Reaction Of Iodine Research Articles

Formation to Transportation: En-Route Fission-Facilitated Formation of Spheres in a Phosphorus-Based Porous Organic Polymer for Transportation of Iodine.

Despite its potential as a clean power source to meet rising electricity demands, nuclear energy generates radioactive waste, including isotopes of iodine, that pose significant environmental and health risks. There is a growing demand to capture radioactive iodine and repurpose it effectively. However, achieving this dual functionality with a single material remains a significant challenge. This study explores phosphorus-based porous organic polymers (P-POPs) as probes for these dual functionalities. By employing 4-formyl(triphenyl)phosphine (BB1) and phenyl-1,4-diacetonitrile (BB2) under the Knoevenagel polycondensation method, P-POPs (PKPOPs) have been synthesized that exhibit a smooth spherical morphology, which efficiently captures and release iodine under ambient conditions, facilitating efficient transportation of molecular iodine. This novel approach aims to potentially transform nuclear waste into valuable organic feedstock via an iodination reaction. The innovative application of PKPOP has also been demonstrated for iodination reactions using ball mills and under continuous flow conditions, showcasing its potential for safer waste management and utilization.

Synthesis and Optical Properties of Binaphthyl Derivatives with Comprehensive Introduction of Phenylethynyl Groups.

In this study, compounds with phenylethynyl (PE) groups introduced at all of the possible positions of the methylene-bridged structure of the 1,1'-bi-2-naphthol backbone (3-PE to 8-PE) were synthesized. Compounds with four or six phenylethynyl groups (3,6-PE, 4,6-PE, 5,6-PE, 6,7-PE, and 3,4,6-PE) were also synthesized. The key reaction for the synthesis of these compounds was the Sonogashira reaction using halogen scaffolds. The new transformation methods include (1) selective bromination of the 5-position of the binaphthyl skeleton and (2) bromination of the 6-position and then iodination of the 4-position, followed by the Sonogashira reaction of iodine at the 4-position and lithiation and protonation of bromine at the 6-position. The optical properties of the compounds were evaluated. The extension of the π system greatly differed depending on the position of the phenylethynyl group. 4-PE, 4,6-PE, and 3,4,6-PE, in which the phenylethynyl groups were introduced in the extended direction of the naphthalene linkage axis, showed longer absorption and emission wavelengths and higher fluorescence quantum yields than the other compounds. In circularly polarized luminescence measurements, 7-PE showed a relatively large glum value, an interesting finding that reverses the sense.

Oxidative Dimerization of (Thiazol-2-yl)acetonitriles with Molecular Iodine: Synthesis and Structure of 2,3-Bis(4-aryl-1,3-thiazol-2-yl)but-2-enedinitriles

Iodination of 2-(4-arylthiazole-2-yl)acetonitriles in DMF proceeds with the formation of previously undescribed 2,3-bis(4-aryl-1,3-thiazole-2-yl)but-2-enedicarbonitriles as a mixture of E- and Z-isomers. The latter were alternatively prepared by the reaction of cyanothioacetamide, α-bromoketones and iodine in DMF. Structure of the key compounds was proven by means of single crystal X-ray diffraction analysis.

Molecular Insights into Converting Hydroxide Adenosyltransferase into Halogenase.

Halogenation plays a unique role in the design of agrochemicals. Enzymatic halogenation reactions have attracted great attention due to their excellent specificity and mild reaction conditions. S-adenosyl-l-methionine (SAM)-dependent halogenases mediate the nucleophilic attack of halide ions (X-) to SAM to produce 5'-XDA. However, only 11 SAM-dependent fluorinases and 3 chlorinases have been reported, highlighting the desire for additional halogenases. SAM-dependent hydroxide adenosyltransferase (HATase) has a similar reaction mechanism as halogenases but uses water as a substrate instead of halide ions. Here, we explored a HATase from the thermophile Thermotoga maritima MSB8 and transformed it into a halogenase. We identified a key dyad W8L/V71T for the halogenation reaction. We also obtained the best performing mutants for each halogenation reaction: M1, M2 and M4 for Cl-, Br- and I-, respectively. The M4 mutant retained the thermostability of HATase in the iodination reaction at 80 °C, which surpasses the natural halogenase SalL. QM/MM revealed that these mutants bind halide ions with more suitable angles for nucleophilic attack of C5' of SAM, thus conferring halogenation capabilities. Our work achieved the halide ion specificity of halogenases and generated thermostable halogenases for the first time, which provides new opportunities to expand the halogenase repertoire from hydroxylase.

