Radical Process Research Articles

Using Excimer Laser for Manufacturing Stimuli Responsive Membranes.

A 248 nm KrF excimer laser can be used to manufacture temperature and pH-responsive polymer-based membranes for controlled transport applications. This is done by a two-step approach. In the first step, well-defined/shaped and orderly pores are created on commercially available polymer films by ablation by using an excimer laser. The same laser is used subsequently for energetic grafting and polymerization of a responsive hydrogel polymer inside the pores fabricated during the first step. Thus, these smart membranes allow controllable solute transport. In this paper, determination of appropriate laser parameters and grafting solution characteristics are illustrated to obtain the desired membrane performance. Fabrication of membranes with 600 nm to 25 μm pore sizes by using the laser through different metal mesh templates is discussed first. Laser fluence and the number of pulses need to be optimized to obtain the desired pore size. Mesh size and film thickness primarily control the pore sizes. Typically, pore size increases with increasing fluence and the number of pulses. Larger pores can be created by using higher fluence at a given laser energy. The vertical cross-section of the pores turns out to be inherently tapered due to the ablative action of the laser beam. The pores created by laser ablation can be grafted with PNIPAM hydrogel by using the same laser to perform a bottom-up grafting-from type pulsed laser polymerization (PLP) in order to achieve the desired transport function controlled by temperature. For this purpose, a set of laser frequencies and pulse numbers need to be determined to obtain the desired hydrogel grafting density and the extent of cross-linking, which ultimately provide controlled transport by smart gating. In other words, on-demand switchable solute release rates can be achieved by controlling the cross-linking level of the microporous PNIPAM network. The PLP process is extremely fast (few seconds) and provides higher water permeability above the lower critical solution temperature (LCST) of the hydrogel. Experiments have shown high mechanical integrity for these pore-filled membranes, which can sustain pressures up to 0.31 MPa. The monomer (NIPAM) and cross-linker (mBAAm) concentrations in the grafting solution need to be optimized in order to control the network growth inside the support membrane pores. The cross-linker concentration typically has a stronger effect on the temperature responsiveness. The pulsed laser polymerization process described can be extended to different unsaturated monomers, which can be polymerized by the free radical process. For example, poly(acrylic acid) can be the grafted to provide pH responsiveness to membranes. As for the effects of thickness, a decreasing trend is observed in the permeability coefficient with increasing thickness. Furthermore, the film thickness has little or no effect on PLP kinetics. The experimental results have shown that membranes manufactured by excimer laser are excellent choices for applications where flow uniformity is the prime requirement, as they possess uniform pore sizes and distribution.

ALT-PLATFORMIZATION: RADICALIZATION OF DISCOURSES AND INFORMATION FLOWS IN THE ALTERNATIVE ECOSYSTEM.

This paper examines the process of radicalization on the alternative social media platform Gab, and the flow of information between Gab and other similar platforms. Corresponding to the socio-political changes and increasing polarization across the globe, some alternative platforms have witnessed a rising popularity among ultra-conservative and/or right-leaning users. Among such platforms, a few have succeeded in surviving the external pressures put on them through “deplatformisation”. Gab, an alternative platform often equated to the far-right copy of Twitter, is one such space (Zannettou et al., 2018). Gab exhibits significant changes in participation and discourse. By analyzing temporal dynamics of posts on three topics—vaccination discourse, music, and food—we trace the process of radicalization on Gab. We also mapped the content from the most shared external sources (domains) across platforms such as BitChute, Odyssey, Rumble etc. to trace the flow of information across the fringe network. We argue that users are overcoming deplatforming or deplatformization by creating sustainable flows of information in a range of services and spaces, all interconnected through their platformized function. We define this as "alt-platformization", the systemic and systematic process of creating a self-sufficient, viable alternative to the platformized web, entailing the necessary infrastructure, production, circulation, consumption, and reproduction of discourses. A key differentiating feature of alt-platformization is the ideological, along with commercial logics dominating this process and space.

