One-pot Approach Research Articles

Antibiotic entrapment in antibacterial micelles as a novel strategy for the delivery of challenging antibiotics from silica nanoparticles

Silica materials are popular in biomedical applications as composites and drug delivery platforms due to their low toxicity and biocompatibility. Mesoporous silica nanoparticles are attractive drug delivery systems based on their porous silica framework with high surface area. In the preparation of mesoporous silica frameworks, most commonly, MCM-41, the efficient removal of the template responsible for introducing porous networks, cetyltrimethyl ammonium bromide (CTAB), is a critical step due to the template's high toxicity in the environment and human health. In this work, we present a new one-pot approach of introducing challenging antibiotics within a silica framework without the need of toxic templates, but instead using micelle formation by an antibacterial agent. We demonstrate that micelles formed by cetylpyridinium chloride (CPC), a known antibacterial agent, entrap antibiotics such as rifampicin and ciprofloxacin. Extensive NMR studies elucidate the precise localisation of the antibiotic within the CPC micelle. Ciprofloxacin is placed between the outer and palisade region while rifampicin is located further into the hydrophobic CPC micelle core. In both cases, the formation of the silica framework can be built around the CPC-antibiotic loaded micelles. The resulting silica nanoparticles show loading of both CPC and antibiotic agents, porosity and dual antibacterial release upon disruption of the micelle within the silica framework. The design not only provides a strategy of a therapeutic design to form porous frameworks but also highlights the potential of precise antibiotic dose and release in nanoparticle systems.

Design, one-pot synthesis, computational and biological evaluation of diaryl benzimidazole derivatives as MEK inhibitors

MEK mutations are more common in various human malignancies, such as pancreatic cancer (70–90%), mock melanoma (50%), liver cancer (20–40%), colorectal cancer (25–35%), melanoma (15–20%), non-small cell lung cancer (10–20%) and basal breast cancer (1–5%). Considering the significance of MEK mutations in diverse cancer types, the rational design of the proposed compounds relies on the structural resemblance to FDA-approved MEK inhibitors like selumetinib and binimetinib. The compound under design features distinct substitutions at the benzimidazole moiety, specifically at positions 2 and 3, akin to the FDA-approved drugs, albeit differing in positions 5 and 6. Subsequent structural refinement was guided by key elements including the DFG motif, hydrophobic pocket and catalytic loop of the MEK protein. A set of 15 diverse diaryl benzimidazole derivatives (S1–S15) were synthesized via a one-pot approach and characterized through spectroscopic techniques, including MASS, IR, 1H NMR and 13C NMR. In vitro anticancer activities of all the synthesized compounds were evaluated against four cancer cell lines, A375, HT −29, A431 and HFF, along with the standard drug trametinib. Molecular docking was performed for all synthesized compounds (S1–15), followed by 950 ns molecular dynamics simulation studies for the promising compounds S1, S5 and S15. The stability of these complexes was assessed by calculating the root-mean-square deviation, solvent accessible surface area and gyration radius relative to their parent structures. Additionally, free energy of binding calculations were performed. Based on the biological and computational results, S15 was the most potent compound and S1 and S5 are comparable to the standard drug trametinib. Communicated by Ramaswamy H. Sarma

One-pot hydrothermal green synthetic approach of fluorescent carbon dots as optical probes for 2-nitrophenol

The pursuit of a cost-effective and green synthetic approach to chemical sensors and their application in the sensing of toxic and harmful substances is a never-ending exercise for scientists and researchers. Preparation of fluorescent carbon dots (C-dots) from biomass using water as a solvent and a hydrothermal autoclave to provide the required synthesis temperature offers a cheap and environmentally friendly synthetic approach. Herein, we report a faster, less costly and ecofriendly hydrothermal synthetic approach of carbon dots from Citrullus vulgaris peels as a precursor. The as-prepared carbon dots exhibited hydroxyl, carbonyl and amide functional groups on the surface and an amorphous structure with a particle size distribution of 1.7–3.0 nm. Moreover, the carbon dots displayed intense blue emission fluorescence at 470 nm after excitation at 400 nm. The as-prepared carbon dots demonstrated effective application without further modification towards the selective and sensitive optical recognition of 2-nitrophenol used in the manufacture of explosives. A limit of detection of 2.28×10−7 M was achieved, and no fluorescence quenching was observed in the presence of other nitroaromatic and benzene derivatives indicating excellent selectivity towards 2-nitrophenol. Finally, further studies are required to investigate the potential for the as-prepared carbon dots to monitor nitroaromatic pollutants in real environmental systems.

