王濤，徐丹

金屬有機(jī)框架材料載體系統(tǒng)在食品抗菌包裝中的應(yīng)用

王濤，徐丹

（西南大學(xué) 食品科學(xué)學(xué)院，重慶 400715）

綜述金屬有機(jī)框架材料（Metal-organic frameworks，MOFs）作為載體系統(tǒng)在食品抗菌包裝領(lǐng)域的研究現(xiàn)狀和應(yīng)用進(jìn)展，以期為MOFs類抗菌包裝材料的研發(fā)和應(yīng)用提供參考。介紹MOFs的基本概念及分類，概述MOFs的制備方法（加熱法、機(jī)械法和電化學(xué)法等），總結(jié)歸納近年來MOFs作為載體系統(tǒng)在無機(jī)抗菌劑、有機(jī)抗菌劑和天然抗菌劑領(lǐng)域的應(yīng)用，并討論MOFs作為載體系統(tǒng)的機(jī)遇和挑戰(zhàn)。MOFs作為一種有機(jī)與無機(jī)相結(jié)合的多孔性復(fù)合材料，不僅可有效封裝抗菌劑，實(shí)現(xiàn)緩釋和控釋，且將MOFs復(fù)合材料作為高分子填料可提高其抗菌性能、力學(xué)性能和抗紫外線性能等，因此在制備高效、安全的食品抗菌包裝方面具有巨大潛力。

金屬有機(jī)框架材料；載體系統(tǒng)；食品抗菌包裝

微生物污染是造成食品變質(zhì)并導(dǎo)致食品安全問題的主要原因之一，可能發(fā)生在原料獲得、加工、貯藏和銷售等各環(huán)節(jié)[1]。為了更好地減少微生物在食品加工和流通各環(huán)節(jié)對(duì)食品的污染，減少食品中防腐劑的添加，抗菌食品包裝逐漸成為近年的研究熱點(diǎn)?？咕b指將抗菌物質(zhì)添加到包裝材料中，通過抗菌物質(zhì)與食品的直接接觸或以一定速度釋放至食品中，起到殺菌或抑制微生物生長(zhǎng)的作用，從而延緩食品的腐敗變質(zhì)，提升食品安全[2]。

在抗菌包裝中添加的抗菌物質(zhì)可分為無機(jī)抗菌劑、有機(jī)抗菌劑和天然抗菌劑。直接將抗菌劑添加至包裝基材中可能存在以下2個(gè)問題：一是抗菌劑與包裝基材的相容性不足，導(dǎo)致抗菌劑在基材中難以分散，對(duì)基材性能存在不良影響；二是釋放型抗菌劑的抗菌效果好，但需對(duì)其釋放速率進(jìn)行調(diào)控。目前，采用載體系統(tǒng)對(duì)抗菌劑進(jìn)行封裝和控釋是解決上述問題的有效策略之一。采用載體系統(tǒng)對(duì)抗菌劑進(jìn)行封裝，不僅能提高其相容性，還能起到控釋效果。有機(jī)和無機(jī)化合物都可作為載體系統(tǒng)，如聚合物[3]、脂質(zhì)體[4]、沸石[5]和量子點(diǎn)[6]等。雖然有機(jī)載體具有生物相容性好、低毒、可化學(xué)改性等優(yōu)點(diǎn)，但其合成過程通常較復(fù)雜，且負(fù)載率較低。雖然無機(jī)多孔材料具有較高的負(fù)載能力，但存在結(jié)構(gòu)單一、缺乏柔性、孔道不規(guī)則等缺點(diǎn)，不具備控釋性能，限制了其應(yīng)用范圍。

