Citation: Xin ZHANG, Xinyi JIAO, Wanqiao BAI, Xuehua SUN, Huali CUI, Yixia REN, Hongmei CHAI. Flexible Gd-MOF@PMMA/BMA composite film fluorescent sensor for highly sensitive detection of tyramine in bananas[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(2): 217-226. doi: 10.11862/CJIC.20250219 shu

Flexible Gd-MOF@PMMA/BMA composite film fluorescent sensor for highly sensitive detection of tyramine in bananas

Shaanxi Key Laboratory of Chemical Reaction Engineering, College of Chemistry and Chemical Engineering, Yan′an University, Yan′an, Shaanxi 716000, China

Corresponding author: Hongmei CHAI, chm8550@163.com
Received Date: 1 July 2025
Revised Date: 24 September 2025

Figures(5)

In this study, using 3, 5-di(3′, 5′-dicarboxylphenyl)-1H-1, 2, 4-triazole (H₄L) as ligands, a gadolinia-based organic framework complex {[GdNa(L)(H₂O)₃]·2H₂O}_n (Gd-Na-MOF) was successfully designed and synthesized by hydrothermal method. The structure and properties were systematically characterized and tested by techniques such as single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and fluorescence spectroscopy. The results indicate that this complex has a unique 3D structure, excellent thermal stability, and outstanding luminescent performance. Based on its luminescent properties, a polymer-embedding method was employed to fabricate the Gd-Na-MOF into a flexible, washable composite fluorescent film, Gd-Na-MOF@PMMA/BMA (PMMA=polymethyl methacrylate, BMA=butyl methacrylate). This fluorescent film exhibited highly sensitive recognition capability for tyramine, with a low detection limit of 1.66 μmol·L^-1. It was used for the detection of tyramine in bananas, with a recovery rate of 96.92%-100.26%.
- metal-organic frameworks,
- Gd-Na-MOF@PMMA/BMA composite fluorescent film,
- fluorescent sensing,
- tyramine
1. [1]
  SHENG W, SUN C C, FANG G Z, WU X N, HU G S, ZHANG Y, WANG S. Development of an enzyme-linked immunosorbent assay for the detection of tyramine as an index of freshness in meat and seafood[J]. J. Agric. Food Chem., 2016, 64(46): 8944-8949 doi: 10.1021/acs.jafc.6b04422
2. [2]
  MA L, CHEN Z C, LI X, LIU W W, YU Z C, LI C G, YU G, XU Q Y. De novo synthesis of tyramine in engineered Escherichia coli using two-stage dissolved oxygen-controlled fermentation[J]. J. Agric. Food Chem., 2025, 73(7): 4174-4184 doi: 10.1021/acs.jafc.4c11385
3. [3]
  KAPOOR A, RAJPUT J K. Electroactive core-shell chitosan-coated lanthanum iron oxide as a food freshness level indicator for tyramine content determination[J]. ACS Sustainable Chem. Eng., 2022, 10(35): 11666-11679 doi: 10.1021/acssuschemeng.2c03747
4. [4]
  WANG T T, LIU F N, CHEN C X, LU Y Z. Fluorometric "AND" logic gate for detection of tyramine and tyrosinase based on in-situ formation of silicon-containing nanoparticles[J]. Anal. Chim. Acta, 2024, 1298: 342415 doi: 10.1016/j.aca.2024.342415
5. [5]
  FAN L H, ZHANG J Y, ZHAO Y, SUN C Y, LI W J, CHANG Z D. A robust Eu-MOF as a multi-functional fluorescence sensor for detection of benzaldehyde, Hg²⁺, and Cr₂O₇^2-/CrO₄^2-[J]. Microchem. J., 2024, 196: 109712 doi: 10.1016/j.microc.2023.109712
6. [6]
  QI D Y, SI X, GUO L L, YAN Z P, SHAO C Y, YANG L R. Two novel and high-efficiency optical chemosensors of detecting Fe³⁺ and CrO₄^2- based on metal-organic frameworks of Cd(Ⅱ)[J]. J. Solid State Chem., 2022, 314: 123400 doi: 10.1016/j.jssc.2022.123400
7. [7]
  YANG C L, ZHANG H W, HOU C H, SUN F F, XU G J. Self-assembly fluorescent copper nanoclusters in alginate-based hydrogel sensor for histamine detection and visual monitoring of food spoilage[J]. Talanta, 2025, 294: 128292 doi: 10.1016/j.talanta.2025.128292
