Alkane-based eutectic phase change materials doped with carbon nanomaterials.

Cold thermal energy storage is an issue of increasing importance on a global scale particularly in the format of passive thermal protection. This study presents three eutectic Phase Change Materials (ePCMs) composed of n-alkanes, which provide passive temperature control (their operation is automatically induced by exceeding the limit temperature without the need for a control system) around 4 °C (277.2 ± 2 K) and are chemically neutral. The solid-liquid equilibrium (SLE) in the following binary systems was investigated: {n-tetradecane + n-heptadecane}, {n-tetradecane + n-nonadecane}, {n-tetradecane + n-heneicosane}, allowing the determination of two ePCMs with enthalpies close to 220 J g-1 and one significantly lower (155.5 J g-1). Moreover, two solid-liquid-liquid equilibrium (SLLE) phase diagrams were determined for systems: {n-tetradecane + 1,6-hexanediol} and {n-tetradecane + 1,12-dodecanediol}. In addition, the work provides a systematic analysis of the problem of designing ePCMs with specific properties and the aspects that need to be considered. The possibility of predicting the parameters of eutectic mixtures using the UNIFAC (Do) equation and the equation of ideal solubility was verified. A method for predicting the enthalpy of melting of eutectic was also proposed and confronted with the results of DSC analysis. Thermodynamic studies have been supplemented with measurements and correlation of experimental data of ePCMs density and dynamic viscosity as a function of temperature. The final issue is the improvement of the thermal conductivity of paraffins by the addition of nanomaterials such as Single Wall Carbon Nanotubes (SWCNTs), Expandable Graphite (GIC) or Expanded Graphite (EG). The possibility of forming a long-lasting composite material composed of ePCMs and 1 wt% of SWCNTs with a thermal conductivity significantly higher compared to pure ePCMs has been proven via stability testing under operating conditions.

Speed of Sound and Ultrasound Absorption in Ionic Liquids.

A complete review of the literature data on the speed of sound and ultrasound absorption in pure ionic liquids (ILs) is presented. Apart of the analysis of data published to date, the significance of the speed of sound in ILs is regarded. An analysis of experimental methods described in the literature to determine the speed of sound in ILs as a function of temperature and pressure is reported, and the relevance of ultrasound absorption in acoustic investigations is discussed. Careful attention was paid to highlight possible artifacts, and side phenomena related to the absorption and relaxation present in such measurements. Then, an overview of existing data is depicted to describe the temperature and pressure dependences on the speed of sound in ILs, as well as the impact of impurities in ILs on this property. A relation between ions structure and speeds of sound is presented by highlighting existing correlation and evaluative methods described in the literature. Importantly, a critical analysis of speeds of sound in ILs vs those in classical molecular solvents is presented to compare these two classes of compounds. The last part presents the importance of acoustic investigations for chemical engineering design and possible industrial applications of ILs.

Supramolecular structure fluctuations of an imidazolium-based protic ionic liquid.

At 20, 25, 30, and 40 °C, the ultrasonic absorption spectra of the protic ionic liquid 3-(butoxymethyl)-1H-imidazol-3-ium salicylate have been measured between 0.6 and 900 MHz. Below 250 MHz, the absorption coefficient decreases with temperature, potentially indicating a major effect of the viscosity and/or a relaxation time. Essentially the broad spectra can be favorably represented by two relaxation terms in addition to an asymptotic high-frequency contribution. One term reflects an asymmetric relaxation time distribution. It is described by a model of noncritical fluctuations in the structure and thermodynamic parameters of the liquid in order to yield the fluctuation correlation length and the mutual diffusion coefficient. Applying the Stokes-Einstein-Kawasaki-Ferrell relation, these quantities can be used to show that the effective shear viscosity controlling the fluctuations is substantially smaller than the steady-state shear viscosity. This result is consistent with dispersion in the shear viscosity as revealed by viscosity measurements at 25, 55, and 81 MHz. The other term can be well described by a Debye-type relaxation function. It has been tentatively assigned to a structural isomerization of the butoxymethyl chain of the imidazole molecule. However, it cannot be completely excluded that this term reflects, at least in parts, a Brønstedt acid-base equilibrium or a specific association process.

Isolation of hydrocarbon-degrading and biosurfactant-producing bacteria and assessment their plant growth-promoting traits.

