One-pot Research Articles

Luminescent tetranuclear copper(I) and gold(I) heterobimetallic complexes: A phosphine acetylide amidinateorthogonal ligand framework for selective complexation.

The synthesis of phosphine acetylide amidinate stabilized copper(I) and gold(I) heterobimetallic complexes was achieved by reacting ligand [{Ph2PC≡CC(NDipp)2}Li(thf)3] (Dipp = N,N'-diisopropylphenyl) with CuCl and Au(tht))Cl, yielding the eight membered ring [{Ph2PC≡CC(NDipp)2}2Cu2] and the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2]. {Ph2PC≡CC(NDipp)2}2Cu2] features a Cu2 unit, which is bridged by two amidinate ligands, served as a metalloligand to synthesize the heterobimetallic CuI/AuI complexes [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X = Cl, C6F5). In these reactions the central ring structure is retained. In contrast, when the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2] was reacted with CuX (X = Cl, Br, I and Mes), the reaction led to rearrangement of the central ring structure to give [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X = Cl, Br, I and Mes), which feature the same the eight membered Cu2 ring as above. These compounds were also synthesized by a one-pot reaction. The luminescent heterobimetallic complexes were further investigated for their photophysical properties.

Mesoporous TiO2 and Fe-containing TiO2 prepared by solution combustion synthesis as catalysts for the photodegradation of paracetamol.

Water pollution due to emerging contaminants, e.g., pharmaceuticals, is one of the most frequently discussed issues. Among them, paracetamol received great attention due to its physico-chemical properties, persistence, and adverse environmental effects. Different techniques were employed for its degradation and, among them, photodegradation is considered one of the most suitable to pursue the aim. This work aimed to synthesize mesoporous TiO2, even with the presence of iron, through a one-pot method, with an enhanced ability to abate paracetamol. Precisely, pure and iron-containing (3.5 wt%) TiO2 were successfully obtained employing an uncommon procedure for this kind of material, mainly solution combustion synthesis (SCS). Moreover, a traditional hydrothermal method and a commercial Degussa P25 were also investigated for comparison purposes. The samples were characterized through N2-physisorption at - 196°C, XRD, XPS, EDX,DR UV-Vis, and FESEM analysis. The catalytic activity was investigated for the abatement of 10ppm of paracetamol, under UV irradiation in acidic conditions (pH = 3) and in the presence of H2O2. As a whole, the best-performing catalysts were those obtained through the SCS procedure, highlighting a complete removal of the organic pollutant after 1h in the case of Fe/TiO2_SCS, thanks to its highly defective structure and the presence of metal Fe. To better investigate the performance of both pure and Fe-containing SCS samples, further oxidation tests were performed at pH = 7 and in the absence of H2O2. Noteworthy, in these conditions, the two samples exhibited different behaviors, highlighting different mechanisms depending on the presence or absence of iron in the structure. Finally, a kinetic study was conducted, demonstrating that a first order is suitable for its abatement.

Engineering a Carotenoid Cleavage Oxygenase for Coenzyme-Free Synthesis of Vanillin from Ferulic Acid.

One-pot biosynthesis of vanillin from ferulic acid without providing energy and cofactors adds significant value to lignin waste streams. However, naturally evolved carotenoid cleavage oxygenase (CCO) with extreme catalytic conditions greatly limited the above pathway for vanillin bioproduction. Herein, CCO from Thermothelomyces thermophilus (TtCCO) was rationally engineered for achieving high catalytic activity under neutral pH conditions and was further utilized for constructing a one-pot synthesis system of vanillin with Bacillus pumilus ferulic acid decarboxylase. TtCCO with the K192N-V310G-A311T-R404N-D407F-N556A mutation (TtCCOM3) was gradually obtained using substrate access channel engineering, catalytic pocket engineering, and pocket charge engineering. Molecular dynamics simulations revealed that reducing the site-blocking effect in the substrate access channel, enhancing affinity for substrates in the catalytic pocket, and eliminating the pocket's alkaline charge contributed to the high catalytic activity of TtCCOM3 under neutral pH conditions. Finally, the one-pot synthesis of vanillin in our study could achieve a maximum rate of up to 6.89 ± 0.3 mM h-1. Therefore, our study paves the way for a one-pot biosynthetic process of transforming renewable lignin-related aromatics into valuable chemicals.

