Electrocatalytic Water Oxidation by Mononuclear Copper Complexes of Bis-amide Ligands with N4 Donor: Experimental and Theoretical Investigation.

The present work describes electrocatalytic water oxidation of three monomeric copper complexes [CuII(L1)] (1), [CuII(L2)(H2O)] (2), and [CuII(L3)] (3) with bis-amide tetradentate ligands: L1 = N,N'-(1,2-phenylene)dipicolinamide, L2 = N,N'-(4,5-dimethyl-1,2-phenylene)bis(pyrazine-2-carboxamide), L3 = N,N'-(1,2-phenylene)bis(pyrazine-2-carboxamide), for the production of molecular oxygen by the oxidation of water at pH 13.0. Ligands and all complexes have been synthesized and characterized by single crystal XRD, analytical, and spectroscopic techniques. X-ray crystallographic data show that the ligand coordinates to copper in a dianionic fashion through deprotonation of two -NH protons. Cyclic voltammetry study shows a reversible copper-centered redox couple with one ligand-based oxidation event. The electrocatalytic water oxidation occurs at an onset potential of 1.16 (overpotential, η ≈ 697 mV), 1.2 (η ≈ 737 mV), and 1.23 V (η ≈ 767 mV) for 1, 2, and 3 respectively. A systematic variation of the ligand scaffold has been found to display a profound effect on the rate of electrocatalytic oxygen evolution. The results of the theoretical (density functional theory) studies show the stepwise ligand-centered oxidation process and the formation of the O-O bond during water oxidation passes through the water nucleophilic attack for all the copper complexes. At pH = 13, the turnover frequencies have been experimentally obtained as 88, 1462, and 10 s-1 (peak current measurements) for complexes 1, 2, and 3, respectively. Production of oxygen gas during controlled potential electrolysis was detected by gas chromatography.

Mechanistic insights into nitric oxide oxygenation (NOO) reactions of {CrNO}5 and {CoNO}8.

Here, we report the nitric oxide oxygenation (NOO) reactions of two distinct metal nitrosyls {Co-nitrosyl (S = 0) vs. Cr-nitrosyl (S = 1/2)}. In this regard, we synthesized and characterized [(BPMEN)Co(NO)]2+ ({CoNO}8, 1) to compare its NOO reaction with that of [(BPMEN)Cr(NO)(Cl-)]+ ({CrNO}5, 2), having a similar ligand framework. Kinetic measurements showed that {CrNO}5 is thermally more stable than {CoNO}8. Complexes 1 and 2, upon reaction with the superoxide anion (O2˙-), generate [(BPMEN)CoII(NO2-)2] (CoII-NO2-, 3) and [(BPMEN)CrIII(NO2-)Cl-]+ (CrIII-NO2-, 4), respectively, with O2 evolution. Furthermore, analysis of these NOO reactions and tracking of the N-atom using 15N-labeled NO (15NO) revealed that the N-atoms of 3 (CoII-15NO2-) and 4 (CrIII-15NO2-) derive from the nitrosyl (15NO) moieties of 1 and 2, respectively. This work represents a comparative study of oxidation reactions of {CoNO}8vs. {CrNO}5, showing different rates of the NOO reactions due to different thermal stability. To complete the NOM cycle, we reacted 3 and 4 with NO, and surprisingly, only 3 generated {CoNO}8 species, while 4 was unreactive towards NO. Furthermore, the phenol ring nitration test, performed using 2,4-di-tert-butylphenol (2,4-DTBP), suggested the presence of a proposed peroxynitrite (PN) intermediate in the NOO reactions of 1 and 2.

Electrocatalytic water oxidation by heteroleptic ruthenium complexes of 2,6-bis(benzimidazolyl)pyridine Scaffold: a mechanistic investigation.

