Observations have demonstrated the ubiquity of short-lived halogens (SLHs)-defined as organic and inorganic chlorine, bromine and iodine compounds with an overall atmospheric lifetime of less than 6 months-in the global atmosphere. They are primarily emitted naturally from the ocean, cryosphere, volcanoes, salt lakes and the biosphere. However, unregulated anthropogenic sources are increasingly contributing to their atmospheric loading. Some of their natural emissions have increased over time due to anthropogenic pollution, for example, the increased oceanic emissions of iodine compounds due to the deposition of ozone on the sea surface. SLHs affect chemical processes, such as ozone and methane chemistry, and therefore influence air quality and climate. Nevertheless, some of their sources and chemistry are not included in air-quality and climate models used in international assessment reports. Here we describe in detail the various impacts of SLHs on air quality and climate, and make a case for the inclusion of more comprehensive SLH chemistry in future atmospheric, air-quality and climate assessments. In doing so, we also identify gaps in our knowledge of SLH emissions, chemistry, and environmental and climate impacts.

Two commercially utilized kelp species, winged kelp (Alaria esculenta) and sugar kelp (Saccharina latissima), can accumulate high amounts of iodine and thereby pose a health concern if consumed in excess. Water blanching is used industrially to reduce the iodine content. This study aimed to optimize the blanching conditions to reduce the energy consumption and environmental impact by investigating the parameters of temperature, duration, use of sea or fresh water, biomass-to-water ratio, and recycling of water. The study investigated the impact of the blanching conditions on composition of the biomass, including nutrient content and potential toxic elements. The iodine content was reduced to 5% of the initial content for S. latissima and to 8% for A. esculenta at the optimal conditions in the present study, which was blanching in seawater at 80 °C for 2 min. Using tap water at the same conditions resulted in a reduction to 7 and 11% of the initial content. The content of arsenic in blanched winged kelp was reduced to levels below the maximum allowed content in feed, whereas the content in blanched sugar kelp remained above this level. This study provides a comprehensive set of data on blanching of the two kelp species, with high relevance for the industrial scale-up of kelp processing.

X-ray photolysis of a hypervalent iodine compound, 4-carboxy-2-iodosobenzoic acid, via iodine K-shell excitations and ionizations

Multivalent iodine compounds, known as iodanes, have gained significant attention in organic chemistry due to their ability to perform selective oxidations and facilitate various group transfer reactions. Despite their fascinating reactivity, their application remains largely restricted to laboratory-scale use. This limitation stems from their high cost and, in some cases, safety concerns. The elevated price of iodanes can be partly attributed to the considerable cost of iodine itself and, subsequently, iodoarenes, which are commonly used as precursors for synthesizing basic iodanes. Basic iodanes, such as 2-iodosylbenzoic acid and 2-iodylbenzoic acid, can be chemically modified to achieve enhanced or more specific reactivity. However, even these basic iodanes are typically at least ten times more expensive than the starting iodoarenes. This cost disparity arises from the challenges posed by chemical synthesis, which often involves hazardous and unpleasant oxidants, as well as potentially dangerous and expensive processes. In this context, electrochemical synthesis of iodanes offers a safer and more cost-effective alternative by eliminating the need for chemical oxidants and high-temperature conditions.In recent years, our group has focused on developing sustainable and practically applicable electrochemical methods for synthesizing selected iodanes, specifically 2-iodosylbenzoic acid and 2-iodylbenzoic acid. This effort has involved the use of inexpensive, environmentally friendly chemicals and solvents, coupled with straightforward and efficient product separation processes. Initially, basic voltammetry and batch experiments were conducted to investigate the electrochemical oxidation of iodobenzenes in solvents such as water and acetic acid. The insights gained from these studies were subsequently applied to optimize the electrosynthesis of iodanes in a flow reactor and to design simple methods for product separation. To evaluate the feasibility of these procedures, they were also analyzed through a basic techno-economic assessment. In order to address safety concerns, stability of the 2-iodylbenzoic acid samples of different purity was investigated as well.During the presentation, both the successes achieved and the challenges encountered throughout the development processes will be highlighted, providing a comprehensive summary of our findings and advancements in this area. Acknowledgement The work was supported by Technology Agency of the Czech Republic within the project No: FW06010097.

