The experimental evidence on depressurization foaming of the amorphous D,L-polylactide, which is plasticized by subcritical (initial pressures below the critical value) or supercritical (initial pressures above the critical value) carbon dioxide at a temperature above the critical value, relates to two extreme cases: a slow quasi-isothermal foam expansion, and a rapid quasi-adiabatic expansion. Under certain conditions, the quasi-isothermal mode is characterized by the non-monotonic dependencies of the foam volume on the external pressure that are associated with the expansion-to-shrinkage transition. The quasi-adiabatic and quasi-isothermal expansions are characterized by a significant increase in the degree of foam expansion under conditions where the CO₂ initial pressure approaches the critical value. The observed features are interpreted in terms of the energy balance in the foam volume and the phenomenological model based on the equation of the foam state. The expansion-to-shrinkage condition is based on the relationship between the average bubble radius and the pressure derivative of the surface tension for the plasticized polylactide. The maximum expansion ratio of the rapidly foamed polylactide in the vicinity of the critical point is interpreted in terms of the maximum decrement of the specific internal energy of the foaming agent (carbon dioxide) in the course of depressurization.

Two approaches are proposed for the synthesis of bimetallic Au/Ag nanoparticles, using the pulsed laser ablation of a target consisting of gold and silver plates in a medium of supercritical carbon dioxide. The differences between the two approaches related to the field of “green chemistry” are in the use of different geometric configurations and different laser sources when carrying out the experiments. In the first configuration, the Ag and Au targets are placed side-by-side vertically on the side wall of a high-pressure reactor and the ablation of the target plates occurs alternately with a stationary “wide” horizontal beam with a laser pulse repetition rate of 50 Hz. In the second configuration, the targets are placed horizontally at the bottom of a reactor and the ablation of their parts is carried out by scanning from above with a vertical “narrow” laser beam with a pulse repetition rate of 60 kHz. The possibility of obtaining Ag/Au alloy nanoparticles is demonstrated using the first configuration, while the possibility of obtaining “core–shell” bimetallic Au/Ag nanoparticles with a gold core and a silver shell is demonstrated using the second configuration. A simple model is proposed to explain the obtained results.

A hydrophobic derivative of ciprofloxacin, hexanoylated ciprofloxacin (CPF-hex), has been used as a photoinitiator (PI) for two-photon polymerization (2PP) for the first time. We present, here, the synthesis of CPF-hex and its application for 2PP of methacrylate-terminated star-shaped poly (D,L-lactide), as well a systematic study on the optical, physicochemical and mechanical properties of the photocurable resin and prepared three-dimensional scaffolds. CPF-hex exhibited good solubility in the photocurable resin, high absorption at the two-photon wavelength and a low fluorescence quantum yield = 0.079. Structuring tests showed a relatively broad processing window and revealed the efficiency of CPF-hex as a 2PP PI. The prepared three-dimensional scaffolds showed good thermal stability; thermal decomposition was observed only at 314 °C. In addition, they demonstrated an increase in Young’s modulus after the UV post-curing (from 336 ± 79 MPa to 564 ± 183 MPa, which is close to those of a cancellous (trabecular) bone). Moreover, using CPF-hex as a 2PP PI did not compromise the scaffolds’ low cytotoxicity, thus they are suitable for potential application in bone tissue regeneration.

Luminescent aerogels based on sodium alginate cross-linked with ions of rare earth elements (Eu³⁺, Tb³⁺, Sm³⁺) and containing phenanthroline, thenoyltrifluoroacetone, dibenzoylmethane, and acetylacetone as ligands introduced into the matrix during the impregnation of alginate aerogels (AEG), were obtained for the first time in a supercritical carbon dioxide medium. The impregnation method used made it possible to introduce organically soluble sensitizing ligands into polysaccharide matrices over the entire thickness of the sample while maintaining the porous structure of the aerogel. It is shown that the pore size and their specific area are 150 nm and 270 m²/g, respectively. Moreover, metal ions with content of about 23 wt.%, acting as cross-linking agents, are uniformly distributed over the thickness of the sample. In addition, the effect of sensitizing ligands on the luminescence intensity of cross-linked aerogel matrices is considered. The interaction in the resulting metal/ligand systems is unique for each pair, which is confirmed by the detection of broad bands with individual positions in the luminescence excitation spectra of photoactive aerogels.

To obtain a supported heterogeneous catalyst, laser ablation of metallic palladium in supercritical carbon dioxide was performed in the presence of a carrier, microparticles of γ-alumina. The influence of the ablation process conditions—including supercritical fluid density, ablation, mixing time of the mixture, and laser wavelength—on the completeness and efficiency of the deposition of palladium particles on the surface of the carrier was studied. The obtained composites were investigated by scanning and transmission electron microscopy using energy dispersive spectroscopy. We found that palladium particles were nanosized and had a narrow size distribution (2–8 nm). The synthesized composites revealed high activity as catalysts in the liquid-phase hydrogenation of diphenylacetylene.

The article is devoted to one of the effective technologies for processing solid transparent materials—thermoplasmonic laser-induced backside wet etching (TP LIBWE). This technology involves aqueous solutions of metal precursors as a working medium. The dependence of the efficiency of sapphire TP LIBWE micromachining on the parameters of laser action is studied with the aqueous solution of the AgNO3 precursor as a working media. The near-optimal range of laser intensities from the point of the etching speed and quality is found. Utilizing the optoacoustic methods, high-speed video, and an optical integrating sphere, the initial stage of the TP LIBWE process is studied in detail. A four-stage model of the TP LIBWE beginning process is proposed, which explains the effects from the beginning of Ag nanoparticle formation in the region of laser exposure to the transition of the TP LIBWE process to a stationary laser microstructuring mode. It is shown that effective microstructuring occurs due to the appearance on the sapphire surface of a thin modified layer in the region of laser action. This thin modified layer is an amorphous Al2O3 with numerous plasmonic Ag nanoparticles inside it and at the sapphire/liquid interface.