食品工业科技

贮藏时间（h）	0 g/L	0.2 g/L	0.4 g/L	0.6 g/L	0.8 g/L	1.0 g/L
0	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA
2	10.46±0.14^gA	8.70±0.04^gB	8.21±0.12^gC	7.40±0.09^gD	6.59±0.05^gE	5.88±0.07^gF
4	14.42±0.16^fA	12.60±0.21^fB	11.21±0.15^fC	9.55±0.10^fD	8.63±0.07^fE	7.81±0.16^fF
6	19.52±0.24^eA	15.58±0.08^eB	14.58±0.15^eC	13.33±0.34^eD	12.02±0.17^eE	11.06±0.08^eF
8	23.46±0.12^dA	20.52±0.39^dB	18.21±0.04^dC	17.19±0.03^dD	16.22±0.17^dE	15.59±0.19^dF
10	29.64±0.34^cA	24.74±0.07^cB	22.09±0.03^cC	20.60±0.26^cD	18.98±0.08^cE	18.34±0.19^cF
12	33.71±0.08^bA	29.55±0.43^bB	27.28±0.07^bC	24.84±0.12^bD	22.69±0.05^bE	21.44±0.22^bF
24	38.60±0.16^aA	33.68±0.06^aB	31.60±0.37^aC	29.42±0.11^aD	27.23±0.07^aE	25.56±0.08^aF

贮藏时间（h）	0 g/L	0.2 g/L	0.4 g/L	0.6 g/L	0.8 g/L	1.0 g/L
0	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA
2	10.46±0.14^gA	8.70±0.04^gB	8.21±0.12^gC	7.40±0.09^gD	6.59±0.05^gE	5.88±0.07^gF
4	14.42±0.16^fA	12.60±0.21^fB	11.21±0.15^fC	9.55±0.10^fD	8.63±0.07^fE	7.81±0.16^fF
6	19.52±0.24^eA	15.58±0.08^eB	14.58±0.15^eC	13.33±0.34^eD	12.02±0.17^eE	11.06±0.08^eF
8	23.46±0.12^dA	20.52±0.39^dB	18.21±0.04^dC	17.19±0.03^dD	16.22±0.17^dE	15.59±0.19^dF
10	29.64±0.34^cA	24.74±0.07^cB	22.09±0.03^cC	20.60±0.26^cD	18.98±0.08^cE	18.34±0.19^cF
12	33.71±0.08^bA	29.55±0.43^bB	27.28±0.07^bC	24.84±0.12^bD	22.69±0.05^bE	21.44±0.22^bF
24	38.60±0.16^aA	33.68±0.06^aB	31.60±0.37^aC	29.42±0.11^aD	27.23±0.07^aE	25.56±0.08^aF

材料	MIC值（mg/mL）
E. coli	Fe/Cu MOF	−	−	−	−	−	+	+
Fe/Cu MOF-TA	−	−	−	−	−	−	+
S. aureus	Fe/Cu MOF	−	−	−	−	−	+	+
Fe/Cu MOF-TA	−	−	−	−	−	−	+

材料	MIC值（mg/mL）
E. coli	Fe/Cu MOF	−	−	−	−	−	+	+
Fe/Cu MOF-TA	−	−	−	−	−	−	+
S. aureus	Fe/Cu MOF	−	−	−	−	−	+	+
Fe/Cu MOF-TA	−	−	−	−	−	−	+

Fe/Cu MOF-酒石酸复合物在香蕉保鲜中的应用

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马钰 , 张靖杭 , 王程宇 , 姜毓君 , 曲波 , 满朝新 ^*

食品工业科技 | 研究与探讨 2026,47(4): 164-171

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食品工业科技 |研究与探讨 2026 , 47 (4) : 164 -171

Fe/Cu MOF-酒石酸复合物在香蕉保鲜中的应用

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马钰, 张靖杭, 王程宇, 姜毓君, 曲波, 满朝新^*

作者信息

东北农业大学食品学院，黑龙江哈尔滨 150030

通讯作者:

满朝新（1978−），男，博士，教授，研究方向：乳品科学技术，E-mail：87402577@qq.com。

作者简介:

