One-pot Aqueous Synthesis Research Articles

Freestanding Penta-Twinned Palladium Nanosheets.

Control over the morphology of nanomaterials to have a 2D structure and manipulating the surface strain of nanostructures through defect control have proved to be promising for developing efficient catalysts for sustainable chemical and energy conversion. Here a one-pot aqueous synthesis route of freestanding Pd nanosheets with a penta-twinned structure (PdPT NSs) is presented. The generation of the penta-twinned nanosheet structure can be succeeded by directing the anisotropic growth of Pd under the controlled reduction kinetics of Pd precursors. Experimental and computational investigations showed that the surface atoms of the PdPT NSs are effectively under a compressive environment due to the strain imposed by their twin boundary defects. Due to the twin boundary-induced surface strain as well as the 2D structure of the PdPT NSs, they exhibited highly enhanced electrocatalytic activity for oxygen reduction reaction compared to Pd nanosheets without a twin boundary, 3D Pd nanocrystals, and commercial Pd/C and Pt/C catalysts.

Copper-based nanodots as efficient biomimetic antibiotics for the treatment of oral bacterial infections

Oral infectious diseases caused by a variety of pathogenic bacteria seriously affect the quality of life. However, these diseases remain a clinical challenge because of the lack of simple, safe, and universal prophylactics. To address these limitations, we synthesize CuOx nanodots (CuOx NDs) with excellent Fenton-like reaction activity and utilize them in the treatment of oral bacterial infections. Different from other complicated approaches, CuOx NDs are rationally prepared using a facile one-pot aqueous synthesis. In the presence of H2O2, these well-developed CuOx NDs can efficiently catalyze the generation of hydroxyl radicals (·OH) around oral pathogens, leading to the death of various bacteria. Meanwhile, results of biosafety indicate the high biocompatibility and extremely low toxicity of these CuOx NDs. After understanding the admirable in vitro antibacterial effect of CuOx NDs in the presence of H2O2, we further explore their in vivo antibacterial performance on several classical animal models including oral mucosal wound model, intragingival bacteria-infected model, and the periodontal infection model. As expected, these CuOx NDs with wide-spectrum antibacterial activity can serve as high-performance antibacterial reagents for the treatment of various oral bacterial infections with the help of H2O2. In brief, current nanoplatform can act as efficient antibiotics against oral pathogens with broadening the biomedical applications of copper-based nanomaterials.

Metal-Catalyst-Free One-Pot Aqueous Synthesis of trans-1,2-Diols from Electron-Deficient α,β-Unsaturated Amides via Epoxidation Using Oxone as a Dual Role Reagent.

In organic synthesis, incorporating two functional groups into the carbon-carbon double bond of α,β-unsaturated amides is challenging due to the electron-deficient nature of the olefin moiety. Although a few examples of dihydroxylation of α,β-unsaturated amides have been demonstrated, producing cis-1,2-diols using either highly toxic OsO4 or other specialized metal reagents in organic solvents, they are limited to several specific amides. We describe herein a general and one-pot direct synthesis of trans-1,2-diols from electron-deficient α,β-unsaturated amides through dihydroxylation using oxone as a dual-role reagent in water. This reaction does not require any metal catalyst and produces non-hazardous and nontoxic K2SO4 as the sole byproduct. Moreover, epoxidation products could also be selectively formed by adjusting the reaction conditions. By the strategy, the intermediates of Mcl-1 inhibitor and antiallergic bioactive molecule can be synthesized in one pot. The gram-scale synthesis of trans-1,2-diol which is isolated and purified by recrystallization further shows the potential applications of this new reaction in organic synthesis.

