Sulfide Derivatives Research Articles

Synthesis, Crystal Structure, and Optical and Magnetic Properties of the New Quaternary Erbium Telluride EuErCuTe3: Experiment and Calculation.

This paper reports for the first time on a new layered magnetic heterometallic erbium telluride EuErCuTe3. Single crystals of the compound were obtained from the elements at 1120 K using CsI as a flux. The crystal structure of EuErCuTe3 was solved in the space group Cmcm (a = 4.3086(3) Å, b = 14.3093(9) Å, and c = 11.1957(7) Å) with the KZrCuS3 structure type. In the orthorhombic structure of erbium telluride, distorted octahedra ([ErTe6]9-) form two-dimensional layers (Er(Te1)2/2e(Te2)4/2k-)∞2, while distorted tetrahedra ([CuTe4]7-) form one-dimensionally connected substructures (Cu(Te1)2/2e(Te2)2/1t5-∞1) along the [100] direction. The distorted octahedra and tetrahedra form parallel two-dimensional layers (CuErTe32-∞2) between which Eu2+ ions are located in a trigonal-prismatic coordination environment (EuTe610-). The trigonal prisms are connected by faces, forming chains (Eu(Te1)2/2(Te2)4/22-∞1) along the [100] direction. Regularities in the variations in structural parameters were established in the series of erbium chalcogenides (EuErCuCh3 with Ch = S, Se, and Te) and tellurides (EuLnCuTe3 with Ln = Gd, Er, and Lu). Ab-initio calculations of the crystal structure, phonon spectrum, and elastic properties of the compound EuErCuTe3 were performed. The types and wavenumbers of fundamental modes were determined, and the involvement of ions in the IR and Raman modes was assessed. The experimental Raman spectra were interpreted. The telluride EuErCuTe3 at temperatures below 4.2 K was ferrimagnetic, as were the sulfide and selenide derivatives (EuErCuCh3 with Ch = S and Se). Its experimental magnetic characteristics were close to the calculated ones. The decrease in the magnetic phase transition temperature in the series of the erbium chalcogenides was discovered.

Visible‐Light Mediated Tandem Oxidation–Organocatalyzed Aromatic C−S Bond Functionalization: Synthesis of 2‐(Benzo[b]thiophen‐2‐yl)benzenesulfonamide Derivatives

AbstractHerein, we demonstrated a visible light mediated tandem oxidation–organo catalyzed C−S bond functionalization protocol for the cleavage of aromatic C−S bond. The investigation encompassed the functionalization of C−S bonds within sulfones, sulfoxides, and aliphatic sulfide derivatives. However, the process of functionalizing the C−S bond in aromatic sulfides remains uncertain. The presented protocol demonstrates the C−S bond functionalization on benzo[b]benzo[4,5]thieno[2,3‐d]thiophene derivative and amines including primary and secondary amines as well. A radical mediated mechanism was proposed for the tandem oxidation–organocatalyzed C−S bond functionalization protocol.

Drug Repurposing of ACT001 to Discover Novel Promising Sulfide Prodrugs with Improved Safety and Potent Activity for Neutrophil-Mediated Antifungal Immunotherapy.

Neutrophil-mediated immunotherapy is a promising strategy for treating Candida albicans infection due to its potential in dealing with drug-resistant events. Our previous study found that ACT001 exhibited good antifungal immunotherapeutic activity by inhibiting PD-L1 expression in neutrophils, but its strong cytotoxicity and high BBB permeability hindered its antifungal application. To address these deficiencies, a series of novel sulfide derivatives were designed and synthesized based on a slow-release prodrug strategy. Among these derivatives, compound 16 exhibited stronger inhibition of PD-L1 expression, less cytotoxicity to neutrophils, and lower BBB permeability than ACT001. Compound 16 also significantly enhanced neutrophil-mediated antifungal immunity in C. albicans infected mice, with acceptable pharmacokinetic properties and good oral safety. Moreover, pharmacological mechanism studies demonstrated that ACT001 and compound 16 reduced PD-L1 expression in neutrophils by directly targeting STAT3. Briefly, this study provided a novel prototype compound 16 which exhibited great potential in neutrophil-mediated antifungal immunotherapy.

