Magneto-Responsive Textiles for Non-Invasive Heating.

Magneto-responsive textiles have emerged lately as an important carrier in various fields, including biomedical engineering. To date, most research has been performed on single magnetic fibers and focused mainly on the physical characterization of magnetic textiles. Herein, from simple woven and non-woven textiles we engineered materials with magnetic properties that can become potential candidates for a smart magnetic platform for heating treatments. Experiments were performed on tissue-mimicking materials to test the textiles' heating efficiency in the site of interest. When the heat was induced with magneto-responsive textiles, the temperature increase in tissue-mimicking phantoms depended on several factors, such as the type of basic textile material, the concentration of magnetic nanoparticles deposited on the textile's surface, and the number of layers covering the phantom. The values of temperature elevation, achieved with the use of magnetic textiles, are sufficient for potential application in magnetic hyperthermia therapies and as heating patches or bandages.

Biocompatible Hydrogel-Based Liquid Marbles with Magnetosomes.

Liquid marbles are widely known for their potential biomedical applications, especially due to their versatility and ease of preparation. In the present work, we prepared liquid marbles with various cores composed of water, agar-based hydrogels, magnetic fluids, or non-aqueous substances. As a coating material, we used biocompatible particles of plant origin, such as turmeric grains and Lycopodium pollen. Additionally, we provided marbles with magnetic properties by incorporating either magnetosomes or iron oxide nanoparticles as a powder or by injecting another magnetic fluid. Structures obtained in this way were stable and susceptible to manipulation by an external magnetic field. The properties of the magnetic components of our marbles were verified using electron paramagnetic resonance (EPR) spectroscopy and vibrating sample magnetometry (VSM). Our approach to encapsulation of active substances such as antibiotics within a protective hydrogel core opens up new perspectives for the delivery of hydrophobic payloads to the inherently hydrophilic biological environment. Additionally, hydrogel marbles enriched with magnetic materials showed promise as biocompatible heating agents under alternating magnetic fields. A significant innovation of our research was also the fabrication of composite structures in which the gel-like core was surrounded without mixing by a magnetic fluid covered on the outside by the particle shell. Our liquid marbles, especially those with a hydrogel core and magnetic content, due to the ease of preparation and favorable properties, have great potential for biomedical use. The fact that we were able to simultaneously produce, functionalize (by filling with predefined cargo), and manipulate (by means of an external magnetic field) several marbles also seems to be important from an application point of view.

Rhodamine-Tagged Polymethacrylate Dyes as Alternative Tools for Analysis of Plant Cells.

A rhodamine B (RhB)-based initiator for atom transfer radical polymerization (ATRP) was synthesized and applied for preparation of poly(2-trimethylammoniumethyl methacrylate) (PChMA), poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(2-trimethylsilyloxyethyl methacrylate) (PHEMATMS). Polymer fluorescence was confirmed by determination of quantum yield by comparative method with piroxicam as the standard exhibiting dependency of emission intensity on the polymer chain hydrophilicity and the kind of solvent. The RhB functionalized polymers were used for biological tests in plant materials except for RhB-PHEMATMS because of weak fluorescence. These two polymers slightly differed in cellular localization. RhB-PChMA was mostly observed in cell walls of root tissues and cotyledon epidermis. It was also observed in cytoplasm and cell organelles of root cap cells and rhizodermis, in contrast with cytoplasm of cotyledon epidermis. RhB-PHEMA was also present in apoplast. A strong signal in protoxylem cell walls and a weak signal in cell walls of rhizodermis and cortex were visible. Moreover, it was also present in cell walls of cotyledon epidermis. However, RhB-PHEMA was mostly observed in cytoplasm and cell organelles of all root tissues and epidermis of cotyledons. Both RhB-polymers did not cause cell death which means that they can be used in living plant material.

Ultrasound Study of Magnetic and Non-Magnetic Nanoparticle Agglomeration in High Viscous Media.

Ultrasound attenuation spectroscopy has found wide application in the study of colloidal dispersions such as emulsions or suspensions. The main advantage of this technique is that it can be applied to relatively high concentration systems without sample preparation. In particular, the use of Epstein-Carhart-Allegra-Hawley's (ECAH) ultrasound scattering theory, along with experimental data of ultrasound velocity or attenuation, provide the method of estimation for the particle or droplet size from nanometers to millimeters. In this study, suspensions of magnetite and silica nanoparticles in high viscous media (i.e., castor oil) were characterized by ultrasound spectroscopy. Both theoretical and experimental results showed a significant difference in ultrasound attenuation coefficients between the suspensions of magnetite and silica nanoparticles. The fitting of theoretical model to experimental ultrasound spectra was used to determine the real size of objects suspended in a high viscous medium that differed from the size distributions provided by electron microscopy imaging. The ultrasound spectroscopy technique demonstrated a greater tendency of magnetic particles toward agglomeration when compared with silica particles whose sizes were obtained from the combination of experimental and theoretical ultrasonic data and were more consistent with the electron microscopy images.

