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The antiparallel π-stacked dimer of compound 6 (left) presenting a large dimerization energy (ΔE5 = −11.2 kcal mol−1) and confirming its relevance in the solid state of compound 6. 3D binding mode of 6 (right) docked in the catalytic domain of urease.

OBJECTIVE To evaluate the reticulorumen pH of beef feedlot steers throughout the feeding period and to assess the association between the respective durations that the reticulorumen pH was ≤ 5.6 (subacute ruminal acidosis) and ≤ 5.2 (acute ruminal acidosis) and liver abscess severity. ANIMALS 59 feedlot steers (mean body weight, 349.5 kg). PROCEDURES On day 0, each steer was orally administered an electronic bolus that monitored the reticulorumen pH every 10 minutes for 150 days. Steers were transitioned from a starter to intermediate ration on day 8 (transition 1) and from the intermediate to finish ration on day 19 (transition 2). The ration carbohydrate and megacalorie contents increased with each transition. During each transition, the lower megacalorie ration was fed at the 8:00 AM feeding and the higher megacalorie ration was fed at the 2:00 PM feeding for 3 days before the higher megacalorie ration was fed extensively. Steers were sent to slaughter after 182 days; each carcass was assessed for liver abscesses. RESULTS The diurnal reticulorumen pH pattern was characterized by a peak at 7:00 AM and nadir at 8:00 PM. The mean percentages of time that the reticulorumen pH was ≤ 5.6 and ≤ 5.2 were more than 10-fold greater during transition 1, compared with during transition 2, and were significantly greater for steers with extensive liver abscesses than for steers without extensive liver abscesses. CONCLUSIONS AND CLINICAL RELEVANCE Efforts to minimize the duration that the reticulorumen pH is ≤ 5.6 might mitigate liver abscess formation in feedlot cattle.

Systemic advocacy has long been seen as an important tool for advancing the rights of people with intellectual disabilities. The New South Wales Council for Intellectual Disability has been a leadi...

In the present report, we describe the synthesis of the amide derivative, N-(2,4-dichlorophenyl)-1-naphthamide, 3, via a facile chemical route. The title compound was isolated in 86% yield. The structure of compound 3 was established using spectroscopic methods and X-ray crystallography. In the crystal structure of 3, supramolecular assembly is dominated by classical N–H⋯O hydrogen bonding and C–Cl … π halogen bonding interactions which were examined in detail using several theoretical methods and DFT calculations. The optimized geometric parameters of compound 3 were calculated using density functional theory (DFT/B3LYP and DFT/M06-2X) quantum chemical methods with the 6-311++G(d,p) basis set using the crystallographic coordinates. Additionally, fragments contributing to the HOMO and LUMO molecular orbitals were investigated at the same level of theory. The nature and various types of intermolecular interactions in the crystal structure were also realized by Hirshfeld surface analysis. The biological properties such as anti-Alzheimer's potential were also assessed which reveals strong acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) inhibitory effects. Compound 3 was 16-fold more active inhibitor of acetylcholinesterase compared to neostigmine with an IC50 value of 1.044 ± 0.76 μM in addition to 21-fold strong inhibition against butyrylcholinesterase. The in vitro bioactivity results were further strengthened by the molecular docking analysis revealing the presence of several important interactions with the active site residues from cholinesterase (AChE & BChE) enzymes.

A series of four closely related 1,2,4-triazole-3-thione (1-4) compounds was obtained by heterocyclization of thiosemicarbazides under basic catalytic conditions. The crystal structures of the 4-alkyl-5-(substituted-phenyl)-2H-1,2,4-triazole-3(4H)-thione derivatives [4-alkyl = 4-ethyl-5-phenyl (1), 4-hexyl-5-phenyl (2), 4-hexyl-5-p-tolyl (3), and 4-ethyl-5-(2,4,6-trimethoxyphenyl) (4)] have been determined. PIXEL lattice energy calculations revealed that dispersion components make the major contributions, with the coulombic terms also contributing significantly to the total energy. Interaction energies for the inversion dimers involving N–H⋯S=C hydrogen bonds indicate a dominant contribution to packing stabilization coming from the coulombic energy component. Hirshfeld surfaces and 2D-fingerprint plots allowed us to visualize different intermolecular contacts and their relative contributions to the total surface in each compound. The comprehensive analysis of the crystal packing and the energetic features demonstrate the key role of the R 2 2 ( 8 ) supramolecular synthon of the type (···HNCS)2 in the solid state structures of these 1,2,4-triazole-3-thiones.

