Organoiodine Compounds Research Articles

Energetic Hypervalent Organoiodine Electrochemistry for Aqueous Zinc Batteries.

Hypervalent organoiodine compounds have been extensively utilized in organic synthesis, yet their electrochemical properties remain unexplored despite their theoretically high redox potential compared with inorganic iodine, which primarily relies on the I-/I0 redox couple in battery applications. Here, the fundamental redox mechanism of hypervalent organoiodine in a ZnCl2 aqueous electrolyte is established for the first time using the simplest iodobenzene (PhI) as a model compound. We validated that the PhI to PhICl2 transition is a single-step and reversible reaction, enabling two-electron transfer of I+/I3+ redox chemistry (1.9 V vs Zn2+/Zn) with high capacity (422 mAh giodine-1, and 262.6 mAh g-1 based on PhI) and high theoretical energy density (801.8 Wh kg-1). It was also elucidated that such organoiodine electrochemistry exhibits rich tunability in terms of the global reactivity of various PhI derivatives, including multiple iodine-substituted isomers and functional substituents. Additionally, the stabilizing anion ligands affect the reversibility and stability of trivalent organoiodine compounds. By limiting side reactions and improving the stability of trivalent organoiodine at low temperatures, the zinc-PhI battery demonstrated the feasibility of I+/I3+ conversion and sustained stable performance over 400 cycles. This work bridges the gap between hypervalent organoiodine chemistry and battery technology, highlighting the potential for future high-performance battery applications.

Electrocatalytic continuous flow chlorinations with iodine(I/III) mediators

Electrochemistry offers tunable, cost effective and environmentally friendly alternatives to carry out redox reactions with electrons as traceless reagents. The use of organoiodine compounds as electrocatalysts is largely underdeveloped, despite their widespread application as powerful and versatile reagents. Mechanistic data reveal that the hexafluoroisopropanol assisted iodoarene oxidation is followed by a stepwise chloride ligand exchange for the catalytic generation of the dichloroiodoarene mediator. Here, we report an environmentally benign iodine(I/III) electrocatalytic platform for the in situ generation of dichloroiodoarenes for different reactions such as mono- and dichlorinations as well as chlorocyclisations within a continuous flow setup.

Enrichment of Geogenic Organoiodine Compounds in Alluvial-Lacustrine Aquifers: Molecular Constraints by Organic Matter.

Organoiodine compounds (OICs) are the dominant iodine species in groundwater systems. However, molecular mechanisms underlying the geochemical formation of geogenic OICs-contaminated groundwater remain unclear. Based upon multitarget field monitoring in combination with ultrahigh-resolution molecular characterization of organic components for alluvial-lacustrine aquifers, we identified a total of 939 OICs in groundwater under reducing and circumneutral pH conditions. In comparison to those in water-soluble organic matter (WSOM) in sediments, the OICs in dissolved organic matter (DOM) in groundwater typically contain fewer polycyclic aromatics and polyphenol compounds but more highly unsaturated compounds. Consequently, there were two major sources of geogenic OICs in groundwater: the migration of the OICs from aquifer sediments and abiotic reduction of iodate coupled with DOM iodination under reducing conditions. DOM iodination occurs primarily through the incorporation of reactive iodine that is generated by iodate reduction into highly unsaturated compounds, preferably containing hydrophilic functional groups as binding sites. It leads to elevation of the concentration of the OICs up to 183 μg/L in groundwater. This research provides new insights into the constraints of DOM molecular composition on the mobilization and enrichment of OICs in alluvial-lacustrine aquifers and thus improves our understanding of the genesis of geogenic iodine-contaminated groundwater systems.

Carboiodanation of Arynes: Organoiodine(III) Compounds as Nucleophilic Organometalloids.

