Acetyl Derivatives Research Articles

Approach to extended polycyclic aromatic hydrocarbons by benzannulation and intramolecular cyclization; improvement of the reaction conditions by microwave irradiation

The extended π-conjugated compounds 1–8 were synthesized by the benzannulation of the corresponding alkyne derivatives followed by Pd-catalyzed intramolecular cyclization. For the Pd-catalyzed intramolecular cyclization, microwave irradiation reduced the amount of the Pd catalyst and the reaction time. Moreover, this protocol can be achieved to prepare the extended and twisted π-conjugated molecule 19, having anthracene, helicene, and picene skeletons.

Surface Functionalization of Gold Nanoparticles Using Alkyne Derivatives: Applications in Chemical Sensing.

Colloidal gold nanoparticles (AuNPs) are important nanomaterials for chemical sensing and therapeutics. For their application, it is vital to develop a reliable and robust surface functionalization method that can be applied to diverse functional molecules and offer better stability under harsh biological conditions. Currently, thiol (SH) is the most commonly used functional group for forming stable covalent bonds with AuNPs. However, thiolated molecules typically require complicated preparation procedures, are susceptible to oxidation, and are not compatible with many electrophiles and reducing groups. In this study, we report that surface functionalization of AuNPs can be achieved using alkyne derivatives, which exhibit several advantages over classical thiolation and peptide-bond methods, including straightforward preparation of alkyne derivatives, rapid and simple conjugation in buffers and complex media, higher conjugation efficiency, long-term stability, and resistance to decomposition under harsh conditions. Several alkynylated biotin and fluorescein derivatives are prepared, and the alkynylated-AuNPs are characterized using a lateral flow assay, gel electrophoresis, and spectroscopy techniques to investigate the conjugation efficiencies, size distributions, protein interaction properties, and binding mode of the Au-alkyne bond. We also demonstrate that alkynylated-AuNPs can be used for the sensitive detection of hydrogen peroxide and streptavidin proteins.

Cellulose Acetates in Hydrothermal Carbonization: A Green Pathway to Valorize Residual Bioplastics.

Bioplastics possess the potential to foster a sustainable circular plastic economy, but their end-of-life is still challenging. To sustainably overcome this problem, this work proposes the hydrothermal carbonization (HTC) of residual bioplastics as an alternative green path. The focus is on cellulose acetate - a bioplastic used for eyewear, cigarette filters and other applications - showing the proof of concept and the chemistry behind the conversion, including a reaction kinetics model. HTC of pure and commercial cellulose acetates was assessed under various operating conditions (180-250 °C and 0-6 h), with analyses on the solid and liquid products. Results show the peculiar behavior of these substrates under HTC. At 190-210 °C, the materials almost completely dissolve into the liquid phase, forming 5-hydroxymethylfurfural and organic acids. Above 220 °C, intermediates repolymerize into carbon-rich microspheres (secondary char), achieving solid yields up to 23 %, while itaconic and citric acid form. A comparison with pure substrates and additives demonstrates that the amounts of acetyl groups and derivatives of the plasticizers are crucial in catalyzing HTC reactions, creating a unique environment capable of leading to a total rearrangement of cellulose acetates. HTC can thus represent a cornerstone in establishing a biorefinery for residual cellulose acetate.

Stabilization and Surface Functionalization of Palladium Disulfide Nanoparticles with Acetylene Derivatives.

Metal chalcogenide nanoparticles have been attracting extensive attention in diverse fields. Traditionally these nanoparticles are stabilized by organic ligands such as thiols and amines involving nonconjugated core-ligand interfacial interactions. In the present study, a facile wet-chemistry method is described for the synthesis of palladium disulfide (PdS2) nanoparticles capped with acetylene derivatives. Spectroscopic and electrochemical measurements suggest that conjugated Pd-C≡ linkages are formed at the core-ligand interface and facilitate electronic coupling and hence manipulation of the nanoparticle optical and electronic properties. The unique interfacial linkages also allow further functionalization of the nanoparticles by metathesis reaction with olefin derivatives, as manifested in the reaction with vinylferrocene. This research opens new avenues for the structural engineering and functionalization of metal chalcogenide nanoparticles.