马钰（2000−），男，硕士研究生，研究方向：食品科学，E-mail：13125906537@163.com

Fe/Cu MOF-Tartaric Acid Complexes for Banana Preservation

Yu MA, Jinghang ZHANG, Chengyu WANG, Yujun JIANG, Bo QU, Chaoxin MAN^*

Affiliations

College of Food Science, Northeast Agricultural University, Harbin 150030, China

出版时间: 2026-02-15 doi: 10.13386/j.issn1002-0306.2025040154

文章导航

摘要

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低温、气调包装等传统保鲜方法往往仅针对单一保鲜需求，无法兼顾水果保鲜过程中的细菌滋生、酶促褐变、风味流失等多重问题，亟需研发兼具高效、环保、多功能的新型保鲜技术。因此，本研究制备了一种具有优异的抗菌及抗褐变能力的Fe/Cu金属有机框架-酒石酸复合物（Fe/Cu MOF-TA），有望为水果提供一种新型、绿色、高效的保鲜材料。以Fe/Cu MOF为框架对酒石酸进行负载，通过扫描电镜和傅里叶红外光谱对其进行表征，并通过抑菌实验和多酚氧化酶抑制率评价其抗菌及抗褐变能力。结果表明，在5种有机酸（柠檬酸、琥珀酸、肉桂酸、酒石酸和苹果酸）中，酒石酸的多酚氧化酶抑制率最高，且酒石酸浓度在0~1.0 g/L范围内时，香蕉多酚氧化酶的活性及褐变程度均随酒石酸的浓度增加而降低。通过扫描电镜观察发现Fe/Cu MOF-TA呈现边缘圆润，表面粗糙的双锥结构，傅里叶变换红外光谱表明酒石酸与MOF通过氢键作用形成复合物。复合物的酒石酸负载率为21.77%。复合物具有优异的抗菌、抗氧化及多酚氧化酶抑制能力，其对金黄色葡萄球菌和大肠杆菌的抑菌圈直径分别为2.5 cm和2.2 cm，最小抑菌浓度为0.0625 mg/mL，多酚氧化酶抑制率为76.03%，显著高于Fe/Cu MOF及酒石酸。

关键词

水果保鲜 / 多酚氧化酶抑制剂 / 抑菌 / MOF-酒石酸复合物

Abstract

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Conventional preservation methods such as low temperature and modified atmosphere packaging often target a single preservation requirement. However, these methods cannot address multiple problems such as bacterial growth, enzymatic browning, and loss of flavor during fruit preservation. Consequently, the development of efficient, environment-friendly, and multifunctional preservation technologies was imperative for maintaining fruit quality. In this study, an Fe/Cu metal–organic framework-tartaric acid complex (Fe/Cu MOF-TA) with excellent antibacterial and anti-browning properties was synthesized, which was expected to provide a new, green, and efficient preservation material for fruits. The successful preparation of the Fe/Cu MOF-TA was confirmed using scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FT-IR). The antibacterial and anti-browning properties of the Fe/Cu MOF-TA were evaluated through antibacterial experiments and the inhibition rate of polyphenol oxidase. The results demonstrated that, among the five organic acids (citric acid, succinic acid, cinnamic acid, TA, and malic acid), TA exhibited the most significant inhibitory effect on polyphenol oxidase activity. Furthermore, when the concentration ranged from 0 to 1.0 g/L, the polyphenol oxidase activity and degree of browning of the bananas exhibited an inversely proportional relationship with increasing concentrations of TA. The SEM images indicated that the Fe/Cu MOF had a bicone structure with a rough surface and rounded edges. FT-IR analysis indicated the formation of a complex between TA and the Cu/Fe MOF through hydrogen bonding. In addition, the TA loading rate of the Fe/Cu MOF-TA was 21.77%. Furthermore, the minimum inhibitory concentration of the Fe/Cu MOF-TA against Escherichia coli and Staphylococcus aureus was 0.0625 mg/mL. The rate of inhibition of polyphenol oxidase by the Fe/Cu MOF-TA was 76.03%. The results demonstrated that Fe/Cu MOF-TA possesses remarkable antibacterial, antioxidant, and polyphenol oxidase inhibitory properties.

Key words

fruit preservation / polyphenol oxidase inhibitor / antibacterial / MOF-tartatic acid complex

引用本文

马钰, 张靖杭, 王程宇, 姜毓君, 曲波, 满朝新. Fe/Cu MOF-酒石酸复合物在香蕉保鲜中的应用. 食品工业科技, 2026 , 47 (4) : 164 -171 . DOI: 10.13386/j.issn1002-0306.2025040154

Yu MA, Jinghang ZHANG, Chengyu WANG, Yujun JIANG, Bo QU, Chaoxin MAN. Fe/Cu MOF-Tartaric Acid Complexes for Banana Preservation[J]. Science and Technology of Food Industry, 2026 , 47 (4) : 164 -171 . DOI: 10.13386/j.issn1002-0306.2025040154