Adaptive Supramolecular Networks: Emergent Sensing from Complex Systems.

Molecular differentiation by supramolecular sensors is typically achieved through sensor arrays, relying on the pattern recognition responses of large panels of isolated sensing elements. Here we report a new one-pot systems chemistry approach to differential sensing in biological solutions. We constructed an adaptive network of three cross-assembling sensor elements with diverse analyte-binding and photophysical properties. This robust sensing approach exploits complex interconnected sensor-sensor and sensor-analyte equilibria, producing emergent supramolecular and photophysical responses unique to each analyte. We characterize the basic mechanisms by which an adaptive network responds to analytes. The inherently data-rich responses of an adaptive network discriminate among very closely related proteins and protein mixtures without relying on designed protein recognition elements. We show that a single adaptive sensing solution provides better analyte discrimination using fewer response observations than a sensor array built from the same components. We also show the network's ability to adapt and respond to changing biological solutions over time.

One-pot synthesis of lanthanide-doped silica film as a ratiometric fluorescent probe for selective amine vapours detection

In this work, the development of a novel paper-supported ratiometric fluorescent sensing platform for amines detection and discrimination based on co-doped Tb3+ and Eu3+ silica film is reported. The sensor film was obtained by the sol-gel process, in a one-pot straightforward synthesis approach. After exposure to different amines, the resulting intensity ratio between Tb3+ and Eu3+ emission bands presents characteristic values that can be ascribed to the different amines. The higher emission intensity ratios were found for amines with the higher pKa values, as in the case of biogenic amines. The sensor can be stored for more than 120 days, keeping the capacity to detect and distinguish different amines. The prepared fluorescent probe was tested as a food freshness indicator in beef and tuna samples, where notable changes were observed during the food degradation. This proof-of-concept shows the capability of the developed sensor platform to be applied in the detection of multiple amines, and in daily and quality control operations by “naked-eye” inspection.

Size-controllable food-grade nanoparticles based on sea cucumber polypeptide with good anti-oxidative capacity to prolong lifespan in tumor-bearing mice

Liver cancer, a malignancy with a rising global incidence, poses a significant challenge in achieving effective treatment outcomes. As food-derived nutrient, sea cucumber peptide (SCP) has shown promising anticancer effects. Therefore, we explored the nanodelivery systems to encapsulate SCP to enhance its stability in the gastrointestinal tract and improve absorption within the tumor microenvironment. This study aimed to develop size-controllable multifunctional nanoparticles using SCP, procyanidins (PCs), and vanillin through molecular assembly via a one-pot Mannich condensation approach. These food-grade nanoparticles demonstrated water solubility and exhibited a spherical structure with sizes ranging from 441 to 1360 nm, depending on the concentration of the reactants. In vitro cell experiments demonstrated that SCP nanoparticles modified with PCs effectively reduced the generation of reactive oxygen species from H2O2 and acrylamide while maintaining normal levels of mitochondrial membrane potential. Furthermore, in vivo nutrition intervention studies conducted on tumor-bearing mice revealed that mice treated with SCP nanoparticles exhibited a survival rate of 40 %, which was significantly higher than the 0 % and 20 % survival rates observed in the control and SCP-treated groups, respectively. These findings suggest that SCP nanoparticles, possessing antioxidative properties and controllable sizes, hold potential for precision nutrition in the field of cancer treatment.