金屬有機(jī)框架材料（Metal-organic frameworks，MOFs）是近年來發(fā)展起來的一種由有機(jī)配體和金屬離子或團(tuán)簇通過配位鍵自組裝形成的具有分子內(nèi)孔隙的有機(jī)?無機(jī)雜化材料，具有比表面積大、孔徑可調(diào)節(jié)、生物相容性好等優(yōu)點(diǎn)[7]，在醫(yī)藥[8]、化工[9]、環(huán)境[10]等多個(gè)領(lǐng)域具有良好的應(yīng)用前景。在食品工程領(lǐng)域，大量研究已經(jīng)將MOFs用作氣體吸附劑[11]或活性物質(zhì)載體[12]，應(yīng)用于食品檢測(cè)、食品加工及食品包裝[13]等領(lǐng)域。同時(shí)，MOFs也被作為多種抗菌劑的載體，用于提高抗菌效率或調(diào)控釋放速率，表現(xiàn)出良好的應(yīng)用前景。文中首先介紹MOFs的基本概念及分類，然后綜述其作為抗菌劑載體系統(tǒng)在食品包裝中的最新研究進(jìn)展，以期為MOFs類抗菌包裝材料的研發(fā)和應(yīng)用提供參考。

1 MOFs簡(jiǎn)介

MOFs主要是由含氧、氮等多齒有機(jī)配體（大多為芳香多酸和多堿）與金屬離子或離子簇通過配位鍵連接而成的一類多孔晶體材料[14]，其孔隙率較高，且孔隙形狀和尺寸可調(diào)[15]，兼具無機(jī)材料的剛性和有機(jī)材料的柔性，是一類極具應(yīng)用前景的多孔材料。根據(jù)MOFs的配體結(jié)構(gòu)，可將其分為羧酸類、氮雜環(huán)類，以及環(huán)糊精等生物分子類，如表1所示。

MOFs可采用以下3種方法合成。

1）加熱法。以水、N,N-二甲基甲酰胺、甲醇等為溶劑體系，將金屬離子和有機(jī)配體等原料混合均勻后加熱合成MOFs。根據(jù)加熱方式，可分為溶劑熱法[22]、超聲波法[23]和微波法[24]。相較于溶劑熱法，超聲波法能在短時(shí)間內(nèi)合成粒徑較小的MOFs材料[25]，微波法有利于合成粒徑均一的MOFs材料[26]。

2）機(jī)械法[27]。機(jī)械法的優(yōu)點(diǎn)在于無須加入溶劑，只需按比例添加金屬鹽和配體后進(jìn)行機(jī)械研磨，即可合成MOFs材料，具有操作簡(jiǎn)便、環(huán)保等優(yōu)點(diǎn)。

3）電化學(xué)法[28]。這種方法以有機(jī)配體為電解質(zhì)，以陽(yáng)極為金屬離子產(chǎn)生源，通電后在電極附近持續(xù)不斷地合成MOFs。這種方法對(duì)配體的利用率較高，可連續(xù)化生產(chǎn)，適用于MOFs的工業(yè)化生產(chǎn)。

通過有機(jī)配體的選擇，可以調(diào)控MOFs比表面積和孔隙結(jié)構(gòu)，使其具有高負(fù)載和可控釋放的能力[29]，為其包封不同種類和尺寸的抗菌劑奠定基礎(chǔ)。此外，MOFs中的金屬活性位點(diǎn)較多且分布均勻[30]，用于抗菌劑負(fù)載時(shí)，不僅負(fù)載率高，且能均勻分散。目前，將MOFs作為載體系統(tǒng)對(duì)抗菌劑進(jìn)行包封包括3種封裝方式（圖1）[31]：原位封裝法，將合成MOFs的原料與抗菌劑溶液混合，在合成MOFs的同時(shí)也將抗菌劑包封在孔內(nèi)；后合成法，將合成后的MOFs與抗菌劑溶液混合，利用兩者之間的相互作用將抗菌劑封裝在MOFs孔內(nèi)；自組裝法，將抗菌劑作為MOFs的配體（或配位中心）合成MOFs，制備的MOFs材料不僅負(fù)載率高，且能負(fù)載其他抗菌劑，實(shí)現(xiàn)協(xié)同抗菌效果。將MOFs載體系統(tǒng)與抗菌劑通過以上3種包封方法形成的復(fù)合物或配合物統(tǒng)稱為MOFs抗菌系統(tǒng)。在使用時(shí)，可將MOFs抗菌系統(tǒng)放入無紡布袋中直接使用，也可與高分子基材成膜，或作為其他薄膜材料的涂層，通過與食品接觸或釋放抗菌劑來發(fā)揮抗菌作用。

