Higher Oxidative Levels Research Articles

Experimental and low-dimensional numerical study on the application of conventional NOx reduction methods in pulse detonation combustion

Although research interest in pressure gain combustion (PGC) remains high, information on pollutant emissions from detonation-based devices such as pulse detonation engines is sparse, especially lacking extensive experimental parameter studies. Nevertheless, available results indicate potentially very high exhaust levels of nitrogen oxides (NOx) due to the significantly increased combustion temperatures and pressures induced by the detonation wave. To counter this issue, this study applies conventional NOx reducing measures in the form of fuel-lean mixtures and nitrogen dilution (emulating exhaust gas recirculation) to a pulse detonation combustor in multi-cycle operation. Their impact on the exhaust gas composition is measured and compared to numerical predictions by two available simplified models. To allow for a broader range of comparison and better assess the capabilities of these numerical models, emissions from fuel-rich and oxygen-enriched mixtures are measured as well. Experimental results confirm high levels of NOx up to several thousand ppm for near-stoichiometric, undiluted mixtures. When conventional NOx reduction measures are applied, significant NOx abatement can be achieved, with further reduction potential primarily limited by unsuccessful deflagration to detonation transition (DDT). Comparison with numerical results shows that simplified models allow for good qualitative agreement and can also deliver good quantitative predictions over a wide range of conditions if a suitable heat-loss model is chosen.

Physiological responses (Hsps 60 and 32, caspase 3, H2O2 scavenging, and photosynthetic activity) of the coral Pocillopora damicornis under thermal and high nitrate stresses

This study explored the physiological responses of the coral Pocillopora damicornis to high nitrate concentrations and thermal stresses. The expression of heat shock proteins Hsp60 and Hsp32, Symbiodiniaceae density, Chl a concentration, Fv/Fm, H2O2 scavenging, and caspase 3 activity varied during 60 h incubations at 28 °C or 32 °C, ambient or high nitrate (~10 μM) concentrations, and their combinations. In combined stresses, corals showed a rapid and high oxidation level negatively affecting the Symbiodiniaceae density and Chl a concentration at 12 h, followed by caspase 3 and Hsps upregulations that induced apoptosis, bleaching and tissue detachment. Corals under thermal stress showed the highest oxidation and upregulation of Hsps and caspase 3 resulting in coral discoloration. High nitrate treatment alone did not seriously affect the coral function. Results showed that combined stress treatment severely affected coral physiology and, judging from the condition of detached tissues, these corals might have lower chances to recover.

Modeling the emissions of rural vehicles based on real-world driving cycles

Characterized by a high frequency of use, harsh working environments, poor maintenance, and low levels of emission controls, rural vehicles (RVs) are becoming an important source of air pollution. Our study used a portable emission measurement system (PEMS) to test the real-world emissions of 35 RVs on provincial, rural, and farm roads. The results show that high emission rates of carbon monoxide (CO) and hydrocarbons (HC) mainly occurred when accelerating at low speeds. However, high levels of nitrogen oxides (NOx) were emitted during high-speed acceleration. The particulate number (PN) of emissions was higher when the RVs were accelerating. According to the overall test results, the vehicle specific power (VSP) on the provincial road mostly ranged within (0, 3], accounting for 68.80% of the total. The VSP on rural and farm roads was concentrated within (0, 2] kW·ton−1, accounting for 67.09% and 76.64% of the total, respectively. We defined 14 bins based on the distribution of the VSP values and calculated the average emission rate of each bin. By comparing the average emission rate among the bins, we found that within Bins 1–7 (VSP < 0 kW·ton−1), CO, HC, and NOx emissions slowly increased as the VSP increased. In Bins 8–13 (VSP ≥ 0 kW·ton−1), the average emission rates of four pollutants increased as the VSP increased. However, all pollutants decreased in Bin 14 (VSP ≥ 6 kW·ton−1). We built a microscopic emission model according to the VSP distribution characteristics of RVs on different road types. We compared the measured and simulated emission factors and found that our emission model can greatly simulate the HC, NOx and PN emission factors of RVs.

