One-pot Research Articles

A Chemically Robust 2D Ni-MOF as an Efficient Heterogeneous Catalyst for One-Pot Synthesis of Therapeutic and Bioactive 2-Amino-3-Cyano-4H-Pyran Derivatives.

Despite possessing numerous catalytic advantages of MOFs, developing 2D frameworks having excellent chemical stability along with new catalytic properties, remains a grand challenge. Herein, by employing a mixed ligand synthetic approach, we have constructed a 2D Ni-MOF, IITKGP-52, which exhibits excellent framework robustness in open air, water, as well as over a wide range of pH solutions (2-12). Benefitting from its robustness and abundant Lewis acidic open metal sites, IITKGP-52 is explored in catalyzing the heterogeneous three-component condensation reaction for the tandem synthesis of bioactive 2-amino-3-cyano-4H-pyran derivatives with low catalytic loading, greater compatibility for a wide range of substrates, excellent recyclability and superior catalytic efficiency than the previously employed homo and heterogeneous systems. IITKGP-52inaugurates the employment of MOF-based catalysts for one-pot synthesis of therapeutic and bioactive 2-amino-3-cyano-4H-pyran derivatives.

Antimony Redox Catalysis: Hydroboration of Disulfides through Unique Sb(I)/Sb(III) Redox Cycling.

The stibinidene ArSbI (Ar = [2,6-(tBuN═CH)2-C6H3], 1) reacts with S2Tol2 (Tol = p-tolyl) to form ArSbIII(STol)2 (2), which upon treatment with pinacolborane, regenerates 1. These processes unveil an unprecedented antimony redox catalysis involving Sb(I)/Sb(III) cycling for the hydroboration of organic disulfides. Elementary reaction studies and density functional theory calculations support that the catalysis mimics transition metal processes, proceeding through oxidative addition, ligand metathesis, and reductive elimination. The thiophenols and sulfidoborates generated from the hydroboration of disulfides react in situ with α,β-unsaturated carbonyl compounds with the assistance of 1 as a base catalyst. These tandem reactions establish a one-pot synthetic method for β-sulfido carbonyl compounds, in which a stibinidene functions as a redox catalyst and a base catalyst successively, illustrating the versatility and efficiency of antimony catalysis in organic synthesis.

One-Pot Synthesis of Silicon Quantum Dots-Based Fluorescent Nanomaterial and Its Application.

Conventionally obtained silicon quantum dots (Si QDs) generally suffer from the disadvantages of a cumbersome preparation process, large fluctuation in the quality of Si QDs, poor water solubility, and aggregation-caused quenching (ACQ) phenomenon. Here we report a facile one-pot strategy to synthesize a novel Si QDs-based fluorescent nanomaterial in which Si QDs are confined into dendritic mesoporous silica, named as SiQDs@DMSNs. The prepared SiQDs@DMSNs, with adjustable particle sizes ranging from 140 to 300 nm, emit blue fluorescence around 410 nm upon excitation by ultraviolet light at a wavelength of 300 nm. It is found that the addition of sodium salicylate (NaSAL) plays a crucial role in the in situ generation of Si QDs. The obtained SiQDs@DMSNs exhibit excellent fluorescence intensity, water solubility, and stability, facilitating easy surface modification, without being limited by the ACQ phenomenon. It is expected to be widely used in many fields such as biosensors, nanomedicines, in vivo imaging, fingerprint identification, and anticounterfeiting labels.

Efficient in Situ One-Pot Synthesis of Water-Soluble Hydroxynaphthoquinones for Redox Flow Batteries.

Given the importance of energy storage and its hybridization with renewable technologies for the energy transition, the development of redox flow batteries (RFB) is receiving particular attention. Among the various emerging technologies, aqueous organic redox flow batteries (AORFBs) are of particular interest, as the objectives in terms of durability, cost, and safety can be achieved thanks to the possibilities offered by molecular engineering. While anthraquinones have been widely explored as negolytes, few works report the use of naphthoquinones. This work aims to exploit an innovative in situ and cost-effective method for the one-pot synthesis of water-soluble naphthoquinones for application as a negolyte in redox flow batteries. As exemplified with alizarin, the energy of the naphthoquinone synthetic reaction in fuel cell mode can be recovered and the electrolyte solution used directly in redox flow batteries without purification. A 0.3 M naphthoquinone solution paired with 0.6 M ferrocyanide demonstrated good stability compared with other naphthoquinones, with a capacity fade rate of 0.017%/cycle (0.84%/day) over 320 cycles. Additionally, the system exhibited one of the highest energy efficiencies (82%) and a power density of 80-105 mW cm-2 at 50% SOC. These first results are promising for further exploration of new water-soluble naphthoquinones efficiently synthesized from hydroxyanthraquinones for application in AORFBs.

