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In this paper, the molecular dynamics of a series of ester derivatives of ibuprofen (IBU), in which the hydrogen atom from the hydroxyl group was substituted by the methyl, isopropyl, hexyl, and benzyl moieties, has been investigated using Broadband dielectric (BD), Nuclear magnetic resonance (NMR), and Raman spectroscopies. We found that except for benzyl IBU (Ben-IBU), an additional process (slow mode, SM) appears in dielectric spectra in all examined compounds. It is worth noting that this relaxation process was observed for the first time in non-modified IBU (a Debye relaxation). According to suggestions by Affouard and Correia [J. Phys. Chem. B. 114, 11397 (2010)] as well as further studies by Adrjanowicz et al. [J. Chem. Phys. 139, 111103 (2013)] on Met-IBU, it was attributed to synperiplanar–antiperiplanar conformational changes within the molecule. Herein, we have shown that with an increasing molecular weight of the substituent, the relaxation times of the SM become longer and its activation energy significantly increases. Moreover, this new relaxation mode was found to be broader than a simple Debye relaxation in Iso-IBU and Hex-IBU. Additional complementary NMR studies indicated that either there is a significant slowdown of the rotation around the O=C—O—R moiety or this kind of movement is completely suppressed in the case of Ben-IBU. Therefore, the SM is not observed in the dielectric loss spectra of this compound. Finally, we carried out isothermal experiments on the samples which have a different thermal history. Interestingly, it turned out that the relaxation times of the structural processes are slightly shorter with respect to those obtained from temperature dependent measurements. This effect was the most prominent in the case of Hex-IBU, while for Ben-IBU, it was not observed at all. Additional time-dependent measurements revealed the ongoing equilibration manifested by the continuous shift of the structural process, until it finally reached its equilibrium position. Further Raman investigations showed that this effect may be related to the rotational/conformational equilibration of the long hexyl chains. Our results are the first ones demonstrating that the structural process is sensitive to the conformational equilibration occurring in the specific highly viscous systems. [ABSTRACT FROM AUTHOR]

This work thoroughly investigates chemical solvent-particles interactions during the formation of composite particles by pulsed laser melting of α-Fe2O3. Two solvents, with different dielectric constants, such as ethyl acetate (εr = 6) and ethanol (εr = 24.6), were examined in terms of their effect on the morphology, size, and phase composition of iron oxide composites. We calculated the laser fluence curves using the heating-melting-evaporation approach to identify the critical particle size that undergoes the phase changes first. We assessed the temperature of the particles irradiated with 390 mJ/pulse.cm2 in both solvents, including the heat dissipation between the particles and the liquid. The phase diagram of the Fe–O–C–H system was calculated to determine the temperature–pressure relationship of the system in equilibrium. We also employed an in situ GC–MS analysis to identify the volatile products during irradiation. Based on our experimental results, we concluded that the final diameter of the composites increases from 400 to 600 nm, along with the decreasing dielectric constant of the solvent, which is related to the different polarization of the organic liquid and the degree of particle agglomeration. The reduction of hematite in ethanol proceeded much faster, ending up with Fe/FeCx, while in ethyl acetate, it ended up with Fe3O4. Among all the particles, those with a diameter of 200 nm have the highest temperature and undergo the phase transition first. The temperature of a 200 nm composite particle in ethanol is slightly lower than in ethyl acetate, i.e. 1870 K as compared to 1902 K. Phase equilibrium diagrams proved the existence of Fe, FeO, and Fe3O4 as the preferred phases at about 1900 K. Our research provides a new insight into the process of submicron particle formation during pulsed laser irradiation and allows proposing a mechanism for the growth of particles of different size and phase composition depending on the solvent. [ABSTRACT FROM AUTHOR]

The comparison between NiFe2O4 (co-precipitation) and NiFe2O4@SiO2 (co-precipitation and microemulsion) ferrite nanoparticles in their as-received and annealed form is presented. The structural characterization revealed the gradual crystallization of as-received samples induced by thermal treatment. The existence of cubic inverse spinel ferrite structure with tetrahedral and octahedral iron occupancy is confirmed in all samples by the comprehensive study. The Fourier-transform infrared (FTIR) spectroscopy confirmed the typical spinel structure and other Fe-based states, whereas the presence of nonstoichiometric hematite is detected in the annealed NiFe2O4 sample. In the case of nanoparticles embedded into the silica matrix, the crystallization of initially amorphous silica is revealed in structural and microstructural characterization. As shown by FTIR, the applied thermal treatment reduces the water molecules and hydroxyl units compared to the initial material. The separation of the rhombohedral hematite α-Fe2O3 phase in the NiFe2O4 ferrite evidenced during the annealing process is demonstrated in structural and magnetic studies. The analysis of saturation magnetization pointed to the spin canting phenomenon in the surface layer with a slight change of the so-called dead layer upon heating. The room temperature superparamagnetic state (SPM) is modified in the NiFe2O4 sample across annealing as an effect of ferrite crystallization and grain growth as well as hematite separation. For as-received NiFe2O4, with temperature decrease, the blocking process preceded by the freezing process is observed. The silica shell is recognized as the sustaining cover for the SPM state. The electronic structure studies confirmed the complex nature of the Fe-based states. [ABSTRACT FROM AUTHOR]