Magnetic mediators for ultrasound theranostics.

The theranostics paradigm is based on the concept of combining therapeutic and diagnostic modalities into one platform to improve the effectiveness of treatment. Combinations of multiple modalities provide numerous medical advantages and are enabled by nano- and micron-sized mediators. Here we review recent advancements in the field of ultrasound theranostics and the use of magnetic materials as mediators. Several subdisciplines are described in detail, including controlled drug delivery and release, ultrasound hyperthermia, magneto-ultrasonic heating, sonodynamic therapy, magnetoacoustic imaging, ultrasonic wave generation by magnetic fields, and ultrasound tomography. The continuous progress and improvement in theranostic materials, methods, and physical computing models have created undeniable possibilities for the development of new approaches. We discuss the prospects of ultrasound theranostics and possible expansions of other studies to the theranostic context.

Correlation between Locally Ordered (Hydrogen-Bonded) Nanodomains and Puzzling Dynamics of Polymethysiloxane Derivative.

We examined the behavior of poly(mercaptopropyl)methylsiloxane (PMMS), characterized by a polymer chain backbone of alternate silicon and oxygen atoms substituted by a polar pendant group able to form hydrogen bonds (-SH moiety), by means of infrared (FTIR) and dielectric (BDS) spectroscopy, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and rheology. We observed that the examined PMMS forms relatively efficient hydrogen bonds leading to the association of chains in the form of ordered lamellar-like hydrogen-bonded nanodomains. Moreover, the recorded mechanical and dielectric spectra revealed the presence of two relaxation processes. A direct comparison of collected data and relaxation times extracted from two experimental techniques, BDS and rheology, indicates that they monitor different types of the mobility of PMMS macromolecules. Our mechanical measurements revealed the presence of Rouse modes connected to the chain dynamics (slow process) and segmental relaxation (a faster process), whereas in the dielectric loss spectra we observed two relaxation processes related most likely to either the association-dissociation phenomenon within lamellar-like self-assemblies or the sub-Rouse mode (α'-slower process) and segmental (α-faster process) dynamics. Data presented herein allow a better understanding of the peculiar dynamical properties of polysiloxanes and associating polymers having strongly polar pendant moieties.

The Effect of Particle Shell on Cooling Rates in Oil-in-Oil Magnetic Pickering Emulsions.

Pickering emulsions (particle-stabilized emulsions) are usually considered because of their unique properties compared to surfactant-stabilized emulsions including better stability against emulsion aging. However, the interesting feature of particle-stabilized emulsions could be revealed during their magnetic heating. When magnetic particles constitute a shell around droplets and the sample is placed in an alternating magnetic field, a temperature increase appears due to energy dissipation from magnetic relaxation and hysteresis within magnetic particles. We hypothesize that the solidity of the magnetic particle shell around droplets can influence the process of heat transfer from inside the droplet to the surrounding medium. In this way, particle-stabilized emulsions can be considered as materials with changeable heat transfer. We investigated macroscopically heating and cooling of oil-in-oil magnetic Pickering emulsions with merely packed particle layers and these with a stable particle shell. The change in stability of the shell was obtained here by using the coalescence of droplets under the electric field. The results from calorimetric measurements show that the presence of a stable particle shell caused a slower temperature decrease in samples, especially for lower intensities of the magnetic field. The retarded heat transfer from magnetic Pickering droplets can be utilized in further potential applications where delayed heat transfer is desirable.

The potential of magnetic heating for fabricating Pickering-emulsion-based capsules.

Pickering emulsions (particle-stabilized emulsions) have been widely explored due to their potential applications, one of which is using them as precursors for the formation of colloidal capsules that could be utilized in, among others, the pharmacy and food industries. Here, we present a novel approach to fabricating such colloidal capsules by using heating in the alternating magnetic field. When exposed to the alternating magnetic field, magnetic particles, owing to the hysteresis and/or relaxation losses, become sources of nano- and micro-heating that can significantly increase the temperature of the colloidal system. This temperature rise was evaluated in oil-in-oil Pickering emulsions stabilized by both magnetite and polystyrene particles. When a sample reached high enough temperature, particle fusion caused by glass transition of polystyrene was observed on surfaces of colloidal droplets. Oil droplets covered with shells of fused polystyrene particles were proved to be less susceptible to external stress, which can be evidence of the successful formation of capsules from Pickering emulsion droplets as templates.

Choline supported poly(ionic liquid) graft copolymers as novel delivery systems of anionic pharmaceuticals for anti-inflammatory and anti-coagulant therapy.

