Department of Chemistry and Chemical Biology, Rutgers University, 123 Bevier Rd., Piscataway, NJ 08854, USA.
J Colloid Interface Sci. 2022 Oct;623:247-256. doi: 10.1016/j.jcis.2022.03.144. Epub 2022 Apr 6.
Blending amphiphilic triblock (A-B-A) and diblock (A-B) copolymers comprised of the same hydrophobic tyrosine-derived oligomeric B-block and hydrophilic poly(ethylene glycol) methyl ether (mPEG) A-block can provide highly tunable self-assembled nanosphere particle sizes suitable for biomedical applications.
Triblock and diblock copolymers were synthesized via carbodiimide chemistry and were characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The amount of free PEG present in the purified copolymers was determined using a standard addition calibration curve and GPC peak deconvolution methods. Nanospheres were prepared by co-precipitation of each copolymer and of copolymer blends over a range of mole ratios. Nanospheres were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM) and % polymer recovery post-preparation.
Precise synthesis control produced triblock and diblock copolymers with narrow molecular weight distributions and minimal residual reactants. Self-assembled nanosphere particle sizes were 33 nm for the triblock and 129 nm for the diblock, and the size of their blends increased continuously as a function of mole ratio within that biomedically relevant range. Addition of unreacted PEG had minimal impact on either triblock or diblock nanosphere particle sizes whereas addition of unreacted oligomeric B-block increased nanosphere sizes.
将由相同疏水性酪氨酸衍生的低聚物 B 嵌段和亲水聚乙二醇甲基醚(mPEG)A 嵌段组成的两亲性三嵌段(A-B-A)和二嵌段(A-B)共聚物进行混合,可以提供高度可调的自组装纳米球粒径,适用于生物医学应用。
通过碳二亚胺化学合成了三嵌段和二嵌段共聚物,并通过核磁共振(NMR)和凝胶渗透色谱(GPC)进行了表征。使用标准添加校准曲线和 GPC 峰分解方法确定了纯化共聚物中存在的游离 PEG 的量。通过共沉淀每种共聚物和共聚物混合物在一系列摩尔比下制备纳米球。通过动态光散射(DLS)、透射电子显微镜(TEM)和制备后聚合物回收率的%对纳米球进行了表征。
精确的合成控制产生了具有窄分子量分布和最小残留反应物的三嵌段和二嵌段共聚物。自组装纳米球粒径分别为三嵌段 33nm 和二嵌段 129nm,其混合物的粒径在该生物医学相关范围内随摩尔比连续增加。未反应的 PEG 的添加对三嵌段或二嵌段纳米球粒径的影响最小,而未反应的低聚物 B 嵌段的添加则增加了纳米球的粒径。