Radical Formation Research Articles

Association of ischemic placental disease in a Southern California Birth Cohort and PM2.5 chemical species and oxidative potential markers

Road traffic is a significant source of particulate matter pollution, whose exposure is a significant risk factor in pregnancy-related health outcomes. The exact mechanisms behind the relationship between traffic-related air pollution (TRAP) exposure and adverse pregnancy outcomes remain unclear. We aim to assess the relationship between exposure to brake and tire wear-associated metals and oxidative potential and ischemic placental disease (IPD). Data were assembled from a final population of 178 women who sought specialized prenatal care at UCLA between 2016 and 2019 in Los Angeles, CA. Modeled first trimester exposures to chemical constituents and oxidative stress potential of PM2.5, black carbon, and PM2.5 mass concentration. Speciated measurements included tracers of brake wear (barium), tire wear (zinc), and oxidative potential markers based on metal concentrations (KM-SUB-ELF ROS) or laboratory assays (DTT loss, OH radical formation). Exposures were modeled by integrating data from filter samples, a low-cost PM2.5 sensor network, and land-use data. We used logistic regression to estimate the associations between air pollution exposures and IPD, adjusting for covariates assessed through medical records and interviews. Scaled to the interquartile range, odds ratios (95% CI) were as follows: barium OR: 1.7 (1.1, 2.7), zinc OR: 1.4 (.86, 2.4), and oxidative potential markers, both modeled as well as measured through DTT loss and OH formation assays (ORs ranging from 1.1-2.0). Point estimates of effect sizes for PM2.5 and black carbon were lower than most measurements (ORs: 1.3-1.4). mass and black carbon. Our findings suggest two key points: (i) metals associated with brake and tire wear, currently unregulated, may play a role in the relationship between TRAP and adverse pregnancy outcomes, and (ii) reducing tailpipe emissions may not be sufficient to protect pregnant women from TRAP.

Oxygen-deficient AgIO3 for efficiently photodegrading organic contaminants under natural sunlight

Defect engineering is regarded as an effective strategy to boost the photo-activity of photocatalysts for organic contaminants removal. In this work, abundant surface oxygen vacancies (Ov) are created on AgIO3 microsheets (AgIO3-OV) by a facile and controllable hydrogen chemical reduction approach. The introduction of surface Ov on AgIO3 broadens the photo-absorption region from ultraviolet to visible light, accelerates the photoinduced charges separation and migration, and also activates the formation of superoxide radicals (•O2−). The AgIO3-OV possesses an outstanding degradation rate constant of 0.035 min−1, for photocatalytic degrading methyl orange (MO) under illumination of natural sunlight with a light intensity is 50 mW/cm2, which is 7 and 3.5 times that of the pristine AgIO3 and C–AgIO3 (AgIO3 is calcined in air without generating Ov). In addition, the AgIO3-OV also exhibit considerable photoactivity for degrading other diverse organic contaminants, including azo dye (rhodamine B (RhB)), antibiotics (sulflsoxazole (SOX), norfloxacin (NOR), chlortetracycline hydrochloride (CTC), tetracycline hydrochloride (TC) and ofloxacin (OFX)), and even the mixture of organic contaminants (MO-RhB and CTC-OFX). After natural sunlight illumination for 50 min, 41.4% of total organic carbon (TOC) for MO-RhB mixed solution can be decreased over AgIO3-OV. In a broad range of solution pH from 3 to 11 or diverse water bodies of MO solution, AgIO3-OV exhibits attractive activity for decomposing MO. The MO photo-degradation process and mechanism over AgIO3-OV under natural sunlight irradiation has been systemically investigated and proposed. The toxicities of MO and its degradation intermediates over AgIO3-OV are compared using Toxicity Estimation Software (T.E.S.T.). Moreover, the non-toxicity of both AgIO3-OV catalyst and treated antibiotic solution (CTC-OFX mixture) are confirmed by E. coli DH5a cultivation test, supporting the feasibility of AgIO3-OV catalyst to treat organic contaminants in real water under natural sunlight illumination.