New type of carriers based on grafted poly(ionic liquid)s was designed for delivery of ionically attached salicylates (Sal). Choline derived ionic liquid monomeric units were successfully introduced with various content in the side chains by the controlled radical polymerization. Properly high amounts of ionic pharmaceutics in the polymer systems were achieved by the well-fitted length and grafting degree of the side chains. In aqueous solution the graft copolymers were self-assembled into the spherical superstructures with sizes up to 73 nm. Delivery studies showed "burst" release within 4 h, after that it was slower yielding ~70% of released drug within 80 h. Proposed nanocarriers supported low toxicity against human cells (NHDF and BEAS-2B), anti-inflammation activity evaluated with the use of pro-inflammatory interleukins (IL-6 and IL-8) and antibacterial activities towards E. coli. Adjustment of ionic drug content by structural parameters of graft copolymers, including grafting degree and graft length, are advantageous to tailor nanocarriers with self-assembly properties in aqueous media. Effective release process by ionic exchange and biological activity with low toxicity are promising for further development of this type of drug delivery (DDS).

Ionic Polymethacrylate Based Delivery Systems: Effect of Carrier Topology and Drug Loading.

The presented drug delivery polymeric systems (DDS), i.e., conjugates and self-assemblies, based on grafted and star-shaped polymethacrylates have been studied for the last few years in our group. This minireview is focused on the relationship of polymer structure to drug conjugation/entrapment efficiency and release capability. Both graft and linear polymers containing trimethylammonium groups showed the ability to release the pharmaceutical anions by ionic exchange, but in aqueous solution they were also self-assembled into nanoparticles with encapsulated nonionic drugs. Star-shaped polymers functionalized with ionizable amine/carboxylic groups were investigated for drug conjugation via ketimine/amide linkers. However, only the conjugates of polybases were water-soluble, giving opportunity for release studies, whereas the self-assembling polyacidic stars were encapsulated with the model drugs. Depending on the type of drug loading in the polymer matrix, their release rates were ordered as follows: Physical ≥ ionic > covalent. The studies indicated that the well-defined ionic polymethacrylates, including poly(ionic liquid)s, are advantageous for designing macromolecular carriers due to the variety of structural parameters, which are efficient for tuning of drug loading and release behavior in respect to the specific drug interactions.

The Effect of Tissue-Mimicking Phantom Compressibility on Magnetic Hyperthermia.

During hyperthermia, magnetite nanoparticles placed in an AC magnetic field become a source of heat. It has been shown that in fluid suspensions, magnetic particles move freely and generate heat easily. However, in tissues of different mechanical properties, nanoparticle movement is limited and leads to a small temperature rise in tissue. Therefore, it is crucial to conduct magnetic hyperthermia experiments in similar conditions to the human body. The effect of tissue-mimicking phantom compressibility on the effectiveness of magnetic hyperthermia was investigated on agar phantoms. Single and cluster nanoparticles were synthesized and used as magnetic materials. The prepared magnetic materials were characterized by transmission electron microscopy (TEM), and zeta potential measurements. Results show that tissue-mimicking phantom compressibility decreases with the concentration of agar. Moreover, the lower the compressibility, the lower the thermal effect of magnetic hyperthermia. Specific absorption rate (SAR) values also proved our assumption that tissue-mimicking phantom compressibility affects magnetic losses in the alternating magnetic field (AMF).

Efficient metal-free strategies for polymerization of a sterically hindered ionic monomer through the application of hard confinement and high pressure.

In this paper, we have studied the effect of both hard confinement (nanoporous membranes treated as nanoreactors) and high pressure (compression of system) on the progress of free-radical (FRP) and reversible addition-fragmentation chain transfer (RAFT) polymerizations of selected hardly polymerizable, sterically hindered imidazolium-based ionic monomer 1-octyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide ([OVIM][NTf2]). These two innovative approaches, affecting (in a different way) the free volume of the polymerizing system, allows the reduction of the number of toxic substrates/catalysts, satisfying the requirement of green chemistry. It was found that at both conditions (high compression and confinement) the polymerizability of monomer, as well as the control over the reaction and the properties of the produced polyelectrolytes, have increased significantly. However, it should be added that there were noticeable differences between FRP carried out under confinement and at high pressures. Interestingly, by appropriate variation in thermodynamic conditions, it was possible to synthesize polymers of moderate molecular weight (M n ∼ 58 kg mol-1) and relatively low dispersity (D ∼ 1.7); while for the reaction performed within AAO pores of varying diameter (d = 35 nm and d = 150 nm), macromolecules of higher M n but slightly broader dispersity indices (D ∼ 2.2-2.7) were recovered. On the other hand, RAFT polymerization carried out under confinement and at elevated pressures yielded polymers with well-defined properties. Noteworthy is also the fact that nanopolymerization leads to polymers of comparable M n to those obtained at high-pressure studies but at significantly shorter reaction time (t ∼ 2 hours). We believe that the presented data clearly demonstrated that both examined approaches (the compression and application of alumina templates, treated as nanoreactors) could be successfully used as additional driving forces to polymerize sterically hindered monomers and produce well-defined polymers in relatively short times. At the same time, it should be mentioned that both proposed polymerization methods enabled us to omit the addition of metal-based initiators/catalysts, which seem to be a crucial step towards further development of the alternative green synthesis of polyelectrolytes in the future.