Radical Process Research Articles

‘Strengthening cooperation with external partners: Looking for a common response to the phenomenon of foreign terrorist fighters’

Addressing the challenge of foreign terrorist fighters (FTFs) and their affiliates who travelled to Syria and Iraq to join Da'esh and other terrorist groups has been a priority for the EU and the EU Counter-Terrorism Coordinator since 2013, both within the EU and internationally. This article sets out comprehensive EU cooperation with international partners on foreign terrorist fighters: It covers EU action related to the camps and prisons in North East Syria where FTFs and family members are held, accountability of FTFs and affiliates, cooperation on FTFs with the EU’s neighbourhood: Turkey, Western Balkans and Middle East and North Africa regions, multilateral engagement with the United Nations and other fora as well as addressing Islamist extremist ideology which is contributing to the radicalization process. From a practitioner's perspective, the article provides the EU policy framework and its evolution, as well as examples of capacity building and other initiatives.

The intensity of free radical processes and chaperone activity in the saliva of patients with type 2 diabetes.

Saliva is a clinically informative biological fluid that contains many biomarkers, allowing multiple analyses to be performed. The objectives of this study were the assessment of the serum and saliva levels of biochemical parameters and intensity of free radical processes in T2DM patients and the identification of the correlation between certain criteria. This case-control study included 40 T2DM patients, which were compared with 40 healthy individuals. The levels of glucose, cholesterol triglycerides, total protein, diene conjugates, and chaperone activity were measured using the spectrophotometric method. The concentration of 8-oxo-2'-deoxyguanosine was assessed by competitive enzyme-linked immunosorbent assay. It was established that the progression of diabetes led to an increase in glucose in saliva. The content of 8-oxo-2'-deoxyguanosine and conjugated dienes increased in serum and this increase was associated with the level of glucose and glycated hemoglobin. The level of protein and chaperone activity increased in the saliva of patients with T2DM compared with the control. The correlation analysis revealed a relationship between total protein concentration and conjugated dienes and between chaperone activity and conjugated dienes in saliva. According to the results of the analysis, the pathological changes in DM affected the salivary glands and their secretions. The obtained results allowed us to recommend using saliva as an alternative to blood for the diagnosis and monitoring of T2DM treatments since it is readily available and quickly responds to changes in metabolism in the body.

Metal‐Free Electrochemical Hydroboration of Olefins

AbstractHerein, we reported the electrochemical hydroboration of olefins to access the organoboron derivatives in a one‐pot reaction under air and at room temperature. This reaction manifold was applied to a broad range of alkenes with 40–90% yields and good functional group tolerance without using a metal catalyst or an additional hydride source. Mechanistic studies suggested that this anodic oxidation conducted in an undivided cell allowing the production of a boron radical species, which initiates the hydroboration of olefins event by a radical addition process.

Synthesis of acetic acid-modulated NH2-MIL-101(Fe) for advanced oxidation of rhodamine B from aqueous solution

A novel composite of acetic acid-modulated AC-NH2-MIL-101(Fe) was prepared by mild chemistry. The catalyst was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), Brunaure-Emmett-Teller (BET) and X-ray photoelectron spectroscopy (XPS). Acetic acid can control the crystal size, so that the catalyst had a large specific surface area (99.35 m2·g−1) and pore size (0.13 cm3·g−1), the adsorption amount of Rhodamine B (RhB) up to 446.965 mg·g−1, after the addition of peroxydisulfate (PDS), the catalytic degradation efficiency of RhB was as high as 99.7%. Electronic paramagnetic resonance spectrometer (EPR) and quenching experiments showed that the catalytic process may involve radical (·OH, SO4-· and O2·-) and non-radical (1O2) processes, in which the contribution of 1O2 to degradation reached 63.55% and played a major role.

