CN113198015A - 一种新型BPs-PEG-Au纳米复合材料的制备方法 - Google Patents
一种新型BPs-PEG-Au纳米复合材料的制备方法 Download PDFInfo
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Abstract
一种新型BPs‑PEG‑Au纳米复合材料的制备方法。本发明涉及一种新型BPs‑PEG‑Au纳米复合材料。本发明的目的是为了解决以往纳米材料生物组织穿透性差,生物相容性低,在生理条件下稳定性差的问题。设计与研制了一种新型BPs‑PEG‑Au纳米复合材料。BPs‑PEG,Au纳米粒子以及BPs‑PEG‑Au的TEM图像如图,对比说明Au纳米粒子成功负载在BPs‑PEG上,成功制备出新型BPs‑PEG‑Au纳米复合材料。制备方法:利用液相剥离法将研磨过的大块状黑鳞在冰水浴下超声制备成2D黑鳞纳米片(BPs),将BPs表面用PEG‑NH2进行修饰,最后将制备好的纳米粒子负载在PEG‑NH2修饰的BPs上。本发明可获得一种新型BPs‑PEG‑Au纳米复合材料的制备方法。
Description
技术领域
本发明一种新型BPs-PEG-Au纳米复合材料。
背景技术
黑磷(BPs)在许多元素磷的同素异形体中是最稳定的,密度最大,在一般常用有机溶剂中都很难溶解,不易发生化学反应,并且由褶皱层的磷通过弱的范德瓦尔斯力构成。由于BPs的独特的电子结构,层状的大量黑磷在垂直方向上可被剥离成一个单原子层,在层内之间的结合依赖于比较强烈的P-P共价键。这种超薄二维(2D)纳米片具有从约0.3 eV到2.0eV的能量带隙,表明其在紫外和整个可见光区域广泛的吸收。考虑到与它的体积相比独一无二和巨大的物理性质的不同,磷的超薄纳米片有望成为一种新型高效光敏剂来产生活性氧(ROS),这在生物学领域和催化应用中具有很大的潜力。
液相剥离法是将大块状的晶体材料进行剥离制成超薄二维纳米片的一种常用方法。它不同于传统的机械剥离法之处是传统的机械剥离法由于其成品率低、产量低,在实际应用中有很强的限制性,而液相剥离法成功的改进了这一不足。液相剥离法的操作过程是将大块状的晶体材料在溶剂中超声,在超声处理的过程中,层与层之间微弱的范德华力被破坏,而层内之间的共价键由于其作用比较强不会被破坏。目前,包括黑磷在内的很多超薄二维纳米材料都是通过液相剥离的方法制成,因此液相剥离法在实际的应用中有很大潜力。
金簇是近几年来兴起的一种新型荧光纳米材料,又名金纳米团簇。它由几个到几十个金原子组成,其细胞毒性低,光学性质稳定,具有大的斯托克斯位移和良好的分散性,在药物检测以及生物学领域有广阔的应用前景。金簇的发射波长受很多因素影响,包括纳米粒子的大小尺寸,合成配体材料的自身性质等。通过不同配体化合物制备出的金簇具有不同的发射波长以及发光范围。
光热治疗(PTT)主要是使用光吸收器吸收并将光照射转化成热。然后升高的温度诱导细胞内蛋白质的变性或膜的破坏,导致癌细胞的热消融;与化疗或手术相比,PTT侵袭性较小,因此在癌症治疗中引起了越来越多的关注;贵金属纳米材料,如金银纳米棒、纳米笼和纳米壳,由于其在NIR区域的强光吸收,已经用作光热治疗剂。
光动力治疗(PDT)作为一种微创、高效的抗癌方法,最近受到广泛研究与关注。PDT涉及一种重要成分——光敏剂,它是一种光敏分子,可以用作光敏药物。当纳米粒子暴露于适当波长的光下时,光敏剂将被激发,并将其能量转移到周围的分子氧,来产生细胞毒性并且产生活性氧以及可以氧化和杀死癌细胞的单线态氧(1O2)。