Synthesis of 1,3-Dicarbonyl Azepines via Photoinitiated Reactions of Aryl Azides with Carbon-Based Nucleophiles.

A photoinduced one-pot method for the synthesis of azepines by the reaction of aryl azides with 1,3-dicarbonyl compounds under weakly basic conditions is described. This method offers a simple route for the synthesis of 1,3-dicarbonyl-substituted azepines in good to excellent yields and high regioselectivity and was tested on 1,3-dicarbonyl compounds with different acidity levels. The resulting azepines have electrophilic and nucleophilic centers of varying degrees of activity, which facilitate reactions leading to further structural transformations.

IMAX FRET (Information Maximized FRET) for Multipoint Single-Molecule Structural Analysis.

Understanding the structure of biomolecules is vital for deciphering their roles in biological systems. Single-molecule techniques have emerged as alternatives to conventional ensemble structure analysis methods for uncovering new biology in molecular dynamics and interaction studies, yet only limited structural information could be obtained experimentally. Here, we address this challenge by introducing iMAX FRET, a one-pot method that allows ab initio 3D profiling of individual molecules using two-color FRET measurements. Through the stochastic exchange of fluorescent weak binders, iMAX FRET simultaneously assesses multiple distances on a biomolecule within a few minutes, which can then be used to reconstruct the coordinates of up to four points in each molecule, allowing structure-based inference. We demonstrate the 3D reconstruction of DNA nanostructures, protein quaternary structures, and conformational changes in proteins. With iMAX FRET, we provide a powerful approach to advance the understanding of biomolecular structure by expanding conventional FRET analysis to three dimensions.

Direct Readout of Homo- vs Heterochiral Ligand Shell of Quantum Dots.

The chiroptical activity of various semiconductor inorganic nanocrystalline materials has typically been tested using circular dichroism or circularly polarized luminescence. Herein, we report on a high-throughput screening method for identifying and differentiating chiroptically active quantum-sized ZnO crystals using Raman spectroscopy combined with principal component analysis. ZnO quantum dots (QDs) coated by structurally diverse homo- and heterochiral aminoalcoholate ligands (cis- and trans-1-amino-2-indanolate, 2-amino-1-phenylethanolate, and diphenyl-2-pyrrolidinemethanolate) were prepared using the one-pot self-supporting organometallic procedure and then extensively studied toward the identification of specific Raman fingerprints and spectral variations. The direct comparison between the spectra demonstrates that it is very difficult to make definite recognition and identification between QDs coated with enantiomers based only on the differences in the respective Raman bands' position shifts and their intensities. However, the applied approach involving the principal component analysis performed on the Raman spectra allows the simultaneous differentiation and identification of the studied QDs. The first and second principal components explain 98, 97, 97, and 87% of the variability among the studied families of QDs and demonstrate the possibility of using the presented method as a qualitative assay. Thus, the reported multivariate approach paves the way for simultaneous differentiation and identification of chirotopically active semiconductor nanocrystals.

Electrocatalytic Coupling of Nitrate and Formaldehyde for Hexamethylenetetramine Synthesis via C-N Bond Construction and Ring Formation.