Metabolomic screening of radioiodine refractory thyroid cancer patients and the underlying chemical mechanism of iodine resistance

Radioiodine refractory (RAIR) patients do not benefit from iodine-131 therapy. Thus, timely identification of RAIR patients is critical for avoiding ineffective radioactive iodine therapy. In addition, determining the causes of iodine resistance will facilitate the development of novel treatment strategies. This study was comprised of 20 RAIR and 14 non-radioiodine refractory (non-RAIR) thyroid cancer patients. Liquid chromatography-mass spectrometry was used to identify differences in the serum metabolites of RAIR and non-RAIR patients. In addition, chemical assays were performed to determine the effects of the differential metabolites on iodine uptake. Metabolic pathway enrichment analysis of the differential metabolites revealed significant differences in the phenylalanine and tyrosine metabolic pathways. Notably, quinate and shikimic acid, metabolites of the tyrosine pathway, were significantly increased in the RAIR group. In contrast, the phenylalanine pathway metabolites, hippuric acid and 2-phenylacetamide, were markedly decreased in the RAIR group. Thyroid peroxidase plays an important role in catalyzing the iodination of tyrosine residues, while the ionic state of iodine promotes the iodination reaction. Quinate, shikimic acid, hippuric acid, and 2-phenylacetamide were found to be involved in the iodination of tyrosine, which is a key step in thyroid hormone synthesis. Specifically, quinate and shikimic acid were found to inhibit iodination, while hippuric acid and 2-phenylacetamide promoted iodination. Abnormalities in phenylalanine and tyrosine metabolic pathways are closely associated with iodine resistance. Tyrosine is required for thyroid hormone synthesis and could be a potential cause of iodine resistance.

Influence of Lattice Defects on Trans-Oligoene Substructure Formation in Graphene.

The photochemical reaction of iodine and graphene induces strong new Raman modes due to the formation of trans-oligoene substructures in graphene domains. This unique reactivity was demonstrated before on defect-free graphene, however leaving the influence of e. g. carbon vacancies, unexplored. Here, we investigate the photochemical reaction applied on graphene with varying average distances of lattice defects and statistically analyze the characteristic Raman modes which develop with the iodination reaction. We show that the iodination reaction does not lead to Raman-active defects and thus, the newly formed trans-oligoene substructures do not contribute to the D-mode of graphene. A statistical analysis reveals the correlation between the average distance of lattice defects and the intensity of the v1-mode. For defective graphene with average defect distances below ~1 nm no new Raman modes evolve, which is the lower limit of the substructure size probed at 532 nm and explains why this observation was not possible before using common graphene oxide as graphene source.

Photocurrent Enhancement by Copper Incorporation in Chemical-Solution-Synthesized Inorganic Lead Perovskite Thin Films.