CAN TOXIC MASCULINITIES BE DE-RADICALISED?: MAPPING THE DYNAMICS AND SPREAD OF INCEL IDEOLOGY ONLINE

In recent years, male supremacist and anti-women formations have become increasingly prevalent online. In particular, considerable attention has been focused on the incel (involuntary celibate) community due to a number of high-profile mass killings in the United States, Canada and, more recently, the UK. Incel ideology is a misogynistic formation, whose male proponents blame women for their lack of sexual activity. It operates in the broader virtual space of the manosphere, a loose conglomerate of online communities spread across various digital platforms, which are united in their antipathy toward feminism, their belief in evolutionary psychology and their adherence to the Red Pill (a process of enlightenment, whereby one comes to understand the world as a liberal feminist conspiracy that disadvantages men). This research tracks the dynamic pathways by which incel ideology spreads within and across online communities, digital platforms and geographical spaces, with a view to better understanding processes of radicalization, including ‘algorithmic radicalization.’ We also explore the dynamic interplay between incel and alt-right rhetoric. Understanding the contagion dynamics of extremist ideas - how such ideas circulate, gain new audiences, and morph into new ones - is crucial to researchers, educators, platforms and security practitioners: However, theoretical and practical understanding of the online contagion of extremist ideologies is lacking. It is only by understanding these ‘pilling pipelines’ (Ging and Murphy 2021) that effective interventions can be developed, whether educational, technological, legal or platform-governance-related.

Прооксидантно-антиоксидантні процеси в крові та печінці мишоподібних гризунів (Myodes Glareolus та Apodemus Flavicollis) за разового опромінення

The effect of total single X-ray irradiation (1.5 Gy) on the course of free radical processes (FRP) in the blood and liver of red fistula (Myodes glareolus) and yellow-throated mouse (Apodemus flavicollis) was studied. It is shown that physicochemical regulation of FRP in the blood of murine rodents under total X-ray irradiation (1.5 Gy) in the early stages is carried out mainly due to catalase and reduced glutathione (GSH). This is evidenced by the stoichiometry of the CL reaction and symbat changes in the prooxidant-antioxidant ratio (PAR) and basic kinetic parameters of the CL reaction (Imax, Ifin) and antibat changes to PAR - catalase and GSH.

Cover Feature: Visible Light‐Triggered Radical Annulation of ortho‐Thioaryl Ynones: A General Approach to Prepare 3‐Sulfenylthiochromones (ChemCatChem 7/2023)

The Cover Feature shows the office environment of an organic synthesis laboratory, centered around a “synthetic tools desk,” which is a place where ideas are discussed on a daily basis. In their Research Article, R. H. Bartz et al. demonstrated one of the few cases in which an intramolecular EDA-complex (the molecule on the desk) is used as a species that can absorb blue light (440 nm) and trigger an annulative radical process. In this sophisticated synthetic transformation, thiols are used as reactants, giving rise to the “most wanted” 3-sulfenylthiochromones. This strategy circumvents the classical use of photocatalytic species in light-mediated reactions, as well as the use of oxidants and heating, readily yielding the desired products in a short reaction time. Taken together, the main features of the developed approach meet some principles of green chemistry and promote sustainable chemistry. More information can be found in the Research Article by R. H. Bartz et al..

Visible-Light-Mediated Regioselective Chlorosulfonylation of Acrylamides

AbstractA one-step chlorosulfonylation of acrylamides via a photocatalytic redox process is described. This reaction provides α-chlorosulfonylamides with a quaternary center with high regioselectivity via radical process. It is amenable to a broad range of substrates and the products are obtained in moderate to good yields.

Persulfate oxidation of tetracycline, antibiotic resistant bacteria, and resistance genes activated by Fe doped biochar catalysts: Synergy of radical and non-radical processes

To reduce the adverse effects of antibiotics and antibiotic resistance genes (ARGs) in the environment, this study employed iron-loaded biochar (Fe-LBH) as an activator in a persulfate (PDS) oxidation system to degrade tetracycline (TC), inactivate antibiotic resistant bacteria (ARB), and remove ARGs. TC was removed efficiently (more than 85%) in the Fe-LBH-PDS system within 30 min, which was higher than that in the pristine biochar-PDS system (15.5%). The Fe doping amount in biochar, PDS, and catalyst dose significantly affected TC degradation. Furthermore, the Fe-LBH-PDS system inactivated 60.4% of ARB (Pseudomonas aeruginosa HLS-6) within 60 min. The removal efficiencies of ARGs (sul1 and sul2) and intI1 were 0.05–0.60- and 1.54–2.74 log2-fold, respectively. Fe (II) and oxygen functional groups (e.g., -C-OH and -C = O) were verified as the reactive sites for PDS activation. In addition, according to the results of electron paramagnetic resonance (EPR) and radical quenching experiments, the radical pathway dominated by OH and the non-radical pathway dominated by singlet oxygen (1O2) play synergistic roles in the Fe-LBH-PDS oxidation process. These findings provide a possible application of Fe-LBH-PDS for TC degradation and hindering antibiotic resistance dissemination in wastewater treatment practice.