Hexamethylenetetramine (HMTA) is extensively used in the defense industry, medicines, food, plastics, rubber, and other applications. Traditional organic synthesis of HMTA relies on ammonia derived from the Haber process at high temperatures and pressures. In contrast, electrochemical methods enable a safe and green one-pot synthesis of HMTA from waste NO3-. However, HMTA synthesis through the electrochemical method is challenging owing to the complex reaction pathways involving C-N bond construction and ring formation. In this study, HMTA was efficiently synthesized over electrochemical oxidation-derived copper (e-OD-Cu), with a yield of 76.8% and a Faradaic efficiency of 74.9% at -0.30 VRHE. The catalytic mechanism and reaction pathway of HMTA synthesis on e-OD-Cu were investigated through a series of in situ characterization methods and density-functional theory calculations. The results demonstrated that the electrocatalytic synthesis of HMTA involved a tandem electrochemical-chemical reaction. Additionally, the results indicated that the presence of Cu vacancies enhanced substrate adsorption and inhibited the further hydrogenation of C═N. Overall, this study provides an electrocatalytic method for HMTA synthesis and an electrochemical strategy for constructing multiple C-N bonds.

Effect of 2-hexanol and methanol on the <i>one-pot</i> process of dehydration and alkoxycarbonylation for the synthesis of esters

Objectives. To study the possibility of one-pot synthesis (combination of two processes in one reactor) for the following pairs of processes: (1) dehydration of 2-hexanol and isomerizing alkoxycarbonylation of the resulting 2-hexene, in order to obtain 2-hexyl heptanoate, and (2) dehydration of 2-hexanol and isomerizing methoxycarbonylation of the resulting 2-hexene, in order to obtain methyl esters of C7 carboxylic acids. To investigate the effect of the concentrations of 2-hexanol and methanol on the rate of the one-pot synthesis.Methods. One-pot synthesis was studied in a toluene medium in a steel batch reactor designed to operate at elevated pressure and equipped with a glass insert, a magnetic stirrer, a sampler, and gas input and discharge devices. Samples of the reaction mass were taken during the combined process and were analyzed by means of gas–liquid chromatography with a flame ionization detector.Results. The possibility of one-pot combination was demonstrated for 2-hexanol dehydration catalyzed by methanesulfonic acid, as well as for the isomerizing alkoxycarbonylation of the resulting 2-hexene with 2-hexanol and CO, catalyzed by the Pd(PPh3)2Cl2–XANTPHOS–methanesulfonic acid system. The dependencies of the rates of the dehydration of 2-hexanol and the formation of esters of C7 carboxylic acids on the concentration of 2-hexanol were shown to pass through a maximum. The possibility of the one-pot process was proved for the synthesis of esters from 2-hexanol, methanol, and CO with the predominant formation of heptanoic acid esters in the presence of the above catalytic system. The rates of dehydration of 2-hexanol and the formation of 2-hexyl esters of C7 carboxylic acids were found to decrease with increasing the concentration of methanol in the reaction mass. Under mild conditions (temperature 115°C, CO pressure 3 MPa) with the addition of methanol, the total fraction of 2-hexyl and methyl heptanoic acid esters among C7 carboxylic acid esters was determined to be 85.5%.Conclusions. The reactions of intramolecular acid–catalytic dehydration of 2-hexanol and isomerizing alkoxycarbonylation of the resulting 2-hexene, catalyzed by the Pd(PPh3)2Cl2–XANTPHOS–methanesulfonic acid system, can be performed as a one-pot process. Methanesulfonic acid simultaneously functions as a catalyst for the dehydration of 2-hexanol and a cocatalyst for the palladium–phosphine system for the alkoxycarbonylation of hexenes. In the presence of the Pd(PPh3) 2Cl2–XANTPHOS–methanesulfonic acid catalytic system, processes for the synthesis of heptanoic acid esters from 2-hexanol, methanol, and CO can be combined within one reactor. An increase in the methanol concentration negatively affects the rate of the dehydration of 2-hexanol and the formation of 2-hexyl esters of C7 carboxylic acids. A small amount of methanol in the reaction mass leads to an increase in the fraction of heptanoic acid esters among C7 carboxylic acid esters.

In situ generation of turbostratic nickel hydroxide as a nanozyme for salivary glucose sensor.