The title salt, C10H21N2O+·C7H12NO4S−, comprises a 3-methacrylamido-N,N,N-trimethylpropan-1-aminium cation and a 2-acrylamido-2-methylpropane-1-sulfonate anion. The salt crystallizes with two unique cation–anion pairs in the asymmetric unit of the orthorhombic unit cell. The crystal studied was an inversion twin with a 0.52 (4):0.48 (4) domain ratio. In the crystal, the cations and anions stack along the b-axis direction and are linked by an extensive series of N—H...O and C—H...O hydrogen bonds, forming a three-dimensional network. Hirshfeld surface analysis was carried out on both the asymmetric unit and the two individual salts. The contribution of interatomic contacts to the surfaces of the individual cations and anions are also compared.

In the title compound, the asymmetric unit comprises an N,N,N-trimethyl-1-(4-vinylphenyl)methanaminium cation and a 4-vinylbenzenesulfonate anion, C12H18N+·C8H7O3S−. The salt has a polymerizable vinyl group attached to both the cation and the anion. The methanaminium and vinyl substituents on the benzene ring of the cation subtend angles of 86.6 (3) and 10.5 (9)° to the ring plane, while the anion is planar excluding the sulfonate O atoms. The vinyl substituent on the benzene ring of the cation is disordered over two sites with a refined occupancy ratio of 0.542 (11):0.458 (11). In the crystal, C—H...O hydrogen bonds dominate the packing and combine with a C—H...π(ring) contact to stack the cations and anions along the a-axis direction. Hirshfeld surface analysis of the salt and of the individual cation and anion components is also reported.

A new Co(II) complex with formula [Co(tptz)Cl2]·2H2O (tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine) has been synthesized and characterized by X-ray crystallography, elemental analyses and spectroscopic methods. It was then supported on modified Fe3O4 nanoparticles using tetraethylorthosilicate (TEOS) and (3-aminopropyl)trimethoxysilane (APTMS) and designated as a Fe3O4@SiO2@APTMS@complex nanocatalyst. The prepared nanocatalyst was characterized by means of FT-IR, Raman, XPS, EDX, XRD, VSM, SEM and TEM studies. The catalytic activity of the [Co(tptz)Cl2]·2H2O complex and Fe3O4@SiO2@APTMS@complex designated as catalysts A and B was used for oxidation of activated secondary alkanes such as fluorene, diphenyl methane, ethylbenzene, cyclooctane and adamantane. Observation of 39–99% conversions and 27–100% selectivities toward the corresponding ketones as well as the heterogeneity and reusability of the catalyst B seem promising.

The present study describes the synthesis of five new hydrazinyl-sulfonamide derivatives incorporating linear and branched alkyl chains. An efficient and straightforward synthetic approach was used to achieve these sulfonamide compounds in good yields. The synthesized compounds were fully characterized by spectroscopic methods and single crystal X-ray diffraction analysis. Structural analysis of U-shaped hydrazinyl-sulfonamides reveals the presence of remarkable similarities in their crystal packing. The supramolecular architectures of these molecules were stabilized by classical hydrogen bonds and C–H⋯O interactions. Furthermore, the U-shaped conformation observed in the solid state of all the compounds has been analyzed using DFT calculations, AIM analysis and the NCI plot index. It reveals the existence of two intramolecular interactions, which are NH⋯π and unconventional π–π interactions involving the hydrazido π-system.

The mol­ecular and crystal structure of bis­[benzyl 2-(heptan-4-yl­idene)hydrazine-1-carboxyl­ate-κ2 N 2,O]bis­(thio­cyanato)­nickel(II) is reported. Hirshfeld surface and simultaneous TGA–DTA analyses are also described, The title centrosymmetric NiII complex, [Ni(NCS)2(C15H22N2O2)2], crystallizes with one half mol­ecule in the asymmetric unit of the monoclinic unit cell. The complex adopts an octa­hedral coordination geometry with two mutually trans benzyl-2-(heptan-4-yl­idene)hydrazine-1-carboxyl­ate ligands in the equatorial plane with the axial positions occupied by N-bound thio­cyanato ligands. The overall conformation of the mol­ecule is also affected by two, inversion-related, intra­molecular C—H⋯O hydrogen bonds. The crystal structure features N—H⋯S, C—H⋯S and C—H⋯N hydrogen bonds together with C—H⋯π contacts that stack the complexes along the b-axis direction. The packing was further explored by Hirshfeld surface analysis. The thermal properties of the complex were also investigated by simultaneous TGA–DTA analyses.