8. [8]
  YAN Y, GUO H, YU Z, YANG Z Y, ZHUANG D K, MA Y Y, WANG M Y, YANG W. A rapid on-site fluorescence sensing platform for malachite green in an aqueous phase based on lanthanide-functionalized MOF[J]. Microchim. Acta, 2025, 192: 253 doi: 10.1007/s00604-025-07113-0
9. [9]
  PAPAGEORGIOU M, LAMBROULOU D, MORRISON C, KŁODZIŃSKA E, NAMIEŚNIK J, PŁOTKA-WASYLKA J. Literature update of analytical methods for biogenic amines determination in food and beverages[J]. Trac‒Trends Anal. Chem., 2018, 98: 128-142 doi: 10.1016/j.trac.2017.11.001
10. [10]
  GU M Y, SUN M R, LU Y, ZENG D C, ZHAO J H, CHANG Z H, XIN D X, ZHOU X Y, HU Y Y, DU E D, ZHANG Y Q, PENG M G. A facile fluorescence Zr-MOF probe for selective sensing tetracycline in water[J]. Inorg. Chem. Commun., 2025, 178: 114548 doi: 10.1016/j.inoche.2025.114548
11. [11]
  LU Y Y, ZHOU H J, YANG H, ZHOU Z, JIANG Z C, PANG H. Anisotropy of metal-organic framework and their composites: Properties, synthesis, and applications[J]. J. Mater. Chem. A, 2024, 12(15): 6243-6260
12. [12]
  GAO Y X, ZHU Y Y, WANG Y P, BI J H. Water-stable Ln-MOF as a multi-emitting luminescent sensor for the detection of metal ions and pharmaceuticals[J]. Spectroc. Acta Pt. A‒Molec. Biomolec. Spectr., 2024, 323: 124915 doi: 10.1016/j.saa.2024.124915
13. [13]
  YAN R K, CHEN X L, REN J, CUI H L, YANG H, WANG J J. Design and synthesis of a new highly efficient adjustable Ln-MOF for fluorescence sensing and information encryption[J]. Spectroc. Acta Pt. A‒Molec. Biomolec. Spectr., 2025, 330: 125669 doi: 10.1016/j.saa.2024.125669
14. [14]
  NINGBO INSTITUTE OF MATERIALS TECHNOLOGY AND ENGINEERING, CHINESE ACADEMY OF SCIENCES. Method for improving dispersibility of MOFs in polymer solution and preparation method of MOFs/polymer composite membrane: CN201810294450.4[P]. 2021-03-26.
15. [15]
  APPELHAN N L, HUGHES L, MCKENZIE B, RODRIGUEZ M, GRIEGO J, BRISCOE J, MOORMAN M, FREDERICK E, WRIGHT B J. Facile microwave synthesis of zirconium metal-organic framework thin films on gold and silicon and application to sensor functionalization[J]. Microporous Mesoporous Mat., 2021, 323: 111133 doi: 10.1016/j.micromeso.2021.111133
16. [16]
  SABZEHEMEIDANI M M, GAFARI S, JAMALI S, KAZEMZAD M. Concepts, fabrication and applications of MOF thin films in optoelectronics: A review[J]. Appl. Mater. Today, 2024, 38: 102153 doi: 10.1016/j.apmt.2024.102153
17. [17]
  WANG X, WANG Y, CHEN L, XIE X F, SUN J. Gel-state MOFs for environmental decontamination: Synthesis, application and optimization[J]. Chem. Eng. J., 2024, 499: 156241 doi: 10.1016/j.cej.2024.156241
18. [18]
  MAKIURA R. Creation of metal-organic framework nanosheets by the Langmuir-Blodgett technique[J]. Coord. Chem. Rev., 2022, 469: 214650 doi: 10.1016/j.ccr.2022.214650
19. [19]
  SUN Z H, ZHAO G K, TANG G Q, ZHAO Z H, LI P. Preparation of high-performance pervaporation membranes for ethanol dehydration using a layer-by-layer self-assembly method[J]. Adv. Membr., 2025, 5: 100132 doi: 10.1016/j.advmem.2025.100132
20. [20]
  CEVIK E, IQBAL A, MUSTAFA A, QAHAN F T, ZEEZHAN M, ISIK O. Metal organic frameworks embedded polymeric membranes: A comprehensive review on application in water purification and seawater desalination[J]. J. Environ. Chem. Eng., 2025, 13(3): 116215 doi: 10.1016/j.jece.2025.116215
21. [21]
  ZHANG Z H, MA W P, YAN B. Multi-step tandem functionalization assembly of MOFs-based hybrid polymeric films for color tuning luminescence and responsive sensing on organic vapors[J]. Colloid Surf. A‒Physicochem. Eng. Asp., 2022, 648: 129416 doi: 10.1016/j.colsurfa.2022.129416
