Citation: Hong CAI, Jiewen WU, Jingyun LI, Lixian CHEN, Siqi XIAO, Dan LI. Synthesis of a zinc-cobalt bimetallic adenine metal-organic framework for the recognition of sulfur-containing amino acids[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(1): 114-122. doi: 10.11862/CJIC.20240382 shu

Synthesis of a zinc-cobalt bimetallic adenine metal-organic framework for the recognition of sulfur-containing amino acids

Hong CAI ^1,, ,
Jiewen WU ¹ ,
Jingyun LI ¹ ,
Lixian CHEN ¹ ,
Siqi XIAO ¹ ,
Dan LI ^2,,

1.
School of Chemical and Environmental Engineering, Hanshan Normal University, Chaozhou, Guangdong 521041, China
2.
College of Chemistry and Materials Science, Jinan University, Guangzhou 510632, China

Corresponding author: Hong CAI, tiddychen@163.com Dan LI, danli@jnu.edu.cn
Received Date: 22 October 2024
Revised Date: 4 December 2024

Figures(6)

Using adenine (HA) and isophthalic acid (H₂IP) as ligands, a bimetallic organic framework, (C₂H₈N)(NH₄)[Zn₄Co₂(μ⁃O)(IP)₄(A)₄]·1.25H₂O (ZnCoIPA), was successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analysis revealed that the 3D ZnCoIPA retains the Watson-Crick sites of HA, with sinusoidal channels along the a⁃axis direction having diameters of approximately 0.42-0.49 nm and a narrow pore size distribution of about 0.07 nm. The channel diameters along the b⁃axis vary from 0.38 to 0.50 nm with a relatively wider pore size distribution of around 0.12 nm. X-ray photoelectron spectroscopy demonstrated the valence-varying nature of cobalt ions in ZnCoIPA, combined with its unique confined space, enabling selective recognition of sulfur- containing amino acids. UV-Vis absorption spectroscopy indicated the electronic transfer between the host and guest, resulting in a color change from colorless to yellow in solution, providing a visual recognition effect. Furthermore, time-dependent UV-Vis absorption spectroscopy tests on reduced and oxidized forms of glutathione (GSH) showed that the absorption peak intensity of the smaller-sized reduced GSH increased gradually over time, while the larger-sized oxidized GSH exhibited a slower change, enhancing only after a delay of approximately 16 min, further demonstrating the influence of the channel properties on the color change behavior of sulfur-containing amino acids.
- metal-organic framework,
- host-guest chemistry,
- amino acid,
- molecular recognition
1. [1]
  FURUKAWA H, CORDOVA K E, O′KEEFFE M, YAGHI O M. The chemistry and applications of metal-organic frameworks[J]. Science, 2013, 341: 1230444 doi: 10.1126/science.1230444
2. [2]
  ZENG H, XIE M, WANG T, WEI R J, XIE X J, ZHAO Y F, LU W G, LI D. Orthogonal-array dynamic molecular sieving of propylene/propane mixtures[J]. Nature, 2021, 595: 542-548 doi: 10.1038/s41586-021-03627-8
3. [3]
  LÁZARO I A, CHEN X, DING M L, ESKANDARI A, FAIREN- JIMENEZ D, GIMÉNEZ-MARQUÉS M, GREF R, LIN W B, LUO T K, FORGAN R S. Metal-organic frameworks for biological applications[J]. Nat. Rev. Method. Prim., 2024, 4: 43 doi: 10.1038/s43586-024-00329-z
4. [4]
  SU Y, YU J H, LI Y B, PHUA S F Z, LIU G F, LIM W Q, YANG X Z, GANGULY R, DANG C, YANG C L, ZHAO Y L. 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
5. [5]
  LIU Y, WANG X Z, LU X Y, WANG D, LI W Z, FU Y, QI W. Bimetallic center metal-organic framework catalysts for the two-electron oxygen reduction reaction[J]. ACS Appl. Nano Mater., 2024, 7(9): 10137-10143 doi: 10.1021/acsanm.4c00544
6. [6]
  YANG M L, WANG X M, GOMEZ-GARCIA C J, JIN Z X, XIN J J, CAO X X, MA H Y, PANG H J, TAN L C, YANG G X, KAN Y H. Efficient electron transfer from an electron-reservoir polyoxometalate to dual-metal-site metal-organic frameworks for highly efficient electroreduction of nitrogen[J]. Adv. Funct. Mater. 2023, 33: 2214495 doi: 10.1002/adfm.202214495