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水果是人类饮食中不可或缺的重要组成部分，富含多种对人体健康至关重要的营养物质，包括维生素、矿物质、膳食纤维和抗氧化物质等^[1−4]。然而，水果在采后运输过程中，其呼吸作用和代谢活动仍在持续，致使水果腐败变质，造成营养流失和品质下降^[5]。此外，微生物侵染、水分流失以及酶促反应等因素也会加速水果的腐败过程^[6−7]。在水果的腐败过程中，多酚氧化酶（Polyphenol Oxidase，PPO）扮演了重要角色。PPO是一种广泛存在于植物组织中的酶，当水果受到机械损伤或暴露于空气中时，PPO会催化酚类物质氧化为醌类物质，进而形成褐色聚合物，导致水果发生褐变^[8]。香蕉作为日常生活中常见的水果，其PPO活性较高，因此在加工和运输过程中极易发生褐变，不仅影响外观，还会降低其营养价值和食用品质^[9]。

为了抑制PPO活性并减缓酶促褐变，目前已有多种方法被研究和应用，主要有化学抑制剂类化合物（如抗坏血酸、亚硫酸盐^[10−11]）、天然提取物类化合物（如槲皮素、绿原酸^[12−13]）、蛋白质类化合物（乳清蛋白、酶解肽段^[14]）和有机酸（柠檬酸、酒石酸^[15]）等。其中，有机酸因其高效、安全且易于操作的特点，成为抑制酶促褐变的常用方法。有机酸通过降低pH、直接抑制PPO活性以及作为还原剂阻断醌类物质的形成，有效延缓褐变过程^[16]。相较于其他方法，使用有机酸抑制酶促褐变具有自身独特的优势，主要包括安全性高，对人体无害；成本低，易于大规模应用和对水果的营养成分和风味影响较小等^[17−18]。

金属有机框架（Metal Organic Framework，MOF）是由中心金属离子与有机配体配位组成的杂化多孔材料^[19]，具有高表面积，孔隙结构，结构可调控等优点^[20−21]。MOF的结构及内部的金属离子赋予了其优异的抗菌能力，使得MOF在抗菌方面得到了广泛应用，He等^[22]制备了具有优异抗菌特性的Co-MOF材料，经近红外光照射10 min后其对大肠杆菌和金黄色葡萄球菌的抑菌率达到了97%和100%。近年来有研究通过将MOF与其他功能物质相结合，以起到增大其功能范围和协同增效的作用^[23]，Cheng等^[24]将表面素与ZIF-8-NH₂相偶联，发现该复合物对荧光假单胞菌的最小抑菌浓度（MIC）为0.0625 mg/mL，具有良好的抑菌能力。除此之外，MOF材料负载其他物质还可以达到对负载物质可控释放的效果，Lei等^[25]利用UIO-66负载姜黄素以运输姜黄素至结肠，实现其在结肠病变部位的缓释作用。将有机酸与MOF相结合既可以做到抑制水果褐变和抗菌的双重作用，又能起到对有机酸可控释放的作用。本研究通过PPO抑制率、褐变指数、总酚含量、DPPH自由基清除能力及ABTS⁺自由基清除能力等指标从5种有机酸（柠檬酸、肉桂酸、酒石酸、苹果酸、琥珀酸）中筛选出抑制香蕉褐变效果最强的有机酸及相应的浓度，将其与Fe/Cu MOF材料结合制备成复合物，对其进行表征，并对其多酚氧化酶抑制率、抗菌性能进行评价。本研究通过制备Fe/Cu MOF-酒石酸复合物为果蔬提供新型保鲜材料，并为有机酸抑制果蔬褐变提供一种新方法。

1　材料与方法

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1.1　材料与仪器

香蕉　当地超市购买；酒石酸（TA）、柠檬酸、FeCl₃　天津市凯通化学试剂有限公司；L-苹果酸　天津市大茂化学试剂厂；肉桂酸、邻苯二酚、对苯二甲酸、CuCl₂·2H₂O　上海麦克林生化科技有限公司；琥珀酸　天津奥普升化工有限公司；三氯乙酸　上海展云化工有限公司；总酚试剂盒　上海生工生物工程有限公司；DPPH　上海阿拉丁生化科技股份有限公司；N,N-二甲基甲酰胺（N,N-Dimethylformamide，DMF）　天津市天力化学试剂有限公司；所有试剂均为分析纯。

FA2204B分析天平　上海诺科仪器仪表有限公司；ThermoX1R离心机　美国Thermo公司；Tecan Infinite 200 PRO多功能酶标仪　北京普天新桥技术有限公司；CM-700D色差仪　日本柯尼卡美能达公司；SU8010场发射扫描电子显微镜　日本日立公司；Nicolet IS15傅里叶变换红外光谱仪　美国赛默飞世尔科技有限公司；TGA8000热重分析仪　美国铂金埃尔默公司。