Novel Meta-Diamide Compounds Containing Sulfide Derivatives Were Designed and Synthesized as Potential Pesticides.

The meta-diamide (m-diamide) insecticide, Broflanilide, was characterized by its high efficiency, low toxicity and lack of cross-resistance with traditional GABA receptors. In accordance with the principles of drug molecular design, easily derivable sulfur with diverse bioactivities was introduced while leading with the parent Broflanilide. Twelve novel m-diamide target compounds containing sulfide derivatives were synthesized through exploration guided by the literature. Their structures were confirmed by melting points, 1H NMR, 13C NMR and HRMS. Insecticidal activity assessments revealed that most target compounds A-D exhibited 100% lethality against Plutella xylostella (P. xylostella) and Aphis craccivora Koch (A. craccivora) at 500 mg·L-1. Notably, for P. xylostella, compounds C-2, C-3, C-4 and D-2 demonstrated 60.00-100.00% insecticidal activity even at a concentration as low as 0.625 mg·L-1. As determined by structure-activity relationship (SAR) analysis, compounds with R1 = CH3 and R2 = Br (B-1, C-2 and D-2) and sulfoxide compound C-3 contained 100.00% lethality against A. craccivora at 500 mg·L-1, surpassing the lethality when leading with the parent Broflanilide in terms of efficacy. Consequently, it can be inferred that the sulfoxide compound (C-3) requires further investigation as a potential active molecule for new insecticides. These explorations provide valuable references for future research on the synthesis and insecticidal activities of sulfide-containing m-diamide compounds.

Structural Relationships to Efficacy for Prazole-Derived Antivirals.

Here, an in vitro characterization of a family of prazole derivatives that covalently bind to the C73 site on Tsg101 and assay their ability to inhibit viral particle production is presented. Structurally, increased steric bulk on the 4-pyridyl of the prazole expands the prazole site on the UEV domain toward the β-hairpin in the Ub-binding site and is coupled to increased inhibition of virus-like particle production in HIV-1. Increased bulk also increased toxicity, which is alleviated by increasing flexibility. Further, the formation of a novel secondary Tsg101 adduct for several of the tested compounds and the commercial drug lansoprazole. The secondary adduct involved the loss of the 4-pyridyl substituent to form an irreversible species, with implications for increasing the half-life of the active species or its specificity toward Tsg101 UEV. It is also determined that sulfide derivatives display effective viral inhibition, presumably through cellular sulfoxidation, allowing for delayed conversion within the cellular environment, and identify SARS-COV-2 as a target of prazole inhibition. These results open multiple avenues for the design of prazole derivatives for antiviral applications.

CoS2/Ni3S4 − N − C heterostructured electrode materials derived from Prussian-blue analogs for supercapacitors

Prussian blue analogues (PBAs) have the advantages of dependable electrochemical performance and long service life when used as energy storage materials because of their face-centered cubic structure. In this case, the appropriate metal sulfide derivatives were created using NiCo prussian blue analogue nano units as a precursor, which took on the precursor's structural traits. More reaction sites are exposed by this distinctive structural design, and a little quantity of nitrogen-doped carbon is produced, which improves charge transfer. The box-like structure has a buffer effect on the stress of the active material during charging and discharging, and the heterostructure of mixed metal sulfides and nitrogen-doped carbon composite cubic can both significantly increase the electrode's electrochemical capacitance and cycling stability. The CoS2/Ni3S4–N–C offers a capacitance of 817C g−1 at 3 A g−1 and 556C g−1 at 20 A g−1. The CoS2/Ni3S4–N–C electrode also has outstanding cycle stability (98.2 % capacitance retention after 10,000 cycles). An asymmetric supercapacitor (ASC) device made of CoS2/Ni3S4–N–C with activated carbon electrodes exhibits exceptional cycle stability. With a retention rate of 103.7 % after 10,000 cycles at 10 A g−1 and an energy density of 40 Wh kg−1. Using density functional theory (DFT), the electron characteristics of Co2NiO4 and CoS2/Ni3S4–N–C are compared. CoS2/Ni3S4–N–C detected more state densities at the Fermi level, which causes more charge to accumulate. This shows that the heterojunction's electron conductivity is significantly greater than the oxide's, and ultimately leads to quicker reaction kinetics.

