Naphthyl-functionalized acetamide derivatives: Promising agents for cholinesterase inhibition and antioxidant therapy in Alzheimer's disease.

This study presents the synthesis and characterization of a series of 13 novel acetamides. These were subjected to Ellman's assay to determine the efficacy of the AChE and BChE inhibitors. Finally, we report their antioxidant activity as an alternative approach for the search for drugs to treat AD. These studies revealed that compounds 1a-1k and 2l-2m were obtained in moderate yield. Four amides (1h, 1j, 1k, and 2l) were selective for one of the enzymes (BChE); thus, those that inhibited BChE were more active than the positive control (galantamine) and showed better IC50 values (3.30-5.03 µM). The theoretical free binding energies calculated by MM-GBSA indicated that all inhibitors were more stable than rivastigmine, and the inhibition mechanisms involved the entire active site: peripheral anionic site, oxyanion hole, acyl-binding pockets, and catalytic site. We examined the cytotoxicity of compounds 1h, 1j, 1k, and 2l in human dermal cells and found that they did not exhibit any toxic effects under the tested conditions. Additionally, these compounds, which also inhibited BChE, displayed mixed inhibition and did not exhibit hemolytic effects on human erythrocytes. Furthermore, the ABTS and DPPH assays indicated that, although none of the compounds showed activity in the DPPH assay, the EC50 values for radical trapping by the ABTS method showed that compounds 1a, 1d, 1e, and 1g had EC50 values lower than 10 µg/mL, indicating their strong radical scavenging capacity. We also report the crystal structures of compounds 1c, 1d, 1f, and 1g, which are found in monoclinic crystal systems.

Synthesis, Characterization, and Photoelectric and Electrochemical Behavior of (CH3NH3)2Zn1-xCoxBr4 Perovskites.

We report the synthesis, characterization, and photoelectric and electrochemical properties of (CH3NH3)2Zn1-xCoxBr4 (x = 0.0, 0.3, 0.5, 0.7, and 1.0) samples. X-ray powder and single-crystal diffraction confirm the formation of solid solution across the entire range. Additionally, as the cobalt concentration increases, the crystallinity of the samples decreases, as indicated by the powder diffraction patterns. All samples remain stable up to 560 K, beyond which they decompose into CH3NH3Br and the respective bromide. The semiconductor behavior of the compounds is confirmed through optical absorption measurements, and band gap values are determined by using the Tauc method from diffuse reflectance spectra. Raman spectroscopy reveals a slight redshift in all vibration modes with increasing cobalt content. Finally, photovoltaic measurements on solar cells constructed with (MA)2CoBr4 perovskite exhibit modest performance, and electrochemical measurements indicate that the compound with the composition (MA)2Zn0.3Co0.7Br4 exhibits the highest current for electrochemical water reduction during oxygen evolution.

Novel Hydrophobic Functionalized UiO-66 Series: Synthesis, Characterization, and Evaluation of Their Structural and Physical-Chemical Properties.

A novel set of four functionalized hydrophobic UiO-66-NHR series were synthesized through postsynthetic procedures, utilizing various benzoyl chlorides and UiO-66-NH2 as starting materials. This synthesis method was carried out by employing p- (1) and o-toluoyl (2), as well as 2- (3) and 4-fluorobenzoyl (4) substituents. The analysis of the resulting compounds was performed using conventional spectroscopic methods such as FT-IR and 1H NMR to quantify the conversion rate into amide. Furthermore, SEM and XPS techniques were employed for morphological and surface analysis. Finally, the evaluation of the chemical stability and contact angle using the sessile drop method was performed to evaluate the technological potential of these compounds for application in aqueous and acidic media (such as selective separation of different metals and wastewater recovery).

Insect Antifeedant Benzofurans from Pericallis Species.

