Search Results (6)

In this paper, a novel mixed Tutton salt (K_0.86Na_0.14)₂Ni(SO₄)₂(H₂O)₆ was successfully synthesized as a single crystal and evaluated as a thermochemical heat storage material. Its thermal and thermochemical properties were correlated with the structure, which was determined by powder X-ray diffraction using the Le Bail and Rietveld methods. The elemental ratio between the K⁺ and Na⁺ monovalent cations was established by energy-dispersive X-ray spectroscopy. Similar compounds such as Na₂Ni(SO₄)₂(H₂O)₄ and K₂Ni(SO₄)₂(H₂O)₆ were also synthesized and used for structural comparisons. The (K_0.86Na_0.14)₂Ni(SO₄)₂(H₂O)₆ salt crystallizes in monoclinic symmetry with the P2₁/c-space group, typical of hexahydrate crystals from the Tutton salt family. The lattice parameters closely resemble those of K₂Ni(SO₄)₂(H₂O)₆. A comprehensive analysis of the intermolecular contacts, based on Hirshfeld surfaces and 2D fingerprint mappings, revealed that the primary interactions are hydrogen bonds (H···O/O···H) and ion-dipole interactions (K/Na···O/O···Na/K). The unit cell exhibits minimal void space, accounting for only 0.2%, indicative of strong atomic packing. The intermolecular molecular and atomic packing are important factors influencing crystal lattice stabilization and thermal energy supplied to release crystallographic H₂O. The thermal stability of mixed Tutton salt ranges from 300 K to 365 K. Under the dehydration of its six H₂O molecules, the dehydration reaction enthalpy reaches 349.8 kJ/mol, yielding a thermochemical energy storage density of 1.79 GJ/m³. With an H₂O desorption temperature ≤393 K and a high energy storage density ≥1.3 GJ/m³ (criteria established for applications at the domestic level), the (K_0.86Na_0.14)₂Ni(SO₄)₂(H₂O)₆ shows potential as a thermochemical material for small-sized heat batteries. Full article

Herein, we described the synthesis and X-ray crystal structure of the new [Pd(3)₂Cl₂] complex with 1,2,3-triazole-based ligand (3). In the unit cell, there are two [Pd(3)₂Cl₂] molecules, and the asymmetric unit comprised half of this formula due to the presence of an inversion symmetry element at the Pd(II) center. The monoclinic unit cell volume is 1327.85(6) ų, with crystal parameters of a = 10.7712(2) Å, b = 6.8500(2) Å, and c = 18.2136(6) Å, while β = 98.851(2)°. The structure comprised two trans triazole ligand units coordinated to the Pd(II) ion via one of the N-atoms of the triazole moiety. In addition, the Pd(II) is further coordinated with two trans chloride groups, where each of the trans bonds is equidistant. The crystal structure of the [Pd(3)₂Cl₂] complex was compared with that for free triazole ligand 3. It was found that the coordinated ligand showed less twist around the C–N bond compared to free triazole ligand 3. The molecular packing of the latter is found controlled by short O…H, N…H, C…N, and C…C interactions in addition to the short Cl…F interhalogen and π–π interactions. H…H (23.5%), Cl…H (14.4%), N…H (14.3%), and O…H (11.2%) are the most dominant contacts. In the [Pd(3)₂Cl₂] complex, no significant interhalogen or π–π interactions were detected. In this case, Cl…H (31.1%), H…H (16.7%), O…H (11.6%), and F…H (9.7%) are the most dominant contacts. Full article

The model of Regularized Quantum Mechanical Force Field (RQMFF) was applied to the joint treatment of ab initio and experimental vibrational data of the four primary nucleobases using a new algorithm based on the scaling procedure in Cartesian coordinates. The matrix of scaling factors in Cartesian coordinates for the considered molecules includes diagonal elements for all atoms of the molecule and off-diagonal elements for bonded atoms and for some non-bonded atoms (1–3 and some 1–4 interactions). The choice of the model is based on the results of the second-order perturbation analysis of the Fock matrix for uncoupled interactions using the Natural Bond Orbital (NBO) analysis. The scaling factors obtained within this model as a result of solving the inverse problem (regularized Cartesian scale factors) of adenine, cytosine, guanine, and thymine molecules were used to correct the Hessians of the canonical base pairs: adenine–thymine and cytosine–guanine. The proposed procedure is based on the block structure of the scaling matrix for molecular entities with non-covalent interactions, as in the case of DNA base pairs. It allows avoiding introducing internal coordinates (or coordinates of symmetry, local symmetry, etc.) when scaling the force field of a compound of a complex structure with non-covalent H-bonds. Full article