Ether, sulfide and sulfone derivatives of cinnamaldehyde: Insights into synthesis, structural elucidation and solvatochromism

Symmetric ether, sulfide and sulfone derivatives based on Schiff base functionalized group (3a-c) were synthesized via classical condensation of 4,4′-diaminodiphenyl precursors (1a-c) and cinnamaldehyde (2) in methanol at ambient reaction settings. The compounds were characterized using CHN, UV–Vis, FTIR, and 1H- and 13CNMR . The origin of absorption spectra was chased using Time-Dependent Density-Functional Theory (TD-DFT) in order to figure out the electronic transitions. The compounds exhibited almost a similar electronic potential as displayed by the molecular electrostatic potential. The energy gap of these materials was extracted from the computational approaches, showing ΔE of 3.778, 3.724, and 4.014 eV respectively for 3a, 3b, and 3c. These values were further harnessed to estimate the global reactivity parameters. Moreover, the electrophilic and nucleophilic points were examined through surface analysis of the optimized structures via DFT simulations. Such investigations support the compounds’ molecular structures via common noncovalent interaction, like hydrogen bonding and non-classical CH…π forces. Experimental and computational findings were in a respectable agreement to display that only compound 3c possesses the ability of altering its maximum absorption under different solvent conditions. A substantial shifting of the maximum absorption was noticed with ethyl alcohol at λmax = 321 nm, referring to a 32 nm of blue shift in respect to acetic acid, which could be responsible for the partial protonation of the sulfone group.

Synthesis and investigation of new indole-containing vinyl sulfide derivatives: In silico and in vitro studies for potential therapeutic applications.

Indoles featuring organosulfur compounds serve as privileged structural scaffolds in various biologically active compounds. This study investigates the biological properties of five synthetic sulphenyl vinyl indoles (3 a-e) using both in silico and in vitro methods. Computational analyses employing Swiss ADME and Molinspiration software reveal the remarkable inhibitory activity of compound 3 d against proteases and kinases (scores of 0.18 and 0.06, respectively). Furthermore, it demonstrates the ability to modulate ionic and G protein-coupled receptors (scores: -0.06 and 0.31, respectively) and serves as a ligand for nuclear receptors (score 0.15). In vitro investigations highlight the compounds' efficacy in countering ABTS+ radical attacks and reducing lipid peroxidation levels. Particularly noteworthy is the superior efficacy of compounds 3 a, 3 b, and 3 e in DPPH (EC50 3 a: 268.5 μM) and TEAC assays (EC50 3 a: 49.9 μM; EC50 3 b: 133.4 μM, and EC50 3 e: 84.9 μM), as well as TBARS levels. Compound 3 c significantly reduces acetylcholinesterase activity, positioning itself as a noteworthy enzyme inhibitor. This study emphasizes the versatile biological potential of synthetic indole derivatives, suggesting their applicability for therapeutic purposes.

Photocatalyzed intermolecular C–N bond formation for the synthesis of imidazo[1,2-a]pyridines

Photocatalyzed intermolecular CN bond formation of 2-aminopyridines with ketones choosing NH4I as the catalyst was explored, affording imidazo[1,2-a]pyridines under milder conditions. The reaction induced by sunlight is able to provide the corresponding products. Our catalytic system is suitable for the reaction of 2-aminopyridine, ketones and sulfide derivatives. Furthermore, the protocol is also applicable for the reaction of 2-aminopyridine and sulfoxonium ylide.