PRODUCTION AND PROPERTIES OF A PHOTOLUMINESCENT COATING BASED ON SEMICONDUCTOR QUANTUM DOTS IN A HOLLOW CORE OF MICROSTRUCTURED GLASS

Microstructured optical fibers (MOF) are a promising tool for improving biosensors, optical sensing, biomedical research, and clinical imaging. Approaches to the modification of the inner surface of microstructured optical fibers with a hollow core (MOF-HC) with polymer and photoluminescent materials using layer-by-layer deposition technology was developed. The method allows not only varying the thickness and charge of the layers, but also controllably introduce functional structures into the layers, in particular nanoparticles. The layer-by-layer deposition of polydiallyldimethylammonium chloride (PDDA) cationic polyelectrolyte with an average molecular weight (200 - 350 kDa) and negatively charged fluorescent nanoparticles - cadmium-free quantum dots (QD) of the AgInS2/ZnS structure, luminescent red (625 nm), orange (606 nm), yellow (570 nm) and green (556 nm) was investigated. QDs of the AgInS2/ZnS core/shell structure were obtained by the one-pot aqueous synthesis and selectively separated by successive deposition into fractions according to the size and color of the luminescence. This ensured the similarity of the properties of QDs with different luminescence colors. It was found that with an increase in the number of bilayers PDDA/QD from 1 to 5, the long-wave shift of the HC-MOF transmittance spectrum is: for layers based on red QD - 10 nm, orange QD - 11 nm, yellow 7 nm and green 8 nm relative to the spectrum of the original HC-MOF. When QD is included in the composition of the photoluminescent coating in the HC-MOF, a decrease in the wavelength of the maximum emission of QD is recorded, while the application of a subsequent layer of PDDA leads to its increase. For citation: Kochergin T.P., Ponomaryova T.S., Goryacheva I.Y. Production and properties of a photoluminescent coating based on semiconductor quantum dots in a hollow core of microstructured glass. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 2. P. 85-91. DOI: 10.6060/ivkkt.20236602.6615.

Surface chemistry dependent toxicity of inorganic nanostructure glycoconjugates on bacterial cells and cancer cell lines

Surface functionalized nanostructures have outstanding potential in biological applications owing to their target-specific design. In this study, we utilized laboratory synthesized carbohydrate-derivatives (i.e., galactose, mannose, lactose, and cellobiose derivatives) for aqueous one-pot synthesis of gold (Au) and silver (Ag) nanostructure glycoconjugates (NSs), and iron metal-organic framework glycoconjugates (FeMOFs). This work aims to test whether differences in the surface chemistry of the inorganic nanostructures play roles in revealing their toxicities towards bacterial cells and cancerous cell lines. As of the first step, biological activity of AuNSs, AgNSs, and FeMOFs were tested against a variety of gram (−) and gram (+) bacterial strains, where AgNSs possessed moderate to high antibacterial activities against all the tested bacterial strains, while AuNSs and FeMOFs showed their bacterial toxicity mostly depending on the strain. Minimum inhibitory concentration (MIC) and Minimum bactericidal concentration (MBC) determination studies were performed for the nanostructure glycoconjugates, for which μg/mL MBC values were obtained such as (Cellobiose p-aminobenzoic acid_AgNS) CBpAB_AgNS gave 50 μg/mL MBC value for P.aeruginosa and S.kentucy. The activity of selected sugar ligands and corresponding glycoconjugates were further tested on MDA-MB-231 breast cancer and A549 lung cancer cell lines, where selective anticancer activity was observed depending on the surface chemistry as well. Besides, d-penicillamine was introduced to galectin specific sugar ligand coated AuNS glycoconjugates, which showed very strong anticancer activities even at low doses. Overall, the importance of this work is that the surface chemistry of the inorganic nanostructures can be critical to reveal their toxicity towards bacterial cells and cancerous cell lines.

Reactive Oxygen Species Responsive Cleavable Hierarchical Metallic Supra-Nanostructure.