2 MOFs載體系統(tǒng)在食品抗菌包裝中的應(yīng)用

根據(jù)常用抗菌劑的化學(xué)組成和來源，可將其分為無機(jī)抗菌劑、有機(jī)抗菌劑和天然抗菌劑3類。針對(duì)以上3類抗菌劑，MOFs均可作為其載體來制備抗菌材料，如圖2所示。

表1 MOFs的分類

Tab.1 Classification of MOFs

圖1 MOFs包封抗菌劑的方式[31]

圖2 MOFs作為抗菌劑載體系統(tǒng)的分類

2.1 MOFs作為無機(jī)抗菌劑載體

按照抗菌機(jī)理可將無機(jī)抗菌劑分為金屬型和光催化型兩大類。金屬型抗菌劑指利用銀、銅、鋅等金屬（或其離子）的抗菌性能，通過物理吸附或離子交換等方式將其固定在載體材料上制成的抗菌劑[32]。它們的抗菌機(jī)制是與微生物內(nèi)蛋白質(zhì)的硫基（—SH）等相互作用，破壞細(xì)胞合成酶的活性，影響細(xì)胞的正常代謝，導(dǎo)致微生物死亡[33]。其中，銀離子的抗菌能力遠(yuǎn)高于其他金屬離子，其應(yīng)用也最廣泛。光催化型抗菌劑主要為一些金屬氧化物（如二氧化鈦、氧化鋅等），在光的作用下金屬離子激活空氣和水中的氧，產(chǎn)生羥基自由基和活性氧離子，與細(xì)菌細(xì)胞膜上的多元不飽和磷脂發(fā)生反應(yīng)，導(dǎo)致細(xì)菌死亡[34]。二氧化鈦具有穩(wěn)定性高、氧化能力強(qiáng)、毒性小等優(yōu)點(diǎn)，應(yīng)用較廣泛。

無機(jī)抗菌劑具有良好的廣譜抗菌活性，在短時(shí)間和低濃度接觸下對(duì)真核細(xì)胞的影響較弱，對(duì)微生物具有很強(qiáng)的毒性[35]，但單獨(dú)使用時(shí)存在分散性差、釋放速率不易控制、長(zhǎng)時(shí)間直接接觸對(duì)人類有毒性作用等缺點(diǎn)[36]。采用多孔性材料（如MOFs）對(duì)其進(jìn)行負(fù)載，能有效解決上述問題。表2列舉了以MOFs為無機(jī)抗菌劑載體在食品保鮮和食品包裝中的研究。其中，Duan等[37]將合成后的金屬有機(jī)框架（HKUST-1）@羧甲基纖維（Carboxymethylated fibers，CFs）作為載體浸入硝酸銀溶液中，利用原位微波還原技術(shù)將納米銀（AgNPs）均勻固定在載體表面和孔隙中，成功制備了納米銀顆粒@金屬有機(jī)框架@羧甲基纖維復(fù)合材料（AgNPs@HKUST-1@CFs）。結(jié)果表明，該復(fù)合材料對(duì)金黃色葡萄球菌的生長(zhǎng)抑制率為99.41%，遠(yuǎn)高于AgNPs@CFs的12.94%和HKUST-1@CFs的64.12%，具有作為高效復(fù)合抗菌包裝膜的潛力。Zhang等[38]利用Ag+和殼聚糖（CS）分子間的相互作用，將Ag+作為配位中心，引導(dǎo)Ag-MOFs在殼聚糖基質(zhì)中生長(zhǎng)，制備出在水中具有良好分散性和穩(wěn)定性的Ag-MOFs@CS復(fù)合材料。結(jié)果表明，Ag-MOFs@CS對(duì)大腸桿菌和金黃色葡萄球菌的抑制能力均高于Ag@CS，且放置100 d后仍能保持良好的抗菌性能。將 Ag-MOFs@CS懸浮液噴灑于火龍果表面，可將其貨架期延長(zhǎng)7 d。以上研究表明，MOFs可用作銀等金屬納米顆粒或離子類抗菌劑的載體，不僅可以防止其過度釋放，也可促進(jìn)其在基材中均勻分散，提高抗菌效果。