Novel potentiometric carbon paste electrodes for trace detection of uranyl(II) ions in petroleum water samples

Two different phosphine sulfide derivatives have been explored as electroactive materials to modify carbon paste electrodes for the accurate detection of uranyl(II) ions. The optimized electrodes based on triphenylphosphine sulfide (L1) and triisobutylphosphine sulfide (L2) responded linearly towards uranyl(II) ions within the range of 1.0 × 10-7 – 1.0 × 10-1 M. Good sensitivity (29.32 ± 0.53 and 27.99 ± 0.61 mV per decade) and detection capability up to 7.9 × 10-8 and 1.0 × 10-7 M uranyl(II) were observed for L1- and L2-based electrodes, respectively. The effect of solution temperature on uranyl(II) determination was studied within 10–60 °C. Selectivity studies showed that the electrodes are capable to discriminate uranyl(II) ions over a large number of possible co-existing inorganic interferents. Moreover, they exhibited speedy response, thermal and long-term stability, and significant reusability. Petroleum water samples spiked with uranyl(II) ions were analyzed utilizing the developed electrodes where good recovery and accuracy were achieved, demonstrating the real-life applicability of the developed electrodes.

Highly selective C3-sulfenylation and C3-selenylation of 3-iodo-5-arylpyrazolo[1,5-a]pyrimidin-7-amine in water

Highly selective C3-sulfenylation and C3-selenylation of 3-iodo-5-aryl pyrazolo[1,5-a]pyrimidin-7-amine in water was established to provide a green and effective method for the construction of diverse C3-aryl sulfide and C3-aryl selenide derivatives. This regioselective C3-sulfenylation and C3-selenylation protocol proceeds efficiently in the presence of phase transfer catalyst PEG-400 with moderate to good yields. The strategy offers the advantages of green reaction conditions, a wide range of substrates, and gram-scale synthesis.

Characterization of a late bronze age “Kohl Box” from the Cilician Plain using FTIR and GC–MS

The subject of this study is a Late Bronze Age kohl box decorated with zoomorphic motifs recovered from Tepebağ Höyük (Cilician Plain, Turkey) and a quantity of black pigment that remained at the bottom of this box tubes. In ancient times, this kind of black pigments was used for the treatment of eye diseases and to reduce the brightness of the sun by applying it intensively around the eyes, rather than for its aesthetic and ornamental function. According to the spectroscopic results, the analyzed sample contains mostly lead-based minerals, which is mainly galena, a lead sulfide derivative known to be used as a kohl in ancient times. The chromatographic results indicated that there may be decomposed organic residues (ORs) in the sample, which may be from oil or fat. When the archaeological and archaeometric data are interpreted together, it is concluded that the powder compound within the sample, in accordance with the existing literature, is kohl and thus, the artifact may be a kohl box imported from Egypt.

Solar Light Driven H2O2 Production and Selective Oxidations Using a Covalent Organic Framework Photocatalyst Prepared by a Multicomponent Reaction

AbstractA chemically stable 2D microporous COF (PMCR‐1) was synthesized via the multicomponent Povarov reaction. PMCR‐1 exhibits a remarkable and long‐term stable photocatalytic H2O2 production rate (60 h) from pure and sea water under visible light. The H2O2 production is markedly enhanced when benzyl alcohol (BA) is added as reductant, which is also due to a strong π–π interaction of BA with dangling phenyl moieties in the COF pores introduced by the multicomponent Povarov reaction. Motivated by the concomitant BA oxidation to benzaldehyde during H2O2 formation, the photocatalytic oxidation of various organic substrates such as benzyl amine and methyl sulfide derivatives was investigated. It is shown that the well‐defined micropores of PMCR‐1 enable size‐selective photocatalytic oxidation.

Solar Light Driven H2 O2 Production and Selective Oxidations Using a Covalent Organic Framework Photocatalyst Prepared by a Multicomponent Reaction.