Efficient degradation of phosphonate via trace Cu(II) mediated activation of peroxymonosulfate

The phosphonates in wastewater have attracted much attention due to their potential risks to the aquatic environment, which is oxidized to orthophosphate (PO43−) is a vital step to achieve their removal. Advanced oxidation processes based on free radicals is usually crucial methods to remove phosphonates, which could be easily disturbed by water matrix. Herein, using 1-hydroxyethane1,1-diphosphonic acid (HEDP) as a model pollutant, a nonradical system was constructed via Cu(II)/PMS process. 82 % HEDP is degraded by trace Cu(II) (5 μM) mediated peroxymonosulfate (PMS) activation process within 60 min at pH = 7.0, which is much higher than that in Cu(Ⅱ)/peroxydisulfate (PDS) and Cu(Ⅱ)/H2O2 systems under identical conditions. The results of multiple experiments reveal that Cu(III) induing intramolecular electron transfer as the dominant reactive species makes responsible for the oxidation of HEDP in the Cu(II)/PMS process, whereas the role of hydroxyl radicals (HO•) and 1O2 is negligible. In addition, the presence of HCO3−, benzoic acid (BA) and phenol shows a negative effect on the oxidation of HEDP in the Cu(II)/PMS process. However, in the actual wastewater, the removal efficiency of HEDP in the Cu(II)/PMS process is much higher than that in other free radical processes (i.e., UV/H2O2, UV/PDS). This study provides a new idea for the removal of phosphonates from actual wastewater.

Irrational rationales: vicarious and fictional justifications among ideological killers

ABSTRACT This article explores the motivations of ideological killers by investigating their justifications for violence. These justifications are divided into three categories: those that are grounded in actual social/political realities that are present in the lives of the perpetrators; those that utilise geographically and/or temporally distant vicarious victimisations; and those that are fictional, i.e., they have no basis in reality. These concepts are illustrated through discussions of a range of perpetrators of ideological violence. The implications of vicarious and fictional motivations are discussed in terms of our understanding of the psychology of perpetrators, the process of radicalisation, and counterterrorism efforts.

Translators' Perceptions on Open Source Translation Tools: Trados and OmegaT

In the last century, great technological development has changed the working principles and methods of institutions and professions worldwide and has started a radical innovation process. While it eliminated those who could not keep up with this innovation, it raised those who did to be the best in their fields. One of the professions affected by this change is undoubtedly translation. Translation technology systems are widely used by translators all over the world today and have a large market. Translators' use of translation technologies more effectively and accurately ensures that their translations are carried out more accurately and in a faster time, and it has become the indispensable equipment of a good translator in the historical process. This has given vital meaning to translation technologies such as translation memories and machine translations. The benefits of translation technologies to the translator are many. Although many studies have been conducted on the problems experienced by translators and the limitations and advantages of translation technologies in general, there are very few studies on the problems experienced by translators individually about the use of translation technologies, the problems they experience and their attitudes. The aim of this article is to identify the various problems that translators experience while using computer-assisted translation tools, to reveal the reasons for using the programs they frequently use, and to get the comments of the translators who use alternative options. By employing a document analysis approach to collect data, the article presents a descriptive analysis of opinions. This analysis is between the paid Trados program, which is known to all translators, and the free alternative program OmegaT. The user comments of the Proz forum, which is known worldwide by translators, are used in the analysis. An analysis is presented by listing the positive and negative opinions about both computer-aided translation tools. The article presents some suggestions regarding translation education based on the findings.

Regiodivergent C-H Acylation of Arenes by Switching from Ionic to Radical Type Chemistry Using NHC-Catalysis.

The Friedel-Crafts acylation which belongs to the class of electrophilic aromatic substitutions is a highly valuable and versatile reaction in synthesis. Regioselectivity is well predictable and determined by electronic as well as steric factors of the (hetero)arene substrate. In this communication, a radical approach for the acylation of arenes and heteroarenes is presented. C-H Acylation is achieved through mild cooperative photoredox/NHC radical catalysis with the cross coupling of an arene radical cation with an NHC-bound ketyl radical as a key step. As compared to the classical Friedel-Crafts acylation, a regiodivergent outcome is observed upon switching from the ionic to the radical mode. In these divergent reactions, aroyl fluorides act as the acylation reagents in both the ionic as well as the radical process.

Regiodivergente C−H‐Acylierung von Aromaten durch Wechsel von ionischer zu radikalischer Chemie unter Verwendung von NHC‐Katalyse

AbstractDie Friedel–Crafts‐Acylierung, die zur Klasse der elektrophilen aromatischen Substitutionen gehört, ist eine äußerst wertvolle und vielseitige Reaktion in der Synthese. Die Regioselektivität ist gut vorhersagbar und wird sowohl durch elektronische als auch durch sterische Faktoren des verwendeten (Hetero)Aromaten bestimmt. In dieser Mitteilung wird ein radikalischer Ansatz für die Acylierung von Aromaten und Heteroaromaten vorgestellt. Die C−H‐Acylierung erfolgt durch milde kooperative Photoredox/NHC‐Radikal‐Katalyse mit der Kreuzkupplung eines Arenradikalkations mit einem NHC‐gebundenen Ketylradikal als Schlüsselschritt. Im Vergleich zur klassischen Friedel–Crafts‐Acylierung wird beim Wechsel vom ionischen zum radikalischen Modus ein regiodivergentes Ergebnis beobachtet. Bei diesen divergenten Reaktionen fungieren Aroylfluoride als Acylierungsreagenzien sowohl im ionischen als auch im radikalischen Prozess.