In this work, we have studied the benzofurans of Pericallis echinata (aerial parts and transformed roots), P. steetzii (aerial parts and transformed roots), P. lanata (aerial parts), and P. murrayi (aerial parts and roots). This work has permitted the isolation of the new benzofurans 10-ethoxy-11-hydroxy-10,11-dihydroeuparin (10), (-)-eupachinin A ethyl ether (12), 11,15-didehydro-eupachinin A (13), 10,12-dihydroxy-11-angelyloxy-10,11-dihydroeuparin (14), 2,4-dihydroxy-5-formyl-acetophenone (15) isolated for the first time as a natural product, 11-angelyloxy-10,11-dihydroeuparin (16), and 12-angelyloxyeuparone (17), along with several known ones (1-9, 11). In addition, the incubation of the abundant component, 6-hydroxytremetone (1), with the fungus Mucor plumbeus has been studied. Benzofurans in the tremetone series (1, 1a, 2-5, 18, 18a), the euparin series (6, 7, 7a, 8-10, 14, 16), and the eupachinin-type (11, 12) were tested for antifeedant effects against the insect Spodoptera littoralis. The antifeedant compounds (1, 4, 6, 11, 12) were further tested for postingestive effects on S. littoralis larvae. The most antifeedant compounds were among the tremetone series, with 3-ethoxy-hydroxy-tremetone (4) being the strongest antifeedant. Glucosylation of 1 by its biotransformation with Mucor plumbeus gave inactive products. Among the euparin series, the dihydroxyangelate 14 was the most active, followed by euparin (6). The eupachinin-type compounds (11, 12) were both antifeedants. Compounds 4, 11, and 12 showed antifeedant effects without postingestive toxicity to orally dosed S. littoralis larvae. Euparin (6) had postingestive toxicity that was enhanced by the synergist piperonyl butoxide.

Enhancing c-Si Solar Cell Efficiency in the UV Region: Photophysical Insights into the Use of Eu3+ Complexes for Down-Shifting Layer Applications.

[Eu(3DPIQC)3] (where DPIQC = 3-(diphenyl phosphoryl)-1-isoquinolinecarboxylate), a luminescent europium complex with antenna ligands, has been carefully embedded within a polyvinyl butyral (PVB) matrix and the resulting material was used to prepare films used as luminescent down-shifting layers (LDSLs) for crystalline Si-based solar cells. The films were characterized using photoluminescence spectroscopy, atomic force spectroscopy (AFM), UV-Vis spectroscopy, and fluorescence microscopy. The AFM analysis shows films with low surface roughness, while fluorescence microscopy revealed that the Eu complex embedded in PVB assumed a spheroidal configuration, a morphology especially beneficial for optical applications. The so-obtained LDSLs were utilized as energy converters in c-Si solar cells to enhance the utilization of high-energy photons, thereby improving their overall efficiency. The determination of photovoltaic parameters carried out before and after the deposition of the LDSLs on the c-Si cells confirms a positive effect on the efficiency of the cell. The Jsc increases from 121.6 mA/cm2 to 124.9 mA/cm2, and the open circuit voltage (Voc) is found to be unrelated to the complex concentration in the films. The fill factor (FF) remains constant with the Eu concentration. The EQE curves indicate an enhancement in the performance of the photovoltaic cells within the UV region of the spectrum for all coated devices. Electrochemical impedance spectroscopy (EIS) was also carried out in order to analyze the effect of the Eu complex in the charge transfer process of the devices.

Phenoxy- and Phenylamino-Heterocyclic Quinones: Synthesis and Preliminary Anti-Pancreatic Cancer Activity.

