Yildirim Adem, Chattaraj Rajarshi, Blum Nicholas T, Goodwin Andrew P
Department of Chemical and Biological Engineering, University of Colorado Boulder. Boulder, Colorado 80303, United States.
Department of Mechanical Engineering, University of Colorado Boulder. Boulder, Colorado 80309, United States.
Chem Mater. 2016 Aug 23;28(16):5962-5972. doi: 10.1021/acs.chemmater.6b02634. Epub 2016 Aug 9.
Ultrasound is widely applied in medical diagnosis and therapy due to its safety, high penetration depth, and low cost. In order to improve the contrast of sonographs and efficiency of the ultrasound therapy, echogenic gas bodies or droplets (with diameters from 200 nm to 10 µm) are often used, which are not very stable in the bloodstream and unable to penetrate into target tissues. Recently, it was demonstrated that nanobubbles stabilized by nanoparticles can nucleate ultrasound responsive microbubbles under reduced acoustic pressures, which is very promising for the development of nanoscale (<100 nm) ultrasound agents. However, there is still very little understanding about the effects of nanoparticle properties on the stabilization of nanobubbles and nucleation of acoustic cavitation by these nanobubbles. Here, a series of mesoporous silica nanoparticles with sizes around 100 nm but with different morphologies were synthesized to understand the effects of nanoparticle porosity, surface roughness, hydrophobicity, and hydrophilic surface modification on acoustic cavitation inception by porous nanoparticles. The chemical analyses of the nanoparticles showed that, while the nanoparticles were prepared using the same silica precursor (TEOS) and surfactant (CTAB), they revealed varying amounts of carbon impurities, hydroxyl content, and degrees of silica crosslinking. Carbon impurities or hydrophobic modification with methyl groups is found to be essential for nanobubble stabilization by mesoporous silica nanoparticles. The acoustic cavitation experiments in the presence of ethanol and/or bovine serum albumin (BSA) demonstrated that acoustic cavitation is predominantly nucleated by the nanobubbles stabilized at the nanoparticle surface not inside the mesopores. Finally, acoustic cavitation experiments with rough and smooth nanoparticles were suggested that a rough nanoparticle surface is needed to largely preserve surface nanobubbles after coating the surface with hydrophilic macromolecules, which is required for in vivo applications of nanoparticles.
由于超声具有安全性、高穿透深度和低成本等特点,其在医学诊断和治疗中得到了广泛应用。为了提高超声图像的对比度和超声治疗的效率,人们经常使用回声气体或液滴(直径从200纳米到10微米),但它们在血液中不太稳定,且无法穿透进入靶组织。最近有研究表明,由纳米颗粒稳定的纳米气泡在降低的声压下可以形成超声响应性微气泡,这对于开发纳米级(<100纳米)超声剂非常有前景。然而,对于纳米颗粒性质对纳米气泡稳定性以及这些纳米气泡引发声空化的影响,人们仍然知之甚少。在此,合成了一系列尺寸约为100纳米但形态各异的介孔二氧化硅纳米颗粒,以了解纳米颗粒孔隙率、表面粗糙度、疏水性以及亲水性表面改性对多孔纳米颗粒引发声空化的影响。对纳米颗粒的化学分析表明,虽然这些纳米颗粒是使用相同的二氧化硅前驱体(TEOS)和表面活性剂(CTAB)制备的,但它们显示出不同数量的碳杂质、羟基含量以及二氧化硅交联程度。发现碳杂质或甲基疏水改性对于介孔二氧化硅纳米颗粒稳定纳米气泡至关重要。在乙醇和/或牛血清白蛋白(BSA)存在下的声空化实验表明,声空化主要由稳定在纳米颗粒表面而非介孔内部的纳米气泡引发。最后,对粗糙和光滑纳米颗粒进行的声空化实验表明,在纳米颗粒表面用亲水性大分子包覆后,需要粗糙的纳米颗粒表面来大量保留表面纳米气泡,这是纳米颗粒体内应用所必需的。