Organic iodine(III) compounds represent the most widely used hypervalent halogen compounds in organic synthesis, where they typically perform the role of an electrophile or oxidant to functionalize electron-rich or -nucleophilic organic compounds. In contrast to this convention, we discovered their unique reactivity as organometallic-like nucleophiles toward arynes. Equipped with diverse transferable ligands and supported by a tethered spectator ligand, the organoiodine(III) compounds undergo addition across the electrophilic C-C triple bond of arynes while retaining the trivalency of the iodine center. This carboiodanation reaction can forge a variety of aryl-alkynyl, aryl-alkenyl, and aryl-(hetero)aryl bonds along with the concurrent formation of an aryl-iodine(III) bond under mild conditions. The newly formed aryl-iodine(III) bond serves as a versatile linchpin for downstream transformations, particularly as an electrophilic reaction site. The amphoteric nature of the iodine(III) group as a metalloid and a leaving group in this sequence enables the flexible and expedient synthesis of extended π-conjugated molecules and privileged biarylphosphine ligands, where all of the iodine(III)-containing compounds can be handled as air- and thermally stable materials.

Freeze-induced acceleration of iodide oxidation and consequent iodination of dissolved organic matter to form organoiodine compounds

Freeze-induced acceleration of I– oxidation and the consequent iodination of dissolved organic matter (DOM) contribute to the formation of organoiodine compounds (OICs) in cold regions. The formed OICs may be a potentially important source of risk and are very closely with the environment and human health. Herein, we investigated the acceleration effects of the freeze process on I– oxidation and the formation of OICs. In comparison to reactive iodine species (RIS) formed in aqueous solutions, I– oxidation and RIS formation were greatly enhanced in frozen solution and were affected by pH, and the content of I– and O2. Freeze-thaw process further promoted I– oxidation and the concentration of RIS reached 45.7 µmol/L after 6 freeze-thaw cycles. The consequent products of DOM iodination were greatly promoted in terms of both concentration and number. The total content of OICs ranged from 0.02 to 2.83 µmol/L under various conditions. About 183–1197 OICs were detected by Fourier transform ion cyclotron resonance mass spectrometry, and more than 96.2% contained one or two iodine atoms. Most OICs had aromatic structures and were formed via substitution and addition reactions. Our findings reveal an important formation pathway for OICs and shed light on the biogeochemical cycling of iodine in the natural aquatic environment.

Evaluation of the chemical composition and nutritional value of lettuce (Lactuca sativa L.) biofortified in hydroponics with iodine in the form of iodoquinolines

Iodine deficiency in the diet creates the need to search for innovative, more sustainable and more effective strategies for enriching food with this microelement. The adopted research hypothesis assumed that the use of organic forms of iodine for supplementation of lettuce (Lactuca sativa L.), compared to mineral iodine, has a more favorable effect not only on the concentration of iodine, but also on the yield and the content of other chemical components determining its nutritional and health-promoting value. Lettuce was planted in a nutrient film technique (NFT) hydroponic study in a greenhouse. The following application of iodine compounds (all in 5 µM molar mass equivalents) were tested in the studies: control (without of iodine application); potassium iodate (positive iodine control), 8-hydroxy-7-iodo-5-quinolinesulfonic acid, 5-chloro-7-iodo-8-quinolinol, 5,7-diiodo-8-quinolinol and 4-hydroxy-8-iodo-3-quinolinecarboxylic acid. In this work, it was shown for the first time that iodoquinolines can be 1) a source of iodine for plants; 2) they have a biostimulating effect on their yielding and 3) they increase the resistance of crops to stress (due to a significant increase in the level of polyphenolic compounds). Lettuce with the addition of 8-hydroxy-7-iodo-5-quinolinesulfonic acid was characterized by the highest content of iodine, which was 221.7 times higher than in control plants. The weight gain of the whole plant was particularly visible in the case of lettuce enriched with 5-chloro-7-iodo-8-quinolinol and amounted to 26.48% compared to the control. Lettuce biofortified with iodine in the form of iodoquinolines can successfully become part of a sustainable diet based on plant products, which has a low impact on the environment and contributes to the long-term good health of an individual or community. Reducing iodine deficiency through the use of organoiodine compounds can help achieve the sustainability goal of eliminating hidden hunger, improving nutritional status and promoting sustainable agriculture.

Freezing-Enhanced Photoreduction of Iodate by Fulvic Acid.

