of the sensors are linearly plotted (Fig. 6c), we achieved a regression coefficient value (R²) of 0.98, with a sensitivity of 0.07961 μA ppm⁻¹ and a limit of detection (LOD) of 43.34 ppm.

The selectivity of the sensor for histamine was tested by analyzing various biogenic amines and amino acids that can be found in spoiled fish. Thus, the electrical current response of the sensor to 1-tyrosine, histidine, and tyramine (50 ppm solution each) was recorded and compared to the electrical response produced from a 50 ppm solution of histamine. As shown in Fig. 6(d), the current output of other biogenic amines and amino acids was significantly lower than the current output of histamine, demonstrating the selectivity of the sensor. Such a result indicates that other biogenic amines and amino acids do not significantly influence the resistance of the sensor surface and do not interfere with the analysis of histamine using the sensor. As a result, the use of the TENG current signal provides much simpler and more visible results in terms of selectivity and sensitivity towards histamine when the analysis is performed through the reduction of enzymatic products.

The mechanism of histamine degradation using a DAO-functionalized gold electrode is shown in Fig. 7. Histamine is oxidized by DAO, producing imidazole acetaldehyde, hydrogen peroxide (H₂O₂), and ammonia (NH₃). These byproducts alter the local charge and resistance on the electrode surface changes as variations in current (μA) output, enabling sensitive detection of histamine concentration.

Fig. 7 Histamine degradation mechanism using a DAO functionalized gold electrode.

The biodegradability of the sensor substrate is important for making a contaminant-free, disposable-type sensor. Therefore, a biodegradation test of the PCL polymer using soil compost by maintaining the temperature and moisture at 60 °C, 50%, was performed. The PCL polymer was cut into square shape, dried, and cleaned to remove any impurities, then weighed. After that, it was placed inside the soil compost as shown in Fig. 8(a). PCL polymer showed 42.4% degradation in 60 days, which makes the sensor substrate sustainable to utilize in upcoming research areas for various biological sensing sectors (Fig. 8b). The digital photograph of the fragmented PCL is shown in Fig. 8(c). The FT-IR analysis of degraded PCL samples after 60 days (as shown in Fig. S6) suggested evidence of biodegradability of the sample inside soil.

Fig. 8 Biodegradability test of the PCL substrate (a) digital photograph of the PCL film placed inside the soil compost and covered, (b) mass loss percentage up to 60 days, (c) digital image of the degradation of the substrate, (d) optical microscope image of the PCL film before and after degradation.

The FTIR spectra (Fig. 3d) clearly show characteristic absorption bands of PCL. The strong ester carbonyl stretching at 1715 cm⁻¹, C–O–C stretching vibrations around 1157–1240 cm⁻¹ and CH₂ asymmetric and symmetric stretching bands at 2937 and 2860 cm⁻¹, respectively. Upon degradation (Fig. S6), noticeable changes are observed: (i) reduction in the intensity of the ester C=O stretching peak (1715 cm⁻¹), indicating hydrolytic cleavage of ester linkages; (ii) decrease in C–O–C stretching vibrations (1157–1240 cm⁻¹), further confirming chain scission and (iii) broadening and intensity increase in the O–H stretching region (3200–3500 cm⁻¹), which is attributed to hydroxyl and carboxyl end groups formed during biodegradation. These spectral changes provide clear evidence of structural modifications in PCL upon degradation, supporting the biodegradability of the PCL beyond just mass loss measurements. Microscopic optical images of the PCL film before and after degradation are shown in Fig. 8(d), depicted cracks, pores, and erosion upon the surface of PCL film.