大多数光敏剂是可以被可见光激活的;因此,由于可见光的穿透深度较低,PDT在活组织中的效率受到限制。鉴于此,将BPs用PEG-NH2修饰后再负载Au纳米团簇,即利用从上转换发光纳米粒子到光敏剂的共振能量转移,通过光敏剂和上转换发光纳米粒子的组合来产生深层PDT。通过大量的文献调研发现上转换过程中能量供体相对较低的量子产率(通常小于3%),一般的纳米材料生物组织穿透性差,生物相容性和稳定性不够好。本发明的目的就是针对以上问题提出的一种可能,合成了一种新型BPs-PEG-Au纳米复合材料的制备方法。
发明内容
本发明的目的是为了解决一般的纳米材料生物组织穿透性差,生物相容性和稳定性不够好的问题。而提供一种新型BPs-PEG-Au纳米复合材料的制备方法。
一种新型BPs-PEG-Au纳米复合材料的制备方法,其特征在于这种新型纳米复合材料负载了Au纳米团簇,利用从上转换纳米粒子(Au纳米团簇)到光敏剂(BPs)的共振能量转移,通过光敏剂和上转换纳米粒子的组合来产生更深层的光动力治疗(PDT)效应。
一种新型BPs-PEG-Au纳米复合材料的制备方法,其特征在于一种新型BPs-PEG-Au纳米复合材料的制备方法是按以下步骤完成的:
一、超薄BPs(黑磷片)的制备:利用液相剥离法来制备超薄BPs。将块状BPs研磨成粉后在冰水浴下真空超声8小时,在4500转速下离心5分钟,回收上清液,三次水洗离心去掉上清液得到超薄BPs;
二、BPs-PEG的制备:PEG-NH2(氨基修饰的聚乙二醇)分散到适量蒸馏水中超声,将其加入到BPs中,超声30 min,搅拌4 h,4500转速下离心和反复水洗除去过量的PEG分子,将制得的样品分散于5ml蒸馏水中;
步骤二中所述的PEG-NH2的质量与蒸馏水的体积比为:0.0055g:5ml;
三、Au纳米团簇的合成:将加有转子的遮光小瓶放在磁力搅拌器上搅拌,向其中加入蒸馏水,HAuCl4·3H2O, MHA (2-羟基-4-甲硫基丁酸钙)形成MHA-Au(I)复合物,再加入NaOH溶液,搅拌15min后加入NaBH4溶液,搅拌3h制得Au纳米团簇;
步骤三中所述的蒸馏水,HAuCl4·3H2O, MHA ,NaOH,NaBH4的摩尔比为1306:0.05:20:3:1148;
四、BPs-PEG-Au纳米复合材料的合成:分别向标号为1,2,3,4的遮光离心管中加入不同量的Au纳米团簇,EDC(1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐)和NHS(N-羟基琥珀酰亚胺),加入适量蒸馏水溶解,活化2小时,分别加入BPs-PEG,另取遮光离心管倒入剩余的BPs-PEG并标号为0作为空白对照组,所有离心管在黑暗中搅拌8-12h,水洗离心后分散到5ml水中;
步骤四中所述的配置好的Au纳米团簇的体积,EDC的质量,NHS的质量,配置好的BPs-PEG的体积比为(0.25 ml,0.5 ml,1 ml,2 ml):6 mg:2 mg:1ml。
与现有技术相比,本发明具有如下特点:
本发明采用液相剥离法制备BPs纳米片,经过PEG-NH2修饰后负载Au纳米团簇成功制备出一种新型BPs-PEG-Au纳米复合材料;通过观察BPs-PEG,Au纳米团簇和BPs-PEG-Au复合材料的TEM图可知,Au纳米团簇成功负载在BPs-PEG上,成功制备出新型BPs-PEG-Au纳米复合材料。利用从上转换发光纳米粒子到光敏剂的共振能量转移,通过光敏剂和上转换发光纳米粒子的组合来产生深层PDT,使材料拥有更好的生物组织穿透性,生物相容性和稳定性。
本发明可获得一种新型BPs-PEG-Au纳米复合材料。
附图说明
图1为黑磷的XRD图谱。
图2为不同倍率下BPs-PEG的透射电镜照片。
图3为不同倍率下Au纳米粒子的透射电镜照片。
图4为不同倍率下BPs-PEG-Au复合材料的透射电镜照片。