Vibrational Features of Oxyamines: A Comparative Study of N,N-Diethylhydroxylamine and N,N-Diethylacetyloxyamine.

The ability of oxyamines to undergo homolytic cleavage of the O-C bond, leading to the formation of stable radicals, is widely used in polymerization processes and to prevent oxidative stress in materials. We present a mid and near-infrared spectroscopy study on two model compounds, N,N-diethylhydroxyloxyamine (C4H11NO) and its acetyl derivative N,N-diethylacetyloxyamine (C6H13NO2) in the liquid phase. The analysis of the spectra is based on a complete exploration of the conformational space, coupled to harmonic and anharmonic calculations performed using the generalized second-order vibrational perturbation theory (GVPT2) formalism at the B3LYP-D3(BJ)/Def2-TZVP level of calculation and potential energy distribution analysis. In the most stable species out of 25, the three amine chains present an all-anti arrangement, with the carbonyl oxygen atom pointing towards the nitrogen lone pair. The simulated spectra are in overall good agreement with the experimental ones, and suitable for the assignment of the main observed bands. Furthermore, similarities and divergences between the two molecules are discussed.

Ni/Cu Dual-Catalyzed Propargylation for the Stereodivergent Synthesis of Methohexital.

The development of efficient methodologies for the controlled manufacture of specific stereoisomers bearing quaternary stereocenters has prompted advances in a variety of scientific disciplines including pharmaceutical chemistry, materials science, and chemical biology. However, complete control of the absolute and relative stereochemical configurations of alkyne derivatives remains an unmet synthetic challenge. Herein, a Ni/Cu dual-catalyzed asymmetric propargylic substitution reaction is presented to produce propargylated products with all-carbon quaternary stereocenters in high yields with significant diastereo- and enantioselectivities (up to >20:1 dr, >99% ee). The synthesis of all stereochemical variants of methohexital, a widely used sedative-hypnotic drug, exemplifies the efficacy of dual-catalyzed stereodivergent propargylation.

Design, Synthesis, and Anticancer and Antibacterial Activities of Quinoline-5-Sulfonamides.

A series of new unique acetylene derivatives of 8-hydroxy- and 8-methoxyquinoline- 5-sulfonamide 3a-f and 6a-f were prepared by reactions of 8-hydroxy- and 8-methoxyquinoline- 5-sulfonyl chlorides with acetylene derivatives of amine. A series of new hybrid systems containing quinoline and 1,2,3-triazole systems 7a-h were obtained by reactions of acetylene derivatives of quinoline-5-sulfonamide 6a-d with organic azides. The structures of the obtained compounds were confirmed by 1H and 13C NMR spectroscopy and HR-MS spectrometry. The obtained quinoline derivatives 3a-f and 6a-f and 1,2,3-triazole derivatives 7a-h were tested for their anticancer and antimicrobial activity. Human amelanotic melanoma cells (C-32), human breast adenocarcinoma cells (MDA-MB-231), and human lung adenocarcinoma cells (A549) were selected as tested cancer lines, while cytotoxicity was investigated on normal human dermal fibroblasts (HFF-1). All the compounds were also tested against reference strains Staphylococcus aureus ATCC 29213 and Enterococcus faecalis ATCC 29212 and representatives of multidrug-resistant clinical isolates of methicillin-resistant S. aureus (MRSA) and vancomycin-resistant E. faecalis. Only the acetylene derivatives of 8-hydroxyquinoline-5-sulfonamide 3a-f were shown to be biologically active, and 8-hydroxy-N-methyl-N-(prop-2-yn-1-yl)quinoline-5-sulfonamide (3c) showed the highest activity against all three cancer lines and MRSA isolates. Its efficacies were comparable to those of cisplatin/doxorubicin and oxacillin/ciprofloxacin. In the non-cancer HFF-1 line, the compound showed no toxicity up to an IC50 of 100 µM. In additional tests, compound 3c decreased the expression of H3, increased the transcriptional activity of cell cycle regulators (P53 and P21 proteins), and altered the expression of BCL-2 and BAX genes in all cancer lines. The unsubstituted phenolic group at position 8 of the quinoline is the key structural fragment necessary for biological activity.