Facile one-pot strategy to fabricate polyurea-based palladium for flow-through catalytic reduction of harmful hexavalent chromium from water

Developing facile approaches for fabrication of supported metallic nanoparticle (NPs) catalysts, and nascent technologies for their efficient application are highly desired. Herein, one-pot approach is developed for anchoring of palladium (Pd) nanoparticles on porous polyurea (PPU). In this process, tolylene-2,4-diisocyanate was poured to a mixture of water, acetone and palladium acetate at a fixed rate. After that, NaBH4 was added to the reaction mixture to obtain Pd/PPU with highly porous morphology. The obtained hybrid composite Pd/PPU was characterized by NMR, BET, SEM, XRD, TEM, ICP-OES, and XPS techniques. The outcomes revealed the efficacious anchoring and uniform dispersion of Pd with average size of 7.81 nm onto PPU containing highly porous structure with surface area of 115.51 m2/g. A packed-bed reactor was designed by using Pd/PPU for flow-through catalytic reduction of harmful hexavalent chromium (Cr(VI)) to benign trivalent (Cr(III)) with formic acid as reducer from water. A good permeation flux of 20,000 L/m2/h with > 99% of Cr(VI) reduction efficiency were obtained. Moreover, it was observed that Pd/PPU was a highly stable (>96% efficiency for 15 h used) catalyst for flow-through transformation of Cr(VI) to Cr(III). This report therefore proposes a facile approach for synthesis of PPU-based Pd, for continuous flow catalytic remediation of wastewaters, an emerging technology.

Silica-pyridine sulfonic acid catalyst for cellulose and glucose hydrolysis

An innovative catalyst was developed for the purpose of simplifying the manufacturing process of biofuels without the need for costly materials. The incorporation of pyridine sulfonic acid (PSA) into silica rice husk (RH) was achieved by two distinct strategies, resulting in the production of a heterogeneous catalyst. The first catalyst, RHAPSA@Dir, was prepared using the Sol-Gel technique through a one-pot synthesis approach. The second catalyst, RHAPSA@Ref, was created through post-synthesis means. BET analysis of RHAPSA@Dir showed a significant improvement in surface area to 416 m2/g, while RHAPSA@Ref only exhibited 48.2 m2/g. Upon conducting elemental research on both catalysts, it was observed that the presence of carbon, nitrogen, and sulfur was apparent. The thermal study conducted indicated that approximately 47–48% of organic matter was lost from the silica at the anticipated temperature. The SEM analysis of RHAPSA@Dir revealed that a minor level of pore arrangement was observed. Furthermore, the TEM analysis of RHAPSA@Dir demonstrated that a few particles exhibited spherical nano shapes that were clearly visible. Conversely, the SEM analysis of RHAPSA@Ref showed a rough and porous surface with large particles. Lastly, the TEM micrograph of RHAPSA@Ref revealed spherical particles with an approximate diameter of 6 nm. The use of electron microscopy revealed the presence of spherical nanostructures. Both cellulose and glucose underwent hydrolyzation over the catalysts within 2–6 h at 140 °C. The essential properties of both catalysts were their stability and reusability.

Biomimetic mineralization of lipase@MOF biocatalyst for ease of biodiesel synthesis: Structural insights into the catalytic behavior

A hybrid lipase@ZIF-8 biocatalyst was fabricated via a facile one-pot approach and coordination-driven self-assembly strategy. Entrapment immobilization of lipase in metal–organic frameworks (MOFs) was meticulously validated. The reduced Km value and apparent activation energy confirmed that the lipase@ZIF-8 registered a superior enzyme-substrate affinity than free ones. A concomitant conformational rearrangement occurred as lipase was encapsulated into the porous zeolite-like topologies, wherein lipase architectures presented more flexibility in character. An approximate 75% biodiesel yield was achieved when the biocomposites-catalyzed transesterification was conducted at given conditions. Notably, the lipase@ZIF-8 exhibited certain substrate-selectivity by deciphering the discrepancy in fatty acid profiles of the resulting biodiesel. Besides, the lipase@ZIF-8 biocomposites showed reasonable reusability and remained around 80% of initial activity after five cycles of transesterification. Consequently, the encapsulation of lipase into MOFs is a viable and sustainable avenue to address free lipase's intrinsic limitation, and underscores the immense potential in biodiesel production.

Heterojunction assembled CoO/Ni(OH)2/Cu(OH)2 for effective photocatalytic degradation and supercapattery applications.

