Abstract
Gold nanoclusters (AuNCs) are widely used in the fluorescence detection of biomolecules in human serum due to their good fluorescence properties, low toxicity, and better biocompatibility. However, the weak fluorescence intensity of AuNCs limits the fluorescence detection of molecules within a wide concentration range. It is reported that coating AuNCs in ZIF-8 with adjustable pore size can effectively improve the fluorescence intensity of AuNCs and broaden the detection range. And the AuNCs wrapped in the gaps of ZIF-8 can prevent the fluorescence quenching caused by the aggregation of AuNCs. However, ZIF-8 has high crystallinity, poor dispersion, and easy deposition, which reduces the fluorescence stability of the detection system and affects the detection. Based on the above research, the highly hydrophilic polymer PEI was modified to the surface of ZIF-8, and a kind of nanocomposite material AuNCs/ChOx@ZIF-8/PEI was obtained by co-encapsulating AuNCs prepared with glutathione as a ligand and cholesterol oxidase (ChOx) into ZIF-8 modified with PEI. The composite material emits strong red light at 650 nm under the excitation of 395-nm light, and the system can sensitively detect cholesterol (Chol) in human serum. Compared with other materials, the PEI-modified composite has better solubility and stability, so the detection effect of Chol is better. Encapsulation of ChOx in the ZIF-8 shell can protect the enzyme and increase the local concentration of ChOx, thereby speeding up the reaction rate. Compared with free AuNCs/ChOx, the quenching rate of AuNCs/ChOx@ZIF-8/PEI system is doubled. Secondly, the addition of Fe2+ to the detection process results in higher quenching rate and detection sensitivity. The system can detect Chol in the concentration range 0.1–2.4 μM, with a detection limit of 0.073 μM. The determination is a fast and sensitive strategy. In addition, the practicability of this assay in the detection of Chol in human serum has been verified. Due to its selectivity and sensitivity, it has potential application value in clinical diagnosis.
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Simon K, Kowalewski W, Dobracki W (1987) Evaluation of the indicators of arteriosclerosis risk factors: cholesterol:HDL cholesterol and LDL cholesterol: HDL cholesterol in acute and chronic diseases of the liver. Przegl Lek 44(11):746–750
Vitali C, Remaley AT, Cuchel M (2018) Is low-density lipoprotein cholesterol the key to interpret the role of lecithin: cholesterol acyltransferase in atherosclerosis? Circulation 138(10):1008–1011
Doggen CJM, Smith NL, Lemaitre RN, Heckbert SR, Rosendaal FR, Psaty BM (2004) Serum lipid levels and the risk of venous thrombosis. Arterioscl Throm Vas 24(10):1970–1975
Chupin SP, Tiuriumin IL, Krikshtopaitis MI, Nikiforov SB, Salenko VL, Kun OV, Vialkov AI, Dmitriev AE, Gritskikh GL (1992) Role of cholestanol in the pathogenesis of cholesterol cholelithiasis. Ross Med Zh:Organ Ministerstva Zdravookhraneniia RSFSR 1:11–13
Koletzko B (2015) Hypercholesterolemia. Pediatric nutrition in practice, 2nd edn, World Rev Nutr Diet. Karger Publications 113:234–238. https://doi.org/10.1159/000375191
Searcy RL, Craig RG, Bergquist LM (1961) Chromatographic estimations of serum lipoprotein cholesterol. Clin Chim Acta 6:475–480
Bhandaru RR, Srinivasan SR, Pargaonkar PS, Berenson GS (1977) A simplified colorimetric micromethod for determination of serum cholesterol. Lipids 12(12):1078–1080
Manasterski A, Zak B (1973) Spectrophotometric study of bromide interference in a cholesterol reaction. Microchem J 18(1):18–28
