CN112891535A - 一种具有四重抗菌作用的纳米复合材料及其制备方法 - Google Patents
一种具有四重抗菌作用的纳米复合材料及其制备方法 Download PDFInfo
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Abstract
本发明属于无机纳米材料及其制备技术领域,涉及一种具有四重抗菌作用的纳米复合材料及其制备方法,先将半乳糖溶于水中,搅拌溶解后加入钼酸盐搅拌至钼酸盐完全溶解制得混合溶液;再向混合溶液中加入盐酸节混合溶液为酸性后倒入带有四氟乙烯内胆的反应釜中,密封、加热,得到蓝色溶液;然后将蓝色溶液用透析袋透析,将透析后剩余的物质冷冻干燥,得到纳米MoO3‑X抗菌剂材料,最后将硝酸银溶液加入到MoO3‑x水溶液中,放入微波炉中加热10‑50秒,制备得到MoO3‑x/Ag纳米复合材料,利用光热、化学动力学、光动力学以及Ag+释放协同治疗策略对细菌结构进行有效的破坏,降低抗菌剂剂量,缩短光照时长,提高抗菌时效。
Description
技术领域:
本发明属于无机纳米材料及其制备技术领域,涉及一种具有四重抗菌作用的纳米复合材料及其制备方法,特别是一种含银氧化钼的绿色制备方法及作为新型长效靶向抗菌剂的应用。
背景技术:
细菌感染仍然对人类健康构成巨大威胁。其中,绿脓杆菌每年会造成全球细菌感染的10-35%,比如常见的呼吸道感染,尿路感染,胃肠道感染,角膜炎,中耳炎等。尽管抗生素可以杀死或者减慢大部分细菌的生长。但是由于细菌膜的低渗透性和药物的通量增加,绿脓杆菌却对常规抗生素具有天然抗性,使抗生素的药效大大降低。因此,迫切需要开发高效的无抗生素抗菌剂。
银(Ag)纳米粒子和基于银的复合材料因其广谱、高效、长效抗菌特性而被广泛用于抗菌治疗。然而,由于Ag+从Ag纳米颗粒中的缓慢释放,通过Ag+进行的单一抗感染疗法通常需要很长时间并且需要高浓度的Ag来对抗细菌,这易于引起细菌耐药性并损害周围的正常组织。因此,需要开发新的组合抗菌策略以协助低浓度的Ag+在短时间内迅速达到高效抗菌效果,同时具有长期抗菌性能。
近年来,光热疗法(PTT)和活性氧自由基(ROS)介导的纳米催化疗法正成为感染性疾病治疗的有希望的非侵入性策略,其中PTT利用光热剂在光照下产生局部高温,从而破坏微生物细胞,尤其是对组织具有深层渗透能力的近红外(NIR,700-1100nm)光;ROS介导的疗法利用产生的高毒性ROS在光照射或化学催化反应过程中在纳米催化剂存在下诱导细胞死亡。纳米酶是一种具有酶活性的纳米材料,由于其高催化活性,良好的稳定性和低成本而具有成为新一代催化剂的潜力,而且光热效应也被证明可以促进类似酶的催化活性,从而产生更多的ROS。因此,开发具有光热效应的纳米酶将在光照下表现出更高的催化性能和治疗效果。
氧缺陷氧化钼(MoO3-x)作为一种新兴的NIR等离子体半导体,因其低廉的原料价格、优异的光热性能及生物降解性而被广泛用于肿瘤治疗。但是,很少有研究关注MoO3-x纳米酶的合成及其在细菌灭活中的应用。尽管Bai等人通过剥离制备了MoO3-x纳米片,但是研究发现MoO3-x纳米片在较高浓度(1.125mg mL-1)以及光照条件下还是展现很低的抗菌活性,而且不具有纳米酶活性。另外,MoO3-x纳米片与Ag立方体复合的过程也非常复杂,需要大量的有机试剂。目前合成的大部分抗菌剂都不具有特异性,容易造成无选择性地杀死正常细胞或者好细菌。据报道来自绿脓杆菌的凝集素LecA特异性靶向半乳糖,而绿脓杆菌的LecB可以牢固地结合岩藻糖和含岩藻糖的寡糖。因此,亟需提供一种具有四重抗菌作用的纳米复合材料及其制备方法,根据绿脓杆菌耐抗生素及大范围感染的严峻形势,通过绿色环保、简单高效的方法,制备高产率、优异生物相容性、长效的纳米MoO3-x/Ag靶向抗菌剂。