4. Conclusions

The importance of ensuring food safety has seen a huge growth due to increasing concern among consumers. Therefore, there is a huge demand for developing a portable, low-cost, rapid detection sensor type for consumers. In this work, a simple battery-free sensor using TENG was developed to detect histamine, which can cause serious health problems like Scombroid food poisoning if found in higher concentrations of more than 50 ppm. To detect the histamine, a PCL-gold sensor substrate functionalized with DAO was used, which was integrated into the TENG device as a load resistor. The TENG device, made up of PCL-wool, generates the highest and most stable output of 213 V, 640 nA, and 70 μW power. In the presence of histamine, the DAO catalyzes the oxidative deamination of histamine to form imidazole acetaldehyde, which results in a sudden drop in the resistance of the sensor surface. The enzymatic reaction ongoing in the sensor surface leads to a change in the resistance, which again leads to a change in the current output of the TENG up to 40 μA and can be detected easily. The sensor shows a great R² value of 0.98, with a sensitivity of 0.07961 μA ppm⁻¹ and a LOD of 43.34 ppm. The fabricated sensor has a simple design, is portable, battery-free, biodegradable, low-cost, small in size, and has less sample and reagent requirements, making this sensor sustainable and effective. In our current setup, the TENG is intended to be operated via simple mechanical contact-separation motions, mimicking biomechanical stimuli that could be generated during handling, transport, or user interaction in real-life scenarios. This demonstrates TENG's potential as a sustainable power source, eliminating the need for external batteries, and highlights its applicability for real-time, portable, and low-power food safety monitoring systems. This self powered histamine sensor approach using TENG can be very useful for the detection and prevention of disease on-site, along with the whole fish production chain, from capture to consumption.

Conflicts of interest

The authors declare no conflict of interest.

Data availability

The data supporting the findings of this study are available from the corresponding author upon reasonable request. All relevant data generated or analyzed during this study are included in this published article.

Supplementary information is available. See DOI: https://doi.org/10.1039/d5tb01337b.

Acknowledgements

This work is supported by the National Research Foundation of Korea (RS-2024-00346135, RS-2024-00431411, RS-2025-25420118). VV thanks Department of Science and Technology, India for the support through PURSE program (SR/PURSE/2023/196).

