B-axis Direction Research Articles

Novel Benzohydrazide Derivative as a Potential Anticarcinogenic Agent for Breast Cancer: Synthesis, Crystal Structure, In Vitro and In Silico Assessments

Polycyclic aromatic compounds (PACs) are a class of organic molecules known for their significant biological activity, including anticancer properties. These compounds often interact with biological macromolecules, making them crucial in the development of new therapeutic agents. In this study, we report a new benzohydrazide derivative, (E)-4-(hexyloxy)-N'-(1-(naphthalen-2-yl)ethylidene)benzohydrazide (2), which incorporates a naphthalene ring, a typical PAC, as a core structural element. The structure of the compound was analyzed using FTIR, 1H NMR, 13C NMR and elemental analysis. Moreover, single crystal X-ray crystallography studies demonstrated that the compound adapted monoclinic crystal system with C 2/c space group. In the crystal structure, the intermolecular N–H···O hydrogen bonds link the molecules into infinite chains along the b-axis direction. The dominant interactions formed in the crystal packing were found to be hydrogen bonding and van der Waals interactions according to the Hirshfeld surface (HS) analysis. The evaluation of energy frameworks showed that stabilization of the compound was dominated by dispersion energy contribution. The anticancer activity of the compound was tested by employing several cellular assays. The compound showed strong anticancer effects, with IC50 values of 85 µM for MCF7 cells and 115 µM for MDA-MB-231 cells, indicating dose-dependent suppression of cell viability, migration, and colony formation. Computational analyses indicated favorable binding of compound 2 to ERRγ and predicted good oral availability of the generated compound. Pathway analysis using KEGG pathways identified significant enrichment in pathways related to cancer. These results highlight the compound's promise as a potential treatment option for breast cancer, prompting further exploration in future studies.

Synthesis, crystal structure and Hirshfeld surface analysis of 2-{4-[(2-chlorophenyl)methyl]-3-methyl-6-oxopyridazin-1-yl}-N-phenylacetamide

In the title molecule, C20H18ClN3O2, the 2-chlorophenyl group is disordered to a small extent [occupancies 0.875 (2)/0.125 (2)]. The phenylacetamide moiety is nearly planar due to a weak, intramolecular C—H...O hydrogen bond. In the crystal, N—H...O hydrogen bonds and π-stacking interactions between pyridazine and phenyl rings form helical chains of molecules in the b-axis direction, which are linked by C—H...O hydrogen bonds and C—H...π(ring) interactions. A Hirshfeld surface analysis was performed, which showed that H...H, C...H/H...C and O...H/H...O interactions to dominate the intermolecular contacts in the crystal.

Loading Self-Assembly Siliceous Zeolites for Affordable Next-Generation Wearable Artificial Kidney Technology.

The global demand for dialysis among patients with end-stage kidney disease has surpassed the capacity of public healthcare, a trend that has intensified. While wearable artificial kidney (WAK) technology is seen as a crucial solution to address this demand, there is an urgent need for both efficient and renewable toxin-adsorbent materials to overcome the long-standing technological challenges in terms of cost, device size, and sustainability. In this study, we employed screening experiments for adsorbent materials, multimodal characterization, and Monte Carlo adsorption simulations to identify a synthetic self-assembly silicalite-1 zeolite that exhibits highly ordered crystal arrays along the [010] face (b-axis) direction, demonstrating exceptional adsorption capabilities for small molecular toxins such as creatinine and urea associated with uremia. Moreover, this metal-free, cost-effective, easily synthesized, and highly efficient toxin adsorbent could be regenerated through calcination without compromising the performance. The simulated toxin adsorption experiments and comprehensive biocompatibility verification position it as an auxiliary adsorbent to reduce dialysate dosages in WAK devices as well as a potential adsorbent for small-molecule toxins in dialysis. This work is poised to propel the development of next-generation WAK devices by providing siliceous adsorbent solutions for small-molecule toxins.

