Diffusion-Limited Processes in Hydrogels with Chosen Applications from Drug Delivery to Electronic Components.

Diffusion is one of the key nature processes which plays an important role in respiration, digestion, and nutrient transport in cells. In this regard, the present article aims to review various diffusion approaches used to fabricate different functional materials based on hydrogels, unique examples of materials that control diffusion. They have found applications in fields such as drug encapsulation and delivery, nutrient delivery in agriculture, developing materials for regenerative medicine, and creating stimuli-responsive materials in soft robotics and microrobotics. In addition, mechanisms of release and drug diffusion kinetics as key tools for material design are discussed.

When Bubbles Are Not Spherical: Artificial Intelligence Analysis of Ultrasonic Cavitation Bubbles in Solutions of Varying Concentrations.

Ultrasonic irradiation of liquids, such as water-alcohol solutions, results in cavitation or the formation of small bubbles. Cavitation bubbles are generated in real solutions without the use of optical traps making our system as close to real conditions as possible. Under the action of the ultrasound, bubbles can grow, oscillate, and eventually collapse or decompose. We apply the mathematical method of separation of motions to interpret the acoustic effect on the bubbles. While in most situations, the spherical shape of a bubble is the most energetically profitable as it minimizes the surface energy, when the acoustic frequency is in resonance with the natural frequency of the bubble, shapes with the dihedral symmetry emerge. Some of these resonance shapes turn unstable, so the bubble decomposes. It turns out that bubbles in the solutions of different concentrations (with different surface energies and densities) attain different evolution paths. While it is difficult to obtain a deterministic description of how the solution concentration affects bubble dynamics, it is possible to separate images with different concentrations by applying the artificial neural network (ANN) algorithm. An ANN was trained to detect the concentration of alcohol in a water solution based on the bubble images. This indicates that artificial intelligence (AI) methods can complement deterministic analysis in nonequilibrium, near-unstable situations.

Separation of motions and vibrational separation of fractions for biocide brass.

The mathematical method of separation of motions represents the effect of fast high-frequency oscillations by an effective averaged force or potential. Ultrasound acoustic vibrations are an example of such rapid oscillations leading to cavitation in water due to the gas phase formation (bubbles). Ultrasound cavitation is used to treat the surface of brass microparticles submerged in water. The formation of bubbles and their collapse triggers the modification of surface roughness and chemical composition. Consequently, the suspension separates into various fractions related to demonstrating biocide properties. While the exact mechanism of this process is complex, it can be explained phenomenologically by using the Onsager reciprocal relations for coupling the copper ion diffusion with the gas phase separation in water as a result of the action of the effective average vibrational force.

Characterization of transient cavitation activity during sonochemical modification of magnesium particles.

Investigation of the cavitation activity during ultrasonic treatment of magnesium particles during nanostructuring has been performed. Cavitation activity is recorded in the continuous mode after switching the ultrasound on with the use of ICA-5DM cavitometer. It has been demonstrated that this characteristic of the cavitation zone may be varied in a wide range of constant output parameters of the generator. The speed and nature of the cavitation activity alteration depended on the concentration of Mg particles in the suspension and the properties of the medium in which the sonochemical treatment has been performed. Three stages of the cavitation area evolution can be distinguished: 1 - the initial increase in cavitation activity, 2 - reaching a maximum with a subsequent decrease, and 3 - reaching the plateau (or the repeated cycles with feedback loops of enlargement/reduction of the cavitation activity). The ultrasonically treated magnesium particles have been characterized by scanning electron microscopy, X-ray diffraction analysis and thermal analysis. Depending on the nature of the dispersed medium the particles can be characterized by the presence of magnesium hydroxide (brucite) and magnesium hydride. It is possible to reach the incorporation of magnesium hydride in the magnesium hydroxide/magnesium matrix by varying the conditions of ultrasonic treatment (duration of treatment, amplitude, dispersed medium etc.). The influence of the magnesium reactivity is also confirmed by the measurements of cavitation activity in organic dispersed media (ethanol, ethylene glycol) and their aqueous mixtures.

The influence of the morphology of titania and hydroxyapatite on the proliferation and osteogenic differentiation of human mesenchymal stem cells.

Herein, the proliferation and osteogenic potential of human mesenchymal stem cells (hMSCs) on the disordered and ordered porous morphology of the titania surface and titania surface modified by hydroxyapatite (HA) are compared for the first time. In 5 days, the MTT-assay showed that the ordered porous morphology of electrochemically fabricated titania nanotubes (TNT) and TNT with chemically deposited hydroxyapatite (TNT-HA) was favorable for stem cell proliferation. In 14 days, RT-qPCR demonstrated that the disordered porous morphology of the sonochemically produced titania mesoporous surface (TMS) and TMS modified by the chemical deposition of HA (TMS-HA) led to the differentiation of hMSCs into the osteogenic direction in the absence of osteogenic inductors. These results originate from the mechanism of mechanotransduction, which sheds a light on the interaction of mesenchymal stem cells with the porous interface through focal adhesion, regulating the expression of genes determining stem cell self-renewal and osteogenic differentiation. The strong focal adhesion of hMSCs adjusted by the disordered TMS and TMS-HA is enough to induce osteogenic differentiation with the delay of cellular self-renewal. The weak focal adhesion of hMSCs tuned by the ordered TNT and TNT-HA affects only cellular self-renewal. The present research makes a new contribution to nanomedicine and engineering of porous implant interfaces for the replacement of bone injuries.