In this paper, we present results of dielectric and shear-mechanical studies for amine (2-ethyl-1-hexylamine) and thiol (2-ethyl-1-hexanethiol) derivatives of the monohydroxy alcohol, 2-ethyl-1-hexanol. The amine and thiol can form hydrogen bonds weaker in strength than those of the alcohol. The combination of dielectric and shear-mechanical data enables us to reveal the presence of a relaxation mode slower than the a-relaxation. This mode is analogous to the Debye mode seen in monohydroxy alcohols and demonstrates that supramolecular structures are present for systems with lower hydrogen bonding strength. We report some key features accompanying the decrease in the strength of the hydrogen bonding interactions on the relaxation dynamics close to the glass-transition. This includes changes (i) in the amplitude of the Debye and a-relaxations and (ii) the separation between primary and secondary modes. [ABSTRACT FROM AUTHOR]

Fossil bone cells (osteocytes) are known mainly from the shape-casting vacuities they leave behind after cell decay; however, they may occasionally be preserved as three-dimensionally fossilized soft parts. Here we present brownish to rust-coloured microbodies, extracted from a Middle Triassic (ca. 245 Ma) bone of the reptile Nothosaurus, which are morphologically consistent with bone cells of present-day vertebrates. In situ imaging shows that these structures, which are reminiscent of bone cells, are harboured in lacunae framed by the bone matrix. Chemical characterization using energy-dispersive X-ray, Raman, and X-ray photoelectron spectroscopy revealed the presence of various phases of iron oxide mineralization. The predominant mineral phases are hematite and goethite; magnetite and maghemite appear to occur sporadically. It is not clear how these nanograined mineral phases were formed. Most likely mineralization proceeded very early and was triggered by local microenvironmental conditions favouring the precipitation of iron phases. The absence of a distinct signal indicating organic molecules suggests that the original bone cells underwent autolysis or other degradative processes before or during mineralization. [ABSTRACT FROM AUTHOR]

In this Communication, we present experimental studies that put new insight into the puzzling nature of the Debye relaxation found in the supercooled liquid state of racemic ibuprofen. The appearance of D-relaxation in the loss spectra of non-hydrogen bonding methylated derivate of ibuprofen has proven that Debye relaxation is related solely with conformational changes of the carboxyl group, termed in this paper as synperiplanar-antiperiplanar. Our studies indicate that the presence of hydrogen bonding capabilities is not here the necessary condition to observe Debye process, however, their occurrence might strongly influence α- and D-relaxations dynamics. Interestingly, the activation energy of the D-process in ibuprofen methyl ester on approaching Tg was found to be perfectly consistent with that reported for ibuprofen by Affouard and Correia [J. Phys. Chem. B 114, 11397-11402 (2010)] (∼39 kJ/mol). Finally, IR measurements suggest that the equilibrium between conformers concentration depends on time and temperature, which might explain why the appearance of D-relaxation in supercooled ibuprofen depends on thermal history of the sample. [ABSTRACT FROM AUTHOR]

Dielectric spectroscopy has been recently used to monitor mutarotation in undercooled D-fructose. This method can be viewed as a universal method to study mutarotation phenomenon in the whole family of monosaccharides. In this paper, we studied kinetics of mutaration of anhydrous D-ribose at ambient pressure as well as pressure effect on the rate constant of this process. Ribose mutarotation behavior is compared to the one obtained for D-fructose. In addition, we attempted to determine the “direction” of mutarotation in undercooled monosaccharides after quenching the melted sample. To this end, analysis of dipole moments of different tautomers of D-fructose and D-ribose have been performed. Conformational analysis of studied carbohydrates was done with use of density functional theory. Geometry optimizations as well as calculations of dipole moments were done on the 6-311++G(d,p)/B3LYP level. Finally, it turned out that data obtained from the mutarotation experiment might be helpful in understanding the origin of γ-process occurring in the whole family of carbohydrates. [ABSTRACT FROM AUTHOR]

Comprehensive FTIR studies on the progress of mutarotation in d-fructose mixed with maltitol have been carried out over a wide range of temperatures, both above and below the glass transition temperature Tg. In addition to the analysis of single bands, we have developed a completely new approach considering the full spectral range to follow the overall progress of the reaction. We have found that at the calorimetric Tg, there is a clear change in the temperature dependence of constant rates. The activation barrier for mutarotation changes from around 59 kJ mol−1 (the supercooled state) to around 249 kJ mol−1 (the glassy state). This dramatic variation in the activation barrier is consistent with the change in the mechanism of this specific chemical conversion, as theoretically considered by Wlodarczyk et al. [Phys. Chem. Chem. Phys., 2014, 16, 4694–4698]. Alternatively, it can also be connected to the change in the viscosity of the sample. Additionally, we investigated the relationship between constant rates (k) of mutarotation, structural relaxation times (τα), and dc conductivity (σdc) above and below the glass transition temperature. It was found that there was a linear correlation between all these quantities; they scale with various exponents changing at Tg. Our results also indicate that a single activation barrier might not be sufficient to describe the mutarotation process. [ABSTRACT FROM AUTHOR]