CN116585469A - 一种光敏剂@Ga-MOF抗菌微粒的制备方法及其应用 - Google Patents
一种光敏剂@Ga-MOF抗菌微粒的制备方法及其应用 Download PDFInfo
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Abstract
本发明涉及生物材料技术领域,公开了一种光敏剂@Ga‑MOF抗菌微粒的制备方法及其应用,其制备包括以下步骤:步骤一、将含镓微粒溶于去离子水形成溶液A;将羧酸配体溶于有机溶剂中形成溶液B;步骤二、将所述溶液A与所述溶液B混合,高温反应;步骤三、将步骤二所得物离心,取下层沉淀,洗涤干燥,得Ga‑MOF粉末;步骤四、将所述Ga‑MOF粉末与光敏剂溶液混合后离心,取下层沉淀,洗涤干燥,得光敏剂@Ga‑MOF抗菌微粒。本发明可以缓慢释放镓离子和光敏剂,抑制细菌生长,并破坏细菌内部的抗氧化系统,在660 nm红光照射时,光敏剂会产生ROS协同镓离子杀死细菌,达到抑制细菌增殖及杀死细菌的目的。
Description
技术领域
本发明涉及生物材料技术领域,具体涉及一种光敏剂@Ga-MOF抗菌微粒的制备方法及其应用。
背景技术
细菌无处不在,细菌感染是全球十大主要死亡原因之一。抗生素的过度使用导致抗生素耐药性不断增加,对人类健康构成严重威胁。传统抗菌剂一般分为无机抗菌剂,有机抗菌剂和天然抗菌剂。无机抗菌剂分为金属及其衍生物和光催化剂。金属抗菌剂是利用银、铜、锌等金属的抗菌能力,通过物理吸附离子交换等方法,将银、铜、锌等金属(或其离子)固定在氟石、硅胶等多孔材料的表面制成抗菌剂,然后将其加入到相应的制品中即获得具有抗菌能力的材料。光催化剂抗菌剂例如纳米二氧化钛和纳米氧化锌。有机抗菌剂的主要品种有香草醛或乙基香草醛类化合物,常用于聚乙烯类食品包装膜中,起抗菌作用。另外还有酰基苯胺类、咪唑类、噻唑类、异噻唑酮衍生物、季铵盐类、双呱类、酚类等。天然抗菌剂主要来自天然植物的提取,如甲壳素、芥末、蓖麻油、山葵、壳聚糖等,使用简便,但抗菌作用有限,耐热性较差,杀菌率低,不能广谱长效使用且数量很少。因此开发替代杀菌剂以开辟新的消毒途径至关重要。
金属有机骨架(MOFs)是一种含有有机配体连接的金属离子的多孔杂化材料,在促进伤口愈合方面具有巨大潜力。作为一种类酶活性物质,可将过氧化氢转化为剧毒羟基,以提高伤口的抗菌效率。镓(III)金属有机框架(Ga-BTC)在中性条件下会分解释放出镓离子,由于其独特的“特洛伊木马”机制,通过在细菌代谢周期中替代铁(III)来处理细菌生长,在与细菌接触后会破坏细菌体内的抗氧化系统,从而诱导细菌体内产生ROS,因此Ga-MOF显示出作为下一代具有控释能力的且兼具抑制细菌生长和杀菌能力的抗菌剂的巨大潜力。
发明内容
发明目的:针对现有技术中存在的问题,本发明提供一种光敏剂@Ga-MOF抗菌微粒的制备方法及其应用,通过镓离子和有机物配体的羧基结合,得到Ga-MOF微粒,再包覆光敏剂,得到包覆光敏剂的Ga-MOF微粒。本发明制备的光敏剂@Ga-MOF抗菌微粒可以缓慢释放镓离子和光敏剂,在细菌代谢周期中替代铁(III)来抑制细菌生长,并破坏细菌内部的抗氧化系统,在660 nm红光照射时,光敏剂会产生ROS协同镓离子杀死细菌。通过此方法,同时达到抑制细菌增殖及杀死细菌的目的。
