Gibbs Entropy Research Articles

Quintessence reconstruction through new Tsallis holographic dark energy model

In statistical theory, the Tsallis entropy is an extended form of the Boltzmann–Gibbs entropy. The dimensionless parameter [Formula: see text] is employed to state the quantitative difference from the standard scenario. The concepts of Tsallis entropy and the future event horizon are employed in formulating the present new Tsallis holographic dark energy (NTHDE) model. The model attempts to explain the properties of dark energy using the foundation of quantum gravity. The differential equation characterizing the evolution of the NTHDE density parameter is obtained. Expressions stating the dynamic behavior such as equation of state (EoS), deceleration and jerk parameters are obtained in terms of the NTHDE density parameter. For [Formula: see text], the quintessence nature of scalar field could completely characterize the NTHDE. A reconstruction of the scalar field’s dynamics and quintessence potential is attempted. We demonstrate that the diagnosis made by statefinder is adaptive enough to distinguish between quintessence and cosmological constant-based dark energy models. Additionally, observational data obtained from CC[Formula: see text] SNIa [Formula: see text] union 2.1 sources are used to evaluate the model’s effectiveness.

The isothermal Boltzmann–Gibbs entropy reduction affects survival of the fruit fly Drosophila melanogaster

To the best of our knowledge, this is the first experimental evidence of the effect of isothermal changes in entropy on a living organism. In greater detail, the effect of the reduction of the total Boltzmann–Gibbs entropy (S) of the aquatic environment on the survival rate and body mass of the fruit fly Drosophila melanogaster was investigated. The tests were carried out in standard thermodynamic states at room temperature of 296.15 K and ambient atmospheric pressure of 1 bar. Two variants of entropy reduction (ΔS) were tested for ΔS = 28.49 and 51.14 J K−1 mol−1 compared to the blind and control samples. The entropy level was experimentally changed, using the quantum system for isothermal entropy reduction. This system is based on quantum bound entanglement of phonons and the phenomenon of phonon resonance (interference of phonon modes) in condensed matter (Silicon dioxide (SiO2) and single crystals of Silicon (Si0), Aluminum (Al0) plates (“chips”), glass, and water). All studied organisms were of the same age (1 day). Mortality was observed daily until the natural death of the organisms. The investigations showed that changes in the Boltzmann–Gibbs entropy affected the survival and body mass of the fruit flies. On the one hand, the reduction in entropy under isothermal conditions in the aquatic environment for ΔS = 28.49 J K−1 mol−1 resulted in an extension of the lifespan and an increase in the body mass of female fruit flies. On the other hand, the almost twofold reduction in this entropy for ΔS = 51.14 J K−1 mol−1 shortened the lives of the males. Thus, the lifespan and body mass of flies turned out to be a specific reaction of metabolism related to changes in the entropy of the aquatic environment.

(Invited) Thermodynamic Properties of Rare-Earth Alloys Relevant for Efficient Rare-Earth Recovery in Molten Salts

Electrode materials of Fe, liquid Bi, and Sn were investigated to enhance the electrochemical recovery of rare-earth elements in molten salts (eutectic LiCl-KCl) at 500‒700 °C, leveraging their chemical interactions with rare-earth elements. Using Nd as a prototypical example, the degree of interactions was quantified based on electromotive force (emf) measurements of Nd alloys (Nd-Fe, Nd-Bi, and Nd-Sn). Temperature-dependent emf values of the Nd alloys were used to determine the thermodynamic properties such as the partial molar Gibbs energy (chemical potential), entropy, and enthalpy of Nd. In addition, the phase behavior of Nd alloys was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) to determine transition temperatures and microstructures of Nd alloy electrodes. Based on these fundamental properties of Nd alloys, the Nd-Sn alloy at mole fraction, x Nd = 0.10 was selected as the reference electrode and employed for electrochemical measurements in three-electrode cells in molten chloride salt (LiCl-KCl-NdCl3). The stability of Nd-Sn reference electrode was maintained less than 1 mV deviation between identical constructs during entire measurements, originating from the two phase (liquid + NdSn3) stability of the binary Nd-Sn alloy at 500‒700 °C. Finally, electrodeposition of Nd onto these interacting electrode materials was conducted to assess the recovery efficiency of Nd from molten chloride salt.