Iodate is a stable form of iodine species in the natural environment. This work found that the abiotic photosensitized reduction of iodate by fulvic acid (FA) is highly enhanced in frozen solution compared to that in aqueous solution. The freezing-induced removal of iodate by FA at an initial pH of 3.0 in 24 h was lower than 10% in the dark but enhanced under UV (77.7%) or visible light (31.6%) irradiation. This process was accompanied by the production of iodide, reactive iodine (RI), and organoiodine compounds (OICs). The photoreduction of iodate in ice increased with lowering pH (pH 3-7 range) or increasing FA concentration (1-10 mg/L range). It was also observed that coexisting iodide or chloride ions enhanced the photoreduction of iodate in ice. Fourier transform ion cyclotron resonance mass spectrometric analysis showed that 129 and 403 species of OICs (mainly highly unsaturated and phenolic compounds) were newly produced in frozen UV/iodate/FA and UV/iodate/FA/Cl- solution, respectively. In the frozen UV/iodate/FA/Cl- solution, approximately 97% of generated organochlorine compounds (98 species) were identified as typical chlorinated disinfection byproducts. These results call for further studies of the fate of iodate, especially in the presence of chloride, which may be overlooked in frozen environments.

Bacterial Sulfate Reduction Facilitates Iodine Mobilization in the Deep Confined Aquifer of the North China Plain.

Bacterial sulfate reduction plays a crucial role in the mobilization of toxic substances in aquifers. However, the role of bacterial sulfate reduction on iodine mobilization in geogenic high-iodine groundwater systems has been unexplored. In this study, the enrichment of groundwater δ34SSO4 (15.56 to 69.31‰) and its significantly positive correlation with iodide and total iodine concentrations in deep groundwater samples of the North China Plain suggested that bacterial sulfate reduction participates in the mobilization of groundwater iodine. Similar significantly positive correlations were further observed between the concentrations of iodide and total iodine and the relative abundance of the dsrB gene by qPCR, as well as the composition and abundance of sulfate-reducing bacteria (SRB) predicted from 16S rRNA gene high-throughput sequencing data. Subsequent batch culture experiments by the SRB Desulfovibrio sp. B304 demonstrated that SRB could facilitate iodine mobilization through the enzyme-driven biotic and sulfide-driven abiotic reduction of iodate to iodide. In addition, the dehalogenation of organoiodine compounds by SRB and the reductive dissolution of iodine-bearing iron minerals by biogenic sulfide could liberate bound or adsorbed iodine into groundwater. The role of bacterial sulfate reduction in iodine mobilization revealed in this study provides new insights into our understanding of iodide enrichment in iodine-rich aquifers worldwide.

MnO2-Induced Oxidation of Iodide in Frozen Solution.

Metal oxides play a critical role in the abiotic transformation of iodine species in natural environments. In this study, we investigated iodide oxidation by manganese dioxides (β-MnO2, γ-MnO2, and δ-MnO2) in frozen and aqueous solutions. The heterogeneous reaction produced reactive iodine (RI) in the frozen phase, and the subsequent thawing of the frozen sample induced the gradual transformation of in situ-formed RI to iodate or iodide, depending on the types of manganese dioxides. The freezing-enhanced production of RI was observed over the pH range of 5.0-9.0, but it decreased with increasing pH. Fulvic acid (FA) can be iodinated by I-/MnO2 in aqueous and frozen solutions. About 0.8-8.4% of iodide was transformed to organoiodine compounds (OICs) at pH 6.0-7.8 in aqueous solution, while higher yields (10.4-17.8%) of OICs were obtained in frozen solution. Most OICs generated in the frozen phase contained one iodine atom and were lignin-like compounds according to Fourier transform ion cyclotron resonance/mass spectrometry analysis. This study uncovers a previously unrecognized production pathway of OICs under neutral conditions in frozen environments.

Iodine emission from the reactive uptake of ozone to simulated seawater.