Ion migration mechanisms in the early stages of drying and degradation of oil paint films

The study of film-formation processes of oil paints has been extensively addressed over the last decade and the influence of metal ions in the drying and degradation stages of oil paints has been demonstrated. This research aimed to determine a suitable methodology for monitoring the early drying stages of selected commercial oil paint films and to gain an insight into the migration mechanisms of material degradation taking place between adjacent paint films, with special attention to the influence of the lead white. For this purpose, a hybrid approach was adopted to characterize the composition of the paint and highlight failure mechanisms in the paint films through a wide range of time. The methods included scribe tests, percentage weight variation (ΔW%), attenuated reflectance Fourier transform infrared spectrophotometry (ATR-FTIR), gas chromatography-mass spectrometry (GC-MS), and thermal analysis with differential scanning calorimetry (TG-DSC). The results show how metal ions interact with the oil binder and the pigment in the adjacent paint film: the transverse migration of lead white is shown to affect the reactivity of polyunsaturated triglycerides, increasing the rate of oxygen uptake and promoting the formation of radicals and bonds between polymer chains, depending on the pigment with which it interacts.

Unlocking clean gas with hydrogen: A combustion optimization study

Combining hydrogen with natural gas, a hydrocarbon fuel, is seen as a critical step towards reaching net-zero emissions and creating a cleaner environment. To tackle climate change, major organizations like the U.S. Department of Energy, Energy Innovation, and the International Renewable Energy Agency are promoting the use of hydrogen blended with natural gas. This approach can potentially cut emissions in half compared to relying solely on natural gas. Using the Ansys 2022 R1 CHEMKIN tool, the study analyses combustion features in H2-CNG (compressed natural gas) -air mixtures, considering atmospheric conditions and operational parameters. Blending 50 % hydrogen with CNG results in significant changes, including an increase in laminar flame speed from 48.78 cm/s to 71.52 cm/s. As the hydrogen content in the CNG blend increases from 0 to 50 %, the concentration of free radicals like H, O, and OH rises by 42.86 %, 28.57 %, and 20.00 %, respectively, reaching these values at a 50 % hydrogen blend compared to pure CNG. NSGA-II multi-objective optimization identified that a 50 % hydrogen-blended CNG surpasses pure CNG in laminar flame speed and free radical generation. The research confirms that H2-CNG creates a promising fuel with several advantages. When combusted, H2-CNG mixtures exhibit superior characteristics, including potentially increased efficiency through increased free radical formation and laminar flame speed. This innovation has the potential to significantly reduce carbon footprint and contribute to achieving carbon neutrality goals. The cleaner and more efficient combustion properties of H2-CNG offer a compelling pathway for mitigating climate change.

Leveraging Propargyl Sulfides as Radical Trappers for the Synthesis of Sulfonyl Allenes

AbstractThis work showcases a novel visible‐light mediated allenylation protocol employing propargyl sulfides as a pioneering radical trapping methodology. A diverse array of substituted sulfonyl allenes were successfully synthesized under mild conditions with commendable levels of chemo‐ and regio‐selectivity. Mechanistically, this process entails the formation of sulfonyl radicals, their subsequent addition to alkynes, the subsequent elimination of S‐centered radicals, and Cl‐atom abstraction, thereby facilitating the propagation of this radical chain reaction.

Investigating H-atom reactions in small PAHs with imperfect aromaticity: A combined experimental and computational study of indene (C9H8) and indane (C9H10).

Polycyclic aromatic hydrocarbons (PAHs) are widely recognized as catalysts for interstellar H2 formation. Extensive exploration into the catalytic potential of various PAHs has encompassed both theoretical investigations and experimental studies. In the present study, we focused on studying the reactivity of an imperfect aromatic molecule, indene (C9H8), and its hydrogenated counterpart, indane (C9H10), as potential catalysts for H2 formation within the interstellar medium. The reactions of these molecules with H atoms at 3.1K were investigated experimentally using the para-H2 matrix isolation technique. Our experimental results demonstrate that both indene and indane are reactive toward H atoms. Indene can participate in H-atom-abstraction and H-atom-addition reactions, whereas indane primarily undergoes H-atom-abstraction reactions. The H-atom-abstraction reaction of indene results in the formation of the 1-indenyl radical (R1) (C9H7) and H2molecule. Simultaneously, an H-atom-addition reaction forms the 1,2-dihydro-indene-3-yl radical (R2) (C9H9). Experiments also reveal that the H-atom-abstraction reaction of indane also produces the R2 radical. To the best of our knowledge, this study represents the first reporting of the infrared spectra of R1 and R2 radicals. The experimental results, combined with theoretical findings, suggest that indane and indene may play a role in the catalytic formation of interstellar H2. Furthermore, these results imply a quasi-equilibrium between the investigated molecules and the formed radicals via H-atom-addition and H-atom-abstraction reactions.