A reactive oxygen species (ROS) responsive cleavable hierarchical metallic supra-nanostructure (HMSN) is reported. HMSN structured with thin branches composed of primary gold (Au) nanocrystals and silver (Ag) nano-linkers is synthesized by a one-pot aqueous synthesis with a selected ratio of Au/Ag/cholate. ROS responsive degradability of HMSN is tested in the presence of endogenous and exogeneous ROS. Significant ROS-responsive structural deformation of HMSN is observed in the ROS exposure with hydrogen peroxide (H2 O2 ) solution. The ROS responsiveness of HMSN is significantly comparable with negligible structural changes of conventional spherical gold nanoparticles. The demonstrated ROS responsive degradation of HMSN is further confirmed in various in vitro ROS conditions of each cellular endogenous ROS and exogeneous ROS generated by photodynamic therapy (PDT) or X-ray radiation. Then, in vivo ROS responsive degradability of HMSN is further evaluated with intratumoral injection of HMSN and exogeneous ROS generation via PDT in a mouse tumor model. Additional in vivo biodistribution and toxicity of intravenously administrated HMSN at 30-day post-injection are investigated for potential in vivo applications. The observed ROS responsive degradability of HMSN will provide a promising option for a type of ROS responsive-multifunctional nanocarriers in cancer treatment and various biomedical applications.

Synthesis and characterization of the `Japanese rice-ball'-shaped Molybdenum Blue Na4[Mo2O2(OH)4(C6H4NO2)2]2[Mo120Ce6O366H12(OH)2(H2O)76]∼200H2O.

The hybridized lanthanide-containing molybdenum blue (Ln-MB) wheel Na4[Mo2O2(OH)4(C6H4NO2)2]2[Mo120Ce6O366H12(OH)2(H2O)76]∼200H2O ({Mo2(C6H4NO2)2}2{Mo120Ce6}) was assembled in an aqueous one-pot synthesis. The Ln-MB was hybridized with 2-picolinic acid through the generation of the organometallic counter-ion [Mo2O2(OH)4(C6H4NO2)2]2+. Control experiments demonstrated that the position of the carboxylic acid group (2-position to the N atom) in the hybridization component is critical in yielding single crystals of Ln-MB. In addition to single-crystal X-ray diffraction (XRD) analysis, which revealed a `Japanese rice-ball'-shaped Ln-MB as the anion, elemental analyses, IR spectroscopy, and thermogravimetric analysis (TGA) were performed to confirm its structure and composition. Bond-valence-sum calculations (BVS) revealed that {Mo2(C6H4NO2)2}2{Mo120Ce6} is composed of a 24-electron reduced anionic ring, which was confirmed by Vis-NIR spectroscopy.

GSH capped Cu-Zn-In-S quantum dots: one-pot aqueous synthesis and cell labeling applications

We report a one-pot method to directly synthesize highly luminescent Cu-In-Zn-S quantum dots(CIZS QDs) in aqueous media by using bio-compatible glutathione (GSH) as capping ligand and stabilizer. The influences of various experimental variables, including reaction time, pH value, and precursor ratio, have been systematically investigated. As a result, the stable ternary CIZS QDs with good photoluminescence emission properties and narrow size distribution can be obtained. In addition, the obtained GSH capped CIZS QDs exhibited excellent optical performance and water stability. It is a promising fluorescent probe for biological labels due to the absence of toxic heavy metal ions.

Gadolinium-doped Cu-In-Zn-S quantum dots: one-pot aqueous synthesis and multimodal bioimaging

We report a one-pot method to directly synthesize magnetic resonance/fluorescence multimodal imaging gadolinium-doped Cu-In-Zn-S quantum dots(GCIZS QDs) in aqueous media by using bio-compatible glutathione (GSH) as capping ligand and stabilizer. The optical features and structure of the GCIZS QDs have been characterized by UV-vis and fluorescence spectroscopy, XRD, TEM, and FT-IR. As a result, The GCIZS QDs possessed a strong fluorescence and r1 value of 4.015 mM-1 s -1 at the Cu/Gd ratio of 1/2. Furthermore, the GCIZS QDs were good water solubility and less cytotoxic up to 250 μg/mL in HUVEC cells. The red emission GCIZS QDs from the MDA-MB-231cells was clearly observed under microscope. It indicated that the GCIZS QDs present great potential as magnetic resonance /fluorescence multimodal imaging contrast agents for biological labels.