Perovskite thin films are at the forefront of highly promising photovoltaic technologies due to their remarkable optoelectronic properties. Herein, we explore a low-cost, reproducible, and industry-scalable methodology to synthesize an all-inorganic CsPbI1.5Br1.5 perovskite thin film with additional incorporation of copper and chloride ions into the lattice structure. The synthesis process involves chemical bath deposition of PbS, followed by a gas-solid iodination reaction to yield PbI2. Subsequently, dip-coating incorporates Cs+, Cu2+, Br-, and Cl- ions into PbI2, and annealing at 270 °C produces perovskite thin films. The results show a large coverage area and a uniform thickness of each perovskite thin film. Comprehensive characterization, including X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and photoluminescence, provides the structural, chemical, and optical properties of the synthesized thin films. To evaluate the practical implications of our methodology, we fabricated photodetectors employing CsPbI1.5Br1.5 and (Cs0.95:Cu0.01)PbI1.5Br1.3Cl0.1 perovskite films. A comparative analysis unequivocally demonstrates a significant increase in photodetector performance when utilizing (Cs0.95:Cu0.01)PbI1.5Br1.3Cl0.1 perovskite films. While our findings quantitatively assess the tangible enhancement in photocurrent, we acknowledge the potential for improvement in device fabrication to enhance the overall performance. This study not only affirms the successful low-cost synthesis of perovskite thin films but also emphasizes the pivotal role of Cu2+ and Cl- ions in enhancing the performance of perovskite-based optoelectronic devices.

Recent Progress in N-Iodosuccinimide (NIS)-Mediated Iodination Reactions

Recent Progress in <i>N</i>-Iodosuccinimide (NIS)-Mediated Iodination Reactions

A FUZZY GRAPHICAL APPROACH TO MODELLING CHEMICAL INTERACTIONS

Chemical interactions are central to many scientific and industrial processes, yet conventional modelling methods can struggle to sufficiently represent the complexity of these interactions or their intrinsic uncertainty. Appearing in: Kobi Gal and Stuart Russell, Logical Bayesian Networks. This model is exemplified through two case studies, the reaction of acetone and iodine in acidic medium, as well as a receptor-ligand system containing Imatinib and BCR-ABL protein; this demonstrates that it can reproduce pertinent properties of chemical reactions. The predictive power of the fuzzy graphical model on reaction outcomes and on interaction strengths provides information about sensitivity and non-linear behavior in such systems. The model is shown to outperform traditional methods in terms of uncertainty handling and flexibility. It also discusses challenges like data quality and rule definition, improvements of the model that can help understand more complex chemical systems (e.g. drug discovery).

Simultaneously Generating Redox Mediator and Hybrid SEI for Lithium–oxygen Batteries by Lewis Acid Catalyzed Ring‐opening Reaction of Organic Iodine

AbstractFacing high overpotential, severe Li corrosion and degradation of electrolytes caused by the reactive oxygen species, the development of lithium–oxygen batteries is seriously limited. Although the iodine species have been considered to be effective redox mediators (RMs) for lowering the charging overpotential, the shuttling of oxidized I3− may attack the Li metal anode, compromising the number of RMs, cycling stability and energy efficiency. Here the intend to introduce 3‐Iodooxetane (C3H5OI, IOD) into TEGDME‐based electrolyte to form a protective SEI layer on the Li surface for defending against the attack of I3−. However, the iodine in IOD is found difficult to dissociate. To solve this problem, hard Lewis acid, aluminum trichloride (AlCl3) is proposed as the catalytic agent for dissociating the I− and triggering the ring‐opening reaction of the detached C3H5O+ ions. The former can dissociate redox couple I3−/I− while the latter can form oligomers or polymers under the attack of a nucleophile. Meanwhile, AlCl3 can form Al2O3 and LiCl inorganic species. Taking together, the introduction of IOD and AlCl3 into electrolytes can effectively derive reduced overpotential and in situ SEI layers consisting of flexible organics and rigid inorganics, endowing lithium–oxygen batteries over 150 cycles with significantly enhanced stability and lifespan.