1.2　实验方法

1.2.1　样品PPO酶液的制备

样品前处理方法参考Zhang等^[26]的方法并稍作修改。将香蕉用清水洗净，均匀切块，称取25 g香蕉加入到100 mL PBS（0.01 mol/L，pH6.8）中并放到榨汁机中进行榨汁。榨汁完毕后将香蕉汁进行离心（10000 r/min，10 min），离心后取上清液作为PPO酶液用于试验。

1.2.2　PPO抑制率测定

参考江宏伟^[27]的方法并加以修改，在试管中加入1 mL、0.1 mol/L邻苯二酚溶液，并加入不同浓度的柠檬酸、肉桂酸、酒石酸、苹果酸、琥珀酸（浓度为0、0.2、0.4、0.6、0.8和1.0 mg/mL）各1 mL，混匀后在30 ℃的水浴锅中水浴10 min，水浴完成后加入1 mL酶液在30 ℃反应1 min，反应完成后立即加入1 mL三氯乙酸终止反应。将反应液于420 nm下测量吸光度值，蒸馏水替代反应液作为对照。PPO抑制率按公式（1）进行计算。

$\rm \text{PPO抑制率}( \text{%}) =\frac{{{\Delta OD}}_{\text{1}}-{{\Delta OD}}_{\text{2}}}{{{\Delta OD}}_{\text{2}}}$

(1)

其中，∆OD₁为样品组在420 nm下的吸光度值；∆OD₂为对照组在420 nm下的吸光度值。

1.2.3　不同酒石酸浓度对香蕉褐变的影响

香蕉内部的酚类物质、抗氧化物质含量能够侧面反映香蕉的褐变程度，本研究以香蕉的褐变指数、总酚含量、抗氧化能力（DPPH自由基清除率、ABTS⁺自由基清除率）为指标评价不同浓度酒石酸（浓度为0、0.2、0.4、0.6、0.8和1.0 mg/mL）对香蕉褐变效果的影响。

1.2.3.1　待测样品的制备

待测样品的制备方法参照1.2.1步骤进行。其中，将PBS溶液替换为浓度为0、0.2、0.4、0.6、0.8和1.0 g/L的酒石酸溶液。

1.2.3.2　褐变指数的测定

参考田学智等^[28]的方法并加以修改，使用色差仪测定褐变指数（BI）。将待测样品在37 ℃下储存24 h，在不同时间点（0、2、4、6、8、10、12和24 h）测定样品。在测定时将待测样品混匀倒入航空杯，将仪器进行白板校正后进行测量，并通过公式（2）进行计算。

$ \text{BI=}\frac{\left[\text{100}\times\left(\dfrac{{{a}}^{\text{*}}\text{+1.75}{{L}}^{\text{*}}}{\text{5.645}{{L}}^{\text{*}}+{{a}}^{\text{*}}{-0.3012}{{b}}^{\text{*}}}{-0.31}\right)\right]}{\text{0.172}}$

(2)

其中，L^*为样品处理后亮度值；a^*为样品处理后红色值；b^*为样品处理后黄色值。

1.2.3.3　总酚含量测定

参考Tian等^[29]的方法，采用Folin-ciocalteu法测定样品的总酚含量，并以不同浓度的没食子酸溶液绘制标准曲线，根据标准曲线得到样品的总酚含量（y=0.2797x−0.0017，R²=0.9993）。植物总酚含量以样品质量计算（mg/g）。

1.2.3.4　抗氧化能力测定

按照Shimada等^[30]描述的方法测量样品的DPPH自由基清除率，并稍作调整。首先，将0.1 mL样品加入2 mL DPPH（0.1 mmol/L）中，充分振荡摇匀，然后避光反应30 min，在517 nm处记录吸光度值。无水乙醇替代DPPH为空白组，0.1 mL样品加入2 mL无水乙醇为对照组。DPPH自由基清除率如式（3）所示：

$\rm \text{DPPH自由基清除率}( \text{%}) =\left(\text{1}-\frac{{{\Delta OD}}_{\text{2}}-{{\Delta OD}}_{\text{1}}}{{{\Delta OD}}_{\text{0}}}\right)\text{×100} $

(3)

其中，∆OD₂为试验组的吸光度；∆OD₁为对照组的吸光度；∆OD₀为空白组的吸光度。

1.2.4　Fe/Cu MOF-TA复合物的表征及性能评价

本研究以FeCl₃和CuCl₂为金属离子，对苯二甲酸为金属框架，通过溶剂热法制备了Fe/Cu MOF，随后将Fe/Cu MOF与TA通过物理搅拌混合制备得到Fe/Cu MOF-TA复合物。材料制备示意图如图1所示。