THE DYNAMICS OF THE DEVELOPMENT OF NEO-NAZISM IN UKRAINE

The purpose of the article is to analyze the causes, forms and dynamics of the development of neo-Nazism in Ukraine. The author analyzes the reasons and events behind the need for the leaders of Ukraine at different stages to resort to radical Ukrainian, russophobic, and, at the last stage, neo-Nazi rhetoric. A cross-temporal political analysis of the processes of development of neo-Nazi ideology and its popularization among the population of both Ukraine as a whole and among the Russian-speaking population of the southeastern regions is carried out. It is assumed that the processes of popularization of the Ukrainian language and culture logically transformed into radical ukrainization, and subsequently into neo-Nazism, and all these processes were supervised by the United States to create a deeply russophobic state, the population of which would be distinguished by a high degree of hatred for Russia and the Russian world. The article also emphasizes that the process of radicalization of the views of the population of Ukraine towards Russia has been carried out for thirty years and became possible only after the formation of a new generation that no longer associated itself with Russia and a single historical past.

Radical Decarboxylative Cyanomethylation of Aliphatic Carboxylic Acids and Uronic Acids via Vinyl Azide Cascade Fragmentation

Comprehensive SummaryA direct oxidative radical decarboxylative cyanomethylation of carboxylic acids is described using 3‐azido‐2‐methylbut‐3‐en‐2‐ol as the carbon‐centered radical acceptor. The transformation is applicable to structurally diverse α‐amino acids, α‐oxy acids, α‐keto acids, pentofuranuronic acids, and hexopyranuronic acids. The mechanistic investigations suggest that a radical process is involved in the transformation. This work provides a potential approach to β‐amino acid, 5‐deoxy‐hexofuranose, and 6‐deoxy‐heptose constructs of biological relevance.

Countering extremist ideologies: What are the synergies between the EU’s internal and external action?

Countering the propaganda of terrorist groups has gradually become a central focus of efforts to prevent terrorism. The aim is ultimately to prevent the dissemination of violent ideas that are likely to encourage a process of radicalisation, which, in turn, is conducive to terrorist action. This objective has attracted more attention given changes in terrorist modus operandi, marked in particular by the use of modern online communication tools to incite/glorify terrorist acts, to provide training for terrorist purposes or to recruit candidates around the world. The EU and its Member States are working on several fronts to tackle the different facets of the ideological allure of extremist groups. This article discusses the fight against extremist ideologies as a new major focus of the EU’s terrorism prevention policy. The aim will be to shed the light on this evolving priority while identifying possible synergies between internal and external efforts to counter extremist propaganda.

Progress in the Electrochemical Synthesis of Organoboron Compounds

AbstractOrganoboron is a class of compounds widely used in organic synthesis, pharmaceuticals, material science, sensors, and so on. Therefore, the development of efficient and selective electrochemical methods to synthesize organoboron has attracted much interest as an emerging sustainable technique of organic synthesis. Here, we summarized research on electrochemical borylations, including the electrochemically driven borylation of arenes, alkanes, aryl, or alkyl halides, activated carboxylic acids etc., based on direct electrolysis and metal‐free organocatalysis. We focus on the reaction mechanisms involved in single‐electron transfer and other radical processes. We believe that this review will inspire electrochemists to discover more efficient transformations to expand this field of borylation.

Interrelation between the parameters of endogenous vascular regulation, oxidative stress and the markers of inflammatory response in COVID-19 patients while on extracorporeal membrane oxygenation