Increasingly life is lived online, yet little is known about the actual nature and extent of online content that people view due to the difficulty of recording real time exposure. This includes people’s exposure to harmful commodity marketing. This study aimed to develop a methodology to assess the nature and extent of exposure to, and engagement with, unhealthy commodity marketing and other public health harms online, particularly children’s exposure. A convenience sample of 16 young adult participants (aged 21–29) recorded their device usage for 2 days using Zoom software. Data were coded and analysed to assess the nature and extent of marketing for alcohol, gambling, junk food and smoking products. Four focus groups were conducted with participants to explore their data collection and coding experiences, and results assessed using thematic analysis. The study found that, with some modifications, this method was feasible for gathering real-time objective data from the online world that can be analysed for a range of public health harms, including marketing of unhealthy commodities. Larger studies are recommended to build global evidence for public health action in the online world.

Five dinuclear organotin(IV) complexes, R4Sn2La (R = Me, Ph) and R4Sn2Lb (R = Me, Ph and Bu) have been synthesized from reaction of R2SnCl2 with 2,4′- and 2,2′-bis-substituted diphenylamine arylidene hydrazones, H4La and H4Lb, respectively. The synthesized compounds have been investigated by elemental analysis and IR, 1H NMR, and 119Sn NMR spectroscopy. The structures of Me4Sn2Lb and Ph4Sn2Lb have been also confirmed by X-ray crystallography. The results show that the fully deprotonated bis-hydrazone ligand provides two contiguous ONO tridentate domains that coordinate to the two SnR2 moieties in the enolate form. Each tin atom in the complexes adopts a five-coordinate environment. Ligands and complexes showed no antibacterial activity against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. However, both ligands and their methyl complexes were found to degrade DNA, an observation that adapt with the mode of interaction suggested by molecular docking.

Three coumarin and 8-hydroxyquinoline hybrids each linked by a methylene bridge were synthesized under Pechmann cyclisation conditions and crystals were grown to study their structural features. All three compounds, 7-methyl-4-((quinolin-8-yloxy)methyl)-2H-chromen-2-one, 2a, 5,7-dimethyl-4-((quinolin-8-yloxy)methyl)-2H-chromen-2-one, 2b and 6-chloro-4-((quinolin-8-yloxy)methyl)-2H-chromen-2-one, 2c, crystallised in the monoclinic crystal system. In each molecule, a quinoline ring system binds to a chromen-2-one sub-unit through an O–CH2 bridge with the molecules distinguished by the substitution pattern on the benzene ring of the chromen-2-one ring system. All three molecules are reasonably planar. The crystal packing in these molecules is dominated by inversion dimer formation involving both non-classical hydrogen bonds and extensive offset π···π stacking interactions. For 2b and 2c, C–H···π contacts are also found. Inversion dimer formation and π···π contacts are particularly important in the crystal packing of three coumarin and 8-hydroxyquinoline hybrids reported here.

To explore the operational role of noncovalent interactions in supramolecular architectures with designed topologies, a series of solid-state structures of 2- and 4-formylphenyl 4-substituted benzenesulfonates was investigated. The compounds are 2-formylphenyl 4-methylbenzenesulfonate, C14H12O4S, 3a, 2-formylphenyl 4-chlorobenzenesulfonate, C13H9ClO4S, 3b, 2-formylphenyl 4-bromobenzenesulfonate, C13H9BrO4S, 3c, 4-formylphenyl 4-methylbenzenesulfonate, C14H12O4S, 4a, 4-formylphenyl 4-chlorobenzenesulfonate, 4b, C13H9ClO4S, and 4-formylphenyl 4-bromobenzenesulfonate, C13H9BrO4S, 4c. The title compounds were synthesized under basic conditions from salicylaldehyde/4-hydroxybenzaldehydes and various aryl sulfonyl chlorides. Remarkably, halogen-bonding interactions are found to be important to rationalize the solid-state crystal structures. In particular, the formation of O...X (X = Cl and Br) and type I X...X halogen-bonding interactions have been analyzed by means of density functional theory (DFT) calculations and characterized using Bader's theory of `atoms in molecules' and molecular electrostatic potential (MEP) surfaces, confirming the relevance and stabilizing nature of these interactions. They have been compared to antiparallel π-stacking interactions that are formed between the arylsulfonates.