Fully Biodegradable Elastomer-Based Device for Oral Macromolecule Delivery.

Oral devices, such as foil-type devices, show great potential for the delivery of poorly permeable macromolecules by enabling unidirectional release of the loaded pharmaceutical composition in close proximity to the epithelium in the small intestine or colon. However, one of the primary concerns associated with the use of foil-type devices so far has been the utilization of nonbiodegradable elastomers in the fabrication of the devices. Therefore, research into biodegradable substitute materials with similar characteristics enables drug delivery in a sustainable and environmentally friendly manner. In this study, a biodegradable elastomer, polyoctanediol citrate (POC), was synthesized via a one-pot reaction, with subsequent purification and microscale pattern replication via casting. The microstructure geometry was designed to enable fabrication of foil-type devices with the selected elastomer, which has a high intrinsic surface free energy. The final elastomer was demonstrated to have an elastic modulus ranging up to 2.2 ± 0.1 MPa, with strain at failure up to 110.1 ± 1.5%. Devices were loaded with acetaminophen and enterically coated, demonstrating 100% release at 2.5 h, following dissolution for 1 h in 0.1 M hydrochloric acid and 1.5 h in pH 6.8 phosphate-buffered saline. The elastomer demonstrated promising properties based on mechanical testing, surface free energy evaluation, and degradation studies.

A facile and efficient one-pot 3-component reaction (3-CR) method for the synthesis of thiazine-based heterocyclic compounds using zwitterion adduct intermediates

Abstract Multicomponent reactions (MCRs) are considered a green strategy by generating diversity of scaffolds from less synthetic effort and safe conditions. This work present the synthesis of dimethyl 8-(tert-butylamino)-4-oxo-4,6-dihydropyrimido[2,1-b][1,3]thiazine-6,7-dicarboxylate in low to moderate yields 33–74 % from the prepared 2-amino-4H-1,3-thiazin-4-one derivatives containing both an acidic proton and a suitable nucleophile with alkyl isocyanides and DMAD/DEtAD. The work portrays facile method under green chemical production processes using green solvents such as acetone, ethanol, isopropanol, and 2-methyl-tetrahydrofuran. This chapter shows the flexibility of zwitterion adduct from the reaction of alkyl isocyanide and DMAD. The zwitterion adduct is trapped by 2-amino-4H-1,3-thiazin-4-one derivatives and forms fused [6-6] heterocyclic compounds. The preparation of starting material thiazine was carried out at different condition from 0 °C temperatures to reflux, while the synthesis of novel dimethyl 8-(tert-butylamino)-4-oxo-4,6-dihydropyrimido[2,1-b][1,3]thiazine-6,7-dicarboxylates was done at room temperature without the use of catalyst.

One-pot synthesis of quinazolinone heterocyclic compounds using functionalized SBA-15 with natural material ellagic acid as a novel nanocatalyst.

The nanoporous compound SBA-15 was functionalized using (3-aminopropyl)trimethoxysilane (APTES). Then the obtained product was modified with ellagic acid (ELA), a bioactive polyphenolic compound. The structure of the prepared nanoporous composition SBA-15@ELA was extensively characterized and confirmed by various techniques, such as Fourier-transform infrared (FT-IR) spectroscopy, Energy dispersive X-ray (EDX) elemental analysis, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and N2 adsorption-desorption isotherms (BET). The novel, recoverable, heterogenous SBA-15@ELA nanoporous compound was used to investigate its catalytic effect in the synthesis of 4-oxo-quinazoline derivatives (19 examples) with high yields (78-96%), as an important class of nitrogen-containing heterocyclic compounds. The use of an inexpensive mesoporous catalyst with a high surface area, along with easy recovery by simple filtration are among the advantages of this catalysis research work. The catalyst has been used in at least 6 consecutive runs without a significant loss of its activity.