Ultrasound-assisted fabrication of gluten-free dough for automatic producing dumplings.

Nowadays celiac disease is becoming more common. It is the autonomic genetic disease that is accompanied by damage to the intestines due to a reaction to eating some proteins. People who are suffering from celiac disease cannot eat food containing gluten, including dough made from gluten-containing seeds. But the gluten-free dough has commonly bad rheological properties and cannot be used for automatic molding the dumplings. In this article, we propose the ultrasonic-assisted technology to fabricate the gluten-free dough with improved rheological properties acceptable for automatic molding of the dumplings. Application of ultrasonic treatment at a frequency of 35 kHz during the dough preparation leads to the homogenization of the dough structure and changing the rheological properties of the dough. The ultrasound induces mechanical, physical and chemical/biochemical changes of the dough components through cavitation. The sonication causes a doubled dough volume increase followed by an additional mass yield of the dumplings equal 2-10% per kilogram of dough. Besides extra beneficial economic effect, our technology provides an additional sterilization effect of the fabricated dough.

Oscillating of physicochemical and biological properties of metal particles on their sonochemical treatment.

Different metal particles are increasingly used to target bacteria as an alternative to antibiotics. Despite numerous data about treating bacterial infections, the utilization of metal particles in antibacterial coatings for implantable devices and medicinal materials promoting wound healing. The antibacterial mechanisms of nanoscale and microscale particles are poorly understood, but the currently accepted mechanisms include oxidative stress induction, metal ion release, and non-oxidative mechanisms. Thus, investigation of the antibacterial mechanisms of nanostructured metal particles is very important for the development of more effective antimicrobial materials. However, it is very difficult to develop a proper model for revealing the antibacterial mechanisms due to difficulty to choose a method that allows obtaining materials of various properties under approximately the same conditions. In this paper, we propose a green and feasible technique to create critical conditions for modification of zinc particles at highly non-equilibrium states. We demonstrate that the sonication process can be useful for fabrication the materials with oscillating physical, chemical and antibacterial properties. We believe this method besides medical applications can be also used in natural science basic research as an experimental tool for modelling the physical and chemical processes. After the sonication, the zinc particles exhibit a different surface morphology and amount of leached Zn2+ ions compared to initial ones. It has been revealed that oscillations of the Zn2+ ions concentration lead to oscillation the antibacterial properties. Thus, the properties of the materials can be easily altered by adjusting the ultrasound energy dissipated via varying the sonication.

Photoelectrochemical photocurrent switching effect on a pristine anodized Ti/TiO2 system as a platform for chemical logic devices.

We report here the effect of the photoelectrochemical photocurrent switching (PEPS) observed on highly-ordered pristine anodized Ti/TiO2 for the first time. At negative potential bias, blue irradiation gives cathodic photocurrent, whereas anodic photocurrent was observed for ultraviolet irradiation. We believe this phenomenon is due to the electron pathway provided by Ti3+ defect states.

Light-controllable systems based on TiO2-ZIF-8 composites for targeted drug release: communicating with tumour cells.

Drug delivery systems based on the zeolitic imidazolate framework ZIF-8 have recently attracted viable research interest owing to their capability of decomposing in acidic media and thus performing targeted drug delivery. In vivo realization of this mechanism faces a challenge of relatively slow decomposition rates, even at elevated acidic conditions that are barely achievable in diseased tissues. In this study we propose to combine drug delivery nanocomposites with a semiconductor photocatalytic agent that would be capable of inducing a local pH gradient in response to external electromagnetic radiation. In order to test this principle, a model drug-releasing nanocomposite comprising photocatalytic titania nanotubes, ZIF-8, and the antitumor drug doxorubicin has been investigated. This system was demonstrated to release the drug in a quantity sufficient for effectively suppressing IMR-32 neuroblastoma cells that were used as a model diseased tissue. With locally applied UV irradiation, this result was achieved within 40 minutes, which is a relatively short time compared to the release duration in systems without photocatalyst, typically taking from several hours to several days.

Sonochemical nanostructuring of titanium for regulation of human mesenchymal stem cells behavior for implant development.

