Search Results (76)

A precise characterization of molecular vibrations and thermodynamic properties is essential for applications in spectroscopy, computational modeling, and chemical process design. In this study, the q-deformed Tietz (qDT) oscillator is applied to examine vibrational energy spectra of diatomic molecules and thermodynamic properties of nonlinear symmetric triatomic molecules. Vibrational energy eigenvalues were obtained analytically using the improved Nikiforov-Uvarov method. The symmetric vibrational mode was described with the qDT oscillator, while asymmetric and bending modes were modeled using the rigid rotor harmonic oscillator (RRHO); translational and rotational contributions were incorporated from standard models. For diatomic molecules (BrF, CO⁺, CrO, ICl, KRb, NaBr), mean absolute percentage errors (MAPE) ranged from 0.53% to 1.73% for vibrational energy eigenvalues and 0.34% to 1.08% for potential fits. Extending the analysis to triatomic molecules, thermodynamic properties of AlCl₂, BF₂, Cl₂O, OF₂, O₃, and SO₂ were calculated with the qDT model, yielding low MAPE benchmarked against NIST-JANAF reference data: entropy 0.203% to 0.614%, enthalpy 1.792% to 5.861%, Gibbs free energy 0.419% to 1.270%, and constant-pressure heat capacity 1.475% to 4.978%. These results demonstrate the versatility and accuracy of the qDT oscillator as an analytical framework connecting molecular potentials, vibrational energies, and thermodynamic functions, providing a practical and tractable approach for modeling both diatomic and symmetric triatomic systems. Full article

Hot-melt extrusion produces a solid dispersion (SD) containing a poorly water-soluble drug (k) and matrix polymer surfactant (PS), thereby enhancing k’s solubility. When dissolving the SD, the PS is first dissolved, forming micelles. The amorphous form of the solid phase k remains and is further dissolved by micellar solubilization. The goal here is to rigorously derive, on the basis of thermodynamics, a new expression for the change in the standard Gibbs free energy (${∆G}_{\Sigma }^0$). This change serves as a measure for increasing the degree of spontaneity in the dissolution of amorphous k from an SD with a polymeric surfactant relative to the dissolution of the crystalline-form k in an aqueous solution without surfactants (reference state). In the micelle-pseudophase model, it was found that ${∆G}_{\Sigma }^0$ depends on the natural logarithm of the ratio of mole fraction k in the aqueous phase to mole fraction k in the micellar pseudophase. In a simpler model, ${∆G}_{\Sigma }^0$ can be expressed as ln of the solubility ratio of the crystalline and SD forms, assuming that the activity coefficient depends on the process of incorporating k into the micellar particles and that the total amount of surfactants is many times smaller than the water amount, which is acceptable for polymeric surfactants with low values of the critical micellar concentration. Full article

Given the multi-basin raw material base for coking that has been formed at most industry enterprises, there is an urgent need to optimize the component composition and improve the basic technological methods of coal raw material preparation, taking into account the petrographic characteristics of coal batches. A comprehensive study of the components included in a coke chemical enterprise’s coking raw material base was carried out. The work used standardized methods for studying coal and coal batches’ technological and plastic–viscous properties. The qualitative characteristics of coke were determined using physical–mechanical and thermochemical methods of studying standardized indicators: crushability (M₂₅), abrasion (M₁₀), reactivity (CRI), post-reaction strength (CSR), and specific electrical resistance (ρ). The results were analyzed using the licensed Microsoft Excel computer program. Based on the results of proximate, plastometric, and petrographic analyses of the studied coal samples and data from experimental industrial coking, proposals were made to optimize the component composition, properties of the coal batch, and technology for its preparation for coking. The established inverse dependence of Gibbs free energy (ΔG_f,total) on the reaction capacity of coke CRI and its direct reliance on its post-reaction strength CSR confirmed the feasibility of using ΔG_f,total as a thermodynamic predictive parameter for optimizing and compiling coal batches that produce less reactive, stronger coke. This made it possible to improve the quality indicators of metallurgical coke. Thus, according to the M₂₅ crushability index, the mechanical strength increased by 0.6%, and the M₁₀ abrasion decreased by 0.4%. Significant improvements in thermochemical properties and an increase in the orderliness of the carbon structure were recorded: the CRI reactivity decreased by 3.1%, the CSR post-reaction strength increased by 8.3%, and the specific resistance decreased by 8.4%. Full article