Phase Reduction and Thermodynamic Analysis of Ilmenite Ore by Carbothermal-Iodination using Different Carbon Reductants

The present study is on the combination of carbothermal reduction and iodination reaction (carboiodination) process for the phase reduction of ilmenite ore (FeTiO3). The aim is to understand the phase reduction and thermodynamic reaction analysis of ilmenite ore by a combined method of carbothermal-iodination using different carbon reductants (graphite and palm char). Graphite was used as a standard carbon reductant while palm char as a renewable carbon reductant was prepared via the pyrolysis technique. Ilmenite was mixed with carbon reductants and then first reduced by using a carbothermal reduction process at 1550℃. Then, the reduced samples were further investigated with iodination reaction in different temperature ranges of 900-1000 °C using a vertical tube furnace with mixed argon and iodine gas (0.2 L/min). The proximate and ultimate analyses of carbon reductants were analysed by CHON analyser and their microstructure by using SEM, while XRF and XRD were used for analyzing the chemical compositions and the phase reductions of raw ilmenite ore and reduced samples, respectively. The thermodynamics of possible reactions during carbothermal-iodination reactions were calculated by HSC Chemistry 6.0 software. By comparing graphite and palm char, palm char had an amorphous structure, with porous and high carbon content showing high potential for usage as a reductant in titanium extraction from ilmenite ore. The phases of ilmenite ore were ilmenite, rutile, and anatase transformed into rutile, pseudobrookite, and titanium oxide detected by XRD. Further reduction was performed by palm char where more rutile (TiO2) and titanium oxide (Ti3O5) developed from the iodination reaction at the highest temperature compared to graphite due to better properties and amorphous structure. The rutile and titanium oxide were found as stable phases from the thermodynamic analysis and confirmed with XRD. From the findings, the combination of carbothermal-iodination of ilmenite ore was possible and promising for rutile (TiO2) production in mineral extractions.

Decarboxylative Iodination and Suzuki-Miyaura Coupling Reactions to Access Chiral 3,3'-Diaryl-1,1'-bi-2-naphthols.

An efficient synthesis of the enantiomerically pure 3,3'-bis-arylated BINOLs is accomplished through decarboxylative iodination of the dimethyl ether derivative of BINOL-3,3'-dicarboxylic acid followed by Suzuki-Miyaura coupling using a one-pot protocol. The decarboxylative iodination is effected with the dimethyl ether derivative of BINOL-3,3'-dicarboxylic acid using iodine as a terminal oxidant and the cheaply available K3PO4 as a base under neat conditions. This protocol facilitated the introduction of the aryl group at the 3,3'-position on the binaphthyl system using aryl boronic acid through a palladium-catalyzed Suzuki-Miyaura coupling reaction.

Halogen addition to NHC-gold(I) chloride complexes in the framework of the Inverted Ligand Field

The conversion of LAuX to LAuX3, where L is a neutral ligand such as a phosphane or a carbene and X = Cl, Br or I, can be performed by halogen addition reactions in mild conditions. The formation of complexes with mixed halides, such as LAuY2X, also evoking the possibility of geometrical isomerization, is less investigated. In this work the iodine and bromine addition reactions, under mild conditions, to a symmetrically disubstituted carbene 1,3-dimethyl-imidazolyl-2-yl-gold(I)chloride were considered. The molecular structures highlight the formation of the trans LAuI2Cl in the case of iodine addition and a mixture of the geometrical isomers for bromine. DFT analysis points out a stepwise addition of halogen atom to the linear gold(I) complex without a net change in metal electronic population, suggesting the occurrence of the Inverted Ligand Field.

A Novel Cu(II)-Iodine Catalyzed Hantzsch Type Synthesis of 2-Aminothiazole Derivatives