Formation of Layered Liquid Crystal by Cooperation of Sidechain Array and Rigid Polyacetylene Mainchain

ABSTRACT An acetylene derivative monomer with a pyrimidine – type sidechain with three rings was synthesized by Steglich esterification. Polymerization of the acetylene derivative was then carried out with a rhodium complex. The acetylene monomer and mono-substituted polyacetylene derivative showed liquid crystals (LCs) because their tricyclic parts worked as a mesogenic core. The monomer as an acetylene derivative showed smectic with a tilted structure in the LC aggregation form. The mono-substituted polyacetylene bearing mesogen via short alkyl spacer showed lyotropic and thermotropic LCs of the smectic phase, although generally flexible long alkyl spacer from the main chain connected to sidechain mesogen is required for exhibiting liquid crystal in sidechain type polymer liquid crystals. In the present study, rigid mainchain aligns the sidechain mesogen array to form non-tilted LC. Properties of LCs were evaluated by various analytical techniques, including polarizing optical microscopy. Structural properties were evaluated by nuclear magnetic resonance spectroscopy, gel permeation chromatography, infrared spectroscopy, and ultraviolet – visible absorption spectroscopy.

Base-Promoted Annulated Aromatization of Aryl Acetylenes with Dimethyl Sulfoxide to Access Symmetrical/Unsymmetric m-Terphenyl.

A protocol for selective and efficient synthesis of symmetrical and unsymmetrical m-terphenyls is presented among aryl acetylene and DMSO in the presence of KOH and methanol. In this reaction, two molecules of aryl acetylene contribute four carbons, and DMSO, as a dual carbon donor, provides two carbons to a new aromatic ring. This protocol can be tolerated for the electron-donating or disubstituted phenylacetylenes as well as the heterocyclic acetylene derivatives.

Vine spacing of <i>Vitis vinifera</i> cv. Shiraz/101-14 Mgt. III. Grape and wine quality

Vine spacing effects of Shiraz/101-14 Mgt on a relatively high potential soil in the Breede River Valley, Robertson, South Africa, on grape composition and wine quality, were investigated. Canopies were VSP trellised and orientated approximately NNE-SSW. Spacing between rows was fixed at 2.2 m. In-row vine spacing changed from 0.3 – 4.5 m with increments of 30 cm (from 15151 – 1010 vines/ha). Grape composition and wine quality were monitored over six seasons and two grape ripeness levels. Decreasing trends of soluble solids (°B) and pH and increasing titratable acidity from narrow to wide spacing were observed. Sugar accumulation of wider spacings seemed delayed. Berry skin total anthocyanin index and phenol content showed virtually no change. Malvidin mono-glucoside and its p-coumaroyl and acetyl derivatives were present in the highest concentrations, followed by peonidin-, petunidin-, delphinidin- and cyanidin mono-glucosides and derivatives, each vine spacing treatment displaying a unique grape anthocyanin profile. The narrower spacing of vines seemed to favour skin anthocyanin accumulation compared to wider spacing. Decreasing trends in wine total anthocyanin intensity, anthocyanin density, and phenols were observed from narrow to wide spacing; all had higher levels in wines from riper grapes. Individual wine anthocyanin concentrations also showed qualitative profile changes. The first regression join points for all anthocyanins occurred around 1.8 – 2.4 m vine spacing; those for malvidin and derivatives consistently appeared at 1.8 m spacing. Although volatile compounds only seemed to respond to ripeness level and not to vine spacing, wine sensory quality generally decreased with wider vine spacing at both grape ripeness levels. Given the changes in biotic and abiotic growth conditions with wider vine spacing, the results likely displayed adaptation to the combined impact of increasing light exposure, berry temperature, physiological functioning, vegetative and reproductive growth ratios, and plant stress. The study showed the prominent role of plant spacing in sustainable grape growing and wine outcomes and thus the importance of judicious decision-making during the establishment and management of vines under any growth conditions and in any terroir.