The escalating crisis of multidrug resistance, together with the persistence of antibiotic residues in clinical and environmental matrices, demands integrated strategies that couple sensitive detection, efficient decontamination, and controlled delivery. However, current techniques for quantifying avibactam (AVI)—a broad-spectrum β-lactamase inhibitor—such as HPLC-UV lack the sensitivity and specificity required for both therapeutic drug monitoring and environmental surveillance. Encapsulation of AVI within cyclodextrins (CDs) may simultaneously enhance its stability, bioavailability, and detectability, while the high binding affinities of CDs position them as molecular traps capable of scavenging residual AVI. In this study, the inclusion complexation of AVI with various CDs was examined through molecular dynamics (MD) simulations, experimental isothermal titration calorimetry (ITC), and non-covalent interaction (NCI) analysis. Stable 1:1 inclusion complexes were observed between AVI and β-cyclodextrin (β-CD), 2,6-dimethyl-β-cyclodextrin (DM-β-CD), and 2-hydroxypropyl-β-cyclodextrin (HP-β-CD), with standard Gibbs free energies of binding (ΔG°) of –3.64, –3.24, and –3.11 kcal/mol, respectively. In contrast, γ-cyclodextrin (γ-CD) exhibited significantly weaker binding (ΔG° = –2.25 kcal/mol). DFT-based NCI analysis revealed that cooperative interaction topology and cavity complementarity, rather than the sheer number of localized contacts, govern complex stability. Combined computational and experimental data establish β-CD derivatives as effective supramolecular hosts for AVI, despite an entropic penalty in the DM-β-CD/AVI complex. These CD–AVI affinities support the development of improved analytical methodologies and pharmaceutical formulations, and they also open avenues for decontamination strategies based on molecular trapping of AVI. Full article

Measurements of the surface tension of aqueous solutions of some trisiloxane surfactants containing various polyether groups (HOL7, HOL9, and HOL12) at 293 K, 303 K, and 313 K were performed. The studied surfactants were synthesized by hydrosilylation reaction and their structural analysis was carried out by the ¹H NMR, ¹³C NMR, ²⁹Si NMR, as well as FT-IR techniques. The thermal stability of HOL7, HOL9, and HOL12, as well as their molecular weight distributions, were also studied. On the basis of the obtained experimental results of the surface tension of aqueous solutions of HOL7, HOL9, and HOL12, the activity of the studied surfactants at the water–air interface was determined and discussed in the light of intermolecular interactions. Using the measured values of the surface tension, the Gibbs surface excess concentration, the area occupied by the surfactant molecule in the adsorption layer, and the standard Gibbs free energy of adsorption of the studied surfactants at the water–air interface were also calculated. Based on the obtained thermodynamic parameters of adsorption of the studied surfactants at the water–air interface, temperature, as well as a number of polyether groups in the hydrophilic part of surfactant, impact on particular surfactant adsorption was deduced. In general, the changes in the standard Gibbs free energy of adsorption of the studied surfactants at the water–air interface indicate that their adsorption tendency decreases with decreasing temperature. In addition, that tendency also diminishes as the number of the polyether groups in the hydrophilic part of the surfactant increases. Full article

In this work, we studied the main decomposition reactions on the ground state of nitromethane (CH₃NO₂) with the CASPT2 approach. The energetics of the main elementary reactions of the title molecule have been analyzed on the basis of Gibbs free energies obtained from standard expressions of statistical thermodynamics. In addition, we describe a mapping method (orthogonalized 3D representation) for the potential energy surfaces (PESs) by defining an orthonormal basis consisting of two $R^n$ orthonormal vectors (n, internal degrees of freedom) that allows us to obtain a set of ordered points in the plane (vector subspace) spanned by such a basis. Geometries and harmonic frequencies of all species and orthogonalized 3D representations of the PESs have been computed with the CASPT2 approach. It is found that all of the analyzed kinetically controlled reactions of nitromethane are endergonic. For such a class of reactions, the dissociation of nitromethane into CH₃ and NO₂ is the process with the lower activation energy barrier (ΔG); that is, the C-N bond cleavage is the most favorable process. In contrast, there exists a dynamically controlled process that evolves through a roaming reaction mechanism and is an exergonic reaction at high temperatures: CH₃NO₂ → [CH₃^…NO₂]* → [CH₃ONO]* → CH₃O + NO. The above assertions are supported by CASPT2 mappings of the potential energy surfaces (PESs) and classical trajectories obtained by “on-the fly” CASSCF molecular dynamics calculations. Full article