发明内容
本发明的目的在于克服现有技术存在的缺点,设计提供一种具有四重抗菌作用的纳米复合材料及其制备方法,采用绿色环保的方法规模化制备具有多重抗菌作用的MoO3-x/Ag纳米复合材料。
为了实现上述目的,本发明所述具有四重抗菌作用的纳米复合材料为MoO3-x/Ag。
本发明制备MoO3-x/Ag纳米复合材料的具体过程为:
S1、将半乳糖溶于水中,搅拌溶解后加入钼酸盐,继续搅拌至钼酸盐完全溶解制得混合溶液;
S2、向S1制得的混合溶液中加入盐酸,调节混合溶液pH为酸性;
S3、将S2中调节为酸性的混合溶液倒入带有四氟乙烯内胆的反应釜中,密封、加热,得到蓝色溶液;
S4、将蓝色溶液用透析袋透析,将透析后剩余的物质冷冻干燥,得到纳米MoO3-X抗菌剂材料,避光密封保存;
S5、将硝酸银溶液加入到MoO3-x水溶液中,放入微波炉中加热10-50秒,制备得到MoO3-x/Ag纳米复合材料。
本发明步骤S1中半乳糖的质量与水的体积比为0.3-2.0g:30mL,半乳糖与钼酸盐的质量比为1-10:1。
本发明步骤S1中钼酸盐为四水合钼酸铵、二水合钼酸钠和七钼酸铵中的一种。
本发明步骤S2中调节为酸性的混合溶液pH值为1–6。
本发明步骤S3中水热反应釜中加热温度为50-100度,反应时间为6-24小时。
本发明步骤S4中硝酸银溶液浓度为1-10mM,MoO3-x水溶液浓度为2-10mg mL-1,二者质量比为1:5~1:20。
本发明制备的纳米MoO3-x抗菌剂材料具有氧化物酶和光动力催化活性,同时还具有NIR光热转换性能。
本发明制备的MoO3-x/Ag纳米复合材料在催化化学动力学治疗联合NIR光热治疗协同特异性抗绿脓杆菌的应用。
本发明采用MoO3-x/Ag纳米复合材料和近红外激光器组成的Ag+缓释、光热治疗、光动力治疗以及化学动力学治疗四重联合的抗菌体系用于抗绿脓杆菌。
本发明与现有技术相比,具有以下优点:一是以无毒、高生物相容性的半乳糖作为还原剂,通过简单高效、绿色环保的水热合成法一步大规模制备了还原态氧化钼纳米材料,不仅提高了氧化钼的产率和生物相容性,而且制备的氧化钼基本为1-2层,比表面积大,与细菌的接触面积更大,更易杀菌;二是在微波辐照以及氧化钼辅助下,快速制备均匀的小尺寸Ag纳米颗粒;三是制备的MoO3-x/Ag纳米材料在不借助外力的作用下能发挥氧化酶活性,产生单线态氧(1O2)和超氧阴离子(O2 -),在近红外光热治疗的同时,能进一步增强自由基(1O2和O2 -)的产生,还能产生羟基自由基(·OH)和增强Ag+的缓释;利用光热效应破坏细菌细胞壁,提高细菌对活性氧自由基的敏感性,增加Ag+的细胞透过率,利用光热、化学动力学、光动力学以及Ag+释放协同治疗策略对细菌结构进行有效的破坏,降低抗菌剂剂量,缩短光照时长,提高抗菌时效,而且利用半乳糖与绿脓杆菌的LecA凝集素的特异性结合,极大地降低了对周围组织的损伤。
附图说明:
图1为本发明制备的MoO3-x/Ag纳米复合材料的透射电子显微镜图。
图2为本发明实施例中MoO3-x/Ag水溶液在808nm的近红外激光照射过程中的升温曲线。
图3为本发明实施例中在黑暗以及近红外光照条件下,1O2的电子自旋共振谱图。
图4为本发明实施例中绿脓杆菌在有无近红外光照的形貌图。
图5为本发明实施例中其他糖基制备的Ag/MoO3-x与半乳糖制备的Ag/MoO3-x抗绿脓杆菌对照图。