References

1. S. Bhaskar, Foodborne diseases—disease burden, in Food safety in the 21st century, 2017, Elsevier, pp. 1–10.
2. O. A. Odeyemi, Public health implications of microbial food safety and foodborne diseases in developing countries, Food Nutrition Res., 2016, 60(1), 29819.
3. E. Todd, Foodborne disease prevention and risk assessment, MDPI, 2020, 5129.
4. R. Nayak and P. Waterson, Global food safety as a complex adaptive system: Key concepts and future prospects, Trends Food Sci. Technol., 2019, 91, 409–425.
5. J. Trienekens and P. Zuurbier, Quality and safety standards in the food industry, developments and challenges, Int. J. Product. Econ., 2008, 113(1), 107–122.
6. D. Doeun, M. Davaatseren and M.-S. Chung, Biogenic amines in foods, Food Sci. Biotechnol., 2017, 26, 1463–1474.
7. K. B. Biji, et al., Biogenic amines in seafood: a review, J. Food Sci. Technol., 2016, 53(5), 2210–2218.
8. M. Papageorgiou, et al., Literature update of analytical methods for biogenic amines determination in food and beverages, TrAC, Trends Anal. Chem., 2018, 98, 128–142.
9. Y.-C. Lee, et al., Determination of histamine in milkfish stick implicated in foodborne poisoning, J. Food Drug Anal., 2016, 24(1), 63–71.
10. G. Rodríguez-Caravaca, et al., Food poisoning caused by scombroids: A case-control study, J. Infect. Public Health, 2019, 12(4), 591–593.
11. C. Feng, S. Teuber and M. E. Gershwin, Histamine (Scombroid) Fish Poisoning: a Comprehensive Review, Clin. Rev. Allergy Immunol., 2016, 50(1), 64–69.
12. Y. V. Zhernov, et al., Molecular mechanisms of scombroid food poisoning, Int. J. Mol. Sci., 2023, 24(1), 809.
13. X. Tian, et al., Immobilizing diamine oxidase on electroactive phase-change microcapsules to construct thermoregulatory smart biosensor for enhancing detection of histamine in foods, Food Chem., 2022, 397, 133759.
14. Y. Liu, et al., Colorimetric detection of diamine using diamine oxidase and horseradish peroxidase co-incorporated hybrid microsphere as biomimetic cascade enzymes, Food Chem., 2024, 140008.
15. R. Torre, et al., Diamine oxidase-modified screen-printed electrode for the redox-mediated determination of histamine, J. Anal. Sci. Technol., 2020, 11(1), 5.
16. I. M. Apetrei and C. Apetrei, Amperometric Biosensor Based on Diamine Oxidase/Platinum Nanoparticles/Graphene/Chitosan Modified Screen-Printed Carbon Electrode for Histamine Detection, Sensors, 2016, 16(4), 422.
17. J. Durner and D. C. Watts, Principles of analytical chemistry for toxicology, Regul. Toxicol., 2021, 455–497.
18. F. M. Colombo, et al., Histamine food poisonings: A systematic review and meta-analysis, Crit. Rev. Food Sci. Nutr., 2018, 58(7), 1131–1151.
19. Q. Zhou and D. Tang, Recent advances in photoelectrochemical biosensors for analysis of mycotoxins in food, TrAC, Trends Anal. Chem., 2020, 124, 115814.
20. T. M. Ngapo and L. Vachon, Biogenic amine concentrations and evolution in “chilled” Canadian pork for the Japanese market, Food Chem., 2017, 233, 500–506.
21. J. Anderegg, et al., Detection of Biogenic Amines and Tyramine-Producing Bacteria in Fermented Sausages from Switzerland, J. Food Prot., 2020, 83(9), 1512–1519.
22. S. Panda, et al., Biocompatible polydopamine based triboelectric nanogenerator for humidity sensing, Sens. Actuators, B, 2023, 394, 134384.
23. R. Garg, et al., Polarization-Induced Mechanically Socketed Ultra-Stretchable and Breathable Textile-Based Nanogenerator and Pressure Sensor, Adv. Funct. Mater., 2024, 34(32), 2401593.
24. S. Panda, et al., Carbohydrate–protein interaction-based detection of pathogenic bacteria using a biodegradable self-powered biosensor, J. Mater. Chem. B, 2023, 11(42), 10147–10157.
25. S. G. Nukala, et al., Development of biodegradable composites using polycaprolactone and bamboo powder, Polymers, 2022, 14(19), 4169.
26. M. Fadaie and E. Mirzaei, Nanofibrillated chitosan/polycaprolactone bionanocomposite scaffold with improved tensile strength and cellular behavior, Nanomed. J., 2018, 5, 77–89.
27. J. Bras, et al., Mechanical, barrier, and biodegradability properties of bagasse cellulose whiskers reinforced natural rubber nanocomposites, Ind. Crops Prod., 2010, 32(3), 627–633.
28. P. Fabbri, et al., Porous scaffolds of polycaprolactone reinforced with in situ generated hydroxyapatite for bone tissue engineering, J. Mater. Sci.: Mater. Med., 2010, 21, 343–351.
29. A. Benkaddour, et al., Grafting of Polycaprolactone on Oxidized Nanocelluloses by Click Chemistry, Nanomaterials, 2013, 3(1), 141–157.
30. B. Sundararajan and B. R. Kumari, Novel synthesis of gold nanoparticles using Artemisia vulgaris L. leaf extract and their efficacy of larvicidal activity against dengue fever vector Aedes aegypti L, J. Trace Elem. Med. Biol., 2017, 43, 187–196.
31. S. Ali, et al., Preparation and characterization of hybrid polycaprolactone/cellulose ultrafine fibers via electrospinning, Macromol. Res., 2014, 22, 562–568.
32. N. Gokalp, C. Ulker and Y. Avcibasi Guvenilir, Enzymatic ring opening polymerization of-caprolactone by using a novel immobilized biocatalyst, Adv. Mater. Lett., 2016, 7(2), 144–149.
33. M. Paula, et al., Gamma irradiation effects on polycaprolactone/zinc oxide nanocomposite films, Polímeros, 2019, 29(1), e2019014.
34. S. Murphy, G. Leeke and M. Jenkins, A Comparison of the use of FTIR spectroscopy with DSC in the characterisation of melting and crystallisation in polycaprolactone, J. Therm. Anal. Calorim., 2012, 107(2), 669–674.
35. J.-P. Sylvestre, et al., Surface chemistry of gold nanoparticles produced by laser ablation in aqueous media, J. Phys. Chem. B, 2004, 108(43), 16864–16869.

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Footnote

† Equal contributions: Swati Panda, Heewon Song.

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