Black hole geometrothermodynamics and critical phenomena: A look from Tsallis entropy-based perspective

We analyze geometrothermodynamics of charged anti-de Sitter (AdS) black holes with a global monopole in the framework of Tsallis statistics. The latter arises from a non-additive generalization of Boltzmann–Gibbs entropy, which is still recovered as a particular sub-case. We examine the effects of Tsallis entropy on small-large black holes phase-transitions and critical exponents, comparing the results with the liquid–gas change of phase occurring in van der Waals fluids. We also discuss some physical constraints on Tsallis parameter and the impact on sparsity of BH radiation. Thermodynamic curvature behavior and the nature of microscopic interactions are then explored from a geometric perspective within Ruppeiner formalism on the S−P coordinate space. Similar considerations are extended to charged (2+1)-dimensional Banados–Teitelboim–Zanelli (BTZ) black holes by computing the entropy-pressure and entropy-volume corrected curvatures. Our analysis shows that Tsallis prescription has non-trivial implications on black hole geometrothermodynamics, emphasizing the role of non-additive entropy in the correspondence between black holes and van der Waals systems.

Effects of solutes on thermodynamic properties of (TMZrU)C (TM = Ta, Y) medium-entropy carbides: a first-principles study

High entropy carbide ceramics have garnered significant interest as a novel class of ultra-high temperature and superhard metallic materials. In the present work, a comparative investigation was conducted for the first time on the stability, mechanical, and thermodynamic properties of two medium entropy carbides (MECs), (TaZrU)C and (YZrU)C, using high-throughput first-principles calculations. Additionally, data from groups IV and V transition metal monocarbides were employed for comparison. The temperature-dependent thermodynamic properties, including bulk modulus (B), constant volume/constant pressure heat capacity (Cv/Cp), Gibbs free energy, volume, entropy, and thermal conductivity, were evaluated using the Debye-Gruneisen model. The results demonstrate that (TaZrU)C and (YZrU)C exhibit similar trends in their thermodynamic properties, with (YZrU)C displaying slightly superior performance as the temperature rises. This work provides valuable insights into the design of innovative high entropy fuels, holding significant implications for the advancement of MEC ceramic fuels in advanced nuclear power systems and nuclear thermal propulsion systems.

Anion exchange material based on polyvinylchloride and urea for the removal of chromium(vi) ions from aqueous solutions

AbstractIn this study, an anion exchange material obtained by chemically modifying granulated polyvinyl chloride with urea was examined. To study the structural morphology of the anion exchanger, polymer PVC‐based anion exchange resin second type (PPE‐2), we applied different characterization techniques including X‐ray diffraction (XRD), Fourier‐transform infrared (FTIR), scanning electron microscopy (SEM), and water vapor adsorption analysis. Moreover, PPE‐2 was used to remove hexavalent chromium ions from aqueous media. A pseudo‐second order model was used to describe sorption kinetics as well as the adsorption mechanism. The Langmuir isotherm and the pseudo‐second order kinetic model led to the most consistent results in describing ion removal from solution. In the case of hexavalent chromium ions, the maximum adsorption capacity was 148.4 mg g−1. The Dubinin‐Radushkevich (D‐R) free energy of adsorption (ED) was >16 kJ mol−1, which indicates chemical interaction between the ion exchange material and Cr(VI) ions. The Gibbs energy ΔG, enthalpy ΔH, and entropy ΔS changes during binding showed that the sorption process is spontaneous and involves chemical sorption through endothermic ion exchange reactions. In addition, the results demonstrate that the anion exchanger (PPE‐2) very efficiently removed hexavalent chromium ions from industrial wastewater.