2.2 MOFs作為有機(jī)抗菌劑載體

有機(jī)抗菌劑指以酚類、醇類、季胺類、鹵化物類、吡啶類、咪唑類等有機(jī)物為主要成分的抗菌劑，根據(jù)分子量可分為高分子和低分子2類。高分子抗菌劑主要通過均聚、接枝等方式引入抗菌官能團(tuán)來獲得抗菌能力[42]，其殺菌速度快、抗菌效果好，在水處理[43]、涂料[44]、家裝[45]等領(lǐng)域得到廣泛應(yīng)用。低分子抗菌劑可與微生物細(xì)胞膜結(jié)合并進(jìn)入細(xì)胞內(nèi)，破壞蛋白質(zhì)結(jié)構(gòu)，阻礙細(xì)胞膜的合成，從而抑制微生物的繁殖[46]。

MOFs作為載體系統(tǒng)已經(jīng)應(yīng)用于一些低分子有機(jī)抗菌劑，如乙醇[47]、乙醛等。Nagarajan等[48]利用環(huán)糊精金屬有機(jī)框架（CD-MOF）作為模板捕獲并儲(chǔ)存己醛，然后將其應(yīng)用于芒果保鮮中。結(jié)果表明，對(duì)照組果實(shí)在貯藏第10天時(shí)已腐爛變質(zhì)，而處理組果實(shí)由于CD-MOF的控釋作用，其貨架期達(dá)到15 d，因此CD-MOF封裝被認(rèn)為是實(shí)現(xiàn)己醛控釋并將其應(yīng)用于食品保鮮的有效途徑之一。

2.3 MOFs作為天然抗菌劑載體

天然抗菌劑直接源于動(dòng)植物體內(nèi)，或由微生物合成，具有抗菌范圍廣、安全性高、無毒、無害、環(huán)保、生物相容性好等突出優(yōu)點(diǎn)[49]，是最古老的抗菌劑。不同來源的天然抗菌劑的抗菌機(jī)制有所不同。其中，植物源抗菌劑的抗菌機(jī)制為破壞微生物的細(xì)胞壁、細(xì)胞膜、細(xì)胞質(zhì)膜，導(dǎo)致細(xì)胞內(nèi)物質(zhì)外流，使細(xì)胞質(zhì)發(fā)生凝聚等抑菌現(xiàn)象，每種作用機(jī)制都存在一定關(guān)聯(lián)性[50]。目前，動(dòng)物源抗菌劑的抗菌機(jī)制尚不完全，在殼聚糖研究中有2種機(jī)制被人們廣泛接受[51]：殼寡糖分子中的氨基帶正電，能夠吸附在微生物表面，破壞細(xì)胞壁和細(xì)胞膜，進(jìn)而導(dǎo)致細(xì)菌死亡；以滲透方式進(jìn)入細(xì)菌細(xì)胞內(nèi)，吸附陰離子等物質(zhì)，導(dǎo)致細(xì)胞活動(dòng)紊亂而死亡。微生物源抗菌劑的抗菌機(jī)制有以下幾種：通過競(jìng)爭(zhēng)的方式獲得生存繁殖能力，抑制微生物生長(zhǎng)；分泌抗菌物質(zhì)，抑制微生物生長(zhǎng)；直接作用于微生物；寄生于微生物上[52]。