22. [22]
  MUTMAINNA I, TAHIR D, GARESO L P, SURYANI S. Development of PVA-chitosan based smart packaging with the addition of red cabbage (Brassica Oleracea Var. capitata F. rubra) anthocyanin extract and copper-based metal-organic material (Cu-MOF)[J]. Int. J. Biol. Macromol., 2025, 313: 14420
23. [23]
  ALI A, ALTAKROORI H H D, GREISH Y E, ALZAMLY A, SIDDIG L A, QAMHIEH N, MAHMOUD S T. Flexible Cu₃(HHTP)₂ MOF membranes for gas sensing application at room temperature[J]. J. Nanomater., 2022, 12(6): 913 doi: 10.3390/nano12060913
24. [24]
  KAZEMI A, MOHAMMADI M, PORDSARI M A, TAMTAJI M, BAESMAT H, KESHAVARZ S, ZEINALI F, MANTEGHI F, FASIHI M, GHAEMI A, ROHANI S, GODDARD A W. Eco-friendly mixed-metal MOF embedded in PVA-based packaging films for ethylene adsorption and enhancing fresh produce shelf-life[J]. Food Packaging Shelf Life, 2025, 49: 101517 doi: 10.1016/j.fpsl.2025.101517
25. [25]
  FANG M, DROBEK M, COT D, MONTORO C, SEMSARILAR M. A straightforward method to prepare MOF-based membranes via direct seeding of MOF-polymer hybrid nanoparticles[J]. J. Membr. Sci., 2023, 13(1): 65
26. [26]
  KRAUSE L, HERBST-IRMER R, SHELDRICK G M, STALKE D. Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination[J]. J. Appl. Crystallogr., 2015, 48(1): 3-10 doi: 10.1107/S1600576714022985
27. [27]
  SHELDRICK G M. Crystal structure refinement with SHELXL[J]. Acta Crystallogr. Sect. A, 2015, A71(1): 3-8
28. [28]
  KIRKAN B. Enzyme inhibition: Mechanisms, types, and applications in drug development[J]. J. Cell. Mol. Pharmacol., 2024, 8(6): 249
29. [29]
  ALLWARDT J R, STEBBINS J F, SCHMIDT B C, FROST D J, WITHERS A C, HIRSCHMANN M M. Aluminum coordination and the densification of high-pressure aluminosilicate glasses[J]. Am. Miner., 2005, 90(7): 1218-1222 doi: 10.2138/am.2005.1836
30. [30]
  GAGNÉ O C, HAWTHORNE F C. Bond-length distributions for ions bonded to oxygen: Results for the transition metals and quantification of the factors underlying bond-length variation in inorganic solids[J]. IUCrJ, 2020, 7(4): 581-629 doi: 10.1107/S2052252520005928
31. [31]
  ESTEBAN T G, SÁNCHEZ L B, EXPÓSITO L, RODRÍGUEZ-SAN-MIGUEL D, ZAMORA F, PARIENTE F, GUTIÉRREZ-SÁNCHEZ C, LORENZO E. Synergistic enhancement of electrochemiluminescence through hybridization of α-Ge nanolayers and gold nanoparticles for highly sensitive detection of tyramine[J]. Sens. Actuator B‒Chem., 2023, 396: 134649 doi: 10.1016/j.snb.2023.134649
32. [32]
  SINGH R, ZHANG W, LIU X C, ZHANG B Y, KUMAR S. WaveFlex biosensor: MXene-immobilized W-shaped fiber-based LSPR sensor for highly selective tyramine detection[J]. Opt. Laser Technol., 2024, 171: 110357 doi: 10.1016/j.optlastec.2023.110357
33. [33]
  AHMAD M W, DEY B, KIM B H, SARKHEL G, YANG D J, HOSSAIN S S, KAMAL T, CHOUDHURY A. Bimetallic copper-cobalt MOFs anchored carbon nanofibers hybrid mat based electrode for simultaneous determination of dopamine and tyramine[J]. Microchem. J., 2023, 193: 109074 doi: 10.1016/j.microc.2023.109074
34. [34]
  TORRE R, CERRATO-ALVAREZ M, NOUWS P A H, DELERUE-MATOS C M, FERNÁNDEZ-ABEDUL T, COSTA-RAMA E. A hand-drawn graphite electrode for affordable analysis: Application to the enzymatic determination of tyramine in fish[J]. Sens. Actuator B‒Chem., 2025, 423: 136705 doi: 10.1016/j.snb.2024.136705
35. [35]
  ZHANG D W, ZHANG Y H, LI K X, WANG S N, MA Y C, LIAO Y H, WANG F H, LIU H. A smartphone-combined ratiometric fluorescence molecularly imprinted probe based on biomass-derived carbon dots for determination of tyramine in fermented meat products[J]. Food Chem., 2024, 454: 139759 doi: 10.1016/j.foodchem.2024.139759