Crystal structure and Hirshfeld surface analyses, crystal voids, intermolecular interaction energies and energy frameworks of 3-benzyl-1-(3-bromopropyl)-5,5-diphenylimidazolidine-2,4-dione

The title molecule, C25H23BrN2O2, adopts a cup shaped conformation with the distinctly ruffled imidazolidine ring as the base. In the crystal, weak C—H...O hydrogen bonds and C—H...π(ring) interactions form helical chains of molecules extending along the b-axis direction that are linked by additional weak C—H...π(ring) interactions across inversion centres. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H...H (51.0%), C...H/H...C (21.3%), Br...H/H...Br (12.8%) and O...H/H...O (12.4%) interactions. The volume of the crystal voids and the percentage of free space were calculated to be 251.24 Å3 and 11.71%, respectively, showing that there is no large cavity in the crystal packing. Evaluation of the electrostatic, dispersion and total energy frameworks indicate that the stabilization is dominated by the dispersion energy.

Machine Learning for Predicting Ultralow Thermal Conductivity and High ZT in Complex Thermoelectric Materials.

Efficient and precise calculations of thermal transport properties and figures of merit, alongside a deep comprehension of thermal transport mechanisms, are essential for the practical utilization of advanced thermoelectric materials. In this study, we explore the microscopic processes governing thermal transport in the distinguished crystalline material Tl9SbTe6 by integrating a unified thermal transport theory with machine learning-assisted self-consistent phonon calculations. Leveraging machine learning potentials, we expedite the analysis of phonon energy shifts, higher-order scattering mechanisms, and thermal conductivity arising from various contributing factors, such as population and coherence channels. Our finding unveils an exceptionally low thermal conductivity of 0.31 W m-1 K-1 at room temperature, a result that closely correlates with experimental observations. Notably, we observe that the off-diagonal terms of heat flux operators play a significant role in shaping the overall lattice thermal conductivity of Tl9SbTe6, where the ultralow thermal conductivity resembles that of glass due to limited group velocities. Furthermore, we achieve a maximum ZT value of 3.17 in the c-axis orientation for p-type Tl9SbTe6 at 600 K and an optimal ZT value of 2.26 in the a-axis and b-axis direction for n-type Tl9SbTe6 at 500 K. The crystalline Tl9SbTe6 not only showcases remarkable thermal insulation but also demonstrates impressive electrical properties owing to the dual-degeneracy phenomenon within its valence band. These results not only elucidate the underlying reasons for the exceptional thermoelectric performance of Tl9SbTe6 but also suggest potential avenues for further experimental exploration.

New polymorph of N-benzoyl-morpholine-4-carbothioamide with ten crystallographically independent molecules in the asymmetric unit: Crystal structure, Hirshfeld surface analysis and Density functional theory calculations

Herein, facile synthesis, single crystal X-ray diffraction (SC-XRD) structure, Hirshfeld surface (HS) analysis and Density functional theory (DFT) calculations of N-benzoyl-morpholine-4-carbothioamide 5(a) are presented. Hence, the synthesized compound, C12H14N2O2S 5(a), crystallizes in monoclinic crystal system having space group of P 21 with a = 22.2226 (9) Å, b = 11.7520 (3) Å, c = 24.9361 (8) Å, α = 90°, β = 111.054 (4)°, γ = 90°, Z = 20 and V = 6077.6 (4) Å3. The asymmetric unit of 5(a) contains ten crystallographically independent molecules, where the morpholine and benzene rings are in respective chair and planar conformations. In the crystal structure, some of the intermolecular, N—H···O, C—H···O and C—H···S, hydrogen bonds link the molecules into a 2D-network parallel to (010), enclosing R22(10) and R22(24) ring motifs, when viewed down the b-axis direction. Furthermore, contribution of the remaining hydrogen bonds consolidates a 3D-architecture. Similarly, HS analysis clarified the importance of hydrogen atom contacts with the major contributions of H…H (46.7 %), H…S/S…H (21.1 %), H…C/C…H (16.5 %), and H…O/O…H (12.5 %). Thus, hydrogen bond and van der Waals interactions play major role in the crystal packing. Finally, optimum molecular structure of compound 5(a) was related to the experimentally determined one employing DFT at B3LYP/6–311++G(d,p) level. Subsequently, the geometry of the optimized and most stable conformation turned out to be complementary with the crystal structure. The computational calculation of compound 5(a) revealed the molecule to be chemically hard in nature with high energy intrinsic reaction pathway. The associated band gap predicted compound 5(a) to be a wide band gap material. The intrinsic reaction pathway predicts hard-core behavior of the molecule.