Three monomeric ruthenium complexes with anionic ligands [RuII(L)(L1)(DMSO)][ClO4] (1), [RuII(L)(L2)(DMSO)] [PF6] (2), and [RuII(L)(L3)(DMSO)][PF6] (3) [L = pyrazine carboxylate, L1 = 2,6-bis(1H-benzo[d]imidazol-2-yl)pyridine, L2 = 4,5-dmbimpy = 2,6-bis(5,6-dimethyl-1H-benzo[d]imidazol-2-yl)pyridine, L3 = 4-Fbimpy = 2,6-bis(5-fluoro-1H-benzo[d]imidazol-2-yl)pyridine, DMSO = dimethyl sulfoxide] as electrocatalysts for water oxidation are reported herein. The single crystal X-ray structure of the complexes reveals the presence of a DMSO molecule, which is supposed to be the labile group undergoing water exchange under the experimental condition of electrocatalysis. Linear sweep voltammetry (LSV) and cyclic voltammetry (CV) study shows the appearance of the catalytic wave for water oxidation at Ru(IV/V) oxidation. LSV, CV, and bulk electrolysis technique has been used to study the redox properties of the complexes and their electrocatalytic activity. A systematic variation on the ligand scaffold has been found to display a profound effect on the rate of electrocatalytic oxygen evolution. Electrochemical and theoretical (density functional theory) studies support the O-O bond formation during water oxidation passes through water nucleophilic attack (WNA) for all the ruthenium complexes. At pH 1, the maximum turnover frequency (TOFmax) has been experimentally obtained as 17556.25 s-1, 31648.41 s-1, and 39.69 s-1 for complexes 1, 2, and 3, respectively, from the foot of wave analysis (FOWA). The high value of TOFmax for complex 2 indicates its efficiency as an electrocatalyst for water oxidation in a homogeneous medium.

Correction to "Visible Light-Mediated Photoactivated Sulfur Quantum Dots as Heightened Antibacterial Agents".

[This corrects the article DOI: 10.1021/acsomega.2c03968.].

Microwave-mediated synthesis of tetragonal Mn3O4 nanostructure for supercapacitor application.

The development of electrode materials plays a vital role in energy storage applications to save and store energy. In the present work, the synthesis of nanorod shaped Mn3O4 supported with amorphous carbon (Mn3O4/AC) is reported by the microwave method for supercapacitor application. The as-prepared electrode material was then characterized using microscopic and spectroscopic techniques. The electrochemical supercapacitor performance of Mn3O4/AC was examined by the cyclic voltammetry and galvanostatic charge-discharge method inside the three-electrode assembly cell. The results showed that the Mn3O4/AC delivers the excellent capacitance value of the 569.5 Fg-1 at the current load of 1 Ag-1, higher than the previously reported Mn3O4 based electrodes. The better performance of the Mn3O4/AC is credited to the excellent redox behaviour of the Mn3O4 and the presence of the amorphous carbon, which facilitated the fast ion interaction between the electrode and electrolyte during the electrochemical reaction.

Manganese Doping in Biomass Derived Carbon Dots Amplifies White Light-Induced Antibacterial Activity.

The prevalence of antibiotic-resistant bacterial infections demands effective alternative therapeutics of antibiotics, whereas biocompatible zero-dimensional nanomaterials are an excellent option due to their small size. In this study, we report the one-step hydrothermal approach that was used to synthesize luminescent manganese doped carbon dots (Mn-Cdots) with an efficient quantum yield of 9.2% by employing green Psidium guajava L. (Guava) leaf as the precursor. High-resolution microscopy TEM was used to investigate the average particle size of Mn-Cdots, which was found to be 2.9 ± 0.045 nm. The structural properties and elemental composition of Mn-Cdots were analyzed by FTIR, XRD, EPR, and XPS spectroscopy, and the optical properties of Mn-Cdots were examined by UV-visible and fluorescent spectroscopy. Light-mediated antibacterial activity of Mn-Cdots was investigated by Gram-negative bacteria E. coli under white, blue, and yellow light. The doping effect of a minute quantity of Mn in Mn-Cdots increased the level of ROS generation in the presence of white lights compared to Cdots. Thus, Mn-Cdots might act as potent antibacterial agents.

Visible Light-Mediated Photoactivated Sulfur Quantum Dots as Heightened Antibacterial Agents.