ДОСЛІДЖЕННЯ АНТИОКСИДАНТНИХ ВЛАСТИВОСТЕЙ ЕКСТРАКТІВ ВІДКАСНИКА БЕЗСТЕБЛОВОГО (Carlina acaulis L.), АРНІКИ ГІРСЬКОЇ (Arnica montana L.) ТА КАЛЕНДУЛИ ЛІКАРСЬКОЇ (Calendula officinalis L.)

The intensity of lipid peroxidation (LPO) and oxidative modification of proteins (OMP) was investigated under the influence of 40 % and 70 % aqueous-ethanol plant extracts (PE) of the root of Carlina acaulis L., flowers of Arnica montana L. and Calendula officinalis L. on rat liver hepatocytes under conditions of free radical oxidation initiation in vitro. Investigated plant extracts reduce the formation of free radicals in proteins and lipids, which is evidently associated with the presence of phenolic compounds, flavonoids, and polyphenols in the extracts. The best results were demonstrated by the plant extracts of arnica and calendula. Arnica extract at a concentration of 40 % exhibited better antioxidant properties than its 70 % extract.

Electrochemical selective deuterium labelling of N-heteroarenes

Hydrogen-deuterium exchange (HIE) reaction is the most direct way to achieve the deuterium labeling as there is no need for extra pre-functionalization. Herein, we report an electrochemical selective deuterium labelling of N-heteroarenes using D2O. The formation of aromatic radicals has been directly identified by using the time-resolved electron paramagnetic resonance (EPR) technique under electrochemical conditions. Mechanistic studies revealed that the hydrogen/deuterium (H/D) exchange involved continuous redox of N-heteroarenes under paired electrolysis and the selectivity of deuteration was established by DFT calculations. This electrochemical synthesis method offers a promising avenue for deuterium incorporation at specific sites of aromatic compounds.

Cationic manganese(II)-based metal-organic framework constructed from viologen derivative with multifunctional properties

Utilizing the rigid and linear viologen carboxylic ligand as an organic linker, we have successfully synthesized and structurally characterized a multifunctional Mn-based cationic metal-organic framework (1). Compound 1 features a three-dimensional framework structure with a positively charged skeleton, wherein triangular pores accommodate [MnCl4]2− anions to preserve charge neutrality. Notably, compound 1 demonstrates a chemical chromism phenomenon, transitioning from yellow-brown to deep green upon exposure to ammonia. This color change is attributed to the nucleophilic attack of electron-rich ammonia molecules on the electron-deficient viologen moiety of viologen carboxylic ligand, leading to the formation of viologen radicals and charge transfer complexes. Moreover, compound 1 exhibits rapid and selective detection of antibiotics like metronidazole (MDZ) and dimetridazole (DTZ) via a competitive absorption-induced luminescence quenching process, featuring high quenching coefficients and low detection limits. Additionally, magnetic property investigations reveal predominant antiferromagnetic coupling between Mn(II) ions within compound 1.

Construction of BiOCl/reduced graphene oxide nanocomposites heterojunction with abundant oxygen vacancies for efficient photocatalytic organic pollutant removal

Precisely manipulating defects in semiconductor is an effective way to improve their photocatalytic activity. In this work, bismuth oxychloride (BiOCl)/reduced graphene oxide (RGO) nanocomposites with abundant oxygen vacancies (OVs) are successfully constructed by a facile solvothermal method. BiOCl nanosheets are uniformly distributed on the RGO with superior conductivity. The RGO served as a pivotal charge transmission bridge substantially accelerates the transfer of photogenerated charge carriers, resulting in the improvement of the charge separation efficiency. The abundant oxygen vacancies in BiOCl/RGO nanocomposites increase light harvesting and enhance the adsorption of O2 to promote the formation of superoxide free radicals (·O2−). By virtue of these merits, the unique BiOCl/RGO nanocomposite shows excellent degradation efficiency. When the mass ratio of RGO was 2 %, 99.07 % of 20 mg/L(100 mL) methyl orange (MO) was removed after 80 min, which was much higher than that of pure BiOCl.

