Preparation and Performance of Palladium Clusters-Loaded Silica-Based Hybrid Micelles
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摘要: 利用Pluronic嵌段共聚物F127的自组装特性和3-巯基丙基三甲氧基硅烷（MPTMS）在碱性环境下的水解缩聚反应，首先制备了具有高稳定性的有机氧化硅基杂化胶束。进一步借助杂化胶束表面的巯基与钯物种的配位作用，利用“原位限域生长”策略制备得到负载钯纳米团簇的有机氧化硅基杂化胶束。采用动态光散射、透射电镜、X射线衍射、红外光谱等表征手段分析了钯簇@氧化硅基杂化胶束的形貌、结构和稳定性，并使用3,3′,5,5′-四甲基联苯胺（TMB）进行显色反应验证了该体系的类过氧化物酶活性，同时探究了其在808 nm近红外光激发下的光热性能。细胞实验结果表明，该钯簇@氧化硅基杂化胶束能够被肿瘤细胞摄取，并具备良好的生物安全性和光热毒性，有望作为一种类过氧化物酶成像引导的光热治疗剂用于癌症的高效安全诊疗。Abstract: Taking advantage of the self-assembly of Pluronic block copolymer F127 and the hydrolysis and condensation of (3-Mercaptopropyl) trimethoxysilane (MPTMS) in alkaline environment, a highly stable silica-based hybrid micelles were firstly synthesized. Furthermore, based on the coordination interaction between palladium species and thiols on the surface of hybrid micelles, the palladium clusters-loaded silica-based hybrid micelles (Pd@FOMs) were prepared via the “in-situ confined growth” strategy. The hydrodynamic diameter and morphology of Pd@FOMs were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The structure of Pd@FOMs was analyzed by X-ray diffraction (XRD), infrared spectroscopy (FT-IR) and Raman spectroscopy. 3,3′,5,5′-tetramethylbenzidine (TMB) was used to verify the peroxidase-like (POD-like) activity of Pd@FOMs. In the presence of hydrogen peroxide, Pd@FOMs could oxidize TMB to TMB oxide with characteristic absorption at 652 nm. The Michaelis constant (Km) of Pd@FOMs was calculated to be 113.91 mmol/L. Besides, the photothermal performance of Pd@FOMs was explored. Under 808 nm laser irradiation (1.0 W/cm2) for 5 min, Pd@FOMs with the concentration of Pd at 100 mg/L induced temperature rise from 18.1 ℃ to 52.9 ℃. In addition, Pd@FOMs had good photothermal stability with a high photothermal conversion efficiency of 65.76%. Cell experiments showed that Pd@FOMs could be endocytosed by SMMC-7721 tumor cells effectively and had good biocompatibility and excellent photothermal toxicity. Thus, Pd@FOMs are expected to be applied as imaging-guided photothermal therapeutic agent for diagnosis and treatment of tumors.
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Key words:
- palladium clusters /
- micelles /
- organosilica particles /
- peroxidase /
- photothermal therapy
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图 2 不同Pd(NH3)4Cl2·H2O浓度制备的Pd@FOMs的（a）动力学直径和（b）Zeta电位; （c）Pd负载效率和负载量
Figure 2. (a) Hydrodynamic diameters, (b) Zeta potentials and (c) Pd loading efficiencies and loading capacities of Pd@FOMs prepared with different conentrations of Pd(NH3)4Cl2·H2O
图 4 FOMs和Pd@FOMs的（a）红外光谱图和（b）拉曼光谱图；（c）FOMs、Pd@FOMs和标准JCPDS卡片（序号46-1043）的XRD谱图
Figure 4. (a) FT-IR spectra and (b) Raman spectra of FOMs and Pd@FOMs; (c) XRD patterns of FOMs and Pd@FOMs with the standard JCPDS file (No. 46-1043)
图 5 Pd@FOMs在PBS（pH=7.4）和RPMI-1640培养基中7 d内的水合动力学粒径变化情况
Figure 5. Hydrodynamic diameters of Pd@FOMs in PBS (pH=7.4) and RPMI-1640 medium in 7 d
图 6 （a）类POD酶活性的紫外吸收曲线，以及反应体系的颜色变化；（b）H2O2，Pd@FOMs和Pd@FOMs+H2O2的ESR谱图；（c）类POD酶活性的米氏动力学曲线；（d）类POD酶活性的双倒数曲线
Figure 6. (a) UV-vis absorbance spectra showing POD-like activity, and color change of reaction solution; (b) ESR spectra of H2O2, Pd@FOMs and Pd@FOMs+H2O2; (c) Michaelis-Menten kinetics plot of POD-like activity; (d) Lineweaver-Burk fitting plot of POD-like activity
图 7 （a）FOMs和Pd@FOMs的紫外-可见光吸收曲线；808 nm激光照射（b）不同Pd质量浓度和（c）不同激光功率密度下Pd@FOMs的光热升温曲线；（d）Pd@FOMs（100 mg/L Pd）的光热稳定性
Figure 7. (a) UV-vis spectra of FOMs and Pd@FOMs; Temperature elevation curves of Pd@FOMs with varying concentrations of Pd (b) or varying laser power densities (c) upon 808 nm laser irradiation; (d) Photothermal stability of Pd@FOMs (100 mg/L Pd)
图 8 （a）使用808 nm激光（1.0 W/cm2）照射Pd@FOMs（100 mg/L Pd）15 min后再自然冷却的温度变化；（b）从冷却阶段（15 min后）得到的线性时间拟合数据
Figure 8. (a) Temperature change of Pd@FOMs (100 mg/L Pd) upon irradiation for 15 min before the 808 nm laser (1.0 W/cm2) was turned-off; (b) Linear time data obtained from a cooling stage (after 15 min)
图 9 SMMC-7721细胞和马来酰亚胺-聚乙二醇-罗丹明标记的Pd@FOMs共培养1、4、12、24 h后的激光共聚焦图像
Figure 9. CLSM images of SMMC-7721 cells incubated with MAL-PEG-Rhodamine-loaded Pd@FOMs for 1, 4, 12, 24 h
图 10 （a）RAW264.7细胞和SMMC-7721细胞与不同浓度的Pd@FOMs共培养24 h后的细胞存活率；（b）SMMC-7721细胞经Pd@FOMs光热治疗后的细胞存活率
*P<0.05, **P<0.01, ***P<0.001
Figure 10. (a) Relative cell viabilities of RAW264.7 and SMMC-7721 cells after incubated with Pd@FOMs at varied Pd concentrations for 24 h. (b) Relative cell viabilities of SMMC-7721 cells after PTT with Pd@FOMs
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