Introduction. Extracorporeal membrane oxygenation has found wide application in clinical practice during the COVID-19 pandemic. Oxidative stress, endothelial dysfunction, and systemic inflammatory response syndrome play an important role in the pathogenesis of COVID-19. Our research was designed to study correlations in-between those factors and the impact of extracorporeal membrane oxygenation on them.Aim. The study of systemic inflammatory response and endothelial function in patients with COVID-19 during extracorporeal membrane oxygenation.Material and methods. In the course of a prospective study, we examined 100 COVID-19 patients aged 26 to 75 years, median 55 years [47;60], who were treated at the N.V. Sklifosovsky Research Institute for Emergency Medicine, using extracorporeal membrane oxygenation. As a control group (normal), 25 practically healthy people whose median age was 32 years [25;39] were examined. The function of the vascular endothelium was assessed by the content of nitric oxide stable metabolites in the blood serum and the level of angiotensin-converting enzyme. Next, the ratio of nitric oxide metabolite to angiotensin-converting enzyme level was calculated, reflecting the imbalance between endotheliumdependent vasodilation and vasoconstriction. To assess the severity of oxidative stress in blood serum, malondialdehyde was determined as a marker of lipid peroxidation. The state of the antioxidant system was assessed in terms of total antioxidant status of blood serum. The presence of an imbalance in the system of lipid peroxidation and the antioxidant system total antioxidant status was judged by the oxidative stress coefficient, i.e. the ratio of malondialdehyde to the total antioxidant activity.Results. The analysis showed the presence and progression of endothelial dysfunction, impaired vascular regulation, activation of free radical processes, the presence of an imbalance in the prooxidant/antioxidant system, as well as the progression of the inflammatory process with a decrease in the level of markers of the COVID-19 severity.Conclusion. Further studies of the correlation between endothelial damage and the severity of the systemic inflammatory response syndrome may be of fundamental importance for explaining the pathophysiological mechanisms of COVID-19 course and developing new treatments for such patients.

Substance abuse and the radicalisation process

Previous research on radicalisation suggests that this process is the result of an accumulation of factors that generate a person’s susceptibility to extremist narratives. The authors of this article analysed the biographies of the perpetrators of terrorist attacks and, given the frequent references in these biographies to the abuse of various stimulants by the attackers, attempted to summarise the available knowledge on the relationship between psychoactive substance addiction and radicalisation. Although no simple causal relationship between addictions and radicalisation was found, the effects of addictions partly overlap with identified vulnerabilities to extremist narratives. A comprehensive approach to terrorism prevention should therefore take into account that addictions may contribute to increasing the vulnerability of some individuals to radicalisation leading to terrorism.

The Concept of De-Radicalization as a Source of Confusion

The theme of the relationship between religious freedom and security has, over the last twenty years, acquired such centrality that hitherto unknown or little-used concepts have entered the public and specialized debates. Prominent among these is regarding the most concrete and important long-term public intervention in the fight against extremism on a religious matrix, i.e., de-radicalization, often simplistically understood as the opposite, or reverse, of a radicalization process. The activity of de-radicalization, therefore, must first be defined in its theoretical sense to grasp its real meaning and objectives; then, it is necessary to identify its content in practice, trying to understand its founding themes and limits. The risk of such a public intervention is interfering with the deepest sphere of the individual, with his or her religiosity and intentions, overstepping the limits derived from the different types of secularism (as Italian laicità or French laïcité) that characterize the State, requiring it to consider individual conscience as impassable territory. On the other hand, ignoring the intimate dimension of the subject can lead to complete ineffectiveness of a de-radicalization activity, which thus risks being reduced to a mere illustration of content. This contribution, starting from these difficulties, intends to outline, from a juridical perspective and specifically from a law and religion perspective, a hypothesis for a public de-radicalization strategy, capable of achieving concrete results but simultaneously respectful of the constitutional principles in which it is necessarily embedded, focused on the concept of responsibility.

New insights into persulfate decomposition by soil minerals: radical and non-radical pathways

Persulfate (PS)-based in situ chemical oxidation (ISCO) has been widely used for pollutant remediation in soil and groundwater. However, the underlying mechanism of interactions between mineral and PS was not fully explored. In this study, several soil model minerals including goethite, hematite, magnetite, pyrolusite, kaolin, montmorillonite, and nontronite were selected to investigate their potential effects on PS decomposition and free radical evolution. It was found the decomposition efficiency of PS by these minerals varied significantly, and both the radical and non-radical decomposition processes were included. Pyrolusite has the highest reactivity for PS decomposition. However, PS decomposition is prone to form SO42- through non-radical pathway, and thus, the amounts of free radicals (e.g., •OH and SO4•-) produced are relatively limited. However, PS mainly decomposed to produce free radicals in the presence of goethite and hematite. In the presence of magnetite, kaolin, montmorillonite, and nontronite, PS both decomposed to produce SO42- and free radicals. Furthermore, the radical process exhibited the high degradation performance for model pollutant such as phenol with relatively high utilization efficiency of PS, while non-radical decomposition has limited contribution to phenol degradation with extremely low utilization efficiency of PS. This study deepened the understanding of interactions between PS and minerals during the PS-based ISCO in soil remediation.