Mixed multimetallic-based nanocomposites have been considered a promising functional material giving a new dimension to environmental remediation and energy storage applications. On this concept, a hybrid ternary CoO/Ni(OH)2/Cu(OH)2 (CNC) composite showing sea-urchin-like morphology was synthesized via one-pot hydrothermal approach, and its photocatalytic and electrochemical performances were investigated. The photocatalytic performance was explored using Congo red (CR) as a dye pollutant under visible light illumination. The presence of mixed phases of ternary metal ions could minimize the recombination efficacy of photogenerated charge carriers on the basis of the heterojunction mechanism, resulting in 90% degradation of CR dye (40mg L-1). The effect of scavengers coupled with electrochemical experiments revealed O2-. radical as the predominating species responsible for the degradation of CR. From the electrochemical analysis of CNC, the well-distinguished redox peaks indicated the redox-type nature with a specific capacity of 405 C g-1. For practical applications, an supercapattery (CNC( +)|KOH|AC( -)) was assembled furnishing an energy density of 42 W h kg-1 at a power density of 5160 W kg-1 at 5 A g-1 along with a high capacity retention and coulombic efficiency of 98.83% over 5000 cycles.

Br-doped Cu nanoparticle formed by in situ restructuring for highly efficient electrochemical reduction of CO2 to formate

Electrochemical conversion of CO2 into chemical feedstock, such as an energy-dense liquid product (formate), is desirable to address the excessive emission of greenhouse gases and store energy. Cu-based catalysts exhibit great advantages in electrochemical CO2 reduction reaction (eCO2RR) due to their low cost and high abundance, but suffer from low selectivity of formate. In this work, a facile one-pot approach is developed to synthesize CuBr nanoparticle (CuBr NP) that can conduct in situ dynamic restructuring during eCO2RR to generate Br-doped Cu NP. The in situ-formed Br-doped Cu NP can afford up to 91.6% Faradaic efficiency (FE) for formate production with a partial current density of 15.1 mA·cm−2 at −0.94 V vs. reversible hydrogen electrode (RHE) in an H-type cell. Moreover, Br-doped Cu NP can deliver excellent long-term stability for up to 25 h. The first-principles density functional theory (DFT) calculations show that the doped Br can regulate the electronic structure of Cu active sites to optimize the adsorption of the HCOO* intermediate, greatly hindering the formation of CO and H2. This work provides a strategy for electronic modulation of metal active site and suggests new opportunities in high selectivity for electrocatalytic reduction of CO2 to formate over Cu-based catalysts.

Sonoelectrochemical nitrided graphene nanosheets with vacancies and their applications for catalysis and sensing of uric acid oxidation

A sonoelectrochemical method for preparing N-doped defective graphene nanosheets (N/O-dGNs) with point defects and 5-9 or 5-8-5 vacancies and oxygen-containing groups was successfully demonstrated. In this one-pot approach, the N-bonding configuration and N content of N/O-dGNs were finely tuned by the ultrasonic power (192, 320, and 640 W). The N content in atomic percentage (at%) for N/O-dGN (N/O-dGN320W) with point defects and 5-8-5 vacancy prepared at 320 W power was 5.6 at%, greater than 3.0 at% and 2.6 at% for N/O-dGN with point defects and 5-9 vacancies at 192 W and 640 W power (N/O-dGN192W and N/O-dGN640W), respectively. N-bonding sites on N/O-dGN320W were dominantly amine N (2.1 at%) and pyrrolic N (2.4 at%). Additionally, the electrocatalytic activity of N/O-dGN192W, N/O-dGN320W, and N/O-dGN640W was successfully demonstrated for the sequential uric acid (UA) oxidation reaction (UOR), in which N/O-dGN320W displayed a significant mass activity (2.51 A/g). As in the transient catalysis of UOR, N/O-dGN320W with amine N showed 400.8 μA mM−1 cm−2 in sensitivity within a wide linear analysis range (1.5 × 10–2–6 mM) for amperometrically sensing UA. The results of real sample experiments using serum samples further demonstrated the potential of N/O-dGN320W as a non-enzymatic UA sensor.