The study aimed to explore novel aromatic ether coumarins as potential anti-allergic lead compounds. The benzene ring of hypervalent iodine compounds was strategically introduced into the coumarin framework to facilitate the efficient synthesis of aromatic ether coumarin derivatives via the one-pot method. Two representative compounds, namely, 4-phenylether coumarin and 7-phenylether coumarin, were successfully designed and synthesized. The compounds were structurally characterized using spectroscopic techniques, including nuclear magnetic resonance (NMR), mass spectrometry (MS), and infrared (IR) spectroscopy. Their inhibitory effects on both IgE- and non-IgE-mediated degranulation of rat basophilic leukemia (RBL-2H3) cells and mouse bone marrow derived mast cells (BMMCs) were subsequently evaluated. Three representative 7-phenylether coumarins (4, 5, and 6) and 4-phenylether coumarin (7) were synthesized with high efficiency. The compounds exhibited potent anti-allergic effects, indicated by the marked inhibition of degranulation and β-HEX release from RBL-2H3 cells and BMMCs. The inhibitory effects of 7-phenylether 3-methyl ketocoumarin (6) were found to be superior to those of the tested compounds. Aromatic ether coumarins can be efficiently constructed via the oxidation of hydroxycoumarins with hypervalent iodine compounds. Compound 6 inhibited both IgE-induced and calcium ionophore (A23187)-mediated degranulation of BMMCs, warranting further in-depth investigation into its pharmacogenetic and therapeutic potential.

Abstract We conducted intensive atmospheric observations and surface seawater sampling in the western tropical Pacific aboard R/V Mirai during the MR21-03 cruise from May to July 2021 to investigate iodine variations and photochemistry over the global sea surface temperature (SST) maxima (warm pool). Consistent with previous studies, high near-surface atmospheric iodine monoxide (IO) mixing ratios of up to ~ 1 pptv were observed. A strong positive correlation ( r = 0.95) was found between the IO mixing ratios and inorganic iodine flux calculated from atmospheric ozone (O 3 ) and sea surface I – data, indicating that the assumed emission flux and the associated processes are qualitatively reasonable for the studied warm pool region. This study provided the first simultaneous observations of atmospheric O 3 , IO, and sea surface I – over the warm pool, thus demonstrating the robust nature of the relationship. The CHASER chemical transport model satisfactorily reproduced the observed positive correlation. The model overestimated the IO levels by 40%, but large systematic uncertainties were associated; refining the assumed emission flux and parameters used in the model is recommended for more quantitative comparisons. The collective findings underscore the significance of concurrent observations of atmospheric O 3 , IO, and sea surface iodide for elucidating ocean–atmosphere processes involving reactive iodine compounds.

Introduction. Protective gloves are widely used in medicine to provide biological protection for patients and medical staff. However, if gloves are used improperly, there is a risk of healthcare-associated infections (HAIs) for both staff and patients. A significant problem is the resulting growth in medical waste and its disposal. Therefore, developing new approaches to ensure maximum protection for staff and patients, and minimize the risk of infection, by creating protective gloves based on biodegradable polymer materials with an antimicrobial coating, is an urgent epidemiological and environmental objective. This paper discusses modern technologies and emerging issues in the creation of new materials for protective gloves with antimicrobial properties. These materials can be made using guanidine derivatives, quaternary ammonium compounds (QACs), chlorinated phenols, essential oils, iodine compounds, silver salts, metal oxides and metal nanoparticles and oxides, vegetable oil extracts, aniline dyes. The introduction of biofillers such as starch and nanocellulose will help improve biodegradability. They will also help maintain the necessary physical and chemical characteristics. The problem of synthetic rubber waste disposal can be solved by the development of new composite materials with improved biodegradation characteristics. These materials are in the form of thermoplastic elastomers (TPE), polylactide (PLA) and polylactone (PLC). Conclusion. A review of the scientific literature revealed a significant global interest in the creation of protective gloves with antimicrobial properties made from biodegradable materials. However, in addition to directly suppressing the growth of pathogenic microflora, their use may also pose a number of problems related to their impact on human health and the ecosystem. The successful implementation of this direction hinges on the continuation of scientific research on imparting the declared properties to gloves. This research should use effective, reliable and safe technologies, as well as the development of unified methods and protocols for assessing antimicrobial activity. Once these are in place, the research can be implemented widely in practice. The production of biodegradable protective gloves offers significant potential, as it will help to reduce the risk of infection spreading in healthcare organizations and contribute to environmental protection.