The successful application of fragment-based drug discovery strategy for the efficient synthesis of phenoxy- or phenylamino-2-phenyl-benzofuran, -benzoxazole and -benzothiazole quinones is described. Interestingly, in the final step of the synthesis of the target compounds, unusual results were observed on the regiochemistry of the reaction of bromoquinones with phenol and aniline. A theoretical study was carried out for better understanding the factors that control the regiochemistry of these reactions. The substituted heterocyclic quinones were evaluated in vitro to determine their cytotoxicity by the MTT method in three pancreatic cancer cell lines (MIA-PaCa-2, BxPC-3, and AsPC-1). Phenoxy benzothiazole quinone 26a showed potent cytotoxic activity against BxPC-3 cell lines, while phenylamino benzoxazole quinone 20 was the most potent on MIA-PaCa-2 cells. Finally, electrochemical properties of these quinones were determined to correlate with a potential mechanism of action. All these results, indicate that the phenoxy quinone fragment led to compounds with increased activity against pancreatic cancer cells.

Structure and Properties of (CH3NH3)3Tl2Cl9: A Thallium-Based Hybrid Perovskite-Like Compound.

The new compound (CH3NH3)3Tl2Cl9 was synthesized and fully characterized. X-ray photoelectron spectroscopy and Raman spectroscopy are consistent with the crystal structure solved by single-crystal X-ray diffraction. This compound is a semiconductor with a measured band gap of Eg = 2.91 eV. It is the first thallium-based hybrid perovskite and shows remarkably high stability to ambient conditions.

Crystal Structure and Hirshfeld Surface Analysis of Acetoacetanilide Based Reaction Products.

We report an unprecedented multicomponent reaction of acetoacetanilide with malononitrile leading to a structurally novel bicyclic product (9) in a high yield. The structure has been confirmed by X-ray crystallography and comparative Hirshfeld surface analysis of 5-cyano-2-hydroxy-2-methyl-N-phenyl-4-(yridine-4-yl)-6-(thiophen-2-yl)-3,4-dihydro-2H-pyran-3-carboxamide 2, 5-cyano-2-hydroxy-2-methyl-6-oxo-N-phenyl-4-(thiophen-2-yl)piperidine-3-carboxamide 4 and 2-(8-amino-7,8a-dicyano-1-imino-4a-methyl-3-oxo-2-phenyl-1,3,4,4a,5,8a-hexahydroisoquinolin-6(2H)-ylidene)-N-phenylacetamide 9.

Promising 2,6,9-Trisubstituted Purine Derivatives for Anticancer Compounds: Synthesis, 3D-QSAR, and Preliminary Biological Assays.

We designed, synthesized, and evaluated novel 2,6,9-trisubstituted purine derivatives for their prospective role as antitumor compounds. Using simple and efficient methodologies, 31 compounds were obtained. We tested these compounds in vitro to draw conclusions about their cell toxicity on seven cancer cells lines and one non-neoplastic cell line. Structural requirements for antitumor activity on two different cancer cell lines were analyzed with SAR and 3D-QSAR. The 3D-QSAR models showed that steric properties could better explain the cytotoxicity of compounds than electronic properties (70% and 30% of contribution, respectively). From this analysis, we concluded that an arylpiperazinyl system connected at position 6 of the purine ring is beneficial for cytotoxic activity, while the use of bulky systems at position C-2 of the purine is not favorable. Compound 7h was found to be an effective potential agent when compared with a currently marketed drug, cisplatin, in four out of the seven cancer cell lines tested. Compound 7h showed the highest potency, unprecedented selectivity, and complied with all the Lipinski rules. Finally, it was demonstrated that 7h induced apoptosis and caused cell cycle arrest at the S-phase on HL-60 cells. Our study suggests that substitution in the purine core by arylpiperidine moiety is essential to obtain derivatives with potential anticancer activity.

The Positional Isomeric Effect on the Structural Diversity of Cd(II) Coordination Polymers, Using Flexible Positional Isomeric Ligands Containing Pyridyl, Triazole, and Carboxylate Fragments.