Eco-friendly one-pot aqueous synthesis of ultra-thin AuPdCu alloyed nanowire-like networks for highly sensitive immunoassay of creatine kinase-MB

• Ultra-thin AuPdCu NWNs were synthesized by an eco-friendly one-pot aqueous method. • 4-Aminopyridine was employed as structure-directing agent in this synthesis. • The ultra-thin nanowire networks provided enlarged specific surface area and abundant active sites. • The resultant immunosensor displayed a satisfactory assay for CK-MB in this research. Advanced nanomaterials have attracted ever-growing interest in design and construction of electrochemical immunosensors, which hold great promise to improve sensitivity in bioanalytical system. In this work, ultra-thin AuPdCu alloyed nanowire networks (NWNs) were controllably synthesized by an eco-friendly one-pot aqueous approach with 4-aminopyridine as a structural directing agent, which served as signal amplifiers in construction of an ultra-sensitive label-free electrochemical immmunosensor for creatine kinase-MB (CK-MB) assay, taking the virtues of the large specific surface area, high electronic conductivity, and good biocompatibility. Importantly, the AuPdCu NWNs efficiently catalyzed the reduction of hydrogen peroxide (H 2 O 2 ) and thereby enhanced the detection responses. Under the optimal conditions, the as-fabricated immmunosensor showed a wide linear range of 0.001–2000 ng mL –1 for CK-MB detection, along with a low limit of detection (LOD = 0.88 pg mL –1 , S/N = 3). Thereby, this research was successfully applied for CK-MB quantitation in serum samples with acceptable results, which would provide some valuable guidelines for monitoring other cardiac markers in clinical applications.

Aqueous one-pot synthesis of well-defined zwitterionic diblock copolymers by RAFT polymerization: an efficient and environmentally-friendly route to a useful dispersant for aqueous pigments

An atom-efficient, wholly aqueous one-pot synthesis of zwitterionic diblock copolymers has been devised. Such copolymers can serve as highly effective aqueous dispersants for nano-sized transparent yellow iron oxide particles.

Aqueous One-pot Synthesis of Glycopolymers by Glycosidase-catalyzed Glycomonomer Synthesis Using 4,6-Dimetoxy Triazinyl Glycoside Followed by Radical Polymerization.

Glycopolymers have attracted increased attention as functional polymeric materials, and simple methods for synthesizing glycopolymers remain needed. This paper reports the aqueous one-pot and chemoenzymatic synthesis of four types of glycopolymers via two reactions: the β-galactosidase-catalyzed glycomonomer synthesis using 4,6-dimetoxy triazinyl β-D-galactopyranoside and hydroxy group-containing (meth)acrylamide and (meth)acrylate derivatives as the activated glycosyl donor substrate and as the glycomonomer precursors, respectively, followed by radical copolymerization of the resulting glycomonomer and excess glycomonomer precursor without isolating the glycomonomers. The resulting glycopolymers bearing galactose moieties exhibited specific and strong interactions with the lectin peanut agglutinin as glycoclusters.

Controlled morphology and dimensionality evolution of NiPd bimetallic nanostructures

Controlling the morphology of noble metal-based nanostructures is a powerful strategy for optimizing their catalytic performance. Here, we report a one-pot aqueous synthesis of versatile NiPd nanostructures at room temperature without employing organic solvents or surfactants. The synthesis can be tuned to form zero-dimensional (0D) architectures, such as core–shell and hollow nanoparticles (NPs), as well as nanostructures with higher dimensionality, such as extended nanowire networks and three-dimensional (3D) nanodendrites. The diverse morphologies were successfully obtained through modification of the HCl concentration in the Pd precursor solution, and the reaction aging time. An in-depth understanding of the formation mechanism and morphology evolution are described in detail. A key factor in the structural evolution of the nanostructures was the ability to tune the reduction rate and to protonate the citrate stabiliser by adding HCl. Spherical core–shell NPs were formed by the galvanic replacement-free deposition of Pd on Ni NPs which can be transformed to hollow NPs via a corrosion process. High concentrations of HCl led to the transition of isotropic spherical NPs into anisotropic wormlike nanowire networks, created through an oriented attachment process. Aging of these nanowire networks resulted in the formation of 3D porous nanodendrites via a corrosion process. The diverse structures of NiPd NPs were anchored onto acid treated-activated carbon (AC) and exhibited improved catalytic efficiency towards the hydrogenation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP).