The α,α‐difluoromethylene amine (NCF2R) motif represents a useful functionality in medicinal chemistry, yet practical and modular methods to access this class of compounds are lacking. Here, we report a safe and scalable flow‐based strategy for the on‐demand generation of NCF2R anions using a packed‐bed microreactor containing caesium fluoride. This protocol enables the late‐stage installation of the CF2 group under mild conditions, avoiding the use of hazardous fluorinating agents and minimizing fluorinated waste. This fully modular strategy features three points of diversification (carboxylic acid, sulfonamide, and electrophile), allowing efficient access to a broad range of α,α‐difluoromethylene amines. The method tolerates a variety of functional groups, supports late‐stage functionalization of pharmaceutically relevant scaffolds, and is compatible with downstream cross‐coupling reactions, demonstrating the robustness of the reaction protocol. This work provides a versatile platform for the streamlined incorporation of NCF2 motifs, expanding the range of synthetic strategies available in medicinal and fluorine chemistry.

Abstract The α,α‐difluoromethylene amine (NCF 2 R) motif represents a useful functionality in medicinal chemistry, yet practical and modular methods to access this class of compounds are lacking. Here, we report a safe and scalable flow‐based strategy for the on‐demand generation of NCF 2 R anions using a packed‐bed microreactor containing caesium fluoride. This protocol enables the late‐stage installation of the CF 2 group under mild conditions, avoiding the use of hazardous fluorinating agents and minimizing fluorinated waste. This fully modular strategy features three points of diversification (carboxylic acid, sulfonamide, and electrophile), allowing efficient access to a broad range of α,α‐difluoromethylene amines. The method tolerates a variety of functional groups, supports late‐stage functionalization of pharmaceutically relevant scaffolds, and is compatible with downstream cross‐coupling reactions, demonstrating the robustness of the reaction protocol. This work provides a versatile platform for the streamlined incorporation of NCF 2 motifs, expanding the range of synthetic strategies available in medicinal and fluorine chemistry.

Although antiseptics are commonly used in wound treatment as antimicrobial agents, their effect on human cells remains debatable. Despite their well-documented bactericidal efficacy, many antiseptics can cause adverse reactions including cytotoxicity towards fibroblasts and keratinocytes, which can negatively affect the wound healing process. The purpose of this paper is to evaluate the available data on the cytotoxicity of selected antiseptics used in wound treatment. Based on the data available in medical literature, it has been demonstrated that octenidine has a relatively high Biocompatibility Index (BI), which makes it safer to use, especially in chronic wounds. In contrast, preparations containing chlorhexidine, iodine, hydrogen peroxide, triclosan, or silver compounds may exhibit pronounced cytotoxicity, which may limit their use.