To systematically investigate the influence of the positional isomeric effect on the structures of polymer complexes, we prepared two new polymers containing the two positional isomers ethyl 5-methyl-1-(pyridin-3-yl)-1H-1,2,3-triazole-3-carboxylate (L1) and ethyl-5-methyl-1-(pyridin-3-yl)-1H-1,2,3-triazole-4-carboxylate (L2), as well as Cd(II) ions. The structures of the metal⁻organic frameworks were determined by a single crystal XRD analysis. The compound [Cd(L1)2·4H2O] (1), is a hydrogen bond-induced coordination polymer, whereas the compound [Cd(L2)4·5H2O]n (2) is a three-dimensional (3-D) coordination polymer. Their structures and properties are tuned by the variable N-donor positions of the ligand isomers. This work indicates that the isomeric effect of the ligand isomers plays an important role in the construction of the Cd(II) complexes. In addition, the thermal and luminescent properties are reported in detail.

(-)-Shikimic Acid as a Chiral Building Block for the Synthesis of New Cytotoxic 6-Aza-Analogues of Angucyclinones.

We describe the syntheses of nine new angucyclinone 6-aza-analogues, achieved through a hetero Diels-Alder reaction between the shikimic acid derivative-azadiene 13, with different naphthoquinones. The cytotoxic activity of the new synthesized compounds and five angucyclinones, previously reported, was evaluated in vitro against three cancer cell lines: PC-3 (prostate cancer), HT-29 (colon cancer), MCF-7 (breast cancer), and one non-tumoral cell line, human colon epithelial cells (CCD841 CoN). Our results showed that most 6-azadiene derivatives exhibited significant cytotoxic activities, which was demonstrated by their IC50 values (less than 10 µM), especially for the most sensitive cells, PC-3 and HT-29. From a chemical point of view, depending on the protected group of ring A and the pattern of substitution on ring D, cytotoxicity elicited these compounds, in terms of their potency and selectivity. Therefore, according to these chemical features, the most promising agents for every cancer cell line were 7a, 17, and 19c for PC-3 cells; 7a, 17, and 20 for HT-29 cells, and 19a for MCF-7 cells.

Additional Insights into the Obtusallene Family: Components of Laurencia marilzae.

The obtusallenes are a significant subset of C15-halogenated acetogenins that incorporate 12-membered cyclic ethers. We have recently reported the isolation from Laurencia marilzae of 12-epoxyobtusallene IV (1) and its related α,ß-unsaturated carboxylate ester (2), both of special biogenetic relevance. Here we describe the final step of our study, the isolation of three new analogues (3-5), among these, the first bromopropargylic derivative (3) of this class of macrocyclic C15-acetogenins. The structures were elucidated by analysis of NMR and X-ray data. 12-Epoxyobtusallene IV (1), its new isomer 4, and known obtusallene IV (6) were evaluated for their apoptosis-inducing activities in a human hepatocarcinoma cell line.

Oxidative phenylamination of 5-substituted 1-hydroxynaphthalenes to N-phenyl-1,4-naphthoquinone monoimines by air and light "on water".

A number of N-phenyl-1,4-naphthoquinone monoimines 6-10 were prepared by on-water oxidative phenylamination of 1,5-dihydroxynaphthalene (1) and 5-acetylamino-1-hydroxynaphthalene (5) with oxygen-substituted phenylamines under aerobic conditions and either solar or green LED radiation, in the presence of rose bengal as singlet oxygen sensitizer. As compared to the conventional oxidative phenylamination procedures, this novel synthetic method offers the advantage of aerobic conditions "on water" instead of hazardous oxidant reagents currently employed in aqueous alcoholic media.

Crystal structure, quantum chemical insights, and molecular docking studies of Naryl-2-(N-disubstituted) acetamide compounds: potential inhibitors for neurodegenerative enzymes.