Tris(aminomethyl)phosphines and Their Copper(I) (Pseudo)halide Complexes with Aromatic Diimines-A Critical Retrospection.

Metal complexes feature a wide range of available geometries, diversified lability, controllable hydrolytic stability, and easily available rich redox activity. These characteristics, combined with the specific properties of coordinated organic molecules, result in many different mechanisms of biological action, making each of the myriads of the classes of metal coordination compounds unique. This focused review presents combined and systematized results of the studies of a group of copper(I) (pseudo)halide complexes with aromatic diimines and tris(aminomethyl)phosphines of a general formula [CuX(NN)PR3], where X = I- or NCS-, NN = 2,2'-bipyridyl, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline or 2,2'-biquinoline, and PR3 = air-stable tris(aminomethyl)phosphines. The structural and electronic properties of the phosphine ligands and luminescent complexes are discussed. The complexes with 2,9-dimethyl-1,10-phenanthroline, apart from being air- and water-stable, exhibit a very high in vitro antimicrobial activity against the Staphylococcus aureus and Candida albicans. Moreover, some of these complexes also show a strong in vitro antitumor activity against human ovarian carcinoma cell lines: MDAH 2774 and SCOV 3, CT26 (mouse colon carcinoma), and A549 (human lung adenocarcinoma) cell lines. The tested complexes are moderately able to induce DNA lesions through free radical processes, however the trends do not reflect observed differences in biological activity.

Influences of Islamist Radicalization: A Configurational Analysis of Balkan Foreign Fighters in Syria

Recent research on Islamist radicalization has directed greater attention to the conjunctions of causes and staged processes that draw individuals into violent extremism. Yet research is still grappling with the varying extents of individual action and external factors, including social networks, peer pressure, propaganda, cultural and socio-economic conditions, on radicalization processes. At bottom, this investigation revolves around the context in which individuals live and the influences acting upon them. Identifying patterns of these conditions is essential to understanding how individuals come to engage in violent extremism. This article presents a configurational analysis of foreign fighters that travelled to fight in the Syrian War. The paper presents data gathered from interviews, security and judicial records, and secondary sources on individuals from the Western Balkans (predominantly Bosnia and Herzegovina) that joined Islamist groups in the Syrian War. Individuals’ relationship with longstanding Balkan radical milieus and with key Islamist preachers were coded. Using qualitative comparative analysis (QCA) techniques, we present a systematic description of characteristics of foreign fighters.

Cobalt-Catalyzed Hypervalent Iodine(III) Promoted Cascade Annulation Reaction of Anilines with Formamides for 2-Aminobenzoxazoles Synthesis.

Herein, we disclose a practical and simple procedure to synthesize 2-aminobenzoxaoles. Simple anilines and formamides were used as substrates. The C-H bond ortho to the amino group in the anilines was directly functionalized under cobalt-catalyzed conditions with high levels of functional group tolerance. Hypervalent iodine(III) was both an oxidant and a Lewis acid for this reaction. The mechanism study showed that this transformation may involve a radical process.

Radical Hydrocarboxylation of Unactivated Alkenes via Photocatalytic Formate Activation.

Herein we disclose a strategy to promote the hydrocarboxylation of unactivated alkenes using photochemical activation of formate salts. We illustrate that an alternative initiation mechanism circumvents the limitations of prior approaches and enables hydrocarboxylation of this challenging substrate class. Specifically, we found that accessing the requisite thiyl radical initiator without an exogenous chromophore eliminates major byproducts that have plagued attempts to exploit similar reactivity for unactivated alkene substrates. This redox-neutral method is technically simple to execute and effective across a broad range of alkene substrates. Feedstock alkenes, such as ethylene, are hydrocarboxylated at ambient temperature and pressure. A series of radical cyclization experiments indicate how the reactivity described in this report can be diverted by more complex radical processes.