One-Pot Synthesis of Vinylogous Cyano Aminoaryls (VinCAs) as Benzenic Fluorophores: Tailoring Diverse Emission Colors for White Light Emitting Materials and Cell Imaging.

Donor-acceptor-based organic small molecules with an electronic push-pull effect can demonstrate intramolecular charge transfer to show interesting photoluminescence properties. This is an essential criterion for designing fluorogenic probes for cell imaging studies and the development of organic light-emitting diodes. Now, to design such optical materials sometimes it is necessary to tune the band gap by controlling the energies of the highest occupied molecular orbital and lowest unoccupied molecular orbital. Typically, the band gaps could be modulated by installing unsaturated handles between electron-rich donors and electron-deficient acceptors. However, these methods are often synthetically and economically challenging due to the involvement of expensive catalysts and difficult reaction setups. In our present study, we show a straightforward, cost-effective method for obtaining a series of donor-acceptor-type Vinylogous Cyano Aminoaryls (VinCAs) with diverse emission colors. Further studies reveal that these VinCAs can serve as effective cell imaging agents, showcasing potential use in chemical biology. Additionally, these molecules could be further used to generate white light emission (WLE), showing their potential utility in advanced lighting technologies.

Metal-Organic Framework Templated Z-Scheme ZnIn2S4/Bi2S3 Hierarchical Heterojunction for Photocatalytic H2O2 Production from Wastewater.

Metal-organic framework derived materials received a lot of attention due to their significant benefits in photocatalytic reactions. In this work, a Z-scheme ZnIn2S4/Bi2S3 hierarchical heterojunction is first developed by a one-pot method using CAU-17 as a template. The specific preparation method endows an intimate interface contact between these two monomers, and CAU-17-derived Bi2S3 possesses a high surface area and porosity, resulting in an efficient charge separation and O2 capture. Thus, for photocatalytic H2O2 production from the O2 reduction reaction, the ZnIn2S4/Bi2S3 heterojunction can achieve an H2O2 yield of 995µmolL-1 in pure water and ambient air under visible light, 4.5 and 4 times that of ZnIn2S4 and Bi2S3, respectively. In addition, in tetracycline solution, ZnIn2S4/Bi2S3 can degrade tetracycline with a degradation rate of 95% by photocatalysis, and at the same time, a final H2O2 production yield of 1223µmolL-1 is reached. Similarly, high yields of H2O2 are also obtained from wastewater containing o-nitrophenol, acid golden yellow, or acid red, and these pollutants are effectively degraded. This work reveals the potential of metal-organic framework-derived materials in photocatalysis, as well as provides insights into H2O2 green synthesis and wastewater treatment.

D-Band Engineering in Pd-Based Nanowire Networks for Further Enhancement in Ethanol Electrooxidation Reaction.

The development of highly efficient electrocatalysts for the ethanol oxidation reaction (EOR) is essential for the commercialization of direct ethanol fuel cells, yet challenges remain. In this study, a one-pot solution-phase method to synthesize Pd nanowire networks (NNWs) with very high surface-to-volume ratio having numerous twin and grain boundaries is developed. Using the same method, the Pd lattice is further engineered by introducing Ag and Cu atoms to produce AgPd, and CuPd alloy structure which significantly shifts the Pd d-band center upward and downward, respectively due to strain and ligand effects. Theoretical analysis employing density functional theory (DFT) demonstrates that such modification of the d-band center significantly influences the adsorption energies of reactants on the catalytic surface. Owing to their notably high surface-to-volume ratio and the presence of multiple twin and grain boundaries, Pd NNWs demonstrate significantly enhanced electrocatalytic activity toward EOR, ≈7.2 times greater than that of commercial Pd/C. Remarkably, compared to Pd NNWs, AgPd, and CuPd NNWs display enlarged and reduced electrocatalytic activity toward EOR, respectively. Specifically, Ag4Pd7 NNWs achieve a remarkable mass activity of 9.00Amgpd -1 for EOR, which is 13.6 times higher than commercial Pd/C.

