Homaeigohar Shahin, Kordbacheh Danial, Banerjee Sourav, Gu Jiacheng, Zhang Yilong, Huang Zhihong
School of Science and Engineering, University of Dundee, Dundee DD1 4HN, UK.
Division of Cancer Research, School of Medicine, University of Dundee, Dundee DD1 9SY, UK.
Polymers (Basel). 2025 Jan 12;17(2):173. doi: 10.3390/polym17020173.
Nanofibrous dressing materials with an antitumor function can potentially inhibit recurrence of melanoma following the surgical excision of skin tumors. In this study, hydrolyzed polyacrylonitrile (hPAN) nanofibers biofunctionalized with L-carnosine (CAR) and loaded with bio (CAR)-synthesized zinc oxide (ZnO) nanoparticles, ZnO/CAR-hPAN (hereafter called ZCPAN), were employed to develop an antimelanoma wound dressing. Inspired by the formulation of the commercial wound healing Zn-CAR complex, i.e., polaprezinc (PLZ), for the first time, we benefitted from the synergy of zinc and CAR to create an antimelanoma nanofibrous wound dressing. According to scanning electron microscopy (SEM) images, ultrafine ZnO nanoparticles were homogenously distributed throughout the nanofibrous dressing. The ZCPAN nanofiber mat showed a significantly higher toughness (18.7 MJ.m vs. 1.4 MJ.m) and an enhanced elongation at break (stretchability) compared to the neat PAN nanofiber mat (12% vs. 9.5%). Additionally, optical coherence elastography (OCE) measurements indicated that the ZCPAN nanofibrous dressing was as stiff as 50.57 ± 8.17 kPa which is notably larger than that of the PAN nanofibrous dressing, i.e., 24.49 ± 6.83 kPa. The optimum mechanical performance of the ZCPAN nanofibers originates from physicochemical interaction of CAR ligands, hPAN nanofibers, and ZnO nanoparticles through hydrogen bonding, electrostatic bonding, and esterification, as verified using ATR-FTIR. An in vitro cell viability assay using human skin melanoma cells implied that the cells are notably killed in the presence of the ZCPAN nanofibers compared to the PAN nanofibers. Thanks to ROS generating ZnO nanoparticles, this behavior originates from the high reactive oxygen species (ROS)-induced oxidative damage of melanoma cells, as verified through a CellROX assay. In this regard, an apoptotic cell response to the ZCPAN nanofibers was recorded through an apoptosis assay. Taken together, the ZCPAN nanofibers induce an antimelanoma effect through oxidative stress and thus are a high potential wound dressing material to suppress melanoma regrowth after surgical excision of skin tumors.
具有抗肿瘤功能的纳米纤维敷料材料可能会抑制皮肤肿瘤手术切除后黑色素瘤的复发。在本研究中，采用用L-肌肽（CAR）进行生物功能化并负载生物（CAR）合成的氧化锌（ZnO）纳米颗粒的水解聚丙烯腈（hPAN）纳米纤维，即ZnO/CAR-hPAN（以下称为ZCPAN），来开发一种抗黑色素瘤伤口敷料。首次受到商业伤口愈合锌-肌肽复合物即聚普瑞锌（PLZ）配方的启发，我们受益于锌和肌肽的协同作用，创造了一种抗黑色素瘤纳米纤维伤口敷料。根据扫描电子显微镜（SEM）图像，超细ZnO纳米颗粒均匀分布在整个纳米纤维敷料中。与纯PAN纳米纤维垫相比，ZCPAN纳米纤维垫显示出显著更高的韧性（18.7 MJ.m对1.4 MJ.m）和增强的断裂伸长率（拉伸性）（12%对9.5%）。此外，光学相干弹性成像（OCE）测量表明，ZCPAN纳米纤维敷料的硬度为50.57±8.17 kPa，明显大于PAN纳米纤维敷料的硬度，即24.49±6.83 kPa。ZCPAN纳米纤维的最佳机械性能源于CAR配体、hPAN纳米纤维和ZnO纳米颗粒通过氢键、静电键和酯化的物理化学相互作用，这通过ATR-FTIR得到验证。使用人皮肤黑色素瘤细胞的体外细胞活力测定表明，与PAN纳米纤维相比，在ZCPAN纳米纤维存在下细胞明显被杀死。由于产生ROS的ZnO纳米颗粒，这种行为源于高活性氧物种（ROS）诱导的黑色素瘤细胞氧化损伤，这通过CellROX测定得到验证。在这方面，通过凋亡测定记录了对ZCPAN纳米纤维的凋亡细胞反应。综上所述，ZCPAN纳米纤维通过氧化应激诱导抗黑色素瘤作用，因此是一种在皮肤肿瘤手术切除后抑制黑色素瘤再生的极具潜力的伤口敷料材料。