Obermer E, Milton R (1933) A micro-photometric method for the determination of free cholesterol and cholesterol esters in blood-plasma. Biochem J 27(2):345–350
Jin LH, Shang L, Guo SJ, Fang YX, Wen D, Wang L, Yin JY, Dong SJ (2011) Biomolecule-stabilized Au nanoclusters as a fluorescence probe for sensitive detection of glucose. Biosens Bioelectron 26(5):1965–1969
Liu JM, Cui ML, Jiang SL, Wang XX, Lin LP, Jiao L, Zhang LH, Zheng ZY (2013) BSA-protected gold nanoclusters as fluorescent sensor for selective and sensitive detection of pyrophosphate. Anal Methods 5(16):3942–3947
Wu H, Qiao J, Hwang YH, Xu CN, Yu T, Zhang RY, Cai HW, Kim DP, Qi L (2019) Synthesis of ficin-protected AuNCs in a droplet-based microreactor for sensing serum ferric ions. Talanta 200:547–552
Li D, Chen ZH, Yang TZ, Wang H, Lu N, Mei XF (2016) Green synthesis of highly fluorescent AuNCs with red emission and their special sensing behavior for Al3+. RSC Adv 6(23):19182–19189
Chen LY, Wang CW, Yuan ZQ, Chang HT (2015) Fluorescent gold nanoclusters: recent advances in sensing and imaging. Anal Chem 87(1):216–229
Cui ML, Zhao Y, Song QJ (2014) Synthesis, optical properties and applications of ultra-small luminescent gold nanoclusters. Trac-Trend Anal Chem 57:73–82
Guo L, Liang MS, Wang XL, Kong RM, Chen G, Xia L, Qu FL (2020) The role of l-histidine as molecular tongs: a strategy of grasping Tb3+ using ZIF-8 to design sensors for monitoring an anthrax biomarker on-the-spot. Chem Sci 11(9):2407–2413
Rodenas T, Luz I, Prieto G, Seoane B, Miro H, Corma A, Kapteijn F, Xamena F, Gascon J (2015) Metal-organic framework nanosheets in polymer composite materials for gas separation. Nat Mater 14(1):48–55
Zhang ZJ, Xian SK, Xi HX, Wang HH, Li Z (2011) Improvement of CO2 adsorption on ZIF-8 crystals modified by enhancing basicity of surface. Chem Eng Sci 66(20):4878–4888
Lu KD, Aung T, Guo NN, Weichselbaum R, Lin WB (2018) Nanoscale metal-organic frameworks for therapeutic, imaging, and sensing applications. Adv Mater 30(37):1707634
Fan C, Lv XX, Liu FJ, Feng LP, Liu M, Cai YY, Liu H, Wang JY, Yang YL, Wang H (2018) Silver nanoclusters encapsulated into metal-organic frameworks with enhanced fluorescence and specific ion accumulation toward the microdot array-based fluorimetric Analysis of Copper in Blood. ACS Sensors 3(2):441–450
Cai Y, Zhu HS, Zhou WC, Qiu ZY, Chen CC, Qileng AR, Li KS, Liu YJ (2021) Capsulation of AuNCs with AIE effect into metal-organic framework for the marriage of a fluorescence and colorimetric biosensor to detect organophosphorus pesticides. Anal Chem 93(19):7275–7282
Wu XL, Ge J, Yang C, Hou M, Liu Z (2015) Facile synthesis of multiple enzyme-containing metal-organic frameworks in a biomolecule-friendly environment. Chem Commun 51(69):13408–13411
Chen WH, Vazquez-Gonzalez M, Zoabi A, Abu-Reziq R, Willner I (2018) Biocatalytic cascades driven by enzymes encapsulated in metal-organic framework nanoparticles. Nat Catal 1(9):689–695
Guo ML, Chi JT, Zhang C, Wang ML, Liang H, Hou JY, Ai SY, Li XY (2021) A simple and sensitive sensor for lactose based on cascade reactions in Au nanoclusters and enzymes co-encapsulated metal-organic frameworks. Food Chem 339:127863
Chi JT, Guo ML, Zhang C, Zhang YH, Ai SY, Hou JY, Wu P, Li XY (2020) Glucose oxidase and Au nanocluster co-encapsulated metal-organic frameworks as a sensitive colorimetric sensor for glucose based on a cascade reaction. New J Chem 44(31):13344–13349
Xian SK, Xu F, Ma C, Wu Y, Xia QB, Wang HH, Li Z (2015) Vapor-enhanced CO2 adsorption mechanism of composite PEI@ZIF-8 modified by polyethyleneimine for CO2/N2 separation. Chem Eng J 280:363–369