Highly Stable Cesium Molybdenum Chloride Perovskite Nanocrystals for Photothermal Semihydrogenation Applications.

Metal halide perovskite materials with excellent carrier transport properties have been regarded as a new class of catalysts with great application potential. However, their development is hampered by their instability in polar solvents and high temperatures. Herein, we report a solution-processed Cs2MoCl6 perovskite nanocrystals (NCs) capped with the Mo6+, showing high thermostability in polar solvents. Furthermore, the Pd single atoms (PdSA) can be anchored on the surface of Cs2MoCl6 NCs through the unique coordination structure of Pd-Cl sites, which exhibit excellent semihydrogenation of different alkyne derivatives with high selectivity at full conversion at room temperature. Moreover, the activity could be improved greatly under Xe lamp irradiation. Detailed experimental characterization and DFT calculations indicate the improved activity under light illumination is due to the synergistic effect of photo-to-heat conversion and photoinduced electron transfer from Cs2MoCl6 to PdSA, which facilitates the activation of the C≡C group. This work not only provides a new catalyst for high selective semihydrogenation of alkyne derivatives but also opens a new avenue for metal halides as photothermal catalysts.

Unveiling the mechanism and selectivity of the [3 + 2] cycloaddition reactions of nitrone with acetylene derivatives leading to anticancer 4-isoxazoline derivatives from the MEDT perspective

The [3 + 2] cycloaddition reactions of N-methyl-C-(2-furyl) nitrone (a) with a series of acetylene derivatives (4b), (5b), and (6b) have been studied at the B3LYP-D3/6-31G(d) computational level within the framework of Molecular Electron Density Theory. Topological analysis allows classifying the nitrone (a) as a zwitterionic (zw-) three-atom component (TAC) associated with high energy barrier. These 32CA reactions follow a one-step mechanism under kinetic control with highly asynchronous bond formation. Bonding Evolution Theory (BET) analysis indicates that no new covalent CO and CC bonds form at the transition states (TSs). Interestingly, the global electron density transfer (GEDT) between 0.08 and 0.18 e predicts low polar character of forward electron density transfer (FEDF) type with the electronic flux from the nitrone (a) to the acetylene derivatives. Electron localization function (ELF) and atom-in-molecules (AIM) topological analysis of the electron density at the TS structures characterize the non-concerted nature of these one-step zw-type 32CA reactions.

Synthesis of a Side Chain Alkyne Analogue of Sitosterol as a Chemical Probe for Imaging in Plant Cells.

Clickable chemical tools are essential for studying the localization and role of biomolecules in living cells. For this purpose, alkyne-based close analogs of the respective biomolecules are of outstanding interest. Here, in the field of phytosterols, we present the first alkyne derivative of sitosterol, which fulfills the crucial requirements for such a chemical tool as follows: very similar in size and lipophilicity to the plant phytosterols, and correct absolute configuration at C-24. The alkyne sitosterol FB-DJ-1 was synthesized, starting from stigmasterol, which comprised nine steps, utilizing a novel alkyne activation method, a Johnson-Claisen rearrangement for the stereoselective construction of a branched sterol side chain, and a Bestmann-Ohira reaction for the generation of the alkyne moiety.

Synthesis, in silico studies and in vitro cytotoxicity evaluation of novel posaconazole derivative as a ALK TK inhibitor