The problems of gene regulatory network (GRN) reconstruction and the creation of disease diagnostic effective systems based on genes expression data are some of the current directions of modern bioinformatics. In this manuscript, we present the results of the research focused on the evaluation of the effectiveness of the most used metrics to estimate the gene expression profiles’ proximity, which can be used to extract the groups of informative gene expression profiles while taking into account the states of the investigated samples. Symmetry is very important in the field of both genes’ and/or proteins’ interaction since it undergirds essentially all interactions between molecular components in the GRN and extraction of gene expression profiles, which allows us to identify how the investigated biological objects (disease, state of patients, etc.) contribute to the further reconstruction of GRN in terms of both the symmetry and understanding the mechanism of molecular element interaction in a biological organism. Within the framework of our research, we have investigated the following metrics: Mutual information maximization (MIM) using various methods of Shannon entropy calculation, Pearson’s ${\chi }^2$ test and correlation distance. The accuracy of the investigated samples classification was used as the main quality criterion to evaluate the appropriate metric effectiveness. The random forest classifier (RF) was used during the simulation process. The research results have shown that results of the use of various methods of Shannon entropy within the framework of the MIM metric disagree with each other. As a result, we have proposed the modified mutual information maximization (MMIM) proximity metric based on the joint use of various methods of Shannon entropy calculation and the Harrington desirability function. The results of the simulation have also shown that the correlation proximity metric is less effective in comparison to both the MMIM metric and Pearson’s ${\chi }^2$ test. Finally, we propose the hybrid proximity metric (HPM) that considers both the MMIM metric and Pearson’s ${\chi }^2$ test. The proposed metric was investigated within the framework of one-cluster structure effectiveness evaluation. To our mind, the main benefit of the proposed HPM is in increasing the objectivity of mutually similar gene expression profiles extraction due to the joint use of the various effective proximity metrics that can contradict with each other when they are used alone. Full article

A newly prepared Cu(II) complex salt, Cu(L¹)(H₂O)₂Br₂, where L¹ is 3,14-dimethyl-2,6,13,17-tetraazatricyclo(16.4.0.0^7,12) docosane, is characterized by elemental and crystallographic analyses. The Cu(II) center is coordinated by four nitrogen atoms of macrocyclic ligand and the axial position by two water molecules. The macrocyclic ligand adopts an optimally stable trans-III conformation with normal Cu–N bond lengths of 2.018 (3) and 2.049 (3) Å and long axial Cu1–O1W length of 2.632 (3) Å due to the Jahn–Teller effect. The complex is stabilized by hydrogen bonds formed between the O atoms of water molecules and bromide anions. The bromide anion is connected to the neighboring complex cations and water molecules through N–H···Br and O–H···Br hydrogen bonds, respectively. The g-factors obtained from the electron spin resonance spectrum show the typical trend of g_∥ > g_⊥ > 2.0023, which is in a good accordance to the d_x²-_y² ground state. It reveals a coordination sphere of tetragonal symmetry for the Cu(II) ion. The infrared and electronic absorption spectral properties of the complex are also discussed. Hirshfeld surface analysis represents that the H···H, H···Br/Br···H and H···O/O···H contacts are the major molecular interactions in the prepared complex. Full article

A basic pattern in the body plan architecture of many animals, plants and some molecular and cellular systems is five-part units. This pattern has been understood as a result of genetic blueprints in development and as a widely conserved evolutionary character. Despite some efforts, a definitive explanation of the abundance of pentagonal symmetry at so many levels of complexity is still missing. Based on both, a computational platform and a statistical spatial organization argument, we show that five-fold morphology is substantially different from other abundant symmetries like three-fold, four-fold and six-fold symmetries in terms of spatial interacting elements. We develop a measuring system to determine levels of spatial organization in 2D polygons (homogeneous or heterogeneous partition of defined areas) based on principles of regularity in a morphospace. We found that spatial organization of five-fold symmetry is statistically higher than all other symmetries studied here (3 to 10-fold symmetries) in terms of spatial homogeneity. The significance of our findings is based on the statistical constancy of geometrical constraints derived from spatial organization of shapes, beyond the material or complexity level of the many different systems where pentagonal symmetry occurs. Full article