The need for antimicrobial or antibacterial fabric has increased exponentially in recent past years, especially after the outbreak of the SARS-CoV-2 pandemic. Several studies have been conducted, and the primary focus is the development of simple, automated, performance efficient and cost-efficient fabric for disposable and frequent-use items such as personal protective materials. In this regard, we have explored the light-driven antibacterial activity of water-soluble Sdots for the first time. Sdots are a new class of non-metallic quantum dots of the nanosulfur family having a polymeric sulfur core. These Sdots exhibited excellent antibacterial activity by generating reactive oxygen species under sunlight or visible light. Under 6 h of sunlight irradiation, it was observed that >90% of the bacterial growth was inhibited in the presence of Sdots. Furthermore, low toxic Sdots were employed to develop antibacterial fabric for efficiently cleaning the bacterial infection. The prominent zone of inhibition of up to 9 mm was observed post 12 h incubation of Sdots treated fabric with E. coli in the presence of visible light. Furthermore, the SEM study confirmed the bactericidal effect of these Sdots-treated fabrics. Moreover, this study might help explore the photocatalytic disinfection application of Sdots in diverse locations of interest, Sdots-based photodynamic antimicrobial chemotherapy application, and provide an opportunity to develop Sdots as a visible light photocatalyst for organic transformations and other promising applications.

Autonomous magnetic microbots for environmental remediation developed by organic waste derived carbon dots.

Biodegradable precursors for micro/nanobots development are key requirements for several sustainable applications. In this regard, we propose an innovative solution for water purification at minimum cost and efforts where organic waste is used for the treatment of organic pollutants. Herein, catalytic magnetic microbots were developed by functionalizing iron oxide nanoparticles with carbon dots (C-Dots), which were synthesized by using household waste such as potato peels as precursors. The speed of these autonomously propelling bots indeed is found very promising for large distance swimming even in viscous medium by using hydrogen peroxide as fuel. These microbots catalytically propel and degrade toxic polar as well as sparingly water-soluble industrial dyes without any external agitation. The degradation of dyes was confirmed by mass-spectra analysis. Furthermore, these microbots can efficiently degrade a mixture of dyes and reused without compromising its performance significantly. Additionally, rate constant (K) and activation energy (Ea) were also determined to establish the catalytic nature of the bots. The present microbots acted as nanozyme owing to its synergistic catalytic activity of Fe3O4 and C-Dots for degradation of mixture of toxic dyes, essential for large scale water treatment.

Modulating catalytic activity of human topoisomerase II α enzyme by fluorescent gold nanoclusters.

Precise monitoring of the enzyme activity by a suitable modulator is one of the very fundamental aspects of drug designing that provides the opportunity to overcome the challenges of several diseases. Herein, inhibition of human Topoisomerase IIα enzyme which serves as a potential target site for several anti-cancer drugs is demonstrated by using ultra-small size gold nanoclusters (Au NCs) with the dimension comparable with size of the active site of the enzyme. Molecular dynamics simulation results demonstrate that the Au NCs strongly interact with the human Topo IIα enzyme at its active site or allosteric site depending on forms of enzyme. Additionally, binding energy and interaction profile provides the molecular basis of understanding of interactions of ultra-small size Au NCs and human Topo IIα enzyme. Enthalpy change (ΔH) and binding constant (K) are measured based on a sequential binding model of the Au NCs with the enzyme as demonstrated by the ITC study. Moreover, the in-vitro inhibition study of the catalytic activity of the enzyme and gel electrophoresis indicates that the ultra-small size Au NCs may be used as a potent inhibitor of human Topo IIα enzyme.

Emergence of sulfur quantum dots: Unfolding their synthesis, properties, and applications.