36. [36]
  SU Y, YU J H, LI Y B, PHUA S F Z, LIU G F, LIM W Q, YANG X Z, GANGULY R. Versatile bimetallic lanthanide metal-organic frameworks for tunable emission and efficient fluorescence sensing[J]. Commun. Chem., 2018, 1: 12 doi: 10.1038/s42004-018-0016-0
37. [37]
  FU Y X, WANG L, XU L, ZHOU Y, GONG H. LIBS detection of trace elements in fruits[J]. Journal of Bengbu University, 2020, 9(5): 71-75
38. [38]
  GAO H J, LIU P, HE W D, BI F C, HU C H, DENG G M, DOU T X, YANG Q S, LI C Y, YI G J, SHENG O, DONG T. Ripening-stage variations in small metabolites across six banana cultivars: A metabolomic perspective[J]. Food Chem., 2025, 478: 143658 doi: 10.1016/j.foodchem.2025.143658
39. [39]
  BORGES C V, BELIN M A F, AMORIM E P, MINATEL I O, MONTEIRO G C, GOMEZ H A G, MONAR G R S, LIMA G P P. Bioactive amines changes during the ripening and thermal processes of bananas and plantains[J]. Food Chem., 2019, 298: 125020 doi: 10.1016/j.foodchem.2019.125020
1. [1]
  Jimin HOU , Mengyang LI , Chunhua GONG , Shaozhuang ZHANG , Caihong ZHAN , Hao XU , Jingli XIE . Synthesis, structures, and properties of metal-organic frameworks based on bipyridyl ligands and isophthalic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 549-560. doi: 10.11862/CJIC.20240348
2. [2]
  Jiaxuan YANG , Chenfa DENG , Jingyang LIU , Chenzexi XU , Hongxin CHEN , Yahui ZHU , Ying LI , Shuhua WANG , Rongping ZHOU , Chao CHEN . Advances in selective hydrogenation of α, β-unsaturated aldehydes/ketones catalyzed by metal-organic frameworks and their derivatives: A review. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 1973-2010. doi: 10.11862/CJIC.20250175
3. [3]
  Ruolin CHENG , Yue WANG , Fei YANG , Huagen LIANG , Shijian LU . Application of metal-organic frameworks (MOFs) in photocatalytic CO₂ cycloaddition reaction: A mini review. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2429-2440. doi: 10.11862/CJIC.20250242
4. [4]
  Haifeng ZHENG , Xingzhe GUO , Yunwei WEI , Xinfang WANG , Huimin QI , Yuting YAN , Jie ZHANG , Bingwen LI . Post-synthetic modification strategy to construct Co-MOF composites for boosting oxygen evolution reaction activity. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 193-202. doi: 10.11862/CJIC.20250029
5. [5]
  Wei GUO , Zhuoyi GUO , Xiaoxin LI , Wei ZHANG , Juanzhi YAN , Tingting GUO . Electrochemical sensor based on a Co(Ⅱ)-based metal-organic framework for the detection of Cd²⁺ and Pb²⁺. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1889-1902. doi: 10.11862/CJIC.20250097
6. [6]
  Yueyue WEI , Xuehua SUN , Hongmei CHAI , Wanqiao BAI , Yixia REN , Loujun GAO , Gangqiang ZHANG , Jun ZHANG . Two Ln-Co (Ln=Eu, Sm) metal-organic frameworks: Structures, magnetism, and fluorescent sensing sulfasalazine and glutaraldehyde. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2475-2485. doi: 10.11862/CJIC.20240193
7. [7]
  Liangji Chen , Zhen Yuan , Fudong Feng , Xin Zhou , Zhile Xiong , Wuji Wei , Hao Zhang , Banglin Chen , Shengchang Xiang , Zhangjing Zhang . A hydrogen-bonded organic framework containing fluorescent carbazole and responsive pyridyl units for sensing organic acids. Chinese Chemical Letters, 2024, 35(9): 109344-. doi: 10.1016/j.cclet.2023.109344
8. [8]
  Ruikui YAN , Xiaoli CHEN , Miao CAI , Jing REN , Huali CUI , Hua YANG , Jijiang WANG . Design, synthesis, and fluorescence sensing performance of highly sensitive and multi-response lanthanide metal-organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 834-848. doi: 10.11862/CJIC.20230301
9. [9]
