Molecular Dynamics and Near-Tg Phenomena of Cyclic Thioethers.

This article presents the synthesis and molecular dynamics investigation of three novel cyclic thioethers: 2,3-(4'-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2-ene (compound 1), 2,3,14,15-bis(4',4″(5″)-methylbenzo)-1,4,7,10,13,16,19,22,25-octathiacyclotetracosa-2,14-diene (compound 2), and 2,3,8,9-bis(4',4″(5″)-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2,8-diene (compound 3). The compounds exhibit relatively high glass transition temperatures (Tg), which range between 254 and 283 K. This characteristic positions them within the so-far limited category of crown-like glass-formers. We demonstrate that cyclic thioethers may span both the realms of ordinary and sizeable molecular glass-formers, each featuring distinct physical properties. Furthermore, we show that the Tg follows a sublinear power law as a function of the molar mass within this class of compounds. We also reveal multiple dielectric relaxation processes of the novel cyclic thioethers. Above the Tg, their dielectric loss spectra are dominated by a structural relaxation, which originates from the cooperative reorientation of entire molecules and exhibits an excess wing on its high-frequency slope. This feature has been attributed to the Johari-Goldstein (JG) process. Each investigated compound exhibits also at least one intramolecular secondary non-JG relaxation stemming from conformational changes. Their activation energies range from approximately 19 kJ/mol to roughly 40 kJ/mol. Finally, we analyze the high-pressure molecular dynamics of compound 1, revealing a pressure-induced increase in its Tg with a dTg/dp coefficient equal to 197 ± 8 K/GPa.

Functionalization of the NiTi Shape Memory Alloy Surface through Innovative Hydroxyapatite/Ag-TiO2 Hybrid Coatings.

The objective of this research was to develop a surface modification for the NiTi shape memory alloy, thereby enabling its long-term application in implant medicine. This was achieved through the creation of innovative multifunctional hybrid layers comprising a nanometric molecular system of silver-rutile (Ag-TiO2), known for its antibacterial properties, in conjunction with bioactive submicro- and nanosized hydroxyapatite (HAp). The multifunctional, continuous, crack-free coatings were produced using the electrophoretic deposition method (EPD) at 20 V/1 min. Structural and morphological analyses through Raman spectrometry and scanning electron microscopy (SEM) provided comprehensive insights into the obtained coating. The silver within the layer existed in the form of nanometric silver carbonates (Ag2CO3) and metallic nanosilver. Based on DTA/TG results, dilatometric measurements, and high-temperature microscopy, the heat treatment temperature for the deposited layers was set at 800 °C for 2 h. The procedures applied resulted in the creation of a new generation of materials with a distinct structure compared with the initial nanopowders. The resulting composite layer, measuring 2 µm in thickness, comprised hydroxyapatite (HAp), apatite carbonate (CHAp), metallic silver, silver oxides, Ag@C, and rutile exhibiting a defective structure. This structural characteristic contributes significantly to its heightened activity, influencing both bioactivity and biocompatibility properties.

Revisiting Dynamic Processes and Relaxation Mechanisms in a Heterocyclic Glass-Former: Direct Observation of a Transient State.

Despite decades of studies, a clear understanding of near-Tg phenomena remains challenging for glass-forming systems. This review delves into the intricate molecular dynamics of the small, heterocyclic thioether, 6-methyl-2,3-dihydro-1,4-benzodithiine (MeBzS2), with a particular focus on its near-Tg cold crystallization and relaxation mechanisms. Investigating isothermal crystallization kinetics at various temperatures reveals a significant interplay between its molecular dynamics and recrystallization from a supercooled liquid. We also identify two independent interconversion paths between energetically privileged conformers, characterized by strained transition states. We demonstrate that these spatial transformations induce substantial alterations in the dipole moment orientation and magnitude. Our investigation also extends to the complex salt PdCl2(MeBzS2), where we observe the transient conformers directly, revealing a direct relationship between their abundance and the local or macroscopic electric field. The initially energetically privileged isomers in an undisturbed system become less favored in the presence of an external electric field or ions, resulting even in an unexpected inversion of states. Consequently, we confirm the intramolecular character of secondary relaxation in MeBzS2 and its mechanism related to conformational changes within the heterocyclic ring. The research is based on the combination of broadband dielectric spectroscopy, X-ray diffraction, and quantum density functional theory calculations.