Lattice Matching and Microstructure of the Aromatic Amide Fatty Acid Salts Nucleating Agent on the Crystallization Behavior of Recycled Polyethylene Terephthalate.

To solve the decrease in the crystallization, mechanical and thermal properties of recycled polyethylene terephthalate (rPET) during mechanical recycling, the aromatic amide fatty acid salt nucleating agents Na-4-ClBeAmBe, Na-4-ClBeAmGl and Na-4-ClAcAmBe were synthesized and the rPET/nucleating agent blend was prepared by melting blending. The molecular structure, the thermal stability, the microstructure and the crystal structure of the nucleating agent were characterized in detail. The differential scanning calorimetry (DSC) result indicated that the addition of the nucleating agent improved the crystallization temperature and accelerated the crystallization rate of the rPET. The nucleation efficiencies (NE) of the Na-4-ClBeAmBe, Na-4-ClBeAmGl and Na-4-ClAcAmBe were increased by 87.2%, 87.3% and 41.7% compared with rPET which indicated that Na-4-ClBeAmBe and Na-4-ClBeAmGl, with their long-strip microstructures, were more conducive to promoting the nucleation of rPET. The equilibrium melting points (Tm0) of rPET/Na-4-ClBeAmBe, rPET/Na-4-ClBeAmGl and rPET/Na-4-ClAcAmBe were increased by 11.7 °C, 18.6 °C and 1.9 °C compared with rPET, which illustrated that the lower mismatch rate between rPET and Na-4-ClBeAmGl (0.8% in b-axis) caused Na-4-ClBeAmGl to be the most capable in inducing the epitaxial crystallization and orient growth along the b-axis direction of the rPET. The small angle X-ray diffraction (SAXS) result proved this conclusion. Meanwhile, the addition of Na-4-ClBeAmGl caused the clearest increase in the rPET of its flexural strength and heat-distortion temperature (HDT) at 20.4% and 46.7%.

Crystal structure and Hirshfeld surface analysis of 1-[6-bromo-2-(4-fluoro-phen-yl)-1,2,3,4-tetra-hydroquinolin-4-yl]pyrrolidin-2-one.

In the title compound, C19H18BrFN2O, the pyrrolidine ring adopts an envelope conformation. In the crystal, mol-ecules are linked by inter-molecular N-H⋯O, C-H⋯O, C-H⋯F and C-H⋯Br hydrogen bonds, forming a three-dimensional network. In addition, C-H⋯π inter-actions connect mol-ecules into ribbons along the b-axis direction, consolidating the mol-ecular packing. The inter-molecular inter-actions in the crystal structure were qu-anti-fied and analysed using Hirshfeld surface analysis.

Structural characterization of the supramolecular complex between a tetraquinoxaline-based cavitand and benzonitrile

The structural characterization is reported of the supramolecular complex between the tetraquinoxaline-based cavitand 2,8,14,20-tetrahexyl-6,10:12,16:18,22:24,4-O,O′-tetrakis(quinoxaline-2,3-diyl)calix[4]resorcinarene (QxCav) with benzonitrile. The complex, of general formula C84H80N8O8·2C7H5N, crystallizes in the space group P\overline{1} with two independent molecules in the asymmetric unit, displaying very similar geometrical parameters. For each complex, one of the benzonitrile molecules is engulfed inside the cavity, while the other is located among the alkyl legs at the lower rim. The host and the guests mainly interact through weak C—H...π, C—H...N and dispersion interactions. These interactions help to consolidate the formation of supramolecular chains running along the crystallographic b-axis direction.

