Effects of Nanobubbles on Photochemical Processes of Levofloxacin Photosensitizer.

Photodynamic therapy (PDT) stands as an efficacious modality for the treatment of cancer and various diseases, in which optimization of the electron transfer and augmentation of the production of lethal reactive oxygen species (ROS) represent pivotal challenges to enhance its therapeutic efficacy. Empirical investigations have established that the spontaneous initiation of redox reactions associated with electron transfer is feasible and is located in the gas-liquid interfaces. Meanwhile, nanobubbles (NBs) are emerging as entities capable of furnishing a plethora of such interfaces, attributed to their stability and large surface/volume ratio in bulk water. Thus, NBs provide a chance to expedite the electron-transfer kinetics within the context of PDT in an ambient environment. In this paper, we present a pioneering exploration into the impact of nitrogen nanobubbles (N2-NBs) on the electron transfer of the photosensitizer levofloxacin (LEV). Transient absorption spectra and time-resolved decay spectra, as determined through laser flash photolysis, unequivocally reveal that N2-NBs exhibit a mitigating effect on the decay of the LEV excitation triplet state, thereby facilitating subsequent processes. Of paramount significance is the observation that the presence of N2-NBs markedly accelerates the electron transfer of LEV, albeit with a marginal inhibitory influence on its energy-transfer reaction. This observation is corroborated through absorbance measurements and offers compelling evidence substantiating the role of NBs in expediting electron transfer within the ambit of PDT. The mechanism elucidated herein sheds light on how N2-NBs intricately influence both electron-transfer and energy-transfer reactions in the photosensitizer LEV. These findings not only contribute to a nuanced understanding of the underlying processes but also furnish novel insights that may inform the application of NBs in the realm of photodynamic therapy.

Evolution of Bulk Nanobubbles under Different Freezing Conditions.

The freezing process of aqueous solutions plays a crucial role in various applications including cryopreservation, glaciers, and frozen materials. However, less research has focused on the influence of nanoscale gas bubble formation or collapse in water during freezing, which may significantly impact the formation of ice crystals. Herein, we report for the first time that the freezing process can produce nanobubbles in aqueous solutions, and their size and number concentration could be changed by different cooling rates, i.e., the size would decrease as the cooling rate increased, and the maximum number concentration was found at the -80 °C system. Furthermore, increasing the dissolved gas content in the solution enhanced the production of nanobubbles, whereas for preexisting nanobubbles, the freezing resulted in a decrease in their number concentration, which was negatively correlated with the cooling rate. Our results indicated that a moderate cooling rate of -80 °C favored nanobubble generation, whereas a higher cooling rate was preferable for maintaining preexisting nanobubbles. Conversely, a lower cooling rate could be employed to eliminate preexisting nanobubbles. This study explored the evolution and stability of nanobubbles during the freezing process, providing valuable insights into the application or elimination of nanobubbles.

An antioxidation strategy based on ultra-small nanobubbles without exogenous antioxidants.

Antioxidation is in demand in living systems, as the excessive reactive oxygen species (ROS) in organisms lead to a variety of diseases. The conventional antioxidation strategies are mostly based on the introduction of exogenous antioxidants. However, antioxidants usually have shortcomings of poor stability, non-sustainability, and potential toxicity. Here, we proposed a novel antioxidation strategy based on ultra-small nanobubbles (NBs), in which the gas-liquid interface was employed to enrich and scavenge ROS. It was found that the ultra-small NBs (~ 10 nm) exhibited a strong inhibition on oxidization of extensive substrates by hydroxyl radicals, while the normal NBs (~ 100 nm) worked only for some substrates. Since the gas-water interface of the ultra-small NBs is non-expendable, its antioxidation would be sustainable and its effect be cumulative, which is different to that using reactive nanobubbles to eliminate free radicals as the gases are consumptive and the reaction is unsustainable. Therefore, our antioxidation strategy based on ultra-small NB would provide a new solution for antioxidation in bioscience as well as other fields such as materials, chemical industry, food industry, etc.

Formation of Bulk Nanobubbles Induced by Accelerated Electrons Irradiation: Dependences on Dose Rates and Doses of Irradiation.

Radiation on aqueous solutions can induce water radiolysis with products of radicals, H2, H2O2, and so on, and their consequent biological effects have long been interested in radiation chemistry. Unlike the decomposition of water by electric current that produces a significant number of bubbles, the gas products from the radiolysis of water are normally invisible by bare eyes, little is known on whether nanosized bubbles can be produced and what their dynamics are upon irradiation. Here, we first presented the formation of nanoscale bulk bubbles by irradiating pure water with accelerated electrons and their concentration and size distribution changes with the dose and rate of irradiation. The nanoparticle tracking analysis showed that irradiation can actually produce a certain amount of bulk nanobubbles in pure water. They exhibited a dependence on the irradiation dose rates and irradiation doses. The results indicated that the concentration of formed bulk nanobubbles increased as the irradiation dose rates increased, but it will increase and then decrease with the increased irradiation doses. The formed bulk nanobubbles could maintain stability for several hours. Our findings will provide a new angle of view for the radiation chemistry of water, and the formed nanobubbles may help elucidate the biological effects of irradiated solutions.