Electrophotocatalytic Reductive 1,2‐Diarylationof Alkenes with Aryl Halides and Cyanoaromatics

Comprehensive SummaryThe radical‐mediated reductive functionalization of aryl halides has been extensively studied. However, the related radical‐mediated intermolecular reductive 1,2‐diarylation of alkenes, using aryl halides as aryl radical sources, remains unexplored. Herein, a new electrophotocatalytic intermolecular reductive 1,2‐diarylation of alkenes is reported using aryl halides and cyanoaromatics to produce polyarylated alkanes. Using synergistic cathodic reduction and visible‐light photoredox catalysis, various electron‐rich and electron‐deficient aryl halides are combined with various alkenes and cyanoaromatics to characterize the broad substrate scope, excellent functional group compatibility, and excellent selectivity of this reaction. Mechanistic investigations reveal that this reaction may proceed via a radical process initiated by the reductive generation of aryl radicals from aryl halides and terminated by radical‐radical coupling with cyanoaromatic radical anions.

Effect of the complex of natural terpenes and vitamin E Renotineх® on free radical processes in patients with urolithiasis

BACKGROUND: One of the leading links in the pathogenesis of urolithiasis is oxidative stress, which occurs as a result of the intensification of free radical oxidation with insufficient activity of the antioxidant defense system of the body.
 AIM: The aim of the study was to study the effect of a complex of natural terpenes and vitamin E Renotineх on the state of oxidative stress in patients with urolithiasis in the postoperative period after percutaneous nephrolithotripsy.
 MATERIALS AND METHODS: The study included 42 patients. Of the 35 people who underwent percutaneous nephrolithotripsy, 2 groups were formed. Patients of the main group (n = 20), in contrast to the control group (n = 15), received Renotinex (Polaris LLC, Russia) before and after surgery, 2 capsules (1 capsule 300 mg) twice a day. To determine the main indicators of the activity of free-radical processes in the body, all patients underwent a blood test on the 3rd day after surgery. The total activity of the pro- and antioxidant systems in blood plasma was determined by the method of induced chemiluminescence. The activity of lipid peroxidation was assessed by determining the concentration of active products of thiobarbituric acid secondary products of lipid peroxidation in blood erythrocytes. The activity of antioxidant enzymes was studied by spectrophotometric method. To determine the ability of blood plasma to crystallize in some of the same patients with urolithiasis while taking Renotinex, the method of wedge dehydration was used. For a comparative analysis of the crystal structure of dried blood plasma samples (facies), 7 healthy volunteers were included in the study, which made up the third group (comparison group).
 RESULTS: The results of the study reliably demonstrate that the composition of the complex of natural terpenes and vitamin E Renotinex has a positive effect on free-radical processes in patients with urolithiasis, biochemical parameters of blood plasma (indicators of induced chemiluminescence, catalase activity, malondialdehyde level), as well as on crystallization processes blood plasma, which is confirmed by the method of wedge dehydration of blood plasma. Any change in the body caused by excessive activity of free-radical oxidation processes is reflected in the composition of the blood, and specifically in the indicators of the mechanical characteristics of blood plasma (viscosity, structure, surface tension), which determine the shape of the resulting structures of the drying drop of biological fluid.
 CONCLUSIONS: The complex of natural terpenes and vitamin E Renotinex has a positive effect on free-radical processes, biochemical parameters of blood plasma, as well as on the systemic structural organization of blood plasma in patients operated on for urolithiasis. The inclusion of the combined product Renotinex in the treatment regimen for patients with urolithiasis is pathogenetically justified.

Visible-light-induced coupling of carboxylic acids with alcohols/amines via a phosphorous linchpin strategy

The combination of activated carboxylic acids and alcohols/amines to access esters and amides, respectively, is a cornerstone of organic chemistry and has been well developed over the past century. These dehydrations are extensively used in medicinal chemistry and natural product synthesis due to the prevalence of these functional groups in bioactive molecules. Here, we report a divergent process from the expected ester/amide outcomes through a light-induced coupling of activated carboxylic acids and alcohols/amines to efficiently prepare α-hydroxy/amino ketones or β-ketophosphonates via single-electron chemistry. A phosphorus linchpin strategy allows for the combination of these simple reagents through an intramolecular triplet state radical process, thereby enabling new carbon-carbon bond formation.