The increase in and concern about neurodegenerative diseases continue to grow in an increasingly long-lived world population. Therefore, the search for new drugs continues to be a priority for medicinal chemistry. We present here the synthesis of a series of compounds with acetamide nuclei. Their structures were established using UV-Visible, NMR, HRMS and IR techniques. Furthermore, we report the crystal structures that were obtained from compounds 5a-5d by X-ray diffraction. The compounds were evaluated as potential inhibitors of the monoxidase enzymes; A (MAO-A) and B (MAO-B), and cholinesterases; acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) through in silico studies using the induced fit docking (IFD) method and binding free energy (ΔGbind) calculations by the MMGBSA method. Interestingly, compounds 5b, 5c and 5d showed much better ΔGbind than the reference drug Zonisamide. Compound 5c is the best in the series, which indicates a potential selective affinity of our compounds against MAO-B, which could be a promising finding in the search for new drugs for Parkinson's disease treatment. The acetamide crystal exhibits moderate NLO properties suggesting that it could be considered a potential candidate for application in nonlinear optical devices.

Nonlinear optical and spectroscopic properties, thermal analysis, and hemolytic capacity evaluation of quinoline-1,3-benzodioxole chalcone.

This article describes the synthesis, characterization (1H NMR, 13C NMR, FT-IR, HRMS and XRD), UV-Vis absorption and fluorescence spectra, theoretical analysis, evaluation of nonlinear optical properties (NLO), thermal analysis and determination of the hemolytic capacity of the compound (E)-N-(4-(3-(benzo[d][1,3]dioxol-5-yl)acryloyl)phenyl)quinoline-3-carboxamide (5). Radiological findings showed that compound 5 crystallized in space group Pca21. Furthermore, theoretical DFT studies performed with the B3LYP and M062X functionals showed good agreement with the experimental results and provided valuable information on the molecular and electronic structure, reactivity, polarizability, and kinematic stability of the compound. Besides, compound 5 did not show any hemolytic effect on human erythrocytes and exhibited strong NLO properties. The TG and DTA thermograms of quinoline-chalcone (5) revealed a multi-step thermal decomposition process with a total mass loss of 83.2%, including water content loss. The DTA curves exhibited endothermic peaks corresponding to decomposition steps, melting point, and thermochemical transition. Additionally, exothermic peaks in the DTA thermograms align with significant mass loss, confirming the compound's melting point and water content, as validated by X-ray diffraction analysis. These results contribute to the advancement of research on compounds with NLO properties and offer a promising avenue for the development of substances potentially applicable to optical devices in the biomedical field.

High Performance of Mn2O3 Electrodes for Hydrogen Evolution Using Natural Bischofite Salt from Atacama Desert: A Novel Application for Solar Saline Water Splitting.

Solar saline water splitting is a promising approach to sustainable hydrogen production, harnessing abundant solar energy and the availability of brine resources, especially in the Atacama Desert. Bischofite salt (MgCl2·6H2O) has garnered significant attention due to its wide range of industrial applications. Efficient hydrogen production in arid or hyper arid locations using bischofite solutions is a novel and revolutionary idea. This work studied the electrochemical performance of Mn2O3 electrodes using a superposition model based on mixed potential theory and evaluated the superficial performance of this electrode in contact with a 0.5 M bischofite salt solution focusing on the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) that occur during saline water splitting. The application of the non-linear superposition model provides valuable electrochemical kinetic parameters that complement the understanding of Mn2O3, this being one of the novelties of this work.

First-Principles Calculations of Magnetite (Fe3O4) above the Verwey Temperature by Using Self-Consistent DFT + U + V.

In this report, we have used the DFT + U + V approach, an extension of the DFT + U approach that takes into account both on-site and intersite interactions, to simulate structural, magnetic, and electronic properties together with the Fe and O K-edge XAS spectra of Fe3O4 above the Verwey temperature (Tv). Moreover, we compared the simulated XAS spectra with experimental XAS data. We examined both orthogonalized and nonorthogonalized atomic orbital projectors and compared DFT + U + V to DFT, DFT + U, and HSE as a hybrid functional. It is noteworthy that, despite the widespread use of the same Hubbard U value for Feoct and Fetet at the DFT + U level in the literature, the HP code identified two distinct values for them using the Hubbard approaches (DFT + U and DFT + U + V). The resulting Hubbard U and V parameters are strongly dependent on the chosen orbital projectors. This study demonstrates how DFT + U + V can improve the structural, magnetic, and electronic properties of Fe3O4 compared to approximate DFT and DFT + U. In this context, DFT + U + V supports the half-metallic character of the bulk crystal Fe3O4 above Tv, since the Fermi level is found in the t2g band with a Feoct down-spin. Thus, the observations in the current study emphasize the significance of intersite interactions in the theoretical analysis of Fe3O4 above the Tv.