Forty-two hydrocarbon-degrading bacterial strains were isolated from the soil heavily contaminated with petroleum hydrocarbons. Forty-one strains were identified based on their whole-cell fatty acid profiles using the MIDI-MIS method. Thirty-three of them belong to species Rhodococcus erythropolis, while the others to the genera Rahnella (4), Serratia (3) and Proteus (1). Isolates were screened for their ability to produce biosurfactants/bioemulsifiers. For all of them the activity of several mechanisms characteristic for plant growth-promoting bacteria was also determined. In order to investigate surface active and emulsifying abilities of isolates following methods: oil-spreading, blood agar, methylene blue agar and determination of emulsification index, were used. Among studied bacteria 12 strains (CD 112, CD 126, CD 131, CD 132, CD 135, CD 147, CD 154, CD 155, CD 158, CD 161, CD 166 and CD 167) have been chosen as promising candidates for the production of biosurfactants and/or bioemulsifiers. Among them 2 strains (R. erythropolis CD 126 and Rahnella aquatilis CD 132) had the highest potential to be used in the bioaugmentation of PH-contaminated soil. Moreover, 15 of tested strains (CD 105, CD 106, CD 108, CD 111, CD 116, CD 120, CD 124, CD 125, CD 130, CD 132, CD 134, CD 154, CD 156, CD 161 and CD 170) showed the activity of four mechanisms (ACC deaminase activity, IAA and siderophore production, phosphate solubilization) considered to be characteristic for plant growth-promoting bacteria. Two of them (R. erythropolis CD 106 and R. erythropolis CD 111) showed the highest activity of above-mentioned mechanisms and thus are considered as promising agents in microbe assisted phytoremediation.

Structure and thermal properties of salicylate-based-protic ionic liquids as new heat storage media. COSMO-RS structure characterization and modeling of heat capacities.

During this research, we present a study on the thermal properties, such as the melting, cold crystallization, and glass transition temperatures as well as heat capacities from 293.15 K to 323.15 K of nine in-house synthesized protic ionic liquids based on the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate ([H-Im-C1OC(n)][Sal]) with n = 3-11. The 3D structures, surface charge distributions and COSMO volumes of all investigated ions are obtained by combining DFT calculations and the COSMO-RS methodology. The heat capacity data sets as a function of temperature of the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate are then predicted using the methodology originally proposed in the case of ionic liquids by Ge et al. 3-(Alkoxymethyl)-1H-imidazol-3-ium salicylate based ionic liquids present specific heat capacities higher in many cases than other ionic liquids that make them suitable as heat storage media and in heat transfer processes. It was found experimentally that the heat capacity increases linearly with increasing alkyl chain length of the alkoxymethyl group of 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate as was expected and predicted using the Ge et al. method with an overall relative absolute deviation close to 3.2% for temperatures up to 323.15 K.

Levulinic Acid.

THE TITLE COMPOUND (SYSTEMATIC NAME: 4-oxo-penta-noic acid), C5H8O3, is close to planar (r.m.s. deviation = 0.0762 Å). In the crystal, the mol-ecules inter-act via O-H⋯O hydrogen bonds in which the hy-droxy O atoms act as donors and the ketone O atoms in adjacent mol-ecules as acceptors, forming C(7) chains along [20-1].

Smoking cessation after coronary angiography and percutaneous coronary intervention.

INTRODUCTION: Smoking is a crucial modifiable risk factor for coronary artery disease. However, effective support in smoking cessation (SC) and data regarding factors related to SC are still inadequate. OBJECTIVES: We aimed to assess SC rates and factors related to effective SC in patients after coronary angiography (CA). PATIENTS AND METHODS: Patients who underwent CA between 2014 and 2018 at a single center in Poland were screened for active smoking. After at least 6 months after the procedure, the patients were contacted by telephone to obtain information about their current smoking status and history of smoking during the follow­up. RESULTS: A total of 3719 consecutive patients were screened. Of these, 921 (24.8%) declared active smoking. At least 6 months after CA, 241 patients were available for a follow­up interview. The mean (SD) age of the patients was 61.2 (9.3) years, 168 (69.7%) were men, and 115 (47.7%) had acute coronary syndrome. The mean (SD) duration of hospitalization was 6 (4.4) days, and 67 patients (27.8%) were scheduled for a second­stage procedure. A total of 80 patients (33.2%) declared SC at the 6­month follow­up. The multivariable logistic regression analysis indicated that duration of hospitalization equal to or greater than 4 days (odds ratio [OR], 3.62; 95% CI, 1.9-6.89), the Fagerström score equal to or lower than 4 points (OR, 1.96; 95% CI, 1.01-3.79), a scheduled second hospitalization (OR, 2.54; 95% CI, 1.32-4.86), and a smoking load greater than or equal to 51 pack­years (OR, 2.28; 95% CI, 1.16-4.47) increased the chance of SC. CONCLUSIONS: A substantial number of patients who underwent CA were current smokers, with low SC rates in the follow­up. A prolonged hospital stay, scheduled second hospitalization, low nicotine dependence but also a high load of pack­years increased the chances of SC, which underscores the need for intensive and repetitive in­hospital counseling in the whole population of smokers.