Over the past few decades, the sphere of applied science has witnessed soaring demand in developing high performance, novel and sustainable materials due to ever-increasing population coupled with need for alternative-green-energy resources. Inevitably, sulfur research expands through the breadth of materials sciences including sustainable use of the by-products obtained from petroleum industry, preparation of biocompatible materials, and constructing energy harvesting devices, indispensable to our everyday lives. Congruous with popular heavy-metal free elemental quantum dots such as the carbon, silicon and phosphorus, emergence of sulfur quantum dots (SQDs) has drawn substantial attention due to their bright luminescence, infrequent to other sulfur allotropes. In this review article, we focus some of the pioneering advances on synthesis and characterizations of luminescent sulfur nanodots and their potential applications in bioimaging, fabrication of light emitting devices, sensing and catalysis. Finally, critical challenges along with future perspectives corresponding to this newly discovered research area have been discussed.

Nanocomposite of Ag nanoparticles and catalytic fluorescent carbon dots for synergistic bactericidal activity through enhanced reactive oxygen species generation.

Microwave mediated synthesis of catalytic fluorescent carbon dots (Cdots) has been reported using biodegradable starch as precursor. The as-synthesized Cdots were then characterized using various techniques such as fluorescence spectroscopy, fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS) analysis. Interestingly, Cdots showed high catalytic activity in the photo-reduction of Ag+ to silver nanoparticles (Ag NPs). During the photo-reduction process, no additional surface passivating agents was needed to stabilize the Ag NPs. Further, TEM results indicated the formation of Cdot-Ag NP nanocomposite i.e. Ag NPs surrounded with Cdots, and the emission intensity of Cdots was significantly decreased whereas the lifetime of Cdots remained almost unaltered in the presence of Ag NPs following static quenching. Finally, combination therapy of Cdots and Ag NPs using Cdot-Ag NP nanocomposite was performed which indicated synergistic bactericidal activity against antibiotic resistant recombinant E. coli bacteria. The treatment elevated the reactive oxygen species (ROS) level as compared to its individual components. Additionally, the flow cytometer study demonstrated that combination therapy causing bacterial cell wall perforation that was possibly leading to synergistic bactericidal activity against both Gram positive and Gram negative bacteria. The presence of Cdots on the surface of the Ag NPs due to their ground state complexation, possibly facilitated electrons towards Ag NPs which enhanced the ROS production in comparison to only Ag NPs.

Role of surface charge in enhancing antibacterial activity of fluorescent carbon dots.

Herein, different surface charged carbon dots (Cdots) were synthesized by using diethylene glycol as a carbon source with various amine containing surface passivating agents. The synthesis method is very simple and fast microwave oven-based, that results in almost similar sized positive, negative and uncharged fluorescent Cdots which has been confirmed by zeta potential analysis in our case. The formation of Cdots was confirmed by characterization using fluorescence spectroscopy, transmission electron microscopy, XRD, FT-IR, and XPS spectroscopy. To find out relative bactericidal activity of these Cdots, green fluorescence protein expressing recombinant E. coli bacteria were taken as a model system. Time-dependent bacterial growth and FACS study demonstrated that both uncharged Cdots and positively charged Cdots were showing better bactericidal activity as compared to negative charged Cdots. The Cdots caused elevation of reactive oxygen species level, which is possibly leading to bacterial cell death.

Mechanically exfoliated MoS2 sheet coupled with conductive polyaniline as a superior supercapacitor electrode material.

The development of electrically conductive metal sulfide-based polymer nanocomposites for energy storage materials has been a major focus by researchers to solve the energy crisis. In this study, a simple and facile method was used to construct a nanocomposite by combining a mechanically exfoliated MoS2 (M-MoS2) sheet with polyaniline (Pani) using a simple and scalable in-situ chemical oxidative polymerization method. The as-prepared nanocomposite (M-MoS2-Pani nanocomposite) was characterized further by usual basic spectroscopic techniques, such as X-ray powder diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller surface area analysis. The electrochemical supercapacitive characteristics of the M-MoS2-Pani nanocomposite was tested in a three-electrode assembly by obtaining cyclic voltammetric (CV) curves and galvanostatic charge-discharge (GCD) measurements. The results were compared with those of a C-MoS2-Pani nanocomposite that had been synthesized using bulk MoS2. The M-MoS2-Pani nanocomposite synthesized using exfoliated MoS2 exhibited a higher specific capacitance of 510.12Fg-1 at a current of 1Ag-1 than the C-MoS2-Pani nanocomposite (225.15Fg-1), which was synthesized using bulk C-MoS2 delivered. The enhanced electrochemical supercapacitive performance was correlated to the synergistic effect and chemical interactions between the Pani and MoS2, which provide high electrical conductivity and a sufficient empty state for electrode/electrolyte contact.