Effect of 4-mercaptophenylboronic acid functionalized MoS2 quantum dots on amyloid aggregation of bovine serum albumin

In recent years, seeking and screening of compounds that can inhibit and/or depolymerize protein aggregation has been a hot issue in the field of pharmaceutical research. As a new material, quantum dots have been widely concerned by medical researchers. In present study, a novel 4-mercaptophenylboronic acid functionalized MoS2 quantum dots (4-MPBA-MoS2 QDs) was successfully synthesized through a one-pot hydrothermal approach by using molybdate dehydrate and 4-mercaptophenylboronic acid as Mo and S source, respectively. Transmission electron microscopy observation showed that the morphology and microstructure of the 4-MPBA-MoS2 QDs displayed uniform spherical shape with a diameter of approximately 1.5 ∼ 3.0 nm. The UV and fluorescence spectra experiments indicated that the prepared QDs had good water solubility and two weak absorption peaks were appeared at 280 nm and 310 nm. When the excitation wavelength was set to 310 nm, the 4-MPBA-MoS2 QDs had the strongest fluorescence intensity, and the maximum emission wavelength appeared at 405 nm. In vitro experiments showed that the 4-MPBA-MoS2 QDs could significantly reduce the aggregation of bovine serum albumin (BSA). Especially when the mass ratio of BSA to 4-MPBA-MoS2 QDs was 1:5, the inhibition rate could reach 76.4%. Cell experiment showed that the presence of 4-MPBA-MoS2 QDs could obviously decrease the cytotoxicity induced by BSA amyloid fibrils. Moreover, the depolymerization of BSA amyloid fibrils by 4-MPBA-MoS2 QDs and its excellent cell permeability were also observed. Molecular docking studies have shown that 4-MPBA-MoS2 QDs may stabilize the BSA structure through van der Waals forces, hydrophobic force, electrostatic interactions and hydrogen bonds formed between the outer layer of 4-MPBA and BSA to prevent fibrosis aggregation. The results of this study suggested that 4-MPBA-MoS2 QDs showed low cytotoxicity, good biocompatibility and solubility, and had a great potential in the design of new drugs for the treatment of amyloid-related diseases.

Synthesis and characterization of graphene via electrochemical exfoliation technique and study its electrochemical properties

In this study, we present a one-pot approach for the large-scale synthesis of multilayer to few-layer graphene nanosheets in an aqueous medium that is cost-effective, environmentally friendly, high-yielding, and simple. This electrochemical exfoliation method produces low defect and high yield graphene nanosheet products and is more efficient than chemical exfoliation methods. Two highly oriented pyrolytic graphite plates (HOPG) are utilized as the anode and cathode in this method, which also incorporates two electrode geometry configurations. XRD, HRTEM, AFM, XPS, and Raman spectroscopy are used to describe graphene nano-sheets. Raman characterization supports graphene’s inherent qualities. By using cyclic voltammetry, the electrochemical performance of the produced nano-sheets is evaluated.

Self-Assembled 2D VS2 /Ti3 C2 Tx MXene Nanostructures with Ultrafast Kinetics for Superior Electrochemical Sodium-Ion Storage.

Constructing nanostructures with high structural stability and ultrafast electrochemical reaction kinetics as anodes for sodium-ion batteries (SIBs) is a big challenge. Herein, the robust 2D VS2 / Ti3 C2 Tx MXene nanostructures with the strong Ti─S covalent bond synthesized by a one-pot self-assembly approach are developed. The strong interfacial interaction renders the material of good structural durability and enhanced reaction kinetics. Meanwhile, the enlarged and few-layered MXene nanosheets can be easily obtained according to this interaction, providing a conductive network for sufficient electrolyte penetration and rapid charge transfer. As predicted, the VS2 /MXene nanostructures exhibit an extremely low sodium diffusion barrier confirmed by DFT calculations and small charge transfer impedance evidenced by electrochemical impedance spectroscopy (EIS) analysis. Therefore, the SIBs based on the VS2 /MXene electrode present first-class electrochemical performance with the ultrahigh average initial columbic efficiency of 95.08% and excellent sodium-ion storage capacity of 424.6mAhg-1 even at 10Ag-1 . It also shows an outstanding sodium-ion storage capacity of 514.2mAhg-1 at 1Ag-1 with a capacity retention of nearly 100% within 500 times high-rate cycling. Such impressive performance demonstrates the successful synthesis strategy and the great potential of interfacial interactions for high-performance energy storage devices.