The heterogeneous reaction of ozone and iodide is both an important source of atmospheric iodine and dry deposition pathway of ozone in marine environments. While the iodine generated from this reaction is primarily in the form of HOI and I2, there is also evidence of volatile organoiodide compound emissions in the presence of organics without biological activity occuring [M. Martino, G. P. Mills, J. Woeltjen and P. S. Liss, A new source of volatile organoiodine compounds in surface seawater, Geophys. Res. Lett., 2009, 36, L01609, L. Tinel, T. J. Adams, L. D. J. Hollis, A. J. M. Bridger, R. J. Chance, M. W. Ward, S. M. Ball and L. J. Carpenter, Influence of the Sea Surface Microlayer on Oceanic Iodine Emissions, Environ. Sci. Technol., 2020, 54, 13228-13237]. In this study, we evaluate our fundamental understanding of the ozonolysis of iodide which leads to gas-phase iodine emissions. To do this, we compare experimental measurements of ozone-driven gas-phase I2 formation in a flow tube to predictions made with the kinetic multilayer model for surface and bulk chemistry (KM-SUB). The KM-SUB model uses literature rate coefficients used in current atmospheric chemistry models to predict I2(g) formation in pH-buffered solutions of marine composition containing chloride, bromide, and iodide compared to solutions containing only iodide. Experimentally, I2(g) formation was found to be suppressed in solutions containing seawater levels of chloride compared to solutions containing only iodide, but the model does not predict this effect using literature rate constants. However, the model is able to predict this trend upon adjustment of two specific reaction rate constants. To more closely represent true oceanic conditions, we add an organic component to the proxy seawater solutions using material generated from Thalassiosira pseudonana phytoplankton cultures. Whereas the rate of ozone deposition is unaffected, the formation rate of I2(g) is strongly suppressed in the presence of biological organic material, indicative of a sink or reduction of reactive iodine formed during the oxidation process.

Release of protein N-glycans by effectors of a Hofmann carboxamide rearrangement.

Background: Chemical methods for glycan release have gained traction because of their cost efficiency, accelerated reaction time and ability to release glycans not amenable to enzymatic cleavage. Oxidative chemical glycan release via hypochlorite treatment has been shown to be a convenient and efficient method that yields N-glycans similar to classical PNGase F digestion. We observed that the initial steps of the suggested mechanism for the oxidative release of glycans from glycoproteins by hypohalites showed similarities to the initiating steps of the classical Hofmann rearrangement of carboxamides. Therefore, we investigated the ability of different stable effectors of a Hofmann-type carboxamide rearrangement to efficiently and selectively release N-glycans from glycoproteins. Methods: Released glycans obtained from different experimental chemical release approaches were analyzed by HILIC-FLD, BHZ-FACE and ESI-MS and evaluated with respect to electrophoretic mobility, retention time and integrated peak area for resolved glycans. Results: We show that the known Hoffmann catalysts 1,3-dichloro-5,5-dimethylhydantoin, the hypervalent organoiodine (III) compound diacetoxy-iodobenzene as well as in-situ hypobromite generation using Oxone® and potassium bromide are all capable of releasing protein-bound N-glycans in good yield. Among the compounds investigated, diacetoxy-iodobenzene was capable of releasing glycans in the absence of alkali. Detailed investigations of the bromide/Oxone® method revealed a dependence of N-glycan release efficiency from the temporal order of bromide addition to the reaction mix as well as from a molar excess of bromide over Oxone®. Conclusions. These findings suggest that the oxidative release of N-glycans occurs via the initiating steps of a Hofmann carboxamide rearrangement. Hypervalent organoiodine compounds hold the promise of releasing glycans in the absence of alkali. The in-situ generation of hypobromite by bromide/Oxone® produces a consistent defined amount of reagent for rapid N-glycan release for both analytical and preparative purposes.

Kinetic investigations of the formation of iron(IV) oxido complexes

Oxido iron(IV) complexes are key intermediates in oxygenation reactions in biological systems. They can form during oxidation experiments with various oxidants such as oxygen, hydrogen peroxide, organoiodine compounds, or ozone. However, kinetic studies for these reactions are rare because the intermediates are usually labile. Here the results of a detailed investigation on the oxidation of iron(II) complexes with macrocyclic (e.g. TMC = tetramethylcyclam = 1,4,8,11-tetramethyl-1,4,8,11-tetraaza-cyclotetradecane) ligands are reported that provide a better understanding of the mechanisms of these reactions. For formation of the quite stable oxido iron complex with an amide derivative of TMC, activation parameters with ΔH ‡ = 28 ± 4 kJ·mol−1 and ΔS ‡ = −144 ± 15 J·mol−1·K−1 could be obtained that allowed postulation of an associative mechanism.

Chip-Based Spectrofluorimetric Determination of Iodine in a Multi-Syringe Flow Platform with and without In-Line Digestion-Application to Salt, Pharmaceuticals, and Algae Samples.