Anticancer potential and through study of the cytotoxicity mechanism of ionic liquids that are based on the trifluoromethanesulfonate and bis(trifluoromethylsulfonyl)imide anions.

Ionic liquids (ILs) are known for their unique physicochemical properties. However, despite the great number of published papers, still little attention has been paid to their biological activity. Anticancer potential and the molecular mechanisms underlying the toxicity of these compounds are especially interesting and still unexplored. In the current work, a broad analysis of the cytotoxicity towards colon and breast cancers as well as glioblastoma of the ILs with pyridinium, piperidinium, pyrrolidinium, and imidazolium cations and trifluoromethanesulfonate or bis(trifluoromethylsulfonyl)imide anions indicated previously as the most toxic for normal human dermal fibroblasts were presented. In the case of MCF-7 cells, the activity of 1-decyl-3-methylimidazolium trifluoromethanesulfonate was more than twice as high as cisplatin. It was found that the inhibition of the cell cycle of colon cancer and glioblastoma cells occurs in different phases. More importantly, the different types of cell death were detected for both selected ILs, namely 1-hexyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and 1-hexyl-3-methylimidazolium trifluoromethane-sulfonate, on colon cancer and glioblastoma, respectively, apoptosis and autophagy, confirmed at the gene and protein levels. Additionally, kinetic studies of the reactive oxygen species indicated that the tested ILs disturbed the cellular redox homeostasis.

Paintable Carbon Nanotube Coating-Based Textronics for Sustained Holter-Type Electrocardiography.

A growing population suffering from or at high risk of developing cardiovascular diseases can benefit from rapid, precise, and readily available diagnostics. Textronics is an interdisciplinary approach for designing and manufacturing high-performance flexible electronics integrated with textiles for various applications, with electrocardiography (ECG) being the most convenient and most frequently used diagnostic technique for textronic solutions. The key challenges that still exist for textronics include expedient manufacturing, adaptation to human subjects, sustained operational stability for Holter-type data acquisition, reproducibility, and compatibility with existing solutions. The present study demonstrates conveniently paintable ECG electroconductive coatings on T-shirts woven from polyester or 70% polyamide and 30% polyester. The up to 600-µm-thick coatings encompass working electrodes of low resistivity 60 Ω sq-1 sheathed in the insulated pathways-conjugable with a wireless, multichannel ECG recorder. Long (800 µm) multiwalled carbon nanotubes, with scalable reproducibility and purity (18 g per round of synthesis), constituted the electroactive components and were embedded into a commercially available screen-printing acrylic base. The resulting paint had a viscosity of 0.75 Pa·s at 56 s-1 and 25 °C and was conveniently applied using a paintbrush, making this technique accessible to manufacturers. The amplified and nondigitally processed ECG signals were recorded under dry-skin conditions using a certified ECG recorder. The system enabled the collection of ECG signals from two channels, allowing the acquisition of cardiac electrical activity on six ECG leads with quality at par with medical diagnostics. Importantly, the Holter-type ECG allowed ambulatory recording for >24 h under various activities (sitting, sleeping, walking, and running) in three male participants. The ECG signal was stable for >5 cycles of washing, a level of stability not reported yet previously. The developed ECG-textronic application possesses acceptable and reproducible characteristics, making this technology a suitable candidate for further testing in clinical trials.

High-Performance Ionanofluids from Subzipped Carbon Nanotube Networks.