表2 MOFs作為無機(jī)抗菌劑載體在食品保鮮和食品包裝中的應(yīng)用

Tab.2 Application of MOFs as inorganic antibacterial agent carrier in food preservation and packaging

MOFs與以上3種天然抗菌劑的結(jié)合均有報(bào)道，但尤以植物源抗菌劑研究最多。植物源天然抗菌劑主要為精油類物質(zhì)，是食品抗菌包裝中研究得最多的一類，它存在揮發(fā)性強(qiáng)、有刺激性氣味、不溶于水等缺點(diǎn)，同時(shí)易與食品中的某些成分（如水、脂質(zhì)、蛋白質(zhì)）發(fā)生反應(yīng)，通常需要大劑量才能實(shí)現(xiàn)有效抗菌，因此將MOFs作為載體系統(tǒng)與植物源抗菌劑結(jié)合使用是發(fā)揮其效用的一種有效策略。列舉了MOFs作為植物源抗菌劑載體的應(yīng)用研究，見表3。Lashkari等[53]用HKUST-1、MOF-74(Zn)和RPM6-Zn 3種金屬有機(jī)框架材料包埋從植物中提取的異硫氰酸烯丙酯（Allyl isothiocyanate，AITC），并測(cè)定了復(fù)合材料在不同濕度環(huán)境下對(duì)AITC的控釋效果。結(jié)果表明，在低濕度環(huán)境（相對(duì)濕度30%～35%）下僅有少量釋放，而在高濕度環(huán)境（相對(duì)濕度95%～100%）下則完全釋放。這種利用濕度作為外部觸發(fā)器為活性物質(zhì)的控釋提供了新策略。Min等[54]使用卟啉金屬有機(jī)框架負(fù)載百里酚，并將其與普魯蘭多糖/聚乙烯醇共混，制備出納米纖維（THY@PCN/PUL/PVA），成功解決了百里酚易于揮發(fā)和難溶于水的問題。這種釋放行為表明，純百里酚的釋放時(shí)間為96 h，而THY@PCN的釋放時(shí)間達(dá)到192 h。細(xì)胞活力測(cè)定結(jié)果表明，該膜具有良好的生物安全性。果蔬保鮮實(shí)驗(yàn)表明，該膜對(duì)葡萄和草莓均具有延長(zhǎng)保鮮時(shí)間的效果。Zhao等[55]將辣椒素負(fù)載于中空金屬有機(jī)框架FeⅢ-HMOF-5中，并加入明膠/殼聚糖制備抗菌包裝膜。結(jié)果表明，F(xiàn)eIII-HMOF-5的添加有效提高了辣椒素在明膠/殼聚糖基質(zhì)中的相容性，顯著增強(qiáng)了膜的拉伸強(qiáng)度、透濕性和抗紫外線性能，以及對(duì)大腸桿菌的抗菌活性，并延長(zhǎng)了鮮切蘋果的保鮮時(shí)間。由此可見，MOFs包埋植物源天然抗菌劑有效解決了其揮發(fā)性強(qiáng)、疏水性高、生物相容性差等問題，為推動(dòng)該抗生劑在食品抗菌包裝領(lǐng)域的實(shí)際應(yīng)用提供了有效途徑。

動(dòng)物源天然抗菌劑一般為甲殼素和殼聚糖及其衍生物，是常用的天然抗菌劑之一，其分子量大，不易被MOFs包封，通常將MOFs作為填料與其共混使用[59]。微生物源天然抗菌劑（如乳酸鏈球菌素、納他霉素、溶菌酶和片球菌素等）在食品抗菌包裝中已得到廣泛應(yīng)用[60-62]。其中，Nisin和納他霉素對(duì)環(huán)境變化較敏感，易與食品中的成分相互作用，通常需要借助包埋系統(tǒng)克服其應(yīng)用局限，目前尚未見以MOFs為載體的相關(guān)研究。雖然MOFs已被證實(shí)可作為酶等蛋白類物質(zhì)的載體[63-65]，但作為具有抗菌活性的酶類載體系統(tǒng)應(yīng)用于抗菌包裝的研究較少。后續(xù)可加強(qiáng)MOFs對(duì)微生物源天然抗菌劑進(jìn)行包封的研究，以提高其耐受性、穩(wěn)定性和重復(fù)利用性。