Multi-heteroatom-substituted sulfur centers are increasingly significant in drug discovery, yet their modular synthesis remains challenging. Current strategies employing sulfinylamines, sulfurdiimides, or SOF4 suffer from inherent limitations. To address this, a general and practical strategy for constructing diverse sulfur centers bearing multiple oxygen or nitrogen substituents is urgently needed. Herein, we report a modular synthesis of such motifs using commercially available DAST-type reagents as underexplored sulfur precursors. This methodology expands the utility of classical fluorination agents as sulfur sources, operates under ambient and mild conditions, and enables rapid access to diverse S(IV) and S(VI) architectures through sequential substitution and further flexible transformations. The practicality of this approach is highlighted by late-stage functionalization of bioactive molecules and gram-scale synthesis. Mechanistic studies support the proposed highly reactive S(IV)-F intermediate.

Abstract Multi‐heteroatom‐substituted sulfur centers are increasingly significant in drug discovery, yet their modular synthesis remains challenging. Current strategies employing sulfinylamines, sulfurdiimides, or SOF 4 suffer from inherent limitations. To address this, a general and practical strategy for constructing diverse sulfur centers bearing multiple oxygen or nitrogen substituents is urgently needed. Herein, we report a modular synthesis of such motifs using commercially available DAST‐type reagents as underexplored sulfur precursors. This methodology expands the utility of classical fluorination agents as sulfur sources, operates under ambient and mild conditions, and enables rapid access to diverse S(IV) and S(VI) architectures through sequential substitution and further flexible transformations. The practicality of this approach is highlighted by late‐stage functionalization of bioactive molecules and gram‐scale synthesis. Mechanistic studies support the proposed highly reactive S(IV)‐F intermediate.

Hypervalent iodine(iii) compounds containing transferable nitrogen functional groups, amino-λ3-iodanes, were synthesized via a straightforward protocol utilizing simple amines and a benziodoxolone framework. This strategy enabled the use of a wide variety of amines, including ammonia, aliphatic and aromatic primary amines, significantly expanding the scope of accessible compounds compared to existing methods. The synthesized aminobenziodoxolones were applied to the oxidative amination of arylboronic acids, offering a practical transition-metal-free protocol for the synthesis of arylamines. To further demonstrate the synthetic utility, a one-pot process using in situ prepared aminobenziodoxolones was developed, allowing efficient coupling of boronic acids with various simple and pharmaceutically relevant amines. Furthermore, the method was extended to the synthesis of 15N-labelled arylamines, highlighting the versatility and practical value of this approach.

ConspectusAlkynes are one of the most fundamental functional groups in organic synthesis due to the versatile chemistry of the triple bond, their unique rigid structure, and their use in bioconjugation. The introduction of alkynes onto organic molecules traditionally relies on nucleophilic activation, often requiring strong bases or metal catalysts. These conditions, however, restrict applications involving biomolecules such as peptides and proteins due to functional group incompatibility. To address this limitation, our group developed an "umpolung" approach, utilizing hypervalent iodine compounds to create electrophilic alkyne transfer reagents such as benziodoxol(on)es (Bx(X)s) and benziodazolones (BZs). The high reactivity of EBx/X/Z reagents enables efficient alkyne transfer to various nucleophilic residues in peptides and proteins under different reaction conditions, providing a versatile tool for biomolecule modification.In this Account, we highlight the residue-selective alkynylation and alkenylation of peptides enabled by the development of novel EBx/X/Z reagents with a focus on progress since 2021. This includes the following: (1) Selective residue modification: We have made significant progress in the residue-selective alkynylation and alkenylation of peptides and proteins. Building on our initial work with Cys-selective alkynylation, we enhanced reactivity and solubility by introducing a sulfonate group on the benziodoxolone arene core, facilitating lipophilic alkynylation in an aqueous environment. Furthermore, we developed perfluoroaryl-modified BZ reagents to achieve sequential Cys-Cys cross-linking and used them for antibody cross-linking with superior reactivity compared to that of conventional methods. Additionally, we expanded the reactivity beyond Cys to achieve Tyr-selective conjugation. All of these achievements underscored the tunability of EBx/X/Z reagents through strategic substituent modification on the iodine core. (2) Peptide stapling and macrocyclization: We designed EBx(X) reagents featuring an additional reactive site on the alkyne moiety, enabling Cys-Cys and Cys-Lys stapling in peptides. This approach enhanced their α-helicity and potential as PPI inhibitors with improved binding affinity to the MDM2 protein. For sequences lacking Cys, we incorporated the whole EBx(X) core onto Lys residues via an activated ester on the alkyne, forming peptide-EBx(X) conjugates. These conjugates facilitated the formation of rigid, functional peptide macrocycles using C-terminal or Trp-selective alkynylation. The utility of these macrocyclizations was demonstrated by achieving improved binding affinity to the KEAP1 protein and by generating fluorescent cyclic peptides suitable for live-cell imaging without additional fluorophores. (3) Broadening applicability with EBx-containing amino acids: We prepared EBx amino acids compatible with both solid-phase peptide synthesis (SPPS) and solution-phase synthesis (SPS), allowing us to apply our cyclization strategies to construct a diverse library of cyclic peptides.