Two Cascade Reactions with Oleate Hydratases for the Sustainable Biosynthesis of Fatty Acid-Derived Fine Chemicals

Oleate hydratases (OHs) are of significant industrial interest for the sustainable generation of valuable fine chemicals. When combined with other enzymes in multi-step cascades, the direct formation of fatty acid congeners can be accomplished with minimal processing steps. In this study, two cascade reactions are presented, which can be applied in one-pot approaches. The first cascade was placed “upstream” of an OH derived from Rhodococcus erythropolis (OhyRe), where a lipase from Candida rugosa was applied to hydrolyze triglycerides into free fatty acids, a crucial step for OH conversion. Further, we tested the lipase–OhyRe cascade with various types of renewable triglycerides of plant and microbial origin. In this context, the most efficient conversion was observed for microbial oil from Cutaneotrichosporon oleaginosus leading the way toward its industrial application. In contrast, the second cascade was placed “downstream” of OhyRe, where a novel secondary alcohol dehydrogenase (secADH) was applied to oxidize the hydroxylated fatty acid into a fatty acid ketone. Optimal reaction parameters for the cascade with the secADH were established, which allows this to be applied to high-throughput screens. Moreover, we describe a light-dependent route, thereby extending the catalytic efficiency of the OH enzyme system.

Wet adhesion enhancement through citric-acid-regulated supramolecular network

Adhesion on wet surface is of significance but remains challenging. Despite large steps forward in wet adhesives, they suffer from complicated preparation procedures and unbalanced properties. Herein, we develop a simple one-pot approach to fabricate a supramolecular adhesive with simultaneous enhancement in wet adhesion and mechanical toughness, which is achieved via citric acid (CA)-regulated supramolecular network of N-hydroxy succinimide (NHS) grafted polyacrylic acid chain and gelatin. CA not only reinforces supramolecular network by forming abundant hydrogen bonds, but also repels the NHS groups exposed outward to increase the opportunity for bonding with the target surface. The resultant adhesive shows fast and robust wet adhesion, high mechanical strength and elongation, as well as good biocompatibility. Such features enable the resultant adhesive with high potential in a variety of biomedical settings, such as tissue adhesion, sealant, and skin-adhesive strain sensor. This study opens a new avenue for the development of advanced bioadhesives, holding broad clinical application prospects.

Synthesis, Characterization, and Catalytic Application of SnP2O7 for the Highly Efficient Synthesis of Xanthene Derivatives

This study introduces a mono-ammonium phosphate-based heterogeneous catalyst that possesses characteristics of simplicity, reusability, and recoverability, making it well-suited for multicomponent reactions. The prepared catalyst underwent comprehensive characterization using Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) patterns, scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). Employing this catalyst in a one-pot multicomponent approach, it becomes possible to synthesize xanthene derivatives efficiently. The results showcase the impressive performance of the novel SnP2O7, which acts as a heterogeneous catalyst in traditional reactions, leading to the desired products with yields ranging from good to excellent and within a short reaction time. Notably, SnP2O7 exhibits remarkable stability in its catalytic activity, enabling its use for up to five cycles without experiencing a significant decrease in yield.

Synthesis and Reduction of Nitrogen-Substituted Diaryl Dihydrophenazine Diradical Dications.

A one-pot synthetic approach to form core-extended N,N'-disubstituted diaryl dihydrophenazine (DADHP) diradical dications (DRDCs) via chemical oxidation from aryl-substituted ortho-phenyldiamines is reported. The isolated N,N'-disubstituted DADHP DRDCs were reduced to their neutral counterparts with hydrazine. The model system featuring an unsubstituted fluorene aryl group, 2a, was tested as a photocatalyst for the polymerization of methyl methacrylate using organocatalyzed atom transfer polymerization (O-ATRP), which yielded a polymer with a controlled molecular weight and narrow polydispersity.

Instant Macrocyclizations via Multicomponent Reactions.

Macrocycles fascinate chemists due to both their structure and their applications. However, we still lack efficient and sustainable synthetic methods, giving us straightforward access to them. Herein, a rapid macrocyclization utilizing a two-step, one-pot approach based on orthogonal multicomponent reaction (MCR) tactics is introduced. This synthetic protocol, which is based on Ugi and Groebke-Blackburn-Bienaymé reactions with isocyanides tethered to alkyl tosylates, yields medium sized macrocycles that are otherwise difficult to achieve. Single crystal structures reveal conformational reorganization via intramolecular hydrogen bonding, and modeling studies profile the synthesized libraries.