7. [7]
  ZHANG X, LUO J S, WAN K, PLESSERS D, SELS B, SONG J X, CHEN L G, ZHANG T, TANG P Y, MORANTE J R, ARBIOL J, FRANSAER J. From rational design of a new bimetallic MOF family with tunable linkers to OER catalysts[J]. J. Mater. Chem. A, 2019, 7: 1616-1628 doi: 10.1039/C8TA08508K
8. [8]
  WU J F, SONG Y H, ZHOU R H, CHEN S H, ZUO L, HOU H Q, WANG L. Zn-Fe-ZIF-derived porous ZnFe₂O₄/C@NCNT nanocomposites as anodes for lithium-ion batteries[J]. J. Mater. Chem. A, 2015, 3: 7793-7798 doi: 10.1039/C5TA00805K
9. [9]
  TAO G Q, CHENG Z X, ZHANG D, XU J Q. Preparation and gas sensing properties of Co-doped ZnO porous materials derived by bimetal MOF[J]. Journal of Functional Materials, 2020, 51(9): 9185-9192 doi: 10.3969/j.issn.1001-9731.2020.09.028
10. [10]
  KHUDHAIR E M, KAREEM Y S, AMMAR S H, MAHDI A S. Bimetallic (Fe/Zn-ZIF-8) crystals: Fabrication and adsorptive removal activity[EB/OL]. [2024-12-05]. https://doi.org/10.1016/j.matpr.2023.04.058
11. [11]
  WANG H, QI X J, YAN G Z, SHI J H. Copper-doped ZIF-8 nanomaterials as an adsorbent for the efficient removal of As􀃰 from wastewater[J]. J. Phys. Chem. Solids, 2023, 179: 111408 doi: 10.1016/j.jpcs.2023.111408
12. [12]
  TONG Q, CAI T, YUAN J, HE D N. Stable ZIF-8-derived iron-immobilized ZnFe/NC catalyst for RhB degradation via persulfate activation[J]. J. Environ. Chem. Eng., 2023, 11: 111311 doi: 10.1016/j.jece.2023.111311
13. [13]
  ZHAI Q G, BU X H, MAO C Y, ZHAO X, FENG P Y. Systematic and dramatic tuning on gas sorption performance in heterometallic metal-organic frameworks[J]. J. Am. Chem. Soc., 2016, 138: 2524-2527 doi: 10.1021/jacs.5b13491
14. [14]
  GU Y J, CHOE Y, PARK D W. Catalytic performance of CPM-200-In/Mg in the cycloaddition of CO₂ and epoxides[J]. Catalysts, 2021, 11: 430 doi: 10.3390/catal11040430
15. [15]
  SIMINSKA E, KOBA M. Amino acid profiling as a method of discovering biomarkers for early diagnosis of cancer[J]. Amino Acids, 2016, 48: 1339-1345 doi: 10.1007/s00726-016-2215-2
16. [16]
  LIU X H, REN B, REN J, GU M Z, YOU L, ZHAO Y P. The significant role of amino acid metabolic reprogramming in cancer[J]. Cell Commun. Signal., 2024, 22: 380 doi: 10.1186/s12964-024-01760-1
17. [17]
  NAGAO K, KIMURA T. Use of plasma-free amino acids as biomarkers for detecting and predicting disease risk[J]. Nutr. Rev., 2020, 78: 79-85 doi: 10.1093/nutrit/nuaa086
18. [18]
  REEST J V D, LILLA S, ZHENG L, ZANIVAN S, GOTTLIEB E. Proteome-wide analysis of cysteine oxidation reveals metabolic sensitivity to redox stress[J]. Nat. Commun., 2018, 9: 1581 doi: 10.1038/s41467-018-04003-3
19. [19]
  LAUOMGER L, KAISER P. Sensing and signaling of methionine metabolism[J]. Metabolites, 2021, 11: 83 doi: 10.3390/metabo11020083
20. [20]
  CAI H, WU Y X, LU Z, LUO D, SUN J X, WU G W, LI M, WEI Y B, ZHONG L M, LI D. Mimicking DNA periodic docking grooves for adaptive identification of L⁃/D-tryptophan in a biological metal- organic framework[J]. J. Am. Chem. Soc., 2022, 144: 9559-9563 doi: 10.1021/jacs.2c03326
21. [21]
  CAI H, HUANG Y L, LI D. Biological metal-organic frameworks: Structures, host-guest chemistry and bio-applications[J]. Coord. Chem. Rev., 2019, 378: 207 doi: 10.1016/j.ccr.2017.12.003
22. [22]
  ZHAO Y F, WAN M Y, BAI J P, ZENG H, LU W G, LI D. pH-modulated luminescence switching in a Eu-MOF: Rapid detection of acidic amino acids[J]. J. Mater. Chem. A, 2019, 7: 11127-11133 doi: 10.1039/C9TA00384C
23. [23]
  ZHAO Y F, ZENG H, ZHU X W, LU W G, LI D. Metal-organic frameworks as photoluminescent biosensing platforms: Mechanisms and applications[J]. Chem. Soc. Rev., 2021, 50: 4484-4513 doi: 10.1039/D0CS00955E
24. [24]