An Electrochemical Non-Enzymatic Glucose Sensor Based on Ultrathin PdAg Single-Crystalline Nanowires.

Electrochemical non-enzymatic sensors have great potential for prompt and efficient detection of glucose. Herein, a novel, highly efficient electrochemical non-enzymatic glucose sensor is reported that is based on ultrathin PdAg single-crystalline nanowires (NWs). Ultrathin PdAg NWs are fabricated by a facile one-pot aqueous synthesis through an in situ growth strategy with an amphiphilic surfactant as the template. A comparison of the activities of PdAg NWs with different compositional ratios and nanostructures shows that ultrathin Pd2 Ag1 NWs hold the best performance toward electrochemical detection of glucose with an operable sensitivity of 11.6 μA mM-1 cm-2 and a linear response range of 0.1-8 mM. Structural and compositional features of the Pd2 Ag1 NWs allow an excellent selectivity, rapid response, and good long-term stability for electrochemical glucose sensor. This work thus provides a new possibility for the rational design and synthesis of noble-metal-based nanomaterials for non-enzymatic sensors.

One-Pot Aqueous Synthesis of Icosahedral Au as Bifunctional Candidates for Enhanced Glucose Electrooxidation and Surface-Enhanced Raman Scattering.

Bifunctional candidates, which could provide catalytic and plasmonic properties simultaneously, could activate a promising development for biomedicine. Here, we kinetically controlled and synthesized a penta-twinned icosahedral Au (Ih Au) by a facile wet-chemical protocol without assistance of stabilizers. Benefiting from icosahedral morphology and kinetic synthesis process, the Ih Au nanoparticles (NPs) incorporate three key advantages: (i) ample active sites/"hot spots" and surface strain, (ii) good stability/chemical inertness and easy functionalization, and (iii) biological compatibility and a clean surface, which could promote their electrocatalysis and photonic capacity. Ih Au NPs, as bifunctional nanomaterials, exert excellent electrocatalytic and surface-enhanced Raman scattering (SERS) performances. Ih Au delivers the highest glucose electrooxidation (GEO) peak current density with 6.87 mA cm-2, which is 14 times larger than that of Turkevich Au (0.49 mA cm-2) under the same condition. Moreover, the SERS signals of rhodamine 6G (R6G) on Ih Au are much stronger than that on the other corresponding Au counterparts. Particularly, the SERS intensity of R6G on Ih Au increases by about four times compared to that on Au NPs. This study motivates the great prospect for combining Ih Au's bifunctionalities and indicates the potential of bifunctional nanomaterials in biologically implanted devices.

Facile one-pot aqueous synthesis of highly soluble and luminescent CdSe quantum dots without nitrogen bubbling

CdSe quantum dots (QDs) have been widely used in a plethora of applications due to their relatively high photocatalytic abilities and unique properties.

One-Pot Aqueous and Template-Free Synthesis of Mesoporous Polymeric Resins

This work explores the novel one-pot aqueous phase synthesis of mesoporous phenolic-hyperbranched polyethyleneimine resins without the use of a template, and their utility as heterogeneous catalysts in batch reactors and continuous microreactors. Catalyst surface areas of up to 432 m2/g were achieved with a uniform Pd distribution and an interconnected, highly porous, network structure, confirmed through Brunauer–Emmett–Teller (BET) surface area measurements, scanning electron microscopes (SEM), X-Ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy (TEM), and Energy-dispersive X-ray spectroscopy (EDS). The heterogeneous catalysts achieved a maximum 98.98 ± 1% conversion in batch Suzuki couplings, with conversions being dependent upon reaction conditions, reactant chemistries, Pd loading and catalyst surface area. The catalysts were shown to be recyclable with only a marginal loss in conversion achieved after five runs. Up to 62 ± 5% and 46.5 ± 8% conversions at 0.2 mL/s and 0.4 mL/s flow rates, respectively, were achieved in a continuous microreactor. Understanding the mechanism of action of this mesoporous resin is a future research area, which could help expand the application vistas for this catalyst platform.