Estimating Emissions of Harmful Exhaust Components by Aircraft Engines During the Takeoff and Landing Cycle in Airport Space

Abstract This article examines, based on the available information and authors’ self-assessments, the environmental impact of turbine engine exhaust gases effect on the environment in the airport space during engines flight phases in the landing and takeoff cycle (LTO). The attention of aviation professionals is drawn to the fact that the amount of exhaust from the turbine engine is so significant that it may adversely change the ambient air at the airport. Consequently, increased emission level of carbon monoxide (CO), hydrocarbons (HC) during engine start-up and idle may pose a threat to the health of ramp staff. Also, high emission levels of nitrogen oxides (NOx) during takeoff, climb, cruise and descent is not without importance for the environment around the airport space. The paper gives CO2, HC, CO and NOx emission estimations based on ICAO Engine Emission Data Bank and the number of passenger operations at a medium-sized airport. It also provides calculation results of aircraft CO2, HC, CO and NOx emission using average times of aircraft maneuvers taken from aircraft Flight Data Recorder (FDR) in the LTO cycle various aircraft types at the airport. The latter, based on actual maneuvering times, lead to significantly reduced estimates of toxic exhaust gas emission volumes.

Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers.

Controlling the flow of electrical current at the nanoscale typically requires complex top-down approaches. Here, a bottom-up approach is employed to demonstrate resistive switching within molecular wires that consist of double-helical metallopolymers and are constructed by self-assembly. When the material is exposed to an electric field, it is determined that ≈25% of the copper atoms oxidize from CuI to CuII , without rupture of the polymer chain. The ability to sustain such a high level of oxidation is unprecedented in a copper-based molecule: it is made possible here by the double helix compressing in order to satisfy the new coordination geometry required by CuII . This mixed-valence structure exhibits a 104 -fold increase in conductivity, which is projected to last on the order of years. The increase in conductivity is explained as being promoted by the creation, upon oxidation, of partly filled orbitals aligned along the mixed-valence copper array; the long-lasting nature of the change in conductivity is due to the structural rearrangement of the double-helix, which poses an energetic barrier to re-reduction. This work establishes helical metallopolymers as a new platform for controlling currents at the nanoscale.

Total Synthesis of Stemarene and Betaerene Diterpenoids: Divergent Ring-Formation Strategy and Late-Stage C–H Functionalization

A unified protecting group-free approach to two stemarene and two betaerene diterpenoids through a bioinspired two-phase strategy has been developed, and three of them were obtained for the first t...

PTH Protects Osteocytes From Oxidative Stress and Cellular Senescence

Age-induced osteoporosis is characterized by a progressive decline in bone formation and increase in bone resorption with uncoupled activities of osteoblasts and osteoclasts. Parathyroid hormone (PTH) is used in the clinic to treat osteoporosis due to its anabolic actions on bone via binding to the PTH receptor (PPR). The receptor is highly expressed in cells of the osteoblastic lineage, including osteocytes. Osteocytes are the most abundant cells in bone and serve as a key regulator of bone remodeling. Despite the significant role of PPR signaling in skeletal homeostasis, its function in osteocytes during aging remains unclear. We have gathered preliminary data demonstrating that mice lacking PPR predominantly in osteocytes (Dmp1-PPRKO) have marked age-induced bone loss due to increased bone resorption and suppressed bone formation. These mice, with aging, develop characteristics of skeletal senescence: a decrease in osteoprogenitors and an increase in bone marrow adiposity and p16Ink4a/Cdkn2a expression in bone. Since senescence of cells in the bone microenvironment has been reported as a cause of age-induced bone loss, we hypothesized that PPR signaling protects osteocytes from senescence. To test this hypothesis, we generated osteocytes (Ocy454-12H), in which the PPR expression was ablated using CRISPR/Cas9 technique. Ocy454-12H-PPRKO and Ocy454-12H-PPRCtrl cells were treated with PTH followed by an exposure to hydrogen peroxide (H2O2). High levels of intracellular reactive oxygen species (ROS), including H2O2, promote protein and DNA oxidation, resulting in cell death and senescence. PTH treatment significantly suppressed the increase in H2O2-induced cell death, measured by resazurin-based assays, in PPRCtrl but not in PPRKO cells. We analyzed intracellular ROS levels using a fluorescent probe and found that PTH treatment significantly suppressed the increase in ROS upon H2O2 exposure, suggesting an antioxidant function of PTH in osteocytes. To further investigate if PTH prevents osteocytes from oxidative stress-induced senescence, we examined senescence-associated β-galactosidase (SA β-gal) activity in cells that were treated with PTH followed by an exposure to low doses of H2O2. Compared to untreated and PPRKO groups, treatment with PTH significantly decreased the number of SA β-gal positive cells, demonstrating that PPR signaling protects osteocytes, and possibly other osteoblastic cells, from H2O2-induced cellular senescence. PTH treatment reduced mRNA expression of p21/Cdkn1a. Taken together these results demonstrate that PPR signaling is important to protect osteocytes from cellular senescence.