Analysis of Flavonoid Content and Antioxidant Activity of Solanum ertianthum Extract

Abstract Solanum erianthum is one of the herbal plants that is believed by the Indonesian people to be a medicinal plant. The flavonoid and polyphenol compounds contained therein have antioxidant activity, but this has not been proven empirically. Solanum erianthum extract is produced using the maceration method. The determination of total flavonoid levels in Solanum erianthum was measured using a method based on complex formation, namely the aluminum trichloride (AlCl3) method. The antioxidant activity of Solanum erianthum was measured using the DPPH (1,1-diphenyl-2-2picrihydrazyl) method because of its stability in the form of free radicals and because it is simple to carry out. The results obtained after determining the total flavonoid content in Solanum erianthum extract with various concentrations using the aluminum trioxide method were 1,430 mg QE/g, 2,282 mg QE/g, 3,180 mg QE/g, 3,567 mg QE/g, 4,291 mg QE/g. Solanum erianthum extract demonstrated antioxidant activity in the DPPH test, with an IC50 value of 66.493 g/ml. This falls into the “strong” category. This research shows that the phytochemical screening content of Solanum erianthum extract contains alkaloids, flavonoids, tannins, saponins, and tritepenoids. The total flavonoid content in Solanum erianthum extract at concentrations of 6 µg/ml, 8 µg/ml, 10 µg/ml, 12 µg/ml, and 14 µg/ml is as follows: 1,430mg QE/g, 2,282mg QE/g, 3,180mg QE/g, 3,567mg QE/g, and 4,291mg QE/g, as well as the antioxidant activity of Solanum erianthum extract with an average yield of 69,493 ppm.

Being You — Or Not: A Challenge for Garfield and Seth

In recent publications, Jay Garfield and Anil Seth have both written about the you. Whereas Garfield is a Buddhist scholar who advocates a no-self view, Seth is a neuroscientist who defends a radical form of representationalism. But is it really possible to speak meaningfully of a you (and of a we) if one denies the existence of the self, and if one declares the world of experience a neuronal fantasy? In the following, I will criticize both accounts. I will argue that they both, in different ways, are unable to deal with a real other, and, drawing on the work of Husserl, I will argue that a proper understanding of the you doesn't merely require accepting the reality of the self, but also the existence of a shared lifeworld.

Experimental and numerical study of stabilized flame in inverse coflow turbulent jet using nanosecond repetitively pulsed discharges

Methane has become increasingly popular in rocket propulsion, but low stability and limited flammability range have always been a concern about methane-powered systems. Many stabilization methods have been developed to change the geometrical or flow characteristics of the burner. However, most of these efforts have yet to be practically successful due to cost and compatibility issues. Alternatively, other methods such as microwave, dielectric barrier, and nanosecond repetitive pulse (NRP) discharges have been proven to be efficient by modifying the kinetic and transport pathways. NRP discharges have shown promising results as one of the most effective low-temperature plasma (LTP) methods. In this paper, chemiluminescence imaging is used to study the effect of NRP discharge on liftoff and blowout, as the important stabilization parameters, by recording the liftoff height and liftoff/blowout velocities under a wide range of discharge (f=0–10 kHz and V=11–19 kV) and jet velocity (ν=2–60 m/s). Depending on these parameters, four different discharge regimes of corona, diffuse, filamentary, and arc were observed. The results have shown that high-intensity plasma in a filamentary discharge regime can provide a significant advantage in delaying the liftoff conditions, but no improvements in the blowout were observed. It was also found that NRP discharge can reduce the liftoff height. To explore the cause of the increased stability, a parametric numerical study is conducted using detailed plasma-assisted methane kinetic modeling coupled to a 1D opposed diffusion flame simulation. Results show that the extinction limits of diffusion flames can be dramatically enhanced by LTP due to the local formation of high radical and excited species concentrations, with subsequent recombination leading to increased temperature and higher reactivity in the flame zone. In addition, a 1D laminar flame speed evaluation shows that the plasma-generated active species can dramatically increase the flame speed, which, in turn, reduces the lifted flame height above the burner surface.