In this work, a flow-based spectrofluorimetric method for iodine determination was developed. The system consisted of a miniaturized chip-based flow manifold for solutions handling and with integrated spectrofluorimetric detection. A multi-syringe module was used as a liquid driver. Iodide was quantified from its catalytic effect on the redox reaction between Ce(IV) and As(III), based on the Sandell–Kolthoff reaction. The method was applied for the determination of iodine in salt, pharmaceuticals, supplement pills, and seaweed samples without off-line pre-treatment. An in-line oxidation process, aided by UV radiation, was implemented to analyse some samples (supplement pills and seaweed samples) to eliminate interferences and release iodine from organo-iodine compounds. This feature, combined with the fluorometric reaction, makes this method simpler, faster, and more sensitive than the classic approach of the Sandell–Kolthoff reaction. The method allowed iodine to be determined within a range of 0.20–4.0 µmol L−1, with or without the in-line UV digestion, with a limit of detection of 0.028 µmol L−1 and 0.025 µmol L−1, respectively.

Freeze-Thaw Cycle-Enhanced Transformation of Iodide to Organoiodine Compounds in the Presence of Natural Organic Matter and Fe(III).

The formation of organoiodine compounds (OICs) is of great interest in the natural iodine cycle as well as water treatment processes. Herein, we report a pathway of OIC formation that reactive iodine (RI) and OICs are produced from iodide oxidation in the presence of Fe(III) and natural organic matter (NOM) in frozen solution, whereas their production is insignificant in aqueous solution. Moreover, thawing the frozen solution induces the further production of OICs. A total of 352 OICs are detected by Fourier transform ion cyclotron resonance mass spectrometry in the freeze-thaw cycled reactions of Fe(III)/I-/humic acid solution, which are five times as many as OICs in aqueous reactions. Using model organic compounds instead of NOM, aromatic compounds (e.g., phenol, aniline, o-cresol, and guaiacol) induce higher OIC formation yields (10.4-18.6%) in the freeze-thaw Fe(III)/I- system than those in aqueous (1.1-2.1%) or frozen (2.7-7.6%) solutions. In the frozen solution, the formation of RI is enhanced, but its further reaction with NOM is hindered. Therefore, the freeze-thaw cycle in which RI is formed in the frozen media and the resulting RI is consumed by reaction with NOM in the subsequently thawed solution is more efficient in producing OICs than the continuous reaction in frozen solution.

Comparative analysis of in vivo and in silico toxicity evaluation of the organoiodine compounds towards D.magna using multivariate chemometric approach: A study on the example of amiodarone phototransformation products

In the present study the photochemical fate of organoiodine compound – amiodarone was performed. The drug turned out to be highly susceptible to UV–Vis irradiation, especially in the presence of humic substances and organic matrix. Qualitative LC-MS analysis revealed formation of twelve – mainly previously unreported – transformation products (TPs). Four major TPs were submitted to the toxicity analysis with the use of D. magna. All of the tested TPs presented higher toxic potential than the parent compound. The phenolic TPs were approximately 100 times more toxic than amiodarone. Toxic properties of the major TPs resulted in steadily increasing toxic potential of the photo-generated mixture over the time of irradiation. Moreover, the experimental toxicity data, concerning the TPs, were compared with results estimated by 6 in silico models with the use of a multivariate chemometric analysis. The results showed that the applied computational methods were able neither to correctly predict toxic properties of the studied compounds, nor the trends in change of their toxic parameters. Additional validation of in silico models ability to predict toxicity of iodinated organic compounds showed that the studied computational methods do not present sufficient prediction ability. Therefore their estimations concerning organoiodines should be verified using experimental tests.