图5为实施例一制备的一种新型BPs-PEG-Au纳米复合材料中Au,BPs-PEG,BPs-PEG-Au的紫外-可见吸收光谱。
图6为实施例一制备的一种新型BPs-PEG-Au纳米复合材料在650 nm, 808 nm,980 nm不同激光照射下( 0.5 W/cm2 ) 20 min时混合BPs-PEG-Au的DPBF的吸收光谱。
图7为实施例一制备的一种新型BPs-PEG-Au纳米复合材料在410 nm波长处650 nm的激光下( 0.5 W/cm2 ),照射混合BPs-PEG-Au的DPBF不同时间的吸收光谱。
图8为实施例一制备的一种新型BPs-PEG-Au纳米复合材料在410 nm波长处650 nm的激光下( 0.5 W/cm2 ),DPBF在不同溶液中的吸收衰减曲线。
具体实施方式
本发明工艺参数及工艺路线不局限于一下所列举具体实施方案,以下所列举具体实施方式,仅说明本发明而并非受限于本发明实施例所描述的工艺参数和工艺路线。本领域的研究人员应当理解,在实际应用中可以对本发明进行修改或等价替换,以达到相同的技术效果。只要满足应用需求,都在本发明的保护范围内。
具体实施方式一:本实施方式是一种新型BPs-PEG-Au纳米复合材料的制备方法。
与现有技术相比,本实施方式具有如下特点:
本发明采用液相剥离法制备BPs纳米片,经过PEG-NH2修饰后负载Au纳米团簇成功制备出一种新型BPs-PEG-Au纳米复合材料;通过观察BPs-PEG,Au纳米团簇和BPs-PEG-Au复合材料的TEM图可知,Au纳米团簇成功负载在BPs-PEG上,成功制备出新型BPs-PEG-Au纳米复合材料。利用从上转换发光纳米粒子到光敏剂的共振能量转移,通过光敏剂和上转换发光纳米粒子的组合来产生深层PDT,使材料拥有更好的生物组织穿透性,生物相容性和稳定性。
具体实施方式二:本实施方式是一种新型BPs-PEG-Au纳米复合材料的制备方法是按以下步骤完成的:
一、超薄BPs(黑磷片)的制备:利用液相剥离法来制备超薄BPs。将块状BPs研磨成粉后在冰水浴下真空超声8小时,在4500转速下离心5分钟,回收上清液,三次水洗离心去掉上清液得到超薄BPs;
二、BPs-PEG的制备:PEG-NH2(氨基修饰的聚乙二醇)分散到适量蒸馏水中超声,将其加入到BPs中,超声30 min,搅拌4 h,4500转速下离心和反复水洗除去过量的PEG分子,将制得的样品分散于5ml蒸馏水中;
步骤二中所述的PEG-NH2的质量与蒸馏水的体积比为:0.0055g:5ml;
四、Au纳米团簇的合成:将加有转子的遮光小瓶放在磁力搅拌器上搅拌,向其中加入蒸馏水,HAuCl4·3H2O, MHA (2-羟基-4-甲硫基丁酸钙)形成MHA-Au(I)复合物,再加入NaOH溶液,搅拌15min后加入NaBH4溶液,搅拌3h制得Au纳米团簇;
步骤三中所述的蒸馏水,HAuCl4·3H2O, MHA ,NaOH,NaBH4的摩尔比为1306:0.05:20:3:1148;
四、BPs-PEG-Au纳米复合材料的合成:分别向标号为1,2,3,4的遮光离心管中加入不同量的Au纳米团簇,EDC(1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐)和NHS(N-羟基琥珀酰亚胺),加入适量蒸馏水溶解,活化2小时,分别加入BPs-PEG,另取遮光离心管倒入剩余的BPs-PEG并标号为0作为空白对照组,所有离心管在黑暗中搅拌8-12h,水洗离心后分散到5ml水中;
步骤四中所述的配置好的Au纳米团簇的体积,EDC的质量,NHS的质量,配置好的BPs-PEG的体积比为(0.25 ml,0.5 ml,1 ml,2 ml):6 mg:2 mg:1ml。