Among the 3d-transition metal hydroxide series, nickel hydroxide is a well-studied electroactive catalyst. In particular, nickel hydroxide and its composite materials are well-suited for non-enzymatic glucose sensing. The electrocatalytic efficiency of nickel hydroxide is attributed to the thickness or to be precise, the thinness of the electroactive layer. Herein, we have successfully prepared metallic nickel@nickel hydroxide nanosheets through a straightforward one-pot solvothermal method. We were able to electrochemically generate a highly sensitive α-Ni(OH)2 on the nanosheets. The dynamic generation and synergy between α- and β-Ni(OH)2, imparts a glucose oxidase enzyme-like ability to the catalyst. Our proposed nickel nanozyme exhibits a good sensitivity of 683 μA mM-1 cm-2 for glucose. The sensor operates in the range of 0.001-3.1 mM, with a lower limit of detection (LOD) of 9.1 μM and exhibits a response time of ≈00.1 s. Nickel-nanozyme demonstrated better selectivity for glucose in the presence of interfering compounds. Notably, the sensor does not suffer from an interfering oxygen evolution reaction. This greatly improves sensitivity in glucose detection in lower concentrations making the sensor viable to measure salivary glucose levels. In this study, we demonstrate that our sensor can detect glucose in human saliva. The real sample analysis was carried out with saliva samples from three healthy human volunteers and one prediabetic volunteer. Our proposed sensor measurements show excellent agreement with calculated salivary glucose levels with 98% accuracy in sensing glucose in real saliva samples.

One-Pot Synthesis of 4-Chloroquinolines via Bis(trichloromethyl) Carbonate and Triphenylphosphine Oxide-Mediated Cascade Reactions of N-Aryl Enaminones.

A novel method for synthesizing substituted 4-chloroquinolines has been devised, utilizing a cascade reaction of N-aryl enaminones promoted by bis(trichloromethyl) carbonate (BTC) and triphenylphosphine oxide (TPPO). This approach features accessible starting materials, a broad substrate range, extensive functional group compatibility, gentle reaction conditions, and straightforward operation. Its versatility is evidenced by its facile scalability and suitability for late-stage derivatization. A plausible mechanism involving α-carbonylation, 6π-azaelectrocyclization, and dehydroxychlorination sequence is proposed.

Light-Assisted Formation of Nucleosides and Nucleotides from Formamide in the Presence of Cerium Phosphate

The abiotic formation of nucleotides from small, simple molecules is of large interest in the context of elucidating the origin of life scenario. In what follows, it is shown that nucleosides and nucleotides can be formed from formamide in a one-pot reaction utilizing the mineral cerium phosphate (CePO4) as a photocatalyst, a catalyst and a reactant that supplies the necessary phosphate groups. While the most abundant RNA/DNA building blocks were thymidine and thymidine monophosphate, considerable yields of other building blocks such as cytidine, cytidine monophosphate, and adenosine cyclic monophosphate were found. Comparing the yield of nucleosides and nucleotides under light conditions to that in the dark suggests that in the presence of cerium phosphate, light promotes the formation of nucleobases, whereas the formation of nucleotides from nucleosides take place even in the absence of light. The scenario described herein is considerably simpler than other scenarios involving several steps and several reactants. Therefore, by virtue of the principle of Occam’s razor, it should be of large interest for the community.

A ratiometric fluorescence sensor for detection of organophosphorus pesticides based on enzyme-regulated multifunctional Fe-based metal-organic framework

The residues of organophosphorus pesticides (OPs) are increasing environmental pollution and public health concerns. Thus, the development of simple, convenient and sensitive method for detection of OPs is crucial. Herein, a multifunctional Fe-based MOF with fluorescence, catalytic and adsorption, is synthesized by a simple one-pot hydrothermal method. The ratiometric fluorescence sensor for detection of OPs is constructed by using only one multifunctional sensing material. The NH2-MIL-101(Fe) is able catalyze the o-phenylenediamine (OPD) into 2,3-diaminophenazine (DAP) in the presence of H2O2. The generated DAP can significantly quench the intrinsic fluorescence of NH2-MIL-101(Fe) by the fluorescence resonance energy transfer (FRET) and internal filtration effect (IFE), while producing a new measurable fluorescence. Without immobilization or molecular imprinting, pyrophosphate ion (PPi) can inhibit the peroxidase-like activity of the NH2-MIL-101(Fe) by chelating with Fe3+/Fe2+ redox couple. Moreover, PPi can also be hydrolyzed by alkaline phosphatase (ALP), the presence of OPs inhibits the activity of ALP, resulting in the increase of extra PPi preservation and signal changes of ratiometric fluorescence, the interactions of ALP with different OPs are explored by molecular docking, the OPs (e.g., glyphosate) interact with crucial amino acid residues (Asp, Ser, Ala, Lys and Arg) are indicated. The proposed sensor exhibits excellent detection performance for OPs with the detection limit of 18.7nM, which provides a promising strategy for detection of OPs.