Interfacial Micropancakes: Gas or Contaminations?

Micropancake, a flat domain with micrometer-scale lateral size and a few nanometer thickness, is usually accompanied by the generation of interfacial nanobubbles at the liquid/solid surfaces. Unlike the nanobubbles, micropancakes are difficult to be produced efficiently, impeding further investigations of their mysterious properties. Very recently, An et al. even argued that the previously observed micropancakes were most likely the contaminate, not the gas layers. Herein, to reveal the nature of micropancakes with solid evidence, we presented the in situ characterization of micropancakes at a highly oriented pyrolytic graphite (HOPG) surface produced by the ethanol-water exchange or gas-supersaturated water. By washing with deeply degassed water (DW), the dissolution of those micropancakes was clearly observed, indicating that they may very well be composed of gas. In addition, the analysis of the force measurements showed the intrinsic differences between those gaseous micropancakes and the insoluble organic films. The data and results supported the interpretation that the real existence of gas micropancakes at liquid/solid surfaces.

Influence of the Dissolved Gas on the Interfacial Properties of Decane Surface Nanodroplets.

Surface nanodroplets have received extensive attention recently due to their potential in the fabrication of functional materials with nanostructures and chemical reactions at micro- and nanoscales. Although the effect of dissolved gas in water has been realized in some important processes such as spontaneous emulsification of oil droplets in water, its roles in the wetting behavior of surface nanodroplets at the hydrophobic interface have been largely neglected. Here, we focused on the influence of dissolved gas on the interfacial properties of surface nanodroplets and characterized their morphological evolution when exposed to different air-saturated water samples. Results indicated that the morphology of surface nanodroplets barely changed in air-oversaturated cold water. However, their contact angle first decreases gradually in deionized water, increases immediately after replacement with degassed water, and eventually decreases gradually with time. Furthermore, the surface tension of nanodroplets would change similarly after the injection of degassed water. We considered these changes to be caused by the removal or reduction of the enriched gas at the substrate interface, in which the surface hydrophobicity was changed. Our findings could shed some light on the wetting behavior of nanodroplets at the hydrophobic surface in different air-saturated water samples and inspire the microscale manipulation and reaction of surface nanodroplets.

Influence of Krypton Gas Nanobubbles on the Activity of Pepsin.

The fact that biologically inert gases can significantly affect the biological function of proteins still lacks a full understanding because they are usually chemically stable and weakly absorbed by biological molecules. Recently, nanobubbles were proposed to play an important role in the activity of a protein (Scientific reports 2013, 3; Scientific reports 2017, 7, 10176). In this study, we developed a controllable method to produce high-concentration krypton (Kr) gas nanobubbles in pure water and measured the concentration influence of those Kr nanobubbles on pepsin protein activity. By combining high-sensitivity synchrotron radiation X-ray fluorescence techniques with a nanoparticle tracking analysis technology, we provided strong evidence that the observed "nanoparticles" were indeed Kr nanobubbles. Activity measurements showed that the activity would be inhibited by the existence of Kr nanobubbles and could be recovered by degassing. More importantly, the inhibition extent of pepsin activity was dominated by the number of nanobubbles in solution. More nanobubbles would cause more inhibition of pepsin activity. Furthermore, the structures of pepsin could be changed by nanobubbles, which might be the reason for inhabitation of activity. Our results would provide a further understanding of the mechanisms of the biological effects of inert gases.

Mechanical Properties of Sub-Microbubbles with a Nanoparticle-Decorated Polymer Shell.

Nanoparticle-decorated polymer-coated sub-microbubbles (NP-P-coated SMBs), as proved, have shown promising application prospects in ultrasound imaging, magnetic resonance imaging, drug delivery, and so forth. However, the quantitative evaluation of the stability and mechanical properties of single NP-P-coated SMB is absent. Here, we first reported the stiffness and Young's modulus of single NP-P-coated SMB obtained by the PeakForce mode of atomic force microscopy. Such NP-P-coated SMBs could maintain perfect spherical shapes and have a thinner shell thickness (about 10 nm), as determined by characterization using a transmission electron microscope. Young's modulus of NP-P-coated SMBs is about 4.6 ± 1.2 GPa, and their stiffness is about 15.0 ± 3.1 N/m. Both modulus and stiffness are obtained from the linear region in the force-deformation curve and are nearly independent of their sizes. These results should be very useful to evaluate their stability, which plays a key role in maintaining the shell drug loading and acoustic capabilities.