Silva JSF, Silva JYR, de Sa GF, Araujo SS, Gomes MA, Ronconi CM, Santos TC, Junior SA (2018) Multifunctional system polyaniline-decorated ZIF-8 nanoparticles as a new chemo-photothermal platform for cancer therapy. ACS Omega 3(9):12147–12157
Wang HH, Li T, Li JW, Tong WJ, Gao CY (2019) One-pot synthesis of poly(ethylene glycol) modified zeolitic imidazolate framework-8 nanoparticles: size control, surface modification and drug encapsulation. Colloid Surface A 568:224–230
Zheng CL, Ji ZX, Zhang J, Ding SN (2014) A fluorescent sensor to detect sodium dodecyl sulfate based on the glutathione-stabilized gold nanoclusters/poly diallyldimethylammonium chloride system. Analyst 139(13):3476–3480
Zhu GX, Zhang MZ, Lu LD, Lou XP, Dong ML, Zhu LQ (2019) Metal-organic framework/enzyme coated optical fibers as waveguide-based biosensors. Sensor Actuat B-Chem 288:12–19
Tan QQ, Zhang RR, Zhang GY, Liu XY, Qu FL, Lu LM (2020) Embedding carbon dots and gold nanoclusters in metal-organic frameworks for ratiometric fluorescence detection of Cu2+. Anal Bioanal Chem 412(6):1317–1324
Tian R, Zhang ST, Li MW, Zhou YQ, Lu B, Yan DP, Wei M, Evans DG, Duan X (2015) Localization of Au nanoclusters on layered double hydroxides nanosheets: confinement-induced emission enhancement and temperature-responsive luminescence. Adv Funct Mater 25(31):5006–5015
Jiao CL, Li ZD, Li XX, Wu M, Jiang HQ (2021) Improved CO2/N2 separation performance of pebax composite membrane containing polyethyleneimine functionalized ZIF-8. Sep and Purif Technol 259:118190
Hui SH, Liu QQ, Huang ZZ, Yang J, Liu YM, Jiang S (2020) Gold nanoclusters-decorated zeolitic imidazolate frameworks with reactive oxygen species generation for photoenhanced antibacterial study. Bioconjugate Chem 31(10):2439–2445
Liu D, Shang H (2014) Copper nanoclusters-based nanoprobes for colorimetric detection of cholesterol in milk. Food Sci 35(12):143–147
Kumar A, Kumari A, Asu S, Laha D, Sahu SK (2019) Synthesis of CDs from beta-cyclodextrin for smart utilization in visual detection of cholesterol and cellular imaging. ChemistrySelect 4(48):14222–14227
Tig GA, Zeybek DK, Pekyardimci S (2016) Fabrication of amperometric cholesterol biosensor based on SnO2 nanoparticles and Nafion-modified carbon paste electrode. Chem Pap 70(6):695–705
Lin XY, Ni YN, Kokot S (2016) Electrochemical cholesterol sensor based on cholesterol oxidase and MoS2-AuNPs modified glassy carbon electrode. Sensor Actuat B-Chem 233:100–106
Soylemez S, Kanik FE, Nurioglu AG, Akpinar H, Toppare L (2013) A novel conducting copolymer: investigation of its matrix properties for cholesterol biosensor applications. Sensor Actuat B-Chem 182:322–329
Li Y, Li SJ, Bao M, Zhang LQ, Carraro C, Maboudian R, Liu AR, Wei W, Zhang YJ, Liu SQ (2021) Pd nanoclusters confined in ZIF-8 matrixes for fluorescent detection of glucose and cholesterol. ACS Appl Nano Mater 4(9):9132–9142
Wu YZ, Ma YJ, Xu GH, Wei FD, Ma YS, Song Q, Wang X, Tang T, Song YY, Shi ML, Xu XM, Hu Q (2017) Metal-organic framework coated Fe3O4 magnetic nanoparticles with peroxidase-like activity for colorimetric sensing of cholesterol. Sensor Actuat B-Chem 249:195–202
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This work was supported by the National Natural Science Foundation of China (No. 11774048) and the Project from Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education (No. 130028723).
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Ding, J., Zhang, W., Xue, F. et al. Highly dispersive AuNCs/ChOx@ZIF-8/PEI nanocomplexes for fluorescent detection of cholesterol in human serum. Microchim Acta 189, 203 (2022). https://doi.org/10.1007/s00604-022-05306-5
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DOI: https://doi.org/10.1007/s00604-022-05306-5