具体实施方式:
为使本发明的技术方案和优点更加清晰,下面将通过具体的实施例以及附图对本发明的技术方案做详细描述,有助于本领域普通技术人员更全面的了解本发明,但是所描述的实施例只是本发明的一部分实施例,而不是全部实施例。基于本发明的实施例,本领域技术人员在没有付出创造性劳动的前提下所获得的其他实施例,都属于本发明保护的范围。
实施例1:
本实施例制备MoO3-x/Ag纳米复合材料的具体过程为:
S1、将1.5g半乳糖和0.5g钼酸铵溶于50mL水中,搅拌20分钟至全部溶解,向混合溶液中滴加盐酸,调节溶液pH为4,再搅拌5分钟;
S2、将混合溶液倒入四氟乙烯反应釜中密封,在80℃下加热12小时后依次透析、冷冻和干燥,得到纳米MoO3-X抗菌剂材料,避光密封保存;
S3、将10ml氧化钼溶液(5mg mL-1)加入200μL硝酸银溶液(10mM),放入微波炉里,反应20秒钟;
S4、将粗产物倒入透析袋(10Kda透析膜),透析12小时,然后冷冻干燥得到MoO3-x/Ag纳米复合材料,密封避光保存。
实施例2:
本实施例通过具体的实验结果来验证MoO3-x/Ag纳米复合材料的近红外光热效应、化学催化以及光催化性能,具体为:
(1)MoO3-x/Ag纳米复合材料的近红外光热效应
反应体系:分别配制浓度为50μg/mL、150μg/mL、200μg/mL和300μg/mL的MoO3-x/Ag水溶液,由于合成的纳米MoO3-x/Ag在近红外区有吸收,并能将近红外光能转换成热能,是其用于光热抗菌的基础,图2为不同浓度的MoO3-x/Ag水溶液在808nm近红外激光器照射5分钟的升温曲线。
(2)氧化酶拟酶催化活性研究
拟酶催化活性高也是协同提高抗菌效果的关键,以实施例1制备得到的MoO3-x/Ag为研究对象,在水溶液体系中,研究MoO3-x/Ag的氧化酶活性,氧化物酶能产生1O2、O2﹒-、·OH三种活性氧自由基,都对细菌具有杀伤作用,本实施例研究了MoO3-x/Ag是否会产生三种自由基以及近红外光照对这三种自由基强度的影响,采用ESR测试样品在黑暗以及近红外激光辐照条件下自由基种类及强度测试;
检测ROS的步骤:将实验体系分为四组,TEMP(4-氨基-2,2,6,6-四甲基哌啶)或DMPO(5,5-二甲基-1-吡咯啉-N-氧化物)溶液为对照组,MoO3-x/Ag+TEMP(或DMPO)为实验组1,MoO3-x/Ag+TEMP(或DMPO)+NIR光照为实验组2,反应5分钟后,测定溶液的电子自旋共振波谱,测试结果如图3;从图3中可以看出,实施例1合成得到的MoO3-x/Ag纳米复合材料能产生活性氧自由基,并且近红外光照能大幅度增强ROS的产生,在光照条件下能产生更多自由基,将有效增敏光热对绿脓杆菌杀伤能力。
实施例3:
本实施例采用实施例1制备的MoO3-x/Ag纳米复合材料构建协同长效抗菌体系,将绿脓杆菌(革兰氏阴性菌)菌株培养液稀释到浓度为1×106CFU/mL,取细菌培养液50μL加入96孔板,然后加入不同浓度的MoO3-x/Ag溶液,震荡混匀,将实验组分为4组:组1在黑暗条件下培养0.5h,组2+NIR光照辐照5min,再继续培养0.5h,组3为黑暗条件下培养12h,组4+NIR光照辐照5min,再继续培养12h,取处理后的菌液均匀涂抹在LB培养基中37度培养12小时,记录细菌的菌落数;从图4结果可知,通过0.5h和12h对比看出,MoO3-x/Ag纳米复合材料具有长效抗菌能力。另外,相比不光照组,光照组细菌存活率更低,说明近红外光照协同抗菌性能更好,这是由于近红外光照条件下,不仅带来光热治疗,还能触发光动力治疗,增强化学动力学治疗和促进Ag+缓释,达到四重策略协同抗菌。