Crystal structure and Hirshfeld surface analysis of 3,3′-[ethane-1,2-diylbis(oxy)]bis(5,5-dimethylcyclohex-2-en-1-one) including an unknown solvate

The title molecule, C18H26O4, consists of two symmetrical halves related by the inversion centre at the mid-point of the central –C—C– bond. The hexene ring adopts an envelope conformation. In the crystal, the molecules are connected into dimers by C—H...O hydrogen bonds with R 2 2(8) ring motifs, forming zigzag ribbons along the b-axis direction. According to a Hirshfeld surface analysis, H...H (68.2%) and O...H/H...O (25.9%) interactions are the most significant contributors to the crystal packing. The contribution of some disordered solvent to the scattering was removed using the SQUEEZE routine [Spek (2015). Acta Cryst. C71, 9–18] in PLATON. The solvent contribution was not included in the reported molecular weight and density.

Synthesis, crystal structure and Hirshfeld surface analysis of 1-[3-(2-oxo-3-phenyl-1,2-dihydroquinoxalin-1-yl)propyl]-3-phenyl-1,2-dihydroquinoxalin-2-one

In the title compound, C31H24N4O2, the dihydroquinoxaline units are both essentially planar with the dihedral angle between their mean planes being 64.82 (4)°. The attached phenyl rings differ significantly in their rotational orientations with respect to the dihydroquinoxaline planes. In the crystal, one set of C—H...O hydrogen bonds form chains along the b-axis direction, which are connected in pairs by a second set of C—H...O hydrogen bonds. Two sets of π-stacking interactions and C—H...π(ring) interactions join the double chains into the final three-dimensional structure.

Anisotropic sensing based on single ReS2 flake for VOCs discrimination

Selective and sensitive detection of volatile organic compounds (VOCs) holds paramount importance in real-world applications. This study proposes an innovative approach utilizing a single ReS2 field-effect transistor (FET) characterized by distinct in-plane anisotropy, specifically tailored for VOC recognition. The unique responses of ReS2, endowed with robust in-plane anisotropic properties, demonstrate significant difference along the a-axis and b-axis directions when exposed to four kinds of VOCs: acetone, methanol, ethanol, and IPA. Remarkably, the responses of ReS2 were significantly magnified under ultraviolet (UV) illumination, particularly in the case of acetone, where the response amplified by 10–15 times and the detection limit decreasing from 70 to 4 ppm compared to the dark conditions. Exploiting the discernible variances in responses along the a-axis and b-axis under both UV and dark conditions, the data points of acetone, ethanol, methanol and IPA gases were clearly separated in the principal component space without any overlap through principal component analysis, indicating that the single ReS2 FET has a high ability to distinguish various gas species. The exploration of anisotropic sensing materials and light excitation strategies can be applied to a broad range of sensing platforms based on two-dimensional materials for practical applications.

Ethidium benzoate methanol monosolvate.

In the title salt solvate (systematic name: 8-amino-5-ethyl-6-phenyl-phenanthridin-5-ium benzoate methanol monosolvate), C21H20N3 +·C6H5CO2 -·CH3OH, two ethidium cations, C21H20N3 +, dimerize about a twofold axis through π-π inter-actions [inter-centroid separation = 3.6137 (4) Å]. The benzoate anions are connected through hydrogen bonding with the -NH2 groups of the ethidium cations and the -OH group of the MeOH mol-ecule. The MeOH mol-ecule also accepts a hydrogen bond from the -NH2 group of the ethidium cation. The result is a one-dimensional hydrogen-bonded chain along the b-axis direction.