A Minimalist Iron Oxide Nanoprobe for the High-Resolution Depiction of Stroke by Susceptibility-Weighted Imaging.

The precise mapping of collateral circulation and ischemic penumbra is crucial for diagnosing and treating acute ischemic stroke (AIS). Unfortunately, there exists a significant shortage of high-sensitivity and high-resolution in vivo imaging techniques to fulfill this requirement. Herein, a contrast enhanced susceptibility-weighted imaging (CE-SWI) using the minimalist dextran-modified Fe3O4 nanoparticles (Fe3O4@Dextran NPs) are introduced for the highly sensitive and high-resolution AIS depiction under 9.4 T for the first time. The Fe3O4@Dextran NPs are synthesized via a simple one-pot coprecipitation method using commercial reagents under room temperature. It shows merits of small size (hydrodynamic size 25.8nm), good solubility, high transverse relaxivity (r2) of 51.3 mM-1s-1 at 9.4 T, and superior biocompatibility. The Fe3O4@Dextran NPs-enhanced SWI can highlight the cerebral vessels readily with significantly improved contrast and ultrahigh resolution of 0.1mm under 9.4 T MR scanner, enabling the clear spatial identification of collateral circulation in the middle cerebral artery occlusion (MCAO) rat model. Furthermore, Fe3O4@Dextran NPs-enhanced SWI facilitates the precise depiction of ischemia core, collaterals, and ischemic penumbra post AIS through matching analysis with other multimodal MR sequences. The proposed Fe3O4@Dextran NPs-enhanced SWI offers a high-sensitivity and high-resolution imaging tool for individualized characterization and personally precise theranostics of stroke patients.

Iron metal organic framework decorated carbon nanofiber-based electrode for electrochemical sensing platform of chlorpyrifos in fruits and vegetables

Chlorpyrifos, a prime insecticide encountered in numerous agricultural products, is associated with an array of adverse health implications, notably endocrine disturbances and carcinogenic tendencies. Monitoring the environment and controlling quality requires a rapid and simple method for determining the organophosphate insecticide. Overcome the universal challenge postured by this contaminant, this study presents a novel strategy to fabricate an electrochemical sensor based on Iron MOFs, synthesized using 3,5-pyrazoledicarboxylic acid (PyDA) using one-pot solvothermal method with carbon nanofiber matrix for sensing the chlorpyrifos. Notably, this MOF anchored electrode owns important fundamental features such as an expansive surface area, abundant active sites, a vast operational spectrum linear range (1.0–150 μM), a minimal detection threshold (15.1 nM), and an amplified sensitivity towards chlorpyrifos. This Fe-PyDA/CNF/GCE electrode not only showcased more extraordinary electrochemical attributes, but its broad linear detection range and low detection threshold emphasize its ability for real-world applications with reasonable recoveries.

Large Scale Synthesis of a Stable Prefunctionalized Silver Nanocluster.

Due to the stability issue, It is difficult to prepare a silver nanocluster bearing functional sites, especially at a large scale. We report the synthesis and structure of a stable silver nanocluster bearing multiple surface aldehyde groups [Ag21(Ph2PO2)10(p-CHOPhC≡C)6]SbF6, which allows for postsynthesis modification such as surface functionalization through aldimine condensation to give homochiral clusters. Remarkably, the preparation of this cluster can be done in ~90% high yield at gram scale, which facilitates further studies and potential applications. Through DFT calculations and geometric structure analysis, the high stability of this cluster is attributed to the geometric closure and electronic structure. This is the first time that an effective one-pot method has been developed to synthesize functional silver nanoclusters in high yield. The title cluster will be useful in the development of a variety of cluster-based materials.