1.2.4.1　Fe/Cu MOF的合成

按照Chen等^[31]的方法合成Fe/Cu MOF，并稍作修改。称取0.54 g FeCl₃、0.152 g CuCl₂·2H₂O和0.166 g对苯二甲酸溶于50 mL DMF，超声1 h使反应物完全溶解，随后装入反应釜中在烘箱中120 ℃条件下反应12 h。反应完毕后离心，随后用DMF和无水乙醇洗涤3次，最后放入烘箱进行烘干，所得样品即为Fe/Cu MOF。

1.2.4.2　Fe/Cu MOF-TA复合物的合成

称取0.1 g Fe/Cu MOF材料和0.01 g酒石酸溶于100 mL蒸馏水中，搅拌1 h后离心。离心完毕后倒出上清液，将沉淀重新溶于蒸馏水中进行冻干，收集冻干粉末用于后续试验。

1.2.4.3　微观形貌观察

采用场发射扫描电子显微镜（Scanning electron microscope，SEM）表征Fe/Cu MOF及Fe/Cu MOF-TA复合物的形貌及分散情况。将干燥的材料分别用玛瑙研钵研磨，挑取少量粉末粘于样品台上，镀膜并观察，仪器的加速电压一般设置为5~15 kV。

1.2.4.4　傅里叶红外变换光谱分析

采用傅里叶变换红外光谱（Fourier transform infrared spectrometer，FTIR）对Fe/Cu MOF及Fe/Cu MOF-TA复合物的化学键组成进行分析。首先将制备得到的样品进行干燥，接着分别取少量干燥样品与一定量的干燥光谱级溴化钾粉末混合，在洁净的玛瑙研钵中充分研磨，将研磨后的测试样通过压片机压片，得到含有样品的较为透明的均匀薄片，放入仪器中检测。待测样品的红外光谱图通过在4000~400 cm⁻¹的范围内以4 cm⁻¹的分辨率扫描64次记录得到。

1.2.4.5　热重分析

通过热重分析对Fe/Cu MOF-TA的热稳定性进行分析，称取0.1 g Fe/Cu MOF和0.1 g Fe/Cu MOF-TA复合物进行热重分析，其中温度范围为25~600 ℃，使用氮气作为保护气，流速为20 mL/min，加热速率为10 ℃/min。

1.2.4.6　TA负载率的测定

TA负载率的测定参考酸碱滴定法进行，以酚酞为指示剂，使用邻苯二甲酸标定的NaOH进行滴定，记录不同浓度酒石酸（0.1、0.08、0.06、0.04、0.02和0 g/L）滴定所需NaOH的体积，并绘制标准曲线y=124.96x+0.087，相关系数为0.9994，其中，y为氢氧化钠体积，mL；x为酒石酸质量浓度，g/L。按照1.2.4.2制备Fe/Cu MOF-TA溶液并进行离心，对离心后的上清液进行滴定，结果代入标准曲线计算出对应TA的质量浓度。TA负载率如式（4）所示：

$ \text{TA负载率}( \text{%}) \text=\frac{({\text{c}}_{\text{1}}-{\text{c}}_{\text{2}}\text{)V}}{\text{m}}\text{×100}$

(4)

其中，c₁为未离心溶液中TA的浓度，0.1 g/L；c₂为离心之后上清液中TA的浓度，g/L；m为Fe/Cu MOF质量，g；V为溶液的体积，L。

1.2.4.7　抗菌能力评价

Fe/Cu MOF-TA的抗菌能力通过MIC和抑菌圈试验进行评价。

最小抑菌浓度（MIC）的测定：参考96孔板微量法对大肠杆菌、金黄色葡萄球菌的MIC进行测定，将所有指示菌培养至对数期，使用分光光度计调节吸光度至0.5（OD_{600 nm}），加入100 μL的菌液，然后在每组菌液中分别加入Fe/Cu MOF及Fe/Cu MOF-TA复合物溶液，配制终体积为200 μL，放置于恒温培养箱中，条件为37 ℃培养24 h，孔板中清晰透明未有微生物生长的最低浓度为最小抑菌浓度。

参考Lei等^[32]的方法通过圆盘琼脂扩散法评估Fe/Cu MOF和Fe/Cu MOF-TA复合物的抗菌性能，使用金黄色葡萄球菌和大肠杆菌作为实验细菌。将消毒后的滤纸片浸入溶液中，并放置在含有细菌的琼脂平板表面，然后将平板在培养箱中37 ℃培养24 h，并测量Fe/Cu MOF和Fe/Cu MOF-TA复合物的抑菌圈直径；MOF、TA、MOF-TA的PPO抑制率测定同1.2.2。