Agronomic biofortification, particularly with iodine, enriches crops with essential nutrients, addressing nutritional deficiencies. This enhances plant resilience, increasing disease resistance and yield. Consuming iodine-biofortified foods helps prevent diseases such as thyroid disorders and developmental issues. In this study, we evaluated freshly harvested and postharvest fruit quality to determine the effect of biofortification with chitosan, iodine salts (KI and KIO3) and chitosan-iodine complexes (CS KI and CS KIO3) at concentrations of 5 and 25 mg (iodine ion) on Syngenta ‘Sweet Sunrise’ hybrid melon (Cucumis melo L.) cultivars. Physicochemical parameters, such as weight, equatorial diameter and flesh firmness, were assessed in freshly harvested fruit. During postharvest storage at 25 °C for 5, 10 and 15 days, weight loss, flesh firmness, peel and flesh color (L, a*, b*, chroma, °hue), pH, total soluble solids (°Brix), titratable acidity and TSS/TA ratio were measured. Chitosan and iodine salts did not significantly affect weight loss or equatorial diameter. However, KIO3 had a notable effect on melon properties, enhancing peel and flesh coloration, increasing pH and improving total soluble solids. These findings suggest that chitosan and iodine salts act as natural preservatives, maintaining postharvest quality and enhancing the sweetness and flavor of fruits, making them promising alternatives for extending shelf life and improving melon quality. Among the treatments, CS + KIO₃ at 25 mg was the most effective in preserving postharvest quality and is recommended as the optimal strategy for biofortification in melon.

Iodinated disinfection byproducts (I-DBPs) are increasingly detected in drinking water due to the widespread use of chlorination and the presence of iodide (I-) in source waters. However, understanding the transformation of iodine species during disinfection remains challenging, particularly under varying ammonia concentrations. In this study, a method based on spectrophotometry and HPLC was applied to quantify I-, hypoiodous acid (HOI), and iodate (IO3-) in various water matrices. With this method, the transformation of iodide during breakpoint chlorination was elucidated for the first time. Results revealed that ammonia inhibited IO3- formation by scavenging free chlorine and promoted the accumulation of HOI, a key intermediate in I-DBPs formation. A comprehensive kinetic model was established, which accurately reproduced the experimental trends and helped elucidate the transformation mechanisms of iodine species. Additionally, the fate of organic iodine compounds, including 4-iodobenzoic acid and diatrizoate (DTZ, a widely used iodinated contrast medium), was examined during breakpoint chlorination. Although typically considered resistant to chlorination, both compounds underwent partial degradation under Cl2/N = 2 conditions, leading to iodide release and enhanced I-DBPs formation. This highlights the risk of converting stable iodine-containing organics into reactive species under high chlorine doses in ammonia-containing water. These findings highlight the importance of precisely controlling ammonia and disinfectant concentrations to reduce water toxicity and ensure safer water disinfection practices.