Crystal structure and Hirshfeld surface analysis of 1-(2-amino-4-methyl-1,3-thia-zol-5-yl)ethan-1-one.

In the title compound, C6H8N2OS, all atoms except for the methyl H atoms are coplanar, with a maximum deviation of 0.026 (4) Å. In the crystal, pairs of mol-ecules are linked by N-H⋯N hydrogen bonds, forming R 2 2(8) ring motifs. Dimers are connected by N-H⋯O hydrogen bonds, forming layers parallel to the (102) plane. Consolidating the mol-ecular packing, these layers are connected by C-H⋯π inter-actions between the center of the 1,3-thia-zole ring and the H atom of the methyl group attached to it, as well as C=O⋯π inter-actions between the center of the 1,3-thia-zole ring and the O atom of the carboxyl group. According to a Hirshfeld surface study, H⋯H (37.6%), O⋯H/H⋯O (16.8%), S⋯H/H⋯S (15.4%), N⋯H/H⋯N (13.0%) and C⋯H/H⋯C (7.6%) inter-actions are the most significant contributors to the crystal packing.

Crystal structure and Hirshfeld surface analysis of 2-amino-5-{(1E)-1-[(carbamo-thioyl-amino)-imino]eth-yl}-4-methyl-1,3-thia-zol-3-ium chloride monohydrate.

In the hydrated title salt, C7H12N5S2 +·Cl-·H2O, the asymmetric unit comprises one 2-amino-5-{(1E)-1-[(carbamo-thioyl-amino)-imino]-eth-yl}-4-methyl-1,3-thia-zol-3-ium cation, one chloride anion and one water mol-ecule of crystallization. The cation is nearly flat (r.m.s. deviation of non-H atoms is 0.0814 Å), with the largest deviation of 0.1484 (14) Šobserved for one of the methyl C atoms. In the crystal, the cations are linked by O-H⋯Cl, N-H⋯Cl, N-H⋯O, N-H⋯S and C-H⋯S hydrogen bonds, forming a tri-periodic network. The most important contributions to the crystal packing are from H⋯H (35.4%), S⋯H/H⋯S (24.4%), N⋯H/H⋯N (8.7%), Cl⋯H/H⋯Cl (8.2%) and C⋯H/H⋯C (7.7%) inter-actions.

Piperonal chalcone derivative incorporating the pyrazolo[3,4-b]pyridine moiety; crystal structure, spectroscopic characterization and quantum chemical investigations.

A single crystal of a piperonal chalcone derivative was obtained, fully characterized, and crystallized by a slow evaporation technique. The synthesized compound was characterized by UV-Visible, FT-IR, HRMS, 1H NMR, and 13C NMR spectroscopic studies and X-ray crystallography, revealing that the crystal belongs to a triclinic crystal system with a P1̄ space group, Z = 2. In the present work, we focus on molecular modeling studies such as Hirshfeld surface analysis, energy framework calculations, frontier molecular orbital analysis, natural bond orbital analysis, and NLO properties of a π-conjugate system combining the chalcone and the pyrazole[3,4-b]pyridine scaffolds to describe the in-depth structural analysis thereof. Good agreement was found between the calculated results and experimental data. In addition, Hirshfeld surface analysis of the crystal structure showed that the intermolecular stabilization in the crystal packing comes mainly from H⋯H bond interactions. The chalcone crystal exhibits significant NLO properties suggesting that it could be considered a potential candidate for application in nonlinear optical devices.