1.3　数据处理

本文中实验均进行了3次平行，数据采用SPSS 2.0软件进行单因素方差分析，结果以平均差±标准差（Mean±SD）进行表示，采用Origin 9.0和GraphPad 8.0软件进行绘图，其中P<0.05表示显著差异，P<0.01表示极显著差异。

2　结果与分析

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2.1　有机酸种类对PPO抑制率的影响

如图2所示，5种有机酸对香蕉PPO活性抑制效果为：酒石酸>肉桂酸>柠檬酸>苹果酸>琥珀酸，酒石酸抑制效果优于其他有机酸，可能是因其分子构象更易与PPO活性中心的Cu²⁺结合，起到抑制作用^[33]。此外，随着有机酸浓度从0.2 g/L增长到0.6 g/L，酒石酸对香蕉PPO的抑制率呈现明显的上升趋势（P<0.05）。当酒石酸大于0.6 g/L时，酒石酸对香蕉PPO抑制率趋于平稳，这可能归因于0.6%时酒石酸对PPO活性中心的螯合作用已接近极限。基于上述结果，后续选择酒石酸作为PPO抑制剂用于后续试验。

2.2　酒石酸对香蕉褐变指数的影响

水果的褐变指数是体现水果褐变程度最直观的指标^[34]。由表1可见，随着贮藏时间的增加，各组样品的褐变指数均显著增加（P<0.05）。在相同时间点，添加了酒石酸的样品组褐变指数均比对照组显著降低（P<0.05），且随着酒石酸浓度的增加，样品的褐变指数逐渐降低。上述结果表明加入酒石酸能够显著抑制香蕉的褐变，且呈剂量依赖性。

2.3　酒石酸对香蕉总酚含量的影响

水果的总酚含量是指水果中所有酚类化合物的含量，酚类化合物是水果中重要的抗氧化剂，而水果中的PPO会氧化酚类化合物为醌类物质，导致水果发生褐变，因此通过测定水果的总酚含量可以反映水果易发生褐变的程度^[35]。图3展示了在不同酒石酸浓度下香蕉的总酚含量，从图3中可以看出，随着酒石酸浓度的增加，香蕉的总酚含量呈增加趋势，当TA浓度为1.0 g/L时，总酚含量相较于对照组从2.60 mg/g提升至4.34 mg/g，提高了66.92%（P<0.05），表明酒石酸能够抑制香蕉中酚类物质被PPO氧化，更好地维持香蕉的颜色稳定。李佩艳等^[36]用草酸处理采后银条，发现0.9 g/L草酸处理后银条的总酚含量提高了12.65%，本研究所得结果高于其研究结果。

2.4　酒石酸对香蕉DPPH自由基清除率的影响

DPPH自由基清除率是衡量物质抗氧化能力的重要指标，反映样品中抗氧化物质清除DPPH自由基（1,1-二苯基-2-三硝基苯肼自由基）的能力^[37]。水果中的多酚类物质及维生素C等抗氧化成分具有清除DPPH自由基的能力，从而起到间接抑制水果褐变的作用^[38]。从图4中可以看出，对照组具有58.23%的DPPH自由基清除率，表明未添加酒石酸的香蕉中仍然具有丰富的酚类物质。而随着酒石酸浓度的增加，DPPH自由基清除率逐渐增加，在1.0 g/L时DPPH自由基清除率升高至74.68%，表明酒石酸能够更好地保护香蕉中的酚类物质，从而达到清除DPPH自由基的效果。孟创鸽等^[39]对菊苣中5种提取物（菊苣酸、木犀草苷、绿原酸、咖啡酸和酒石酸）进行抗氧化能力测定，发现在5种提取物中酒石酸具有最好的自由基清除能力，本实验结果与之一致。

2.5　Fe/Cu MOF-TA微观形貌观察

图5为Fe/Cu MOF和Fe/Cu MOF-TA的SEM图像，通过观察图5（a）发现，Fe/Cu MOF材料呈现棱角分明的十二双锥结构，表明Fe/Cu MOF的成功合成。而观察图5（b）发现，合成的Fe/Cu MOF-TA呈现边缘圆润，表面粗糙的双锥结构，其原因可能是TA吸附在了Fe/Cu MOF表面，并未通过内部作用力改变Fe/Cu MOF的晶体形态。