技术方案:本发明提供了一种光敏剂@Ga-MOF抗菌微粒的制备方法,包括以下步骤:
步骤一、将含镓微粒溶于去离子水形成溶液A;将羧酸配体溶于有机溶剂中形成溶液B;
步骤二、将所述溶液A与所述溶液B混合,高温反应;
步骤三、将步骤二所得物离心,取下层沉淀,洗涤干燥,得Ga-MOF粉末;
步骤四、将所述Ga-MOF粉末与光敏剂溶液混合后离心,取下层沉淀,洗涤干燥,得光敏剂@Ga-MOF抗菌微粒。
进一步地,步骤一中,所述含镓微粒为硝酸镓和氧化镓中的任一种;
和/或,步骤一中,所述羧酸配体为均苯三甲酸和对苯二甲酸中任一种;
和/或,步骤一中,所述有机溶剂为乙醇和N,N-二甲基甲酰胺中的任一种。
进一步地,步骤一中,所述溶液A中镓离子浓度为0.001-0.01 M;所述溶液B中羧酸配体浓度为0.005-0.015 M。
进一步地,步骤二中,所述溶液A与所述溶液B的体积比为1:3-10:3。
进一步地,步骤二中,所述高温反应的具体条件为80-150 ℃反应3-15 h。
进一步地,步骤四中,所述光敏剂溶液为亚甲基蓝和二氢卟吩e6中的任一种。
进一步地,步骤四中,所述Ga-MOF粉末质量为1-10 mg;所述光敏剂浓度0.1-0.5mg/ml。
优选地,步骤三中,所述洗涤具体为将下层沉淀用乙醇反复重悬-离心多次。
优选地,步骤三中,所述离心的转速为5000-10000 r/min;
和/或,步骤四中,所述离心的转速为5000-10000 r/min。
优选地,步骤三中,所述干燥具体为冷冻干燥8-48 h;
和/或,步骤四中,所述干燥具体为冷冻干燥8-48 h。
本发明还提供了一种如上述任一项方法制备的光敏剂@Ga-MOF抗菌微粒的应用,具体步骤如下:
将所述光敏剂@Ga-MOF抗菌微粒置于待杀菌溶液内,混合振荡1-2 h,然后600-700nm红光下照射20-30 mins。
有益效果:与现有技术相比,本发明以镓离子为金属离子结点,有机物为有机配体联接桥,构成MOF,使之能缓慢降解,释放出镓离子和光敏剂,达到缓释的效果;本发明利用镓离子和有机物配体的羧基结合,制备了Ga-MOF微粒,再包覆光敏剂,制得包覆光敏剂的Ga-MOF微粒,通过缓慢释放出镓离子和光敏剂,在细菌代谢周期中替代铁(III)来抑制细菌生长,并破坏细菌内部的抗氧化系统,且在660 nm红光照射时,光敏剂会产生ROS协同镓离子杀死细菌。该方法简单易行,工艺简单,将镓离子作为ROS的放大器,放大ROS对细菌的伤害,实现协同抗菌。
附图说明
图1为本发明实施方式1中制备的光敏剂@Ga-MOF的表面形貌图(SEM);
图2为本发明实施方式1-2中制备的光敏剂@Ga-MOF对大肠杆菌抗菌效果图;
图3是本发明实施方式1-2中制备的光敏剂@Ga-MOF对金黄色葡萄球菌抗菌效果图。
具体实施方式
下面结合附图对本发明进行详细的介绍。
实施方式1:
将15mg硝酸镓加入8ml去离子水中,搅拌均匀;将13mg均苯三甲酸加入6ml乙醇中,搅拌直至完全溶解;将两种制备好的溶液加入反应釜中,在120℃的烘箱中干燥12h,反应完全后,以8000r/min的转速离心分离,除去上清液,再用乙醇重悬,重复该步骤三次,将沉积物清洗干净,将最后一次离心得到的沉积物用水重悬,放入冷冻干燥机中28h,得到Ga-MOF微粒,称取5mg微粒溶于亚甲基蓝溶液中,振荡5h,离心清洗,冷冻干燥28h,得到亚甲基蓝@Ga-MOF微粒,其表面形貌如图1所示。