A new molecular theory of slag suggests that complex oxides in the phase diagram are also present in liquid slag. In contrast to the ion‒molecule coexistence theory, basic oxides (CaO, MgO, MnO, FeO, etc.) in slag are considered to agglomerate in the liquid state due to their strong mutual attraction, although they are ionized (M²⁺ and O²⁻). The predicted slag structure agrees with the experimental results, and when the model is applied to the CaO-SiO₂, CaO-Al₂O₃, and CaO-SiO₂-Al₂O₃ slag systems, the calculated molar fractions of CaO, SiO₂, and Al₂O₃ ($N_{\mathrm{CaO}},N_{{\mathrm{SiO}}_2},N_{{\mathrm{Al}}_2{\mathrm{O}}_3}$) are close to the measured activities (${\alpha }_{\mathrm{CaO}},a_{{\mathrm{SiO}}_2} \mathrm{and} a_{{\mathrm{Al}}_2{\mathrm{O}}_3}$) reported by different researchers. In the CaO-Al₂O₃ slag system, the results based on the new molecular theory are closer to the experimental values than the results of other theoretical calculations. In the practical application of the new molecular theory, the maximum concentration of each complex molecule is consistent with the position of the melting point of the same solid‒liquid components in the phase diagram, indicating that complex molecules have a strong influence on the melting point of slag. In addition, it is believed that the formation and decomposition of different complex molecules are responsible for changes in component activity in the CaO-SiO₂ and CaO-Al₂O₃ slag systems, and it is further deduced that 3CaO-SiO₂ is formed in two steps. Full article

This study presents analytical models for simulating the thermal properties of linear triatomic systems, using the modified Rosen–Morse oscillator and harmonic oscillator potential to represent vibrational modes. The models employ existing partition functions to derive the thermodynamic functions for the symmetric, asymmetric, and 2-fold degenerate bending modes. These thermodynamic functions are applied to gaseous triatomic molecules such as BO₂, HCN, N₃, and Si₂N. The results demonstrate high accuracy, with mean percentage absolute deviations (MPAD) of less than 0.17% for molar entropy and Gibbs free energy. For enthalpy and heat capacity, MPAD values are below 2% compared to National Institute of Standards and Technology (NIST) data. The findings are in strong agreement with the existing literature on gaseous triatomic molecules, confirming the reliability of the proposed models. Full article

The Gibbs free energies of gallic acid (GA) and its anionic forms in aqueous solution were computed utilizing density functional theory (DFT) at the LSDA, M062X, B3LYP/QZVP levels, in conjunction with the SMD solvation model. The pK_a values corresponding to the four-step deprotonation of GA were determined through a non-linear self-similar transformation expressed as, pK_a = a⋅pK_a(the)^c which establishes a link between theoretical and experimental pK_a values. This approach replaces the previously employed linear relationship, pK_a = a⋅pK_a(the) + b. The proposed model demonstrates high accuracy in reproducing the experimental pK_a1 = 4.16 ± 0.02, pK_a2 = 8.55 ± 0.01, pK_a3 =11.40 ± 0.10, pK_a4 =12.8 ± 0.40 values of GA, with a standard error (SE) of 0.045 and a mean absolute error (MAE) of 0.019 in pK_a unit. Furthermore, it facilitates the precise determination of the Gibbs free energy of the proton hydration, yielding ∆G(H⁺)_aq = 259.4272(75) [kcal mol⁻¹]. This result conforms acceptably with the experimental value of ∆G(H⁺)_aq = −259.5 [kcal mol⁻¹]. Full article