Oncology research progresses, yet cancer remains the largest medical need. The use of a medication with an accessible lead molecule shows great potential for long-term cancer therapy. It may help target cancer therapy and drug resistance. This work uses FDA-approved, clinically proven compounds to build novel cancer therapeutic ligands to prevent treatment resistance. Based on the reported findings, an in-silico docking experiment was performed using FDA-licensed fungus medication posaconazole. The ALK TK pdb:4cmu ligand and posaconazole docked similarly in the research. Posaconazole's in silico docking findings were then tested against A549 lung cancer cells. Posaconazole, the lead, underwent an ADME investigation. Given in silico and experimental confirmation, acetyl, benzyl, and benzoyl derivatives of the lead molecule posaconazole was synthesized. IR, mass, 1H NMR, 13C NMR, and elemental analysis were performed on the synthesized compounds. Next, the three variants were evaluated against A549 lung cancer cells. They were then examined by utilizing computational approaches such as molecular docking, DFT analysis, MD simulation, and MMGBSA analysis. The ADME studies were conducted on posaconazole and its derivatives based on the in-vitro cell line investigation. Based on the results of an ADME study, two new ALK TK inhibitors that don't work as Pgp substrates are good lead candidates. Thus, the present investigation fruitfully reported two lead drug candidates against the issue of resistance in cancer therapy.

A Homodimer of Withaferin A Formed by Base-Promoted Elimination of Acetic Acid from 27-O-Acetylwithaferin A Followed by a Diels-Alder Reaction.

Treatment of 27-O-acetylwithaferin A (2) with the non-nucleophilic base, 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), afforded 5β,6β-epoxy-4β-hydroxy-1-oxo-witha-2(3),23(24),25(27)-trienolide (3) and 4, a homodimer of withaferin A resulting from a Diels-Alder [4 + 2] type cycloaddition of the intermediate α,β-dimethylene-δ-lactone (9). Structures of 3 and 4 were elucidated using HRMS and 1D and 2D NMR spectroscopic data. The structure of 4 was also confirmed by single crystal X-ray crystallographic analysis of its bis-4-O-p-nitrobenzoate (8). Formation of withaferin A homodimer (4) as the major product suggests regio- and stereoselectivity of the Diels-Alder [4 + 2] cycloaddition reaction of 9. Acetylation of 2-4 afforded their acetyl derivatives 5-7, respectively. Compounds 2-4 and 6-8 were evaluated for their cytotoxic activities against four prostate cancer (PC) cell lines (LNCaP, 22Rv1, DU-145, and PC-3) and normal human foreskin fibroblast (HFF) cells. Significantly, 4 exhibited improved activity compared to the other compounds for most of the tested cell lines.

Alkyne-Functionalized Platinum Chalcogenide (S, Se) Nanoparticles.

Metal chalcogenide nanoparticles play a vital role in a wide range of applications and are typically stabilized by organic derivatives containing thiol, amine, or carboxyl moieties, where the nonconjugated particle-ligand interfaces limit the electronic interactions between the inorganic cores and organic ligands. Herein, a wet-chemistry method is developed for the facile preparation of stable platinum chalcogenide (S, Se) nanoparticles capped with acetylene derivatives (e.g., 4-ethylphenylacetylene, EPA). The formation of Pt-C≡ conjugated bonds at the nanoparticle interfaces, which is confirmed by optical and X-ray spectroscopic measurements, leads to markedly enhanced electronic interactions between the d electrons of the nanoparticle cores and π electrons of the acetylene moiety, in stark contrast to the mercapto-capped counterparts with only nonconjugated Pt-S- interfacial bonds, as manifested in spectroscopic measurements and density functional theory calculations. This study underscores the significance of conjugated anchoring linkages in the stabilization and functionalization of metal chalcogenides, a unique strategy for diverse applications.

Recent advances in the application of alkynes in multicomponent reactions.

Alkynes have two active positions to carry out chemical reactions: C[triple bond, length as m-dash]C and C-H. These two positions are involved and activated in different reactions using different reagents. In this study, we investigated the reactions of alkynes that are involved in multi-component reactions through the C-C and C-H positions and examined the progress and gaps of each reaction by carefully studying the mechanism of the reactions. Firstly, we investigated and analyzed the reactions involving the C[triple bond, length as m-dash]C position of alkynes, including the reactions between derivatives of alkynes with RN3, sulfur compounds (RSO2R', DMSO, S8, DABCO(SO2)2 and DABSO), barbituric acids, aldehydes and amines, COOH, α-diazoesters or ketones, and isocyanides. Then, we examined and analyzed the important reactions involving the C-H position of alkynes and the progress and gaps in these reactions, including the reaction between alkyne derivatives with amines and aldehydes for the synthesis of propargylamines, the reaction between alkynes with CO2 and the reaction between alkynes with CO.