实施方式2:
将15mg硝酸镓加入8ml去离子水中,搅拌均匀;将13mg均苯三甲酸加入6ml乙醇中,搅拌直至完全溶解;将两种制备好的溶液加入反应釜中,在120℃的烘箱中干燥12h,反应完全后,以8000r/min的转速离心分离,除去上清液,再用乙醇重悬,重复该步骤三次,将沉积物清洗干净,将最后一次离心得到的沉积物用水重悬,放入冷冻干燥机中28h,得到Ga-MOF微粒,称取5mg微粒溶于二氢卟吩e6溶液中,振荡5h,离心清洗,冷冻干燥28h,得到二氢卟吩e6@Ga-MOF微粒。
实施方式3:
将15mg硝酸镓加入8ml去离子水中,搅拌均匀;将13mg均苯三甲酸加入6ml乙醇中,搅拌直至完全溶解;将两种制备好的溶液加入反应釜中,在120℃的烘箱中干燥12h,反应完全后,以8000r/min的转速离心分离,除去上清液,再用乙醇重悬,重复该步骤三次,将沉积物清洗干净,将最后一次离心得到的沉积物用水重悬,放入冷冻干燥机中28h,得到Ga-MOF微粒。
对比例1:
将15mg硝酸镓加入8ml去离子水中,搅拌均匀;将13mg均苯三甲酸加入6ml乙醇中,搅拌直至完全溶解;将两种制备好的溶液加入反应釜中,在120℃的烘箱中干燥12h,反应完全后,以8000r/min的转速离心分离,除去上清液,再用乙醇重悬,重复该步骤三次,将沉积物清洗干净,将最后一次离心得到的沉积物用水重悬,放入冷冻干燥机中28h,得到Ga-MOF微粒,称取5mg微粒溶于二氢卟吩e6溶液中,振荡5h,离心清洗,冷冻干燥28h,得到二氢卟吩e6@Ga-MOF微粒。
对比例2:
将19mg硝酸镓加入8ml去离子水中,搅拌均匀;将13mg对苯二甲酸加入6ml乙醇中,搅拌直至完全溶解;将两种制备好的溶液加入反应釜中,在120℃的烘箱中干燥12h,反应完全后,以8000r/min的转速离心分离,除去上清液,再用乙醇重悬,重复该步骤三次,将沉积物清洗干净,将最后一次离心得到的沉积物用水重悬,放入冷冻干燥机中28h,得到Ga-MOF微粒。
对比例3:
将15mg氧化镓加入8ml去离子水中,搅拌均匀;将13mg对苯二甲酸加入6mlDMF中,搅拌直至完全溶解;将两种制备好的溶液加入反应釜中,在120℃的烘箱中干燥12h,反应完全后,以8000r/min的转速离心分离,除去上清液,再用乙醇重悬,重复该步骤三次,将沉积物清洗干净,将最后一次离心得到的沉积物用水重悬,放入冷冻干燥机中28h,得到Ga-MOF微粒,称取5mg微粒溶于二氢卟吩e6溶液中,振荡5h,离心清洗,冷冻干燥28h,得到二氢卟吩e6@Ga-MOF微粒。
对实施方式1-3及对比例1-3制备的光敏剂@Ga-MOF微粒和Ga-MOF微粒的杀菌性能进行测试:将实施方式1-3及对比例1-3制备的光敏剂@Ga-MOF微粒和Ga-MOF微粒用PBS配制成浓度为2mg/ml的溶液,取500μl分别加入到500μl细菌菌液(1×105 CFUmL-1)中,混合振荡2h,对实施方式1、2及对比例1、3进行660nm红光照射30min,利用平板计数法观察各样品的杀菌效果,结果如表1所示。
表1本发明实施方式1-2制备的光敏剂@Ga-MOF微粒及对比例1-3制备的Ga-MOF微粒杀菌测试结果
杀菌率 | 对比例1 | 对比例2 | 对比例3 | 实施方式1 | 实施方式2 | 实施方式3 |
大肠杆菌 | 20% | 15% | 12.5% | 71.7% | 70% | 17% |