Optimal product synthesis in bioelectrochemical systems (BESs) requires a comprehensive understanding of the relationship between external voltage and microbial yield. While most studies assume constant growth yields or rely on empirical estimates, this study presents a novel thermodynamic model, linking anodic oxidation and cathodic carbon dioxide (${CO}_2$) reduction to methane (${CH}_4$) by growing microbial biofilm. Through integrating theoretical Gibbs free energy calculations, the model predicts electron and proton transfers for autotrophic methanogen and anode-respiring bacteria (ARB) growth, accounting for varying applied voltages and substrate concentrations. The findings identify an optimal applied cathodic potential of −0.3 V vs. the standard hydrogen electrode (SHE) for maximizing ${CH}_4$ production under standard conditions (pH 7, 25 °C, 1 atm) regardless of ohmic losses. The model bridges the stoichiometry of anodic and cathodic biofilms, addressing research gaps in simulating anodic and cathodic biofilm growth simultaneously. Additionally, sensitivity analyses reveal that lower substrate concentrations require more negative voltages than standard condition to stimulate microbial growth. The model was validated using experimental data, demonstrating reasonable predictions of biomass growth and ${CH}_4$ yield under different operating voltages in a multi substrate system. The results show that higher voltage inputs increase biomass yield while reducing ${CH}_4$ output due to non-optimal voltage. This validated model provides a tool for optimizing BES performance to enhance ${CH}_4$ recovery and biofilm stability. These insights contribute to finding optimum voltage for the highest ${CH}_4$ production for energy efficient ${CO}_2$ reduction for scaling up BES technology. Full article

The synthesis of tetra- and pentanorlabdane compounds with rearranged cycle B based on commercially available (+)-sclareolide is reported. Desired compounds were prepared from intermediate ketones via Baeyer–Villiger oxidation. The structures of synthesized compounds were confirmed by spectral IR, 1D (¹H, ¹³C, and DEPT), and 2D (H-COSY, H,C-HSQC, H,C-HMBC, H,N-HMBC, NOESY) NMR analyses, mass-spectrometry and single crystal X-rays diffraction. Two out of the four synthesized compounds showed high antifungal and antibacterial activities comparable to and exceeding standard antifungal (caspofungin) and antibacterial (kanamycin) agents. DFT calculations show that in gas and DCM, compound 4 is more stable than 3 with a difference in the Gibbs free energy of 23.3 kJ/mol and 20.7 kJ/mol, respectively. In water and methanol, compound 3 is slightly more stable, by 2.4 kJ/mol and 2.78 kJ/mol, respectively. Molecular docking to four targets DNA gyrase from E. coli (1KZN), Fabz from P. aeruginosa (1U1Z), dihydrofolate reductase from C. albicans (3QLS) and MurB from E. coli (2Q85) showed good agreement with the results of in vitro evaluation and confirmed the biological activity of compounds 3 and 4, with binding affinities comparable and for some targets exceeding that of Caspofungin and Kanamycin. Full article

Photosystem I is a key component of primary energy conversion in oxygenic photosynthesis. Electron transfer reactions in Photosystem I take place across two parallel electron transfer chains that converge after a few electron transfer steps, sharing both the terminal electron acceptors, which are a series of three iron–sulphur (Fe-S) clusters known as $F_{\mathrm{X}}$, $F_{\mathrm{A}}$, and $F_{\mathrm{B}}$, and the terminal donor, $P_{700}$. The two electron transfer chains show kinetic differences which are, due to their close geometrical symmetry, mainly attributable to the tuning of the physicochemical reactivity of the bound cofactors, exerted by the protein surroundings. The factors controlling the rate of electron transfer between the terminal Fe-S clusters are still not fully understood due to the difficulties of monitoring these events directly. Here we present a discussion concerning the driving forces associated with electron transfer between $F_{\mathrm{X}}$ and $F_{\mathrm{A}}$ as well as between $F_{\mathrm{A}}$ and $F_{\mathrm{B}}$, employing a tunnelling-based description of the reaction rates coupled with the kinetic modelling of forward and recombination reactions. It is concluded that the reorganisation energy for $F_{\mathrm{X}}^{-}$ oxidation shall be lower than 1 eV. Moreover, it is suggested that the analysis of mutants with altered $F_{\mathrm{A}}$ redox properties can also provide useful information concerning the upstream phylloquinone cofactor energetics. Full article