Measurement report: Indirect evidence for the controlling influence of acidity on the speciation of iodine in Atlantic aerosols

Abstract. The speciation of soluble iodine and major-ion composition were determined in size-fractionated aerosols collected during the AMT21 cruise between Avonmouth, UK, and Punta Arenas, Chile, in September–November 2011. The proportions of iodine species (iodide, iodate and soluble organic iodine (SOI)) varied markedly between size fractions and with the extent to which the samples were influenced by pollutants. In general, fine mode aerosols (< 1 µm) contained higher proportions of both iodide and SOI, while iodate was the dominant component of coarse (< 1 µm) aerosols. The highest proportions of iodate were observed in aerosols that contained (alkaline) unpolluted sea spray or mineral dust. Fine mode samples with high concentrations of acidic species (e.g. non-sea-salt sulfate) contained very little iodate and elevated proportions of iodide and SOI. These results are in agreement with modelling studies that indicate that iodate can be reduced under acidic conditions and that the resulting hypoiodous acid (HOI) can react with organic matter to produce SOI and iodide. Further work that investigates the link between iodine speciation and aerosol pH directly, as well as studies on the formation and decay of organo-iodine compounds under aerosol conditions, will be necessary before the importance of this chemistry in regulating aerosol iodine speciation can be confirmed.

Iodine(III)-Based Halogen Bond Donors: Properties and Applications.

Halogen bonding, the non-covalent interaction of Lewis bases with an electron-deficient region of halogen substituents, received increased attention recently. Consequently, the design and evaluation of numerous halogen-containing species as halogen bond donors have been subject to intense research. More recently, organoiodine compounds at the iodine(III) state have been receiving growing attention in the field. Due to their electronic and structural properties, they provide access to unique binding modes. For this reason, our groups have been involved in the development of such compounds, in the quantification of their halogen bonding strength (through the evaluation of their Lewis acidities), as well as in the evaluation of their activities as catalysts in several model reactions. This account will describe these contributions.

Remote Substituents as Potential Control Elements for the Solid-State Structures of Hypervalent Iodine(III) Compounds.

Hypervalent iodine (HVI) compounds are very important selective oxidants often employed in organic syntheses. Most HVI compounds are strongly associated in the solid state involving interactions between the electropositive iodine centers and nearby electron lone pairs of electronegative atoms. This study examines the impact of remote substituents on select families of HVI compounds as means to achieve predictable two-dimensional extended solid-state materials. Crystallographic analyses of 10 HVI compounds from several related classes of λ3 organoiodine(III) compounds, (diacetoxyiodo)benzenes, (dibenzoatoiodo)benzenes, [bis(trifluoroacetoxy)iodo]benzenes, and μ-oxo-[(carboxylateiodo)benzenes], provide insights into how remote substituents and the choice of carboxylate groups can impact intermolecular interactions in the solid state.

Hypervalent Organo-λ3-chloranes

Abstract Hypervalent halogen species such as organoiodine(III and V) compounds have long been used as electrophiles/oxidants in organic synthesis, but recent years have seen the emergence of a new class of hypervalent halogen species, organobromine(III) and organochlorine(III) compounds (also termed organo-λ3-bromanes and λ3-chloranes). In this review, we will cover recent developments in the synthesis and synthetic applications of functionalized λ3-chloranes. 1. Introduction; 2. Diaryl-λ3-chloranes; 3. Alkenyl(aryl)-λ3-chloranes; 4. Dialkyl-λ3-chloranes; 5. Chloronium ylides; 6. Carboranyl-λ3-chloranes; 7. Conclusion

2-Iodomalondialdehyde is an abundant component of soluble organic iodine in atmospheric wet precipitation

Iodine plays an important role in the environment and life. In the atmosphere, iodine is present in the form of inorganic and organic compounds. In this study, we have analyzed atmospheric wet precipitation using ultra-high performance liquid chromatography coupled to high resolution mass spectrometry (UHPLC-HRMS) for the presence of organoiodine compounds and found that the main organoiodine compound in atmospheric waters is 2-iodomalondialdehyde. The structure of this compound is supported by independent synthesis. A plausible mechanism of the formation of 2-iodomalondialdehyde from acrolein, iodine and water in the atmosphere is proposed. Our measurements reveal the presence of ten other organoiodine compounds in atmospheric wet precipitation but their structures remain unknown, mainly due to very low concentrations prohibiting mass spectrometry studies. The results described in this paper enhance our knowledge about the circulation of iodine in nature. It provides insights into the chemical nature of soluble organic iodine, whose presence in the atmosphere has been known for two decades. In addition, it also shows the potential of using liquid chromatography coupled to mass spectrometry (LC-MS) technique to further explore iodine chemistry in the atmosphere.