  Yijian Zhao , Jvzhe Li , Yunyi Shi , Jie Hu , Meiyi Liu , Yao Shen , Xinglin Hou , Qiuyue Wang , Qi Wang , Zhiyi Yao . A label-free and ratiometric fluorescent sensor based on porphyrin-metal-organic frameworks for sensitive detection of ochratoxin A in cereal. Chinese Chemical Letters, 2025, 36(4): 110132-. doi: 10.1016/j.cclet.2024.110132
10. [10]
  Xinyu Wu , Jianfeng Lu , Zihao Zhu , Suijun Liu , Herui Wen . Recent advances of metal-organic frameworks and MOF-derived materials based on p-block metal for the electrochemical reduction of carbon dioxide. Chinese Chemical Letters, 2025, 36(7): 110151-. doi: 10.1016/j.cclet.2024.110151
11. [11]
  Ya-Ping Liu , Zhi-Rong Gui , Zhen-Wen Zhang , Sai-Kang Wang , Wei Lang , Yanzhu Liu , Qian-Yong Cao . A phenylphenthiazide anchored Tb(Ⅲ)-cyclen complex for fluorescent turn-on sensing of ClO⁻. Chinese Chemical Letters, 2025, 36(2): 109769-. doi: 10.1016/j.cclet.2024.109769
12. [12]
  Deshuai Zhen , Chunlin Liu , Qiuhui Deng , Shaoqi Zhang , Ningman Yuan , Le Li , Yu Liu . A review of covalent organic frameworks for metal ion fluorescence sensing. Chinese Chemical Letters, 2024, 35(8): 109249-. doi: 10.1016/j.cclet.2023.109249
13. [13]
  Li Li , Lin-Lin Zhang , Yansha Gao , Lu-Ying Duan , Wuying Yang , Xigen Huang , Yanping Hong , Jiaxin Hong , Lin Yuan , Limin Lu . Target self-calibration ratiometric fluorescent sensor based on facile-synthesized europium metal-organic framework for multi-color visual detection of levofloxacin. Chinese Chemical Letters, 2025, 36(7): 110436-. doi: 10.1016/j.cclet.2024.110436
14. [14]
  Mingyue Luo , Kehui Zhang , Honghong Rao , Jianying Li , Xin Xue , Panpan Sun , Xiaoquan Lu , Zhonghua Xue . A simplified ratiometric fluorescent sensing strategy for enhanced detection of alkaline phosphatase employing Prussian blue nanozymes and commercially available chromogen. Chinese Chemical Letters, 2025, 36(9): 110703-. doi: 10.1016/j.cclet.2024.110703
15. [15]
  Xin Chen , Meng Zhao , Yan-Yuan Jia . Stable Eu(III)-based metal-organic framework for fluorescence sensing of benzaldehyde and its analogues. Chinese Journal of Structural Chemistry, 2025, 44(3): 100445-100445. doi: 10.1016/j.cjsc.2024.100445
16. [16]
  Ze Liu , Xiaochen Zhang , Jinlong Luo , Yingjian Yu . Application of metal-organic frameworks to the anode interface in metal batteries. Chinese Chemical Letters, 2024, 35(11): 109500-. doi: 10.1016/j.cclet.2024.109500
17. [17]
  Xiaofei NIU , Ke WANG , Fengyan SONG , Shuyan YU . Self-assembly of [Pd₆(L)₄]⁸⁺-type macrocyclic complexes for fluorescent sensing of HSO₃^-. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1233-1242. doi: 10.11862/CJIC.20240057
18. [18]
  Yuxin Wang , Zhengxuan Song , Yutao Liu , Yang Chen , Jinping Li , Libo Li , Jia Yao . Methyl functionalization of trimesic acid in copper-based metal-organic framework for ammonia colorimetric sensing at high relative humidity. Chinese Chemical Letters, 2024, 35(6): 108779-. doi: 10.1016/j.cclet.2023.108779
19. [19]
  Xiaoyan Peng , Xuanhao Wu , Fan Yang , Yefei Tian , Mingming Zhang , Hongye Yuan . Gas sensors based on metal-organic frameworks: challenges and opportunities. Chinese Journal of Structural Chemistry, 2024, 43(3): 100251-100251. doi: 10.1016/j.cjsc.2024.100251
20. [20]
  Kang Wang , Qinglin Zhou , Weijin Li . Conductive metal-organic frameworks for electromagnetic wave absorption. Chinese Journal of Structural Chemistry, 2024, 43(10): 100325-100325. doi: 10.1016/j.cjsc.2024.100325

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(8)
HTML views(2)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142