Crystal structure and Hirshfeld surface analysis of dimethyl 4'-bromo-3-oxo-5-(thio-phen-2-yl)-3,4,5,6-tetra-hydro-[1,1'-biphen-yl]-2,4-di-carboxyl-ate.

In the title compound, C20H17BrO5S, mol-ecules are connected by inter-molecular C-H⋯S hydrogen bonds with R 2 2(10) ring motifs, forming ribbons along the b-axis direction. C-H⋯π inter-actions consolidate the ribbon structure while van der Waals forces between the ribbons ensure the cohesion of the crystal structure. According to a Hirshfeld surface analysis, H⋯H (40.5%), O⋯H/H⋯O (27.0%), C⋯H/H⋯C (13.9%) and Br⋯H/H⋯Br (11.7%) inter-actions are the most significant contributors to the crystal packing. The thio-phene ring and its adjacent di-carboxyl-ate group and the three adjacent carbon atoms of the central hexene ring to which they are attached were refined as disordered over two sets of sites having occupancies of 0.8378 (15) and 0.1622 (15). The thio-phene group is disordered by a rotation of 180° around one bond.

Magnetoelastic Coupling Evidence by Anisotropic Crossed Thermal Expansion in Magnetocaloric RSrCoFeO6 (R = Sm, Eu) Double Perovskites.

Double perovskite oxides, characterized by their tunable magnetic properties and robust interconnection between the lattice and magnetic degrees of freedom, present an enticing foundation for advanced magnetic refrigeration materials. Herein, we delve into the influence of rare-earth elements on RSrCoFeO6 (R = Sm, Eu) disordered double perovskites by examining their structural, electronic, magnetic, and magnetocaloric properties. Temperature-dependent synchrotron X-ray diffraction analysis confirmed the stability of the orthorhombic phase (Pnma) across a wide temperature range. X-ray photoemission spectroscopy revealed that both Sm and Eu are in the 3+ state, whereas multiple states for Co2+/3+ and Fe3+/4+ are identified. The magnetic investigation and magnetocaloric effect (MCE) analysis brought to light the presence of a long-range antiferromagnetic (AFM) order with a second-order phase transition (SOPT) in both samples. The maximum magnetic entropy change ΔSMmax was approximately 0.9 J/kg K for both samples at applied field 0-7 T, manifesting prominently above Neel temperatures TN ≈ 93 K (Sm) and 84 K (Eu). Nevertheless, different relative cooling powers (RCP) of 112.6 J/kg (Sm) and 95.5 J/kg (Eu) were observed. A detailed analysis of the temperature-dependent lattice parameters shed light on a distinct magnetocaloric effect across the magnetic transition temperature, unveiling an anisotropic thermal expansion [αV = 1.41 × 10-5 K-1 (Sm) and αV = 1.54 × 10-5 K-1 (Eu)] wherein the thermal expansion axial ratio αbSm/αbEu = 0.61 became lower with increasing temperature, which suggests that the Eu sample experiences a greater thermal expansion in the b-axis direction. At the atomic bonding level, the evidence for magnetoelastic coupling around the magnetic transition temperatures TN was found through the anomalies along the average Co/Fe-O bond distance, formal valence, octahedral distortion, as well as an anisotropic lattice expansion.

Crystal structure and Hirshfeld surface analysis of ethyl 2-(7-chloro-3-methyl-2-oxo-1,2-di-hydro-quinoxalin-1-yl)acetate.

The quinoxaline moiety in the title mol-ecule, C13H13ClN2O3, is almost planar (r.m.s. deviation of the fitted atoms = 0.033 Å). In the crystal, C-H⋯O hydrogen bonds plus slipped π-stacking and C-H⋯π(ring) inter-actions generate chains of mol-ecules extending along the b-axis direction. The chains are connected by additional C-H⋯O hydrogen bonds. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (37.6%), H⋯O/O⋯H (22.7%) and H⋯Cl/Cl⋯H (13.1%) inter-actions.