与现有技术相比,本实施方式具有如下特点:
本发明采用液相剥离法制备BPs纳米片,经过PEG-NH2修饰后负载Au纳米团簇成功制备出一种新型BPs-PEG-Au纳米复合材料;通过观察BPs-PEG,Au纳米团簇和BPs-PEG-Au复合材料的TEM图可知,Au纳米团簇成功负载在BPs-PEG上,成功制备出新型BPs-PEG-Au纳米复合材料。利用从上转换发光纳米粒子到光敏剂的共振能量转移,通过光敏剂和上转换发光纳米粒子的组合来产生深层PDT,使材料拥有更好的生物组织穿透性,生物相容性和稳定性。
本实施方式可获得一种新型BPs-PEG-Au纳米复合材料。
具体实施方式三:本实施方式与具体实施方式二的不同点是:步骤二中所述的PEG-NH2的质量与蒸馏水的体积比为:0.0055g:5ml。其他与具体实施方式二相同。
具体实施方式四:本实施方式与具体实施方式二至三的不同点是:步骤三中所述的蒸馏水,HAuCl4·3H2O, MHA ,NaOH,NaBH4的摩尔比为1306:0.05:20:3:1148。其他与具体实施方式二或三相同。
具体实施方式五:本实施方式与具体实施方式二至四的不同点是:步骤四中所述的配置好的Au纳米团簇的体积,EDC的质量,NHS的质量,配置好的BPs-PEG的体积比为(0.25ml,0.5 ml,1 ml,2 ml):6 mg:2 mg:1ml。其他与具体实施方式二至四相同。
采用以下实施例验证本发明的有益效果:
实施例一: 一种新型BPs-PEG-Au纳米复合材料的制备方法是按以下步骤完成的:
一、超薄BPs(黑磷片)的制备:利用液相剥离法来制备超薄BPs。将块状BPs研磨成粉后在冰水浴下真空超声8小时,在4500转速下离心5分钟,回收上清液,三次水洗离心去掉上清液得到超薄BPs;
二、BPs-PEG的制备:PEG-NH2(氨基修饰的聚乙二醇)分散到适量蒸馏水中超声,将其加入到BPs中,超声30 min,搅拌4 h,4500转速下离心和反复水洗除去过量的PEG分子,将制得的样品分散于5ml蒸馏水中;
步骤二中所述的PEG-NH2的质量与蒸馏水的体积比为:0.0055g:5ml;
五、Au纳米团簇的合成:将加有转子的遮光小瓶放在磁力搅拌器上搅拌,向其中加入蒸馏水,HAuCl4·3H2O, MHA (2-羟基-4-甲硫基丁酸钙)形成MHA-Au(I)复合物,再加入NaOH溶液,搅拌15min后加入NaBH4溶液,搅拌3h制得Au纳米团簇;
步骤三中所述的蒸馏水,HAuCl4·3H2O, MHA ,NaOH,NaBH4的摩尔比为1306:0.05:20:3:1148;
四、BPs-PEG-Au纳米复合材料的合成:分别向标号为1,2,3,4的遮光离心管中加入不同量的Au纳米团簇,EDC(1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐)和NHS(N-羟基琥珀酰亚胺),加入适量蒸馏水溶解,活化2小时,分别加入BPs-PEG,另取遮光离心管倒入剩余的BPs-PEG并标号为0作为空白对照组,所有离心管在黑暗中搅拌8-12h,水洗离心后分散到5ml水中;
步骤四中所述的配置好的Au纳米团簇的体积,EDC的质量,NHS的质量,配置好的BPs-PEG的体积比为(0.25 ml,0.5 ml,1 ml,2 ml):6 mg:2 mg:1ml。
实施例一制备的一种新型BPs-PEG-Au纳米复合材料的数据如下。
图1为黑磷的XRD图谱,与黑磷的标准卡片对比,我们可以明显地观察到黑磷纳米片的晶格面,这表明在xy平面上剥离的黑磷纳米片具有良好的z取向并且与大块状的黑磷相比显示出典型的二维片状结构。