First-Principles Study of Properties and Helium Behavior of Tungsten/Beryllium Interface Structure

A computational study of the thermodynamic and elastic properties of the tungsten-berylliuminterface structure and the behavior of a helium-vacancy pair near the tungsten/beryllium interface is carried out by first-principles calculations. Briefly, the following properties were calculated: (1) electronic properties of the tungsten/beryllium interface structure and (2) thermodynamic functions, Gibbs free energy, entropy, and enthalpy and anisotropies and isotropic (poly-crystalline) elastic moduli (bulk, torsion, Young’s moduli) of the tungsten/beryllium interface structure containing helium interstitial atoms or helium-vacancy pairs. The computational study was to provide a critical appraisal of the effect of helium interstitial atoms on the properties of the tungsten/beryllium interface structure. Calculated interface properties could be incorporated in an antiradiation damaging feature evaluation system to develop and test tungsten-based composites as plasma-facing materials.

Adsorption of Th(IV) ions from aqueous solutions by ZnO functionalized graphene oxide

Abstract Graphene oxide (GO) and zinc oxide (ZnO) were synthesized via the Tour’ and sol-gel methods, respectively. Adsorption potentials of Th(IV) ions were investigated with the functionalization of GO with ZnO nanoparticles (GO-ZnO) and compared with the GO. Studies concerning factors affecting the adsorption process, kinetics, adsorption isotherms, and thermodynamic properties were carried out. In this study, the optimum pH for the adsorption of Th(IV) ions is 3.0, and quickly reaching equilibrium is an indication of the high efficacy of the sorbent. A pseudo-second order adsorption model fits the kinetic data well. Experimental results were compared with Langmuir, Freundlich, and Dubinin–Radushkevich isotherm models. These results show that the Langmuir model fits the data well. Measured thermodynamic parameters, Gibbs free energy change (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) indicate that the adsorption of Th(IV) on GO−ZnO is spontaneous and endothermic in nature. According to the linear fit in the Langmuir isotherm model, the maximum adsorption capacity of GO and GO-ZnO at 298 K occurs at 109.89 mg/g and 243.90 mg/g, respectively. The results show that decoration with ZnO nanoparticles is a good method to improve the adsorption capacity of GO for Th(IV) removal.

Studies on synthesis, physicochemical properties, biological activities of two novel berberine-based salts with DL-mandelate and cinnamate anions

Berberine (BBR) is a natural quaternary isoquinoline alkaloid which is derived from the traditional Chinese medicine Coptis chinensis and exerts various pharmacological effects. However, low solubility in water has greatly limited its clinical application. This study prepared two novel berberine-based salts (berberine DL-mandelate ([BBR][MAN]) and berberine cinnamate ([BBR][CIN])) to improve the physicochemical properties and bioavailability of berberine. Many techniques, like 1H and 13C NMR, FTIR, ESI-MS, and thermogravimetric analyzes were utilized to characterize two salts. The solubility and octanol/water partition coefficient in water and simulated body fluids (simulated body, simulated intestinal and simulated gastric fluids) were determined. Self-aggregation behaviors of two salts in water have been investigated by conductometry at different temperatures. The obtained critical aggregation concentration (cac) was used for the calculation of various thermodynamic properties namely standard Gibbs energy change (ΔGm0), enthalpy change (ΔHm0), and entropy change (ΔSm0) in the aggregation progress. The volumetric properties including the infinite dilution apparent molar volumes (V2,φ0), infinite dilution apparent molar expansibility (Eφ0) and thermal expansion coefficient (β) for [BBR][MAN] were also determined to study its solvation behavior in aqueous solution. In addition, the antibacterial effect of two salts on three strains (Staphylococcus aureus, Bacillus subtilis and Candida albicans) was measured, and the minimum inhibitory concentration (MIC) and minimal bactericidal concentration (MBC) values were obtained. The results show that [BBR][MAN] has better antibacterial effect than [BBR][CIN]. The esterase-like activity assay demonstrated a decrease in enzyme activity of BSA in presence of two berberine-based salts. Cytotoxicity evaluation shows that two salts have potent in vitro anticancer activities against B16-F10 cancer cell lines.

