Isolated Neutral [4]Helicene Radical Provides Insight into Consecutive Two-Photon Excitation Photocatalysis

Direct activation of strong bonds in readily available, benchtop substrates offer a straightforward simplification, albeit in most cases existing catalytic systems are limited to unlock such activation. In recent years, a surge of in-situ generated organic radicals that can act as potent photoinduced electron transfer (PET) agents have proved to be a powerful manifold for the activation of remarkably stable bonds. Herein we document the use of N,N′-di-n-propyl-1,13-dimethoxyquinacridine (nPr-DMQA•), an isolated and stable neutral helicene radical, as a highly photoreducing species. This isolable doublet state open shell radical offers a unique opportunity to shed light on the mechanism behind PET reactions of organic radicals. Experimental and spectroscopic studies revealed that this doublet radical has a long lifetime of 4.6 ± 0.2 ns, an estimated excited state oxidation potential of -3.31 V vs SCE, and can undergoes PET with organic substrates. The strongly photoreducing nature of the nPr-DMQA• was experimentally confirmed by the demonstration of photo activation of electron rich aryl bromides and chlorides. We further demonstrated that nPr-DMQA• can be photochemically generated from its cation analog (nPr-DMQA+) allowing catalytic functionalization of aryl halide via a consecutive photoexcitation mechanism (ConPET). Dehalogenation, photo-Arbuzov, photo-borylation and C-C bond formation reactions with aryl chlorides and bromides are reported herein, as well as the α-arylation of carbonyl using cyclic ketones. The latter transformation exhibits the facile synthesis of α-arylated cyclic ketones as critical feedstock chemical for diverse useful molecules, especially in the biomedical enterprises.

Push-Pull Heterocyclic Dyes Based on Pyrrole and Thiophene: Synthesis and Evaluation of Their Optical, Redox and Photovoltaic Properties

Three heterocyclic dyes were synthesized having in mind the changes in the photovoltaic, optical and redox properties by functionalization of 5-aryl-thieno[3,2-b]thiophene, 5-arylthiophene and bis-methylpyrrolylthiophene π-bridges with different donor, acceptor/anchoring groups. Knoevenagel condensation of the aldehyde precursors with 2-cyanoacetic acid was used to prepare the donor-acceptor functionalized heterocyclic molecules. These organic metal-free dyes are constituted by thieno[3,2-b]thiophene, arylthiophene, bis-methylpyrrolylthiophene, spacers and one or two cyanoacetic acid acceptor groups and different electron donor groups (alkoxyl, and pyrrole electron-rich heterocycle). The evaluation of the redox, optical and photovoltaic properties of these compounds indicate that 5-aryl-thieno[3,2-b]thiophene-based dye functionalized with an ethoxyl electron donor and a cyanoacetic acid electron acceptor group/anchoring moiety displays as sensitizer for DSSCs the best conversion efficiency (2.21%). It is mainly assigned to the higher molar extinction coefficient, long π-conjugation of the heterocyclic system, higher oxidation potential and strong electron donating capacity of the ethoxyl group compared to the pirrolyl moiety.

Antimicrobials Functioning through ROS-Mediated Mechanisms: Current Insights

Antibiotic resistance and infections caused by multidrug-resistant bacteria are global health concerns. Reducing the overuse and misuse of antibiotics is the primary step toward minimizing the antibiotic resistance crisis. Thus, it is imperative to introduce and implement novel antimicrobial strategies. Recently, several alternative antimicrobials targeting oxidative stress in bacteria have been studied and shown to be promising. Oxidative stress occurs when bacterial cells fail to detoxify the excessive reactive oxygen species (ROS) accumulated in the cells. Bacteria deploy numerous defense mechanisms against oxidative stress. The oxidative stress response is not essential for the normal growth of bacteria, but it is crucial for their survival. This toxic oxidative stress is created by the host immune response or antimicrobials generating ROS. ROS possess strong oxidation potential and cause serious damage to nucleic acids, lipids, and proteins. Since ROS-based antimicrobials target multiple sites in bacteria, these antimicrobials have attracted the attention of several researchers. In this review, we present recent ROS-based alternative antimicrobials and strategies targeting oxidative stress which might help in mitigating the problem of antibiotic resistance and dissemination.