A chemically stable 2D microporous COF (PMCR-1) was synthesized via the multicomponent Povarov reaction. PMCR-1 exhibits a remarkable and long-term stable photocatalytic H2 O2 production rate (60 h) from pure and sea water under visible light. The H2 O2 production is markedly enhanced when benzyl alcohol (BA) is added as reductant, which is also due to a strong π-π interaction of BA with dangling phenyl moieties in the COF pores introduced by the multicomponent Povarov reaction. Motivated by the concomitant BA oxidation to benzaldehyde during H2 O2 formation, the photocatalytic oxidation of various organic substrates such as benzyl amine and methyl sulfide derivatives was investigated. It is shown that the well-defined micropores of PMCR-1 enable size-selective photocatalytic oxidation.

Introducing Structural Diversity: Fe2(MoO4)3 Immobilized in Chitosan Films as an Efficient Catalyst for the Selective Oxidation of Sulfides to Sulfones

AbstractThis work reports how the immobilization of Fe2(MoO4)3 in chitosan films affects the oxidation reaction of sulfide derivatives to sulfates in the dark, resulting in good yields and excellent selectivity. As demonstrated, a variety of substituted sulfides were tolerated even in the presence of oxidative‐sensitive functional groups, leading to a regioselective application of the catalyst under mild reaction conditions and guaranteeing its reuse for at least 6 cycles without losing its catalytic performance. Specifically, films containing 1 mg of Fe2(MoO4)3 per ml of chitosan showed a yield and selectivity of 99 %. The key success of the selective oxidation was associated with the presence of the hydroxyl radical, ⋅OH, and the Fe3+/Fe2+ Fenton‐like process. As a proof of concept, the selective oxidation of sulfides to the corresponding sulfones was performed to demonstrate the synergistic effect between Fe2(MoO4)3 and chitosan. This work offers a design strategy for efficient catalysts that may extend to other semiconductors and oxidation processes.

Thioether-substituted Benzimidazolium Salts: Synthesis, Characterization, Crystal Structure, and Their Inhibitory Properties Against Acetylcholinesterase and Xanthine Oxidase

The sulfurous compounds are known as organosulfur, which has been associated with numerous biological activities in both natural products and synthetic organic compounds. In this work, we present the synthesis of a series of 4-(methylthio)benzyl substituted benzimidazolium salts. All compounds were characterized using NMR (1H and 13C) and FTIR spectroscopic methods as well as an elemental analysis technique. The molecular and crystal structures of the compound 1a were determined by X-ray crystallography revealing that the compound crystallized in the trigonal space group R-3. Enzyme inhibition studies demonstrated that a new series of sulfurous compounds precursors were highly potent inhibitors for xanthine oxidase (XO) and acetylcholinesterase (AChE) enzyme. The IC50 values were found in the range of 0.548 ± 0.033 to 0.725 ± 0.043 µM for XO promising strategy for the treatment from gout disease, while IC50 values were found in the range 0.813 ± 0.076 to 1.149 ± 0.072 µM toward AChE as the key enzyme promising strategy for the treatment of neurological disorders such as Alzheimer's disease (AD). Furthermore, pharmacodynamics studies prove the binding interaction patterns, structural orientations and drug potential of sulfide derivatives in the binding sites of xanthine oxidase (XO) and acetylcholinesterase (AChE) enzymes. Potential inhibitors (compounds 1d-f) were compared with standard compounds allopurinol (for XO) and donepezil (for AChE). Compared to the positive compound of target XO, the 4-vinylbenzyl group of potential compound 1f and the 4-methylbenzyl group of compound le more effectively formed electrostatic and hydrophobic interactions with the target's interaction site. While donepezil as standard compound interacts only at the peripheral anionic site of AChE, the related compounds interact with both regions (PAS and CAS sites) of the same target. These compounds were placed at the active sites of the respective targets by molecular docking method using AutoDock software. Binding energy, binding modes and interaction types were used to evaluate the series of 4-(methylthio)benzyl substituted benzimidazolium salts's ability to bind to each target. Binding energy lower than zero remarks spontaneous binding, and equal and/or lower than -5 kcal/mol remarks good binding. Besides XO, the related compounds show higher activity against the AChE enzyme. They can also be analyzed as strong candidate compounds in biological studies of related enzymes.