表3 MOFs作為植物源天然抗菌劑載體在食品保鮮和食品包裝中的應(yīng)用

Tab.3 Application of MOFs as plant-derived natural antibacterial agent carriers in food preservation and packaging

3 結(jié)語(yǔ)

MOFs作為一種有機(jī)與無機(jī)結(jié)合的多孔性復(fù)合材料，具有比表面積高、孔隙結(jié)構(gòu)可調(diào)、適應(yīng)性強(qiáng)、生物相容性好等優(yōu)點(diǎn)，不僅可有效封裝抗菌劑，實(shí)現(xiàn)緩釋和控釋，將MOFs復(fù)合材料作為高分子填料還可提高其抗菌性能、力學(xué)性能和抗紫外線性能等，因此在制備高效、安全的食品抗菌包裝方面具有巨大潛力。目前，MOFs作為載體系統(tǒng)用于食品包裝領(lǐng)域雖已有較多研究，但仍需在以下幾方面進(jìn)一步深入探討，以推動(dòng)其實(shí)際應(yīng)用。

1）根據(jù)抗菌劑的結(jié)構(gòu)和性能特點(diǎn)，制備和選擇具有適宜孔徑和化學(xué)特性的MOFs，以提高抗菌劑的負(fù)載效率，實(shí)現(xiàn)不同環(huán)境下的控釋。

2）不同種類的MOFs載體對(duì)抗菌劑的活性、結(jié)構(gòu)、釋放等方面的影響仍有待進(jìn)一步研究。

3）粉末狀MOFs與合成高分子復(fù)合可能對(duì)回收利用造成一定影響，可將其與天然/可降解高分子材料復(fù)合，并進(jìn)一步研究其可降解性能。

4）MOFs中的金屬離子或有機(jī)配體可能存在潛在毒性，應(yīng)盡量選用低毒的金屬離子和生物相容性好的有機(jī)配體，且在用于食品接觸材料時(shí)需對(duì)其遷移風(fēng)險(xiǎn)進(jìn)行評(píng)估。

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Application of Metal-organic Frameworks as Carrier System in Food Antibacterial Packaging

WANG Tao, XU Dan

(College of Food Science, Southwest University, Chongqing 400715, China)

The work aims to review the research status and application progress of metal-organic frameworks (MOFs) as carrier systems in the field of food antibacterial packaging, so as to provide reference for the development and application of MOFs antibacterial packaging materials. Firstly, the basic concepts and classification of MOFs were introduced. Secondly, the preparation methods of MOFs (heating method, mechanical method and electrochemical method) were analyzed. Then, the applications of MOFs as carrier systems in the fields of inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents in recent years were summarized. Finally, the opportunities and challenges of MOFs as carrier systems were discussed. In general, as a porous composite material combining organic and inorganic materials, MOFs can not only effectively encapsulate antibacterial agents to achieve sustained release and controlled release, but also improve their antibacterial properties, mechanical properties and UV resistance when used as polymer fillers. Therefore, MOFs have great potential in the preparation of efficient and safe food antibacterial packaging.

metal-organic frameworks; carrier system; food antibacterial packaging

TS206.4

A

1001-3563(2023)15-0086-08

10.19554/j.cnki.1001-3563.2023.15.012

2023?01?18

王濤（1998—），男，碩士生，主攻活性包裝材料。

徐丹（1983—），女，博士，教授，主要研究方向?yàn)槭称钒b材料與農(nóng)產(chǎn)品保鮮。

責(zé)任編輯：彭颋