Study on the Pyrolysis Kinetic Behaviors of Different Vegetable-Tanned Sheepskin Leathers

The pyrolysis behaviors of leathers tanned with hydrolyzable tannins (Tara and Chestnut extracts), and condensed tannins (Quebracho and Mimosa extract) were studied by Thermogravimetric (TG) analysis in the present work. The TG/derivative thermogravimetry (DTG) results showed that the thermal stability of Tara- and Chestnut-tanned samples is poorer than that of Quebracho- and Mimosa-tanned ones. In order to study pyrolysis kinetics, TG experiments at different heating rates were carried out. Two methods of Flynn-Wall-Ozawa (FWO) and Friedman (FR) were employed to calculate the pyrolysis activation energy (Eα) of the samples. It was found that the average Eα of the vegetable-tanned samples is located at the range of 191.7-206.1 kJ/mol. The thermodynamic parameters (pre-exponential factor, Gibbs free energy, enthalpy, and entropy) of the samples were subsequently calculated based on the average Eα by the FR method. The Gibbs free energies of the Chestnut-, Tara-, Quebracho-, and Mimosa-tanned leathers were 176.9 kJ/mol, 179.8 kJ/mol, 179.3 kJ/mol, and 178.2 kJ/mol, respectively. The difference between the average enthalpies and the Eα is less than 5 kJ/mol, which indicated that the pyrolysis process is conductive to the product formation. The mean entropy (ΔS) of the four vegetable-tanned samples is all positive, which suggested that the pyrolysis of the samples could easily take place. This work might provide theoretical guidance for the optimization of vegetable-tanned leather waste pyrolysis.

Canarium schweinfurthii stone-derived biochar: A promising adsorbent for crystal violet dye removal

In this study, the effectiveness of C. schweinfurthii biochar (CSSB) for the adsorption of aqueous crystal violet dye (CVD) was investigated. Batch mode experiments were conducted to examine the influence of different process variables on the dye adsorption capacity of the CSSB. The surface chemistry and morphology of the adsorbent were elucidated using the Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy/energy dispersion X-ray (SEM/EDX), respectively. At optimum adsorption conditions (50 mg/L adsorbate concentration, 303 K and 35 min), a maximum removal efficiency of 90.04% was achieved. The experimental equilibrium and kinetic data were best fit to the Freundlich isotherm and Elovich kinetics models, respectively. The thermodynamic evaluation showed average Gibbs free energy (ΔGo), entropy change (ΔSo) and enthalpy change, (ΔHo) values of −1647.18 KJ/mol, −58.69 KJ/mol K and −173.10 KJ/mol, respectively. These thermodynamic data demonstrated that CVD adsorption onto CSSB was favourable, spontaneous, and exothermic. Any doubts about the adsorbent's economic viability were allayed by its projected cost of 0.0003 USSD/g per gram of adsorbate. Thus, according to the experimental results, the CSSB is considered an economical, effective, and environmentally friendly adsorbent for aqueous CVD adsorption.

A Novel Method to Analyze the Relationship between Thermoelectric Coefficient and Energy Disorder of Any Density of States in an Organic Semiconductor.

In this work, a unified method is proposed for analyzing the relationship between the Seebeck coefficient and the energy disorder of organic semiconductors at any multi-parameter density of states (DOS) to study carrier transport in disordered thermoelectric organic semiconductors and the physical meaning of improved DOS parameters. By introducing the Gibbs entropy, a new multi-parameter DOS and traditional Gaussian DOS are used to verify this method, and the simulated result of this method can well fit the experiment data obtained on three organic devices. In particular, the impact of DOS parameters on the Gibbs entropy can also influence the impact of the energy disorder on the Seebeck coefficient.