Explicit modeling of isoprene chemical processing in polluted air masses in suburban areas of the Yangtze River Delta region: radical cycling and formation of ozone and formaldehyde

Abstract. In recent years, ozone pollution has become one of the most severe environmental problems in China. Evidence from observations have showed increased frequency of high O3 levels in suburban areas of the Yangtze River Delta (YRD) region. To better understand the formation mechanism of local O3 pollution and investigate the potential role of isoprene chemistry in the budgets of ROx (OH+HO2+RO2) radicals, synchronous observations of volatile organic compounds (VOCs), formaldehyde (HCHO), and meteorological parameters were conducted at a suburban site of the YRD region in 2018. Five episodes with elevated O3 concentrations under stagnant meteorological conditions were identified; an observation-based model (OBM) with the Master Chemical Mechanism was applied to analyze the photochemical processes during these high O3 episodes. The high levels of O3, nitrogen oxides (NOx), and VOCs facilitated strong production and recycling of ROx radicals with the photolysis of oxygenated VOCs (OVOCs) being the primary source. Our results suggest that local biogenic isoprene is important in suburban photochemical processes. Removing isoprene could drastically slow down the efficiency of ROx recycling and reduce the concentrations of ROx. In addition, the absence of isoprene chemistry could further lead to a decrease in the daily average concentrations of O3 and HCHO by 34 % and 36 %, respectively. Therefore, this study emphasizes the importance of isoprene chemistry in the suburban atmosphere, particularly with the participation of anthropogenic NOx. Moreover, our results provide insights into the radical chemistry that essentially drives the formation of secondary pollutants (e.g., O3 and HCHO) in suburban areas of the YRD region.

Pre-Exercise Carbohydrate or Protein Ingestion Influences Substrate Oxidation but Not Performance or Hunger Compared with Cycling in the Fasted State

Nutritional intake can influence exercise metabolism and performance, but there is a lack of research comparing protein-rich pre-exercise meals with endurance exercise performed both in the fasted state and following a carbohydrate-rich breakfast. The purpose of this study was to determine the effects of three pre-exercise nutrition strategies on metabolism and exercise capacity during cycling. On three occasions, seventeen trained male cyclists (VO2peak 62.2 ± 5.8 mL·kg−1·min−1, 31.2 ± 12.4 years, 74.8 ± 9.6 kg) performed twenty minutes of submaximal cycling (4 × 5 min stages at 60%, 80%, and 100% of ventilatory threshold (VT), and 20% of the difference between power at the VT and peak power), followed by 3 × 3 min intervals at 80% peak aerobic power and 3 × 3 min intervals at maximal effort, 30 min after consuming a carbohydrate-rich meal (CARB; 1 g/kg CHO), a protein-rich meal (PROTEIN; 0.45 g/kg protein + 0.24 g/kg fat), or water (FASTED), in a randomized and counter-balanced order. Fat oxidation was lower for CARB compared with FASTED at and below the VT, and compared with PROTEIN at 60% VT. There were no differences between trials for average power during high-intensity intervals (367 ± 51 W, p = 0.516). Oxidative stress (F2-Isoprostanes), perceived exertion, and hunger were not different between trials. Overall, exercising in the overnight-fasted state increased fat oxidation during submaximal exercise compared with exercise following a CHO-rich breakfast, and pre-exercise protein ingestion allowed similarly high levels of fat oxidation. There were no differences in perceived exertion, hunger, or performance, and we provide novel data showing no influence of pre-exercise nutrition ingestion on exercise-induced oxidative stress.