Thermodynamics, kinetics and structure-activity relationship of hydroxyanthraquinones scavenging free radicals

Hydroxyanthraquinones (HAQs) have a significant antioxidant activity. In this study, the thermodynamic parameters, frontier molecular orbitals, and dynamic process of HAQs scavenging free radicals were systematically evaluated by density functional theory, and the results were verified by in vitro experiments. The results indicated that, in gas and benzene systems, the hydrogen atom transfer (HAT) was the main mechanism in the antioxidant process of HAQs because the bond dissociation enthalpies were much lower than the ionization potentials (IPs) and proton affinities. The polarity of the solvent (ethanol and water) led to a significant decrease of IPs, and the single electron transfer followed by proton transfer mechanism was the main mechanism. Furthermore, polar solvents were more conducive to the antioxidant activity of HAQs than non-polar solvents. Moreover, the antioxidant activity of HAQs increased with the increase of the number of hydroxyl groups. However, in the non-polar system, α-OH of HAQs was more likely to form hydrogen bonds with neighboring carbonyl O atoms, reducing its contribution to the antioxidation. In the polar system, α-OH can enhance the electron-donating ability to increase the antioxidant capacity.

Italian far-right foreign fighters in the Ukrainian war. The long chain of Transnational Recruitment Network (TRN)

ABSTRACT This study investigates the phenomenon of far-right foreign fighters engaged on the Ukrainian war alongside pro-Russian separatists. Before the Russian invasion of Ukraine in February 2022, the phenomenon, albeit limited, also affected Italy. This article aims to map the ties and to analyze the interactions between the various actors involved in the distribution of the call to arms, from recruitment to the reception of foreign fighters in the host country. The article is divided in two parts. First, the aspects relating to the conceptualization of the phenomenon and the motivations underlying the choices to become a foreign fighter will be analyzed. Radicalization processes and their interpretations will also be explored. The second part presents the empirical analysis of Italian far-right foreign fighters operating in the Donbass area. This research uncovered a complex Transnational Recruitment Network (TRN) enabling Italian far-right activists to reach the Ukrainian theater of war. The study findings show that the links between the network nodes of far-right organizations are relevant factors for the activation and radicalization of foreign fighters.

How street‐level dilemmas and politics shape divergence: The accountability regimes framework

AbstractHierarchical accountability often proves insufficient to control street‐level implementation, where complex, informal accountability relations prevail and tasks must be prioritized. However, scholars lack a theoretical model of how accountability relations affect implementation behaviors that are inconsistent with policy. By extending the Accountability Regimes Framework (ARF), this paper explains how multiple competing subjective street‐level accountabilities translate into policy divergence. The anti‐terrorism “Prevent Duty” policy in the United Kingdom requires university lecturers to report any student they suspect may be undergoing a process of radicalization. We ask: what perceived street‐level accountabilities and dilemmas does this politically contested policy imply for lecturers, and how do they affect divergence? An online survey of British lecturers (N = 809), combined with 35 qualitative follow‐up interviews, reveals that accountability dilemmas trigger policy divergence. The ARF models how street‐level bureaucrats become informal policymakers in the political system when rules clash with their roles as professionals, citizen‐agents, or “political animals.”

Late-Stage C-H Functionalization of Azines.

Azines, such as pyridines, quinolines, pyrimidines, and pyridazines, are widespread components of pharmaceuticals. Their occurrence derives from a suite of physiochemical properties that match key criteria in drug design and is tunable by varying their substituents. Developments in synthetic chemistry, therefore, directly impact these efforts, and methods that can install various groups from azine C-H bonds are particularly valuable. Furthermore, there is a growing interest in late-stage functionalization (LSF) reactions that focus on advanced candidate compounds that are often complex structures with multiple heterocycles, functional groups, and reactive sites. Because of factors such as their electron-deficient nature and the effects of the Lewis basic N atom, azine C-H functionalization reactions are often distinct from their arene counterparts, and the application of these reactions in LSF contexts is difficult. However, there have been many significant advances in azine LSF reactions, and this review will describe this progress, much of which has occurred over the past decade. It is possible to categorize these reactions as radical addition processes, metal-catalyzed C-H activation reactions, and transformations occurring via dearomatized intermediates. Substantial variation in reaction design within each category indicates both the rich reactivity of these heterocycles and the creativity of the approaches involved.