Nickel/ligand loading-controlled divergent and selective coupling between redox-active methylenecyclopropanes and ArBr

Diverse alkyne and dibenzylethylene derivatives were obtained via selective coupling of redox-active MCPs and ArBr under Ni/photoredox catalysis. The nickel/ligand loading tuning method played a crucial role in this divergent synthesis protocol.

Oxidation of N-trifluoromethylthio sulfoximines using NaOCl·5H2O.

N-Trifluoromethylthio sulfoximines are biologically interesting compounds, but their potential is still poorly understood. The oxidation of N-trifluoromethylthio sulfoximines led to their corresponding sulfoxide derivatives as a new class of compounds, when using sodium hypochlorite pentahydrate (NaOCl·5H2O) as a green and relatively unexplored reagent. The reactions took place with a small excess of oxidant under environmentally friendly conditions in EtOAc for 16 h at room temperature. Noteworthy distinctions of this transformation are the simplicity, high selectivity, energy and cost efficiency, minimal amounts of non-hazardous waste, isolation of most of the products without the additional need for chromatographic purification, and simple scalability to gram reactions without deterioration of the yield. The reaction exhibited excellent green chemistry metrics with high atom economy (82.0%), actual atom economy (79.5%), reaction mass efficiency (79.7%), E-factor (16.48) and a very high EcoScale score (84.5). Competitive experiments demonstrated that electron-rich substrates are more reactive than their electron-poor counterparts. Furthermore, the Suzuki-Miyaura functionalization of N-trifluoromethylsulfaneylidene sulfoximine could be achieved depending on the conditions, resulting in coupling products with or without an introduced sulfoxide moiety. Sonogashira coupling of N-trifluoromethylsulfaneylidene sulfoximine furnished the expected acetylene derivative in high yield, and the reaction conditions are compatible with the newly introduced sulfaneylidene functionality. Bromine and nickel catalysts were also shown to be deprotecting agents of the sulfoxide group. A selected N-trifluoromethylsulfaneylidene sulfoximine demonstrated its stability in water in the presence of air and in dilute hydrochloric acid, while it converted back to the parent sulfoximine under basic conditions.

Effect of Milling on Reduction of Fusarium Mycotoxins in Barley

Milling can affect the distribution of mycotoxins in small grains. To investigate the effects on barley, seven hulled barley and three naked barley samples naturally contaminated with trichothecenes and zearalenone were obtained and milled at commonly used rates. Both barleys were simultaneously contaminated with deoxynivalenol and its acetyl derivatives (98.1–2,197.8 μg/kg), nivalenol and its acetyl derivative (468.5–3,965.1 μg/kg), and zearalenone (4.1–274.2 μg/kg). Milling hulled barleys at a rate of 67% reduced the mycotoxins in the grain by 90.9% for deoxynivalenol, 87.7% for nivalenol, and 93.2% for zearalenone. The reduction in naked barleys (milled at a rate of 70%) was slightly lower than in hulled barleys, with 88.6% for deoxynivalenol, 80.2% for nivalenol, and 70.1% for zearalenone. In both barleys, the acetyl derivatives of deoxynivalenol and nivalenol were reduced by 100%. However, barley bran had significantly higher mycotoxin concentrations than the pre-milled grains: bran from hulled barley had a 357% increase in deoxynivalenol, 252% increase in nivalenol, and 169% increase in zearalenone. Similarly, bran from naked barley had a 337% increase in deoxynivalenol, 239% increase in nivalenol, and 554% increase in zearalenone. These results show that mycotoxins present in the outer layers of barley grain can be effectively removed through the milling process. As milling redistributes mycotoxins from the grain into the bran, however, it shows that advance monitoring of barley bran is recommended when using barley bran for human or animal consumption.