Valorization of solid waste incinerator fly ash by geopolymer production for removal of anionic bromocresol green dye from water: Kinetics, isotherms and thermodynamics studies

In this study, solid waste incinerator fly ash (SWI-FA) based geopolymer adsorbents were prepared by alkalination of hazardous SWI-FA and cured at different temperatures of 30 0C (GP30), 50 0C (GP50), 70 0C (GP70), and 90 0C (GP90). The geopolymers were applied as low-cost adsorbents for the removal of anionic bromocresol green (BCG) dye from water under varying conditions. The precursor and geopolymers were characterized by XRD, SEM-EDS, FT-IR, and point of zero charge (PZC). The geopolymers were morphologically different with varying chemical compositions. The kinetic data were best described by the pseudo second order model. The experimental equilibrium adsorption data were fitted to Langmuir, Freundlich, Temkin and Dubinin-Radushkevich-Kaganer adsorption isotherm models. The Langmuir monolayer maximum adsorption capacities increased consistently with curing temperature, from 41.70 mg/g to 515.5 mg/g for GP30 and GP90, respectively, a new benchmark for these materials for anionic dyes. The thermodynamic parameters, namely enthalpy (ΔH<0), Gibbs free energy (ΔG<0), entropy (ΔS >0) and activation energy (Ea) indicated that the processes are spontaneous, exothermic, physical (Ea<5kJ/mol and ΔH<40kJ/mol) and enthalpy-driven. The adsorption mechanisms included strong electrostatic interactions and hydrogen bonding. The production of these geopolymers provides dual advantage of waste valorization with applications in depollution of water.

Entropy evolution at generic power-law edge of chaos

For strongly chaotic classical systems, a basic statistical–mechanical connection is provided by the averaged Pesin-like identity (the production rate of the Boltzmann–Gibbs entropy SBG=−∑i=1Wpilnpi equals the sum of the positive Lyapunov exponents). In contrast, at a generic edge of chaos (vanishing maximal Lyapunov exponent) we have a subexponential divergence with time of initially close orbits. This typically occurs in complex natural, artificial and social systems and, for a wide class of them, the appropriate entropy is the nonadditive one Sqe=1−∑i=1Wpiqeqe−1(S1=SBG) with qe≤1. For such weakly chaotic systems, power-law divergences emerge involving a set of microscopic indices {qk}’s and the associated generalized Lyapunov coefficients. We establish the connection between these quantities and (qe,Kqe), where Kqe is the Sqe entropy production rate.

Sorption of Lead, Zinc and Copper from Simulated Wastewater by Amberlite Ir-120 Resin

The presence of heavy metals in the environment is major concern due to their toxicity. In the present study a strong acid cation exchange resin, Amberlite IR 120 was used for the removal of lead, zinc and copper from simulated wastewater. The optimum conditions were determined in a batch system of concentration 100 mg/L, pH range between 1 and 8, contact time between 5 and 120 minutes, and amount of adsorbent was from 0.05 to 0.45 g/100 ml. A constant stirring speed, 180 rpm, was chosen during all of the experiments. The optimum conditions were found to be pH of 4 for copper and lead and pH 6 for zinc, contact time of 60 min and 0.35 g of adsorbent. Three different temperatures (25, 40 and 60°C) were selected to investigate the effect of adsorption temperature on heavy metals adsorption onto Amberlite IR. The equilibrium data were analyzed by the Langmuir and Freundlich isotherms. The thermodynamic parameters such as Gibbs free energy, enthalpy and entropy changes were calculated. Moreover, in order to understand the heavy metal extraction kinetics in the presence of Amberlite IR 120, the ion exchange kinetics was also studied. The ion exchange kinetics data were regressed by the pseudo first-order, second-order models. The results obtained show that the Amberlite IR 120 strong acid cation exchange resin performed well for the removal of lead, zinc and copper.