The molar heat capacity of 1,4-bis(3-methylimidazolium-1-yl)butane bis(trifluoromethylsulfonyl)imide dicationic ionic compound ([C₄(MIm)₂][NTf₂]₂) has been studied over the temperature range from 6 to 350 K by adiabatic calorimetry. In the above temperature interval, this compound has been found to form crystal, liquid, and supercooled liquid. For [C₄(MIm)₂][NTf₂]₂, the temperature of fusion T°_fus = (337.88 ± 0.01) K has been determined by the fractional melting experiments, the enthalpy of fusion Δ_fusH° = (52.79 ± 0.28) kJ mol⁻¹ has been measured using the calorimetric method of continuous energy input, and the entropy of fusion Δ_fusS° = (156.2 ± 1.7) J K⁻¹ mol⁻¹ has also been evaluated. The standard thermodynamic functions of the studied dicationic ionic compound, namely, the heat capacity C_p°(T), the enthalpy [H°(T) − H°(0)], the entropy S°(T) and the Gibbs free energy [G°(T) − H°(0)] have been calculated on the basis of the experimental data for the temperature range up to 350 K. The results have been discussed and compared with those available in the literature and in the NIST Ionic Liquids Database (ILThermo) for monocationic ionic compounds. Full article

Background: Wiedemann–Steiner syndrome (WSS), a rare autosomal-dominant disorder caused by haploinsufficiency of the KMT2A gene product, is part of a group of disorders called chromatinopathies. Chromatinopathies are neurodevelopmental disorders caused by mutations affecting the proteins responsible for chromatin remodeling and transcriptional regulation. The resulting gene expression dysregulation mediates the onset of a series of clinical features such as developmental delay, intellectual disability, facial dysmorphism, and behavioral disorders. Aim of the Study: The aim of this study was to investigate a 10-year-old girl who presented with clinical features suggestive of WSS. Methods: Clinical and genetic investigations were performed. Whole exome sequencing (WES) was used for genetic testing, performed using Illumina technology. The bidirectional capillary Sanger resequencing technique was used in accordance with standard methodology to validate a mutation discovered by WES in all family members who were available. Utilizing computational protein modeling for structural and functional studies as well as in silico pathogenicity prediction models, the effect of the mutation was examined. Results: WES identified a de novo heterozygous missense variant in the KMT2A gene KMT2A(NM_001197104.2): c.3451C>G, p.(Arg1151Gly), absent in the gnomAD database. The variant was classified as Likely Pathogenetic (LP) according to the ACMG criteria and was predicted to affect the CXXC-type zinc finger domain functionality of the protein. Modeling of the resulting protein structure suggested that this variant changes the protein flexibility due to a variation in the Gibbs free energy and in the vibrational entropy energy difference between the wild-type and mutated domain, resulting in an alteration of the DNA binding affinity. Conclusions: A novel and de novo mutation discovered by the NGS approach, enhancing the mutation spectrum in the KMT2A gene, was characterized and associated with WSS. This novel KMT2A gene variant is suggested to modify the CXXC-type zinc finger domain functionality by affecting protein flexibility and DNA binding. Full article

Using quantum chemical calculation data obtained by the DFT method with the B3PW91/TZVP and M062X/def2TZVP theory levels, the possibility of the existence of four Be(II) coordination compounds, each of which contains in the inner coordination sphere and the double deprotonated forms of subporphyrazine (H₂SP), mono[benzo]subporphyrazine (H₂MBSP), di[benzo]subporphyrazine (H₂DBSP), and tri[benzo]subporphyrazine (subphthalocyanine) (H₂TBSP) with a ratio Be(II) ion/ligand = 1:1, were examined Selected geometric parameters of the molecular structures of these (666)macrotricyclic complexes with closed contours are given; it was noted that BeN3 chelate nodes have a trigonal–pyramidal structure and exhibit a very significant (almost 30°) deviation from coplanarity; however, all three 6-membered metal-chelate and three 5-membered non-chelate rings in each of these compounds are practically planar and deviate from coplanarity by no more than 2.5°. The bond angles between two nitrogen atoms and a Be atom are equal to 60° (in the [BeSP] and [BeTBSP]) or less by no more than 0.5° (in the [BeMBSP] and [BeDBSP]). The presence of annulated benzo groups has little effect on the parameters of the molecular structures of these complexes. Good agreement between the structural data obtained using the above two versions of the DFT method was noticed. NBO analysis data for these complexes are presented; it was noted that, according to both DFT methods used, the ground state of the each of complexes under study is a spin singlet. Standard thermodynamic parameters of formation (standard enthalpy Δ_fH⁰, entropy S⁰, and Gibbs free energy Δ_fG⁰) for the above-mentioned macrocyclic compounds were calculated. Full article