Multifunctional trimetal-organic frameworks with enhanced fenton-like catalytic activity for inhibiting bacteria

AbstractAntibiotics and chemical disinfectants usually have serious problems of drug resistance and biosafety. Metal-organic frameworks (MOFs), as a new alternative method, have been studied to inhibit bacteria attributed to their tunability of compositions and structures, ideal biocompatibility and great catalytic properties. In the current study, two trimetal-organic frameworks (Ni1Co1Fe1-MOFs and Ni6Co3Fe1-MOFs) with different atomic ratios of Ni/Co/Fe were synthesized by a simple one-pot room temperature method. The fabricated MOFs showed outstanding Fenton-like catalytic activities and Ni1Co1Fe1-MOFs exerted greater catalytic activity. Based on a Fenton-like reaction, a high-efficiency antibacterial system was constructed. The manufactured Ni1Co1Fe1-MOF/sodium alginate composite coating delayed the weight loss of apple chunks and effectively inhibited E. coli bacteria from polluted apple chunks after storage for 2 d, significantly improving the fruit storage. This study proposed a novel and effective antibacterial strategy, which would open up a promising idea for the exploitation of food antibacterial agents in the future.

Visible-light-driven BiOI and GO/BiOI photocatalysts for organic pollutants degradation and hydrogen production using low power sources

BiOI and (3 wt%)GO/BiOI visible-light-driven photocatalysts were obtained by a one-pot solvothermal method and successfully applied to the degradation of single and binary dye solutions of rhodamine B (RhB) and methylene blue (MB) and H2 production using very low-power sources. The GO/BiOI with hierarchical flower morphologies exhibited the highest activity, achieving RhB and MB photodegradation percentages (%Xdye) of 100% and 80%, respectively, in 240 min employing a simple 19 W white LED array. Furthermore, GO/BiOI dosage and RhB initial concentration play an essential role in dye degradation, and scavenger assays confirmed that holes and superoxides are the main species causing RhB oxidation. TOC analysis determined an efficiency of 70%, and after three uses, the GO/BiOI attained a %XRhB of 84%. The H2 evolution was performed under 2 W UV light, yielding 323.25 μmol/h∙g of H2 for BiOI, and the addition of GO nanosheets increased the photoactivity of GO/BiOI up to 63% (509.61 μmol/h∙g). The catalytic activity of GO/BiOI is superior to values reported in the literature considering nominal power consumption (kWh) vs. efficiency of RhB degradation or H2 production.

Chemoenzymatic Synthesis of 2-Aryl Thiazolines from 4-Hydroxybenzaldehydes Using Vanillyl Alcohol Oxidases.

Nitrogen heterocycles are commonly found in bioactive natural products and drugs. However, the biocatalytic tools for nitrogen heterocycle synthesis are limited. Herein, we report the discovery of vanillyl alcohol oxidases (VAOs) as efficient biocatalysts for the one-pot synthesis of 2-aryl thiazolines from various 4-hydroxybenzaldehydes and aminothiols. The wild-type biocatalyst features a broad scope of 4-hydroxybenzaldehydes. Though the scope of aminothiols is limited, it could be improved via semi-rational protein engineering, generating a variant to produce previously inaccessible cysteine-derived bioactive 2-aryl thiazolines using the wild-type VAO. Benefiting from the derivatizable functional groups in the enzymatic products, we further chemically modified these products to expand the chemical space, offering a new chemoenzymatic strategy for the green and efficient synthesis of structurally diverse 2-aryl-thiazoline derivatives to prompt their use in drug discovery and catalysis.

Regioselective Syntheses of 2,3,5-Trisubstituted Pyridines via 5-Chloro-3-fluoro-2-(methylsulfonyl)pyridine.