Characterization of the pH-dependent protein stability of 3α-hydroxysteroid dehydrogenase/carbonyl reductase by differential scanning fluorimetry.

The characterization of protein stability is essential for understanding the functions of proteins. Hydroxysteroid dehydrogenase is involved in the biosynthesis of steroid hormones and the detoxification of xenobiotic carbonyl compounds. However, the stability of hydroxysteroid dehydrogenases has not yet been characterized in detail. Here, we determined the changes in Gibbs free energy, enthalpy, entropy, and heat capacity of unfolding for 3α-hydroxysteroid dehydrogenase/carbonyl reductase (3α-HSD/CR) by varying the pH and urea concentration through differential scanning fluorimetry and presented pH-dependent protein stability as a function of temperature. 3α-HSD/CR shows the maximum stability of 30.79 kJ mol-1 at 26.4°C, pH 7.6 and decreases to 7.74 kJ mol-1 at 25.7°C, pH 4.5. The change of heat capacity of 30.25 ± 1.38 kJ mol-1 K-1 is obtained from the enthalpy of denaturation as a function of melting temperature at varied pH. Two proton uptakes are linked to protein unfolding from residues with differential pKa of 4.0 and 6.5 in the native and denatured states, respectively. The large positive heat capacity change indicated that hydrophobic interactions played an important role in the folding of 3α-HSD/CR. These studies reveal the mechanism of protein unfolding in HSD and provide a convenient method to extract thermodynamic parameters for characterizing protein stability using differential scanning fluorimetry.

Operative utilization of the feasible anion exchange membrane BIII for Sorptive exclusion of acid orange 7 from Hydrated media

Anion exchange membranes have received great deal of attention for their ability to remove harmful dye contamination from industrial wastewater while also ensuring profitable and fuel-efficient commercialization. The ability of anion exchange membrane BIII to eradicate acid orange 7 dye from aquatic environment is demonstrated here. SEM and FTIR analyses revealed the surface properties and existence of distinct operational groups on the sorbent. Numerous constraints on AO7exclusion in an aquatic environment, such as contact duration, temperature, sorbent dose, and starting dye concentration were also scrutinized. For the purpose of assessing kinetics, Liquid film diffusion, Elovich, Lagergren first-order, Bangham, pseudo-second-order, and modified Freundlich models, were employed. These findings imply that the AO7 dye sorption onto the BIII membrane is well controlled by the liquid-film diffusion process and that the sorption comprehends pseudo-second-order kinetics with an utmost value of R2(0.99). To evaluate tentative data, multiple linear and nonlinear isotherm models were utilized. Freundlich isotherm was found to be in excellent agreement with sorption data. Thermodynamic specifications, such as a change in Gibb's free energy, enthalpy, and entropy, for dye sorption on the anion exchange BIII membrane were optimized between 308 and 338 K to maximize AO7 dye removal. Since ΔGo is negative and, ΔHo and ΔSo are positive, inferred that the sorption is spontaneous and endothermic. Anion exchange membrane BIII was effective for up to four successive cycles without losing its competence.

