Silica-Supported Assemblage of CuII Ions with Carbon Dots for Self-Boosting and Glutathione-Induced ROS Generation

The present work introduces coordinative binding of CuII ions with both amino-functionalized silica nanoparticles (SNs) and green-emitting carbon dots (CDs) as the pregrequisite for the CuII-assisted self-assembly of the CDs at the surface of the SNs. The produced composite SNs exhibit stable in time stimuli-responsive green fluorescence derived from the CuII-assisted assemblage of CDs. The fluorescence response of the composite SNs is sensitive to the complex formation with glutathione (GSH), enabling them to detect it with the lower limit of detection of 0.15 μM. The spin-trap-facilitated electron spin resonance technique indicated that the composite SNs are capable of self-boosting generation of ROS due to CuII→CuI reduction by carbon in low oxidation states as a part of the CDs. The intensity of the ESR signals is enhanced under the heating to 38 °C. The intensity is suppressed at the GSH concentration of 0.35 mM but is enhanced at 1.0 mM of glutathione, while it is suppressed once more at the highest intracellular concentration level of GSH (10 mM). These tendencies reveal the concentrations optimal for the scavenger or reductive potential of GSH. Flow cytometry and fluorescence and confocal microscopy methods revealed efficient cell internalization of SNs-NH2-CuII-CDs comparable with that of “free” CDs.

Stability and Free Radical Production for CO2 and H2 in Air Nanobubbles in Ethanol Aqueous Solution

In this study, 8% hydrogen (H2) in argon (Ar) and carbon dioxide (CO2) gas nanobubbles was produced at 10, 30, and 50 vol.% of ethanol aqueous solution by the high-speed agitation method with gas. They became stable for a long period (for instance, 20 days), having a high negative zeta potential (−40 to −50 mV) at alkaline near pH 9, especially for 10 vol.% of ethanol aqueous solution. The extended Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory was used to evaluate the nanobubble stability. When the nanobubble in ethanol alkaline aqueous solution changed to an acidic pH of around 5, the zeta potential of nanobubbles was almost zero and the decrease in the number of nanobubbles was identified by the particle trajectory method (Nano site). The collapsed nanobubbles at zero charge were detected thanks to the presence of few free radicals using G-CYPMPO spin trap reagent in electron spin resonance (ESR) spectroscopy. The free radicals produced were superoxide anions at collapsed 8%H2 in Ar nanobubbles and hydroxyl radicals at collapsed CO2 nanobubbles. On the other hand, the collapse of mixed CO2 and H2 in Ar nanobubble showed no free radicals. The possible presence of long-term stable nanobubbles and the absence of free radicals for mixed H2 and CO2 nanobubble would be useful to understand the beverage quality.

A Combined Atomic and Molecular Probe Characterization of Aromatic Hydrocarbons via PALS and ESR: Methylbenzene

A combined study of one of the simplest aromatic hydrocarbons, i.e., methylbenzene (toluene) (TOL), via the annihilation of an ortho-positronium (o-Ps) probe via positron annihilation lifetime spectroscopy (PALS) and the rotation dynamics of nitroxide spin probe 2,2,6,6-tetramethyl-piperidinyl-1-oxy (TEMPO) using electron spin resonance (ESR) over a wide temperature range, 10–300 K, is reported. The o-Ps lifetime, τ3, and the relative o-Ps intensity, I3, as a function of temperature exhibit changes defining several characteristic PALS temperatures in the slowly and rapidly cooled samples. Similarly, the spectral parameter of TEMPO mobility in TOL, 2Azz‘, and its correlation time, τc, reveal several effects at a set of the characteristic ESR temperatures, which were determined and compared with the PALS results. Finally, the physical origins of the changes in free volume expansion and spin probe mobility are revealed. They are reflected in a series of the mutual coincidences between the characteristic PALS and ESR temperatures and appropriate complementary thermodynamic and dynamic techniques.