Microwave-supported one-pot reaction for the synthesis of 5-alkyl/arylidene-2-(morpholin/thiomorpholin-4-yl)-1,3-thiazol-4(5H)-one derivatives over MgO solid base

Abstract In this study, we synthesized 5-alkyl/arylidene-2-(morpholin/thiomorpholin-4-yl)-1,3-thiazol-4(5H)-one through a one-pot reaction using all starting materials in a microwave oven. The presence of the solid base MgO catalyzed the reaction in the eco-friendly solvent of ethanol as a green chemistry approach owing to the noticeable advantages of short reaction times to save energy and less toxic starting materials for environmental friendliness. This indicates that the one-pot reaction makes the process simpler, in which the reaction time (1 h) is shorter than that of conventional methods (10 h). The yield of the reactions reached 55–76% for 18 final products consisting of 17 derivatives of morpholine or thiomorpholine with various aldehydes and one extended moiety of the primary amine, of which 13/18 final compounds were new. The purification procedure was performed without using polluting solvents. The structures were confirmed using IR, 1H-NMR, 13C-NMR, and MS analyses.

Grafting Carbon Fibers with Graphene via a One-Pot Aryl Diazonium Reaction to Refine the Interface Performance of T1100-Grade CF/BMI Composites

In this study, a one-pot aryl diazonium reaction was used as a simple and mild method to graft graphene onto the smooth and inert surface of T1100-grade carbon fiber (CF) through covalent bonding without any damage on CF, to refine the interface performance of CF/bismaleimide (BMI) composites. XPS, SEM, AFM, and dynamic contact angle testing (DCAT) were used to characterize chemical activity, morphologies, and wettability on untreated and grafted CF surfaces. Meanwhile, the impact of the graft method on the tensile strength of CF was also examined using the monofilament tensile test. IFSS between CF grafted with graphene and BMI resin achieved 104.2 MPa after modification, increasing from 85.5 MPa by 21.8%, while the tensile strength did not decrease compared to the pristine CF. The mechanism of this interface enhancement might be better chemical bonding and mechanical interlock between CF grafted with graphene and BMI resin, which is generated from the high surface chemical activity and rough structure of graphene. This study may propose a simple and mild method to functionalize the CF surface and enhance the interface performance of composites without compromising the tensile properties of T1100-grade CF.

The Application of Tannic Acid-Coated Magnetite Nanoparticles for Recovery of Microplastics from the Water System

The presence of microplastics (MPs) is rapidly increasing in the environment, posing a significant threat to public health and the ecosystem. To monitor the impact of MPs, it is crucial to have standardized detection methods and MPs remediation techniques. Therefore, this study aimed to use tannic acid-coated magnetite nanoparticles to recover MPs, specifically polystyrene (PS) and polyethylene terephthalate (PET), from water bodies. A facile method for MPs recovery was established using the synthesized tannic acid-coated magnetite (TA-Fe3O4) as an adsorbent. TA-Fe3O4 was synthesized using tannic acid, iron (II) sulfate heptahydrate, and iron (III) chloride hexahydrate through a one-pot co-precipitation method. The adsorbent material was then characterized using a scanning electron microscope coupled with an energy dispersive x-ray spectroscopy (SEM–EDS), x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, zeta potential, and N2 adsorption–desorption (BET) techniques, confirming its successful synthesis. The maximum adsorption efficiencies for PS and PET were 83% and 98%, respectively, under the experimental conditions of pH 6–7, a contact time of 300 min, an adsorbent dose of 2.5 g/L, and an initial MPs concentration of 1.25 g/L. The study also found that the presence of ions in wastewater had a significant effect on MP recovery. However, when it came to recovering MPs from the spent adsorbent, the maximum values were observed in an acidic medium at pH 3–4 under sonification conditions. In conclusion, TA-Fe3O4 showed potential and efficiency in the recovery of MPs in aqueous media. However, further investigation is needed to improve the method and explore its application for multi-MPs recovery performance.

Photoinduced Redox Cascade Reaction of Isatins and Aliphatic Carboxylic Acids to Access 6-Hydroxyindoloquinazolinones.

A visible-light-induced cascade reaction is described for the one-pot synthesis of 6-hydroxyindoloquinazolinones using isatins (or isatins and isatoic anhydrides) and aliphatic carboxylic acids. The method provides 36 desired products in 33-96% yield, exhibiting broad substrate scope and good functional group tolerance. This approach utilizes inexpensive and commercially available starting materials, enabling the direct construction of high-value complex structures under mild conditions without the need for photocatalyst, showcasing significant applicability and environmental friendliness.