An Interactive Quantum Dot and Carbon Dot Conjugate for pH-Sensitive and Ratiometric Cu2+ Sensing.

Herein we report the photoinduced electron transfer from Mn2+ -doped ZnS quantum dots (Qdots) to carbon dots (Cdots) in an aqueous dispersion. We also report that the electron transfer was observed for low pH values, at which the oppositely charged nanoparticles (NPs) interacted with each other. Conversely, at higher pH values the NPs were both negatively charged and thus not in contact with each other, so the electron transfer was absent. Steady-state and time-resolved photoluminescence studies revealed that interacting particle conjugates were responsible for the electron transfer. The phenomenon could be used to detect the presence of Cu2+ ions, which preferentially, ratiometrically, and efficiently quenched the luminescence of the Qdots.

Conducting Carbon Dot-Polypyrrole Nanocomposite for Sensitive Detection of Picric acid.

We report the conducting nature of carbon dots (Cdots) synthesized from citric acid and ethylene diamine. Chemically synthesized conducting nanocomposite consisting of Cdots and polypyrrole (PPy) is further reported, which showed higher electrical conductiviy in comparison to the components i.e., Cdots or PPy. The conductive film of the composite material was used for highly sensitive and selective detection of picric acid in water as well as in soil. To the best of our knowledge, this is the first report on the conductivity based sensing application of Cdot nanocomposite contrary to the traditional fluorescence based sensing approaches.

Luminescent carbon dots for logic operations in two phases.

Basic and higher integrated logic operations have been achieved by using luminescent carbon dots through interactions with metal ions and organic molecules in liquid dispersions as well as in the solid phase. The biphasic simple and complex logic systems could be potentially used for various analytical applications as well as for the detection of important elements in diverse environments.

Presence of amorphous carbon nanoparticles in food caramels.

We report the finding of the presence of carbon nanoparticles (CNPs) in different carbohydrate based food caramels, viz. bread, jaggery, sugar caramel, corn flakes and biscuits, where the preparation involves heating of the starting material. The CNPs were amorphous in nature; the particles were spherical having sizes in the range of 4-30 nm, depending upon the source of extraction. The results also indicated that particles formed at higher temperature were smaller than those formed at lower temperature. Excitation tuneable photoluminescence was observed for all the samples with quantum yield (QY) 1.2, 0.55 and 0.63%, for CNPs from bread, jaggery and sugar caramels respectively. The present discovery suggests potential usefulness of CNPs for various biological applications, as the sources of extraction are regular food items, some of which have been consumed by humans for centuries, and thus they can be considered as safe.

Plasmid DNA linearization in the antibacterial action of a new fluorescent Ag nanoparticle-paracetamol dimer composite.

Herein, we report the generation of a composite comprised of p-hydroxyacetanilide dimer and Ag nanoparticles (NPs) by reaction of AgNO(3) and p-hydroxyacetanilide. The formation of the composite was established by UV-vis, FTIR and NMR spectroscopy, transmission electron microscopy and X-ray diffraction along with substantiation by mass spectrometry. Interestingly, the composite exhibited an emission spectrum with a peak at 435 nm when excited by light of wavelength 320 nm. The composite showed superior antimicrobial activity with respect to its individual components against a wide range of Gram positive and Gram negative bacteria at relatively low concentrations of Ag NPs and at which there was no apparent cytotoxicity against mammalian cells. Our results suggest that the composite strongly interacted with the bacterial cell walls leading to cell bursting. Interestingly, enhancement in the reactive oxygen species (ROS) generation in bacteria was observed in the presence of the composite. It is proposed that the ROS generation led to oxidation of the dimer to N-acetyl-p-benzoquinone imine (NAPQI). The generated NAPQI acted as a DNA gyrase inhibitor causing cell death following linearization of DNA.