Metallic nanoparticle actions on the outer layer structure and properties of Bacillus cereus and Staphylococcus epidermidis.

Although the antimicrobial activity of nanoparticles (NPs) penetrating inside the cell is widely recognised, the toxicity of large NPs (>10 nm) that cannot be translocated across bacterial membranes remains unclear. Therefore, this study was performed to elucidate the direct effects of Ag-NPs, Cu-NPs, ZnO-NPs and TiO2-NPs on relative membrane potential, permeability, hydrophobicity, structural changes within chemical compounds at the molecular level and the distribution of NPs on the surfaces of the bacteria Bacillus cereus and Staphylococcus epidermidis. Overall analysis of the results indicated the different impacts of individual NPs on the measured parameters in both strains depending on their type and concentration. B. cereus proved to be more resistant to the action of NPs than S. epidermidis. Generally, Cu-NPs showed the most substantial toxic effect on both strains; however, Ag-NPs exhibited negligible toxicity. All NPs had a strong affinity for cell surfaces and showed strain-dependent characteristic dispersion. ATR-FTIR analysis explained the distinctive interactions of NPs with bacterial functional groups, leading to macromolecular structural modifications. The results presented provide new and solid evidence for the current understanding of the interactions of metallic NPs with bacterial membranes.

Normal-to-Supercooled Liquid Transition in Molecular Glass-Formers: A Hidden Structural Transformation Fuelled by Conformational Interconversion.

Molecular dynamics and transport coefficients change significantly around the so-called Arrhenius crossover in glass-forming systems. In this article, we revisit the dynamic processes occurring in a glass-forming macrocyclic crown thiaether MeBzS2O above its glass transition, revealing two crossover temperatures: TB at 309 and TA at 333 K. We identify the second one as the Arrhenius crossover that is closely related to the normal-to-supercooled liquid transition in this compound. We show that the transformation occurring at this point goes far beyond molecular dynamics (where the temperature dependence of structural relaxation times changes its character from activation-like to super-Arrhenius), being reflected also in the internal structure and diffraction pattern. In this respect, we found a twofold local organization of the nearest-neighbor molecules via weak van der Waals forces, without the formation of any medium-range order or mesophases. The nearest surrounding of each molecule evolves structurally in time due to the ongoing fast conformational changes. We identify several conformers of MeBzS2O, demonstrating that its lowest-energy conformation is preferred mainly at lower temperatures, i.e., in the supercooled liquid state. Its increased prevalence modifies locally the short-range intermolecular order and promotes vitrification. Consequently, we indicate that the Arrhenius transition is fuelled rather by conformational changes in this glass-forming macrocyclic crown thiaether, which is a different scenario from the so-far existing concepts. Our studies combine broadband dielectric spectroscopy (BDS), X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, molecular dynamics (MD) simulations, and density functional theory (DFT) calculations.

Multifaceted Assessment of Porous Silica Nanocomposites: Unraveling Physical, Structural, and Biological Transformations Induced by Microwave Field Modification.

In response to the persistent challenge of heavy and noble metal environmental contamination, our research explores a new idea to capture silver through porous spherical silica nanostructures. The aim was realized using microwave radiation at varying power (P = 150 or 800 W) and exposure times (t = 60 or 150 s). It led to the development of a silica surface with enhanced metal-capture capacity. The microwave-assisted silica surface modification influences the notable changes within the carrier but also enforces the crystallization process of silver nanoparticles with different morphology, structure, and chemical composition. Microwave treatment can also stimulate the formation of core-shell bioactive Ag/Ag2CO3 heterojunctions. Due to the silver nanoparticles' sphericity and silver carbonate's presence, the modified nanocomposites exhibited heightened toxicity against common microorganisms, such as E. coli and S. epidermidis. Toxicological assessments, including minimum inhibitory concentration (MIC) and half-maximal inhibitory concentration (IC50) determinations, underscored the efficacy of the nanocomposites. This research represents a significant stride in addressing pollution challenges. It shows the potential of microwave-modified silicas in the fight against environmental contamination. Microwave engineering underscores a sophisticated approach to pollution remediation and emphasizes the pivotal role of nanotechnology in shaping sustainable solutions for environmental stewardship.