Investments in the transfer and storage of thermal energy along with renewable energy sources strengthen health and economic infrastructure. These factors intensify energy diversification and the more rapid post-COVID recovery of economies. Ionanofluids (INFs) composed of long multiwalled carbon nanotubes (MWCNTs) rich in sp2-hybridized atoms and ionic liquids (ILs) display excellent thermal conductivity enhancement with respect to the pure IL, high thermal stability, and attractive rheology. However, the influence of the morphology, physicochemistry of nanoparticles and the IL-nanostructure interactions on the mechanism of heat transfer and rheological properties of INFs remain unidentified. Here, we show that intertube nanolayer coalescence, supported by 1D geometry assembly, leads to the subzipping of MWCNT bundles and formation of thermal bridges toward 3D networks in the whole INF volume. We identified stable networks of straight and bent MWCNTs separated by a layer of ions at the junctions. We found that the interactions between the ultrasonication-induced breaking nanotubes and the cations were covalent in nature. Furthermore, we found that the ionic layer imposed by close MWCNT surfaces favored enrichment of the cis conformer of the bis(trifluoromethylsulfonyl)imide anion. Our results demonstrate how the molecular perfection of the MWCNT structure with its supramolecular arrangement affects the extraordinary thermal conductivity enhancement of INFs. Thus, we gave the realistic description of the interactions at the IL-CNT interface with its (super)structure and chemistry as well as the molecular structure of the continuous phase. We anticipate our results to be a starting point for more complex studies on the supramolecular zipping mechanism. For example, ionically functionalized MWCNTs toward polyionic systems─of projected and controlled nanolayers─could enable the design of even more efficient heat-transfer fluids and miniaturization of flexible electronics.

Effect of ultrasonication time on microstructure, thermal conductivity, and viscosity of ionanofluids with originally ultra-long multi-walled carbon nanotubes.

The stability along with thermal and rheological characteristics of ionanofluids (INFs) profoundly depend on the protocol of preparation. Therefore, in this work, the effect of ultrasonication time on microstructure, thermal conductivity, and viscosity of INFs containing 0.2 wt% of originally ultra-long multi-walled carbon nanotubes (MWCNTs) and four different ILs, namely 1-propyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium thiocyanate, or 1-ethyl-3-methylimidazolium tricyanomethanide, was studied. The INFs were obtained by a two-step method using an ultrasonic probe. The ultrasonication process was performed for 1, 3, 10, or 30 min at a constant nominal power value of 200 W. The obtained results showed that for the shortest sonication time, the highest thermal conductivity enhancement of 12% was obtained. The extended sonication time from 1 to 30 min caused the cutting of MWCNTs and breaking the nanoparticle clusters, leading to a decrease in the average length of the nanotube bundles by approx. 70%. This resulted in a decline in thermal conductivity even by 7.2% and small deviations from the Newtonian behavior of INFs.

Enhancing the CO2 capturing ability in leaf via xenobiotic auxin uptake.

Plants are masterpieces of evolution that is based on carbon chemistry. In particular, plant leaves are biosynthetic factories able to convert CO2 into carbohydrates and oxygen. It is worth noting that mimicking the efficiency of a natural plant and natural leaf is still a challenge for contemporary chemistry. We can even better realize this when we notice that a plant and an industrial factory are equivalent in meaning. On the other hand, green technologies are under development in a quest for the artificial leaf. If we could modify the synthetic pathways in leaves, we could also design green chemistry schemes in natural leaves to produce useful chemicals or to digest wastes or toxins. Specifically, can we intensify the potential for capturing atmospheric CO2 in leaves? Auxins are plant hormones that control the growth and development of plants. Herein, we determined whether we could efficiently transport xenobiotic auxin into leaves and if so, whether this supply could enhance the metabolism and CO2 capturing ability. By exploring a series of dioxolanes as potential enhancers of auxin transport, we discovered for the first time that a small molecular compound, 2,2-dimethyl-1,3-dioxolane (DMD), enhances the xenobiotic auxin transport to leaves, which boosts the metabolism that is measured by H2O2 production as well as CO2 capturing ability in leaves.

Remarkable Thermal Conductivity Enhancement in Carbon-Based Ionanofluids: Effect of Nanoparticle Morphology.