We report the high-yielding, large-scale, one-pot synthesis of two versatile building blocks (1-Cl and 1-Br) for the regioselective synthesis of a variety of 2,3,5-trisubstituted pyridines from inexpensive materials. These molecules are readily derivatized at positions 2, 3, and 5. These building blocks can also be used for the synthesis of fused pyrido-oxazines and for the synthesis of 2,3,4,5-tetrasubstituted pyridines.

Boosting Up Electrosynthesis of Urea with Nitrate and Carbon Dioxide via Synergistic Effect of Metallic Iron Cluster and Single-Atom.

Electrocatalytic conversion of nitrates and carbon dioxide to urea under ambient conditions shows promise as a potential substitute for traditional urea synthesis processes characterized by high consumption and pollution. In this study, a straightforward one-pot method is employed to prepare a highly efficient FeNC-Fe1N4 electrocatalyst, consisting of atomically dispersed Fe1N4 sites and metallic Fe clusters (FeNC) with particle size of 4-7nm. The FeNC-Fe1N4 catalyst exhibits remarkable electrocatalytic activity for urea synthesis from nitrate anion (NO3 -) and carbon dioxide (CO2), achieving a urea production rate of 38.2mmolgcat -1h-1 at -0.9V (vs RHE) and a Faradaic efficiency of 66.5% at -0.6V (vs RHE). Both experimental and theoretical results conclusively demonstrate that metallic Fe clusters and Fe1N4 species provide active sites for the adsorption and activation of NO3 - and CO2, respectively, and the synergistic effect between Fe1N4 and metallic Fe clusters significantly enhances the electrochemical efficiency of urea synthesis. In all, this work contributes to the rational design and comprehensive synthesis of a dual-active site iron-based electrocatalyst, facilitating efficient and sustainable urea synthesis.

Rh-Catalyzed α-Arylation of Cyclic 1,3-Dicarbonyls with Benzocyclobutenols Enabled by a Cyclic Iodonium Ylide Strategy.

To date, the general and catalytic α-arylation of cyclic 1,3-dicarbonyls remains elusive. We now report the first Rh-catalyzed α-arylation of cyclic 1,3-dicarbonyls with benzocyclobutenols through a cyclic iodonium ylide strategy. Our strategy represents a good solution for the previously challenging α-arylation of cyclic 1,3-dicarbonyls with sterically demanding aryl partners, which is especially appropriate for structurally unique heteroaromatic 1,3-dicarbonyls. Our approach features mild conditions, readily available starting materials, high yields, excellent functional group-tolerance, and simple operation, providing expedient access toward medically important 2-aryl (hetero)cyclic 1,3-dicarbonyls. The practicality of this approach is demonstrated by the gram-scale synthesis, one-pot synthesis, and numerous downstream transformations.

One-Pot Synthesis of Structurally Diverse Sulfurized/ Selenated 4-Aminopyrimidines

One-Pot Synthesis of Structurally Diverse Sulfurized/ Selenated 4-Aminopyrimidines

Vitamin B1-based thiazol-2-ylidene-Ru(II) complexes: recyclable transfer hydrogenation catalysts in water.

The [(p-cymene)RuCl(κ2C,N-{CNHC-NH})]+X- (CNHC = thiazol-2-ylidene) complexes with a bidentate ligand (2: X = Cl and 3: X = PF6) were prepared by a one-pot reaction of vitamin B1 (VB1, 1), Ag2O and [(p-cymene)RuCl2]2. In the complexes, VB1 coordinates through C2 and the exocyclic N in the imino form with the κ2-(C,N) coordination mode. The complexes 2 and 3 are stable in the solid state, but slowly release p-cymene in solution. Furthermore, upon heating in polar solvents, 2 or 3 can be converted by ligand exchange reactions to produce [(L)3RuCl(κ2C,N-{CNHC-NH})]+PF6- (4: L = py).Robustness was improved remarkably for 4. The complex 4 is stable in the solid state and in solution. The complexes 2-4 have been identified by 1H and 13C{1H} 2D NMR spectroscopy and 2 and 4 were studied by X-ray crystallography. In an effort to develop a recyclable catalyst in water, 2-4 were evaluated for TH of ketones and aldehydes with an azeotropic mixture of HCOOH/Et3N in water. The complexes 3 and 4 exhibited very good catalytic activity and 4 could be reused nine times without significant loss of activity, giving a high turnover frequency (TOF50%(h-1) = 1286).