图2为不同倍率下BPs-PEG的透射电镜照片。从图中可以看出,块状黑磷经过液相剥离法处理之后成为具有超薄的二维层状结构的黑磷片。
图3为不同倍率下Au纳米粒子的透射电镜照片。从图中可以看出,Au纳米粒子具有良好的单分散性,其形貌大小较均匀,尺寸较小,形状多呈球形或短棒状。
图4为不同倍率下BPs-PEG-Au复合材料的透射电镜照片。从图中可以看出,Au纳米粒子已经成功负载在BPs上。图B,C,D是放大倍数的透射电镜照片,我们从中更能看出二者已成功相连。
图5为Au,BPs-PEG,BPs-PEG-Au的紫外-可见吸收光谱。在Au的紫外-可见吸收光谱中可以看出600~700 nm处有一个微弱的吸收峰,此峰为Au的紫外吸收峰。在BPs-PEG的紫外吸收峰中可以看出,由于BPs独特的电子结构,其吸收几乎跨越紫外和整个可见光区域。此外,在200~900 nm的所有吸光度范围内,我们发现复合材料比任何单一模式展示出更强的吸收。
图6为在650 nm, 808 nm, 980 nm不同激光照射下( 0.5 W/cm2 ) 20 min时混合BPs-PEG-Au的DPBF的吸收光谱。用650 nm的光激发的DPBF光降解程度高于808 nm波长的光和980 nm波长的光激发的DPBF光降解程度,表明650 nm光照时复合材料的吸收更广阔,这意味着650 nm光激发下的BPs-PEG-Au复合材料具有最高的活性氧的产生能力和光动力性质。
图7为在410 nm波长处650 nm的激光下( 0.5 W/cm2 ),照射混合BPs-PEG-Au的DPBF不同时间的吸收光谱。随着照射时间的延长,混合BPs-PEG-Au的DPBF的紫外吸收逐渐下降,因此表明650 nm激光照射下BPs-PEG-Au能够有效产生ROS。
图8为在410 nm波长处650 nm的激光下( 0.5 W/cm2 ),DPBF在不同溶液中的吸收衰减曲线。图中的点分别对应于DPBF,BPs-PEG,BPs-PEG-Au三种不同溶液在650 nm激光照射5 min,10 min,15 min,20 min时的紫外吸收峰值。图中的衰减曲线表明纯DPBF不能通过650 nm NIR光降解,然而在BPs-PEG-Au的存在下, DPBF吸收显着降低,这说明随着延长照射时间可以有效产生ROS,这可能是由于Au和BPs产生的双模态ROS使BPs-PEG-Au有更高的ROS产生能力。
综上,本实施例运用液相剥离法制备BPs纳米片,经过PEG-NH2修饰后负载Au纳米团簇成功制备出一种新型BPs-PEG-Au纳米复合材料。
Claims (9)
1.一种新型BPs-PEG-Au纳米复合材料的制备方法,其特征在于这种新型纳米复合材料负载了Au纳米团簇,利用从上转换纳米粒子(Au纳米团簇)到光敏剂(BPs)的共振能量转移,通过光敏剂和上转换纳米粒子的组合来产生更深层的光动力治疗(PDT)效应。
2.一种新型BPs-PEG-Au纳米复合材料的制备方法,其特征在于一种新型BPs-PEG-Au纳米复合材料的制备方法是按以下步骤完成的:
一、超薄BPs(黑磷片)的制备:利用液相剥离法来制备超薄BPs,将块状BPs研磨成粉后在冰水浴下真空超声8小时,在4500转速下离心5分钟,回收上清液,三次水洗离心去掉上清液得到超薄BPs;
二、BPs-PEG的制备:PEG-NH2(氨基修饰的聚乙二醇)分散到适量蒸馏水中超声,将其加入到BPs中,超声30min,搅拌4h,4500转速下离心和反复水洗除去过量的PEG分子,将制得的样品分散于5ml蒸馏水中;
步骤二中所述的PEG-NH2的质量与蒸馏水的体积比为:0.0055g:5ml;