A series of mononuclear cobalt and nickel complexes of the types [M(NCS)2(L1)2], M = Co 1 or Ni 2, [M(NCS)2(L2)2]·nH2O, M = Co (n = 0) 3 or Ni (n = 2) 4 and [M(NCS)2(L3)2], M = Co 5 or Ni 6, where L1 = benzyl 2-(cyclobutanylidene)hydrazinecarboxylate, L2 = benzyl 2-(cyclopentanylidene)hydrazinecarboxylate and L3 = benzyl 2-(cyclohexanylidene)hydrazinecarboxylate, were synthesized by template reactions of the metal nitrates, ammonium thiocyanate and benzyl carbazate (bc) with cyclobutanone (cb), cyclopentanone (cp) or cyclohexanone (ch). These compounds have been characterized by elemental analysis, infrared, electronic absorption and 1H NMR spectroscopies, together with single crystal X-ray diffraction. Crystal structures of the complexes 1, 3–6 showed that the Schiff base ligands coordinate to the metal ions via the azomethine nitrogen and carbonyl oxygen atoms. In each case the two thiocyanate ligands coordinate through their nitrogen atoms resulting in complexes with a six coordinate octahedral geometry. The thermal stability of the complexes was investigated by TG-DTA and all of the compounds (1–6) undergo endothermic followed by exothermic decomposition processes to form the respective metal oxides. The antibacterial activity of the cobalt(II) and nickel(II) complexes was examined against Gram positive and Gram negative bacteria at concentrations between 40 and 80 μg mL−1. The binding interaction of human serum albumin (HSA) with compounds 1–6 was explored by multi-spectroscopic techniques and docking studies revealed the complexes bind to HSA through hydrophobic interactions. The cytotoxic activity of all of the compounds was evaluated against the K-562 (leukemia cell line) by MTT assays and, remarkably, all of the complexes were found to show good activity towards this cancer cell line. DAPI (4′,6-diamidino-2-phenylindole) staining assay further confirmed that complexes induced leukemia cancer cell death by an apoptosis mechanism.

Amide derivatives have gained considerable attention because of their extensive range of biological activities and pharmaceutical applications. The current paper presents the synthesis of N, N′-(ethane-1,2-diyl) bis (3-methylbenzamide), (I), its molecular and crystal structure and an evaluation of its likely biological activity, including cytotoxicity (LD50 = 37.21 μg/ml) and antileishmanial activity (IC50 = 5.77 μg/ml). Moreover, a docking simulation was used to determine the possible interaction sites of the compound (I) with TryR, an enzyme involved in the redox metabolism of the leishmania parasite. Docking computations demonstrate that the compound established prominent binding interactions with the key residues of the TryR and possess the potential to effectively inhibit the catalytic activities of the enzyme. Thus the results suggest that this compound can serve as a potential scaffold for the treatment of leishmaniasis and deserves further development.

The new ternary complexes, ZnLL′ [L = 1-((2-hydroxynaphthalen-1-yl)methylene)-4-phenylthiosemicarbazide and L′ = imidazole (1), 2, 2′-bipyridine (2) and 2-methyimidazole (3)], Zn2L2L′ [L′ = 4, 4′-bipy (4)] and CuLL′ [L′ = 2, 2′-bipy (5)] have been synthesized by the reaction of a metal(II) acetate salt with the thiosemicarbazone and in presence of heterocyclic bases as auxiliary ligands. The synthesized compounds were investigated by elemental analysis and IR, 1H NMR, and 13C NMR spectroscopy and complex 5 was structurally characterized by X-ray crystallography. The results indicate the thiosemicarbazone doubly deprotonated and coordinates to metal through the thiolate sulfur, imine nitrogen and phenolic oxygen atoms. The nitrogen atom(s) of the auxiliary ligand complete the coordination sphere. Complex 4 is binuclear with 4, 4′-bipy acting as a bridging ligand. The structure of 5 is a distorted square pyramid with one of the bipyridine nitrogen atoms in the apical position. This compound creates an inversion dimer in solid state by intermolecular hydrogen bonds of N H⋯S type. The in vitro antibacterial activity of the synthesized compounds were evaluated against Gram-positive (B. subtilis and S. aureus) and Gram-negative (P. aeruginosa) bacteria and is compared to that of standard antibacterial drugs. All complexes exhibit good inhibitory effects and are significantly more effective than the parent ligand.