Abstract: Heterocycles having nitrogen and sulphur atoms attract chief attention due to their importance in diverse fields, especially in medicinal chemistry and pharmaceutical industry. Among those, 2-aminothiazole, one of the most flexible and pervasive heterocyclic scaffolds found in many natural and synthetic products, exhibits a wide variety of biological activities. A one-pot method for the synthesis of 2-aminothiazoles through Cu(II)-iodine-catalyzed Hantzsch condensation has been achieved for the first time. This novel green methodology facilitates the formation of a broad range of 2-aminothiazole derivatives utilizing catalytic quantities of Cu(II) salts and iodine, incorporating various methyl aryl ketones and thiourea as substrates. This novel strategy involves a Hantzsch-type condensation between thiourea and in situ generated α-iodoketones, formed from the reaction of methyl aryl ketones and iodine. The present protocol reveals PEG-400 as the best solvent, which furnishes moderate to good yields of the desired 2-aminothiazole derivatives. The addition of a catalytic quantity of copper acetate ensures the continuous availability of iodine for several catalytic cycles, as copper(II) allows the oxidation of iodide to iodine. The feasibility of this novel route is studied with electron-withdrawing, electron-donating, and halo-substituted derivatives of methyl aryl ketones with thiourea to confirm the functional group compatibility of the reaction. Moreover, this efficient strategy evades the direct use of noxious and lachrymatory α–halocarbonyls as reaction substrates and strong oxidants. Using a catalytic quantity of iodine in the reaction makes the separation of the desired products much easier by reducing the amount of unwanted side-products than utilizing a stoichiometric amount of iodine.

Methyl Ketones as Alkyl Halide Surrogates: A Deacylative Halogenation Approach for Strategic Functional Group Conversions.

Alkyl halides are versatile precursors to access diverse functional groups (FGs). Due to their lability, the development of surrogates for alkyl halides is strategically important for complex molecule synthesis. Given the stability and ease of derivatization inherent in common alkyl ketones, here we report a deacylative halogenation approach to convert various methyl ketones to the corresponding alkyl chlorides, bromides, and iodides. The reaction is driven by forming an aromatic byproduct, i.e., 1,2,4-triazole, in which N'-methylpicolinohydrazonamide (MPHA) is employed to form a prearomatic intermediate and halogen atom-transfer (XAT) reagents are used to quench the alkyl radical intermediate. The reaction is efficient in yielding primary and secondary alkyl halides from a wide range of methyl ketones with broad FG tolerance. It also works for complex natural-product-derived and fluoro-containing substrates. In addition, one-pot conversions of methyl ketones to various other FGs and annulations with alkenes and alkynes through deacylative halogenation are realized. Moreover, an unusual iterative homologation of alkyl iodides is also demonstrated. Finally, mechanistic studies reveal an intriguing double XAT process for the deacylative iodination reaction, which could have implications beyond this work.

Synergic anchoring of Fe2N nanoclusters on porous carbon to enhance reversible conversion of iodine for high-temperature zinc-iodine battery

The coupling of zinc with iodine evokes the fabrication of advanced rechargeable batteries via redox conversion. However, the easy sublimation of iodine and high solubility of polyiodides restrict the application of the battery. Herein, the dispersion of iron nitride nanoclusters among three-dimensional porous carbon frameworks (PC@Fe2N) enables the efficient accumulation of iodine in combination with the promising electrocatalysis for reversible conversion. The experimental and theoretical results revealed that the Fe2N nanoclusters anchored on the carbon support is more efficient to inspire the ensemble effect for reversible redox reactions of iodine via suppressing the formation of polyiodide. Therefore, the zinc-iodine (Zn-I2) battery delivers excellent rate performance and ultralong cycling life for 20,000 cycles. Even at an elevated temperature of 60 °C, the pouch cell with a high iodine loading exhibited a reversible capacity 148 mAh g−1, which exemplifies rational fabrication of advanced Zn-I2 batteries for safe high-temperature energy storage.

Aliphatic Sulfonyl Fluoride Synthesis via Decarboxylative Fluorosulfonylation of Hypervalent Iodine(III) Carboxylates.

We disclose herein a photocatalytic decarboxylative fluorosulfonylation reaction of various hypervalent iodine(III) carboxylates in combination with 1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct as a sulfonyl source and KHF2 as a desirable fluorine source via a radical sulfur dioxide insertion and fluorination strategy. A one-pot photocatalytic decarboxylative fluorosulfonylation reaction of various carboxylic acids mediated by PhI(OAc)2 was realized, as well. Notably, this transformation can be performed under heating conditions without the need for catalysts.

Direct Reaction - One Step Route to Synthesize Lanthanoid-iodide Formamidinates.