Electronic and Spin-State Effects on Dinitrogen Splitting to Nitrides in a Rhenium Pincer System.

Bimetallic nitrogen (N2) splitting to form metal nitrides is an attractive method for N2 fixation. Although a growing number of pincer-supported systems can bind and split N2, the precise relationship between the ligand properties and N2 binding/splitting remains elusive. Here we report the first example of an N2-bridged rhenium(III) complex, [(trans-P2tBuPyrr)ReCl2]2(μ-η1:η1-N2) (P2tBuPyrr = [2,5-(CH2PtBu2)2C4H2N]-). In this case, N2 binding occurs at a higher oxidation level than that in other reported pincer analogues. Analysis of the electronic structure through computational studies shows that the weakly π-donor pincer ligand stabilizes an open-shell electronic configuration that leads to enhanced binding of N2 in the bridged complex. Utilizing SQUID magnetometry, we demonstrate a singlet ground state for this Re-N-N-Re complex, and we offer tentative explanations for antiferromagnetic coupling of the two local S = 1 sites. Reduction and subsequent heating of the rhenium(III)-dinitrogen complex leads to chloride loss and cleavage of the N-N bond with isolation of the terminal rhenium(V) nitride complex (P2tBuPyrr)ReNCl.

Mathematical modelling of ageing acceleration of the human follicle due to oxidative stress and other factors.

There is a gradual telomere shortening due to the inability of the replication machinery to copy the very ends of chromosomes. Additionally, other factors such as high levels of oxidation (free radicals or reactive oxygen species (ROS)), e.g. due to cumulated stress, inflammation or tobacco smoke, accelerate telomere shortening. In humans, the average telomere length is about 10-15 kb at birth and telomeres shorten at a pace of 70 bp per year. However, when cells are exposed to ROS, telomere attrition happens at a faster pace, generating a wide variety of telomere size distribution in different length percentiles, which are different to what is expected just by age. In this work, the generational age of a cell is associated with its telomere length (TL), from certain maximum to the minimal TL that allows replication. In order to study the accumulation of aged granulosa cells in human follicles, from preantral to preovulatory size, a mathematical model is proposed, regarding different degrees of accelerated telomere shortening, which reflect the action of ROS in addition to the telomere shortening that happens after cell division. In cases of cells with TL shorter than cells with average TL, with low telomerase activity and accelerated telomere shortening, the mathematical model predicts an aged outcome in preovulatory follicles. The model provides a plausible explanation for what has been observed in oocytes from older women, which have been exposed to ROS for a longer period of time and have bad outcomes after in vitro fertilization.

High fractional exhaled nitric oxide levels in asthma patients: Does size matter?