  ZHANG T, CHEN H T, WANG L Y, LIANG Y R, ZHANG X T. Nanochannel-based heterometallic {Co^ⅡTb^Ⅲ}⁃organic framework for fluorescence recognition of tryptophan and catalytic cycloaddition of epoxides with CO₂[J]. ACS Appl. Nano Mater., 2022, 5: 15220-15227 doi: 10.1021/acsanm.2c03341
25. [25]
  WANG K, ZHU Y L, ZHENG T F, XIE X, CHEN J L, WU Y Q, LIU S J, WEN H R. Highly pH-responsive sensor based on a Eu^Ⅲ metal-organic framework with efficient recognition of arginine and lysine in living cells[J]. Anal. Chem., 2023, 95: 4992-4999 doi: 10.1021/acs.analchem.2c05224
26. [26]
  SANNER M F, SPEHNER J C, OLSON A J. Reduced surface: An efficient way to compute molecular surfaces[J]. Biopolymers, 1996, 38: 305-320 doi: 10.1002/(SICI)1097-0282(199603)38:3<305::AID-BIP4>3.0.CO;2-Y
27. [27]
  SMART O S, NEDUVELIL J G, WANG X N, WALLACE B A, SANSOM M S. HOLE: A program for the analysis of the pore dimensions of ion channel structural models[J]. J. Mol. Graph., 1996, 14: 354-360 doi: 10.1016/S0263-7855(97)00009-X
28. [28]
  SMART O S, GOODFELLOW J M, WALLACE B A. The pore dimensions of gramicidin A[J]. Biophys. J. 1993, 65: 2455-2460
29. [29]
  CAI H, WU J W, CAI X J, LU Z, LAI Y L, SUN J X, YUAN Z L, HUANG Y Y, CAI J W, LU W, LU Y H, ZHANG H Y, LI D. Recognition, detection and host-guest chemistry of hydrogen peroxide in a fluorescent metal-organic framework with chiral helical channels[J]. Inorg. Chem. Front., 2023, 10: 5144-5151
30. [30]
  CAI H, WU G W, LAI J L, CHEN J P, CHEN Y F, LI D. Selective adsorption of CO₂ by biological metal-organic framework ZnBTCA[J]. Chinese J. Inorg. Chem., 2019, 35(11): 2083-2088 doi: 10.11862/CJIC.2019.236
31. [31]
  LI T, CHEN D L, SULLIVAN J E, KOZLOWSKI M T, JOHNSON J K, ROSI N L. Systematic modulation and enhancement of CO₂: N₂ selectivity and water stability in an isoreticular series of bio-MOF-11 analogues[J]. Chem. Sci., 2013, 4: 1746-1755 doi: 10.1039/c3sc22207a
32. [32]
  DUAN J G, HIGUCHI M, KRISHNA R, KIYONAGA T, TSUTSUMI Y, SATO Y, KUBOTA Y, TAKATA M, KITAGAWA S. High CO₂/N₂/O₂/CO separation in a chemically robust porous coordination polymer with low binding energy[J]. Chem. Sci., 2014, 5: 660-666 doi: 10.1039/C3SC52177J
33. [33]
  CHAI L L, HU Z Y, WANG X, XU Y W, ZHANG L J, LI T T, HU Y, QIAN J J, HUANG S M. Stringing bimetallic metal-organic framework-derived cobalt phosphide composite for high-efficiency overall water splitting[J]. Adv. Sci., 2020, 7: 1903195 doi: 10.1002/advs.201903195
34. [34]
  YAN L T, CAO L, DAI P C, GU X, LIU D D, LI L J, WANG Y, ZHAO X B. Metal-organic frameworks derived nanotube of nickel-cobalt bimetal phosphides as highly efficient electrocatalysts for overall water splitting[J]. Adv. Funct. Mater., 2017, 27: 1703455 doi: 10.1002/adfm.201703455
1. [1]
  Wenjie SHI , Fan LU , Mengwei CHEN , Jin WANG , Yingfeng HAN . Synthesis and host-guest properties of imidazolium-functionalized zirconium metal-organic cage. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 105-113. doi: 10.11862/CJIC.20240360
2. [2]
  Yi DING , Peiyu LIAO , Jianhua JIA , Mingliang TONG . Structure and photoluminescence modulation of silver(Ⅰ)-tetra(pyridin-4-yl)ethene metal-organic frameworks by substituted benzoates. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 141-148. doi: 10.11862/CJIC.20240393
3. [3]
  Zhuo Wang , Xue Bai , Kexin Zhang , Hongzhi Wang , Jiabao Dong , Yuan Gao , Bin Zhao . MOF模板法合成氮掺杂碳材料用于增强电化学钠离子储存和去除. Acta Physico-Chimica Sinica, 2025, 41(3): 2405002-. doi: 10.3866/PKU.WHXB202405002
4. [4]
  Zelong LIANG , Shijia QIN , Pengfei GUO , Hang XU , Bin ZHAO . Synthesis and electrocatalytic CO₂ reduction performance of metal-organic framework catalysts loaded with silver particles. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 165-173. doi: 10.11862/CJIC.20240409