本实施例同时采用其他糖基在同样条件下制备Ag/MoO3-x,与半乳糖制备的Ag/MoO3-x抗绿脓杆菌对照图如图5所示。
本实施例的实验结果表明,利用绿色环保、简单高效的方法合成了“集多种功能于一身”的新型抗菌剂纳米MoO3-x/Ag,该抗菌剂具有水溶性好、生物相容性好、拟酶催化活性高、NIR光热转换效率高等独特优势,为开发高效协同抗菌体系提供了新思路,克服了单一治疗体系的诸多问题,也极大地简化了通常合成多功能治疗体系的繁琐步骤,MoO3-x/Ag纳米复合材料的氧化酶催化活性能产生活性氧自由基,自身就具有杀菌作用,在NIR光热治疗的同时,NIR光不仅能增强MoO3-x/Ag的氧化酶活性产生更多自由基,还能产生毒性更强的·OH自由基并增强Ag+离子释放,进一步破坏细胞结构,增强抗菌效率,能够弥补单纯光热抗菌热疗效果差的不足。
本实施例通过一般性说明、具体实施案例及试验,对本发明做了详细说明,但在不超出所附的权利要求所限定的本发明的精神和范围的情况下,本领域内普通技术人员可以在此基础上做出修改或者改进。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
Claims (9)
1.一种具有四重抗菌作用的纳米复合材料,其特征在于,所述纳米复合材料为MoO3-x/Ag。
2.一种如权利要求1所述具有四重抗菌作用的纳米复合材料的制备方法,其特征在于,具体制备过程为:
S1、将半乳糖溶于水中,搅拌溶解后加入钼酸盐,继续搅拌至钼酸盐完全溶解制得混合溶液;
S2、向S1制得的混合溶液中加入盐酸,调节混合溶液pH为酸性;
S3、将S2中调节为酸性的混合溶液倒入带有四氟乙烯内胆的反应釜中,密封、加热,得到蓝色溶液;
S4、将蓝色溶液用透析袋透析,将透析后剩余的物质冷冻干燥,得到纳米MoO3-X抗菌剂材料,避光密封保存;
S5、将硝酸银溶液加入到MoO3-x水溶液中,放入微波炉中加热10-50秒,制备得到MoO3-x/Ag纳米复合材料。
3.根据权利要求2所述具有四重抗菌作用的纳米复合材料的制备方法,其特征在于,步骤S1中半乳糖的质量与水的体积比为0.3-2.0g:30mL,半乳糖与钼酸盐的质量比为1-10:1。
4.根据权利要求2所述具有四重抗菌作用的纳米复合材料的制备方法,其特征在于,步骤S1中钼酸盐为四水合钼酸铵、二水合钼酸钠和七钼酸铵中的一种。
5.根据权利要求2所述具有四重抗菌作用的纳米复合材料的制备方法,其特征在于,步骤S2中调节为酸性的混合溶液pH值为1–6。
6.根据权利要求2所述具有四重抗菌作用的纳米复合材料的制备方法,其特征在于,步骤S3中水热反应釜中加热温度为50-100度,反应时间为6-24小时。
7.根据权利要求2所述具有四重抗菌作用的纳米复合材料的制备方法,其特征在于,步骤S4中硝酸银溶液浓度为1-10mM,MoO3-x水溶液浓度为2-10mg mL-1,二者质量比为1:5~1:20。
8.一种如权利要求2制备的具有四重抗菌作用的纳米复合材料在催化化学动力学治疗联合NIR光热治疗协同特异性抗绿脓杆菌的应用。
9.根据权利要求8所述具有四重抗菌作用的纳米复合材料的应用,其特征在于,采用MoO3-x/Ag纳米复合材料和近红外激光器组成的Ag+缓释、光热治疗、光动力治疗以及化学动力学治疗四重联合的抗菌体系用于抗绿脓杆菌。
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