金黄色葡萄球菌 | 25% | 16% | 18% | 98.5% | 99% | 17.3% |
通过表1中的测试结果对照可知,对比例1-3制备的Ga-MOF微粒对大肠杆菌和金黄色葡萄球菌的杀菌效果较弱,而实施方式1-2制备得到的光敏剂@Ga-MOF微粒对大肠杆菌的杀菌效果达70%以上(见图2),对金黄色葡萄球菌的杀菌效果达98%以上(见图3),说明本发明制备的光敏剂@Ga-MOF微粒可以有效杀死周围细菌并且抑制细菌的增殖。
上述实施方式只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种光敏剂@Ga-MOF抗菌微粒的制备方法,其特征在于,包括以下步骤:
步骤一、将含镓微粒溶于去离子水形成溶液A;将羧酸配体溶于有机溶剂中形成溶液B;
步骤二、将所述溶液A与所述溶液B混合,高温反应;
步骤三、将步骤二所得物离心,取下层沉淀,洗涤干燥,得Ga-MOF粉末;
步骤四、将所述Ga-MOF粉末与光敏剂溶液混合后离心,取下层沉淀,洗涤干燥,得光敏剂@Ga-MOF抗菌微粒。
2.根据权利要求1所述的光敏剂@Ga-MOF抗菌微粒的制备方法,其特征在于,步骤一中,所述含镓微粒为硝酸镓和氧化镓中的任一种;
和/或,步骤一中,所述羧酸配体为均苯三甲酸和对苯二甲酸中的任一种;
和/或,步骤一中,所述有机溶剂为乙醇和N,N-二甲基甲酰胺中的任一种。
3. 根据权利要求1所述的光敏剂@Ga-MOF抗菌微粒的制备方法,其特征在于,步骤一中,所述溶液A中镓离子浓度为0.001-0.01 M;所述溶液B中羧酸配体浓度为0.005-0.015M。
4.根据权利要求1所述的光敏剂@Ga-MOF抗菌微粒的制备方法,其特征在于,步骤二中,所述溶液A与所述溶液B的体积比为1:3-10:3。
5. 根据权利要求1所述的光敏剂@Ga-MOF抗菌微粒的制备方法,其特征在于,步骤二中,所述高温反应的具体条件为80-150 ℃反应3-15 h。
6.根据权利要求1所述的光敏剂@Ga-MOF抗菌微粒的制备方法,其特征在于,步骤四中,所述光敏剂溶液为亚甲基蓝和二氢卟吩e6中的任一种。
7. 根据权利要求1所述的光敏剂@Ga-MOF抗菌微粒的制备方法,其特征在于,步骤四中,所述Ga-MOF粉末质量为1-10 mg;所述光敏剂浓度0.1-0.5 mg/ml。
8.根据权利要求1至7中任一项所述的光敏剂@Ga-MOF抗菌微粒的制备方法,其特征在于,步骤三中,所述洗涤具体为将下层沉淀用乙醇反复重悬-离心多次;
和/或,步骤三中,所述离心的转速为5000-10000 r/min;
和/或,步骤四中,所述离心的转速为5000-10000 r/min。
9. 根据权利要求1至8中任一项所述的光敏剂@Ga-MOF抗菌微粒的制备方法,其特征在于,步骤三中,所述干燥具体为冷冻干燥8-48 h;
和/或,步骤四中,所述干燥具体为冷冻干燥8-48 h。
10.一种如权利要求1-9中任一项所述方法制备的光敏剂@Ga-MOF抗菌微粒的应用,其特征在于,具体步骤如下:
将所述光敏剂@Ga-MOF抗菌微粒置于待杀菌溶液内,混合振荡1-2 h,然后600-700 nm红光下照射20-30 mins。
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