Fractional exhaled nitric oxide (FeNO) is a biomarker for eosinophilic inflammation used for diagnosis and monitoring of asthma. High FeNO indicates significant airway eosinophilia and steroid-responsive airway inflammation. Some children with asthma have extremely high FeNO levels, but whether these levels represent a different asthma phenotype compared with those with mildly elevated FeNO is unclear. The objective of this study is to investigate whether the extent of high FeNO levels correlates with clinical phenotype, asthma control, comorbidity, and pulmonary function test (PFT) findings in children with asthma. Anthropometric data, daytime and nighttime symptoms, controller treatment, comorbidity, and PFT findings were retrieved from the Pediatric Pulmonology Unit database (2014-2020) and correlated with FeNO levels in pediatric asthma patients with high FeNO levels. Two-hundred children and adolescents with high FeNO levels (range 36-227 ppb) were included. Within this range, higher FeNO levels positively correlated with increased daytime and nighttime symptoms (p = .013 and p = .01, respectively) and poorly controlled asthma (p = .034). A FeNO level of ≥80 ppb was the cutoff for significantly more severe daytime and nighttime symptoms and very poorly controlled asthma compared with levels <80 ppb (p = .004, p = .005, and p = .036, respectively). No correlation was found between FeNO and controller treatment, comorbidity, and PFT performance. In pediatric asthma patients, high FeNO levels correlate with increased symptom severity and poor asthma control. A FeNO level of ≥80 ppb may serve as an objective indicator for severe asthma.

A Study on the Microstructure and Corrosion Characteristics of Early Iron Age Bronze Mirrors Excavated from the Korean Peninsula

Bronze mirrors, considered important grave goods, were widely used before glass mirrors in ancient times. Most excavated bronze artifacts are covered with corrosive materials and lose their original colors. More importantly, identifying corrosion characteristics and the manufacturing techniques used for these artifacts are essential for proper artifact preservation. In this study, Early Iron Age bronze mirrors excavated from the Korean Peninsula were examined to determine their microstructures, corrosion characteristics, and production techniques using various analytical methods, such as Micro-Raman spectroscopy and field emission electron probe microanalysis. As a result, sulfides containing iron suggested chalcopyrite use during production or that the sulfides originated from copper, iron, and sulfur residual matte. The analysis also detected corrosion layers with high tin oxide (SnO2) levels and selective corrosion in the α + δ eutectoid phase on the artifact’s surface. In the corrosive layer, cuprite, malachite, and cassiterite corrosion products were detected, and nanocrystalline SnO2 was identified as a characteristic of long-term soil erosion. Identifying these artifacts’ corrosion characteristics and manufacturing techniques is essential and can greatly contribute to proper artifact preservation.

Graphene Oxide and Graphene Oxide-TiO₂ Nanocomposites: Synthesis, Characterization, and Rhodamine B Photodegradation Investigation.

In this study, graphene oxide (GO) sheets were successfully synthesized using two routes: conventional Hummers' (HGO) and modified Hummers' (or Marcano's) (MGO) methods. GO sheets were then assembled with TiO₂ nanoparticles to form nanocomposites (i.e., HGO-TO and MGO-TO). The properties of HGO and MGO and their nanocomposites with TiO₂ were evaluated by Fouriertransform infrared (FTIR), Raman, ultraviolet-visible (UV-Vis) adsorption, and diffuse reflectance (DRS) spectroscopies, X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). The specific surface area, pore volume, and pore size of MGO, determined by Brunauer-Emmett-Teller (BET) equation, were 565 m²g-1, 376 cm³ g-1, and 30 nm, respectively; all of these parameters decreased after MGO was combined with TiO₂. In addition, compared with HGO, MGO possessed higher oxidation level and more stable bonding with TiO₂ nanoparticles. The morphology of HGO and MGO, which were characterized by scanning electron (SEM) and transmission electron microscopies (TEM), together with energy-dispersive X-ray (EDX) spectroscopy and elemental mapping technique, was determined to consist of TiO₂ nanoparticle-assembled GO sheets. All GO-TiO₂ nanocomposite samples exhibited a very high activity (˜100%) toward rhodamine B (RhB) dye photodegradation under natural sunlight exposure within 60 min. The obtained results for the GO-TiO₂ nanocomposite showed the potential of its application in wastewater purification and other environmental aspects.