三、Au纳米团簇的合成:将加有转子的遮光小瓶放在磁力搅拌器上搅拌,向其中加入蒸馏水,HAuCl4·3H2O,MHA(2-羟基-4-甲硫基丁酸钙)形成MHA-Au(I)复合物,再加入NaOH溶液,搅拌15min后加入NaBH4溶液,搅拌3h制得Au纳米团簇;
步骤三中所述的蒸馏水,HAuCl4·3H2O,MHA,NaOH,NaBH4的摩尔比为1306:0.05:20:3:1148;
四、BPs-PEG-Au纳米复合材料的合成:分别向标号为1,2,3,4的遮光离心管中加入不同量的Au纳米团簇,EDC(1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐)和NHS(N-羟基琥珀酰亚胺),加入适量蒸馏水溶解,活化2小时,分别加入BPs-PEG,另取遮光离心管倒入剩余的BPs-PEG并标号为0作为空白对照组,所有离心管在黑暗中搅拌8-12h,水洗离心后分散到5ml水中;
步骤四中所述的配置好的Au纳米团簇的体积,EDC的质量,NHS的质量,配置好的BPs-PEG的体积比为(0.25ml,0.5ml,1ml,2ml):6mg:2mg:1ml。
3.根据权利要求2所述的一种新型BPs-PEG-Au纳米复合材料的制备方法,其特征在于步骤一中所述的制备的黑磷为2D纳米片状材料。
4.根据权利要求2所述的一种新型BPs-PEG-Au纳米复合材料的制备方法,其特征在于步骤一中所述的制备黑鳞的方法为液相剥离法。
5.根据权利要求2所述的一种新型BPs-PEG-Au纳米复合材料的制备方法,其特征在于步骤二中所述的对2D黑鳞纳米片进行了PEG-NH2修饰。
6.根据权利要求2所述的一种新型BPs-PEG-Au纳米复合材料的制备方法,其特征在于步骤二中所述的PEG-NH2的质量与蒸馏水的体积比为:0.0055g:5ml。
7.根据权利要求2所述的一种新型BPs-PEG-Au纳米复合材料的制备方法,其特征在于步骤三中所述的蒸馏水,HAuCl4·3H2O,MHA,NaOH,NaBH4的摩尔比为1306:0.05:20:3:1148。
8.根据权利要求2所述的一种新型BPs-PEG-Au纳米复合材料的制备方法,其特征在于步骤四中所述的对PEG-NH2修饰过的BPs负载Au纳米团簇。
9.根据权利要求2所述的一种新型BPs-PEG-Au纳米复合材料的制备方法,其特征在于步骤四中所述的配置好的Au纳米团簇的体积,EDC的质量,NHS的质量,配置好的BPs-PEG的体积比为(0.25ml,0.5ml,1ml,2ml):6mg:2mg:1ml。
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Cited By (5)
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CN114887072A (zh) * | 2021-12-14 | 2022-08-12 | 汕头大学 | 一种基于peg-mal修饰的靶向her2阳性乳腺癌的二维黑磷杂化纳米药物 |
CN114887072B (zh) * | 2021-12-14 | 2023-06-09 | 汕头大学 | 一种基于peg-mal修饰的靶向her2阳性乳腺癌的二维黑磷杂化纳米药物 |
CN115321499A (zh) * | 2022-08-11 | 2022-11-11 | 哈尔滨理工大学 | 一种用于生物成像的黑磷纳米片复合材料的制备 |
CN115321499B (zh) * | 2022-08-11 | 2023-10-13 | 哈尔滨理工大学 | 一种用于生物成像的黑磷纳米片复合材料的制备 |
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