Planar Core and Macrocyclic Shell Stabilized Atomically Precise Copper Nanocluster Catalyst for Efficient Hydroboration of C-C Multiple Bond.

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design and development of bond-forming reaction catalysts based on copper NCs are still in their early stages. Herein, we report the synthesis of an atomically precise copper nanocluster with a planar core and unique shell, [Cu45(TBBT)29(TPP)4(C4H11N)2H14]2+ (Cu45) (TBBT: 4-tert-butylbenzenethiol; TPP: triphenylphosphine), in high yield via a one-pot reduction method. The resulting structurally well-defined Cu45 is a highly efficient catalyst for the hydroboration reaction of alkynes and alkenes. Mechanistic studies show that a single-electron oxidation of the in situ-formed ate complex enables the hydroboration via the formation of boryl-centered radicals under mild conditions. This work demonstrates the promise of tailored copper nanoclusters as catalysts for C-B heteroatom bond-forming reactions. The catalysts are compatible with a wide range of alkynes and alkenes and functional groups for producing hydroborated products.

Anxiety, Hope and Meaning in Times of Ecological Crisis: An Existential-Phenomenological Perspective on Environmental Emotions

AbstractEnvironmental anxiety is often thought of as a psychopathological condition. Our paper aims to challenge this narrow understanding by offering an existential-phenomenological interpretation of environmental anxiety that posits it as an existential attunement with a transformative potential, capable of opening the anxious individual to a hopeful and meaningful outlook on the future. In the first part of the paper, we provide a conceptual analysis of environmental anxiety, drawing on current interdisciplinary taxonomies of environmental emotions as well as on existential-phenomenological definitions of anxiety. We then proceed to define the two key existential characteristics of environmental anxiety, firstly (i) its ability to reframe the aesthetic perception of nature, and secondly (ii) its impact on the subjective constitution of meaning. In the second part of the paper, drawing on the work of Kierkegaard and contemporary ecopsychological and ecotheological thinkers, a distinction is made between a naïve and a radical form of environmental hope. It is argued that while the former type of hope leads to inactivity, the latter is capable of motivating individuals to pro-environmental action.

The Role of Curcumin in Oral Health and Diseases: A Systematic Review.

Curcumin (Curcumin) belongs to the polyphenol family. It is extracted by drying the root of a plant of Asian origin, belonging to the Zingiberaceae family. The best-known species is Curcumincuma Longa. Curcumin has been recognized as having great therapeutic powers since ancient times. Studies on curcumin have since confirmed its powerful antioxidant properties, preventing both the formation of free radicals and their neutralization, having anti-inflammatory, antibacterial, immunological, and neuroprotective properties, as well as being a regulator of the intestinal microbiota with beneficial effects on the clinical manifestations of metabolic syndrome. Our study aimed to highlight how all these therapeutic aspects could benefit oral health, both preventing and improving the course of pathological processes. The effect of mouthwashes, and curcumin-based gels on the regulation of bacterial plaque and in the control of gingivitis, was largely comparable to that of using 0.20% chlorhexidine, with fewer side effects. Being a highly hydrophobic substance, it has a high permeability to cross the cell membrane. Bioavailability increases when combined with liposoluble substances (e.g., olive oil) and piperine, which improves absorption. Curcumin also has a negligible degree of toxicity, making it an excellent alternative to the use of gold standard products for oral disinfection.

Understanding the Red Shift in the Absorption Spectrum of the FAD Cofactor in ClCry4 Protein.