Soil arsenic toxicity differentially impacts C3 (barley) and C4 (maize) crops under future climate atmospheric CO2

Soil arsenic (As) contamination limits global agricultural productivity. Anthropogenic emissions are causing atmospheric CO2 levels to rise. Elevated CO2 (eCO2) boosts plant growth both under optimal and suboptimal growth conditions. However, the crop-specific interaction between eCO2 and soil arsenic exposure has not been investigated at the whole plant, physiological and biochemical level. Here, we tested the effects of eCO2 (620 ppm) and soil As exposure (mild and severe treatments, 25 and 100 mg As/Kg soil) on growth, photosynthesis and redox homeostasis in barley (C3) and maize (C4). Compared to maize, barley was more susceptible to soil As exposure at ambient CO2 levels. Barley plants accumulated more As, particularly in roots. As accumulation inhibited plant growth and induced oxidative damage in a species-specific manner. As-exposed barley experienced severe oxidative stress as illustrated by high H2O2 and protein oxidation levels. Interestingly, eCO2 differentially mitigated As-induced stress in barley and maize. In barley, eCO2 exposure reduced photorespiration, H2O2 production, and lipid/protein oxidation. In maize eCO2 exposure led to an upregulation of the ascorbate-glutathione (ASC/GSH)-mediated antioxidative defense system. Combined, this work highlights how ambient and future eCO2 levels differentially affect the growth, physiology and biochemistry of barley and maize crops exposed to soil As pollution.

Walnut (Juglans regia L.) Volatile Compounds Indicate Kernel and Oil Oxidation.

Kernel oxidation susceptibility and pellicle darkening are among the biggest concerns regarding walnut quality. Monitoring oxidation is crucial to preserve quality from production to consumption. Chemical oxidation parameters (peroxide value and UV absorbances), fatty acid profile, tocopherols, phenols, and volatiles in ‘Chandler’ and ‘Howard’ kernels were studied at different time points during 28 weeks of storage to evaluate potential oxidation markers. During storage, peroxide value, UV absorbances, and volatiles concentration increased; oxidative stability, phenols, and tocopherols decreased, while fatty acid profile was unaffected. ‘Chandler’ had a lower peroxide value, K232, and K268; and higher kernel and oil oxidative stability compared to ‘Howard’. Phenols and tocopherols decreased 1.2-fold in ‘Chandler’ and 1.3-fold in ‘Howard’. Using multivariate analysis, samples were discriminated in three groups according with their oxidative levels. Increases of volatiles in oil and kernel were associated with higher oxidative levels. Pentanal, 2-methylpropanal, hexanal, (E)-2-pentenal, 3-octanone, octanal, (Z)-2-penten-1-ol, hexanol, (E)-2-octenal, 1-octen-3-ol, benzaldehyde, (E,E)-2,4-nonadienal, and hexanoic acid in kernels were adequate at distinguishing oxidation levels and as oxidative markers in walnuts. Kernel volatiles is a useful measurement for walnut oxidation during storage without any prior fat extraction.

Extraordinary thermal behavior of graphene oxide in air for electrode applications.

The thermal stability of solution-exfoliated graphene oxide (GO) in air is one of the most important physical properties influencing its potential applications. To date, the majority of the GO prepared by the KMnO4-based oxidation of graphite is thermally unstable in air due to the presence of highly oxidative functional groups, such as carboxyl and lactol groups that possess defective basal plane structures. Here, we demonstrate that less defective and metal ion-free GO nanosheets including those with a high oxidation level can remain very stable even above 300 °C under ambient conditions. These GO nanosheets were produced by the exfoliation of graphite oxide fabricated by the modified Brodie method in NH4OH solution, effectively excluding metal ions that can promote the thermal decomposition of GO in air at elevated temperatures. The deoxygenation of ammonia-assisted GO (AGO) was initiated at temperatures above 200 °C, while GO exfoliated in the KOH solution (KGO) decomposed, even at 180 °C. Notably, AGO was exceptionally resistant at 400 °C, even at a very slow heating rate of 2 °C min−1. Conversely, KGO was significantly oxidized, even at 250 °C. The superior thermal stability of AGO is favorable for the fabrication of conductive surface graphene films and conductive fibers by low-temperature annealing.