This paper describes a novel and simple method - direct reaction of lanthanoid metals with equimolar amounts of iodine and a formamidine under ultrasonication as an effective, metal-based route to lanthanoid(III) diiodide formamidinates, namely I. N,N'-Bis(2,6-diisopropylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(DippForm)I2 (thf)3 ] (Ln=La, 1, Ce, 2, Tb, 3, Ho, 4, Er, 5, Tm, 6); II. N,N'-Bis(2,6-diethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(EtForm)I2 (thf)3 ] (Ln=Ce, 7, Nd, 8, Gd, 9, Tb, 10, Dy, 11, Ho, 12, Er, 13, Lu, 14). III. N,N'-bis(2,6-dimethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(XylForm)I2 (thf)3 ] (Ln=Ce, 15, Nd, 16, Gd, 17, Tm, 18, Lu 19); IV. N,N'-bis(phenyl)formamidinatodiiodidolanthanoid complexes [Ln(PhForm)I2 (thf)3 ] (Ln=Nd, 20, Gd, 21, Er, 22). Compound [Ce(XylForm)2 I(thf)2 ] (23) was also synthesized by the same method except the ratio of I2 to XylFormH was 1 : 4. Divalent N,N'-bis(2,6-diisopropylphenyl)formamidinato-iodido-lanthanoid(II) complexes [Eu(DippForm)I(thf)4 ] ⋅ thf (24), [Yb(DippForm)I(thf)3 ] ⋅ 2DippFormH (25), [Sm(DippForm)I(thf)4 ] ⋅ thf (26) have also been synthesized by direct reactions of the free metals, iodine and DippFormH. Interestingly, [Sm(DippForm)I2 (thf)3 ] (27) was obtained by the oxidation of [Sm(DippForm)I(thf)4 ] ⋅ thf (26) on exposure to air. N,N'-Bis(2,6-dimethylphenyl)formamidinatoiodidosamarium(II) [Sm(XylForm)I(thf)3 ]n (28) was also prepared by direct reaction of Sm, iodine and XylFormH (mole ratio of I2 : XylFormH=1 : 2). All products have been identified by X-ray crystallography and all the trivalent complexes [Ln(Form)n I3-n ] (n=1 or 2) are stable to rearrangement.

Synthesis and functionalization of electron-deficient perfluoroalkyl porphyrin building blocks for supermolecular systems

Synthetic strategies for electron-deficient meso-perfluoroalkylporphyrins bearing diverse functional groups are described. Scalable and efficient syntheses for 5-triisopropylsilylethynyl-10,15,20-tris(heptafluoropropyl)porphyrin and 5-triisopropylsilylethynyl-10,20-bis(heptafluoropropyl)porphyrin that equip meso-ethynyl functional groups via the bilane route have been established, along with a refined route to [5,15-bis(heptafluoropropyl)porphinato]zinc(II). meso-Position halogenation of [5,15-bis(heptafluoropropyl)porphinato]zinc(II) was achieved by selective meso-nitration and subsequent reduction, diazonium salt formation, and iodination reactions. Computational data describe the low energy excited states of these chromophores and the electronic structural factors that control reactivity of these meso-perfluoroalkyl substituted porphyrin complexes. meso-Functionalized [5-triisopropylsilylethynyl-10,20-bis(heptafluoropropyl)porphinato]zinc(II) and [5-iodo-10,20-bis(heptafluoropropyl)porphinato]zinc(II) building blocks lay the foundation for the construction of highly conjugated multiporphyrin arrays that feature electronic structural properties important for the development of n-type materials and high potential photooxidants.

Selective Iodination Enables Anthocyanin Synthesis to Be More General.

The current synthesis routes of anthocyanins are relatively complicated, which significantly hinders their development. We optimized the method by introducing a selective iodination reaction and also established a general scheme for preparing anthocyanin diglycosides. This method allows anthocyanin synthesis to require fewer steps and costs. Based on this, we prepared four common anthocyanins and two anthocyanin diglucosides and measured their antioxidant and anti-insulin resistance activities.