Transfer of the excellent intrinsic properties of individual carbon nanoparticles into real-life applications of the corresponding heat transfer fluids remains challenging. This process requires identification and quantification of the nanoparticle-liquid interface. Here, for the first time, we have determined geometry and properties of this interface by applying transmission electron cryomicroscopy (cryo-TEM). We have systematically investigated how the particle morphology of carbon-based nanomaterials affected the thermal conductivity, specific isobaric heat capacity, thermal diffusivity, density, and viscosity of ionanofluids and/or bucky gels, using a wide range of fillers, especially single-walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWCNTs), both with extreme values of aspect ratio (length to diameter ratio) from 150 to 11 000. Accordingly, hybrid systems composed of various carbon nanomaterials and ionic liquid, namely 1-ethyl-3-methylimidazolium thiocyanate [EMIM][SCN], were prepared and characterized. Most of the analyzed nanodispersions exhibited long-term stability even without any surfactant. Our study revealed that the thermal conductivity could be remarkably improved to the maximum values of 43.9% and 67.8% for ionanofluid and bucky gel (at 1 wt % loadings of MWCNTs and SWCNTs), respectively, compared to the pristine ionic liquid. As a result, the model proposed by Murshed and co-workers has been improved for realistic description of the concentration-dependent thermal conductivity of such hybrid systems. The obtained results undoubtedly indicate the potential of ionanofluids and bucky gels for energy management.

Density Scaling Based Detection of Thermodynamic Regions of Complex Intermolecular Interactions Characterizing Supramolecular Structures.

In this paper, applying the density scaling idea to an associated liquid 4-methyl-2-pentanol used as an example, we identify different pressure-volume-temperature ranges within which molecular dynamics is dominated by either complex H-bonded networks most probably leading to supramolecular structures or non-specific intermolecular interactions like van der Waals forces. In this way, we show that the density scaling law for molecular dynamics near the glass transition provides a sensitive tool to detect thermodynamic regions characterized by intermolecular interactions of different type and complexity for a given material in the wide pressure-volume-temperature domain even if its typical form with constant scaling exponent is not obeyed. Moreover, we quantify the observed decoupling between dielectric and mechanical relaxations of the material in the density scaling regime. The suggested methods of analyses and their interpretations open new prospects for formulating models based on proper effective intermolecular potentials describing physicochemical phenomena near the glass transition.

High pressure thermodynamic and acoustic properties of decan-1-ol+heptane mixtures. A theoretical and experimental study.

This paper reports a theoretical study of decan-1-ol+heptane and ethanol+heptane systems and experimental data of decan-1-ol+heptane mixtures as a function of temperature and pressure over the whole composition range. The ability of the modifications introduced into the original ERAS model in determining thermodynamic excess properties of decan-1-ol+heptane and ethanol+heptane mixtures at high pressures is tested. This model was found to be sufficient for describing semiquantitatively excess volumes and excess enthalpies and qualitatively excess heat capacities under high pressure. The densities and speeds of sound in decan-1-ol+heptane mixtures were measured over the whole concentration range within the temperature interval from 293 to 318 K at atmospheric pressure and at pressures up to 101 MPa, respectively. The densities, heat capacities and appropriate excesses of these binaries were calculated for the same temperatures and pressures up to 100 MPa. In the calculations the acoustic method was applied. The effects of pressure and temperature on the excess volume, excess enthalpy, and the excess heat capacity of decan-1-ol+heptane mixtures are analyzed and compared with those of ethanol + heptane and dodecane+heptane mixtures. Properties of the alkan-1-ol+alkane mixtures are explained in terms of the self-association of the alkanols, free volume effect and the nonspecific interactions between the alcohol and heptane basing on the results obtained from the modified ERAS model.

Ultrasonic Relaxation Spectra for Pyrrolidinium Bis(trifluoromethylsulfonyl)imides: A Comparison with Imidazolium Bis(trifluoromethylsulfonyl)imides.

Ultrasound absorption spectra within the frequency range 10-300 MHz were determined for 1-propyl- and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imides at ambient pressure and at temperatures in the ranges 293.15-313.15 and 293.15-323.15 K, respectively. For both compounds, a single Debye model (relaxation times between 0.451 and 0.778 ns) thoroughly describes the observed ultrasound absorption spectra in the investigated ranges. The spectra resemble those observed for imidazolium-based ionic liquids with the same anion. The ultrasound relaxation is dependent on the alkyl chain length of pyrrolidinium ring. In comparison to adequate imidazolium-based bis(trifluoromethylsulfonyl)imides, the relaxation in pyrrolidinium-based bis(trifluoromethylsulfonyl)imides is stronger; the pyrrolidinium cation causes clearly greater absorption than the imidazolium cation. Also, estimated ultrasound velocity dispersion is stronger in the case of pyrrolidinium imides in comparison to imidazolium imides. In turn, comparison of the ultrasonic data and literature data for the dielectric spectra exemplified for the 1-butyl- side chain in the cation indicates strong coupling in the case of imidazolium ring and weak coupling in the case of pyrrolidinium ring. The effect of absorption on the speed of sound is also discussed.