5. [5]
  Jiarui Wu , Gengxin Wu , Yan Wang , Yingwei Yang . Crystal Engineering Based on Leaning Towerarenes. University Chemistry, 2024, 39(3): 58-62. doi: 10.3866/PKU.DXHX202304014
6. [6]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
7. [7]
  Jing SU , Bingrong LI , Yiyan BAI , Wenjuan JI , Haiying YANG , Zhefeng Fan . Highly sensitive electrochemical dopamine sensor based on a highly stable In-based metal-organic framework with amino-enriched pores. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1337-1346. doi: 10.11862/CJIC.20230414
8. [8]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
9. [9]
  Shengbiao Zheng , Liang Li , Nini Zhang , Ruimin Bao , Ruizhang Hu , Jing Tang . Metal-Organic Framework-Derived Materials Modified Electrode for Electrochemical Sensing of Tert-Butylhydroquinone: A Recommended Comprehensive Chemistry Experiment for Translating Research Results. University Chemistry, 2024, 39(7): 345-353. doi: 10.3866/PKU.DXHX202310096
10. [10]
  Tiantian MA , Sumei LI , Chengyu ZHANG , Lu XU , Yiyan BAI , Yunlong FU , Wenjuan JI , Haiying YANG . Methyl-functionalized Cd-based metal-organic framework for highly sensitive electrochemical sensing of dopamine. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 725-735. doi: 10.11862/CJIC.20230351
11. [11]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
12. [12]
  Xiaofang DONG , Yue YANG , Shen WANG , Xiaofang HAO , Yuxia WANG , Peng CHENG . Research progress of conductive metal-organic frameworks. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 14-34. doi: 10.11862/CJIC.20240388
13. [13]
  Tian TIAN , Meng ZHOU , Jiale WEI , Yize LIU , Yifan MO , Yuhan YE , Wenzhi JIA , Bin HE . Ru-doped Co₃O₄/reduced graphene oxide: Preparation and electrocatalytic oxygen evolution property. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 385-394. doi: 10.11862/CJIC.20240298
14. [14]
  Shicheng Yan . Experimental Teaching Design for the Integration of Scientific Research and Teaching: A Case Study on Organic Electrooxidation. University Chemistry, 2024, 39(11): 350-358. doi: 10.12461/PKU.DXHX202408036
15. [15]
  Shiyang He , Dandan Chu , Zhixin Pang , Yuhang Du , Jiayi Wang , Yuhong Chen , Yumeng Su , Jianhua Qin , Xiangrong Pan , Zhan Zhou , Jingguo Li , Lufang Ma , Chaoliang Tan . 铂单原子功能化的二维Al-TCPP金属-有机框架纳米片用于增强光动力抗菌治疗. Acta Physico-Chimica Sinica, 2025, 41(5): 100046-. doi: 10.1016/j.actphy.2025.100046
16. [16]
  Shasha Ma , Zujin Yang , Jianyong Zhang . Facile Synthesis of FeBTC Metal-Organic Gel and Its Adsorption of Cr₂O₇²⁻: A Physical Chemistry Innovation Experiment. University Chemistry, 2024, 39(8): 314-323. doi: 10.3866/PKU.DXHX202401008
17. [17]
  Yong Wang , Yingying Zhao , Boshun Wan . Analysis of Organic Questions in the 37th Chinese Chemistry Olympiad (Preliminary). University Chemistry, 2024, 39(11): 406-416. doi: 10.12461/PKU.DXHX202403009
18. [18]
  Ke Li , Chuang Liu , Jingping Li , Guohong Wang , Kai Wang . 钛酸铋/氮化碳无机有机复合S型异质结纯水光催化产过氧化氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2403009-. doi: 10.3866/PKU.WHXB202403009
19. [19]
  Yukun Chang , Haoqin Huang , Baolei Wang . Preparation of Trans-Cinnamic Acid via “One-Pot” Protocol of Aldol Condensation-Hydrolysis Reaction: Recommending an Improved Organic Synthesis Experiment. University Chemistry, 2024, 39(4): 322-328. doi: 10.3866/PKU.DXHX202309095
20. [20]
  Aiai WANG , Lu ZHAO , Yunfeng BAI , Feng FENG . Research progress of bimetallic organic framework in tumor diagnosis and treatment. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1825-1839. doi: 10.11862/CJIC.20240225

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(348)
HTML views(52)

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