In situ temperature monitoring with photoacoustic measurements is introduced in an integrated setup, specifically designed for photothermotherapy treatmentof the glioblastoma, aided by nanoparticles and HIFU blood-brain barrier opening.
The presentation will overview our on-going activities on laser ablative synthesis of plasmonic colloidal nanomaterials and their biomedical applications. Our approach is based on ultra-short (fs) laser ablation from a solid target or already formed water-suspended colloids, which makes possible the fabrication of ultrapure bare (ligand-free) nanoparticles having controlled mean size and low size dispersion. The presentation will describe different approaches to achieve appropriate characteristics of nanomaterials (Au-based nanomaterials and alternative structures) and overview their biomedical applications. In particular, we show that Au nanoparticles can efficiently enhance Raman signals from different biological objects. Profiting from the observed enhancement and purity of laser-synthesized nanomaterials, we demonstrate successful identification of 2 types of bacteria (Listeria innocua and Escherichia coli). We also show that bare metal nanoparticles synthesized by laser ablation can provide an order of magnitude better response in glucose oxidation tasks, which promises their use as elecrocatalysts in bioimplantable therapeutic devices. Finally, we overview applications of bare plasmonic nanomaterials in phototherapy and tissue engineering tasks
In food industry, detection of spoilage yeasts such as W. anomalus and B. bruxellensis and pathogens such as certain Listeria and E. coli species can be laborious and time-consuming. In the present study, a simple and repeatable technique was developed for rapid yeast detection using a combination of patterned gold coated polymer SERS substrates and gold nanoparticles [1−4]. For the first time, a state-of-the-art time-gated Raman detection approach was used as a complementary technique to show the possibility of using 532-nm pulsed laser excitation and avoid the destructive influence of induced fluorescence [3].
Conventional nanoparticles synthesized by colloidal chemistry are typically contaminated by non-biocompatible by-products (surfactants, anions), which can have negative impacts on many live objects under examination (cells, bacteria) and thus decrease the precision of bioidentification. Here, we explore novel ultrapure laser-synthesized Au-based nanomaterials, including Au NPs and Au Si hybrid nanostructures, as mobile SERS probes in tasks of bacteria detection [3].
We demonstrate successful identification of two types of bacteria (L. innocua and E. coli) and yeast (W. anomalus and B. bruxellensis). They showed several differing characteristic peaks making the discrimination of these yeasts possible without the need for chemometric analysis [2]. The use of composite gold-silicon laser-ablated nanoparticles in combination with the SERS substrate gave distinctive spectra for all the detected species. The detection limit of the studied species varied within 104-107 CFU/ml. The obtained results open up opportunities for non-disturbing investigation of biological systems by profiting from excellent non-disturbing nature of laser-synthesized nanomaterials in combination with outstanding optical detection technologies [2, 3].
[1] Uusitalo et al. 2016, http://pubs.rsc.org/en/content/articlehtml/2016/ra/c6ra08313g
[2] Uusitalo et al. 2017a, https://www.sciencedirect.com/science/article/pii/S0260877417302054
[3] Kögler et al. 2018, https://onlinelibrary.wiley.com/doi/abs/10.1002/jbio.201700225
[4] Uusitalo et al. 2017b, https://www.spiedigitallibrary.org/journalArticle/Download?fullDOI=10.1117/1.OE.56.3.037102
Methods of femtosecond laser ablation were used to fabricate bare (ligand-free) silicon (Si) nanoparticles in deionized water. The nanoparticles were round in shape, crystalline, free of any impurities, and water-dissolvable, while the dissolution rate depended on the concentration of oxygen defects in their composition. The nanoparticles were then eletrospun with chitosan to form nanoparticle decorated nanofibrous matrices. We found that the functionalization of nanofibers by the nanoparticles can affect the morphology and physico-chemical characteristics of resulting nanostructures. In particular, the presence of Si nanoparticles led to the reduction of fibers thickness, suggesting a potential improvement of fiber’s surface reactivity. We also observed the improvement of thermal stability of hybrid nanofibers. We believe that the incorporated Si nanoparticles can serve as functional elements to improve characteristics of chitosan-based matrices for cellular growth, as well as to enable novel imaging or therapeutic functionalities for tissue engineering applications.
Femtosecond laser fragmentation from preliminarily prepared water-dispersed Si microcolloids was used to synthesize bare (ligand-free) spherical silicon nanoparticles (Si-NPs) with low size dispersion and controllable mean size from a few nm to several tens of nm. In order to control the oxidation state of Si-NPs, the fragmentation was performed in normal oxygen-saturated water (oxygen-rich conditions) or in water disoxygenated by pumping with noble gases (Ag, He) before and during the experiment (oxygen-free conditions). XPS and TEM studies revealed that Si-NPs were composed of Si nanocrystals with inclusions of silicon oxide species, covered by SiOx (1 < x < 2) shell, while the total oxide content depended whether Si-NPs were prepared in oxygen-rich or oxygen-free conditions. When placed into a dialysis box, waterdispersed Si-NPs rapidly dissolved, which was evidenced by TEM data. In this case, NPs prepared under oxygen-rich conditions demonstrated much faster dissolution kinetics and their complete disappearance after 7-10 days, while the dissolution process of less oxidized counterparts could last much longer (25-30 days). Much fast dissolution kinetics of more oxidized Si-NPs was attributed to more friable structure of nanoparticle core due to the presence of numerous oxidation-induced defects. Laser-synthesized Si-NPs are of paramount importance for biomedical applications.
We review our recently obtained data on the employment of Si nanoparticles as sensitizers of radiofrequency (RF) - induced hyperthermia for mild cancer therapy tasks. Such an approach makes possible the heating of aqueous suspensions of Si nanoparticles by tens of degrees Celsius under relatively low intensities (1–5 W/cm2) of 27 MHz RF radiation. The heating effect is demonstrated for nanoparticles synthesized by laser ablation in water and mechanical grinding of porous silicon, while laser-ablated nanoparticles demonstrate a remarkably higher heating rate than porous silicon-based ones for the whole range of the used concentrations. The observed RF heating effect can be explained in the frame of a model considering the polarization of Si NPs and electrolyte in the external oscillating electromagnetic field and the corresponding release of heat by electric currents around the nanoparticles. Our tests evidence relative safety of Si nanostructures and their efficient dissolution in physiological solutions, suggesting potential clearance of nanoparticles from a living organism without any side effects. Profiting from Si nanoparticle-based heating, we finally demonstrate an efficient treatment of Lewis Lung carcinoma in vivo. The obtained data promise a breakthrough in the development of mild, non-invasive methods for cancer therapy.
Gold nanoparticles (Au NPs) attract particular attention because of their unique size-dependent chemical, physicochemical and optical properties and, hence, their potential applications in catalysis, nanoelectronics, photovoltaics and medicine. In particular, laser-produced colloidal nanoparticles are not only biocompatible, but also reveal unique chemical properties. Different laser systems can be used for synthesis of these colloids, varying from continuous wave (CW) to ultra-short femtosecond lasers. The choice of an optimum laser system is still a challenge in application development. To bring more light at this issue, we investigate an influence of laser parameters on nanoparticle formation from a gold target immersed in deionized water. First, an optical diagnostics of laser-induced hydrodynamic processes taking place near the gold surface is performed. Then, gold nanoparticle colloids with average particle sizes smaller than 10 nm and a very narrow dispersion are shown to be formed by CW laser ablation. The obtained results are compared with the ones obtained by using the second harmonics and with previous results obtained by using femtosecond laser systems.
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