Ultrasonic Relaxation Study of 1-Alkyl-3-methylimidazolium-Based Room-Temperature Ionic Liquids: Probing the Role of Alkyl Chain Length in the Cation.

Ultrasound absorption spectra of four 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides were determined as a function of the alkyl chain length on the cation from 1-propyl to 1-hexyl from 293.15 to 323.15 K at ambient pressure. Herein, the ultrasound absorption measurements were carried out using a standard pulse technique within a frequency range from 10 to 300 MHz. Additionally, the speed of sound, density, and viscosity have been measured. The presence of strong dissipative processes during the ultrasound wave propagation was found experimentally, i.e., relaxation processes in the megahertz range were observed for all compounds over the whole temperature range. The relaxation spectra (both relaxation amplitude and relaxation frequency) were shown to be dependent on the alkyl side chain length of the 1-alkyl-3-methylimidazolium ring. In most cases, a single-Debye model described the absorption spectra very well. However, a comparison of the determined spectra with the spectra of a few other imidazolium-based ionic liquids reported in the literature (in part recalculated in this work) shows that the complexity of the spectra increases rapidly with the elongation of the alkyl chain length on the cation. This complexity indicates that both the volume viscosity and the shear viscosity are involved in relaxation processes even in relatively low frequency ranges. As a consequence, the sound velocity dispersion is present at relatively low megahertz frequencies.

Compressibility and Dielectric Relaxation of Mixtures of Water with Monohydroxy Alcohols.

Isentropic compressibility data and principal dielectric relaxation times, mostly for normal alcohols and for mixtures of monohydroxy alcohols with water, are evaluated and compared to one another. It is found that the microdynamics of the liquids, as reflected by the dielectric relaxation times, can be generally explained in the light of a defect diffusion model. Within the framework of that model, the principal relaxation time is predominantly controlled by the local concentration of hydrogen bonding sites. The alkyl groups of the alcohols are shown to have a 2-fold influence by reducing the concentration of the H-bonding sites and by also contributing to the activation enthalpy of relaxation. The effect of alkyl groups on the compressibility is quite different. The compressibility of methanol exceeds that of water by a substantial amount. Within the series of normal alcohols, in correspondence with the behavior of normal alkanes, the liquids become less compressible with increasing alkyl chain length. Relative molal shifts Bκ and Bd of the compressibility and dielectric relaxation time, respectively, of dilute solutions of alcohols in water are consistent with the behavior of aqueous solutions of other organic solutes. The Bd values increase with hydrophobic character of the solute (ΔBd = 0.045 (mol/kg)(-1) for an additional methyl group per solute molecule or organic ion), whereas Bκ decreases (ΔBκ = -0.012 (mol/kg)(-1)). Reduced orientational mobility combined with decreased compressibility appears to be characteristic of hydration shells around hydrophobic solutes.

Molecular dynamics changes induced by solvent in 2-ethyl-1-hexanol.

Apart from other classes of materials, supramolecular structures may exist in H-bonded liquids due to the existence of hydrogen bonding. The dynamics of these structures remains one of the most exciting topics of interest of modern science because of its crucial meaning for the behavior of water and its participation in biological processes. A special group of these liquids form monohydroxy alcohols due to their similarity to water, their ability to vitrification, and the existence of the Debye relaxation process in dielectric loss spectra reflecting the dynamics of H-bond structures. Dynamics of these structures can be studied by changes of thermodynamic conditions, by immersion of the liquid into the constraint geometry, and by dilution in a nonassociated solvent. Herein we studied the behavior of relaxation dynamics of mixtures of 2-ethyl-1-hexanol with bromobutane using broadband dielectric spectroscopy. Analysis of the results exhibits the existence of crossover in temperature dependence of static permittivity of the Debye process at some particular temperature T(c). This temperature shifts to lower values with increasing concentration of bromobutane. Moreover, below some "critical" concentration of alcohol in the mixture the shape of the Debye process loses exponentiality and the temperature dependence of relaxation times starts to change. This change was illuminated based on the analysis of the steepness index. For the lowest concentration, the value of this parameter becomes the same as the value of the steepness index of faster relaxation, called process II, of pure alcohol at ambient pressure. The observed change in relaxation dynamics with lowering concentration of alcohol is astonishingly similar to the behavior observed in the same material at elevated pressure. A possible origin of these similarities is also discussed.