Abstract The incorporation of fluorine into organic molecules holds significant value. The three-component reaction provides a more convenient approach for the synthesis of organofluorine compounds. Radical monofluorination will be fully discussed in this review. Besides, other methods like transition metal-catalyzed, electrophilic, nucleophilic, and carbine-mediated conditions will also be discussed. There are two main methods for producing monofluorinated compounds: forming C–F bonds using fluorinating agents or creating C–C bonds with fluorinated substrates. The latter method boasts a wider range of applicable substrates. We will discuss reactions involving various substrates, including NFSI, KHF2, Selectfluor, FABI, Et3N·3HF, COF2, ICH2F, DAST, and others. We will review the advancements made over the past decade (2014–2024) and offer explanations of the underlying mechanisms. Additionally, how the additive reagents work will also be discussed.

Carboxymethyl-starch:iodine complexes as virucidal agents: salivary amylase triggers on-site iodine release, preventing human coronavirus OC43 replication.

The influence of antimicrobial agents on aquatic fauna has been described in many studies, but few have tested the effects on invertebrate embryos and the associated epibiotic community. The role of epibiotic microorganisms in embryonic development needs to be better understood due to their ecological role and use for aquaculture purposes. Therefore, enabling the removal of the microbiota without affecting embryonic development is the first step to understanding the effects of microbiota on organism development. We tested the impact of two antimicrobial agents, Terramycine (oxytetracycline compound) and Biofor (iodine compound), during the embryonic development of the crab Leptuca thayeri to verify their effectiveness in reducing the microbial load and the impact on embryonic development. The mortality rate, time and rate of embryo hatching, and microbial growth in Petri dishes were evaluated over 30 days of embryonic development under laboratory conditions. Biofor reduced the hatching rate and increased mortality, whereas Terramycin did not differ from the control for both variables. The time in days to hatching was not influenced by contact with Terramycin. Both antimicrobial agents efficiently reduced the microbial load, with greater effectiveness over time for Biofor. The concentrations and exposure time tested for Terramycin were promising in reducing the microbial load without harming the embryos, facilitating future studies. In addition to ecological importance, our results apply to sterilizing live embryos.

Phenolic compounds (PCs) are those chemical compounds that involve one or more hydroxyl groups (-OH) bound directly to an aromatic ring. These compounds are widely studied and can be divided into several classes including flavonoids, phenolic acids, tannins, and cannabinoids to name a few. While some PCs are naturally occurring and have some health benefits, some other classes of PCs are widely used in various industrial processes and are quite toxic if released into environmental waterways. In all cases, there is an interest in quick and efficient quantification of PCs. While electrochemical oxidation of PCs into quinones has several attractive qualities, the oxidation pathway for these compounds often results in electrode fouling. For example, the oxidation of some PCs results in the formation of dimers or large polymeric structures that precipitate onto the electrode surface. This prohibits this method from being used for continuous monitoring.While the electrochemical oxidation of PCs often fouls electrode surfaces, the electrochemical reduction of quinones does not. Therefore, a possible alternative method for detecting PCs involves modifying the electrode surface with a species that first chemically oxidizes the analyte to a quinone, and then detecting it based on the electrochemical reduction of the oxidized product. This detection scheme has often been employed using polyphenol oxidases such as tyrosinase or laccase. However, polyphenol-oxidase-based electrochemical sensors suffer from their relatively high cost and low stability. This presentation will present our work using the hypervalent iodine compound [hydroxy(tosyloxy)iodo]benzene (HTIB) to chemically oxidize simple PCs. Preliminary work has shown that HTIB effectively converts simple phenols into quinones, however no electrochemical study has specifically been performed on these products to determine whether this could serve as a potential mechanism for continuous monitoring.This presentation will use spectroscopic and electrochemical methods to expand this idea by initially comparing three hydroxybenzene isomers as well as phenol to both understand the different oxidation pathways caused by HTIB as well as determine whether electrochemical reduction could potentially selectively detect each species. In addition to simple PCs, the investigation on using HTIB towards some environmentally relevant PCs will be presented.