Bonding Ability of Isopthalic Acid-bis(thiosemicarbozone) to Manganese and Cobalt Metal Ions: Preparation, Spectral Investigation, Computational and in vitro Antipathogenic Screening

Manganese and cobalt complexes have been designed and prepared with a tetradentate ligand i.e. isopthalic acid-bis(thiosemicarbozone) (IPBT), which bind to metal ions via donor atoms present in ligand. Different spectroscopic techniques viz. nuclear magnetic resonance, infra red, mass, electronic spin resonance and analytical studies have been used to determine the chemical composition of synthesized IPBT and its Mn(II) and Co(II) complexes. The spectroscopic data exposed that IPBT behaves in a tetradentate (N2S2) mode by having ability to bind with metal ions through N2S2 atoms. An octahedral structure for manganese and cobalt complexes has been suggested on the basis of spectroscopic as well as analytical studies. The ligand (IPBT) and its metal(II) complexes have been screened to determine their antipathogenic activity against some selective microorganisms S. aureus, P. aeruginosa, E. coli, A. niger, M. phasolina and P. glomerata. In this experimental work, well diffusion and poisoned food techniques have been introduced for screening purpose and as standard drugs neomycin and chlorothalonil have been used. Data for antipathogenic screening exposed that metal complexes exerted higher activity towards all examined microbes (bacteria and fungi) even than ligand.

Electrochemical and Mechanistic Study of Reactivities of α-, β-, γ-, and δ-Tocopherol toward Electrogenerated Superoxide in N,N-Dimethylformamide through Proton-Coupled Electron Transfer

Scavenging of superoxide radical anion (O2•−) by tocopherols (TOH) and related compounds was investigated on the basis of cyclic voltammetry and in situ electrolytic electron spin resonance spectrum in N,N-dimethylformamide (DMF) with the aid of density functional theory (DFT) calculations. Quasi-reversible dioxygen/O2•− redox was modified by the presence of TOH, suggesting that the electrogenerated O2•− was scavenged by α-, β-, γ-TOH through proton-coupled electron transfer (PCET), but not by δ-TOH. The reactivities of α-, β-, γ-, and δ-TOH toward O2•− characterized by the methyl group on the 6-chromanol ring was experimentally confirmed, where the methyl group promotes the PCET mechanism. Furthermore, comparative analyses using some related compounds suggested that the para-oxygen-atom in the 6-chromanol ring is required for a successful electron transfer (ET) to O2•− through the PCET. The electrochemical and DFT results in dehydrated DMF suggested that the PCET mechanism involves the preceding proton transfer (PT) forming a hydroperoxyl radical, followed by a PCET (intermolecular ET–PT). The O2•− scavenging by TOH proceeds efficiently along the PCET mechanism involving one ET and two PTs.

Thermal behaviour of organic radicals and paramagnetic centres in chert: A case study of Bergeracois brown chert, Dordogne, France

In order to successfully understand the complex evolution of prehistoric societies, archaeologists require absolute dating tools, which are not only accurate but also widely applicable. Thermoluminescence (TL) dating is one such approach that has been successfully used to establish a general chronological framework for prehistoric sites and is particularly suited for use on heated lithic artefacts. Experiments conducted in this study have clearly shown the applicability of Electron Spin Resonance (ESR) isothermal modelling in combination with TL dating to constrain firing temperature. This expands the potential application for TL dating to include artefacts treated at low firing temperatures. The present study shows potential in terms of precision and accuracy for framing the “equivalent firing temperature”. At the same time, the comparison of the TL signal with the lattice-defects and aluminium centres invigorate the use of ESR dating on heated flint, especially with samples that have received low thermal treatment. The presence of organic matter in large quantity raises concern on the pyrolysis effect on the luminescence signal; however, the use of ESR isothermal and isochronal modelling could potentially lead to the ability to overcome current interferences of the organic radicals within the dating signal of TL.