General Method for Selective Three-Component Carboacylation of Alkenes via Visible-Light Dual Photoredox/Nickel Catalysis

A photoredox/nickel dual catalytic protocol for the regioselective three-component carboacylation of alkenes with tertiary and secondary alkyltrifluoroborates as well as acyl chlorides is described. This redox-neutral protocol can be applied to the rapid synthesis of ketones with high diversity and complexity via a radical relay process. Many functional groups, allowing for various commercially available acyl chlorides, alkyltrifluoroborates, and alkenes, are tolerated under these mild conditions.

Understanding the hydration of arylacetylenes to synthesize the carbonyl compounds via electroreduction of bromide intermediates

A deeper understanding of the electrochemical hydration of the alkynes may promote the development of such reactions. By using 4-tert-butylphenylacetylene as the model substrate, the mechanism of the electro-hydration of acetylenes is investigated through the designed experiments and theoretical calculations. It is suggested that the reaction may follow two possible radical processes simultaneously. The major is a cascade pathway including an oxidative halogenation followed by an electrochemical stepwise-dehalogenation, and the minor is the direct hydration of the substrate on the electrode surface. The inference is further confirmed by the corresponding thermodynamic calculations. This mechanistic study provides a theoretical basis for the future design and synthesis of various functionalized aryl ketones from the arylacetylenes by the electrochemistry strategy.

Copper-catalyzed cross-dehydrogenative coupling of P(O)−H compounds with O-/S-nucleophiles

The copper-catalyzed cross-dehydrogenative coupling of P(O)−H compounds with O-/S-nucleophiles to construct P−O bonds and P−S bonds for the synthesis of phosphinates and phosphinothioates was developed. A broad range of O- and S-nucleophiles are well tolerated in this transformation, affording the target products with good to excellent yields. This protocol is effective and convenient, which not only employed inexpensive copper iodide as the catalyst, but also avoided the use of hazadous and toxic reagents. Through the step-by-step control experiments and competitive experiments, we proposed a plausible reaction mechanism, and further confirmed that the reaction may follow a radical process.

Microenvironment modulation of cobalt single-atom catalysts for boosting both radical oxidation and electron-transfer process in Fenton-like system

Two coordination structures (Co-N4 or Co-N3) of cobalt single-atom catalysts (Co-SACs) were prepared by using the chitosan as starting precursor to evaluate the modulated coordination microenvironment of Co-SACs for organics degradation. The degradation performances for carbamazepine (CBZ) as well as the radical/nonradical pathways in Co-N4/PMS and Co-N3/PMS systems was evaluated. Results showed that more radicals could be produced by the Co-N3 catalyst via stronger PMS adsorption as well as the subsequent peroxide bond cleavage of PMS. In addition, a lower energy gap between the CBZ and Co-N3/PMS complex was endowed for the Co-N3 coordination to boost stronger electron-transfer process for CBZ. As a result, both radical and electron-transfer process was boosted by the coordinated Co-N3 sites than those of Co-N4 coordination. This work provides a new insight on the versatile catalytic pathways with modulated coordination microenvironment of carbon-based SACs for high-efficiency PMS activation.

"Our Cruel Polish Brothers": Moroccan Jews between Casablanca and Wadi Salib, 1956–59

Abstract: This article reconsiders three years in the lives of Jews in Morocco and their families who chose to immigrate to Israel. Relying on private correspondence between Moroccan Jews in Israel and in Morocco that was secretly intercepted by the Israeli intelligence apparatus, I argue that Moroccan Jews in Israel underwent a major process of radicalization between Moroccan independence in 1956 and the Moroccan uprising in Israel in 1959, known as the Wadi Salib revolt. In the Moroccan-Israeli case, Moroccan Jews introduced race into the Israeli discourse, and sought to leverage this discourse for a redistribution of resources, primarily among Jews. This radicalization initially developed against the backdrop of the Moroccan struggle for independence against French colonialism; however, other anticolonial and antiracist struggles of the 1950s were also influential. Thus, the prevailing assessment of the Wadi Salib revolt solely as "an Israeli event" diminishes the longer trajectories of Moroccan radicalization.