The influence of surface nanotopography of sonochemically generated mesoporous titania coatings (TMS) on the adhesion, proliferation, and osteogenic differentiation of human mesenchymal stem cells (hMSCs) have been investigated in vitro for the first time. It has been revealed that adhesion and proliferation of hMSCs is higher on disordered TMS surfaces compared to smooth polished titania surface after five days of incubation. Surprisingly, the sonochemically generated disordered nanotopography induces the differentiation of hMSCs into osteogenic direction in the absence of osteogenic medium in 14 days of incubation. Thus sonochemical nanostructuring of titanium based implants stimulates the regenerative process of bone tissue.

Nanostructured Layer-by-Layer Polyelectrolyte Containers to Switch Biofilm Fluorescence.

The development of stimuli-responsive nanocontainers is an issue of utmost importance for many applications such as targeted drug delivery, regulation of the cell and tissue behavior, making bacteria have useful functions and here converting light. The present work shows a new contribution to the design of polyelectrolyte (PE) containers based on surface modified mesoporous titania particles with deposited Ag nanoparticles to achieve chemical light upconversion via biofilms. The PE shell allows slowing down the kinetics of a release of loaded l-arabinose and switching the bacteria luminescence in a certain time. The hybrid TiO2/Ag/PE containers activated at 980 nm (IR) illumination demonstrate 10 times faster release of l-arabinose as opposed to non-activated containers. Fast IR-released l-arabinose switch bacteria fluorescence which we monitor at 510 nm. The approach described herein can be used in many applications where the target and delayed switching and light upconversion are required.

Towards sustainable diagnostics: replacing unstable H2O2 by photoactive TiO2 in testing systems for visible and tangible diagnostics for use by blind people.

Blind and color blind people cannot use colorimetric diagnostics; the problem is especially severe in rural areas where high temperatures and the absence of electricity challenge modern diagnostics. Here we propose to replace the unstable component of a diagnostic test, H2O2, with stable TiO2. Under UV irradiation, TiO2 forms reactive oxygen species that initiate polymerization of acrylamide causing liquid-to-gel transition in an analyte-dependent manner. We demonstrate that specific DNA sequences can be detected using this approach. This development may enable the detection of biological molecules by users with limited resources, for example in developing countries or for travelers in remote areas.

Ultrasound-driven titanium modification with formation of titania based nanofoam surfaces.

Titanium has been widely used as biomaterial for various medical applications because of its mechanical strength and inertness. This on the other hand makes it difficult to structure it. Nanostructuring can improve its performance for advanced applications such as implantation and lab-on-chip systems. In this study we show that a titania nanofoam on titanium can be formed under high intensity ultrasound (HIUS) treatment in alkaline solution. The physicochemical properties and morphology of the titania nanofoam are investigated in order to find optimal preparation conditions for producing surfaces with high wettability for cell culture studies and drug delivery applications. AFM and contact angle measurements reveal, that surface roughness and wettability of the surfaces depend nonmonotonously on ultrasound intensity and duration of treatment, indicating a competition between HIUS induced roughening and smoothening mechanisms. We finally demonstrate that superhydrophilic bio-and cytocompatible surfaces can be fabricated with short time ultrasonic treatment.

Light-Induced Water Splitting Causes High-Amplitude Oscillation of pH-Sensitive Layer-by-Layer Assemblies on TiO2.

We introduce a simple concept of a light induced pH change, followed by high amplitude manipulation of the mechanical properties of an adjacent polymer film. Irradiation of a titania surface is known to cause water splitting, and this can be used to reduce the environmental pH to pH 4. The mechanical modulus of an adjacent pH sensitive polymer film can thus be changed by more than an order of magnitude. The changes can be localized, maintained for hours and repeated without material destruction.

Switching the Stiffness of Polyelectrolyte Assembly by Light to Control Behavior of Supported Cells.

Polyelectrolyte block copolymer micelles assembled thin film is switched in response to local photocatalytic reactions on titanium dioxide, resulting in a layer of variable height, stiffness in response to visible light irradiation. Preosteoblasts migrate toward stiffer side of the substrates.

Photocatalytic Deposition of Hydroxyapatite onto a Titanium Dioxide Nanotubular Layer with Fine Tuning of Layer Nanoarchitecture.

A new effective method of photocatalytic deposition of hydroxyapatite (HA) onto semiconductor substrates is proposed. A highly ordered nanotubular TiO2 (TNT) layer formed on titanium via its anodization is chosen as the photoactive substrate. The method is based on photodecomposition of the phosphate anion precursor, triethylphosphate (TEP), on the semiconductor surface with the following reaction of formed phosphate anions with calcium cations presented in the solution. HA can be deposited only on irradiated areas, providing the possibility of photoresist-free HA patterning. It is shown that HA deposition can be controlled via pH, light intensity, and duration of the process. Energy-dispersive X-ray spectroscopy profile analysis and glow discharge optical emission spectroscopy of HA-modified TNT prove that HA deposits over the entire TNT depth. High biocompatibility of the surfaces is proven by protein adsorption and pre-osteoblast cell growth.