Simple one-pot aqueous synthesis of 3D superstructured PtCoCuPd alloyed tripods with hierarchical branches for ultrasensitive immunoassay of cardiac troponin I

By integrating the amplified electrochemical signals and effective capture of antibodies together, advanced multimetallic superstructured nanocrystals endow label-free immunosensors promising applications in early diagnosis and monitoring of diseases. Herein, four-metallic PtCoCuPd hierarchical branch-like tripods (HBTPs) were directly synthesized by a green one-pot aqueous method without any seed or organic solvent involved, which were applied to construct a novel label-free immunosensor for detecting cardiac troponin I (cTnI). The specific hierarchical micro/nanostructures greatly improved the immobilization of antibodies and enhanced the catalytic activity for K3Fe(CN)6, which would effectively amplify the electrochemical signals, thereby improving the detection sensitivity. Under the optimal conditions, the as-developed immunosensor exhibited a wide linear range (0.001–100.0 ng mL−1) and a low detection limit (0.2 pg mL−1, S/N = 3) for the assay of cTnI. The immunosensor provides a powerful platform for quantitative detection of cTnI, which can be explored to detect other tumor markers in actual sample analysis.

Ultrathin PdFePb nanowires: One-pot aqueous synthesis and efficient electrocatalysis for polyhydric alcohol oxidation reaction

Synthesis of high-efficiency catalysts for alcohol oxidation reaction caused great interest in direct alcohol fuel cells (DAFCs). Ultrathin PdFePb nanowires (NWs) with an average diameter of 2.3 nm were synthesized by a simple and fast one-pot aqueous synthesis, using octylphenoxypolyethoxyethanol (NP-40) as the structure-directing agent. The as-prepared PdFePb NWs displayed an increscent electrochemically active surface area (ECSA, 121.18 m2 g−1 Pd). For ethylene glycol oxidation reaction (EGOR) and glycerol oxidation reaction (GOR), PdFePb NWs exhibited much higher activity and superior stability, outperforming those of homemade PdFe NWs, PdPb NWs, commercial Pd black and Pd/C (20 wt%). These results reveal dramatically high catalytic activity and durability of ultrathin PdFePb NWs in enhancing polyols electrooxidation.

One-pot aqueous synthesis of two-dimensional porous bimetallic PtPd alloyed nanosheets as highly active and durable electrocatalyst for boosting oxygen reduction and hydrogen evolution

Recently, two-dimensional materials have gained increasing research attention due to their large surface area, high physical and chemical stability, and excellent electrocatalytic performances. Herein, we reported a simple and fast one-pot aqueous method for synthesis of two-dimensional porous bimetallic PtPd alloyed nanosheets (NSs) using benzyldimethylhexadecylammonium chloride (HDBAC) as the capping agent and stabilizer. The formation mechanism involved the oriented attachment and self-assembly. The PtPd NSs exhibited excellent oxygen reduction reaction (ORR) activity with the positive shift (c.a. 43 mV) of the half-wave potential in 0.1 M KOH solution, clearly outperforming that of commercial Pt/C (50 wt%). Moreover, the as-prepared catalyst displayed 2.4 times enlargement in mass activity (MA, 382.10 mA mg−1) and 3.5 times enhancement in specific activity (SA, 0.95 mA cm−2) relative to those of Pt/C at 0.80 V. Meanwhile, the as-obtained catalyst demonstrated highly boosted hydrogen evolution reaction (HER) in 0.5 M H2SO4 electrolyte, surpassing that of Pt/C. These results reveal the practical applications of the catalyst in energy storage and conversion.