It is still a puzzle that has not been entirely solved how migratory birds utilize the Earth's magnetic field for biannual migration. The most consistent explanation thus far is rooted in the modulation of the biological function of the cryptochrome 4 (Cry4) protein by an external magnetic field. This phenomenon is closely linked with the flavin adenine dinucleotide (FAD) cofactor that is noncovalently bound in the protein. Cry4 is activated by blue light, which is absorbed by the FAD cofactor. Subsequent electron and proton transfers trigger radical pair formation in the protein, which is sensitive to the external magnetic field. An important long-lasting redox state of the FAD cofactor is the signaling (FADH•) state, which is present after the transient electron transfer steps have been completed. Recent experimental efforts succeeded in crystallizing the Cry4 protein from Columbia livia (ClCry4) with all of the important residues needed for protein photoreduction. This specific crystallization of Cry4 protein so far is the only avian cryptochrome crystal structure available, which, however, has great similarity to the Cry4 proteins of night migratory birds. The previous experimental studies of the ClCry4 protein included the absorption properties of the protein in its different redox states. The absorption spectrum of the FADH• state demonstrated a peculiar red shift compared to the photoabsorption properties of the FAD cofactor in its FADH• state in other Cry proteins from other species. The aim of this study is to understand this red shift by employing the tools of computational microscopy and, in particular, a QM/MM approach that relies on the polarizable embedding approximation.

Promoting ultrasonic cavitation via Negative-Curvature nanoparticles

It is a challenge to study the nucleation of cavitation bubbles, which critically depends on nanoscale morphological features. Our recent advances in synthesizing colloidal negative-curvature nanoparticles (NGC-NPs) offer a rare opportunity, in comparison to the conventional studies of bulk substrates, where it is difficult to obtain consistent and well-defined surface features. In order to quantitatively assess their effects, we exploit the radical-induced color change of [Fe(SCN)6]3−, which turned out to be a more convenient method than the bending of AgNWs and the fluorescence-based methods. We show that the NGC-NPs outperform positive-curvature nanoparticles (PSC-NPs) and homogeneous nucleation, in terms of promoting cavitation. The NGC-NPs provide a higher percentage of gas–solid interface, and thus reduces the activation barrier during the critical stage of bubble nucleation. This leads a higher probability of cavitation and transforms more energy from ultrasonication to radical formation and shockwaves.

Pyrogallol intermediates elicit beta-amyloid secretion via radical formation and alterations in intracellular trafficking, distinct from pyrogallol-generated superoxide

This study unveils a novel role of pyrogallol (PG), a recognized superoxide generator, in inducing beta-amyloid (Aβ) secretion in an Alzheimer's disease (AD) cellular model. Contrary to expectations, the analysis of dihydroethidium fluorescence and UV-VIS spectrum scanning reveals that Aβ secretion arises from PG reaction intermediates rather than superoxide or other by-products. Investigation into Aβ secretion mechanisms identifies dynasore-dependent endocytosis and BFA-dependent exocytosis as independent pathways, regulated by tiron, tempol, and superoxide dismutase. Cell-type specificity is observed, with 293sw cells showing both pathways, while H4sw cells and primary astrocytes from an AD animal model exclusively exhibit the Aβ exocytosis pathway. This exploration contributes to understanding PG's chemical reactions and provides insights into the interplay between environmental factors, free radicals, and AD, linking occupational PG exposure to AD risk as reported in the literature.

Unusual facet and co-catalyst effects in TiO2-based photocatalytic coupling of methane

Photocatalytic coupling of methane to ethane and ethylene (C2 compounds) offers a promising approach to utilizing the abundant methane resource. However, the state-of-the-art photocatalysts usually suffer from very limited C2 formation rates. Here, we report our discovery that the anatase TiO2 nanocrystals mainly exposing {101} facets, which are generally considered less active in photocatalysis, demonstrate surprisingly better performances than those exposing the high-energy {001} facet. The palladium co-catalyst plays a pivotal role and the Pd2+ site on co-catalyst accounts for the selective C2 formation. We unveil that the anatase {101} facet favors the formation of hydroxyl radicals in aqueous phase near the surface, where they activate methane molecules into methyl radicals, and the Pd2+ site participates in facilitating the adsorption and coupling of methyl radicals. This work provides a strategy to design efficient nanocatalysts for selective photocatalytic methane coupling by reaction-space separation to optimize heterogeneous-homogeneous reactions at solid-liquid interfaces.