2.6　傅里叶红外光谱分析

由图6可见，Fe/Cu MOF和Fe/Cu MOF-TA在1589、1406、1316、1031和556 cm⁻¹处出现吸收峰，分别对应对苯二甲酸羧酸根的不对称伸缩振动（1550~1650 cm⁻¹）、苯环C=C振动（1400~1600 cm⁻¹）、羧酸根对称伸缩振动（1300~1400 cm⁻¹）、C-O伸缩振动（1000~1300 cm⁻¹）及MOF中金属-氧伸缩振动（<700 cm⁻¹）。与Fe/Cu MOF相比，Fe/Cu MOF-TA的上述波峰未发生偏移，表明TA的加入未对Fe/Cu MOF结构造成破坏。氢键的O-H伸缩在3200~3400 cm⁻¹范围内，由图6中可见Fe/Cu MOF-TA在3283 cm⁻¹处的峰相较于Fe/Cu MOF在3307 cm⁻¹处的波峰发生了偏移，表明氢键的形成。

2.7　Fe/Cu MOF-TA的热重分析

图7为Fe/Cu MOF和Fe/Cu MOF-TA的热重曲线，可以看出在0~200 ℃之间2种材料的质量损失率较为接近，主要是因为在这一阶段主要挥发成分为材料中残留的水；从200 ℃开始Fe/Cu MOF-TA的质量损失率逐渐高于Fe/Cu MOF，其中在200~400 ℃时Fe/Cu MOF中的有机配体开始挥发，而Fe/Cu MOF-TA中除有机配体挥发外，其中的TA也开始挥发，从而使得其质量损失率高于Fe/Cu MOF；在400~600 ℃时2种材料中的MOF骨架发生坍塌，最终残留物为Fe和Cu的氧化物。

2.8　Fe/Cu MOF-TA抗菌性能评价

对复合物中TA负载率进行测定得到复合物中TA的负载率为21.77%。后续通过抑菌圈和最小抑菌浓度对Fe/Cu MOF-TA复合物的抑菌性能进行了评价。

抑菌圈可以更为直观地反映材料对致病菌的抑制能力^[40]。大肠杆菌（E. coli）和金黄色葡萄球菌（S. aureus）作为环境中最常见的2类致病菌，通过研究材料对2类致病菌的抑制效果可以评估材料对致病菌的广谱抗菌能力。通过图8可以看到，Fe/Cu MOF和Fe/Cu MOF-TA都具有显著的抑菌作用，主要是因为MOF可以通过破坏细胞膜、产生氧化应激损伤及干扰细菌代谢等机制达到抑菌作用^[41]。Fe/Cu MOF对大肠杆菌和金黄色葡萄球菌的抑菌圈直径为2.2 cm和2.0 cm。相较于Fe/Cu MOF，Fe/Cu MOF-TA对大肠杆菌和金黄色葡萄球菌的抑菌圈直径可以达到2.5 cm和2.2 cm，表明添加了TA后复合物具有了更强的抑菌能力，其主要原因可能是TA中的羧基和羟基可以破坏细菌细胞膜和抑制细菌代谢，从而起到抑菌作用^[42]，加入TA可以增强材料的抑菌能力。Cheng等^[43]制备的ZnAg@PAN双金属MOF纳米材料对金黄色葡萄球菌和大肠杆菌的抑菌圈直径分别为1.71 cm和1.51 cm，本研究所得结果高于其结果。

最小抑菌浓度（Minimum inhibitory concentration，MIC）是抗菌剂完全抑制细菌生长的最小浓度，能够精确反映抗菌剂的效力^[44]。由表2可知，Fe/Cu MOF对E. coli和S. aureus的MIC均为0.125 mg/mL，而Fe/Cu MOF-TA对两种致病菌的MIC降低至0.0625 mg/mL，表明Fe/Cu MOF-TA的抑菌效果明显优于Fe/Cu MOF，该结果与上述抑菌圈结果保持一致。

2.9　MOF-TA的PPO抑制效果分析

由图9可以看出，单一的Fe/Cu MOF材料PPO抑制率较低，仅为16.6%，其PPO抑制能力来源于Fe/Cu MOF中的Cu²⁺对PPO的抑制作用。而Fe/Cu MOF-TA的抑制率为76.03%，高于单一TA的抑制率（59.80%）（P<0.05），一方面因为Fe/Cu MOF和TA对PPO具有双重抑制作用，另一方面Fe/Cu MOF的多孔结构具有缓释作用，维持TA在局部处于高浓度水平，持续抑制PPO^[45]。