Role of Iron Phthalocyanine Coordination in Catecholamines Detection

Catecholamines are an important class of neurotransmitters responsible for regularizing, controlling, and treating neural diseases. Based on control and diseases treatment, the development of methodology and dives to sensing is a promissory technology area. This work evaluated the role of iron phthalocyanine coordination (FePc) with the specific groups from catecholamine molecules (L-dopa, dopamine, epinephrine, and the amino acid tyrosine) and the effect of this coordination on electrochemical behavior. The in situ coordination analysis was performed through isotherms π-A of FePc Langmuir films in the absence and presence of catecholamines. The π-A isotherm indicates a strong interaction between FePc monolayer and L-Dopa and DA, which present a catechol group and a side chain with a protonated amino group (-NH3+). These strong interactions with catechol and amine groups were confirmed by characterization at the molecular level using the surface-enhanced Raman spectroscopy (SERS) from a Langmuir–Schaefer monolayer deposited onto Ag surfaces. The electrochemical measurements present a similar tendency, with lower oxidation potential observed to DA>L-Dopa>Ep. The results corroborate that the coordination of the analyte on the electron mediator surface plays an essential role in an electrochemical sensing application. The FePc LS film was applied as a sensor in tablet drug samples, showing a uniformity of content of 96% for detecting active compounds present in the L-Dopa drug samples.

A Novel Wastewater Treatment Method Using Electrical Pulsed Discharge Plasma over a Water Surface

Electrical pulsed discharge plasma produces various powerful oxidizing agents, such as hydroxyl radicals and ozone, which have high oxidation potential. These species play an important role in the decomposition of persistent organic compounds in wastewater. Because highly concentrated oxidants are directly produced inside the plasma, plasma realizes high-speed wastewater treatment without pretreatment of samples, such as pH adjustment. The pulsed discharge plasma generated over the water surface and inside bubbles is highlighted as a highly efficient method for plasma generation and radical supply into wastewater. In this paper, the physical and chemical properties of the discharge plasma generated over a water surface are described. The decomposition of persistent organic compounds dissolved in wastewater, such as 1,4-dioxane, formic acid, and dichloromethane, by plasma discharge is demonstrated, and their mechanisms are discussed. These persistent compounds, which have strong toxicity and stability, can be efficiently decomposed and removed quickly from solutions by plasma treatment. Furthermore, the treatment of nutrient solutions used in hydroponic systems for plant cultivation is also introduced as a novel application of plasma, and the effects of bacterial inactivation, decomposition of allelochemicals, and improvement in plant growth by plasma are demonstrated.

Optical properties and oxidative potential of aqueous-phase products from OH and ³C^*-initiated photolysis of eugenol

In ambient air, aqueous-phase oxidation may turn precursors into more light-absorbing and toxic products, leading to air quality deterioration and adverse health effects. In this study, we investigated eugenol degradation in aqueous phase under direct photolysis, and triplet excited organic (3C*) and hydroxyl radical (OH) as oxidants. Results showed degradation rates of eugenol followed the order of 3C* > OH > direct photolysis. Relative contributions of reactive oxygen species (ROS) and 3C* were evaluated via quenching and O2-free experiments. 3C* played a dominant role in eugenol degradation for 3C*-initiated oxidation, while both O2 and O2•-generated were important for eugenol degradation for OH-initiated oxidation. Rate constants under O2, air and N2 followed the order of ko2＞kAir＞kN2 under both direct photolysis and OH oxidation, and it changed to kAir＞kN2＞ko2 in 3C*-initiated oxidation. Light absorption spectra showed absorbance at 300–400 nm increased as photolysis progressed, and there were new broad fluorescent spectra at excitation/emission (Ex/Em) = 250/(400–500) nm, suggesting the formation of new chromophores and fluorophores, such as humic-like substances (HULIS). Additionally, distinct fluorescence peaks appeared at Ex/Em=(300–350)/300 nm at different stages. Concentration of generated HULIS increased gradually over time, then leveled off. Dithiothreitol (DTT) assay was applied to assess the oxidation potential of products, which was greater than pure eugenol, suggesting more harmful species were produced during oxidation. Detailed reaction pathways were elucidated via analyses of chemical characteristics of the products.