Discovery of urea-based pleuromutilin derivatives as potent gram-positive antibacterial agents

There is an urgent need to discover new antibacterial drugs and provide new treatment options for clinical antimicrobial resistance (AMR) pathogen infections. Inspired by the structural insights from analyzing the co-crystal structure of lefamulin with the ribosomes of S. aureus, a series of novel pleuromutilin derivatives of phenylene sulfide incorporated with urea moiety were designed and synthesized. The structure–activity relationship (SAR) study revealed that derivatives with urea in the meta position of phenylene sulfide had optimal antibacterial activities in vitro. Among them, 21h was the most potent one against Methicillin-resistant Staphylococcus aureus (MRSA) and clinical AMR Gram-positive bacteria with minimum inhibitory concentrations (MICs) in the range of 0.00195–0.250 μg/mL. And it possessed low resistance frequency, prolonged Post-Antibiotic Effect and the capability to overcome lefamulin-induced resistance. Furthermore, 21h exhibited potent antibacterial activity in vivo in both the thigh infection model and trauma infection model, representing a promising lead for the development of new antibiotics against Gram-positive pathogens, especially for AMR bacteria.

A safety-catch protecting group strategy compatible with Boc-chemistry for the synthesis of peptide nucleic acids (PNAs).

Peptide Nucleic Acids (PNAs) are an intriguing class of synthetic biomolecules with great potential in medicine. Although PNAs could be considered analogs of oligonucleotides, their synthesis is more like that of peptides. In both cases, a Solid-Phase Synthesis (SPS) approach is used. Herein, the advantage using Boc as a temporal protecting group has been demonstrated to be more favored than Fmoc. In this context, a new PNA SPS strategy has been developed based on a safety-catch protecting group scheme for the exocyclic nitrogen of the side-chain bases and the linker. Sulfinyl (sulfoxide)-containing moieties are fully stable to the trifluoroacetic acid (TFA) used to remove the Boc group, but they can be reduced to the corresponding sulfide derivatives, which are labile in the presence of TFA. The efficiency of this novel synthetic strategy has been demonstrated in the synthesis of the PNA pentamer H-PNA(TATCT)-βAla-OH.

Facile synthesis of telechelic poly(phenylene sulfide)s by means of electron-deficient aromatic sulfonium electrophiles.

We report the facile synthesis of telechelic poly(phenylene sulfide) (PPS) derivatives bearing functional groups at both termini. α,ω-Dihalogenated dimethyl-substituted PPS were obtained in high yield with a high degree of end-functionalization by using soluble poly(2,6-dimethyl-1,4-phenylenesulfide) (PMPS) and 4,4'-dihalogenated diphenyl disulfide (X-DPS, X = Cl, Br) as a precursor and an end-capping agent, respectively. Further end-functionalization is achieved through cross-coupling reactions; particularly, the Kumada-Tamao cross-coupling reaction of bromo-terminated telechelic PMPS and a vinylated Grignard reagent afforded end-vinylated PMPS with thermosetting properties. This synthetic approach can be applied to the preparation of various aromatic telechelic polymers with the desired structures and functionalities.

Preparation and characterization of a Cu complex based on 5-aminoisophthalic acid as a recyclable metal-organic framework for C-S cross coupling

A new heterogeneous and recyclable catalyst was designed by immobilizing Cu based on 5-aminoisophthalic acid ([CuAIPA·2H2O]n) as a metal-organic framework (MOF). This catalyst used for the synthesis of diphenyl sulfide derivatives by C-S cross coupling reaction between thiophenols and various iodobenzenes in DMF solvent. The prepared catalyst was characterized with analytical techniques such as FT-IR, XRD, SEM, EDX, BET and ICP-AES analysis. [CuAIPA·2H2O]n MOF catalyst displayed good to excellent yields for catalytic C-S cross coupling reactions in comparison to other catalysts. The recoverability and reusability related to this catalyst were checked by a simple filtration and retaining its activity after several cycles.