Oxidative etching of S-vacancy defective MoS2 monolayer upon reaction with O2.

The reactions of O2 with S vacancy sites within a MoS2 monolayer were investigated using density functional theory calculations. We considered the following defects: single S vacancy, double S vacancy, two adjacent S vacancies and two S vacancies separated by a sulphur atom. We found that the surface distribution of S vacancy sites plays a key role in determining the surface reactivity towards O2. We observed the desorption of SO2 only for the last vacancy distribution. For the other cases, the surface becomes passivated with very stable structures having O atoms on the original vacancy sites and in some cases an SO group in an adjacent position. The ab initio molecular dynamics simulations showed that the impingement of the O2 molecule on an S vacancy site produces a stable chemisorbed O2 molecule with an upright configuration. The surface reactions initiate after the O2 molecule switches to the lying-down configuration which favours the breakage of the O-O bond and the concurrent formation of S-O bonds. In the most reactive vacancy site configuration, the dissociation of the first O2 molecule produces an SO intermediate which finally leads to desorption of SO2 after oxygen abstraction from the other adjacent O2 molecule. The formation of a MoO3 moiety within the monolayer was also observed in the molecular dynamic simulations at higher oxidation levels.

Oxidative Effects during Irreversible Electroporation of Melanoma Cells-In Vitro Study.

Irreversible electroporation (IRE) is today used as an alternative to surgery for the excision of cancer lesions. This study aimed to investigate the oxidative and cytotoxic effects the cells undergo during irreversible electroporation using IRE protocols. To do so, we used IRE-inducing pulsed electric fields (PEFs) (eight pulses of 0.1 ms duration and 2–4 kV/cm intensity) and compared their effects to those of PEFs of intensities below the electroporation threshold (eight pulses, 0.1 ms, 0.2–0.4 kV/cm) and the PEFs involving elongated pulses (eight pulses, 10 ms, 0.2–0.4 kV/cm). Next, to follow the morphology of the melanoma cell membranes after treatment with the PEFs, we analyzed the permeability and integrity of their membranes and analyzed the radical oxygen species (ROS) bursts and the membrane lipids’ oxidation. Our data showed that IRE-induced high cytotoxic effect is associated both with irreversible cell membrane disruption and ROS-associated oxidation, which is occurrent also in the low electric field range. It was shown that the viability of melanoma cells characterized by similar ROS content and lipid membrane oxidation after PEF treatment depends on the integrity of the membrane system. Namely, when the effects of the PEF on the membrane are reversible, aside from the high level of ROS and membrane oxidation, the cell does not undergo cell death.

Effect of Substrate on Structural Phase Transition in a Conducting Polymer during Ion Injection and Water Intake: A View from a Computational Microscope

Conducting polymers operating in aqueous electrolyte represent mixed electron-ion conductors, where the ion injection and water intake can lead to structural and morphological changes that can strongly affect the material morphology and device performance. In the present paper, using molecular dynamics simulations, we provide an atomistic understanding of the structural phase transitions during electrochemical oxidation and ion injection in a conjugated polymer with glycolated side chains recently reported by Bischak et al. [J. Am. Chem. Soc., 2020, 142, 7434], where the polymer switched between two structurally distinct phases corresponding to different oxidation levels. To outline the structural changes, we calculated the polymer film morphology and X-ray diffraction patterns at different oxidation levels. We demonstrated that the observed phase transition arises due to interplay between several factors, including the effect of the substrate leading to the preferential edge-on arrangement of the chains and formation of lamellas; unzipping of the interdigitated polymer chains during oxidation and ion intake; and changes in the morphology when π–π stacking is absent at low oxidation level and forms at the high oxidation level facilitating the electron mobility and enabling the oxidation of the polymer film. Our calculations quantitatively reproduce the experimental data, which outlines the predictive power of the molecular modeling of the polymer systems that can be utilized for the design of materials and devices with improved performance.