Bioorthogonal Cycloadditions of C3-Trifluoromethylated 1,2,4-Triazines with trans-Cyclooctenes.

1,2,4-triazines are a valuable class of heterodienes that can be employed in inverse electron-demand Diels-Alder reactions. However, their broader application in bioorthogonal chemistry is limited due to their low reactivity. This article focuses on 3-(trifluoromethyl)-1,2,4-triazines, which can be efficiently prepared in a one-pot reaction from NH-1,2,3-triazoles. These triazines are highly reactive in reactions with strained cyclooctenes, giving second-order rate constants as high as 230 M-1 s-1. Despite their high reactivity, the compounds remain sufficiently stable under biologically relevant conditions. We show that some of the compounds are fluorogenic, a property of potential use in bioimaging. In addition, we demonstrate the successful application of the triazines in labeling model biomolecules. Our work shows that the reactivity of 1,2,4-triazines can be enhanced by the 3-CF3-substitution, which we consider an important step toward the wider use of this promising class of reagents.

One-Pot Synthesis of 1,3-Cyclohexadienes by Birch Reduction in the Presence of Carbonyl Compounds.

Birch reductions are well-known transformations of arenes, applied for large scale synthesis of 1,4-cyclohexadienes. Herein, we describe first reactions of benzoic acids in the presence of carbonyl compounds, affording aldol products in moderate to high yields. Alkyl aldehydes give the expected nonconjugated dienes by reaction at the α-position. Interestingly, the intermediately formed enolate attacks aryl aldehydes and ketones from its γ-position, which can be explained by steric hindrance. This opens the door for the one-pot synthesis of 1,3-cyclohexadienes, which are not accessible by classical Birch reductions. Our method is applicable to benzoic, m- and p-toluic acid and various carbonyl compounds, and more than 25 new products were isolated in up to 93% yield. Prochiral aryl aldehydes afford diastereomeric mixtures in ratios of about 4:1, but in the cyclohexadiene ring only trans isomers are formed with high selectivity. Finally, the 1,3-cyclohexadienes are suitable precursors for further transformations, which we have demonstrated in first examples. Thus, aromatization affords products of a formal meta selective Friedel-Crafts alkylation, and four new stereocenters were generated by cycloaddition of singlet oxygen with excellent selectivity.

One-pot synthesis of NiCo-phyllosilicate supported on zeolite for enhanced degradation of antibiotic contaminants

The overuse of antibiotics currently results in the presence of various antibiotics being detected in water bodies, which poses potential risks to human health and the environment. Therefore, it is highly significant to remove antibiotics from water. In this study, we developed novel rod-like NiCo-phyllosilicate hybrid catalysts on calcined natural zeolite (NiCo@C-zeolite) via a facile one-pot process. The presence of the zeolite served as both a silicon source and a support, maintaining a high specific surface area of the NiCo@C-zeolite. Remarkably, NiCo@C-zeolite exhibited outstanding catalytic performance in antibiotic degradation under PMS activation. Within just 5 min, the degradation rate of metronidazole (MNZ) reached 96.14%, ultimately achieving a final degradation rate of 99.28%. Furthermore, we investigated the influence of catalyst dosage, PMS dosage, MNZ concentration, initial pH value, and various inorganic anions on the degradation efficiency of MNZ. The results demonstrated that NiCo@C-zeolite displayed outstanding efficacy in degrading MNZ under diverse conditions and maintained a degradation rate of 94.86% at 60 min after three consecutive cycles of degradation. Free radical quenching experiments revealed that SO•− 4 played a significant role in the presence of NiCo@C-zeolite-PMS system. These findings indicate that the novel rod-like NiCo-phyllosilicate hybrid catalysts had excellent performance in antibiotic degradation.