3　结论

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本研究通过溶剂热法成功构建Fe/Cu MOF载体，并通过氢键作用高效负载酒石酸，形成兼具抑菌和抑制褐变能力的Fe/Cu MOF-TA复合物。对比研究柠檬酸、苹果酸、酒石酸、肉桂酸和琥珀酸对香蕉多酚氧化酶的抑制效果，证实酒石酸抑制能力最为突出。浓度梯度实验表明，在0~1.0 g/L范围内，随酒石酸浓度升高，香蕉PPO活性及褐变程度呈下降趋势。Fe/Cu MOF-TA复合物呈现边缘圆润，表面粗糙的双锥结构，具有良好的热稳定性。TA负载率为21.77%时，Fe/Cu MOF-TA对大肠杆菌和金黄色葡萄球菌的MIC均为0.0625 mg/mL，PPO抑制率为76.03%，展现出优异的抑菌和抑制PPO活性的能力，在香蕉保鲜中具有良好的应用潜力。

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2026年第47卷第4期

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doi: 10.13386/j.issn1002-0306.2025040154

接收时间：2025-04-14
首发时间：2026-10-24
出版时间：2026-02-15

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收稿日期：2025-04-14

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东北农业大学食品学院，黑龙江哈尔滨 150030

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满朝新（1978−），男，博士，教授，研究方向：乳品科学技术，E-mail：87402577@qq.com。

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https://castjournals.cast.org.cn/joweb/spgykj/CN/10.13386/j.issn1002-0306.2025040154

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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贮藏时间（h）	0 g/L	0.2 g/L	0.4 g/L	0.6 g/L	0.8 g/L	1.0 g/L
0	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA	4.70±0.25^hA
2	10.46±0.14^gA	8.70±0.04^gB	8.21±0.12^gC	7.40±0.09^gD	6.59±0.05^gE	5.88±0.07^gF
4	14.42±0.16^fA	12.60±0.21^fB	11.21±0.15^fC	9.55±0.10^fD	8.63±0.07^fE	7.81±0.16^fF
6	19.52±0.24^eA	15.58±0.08^eB	14.58±0.15^eC	13.33±0.34^eD	12.02±0.17^eE	11.06±0.08^eF
8	23.46±0.12^dA	20.52±0.39^dB	18.21±0.04^dC	17.19±0.03^dD	16.22±0.17^dE	15.59±0.19^dF
10	29.64±0.34^cA	24.74±0.07^cB	22.09±0.03^cC	20.60±0.26^cD	18.98±0.08^cE	18.34±0.19^cF
12	33.71±0.08^bA	29.55±0.43^bB	27.28±0.07^bC	24.84±0.12^bD	22.69±0.05^bE	21.44±0.22^bF
24	38.60±0.16^aA	33.68±0.06^aB	31.60±0.37^aC	29.42±0.11^aD	27.23±0.07^aE	25.56±0.08^aF

贮藏时间（h）

0 g/L

0.2 g/L

0.4 g/L

0.6 g/L

0.8 g/L

1.0 g/L

4.70±0.25^hA

10.46±0.14^gA

8.70±0.04^gB

8.21±0.12^gC

7.40±0.09^gD

6.59±0.05^gE

5.88±0.07^gF

14.42±0.16^fA

12.60±0.21^fB

11.21±0.15^fC

9.55±0.10^fD

8.63±0.07^fE

7.81±0.16^fF

19.52±0.24^eA

15.58±0.08^eB

14.58±0.15^eC

13.33±0.34^eD

12.02±0.17^eE

11.06±0.08^eF

23.46±0.12^dA

20.52±0.39^dB

18.21±0.04^dC

17.19±0.03^dD

16.22±0.17^dE

15.59±0.19^dF

29.64±0.34^cA

24.74±0.07^cB

22.09±0.03^cC

20.60±0.26^cD

18.98±0.08^cE

18.34±0.19^cF

33.71±0.08^bA

29.55±0.43^bB

27.28±0.07^bC

24.84±0.12^bD

22.69±0.05^bE

21.44±0.22^bF

38.60±0.16^aA

33.68±0.06^aB

31.60±0.37^aC

29.42±0.11^aD

27.23±0.07^aE

25.56±0.08^aF

材料	MIC值（mg/mL）
E. coli	Fe/Cu MOF	−	−	−	−	−	+	+
Fe/Cu MOF-TA	−	−	−	−	−	−	+
S. aureus	Fe/Cu MOF	−	−	−	−	−	+	+
Fe/Cu MOF-TA	−	−	−	−	−	−	+

材料

MIC值（mg/mL）

0.5

0.25

0.125

0.0625

0.03125

E. coli

Fe/Cu MOF

−

Fe/Cu MOF-TA

−

S. aureus

Fe/Cu MOF

−

Fe/Cu MOF-TA

−