Crystal structure and Hirshfeld surface analysis of 4-oxo-3-phenyl-2-sulfanyl-idene-5-(thio-phen-2-yl)-3,4,7,8,9,10-hexa-hydro-2H-pyrido[1,6-a:2,3-d']di-pyrimidine-6-carbo-nitrile.

In the title compound, C21H15N5OS2, mol-ecular pairs are linked by N-H⋯N hydrogen bonds along the c-axis direction and C-H⋯S and C-H⋯O hydrogen bonds along the b-axis direction, with R 2 2(12) and R 2 2(16) motifs, respectively, thus forming layers parallel to the (10) plane. In addition, C=S⋯π and C≡N⋯π inter-actions between the layers ensure crystal cohesion. The Hirshfeld surface analysis indicates that the major contributions to the crystal packing are H⋯H (43.0%), C⋯H/H⋯C (16.9%), N⋯H/H⋯N (11.3%) and S⋯H/H⋯S (10.9%) inter-actions.

(2,2′-Bipyridine-κ2 N,N′)(4,4′-dimethoxy-2,2′-bipyridine-κ2 N,N′)palladium(II) bis(trifluoromethanesulfonate)

In the title complex salt, [Pd(C10H8N2)(C12H12N2O2)](CF3SO3)2, the palladium(II) atom is fourfold coordinated by two chelating ligands, 2,2′-bipyridine and 4,4′-dimethoxy-2,2′-bipyridine, in a distorted square-planar environment. In the crystal, weak π–π stacking interactions between the 2,2′-bipyridine rings [centroid-to-centroid distances = 3.8984 (19) Å] and between the 4,4′-dimethoxy-2,2′-bipyridine rings [centroid-to-centroid distances = 3.747 (18) Å] contribute to the alignment of the complex cations in columns parallel to the b-axis direction.

N-(2,4-Difluorophenyl)-2-fluorobenzamide

The title compound N-(2,4-difluorophenyl)-2-fluorobenzamide (Fo24) was synthesized in high yield (1.09 g; 87%) using standard synthetic procedures from the condensation reaction of 2-fluorobenzoyl chloride with 2,4-difluoroaniline. Crystals of Fo24 were grown from CH2Cl2 at room temperature. The Fo24 crystal structure was determined using single-crystal X-ray diffraction methods at 294 (1) K in space group Pn (No. 7). Fo24 is the second regular tri-fluorinated benzamide with the formula C13H8F3N1O1 to be reported and contrasts with the more common difluorinated and tetra-fluorinated analogues. In Fo24, both aromatic rings are effectively coplanar with an interplanar angle of 0.7(2)°. The central amide group plane is oriented by 23.04(18)° and 23.69(17)° from both aromatic rings, forming an intramolecular contact with an ortho-F12 atom with H1⋯F12 = 2.12(4) Å. The primary hydrogen bonds are 1D amide–amide interactions that form along the b-axis direction. In addition, weaker C-H⋯F/O interactions are noted: a R22(12) synthon involving two C-H, a N-H and two C-F groups, with C-F⋯C ring–ring stacking contacts completing the interactions.

Synthesis, crystal structure and Hirshfeld surface analysis of 2-({5-[(naphthalen-1-yl)methyl]-4-phenyl-4H-1,2,4-triazol-3-yl}sulfanyl)-1-(4-nitrophenyl)ethanone

The title compound, C27H20N4O3S, crystallizes in the monoclinic system, space group P21/n, with Z = 4. The global shape of the molecule is determined by the orientation of the substituents on the central 4H-1,2,4-triazole ring. The nitrophenyl ring, phenyl ring, and naphthalene ring system are oriented at dihedral angles of 82.95 (17), 77.14 (18) and 89.46 (15)°, respectively, with respect to the triazole ring. The crystal packing features chain formation in the b-axis direction by S...O interactions. A Hirshfeld surface analysis indicates that the highest contributions to surface contacts arise from contacts in which H atoms are involved.