Separation of m-cresol and p-cresol by NaZSM-5 with different Si/Al ratios

ABSTRACT m-Cresol and p-cresol are widely used in medicine and pesticides as important chemical intermediates. They are generally produced as a mixture in industry and are difficult to separate due to the similarities in both chemical structures and physical properties. The adsorption behaviours of m-cresol and p-cresol on zeolites (NaZSM-5 and HZSM-5) with different Si/Al ratios have been compared by static experiments. Selectivity on NaZSM-5(Si/Al = 80) could be greater than 6.0. Adsorption kinetics and isotherms were investigated in detail. The kinetic data was correlated by PFO, PSO, and ID models, the NRMSE of which were 14.03%, 9.41%, and 21.11%, respectively. In the meanwhile, according to the NRMSE of Langmuir (6.01%), Freundlich (57.80%), D-R (1.1%), and Temkin (0.56%) isotherms, adsorption on NaZSM-5(Si/Al = 80) was mainly a monolayer and chemical adsorption process. It was endothermic for m-cresol and exothermic for p-cresol. The Gibbs free energy, entropy, and enthalpy were calculated accordingly. The adsorption of cresol isomers on NaZSM-5(Si/Al = 80) were both spontaneous, and it was exothermic (ΔH = −37.11kJ/mol) for p-cresol while endothermic (ΔH = 52.30kJ/mol) for m-cresol. Additionally, ΔS were respectively −0.05 and 0.20 kJ·mol−1·K−1for p-cresol and m-cresol, which were both close to zero. The adsorption was mainly driven by enthalpy. The result of breakthrough further demonstrated m-cresol and p-cresol could be separated effectively by NaZSM-5(Si/Al = 80). Additionally, the selectivity increased from 7.53 to 14.72 after four cycles regeneration with 9.95% and 53.96% decreases in the adsorption amounts for m-cresol and p-cresol, respectively. In conclusion, NaZSM-5(Si/Al = 80) could be a feasible adsorbent for the separation of m-cresol and p-cresol.

Preparation and Embedding Characterization of Hydroxypropyl-β-cyclodextrin/Menthyl Acetate Microcapsules with Enhanced Stability.

Hydroxypropyl-β-cyclodextrin (HP-β-CD)/menthyl acetate (MA) microcapsules were developed to overcome the volatile and unstable defects of MA and improve the ease of use and storage. MA microcapsules were prepared via spray drying using HP-β-CD as the wall material. The embedding rate of MA microcapsules was determined through gas chromatography. The embedding characteristics were studied using phase solubility and nuclear magnetic resonance (NMR). The stability was characterized via differential scanning calorimetry (DSC) and the release and retention rates of MA microcapsules at different temperatures. The embedding rate of HP-β-CD /MA microcapsules was 96.3%. The Gibbs free energy change, enthalpy change and entropy change of the embedding reaction between HP-β-CD and MA were all less than zero, indicating that the embedding process was a spontaneous exothermic reaction. NMR spectra showed that MA entered the cavity of HP-β-CD through the large opening end and interacted with the inner wall of the small opening end. DSC and the release and retention rates of MA microcapsules at different temperatures showed that the stability of MA was significantly enhanced after being embedded in HP-β-CD. The HP-β-CD/MA microcapsules are able to significantly improve the stability of MA and reduce the volatilization of MA.

Right Answer for the Right Reason? Benchmarking Protocols and Pitfalls on a Ru-Metathesis Example.

A layered meta-benchmarking analysis was devised with the aim of illustrating how to produce an experimental/computational protocol for the method selection and estimation of Gibbs energies of catalytically prominent reactions. Our test subject involved the active-latent equilibrium through the cis-trans isomerism of two metathesis catalysts: mesitylene-Ru-SCF3-Cl and diisopropylphenyl-Ru-SCF3-Cl. The strategy was two-fold: first to perform a computational benchmark for the energies in the gas phase, followed by benchmarking the enthalpy and the Gibbs energy, including solvation and entropy, from experimental references. This "wedding cake" build-up of subsequent methods applied to our particular small test reaction indicates that: (1) DLPNO-CCSD(T)/CBS works well as a reference method for large systems. (2) Among several functionals ωB97XD and M06 were the most accurate. (3) Choosing between IEF-PCM and SMD solvation models turned out to be case dependent. (4) For the vibrational entropic component, low-frequency vibrations often produce humungous errors, which can be improved by Cramer and Truhlar's or Grimme's methods; however, their cut-off parameters had to be lowered from their standard values. (5) Solvation methods are important for enthalpies, but they are inadequate for entropies. (6) All of these components are equally important for the accuracy of organometallic complexes' reactions. The only way to find the right method for the right reasons is to be sure to match all of the Gibbs energy terms to benchmarked experimental and computational values.