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This minireview describes chemistry of hypervalent organoiodine triflates, which have received wide synthetic application as powerful electrophilic reagents and oxidants. The first representative of these compounds, μ-oxo-bis[(trifluoromethanesulfonato)(phenyl)iodine], was originally prepared and investigated in N. S. Zefirov's laboratory at Moscow State University in the early 1980s. This compound, now commonly known as Zefirov's reagent, is a useful reagent for the synthesis of various iodonium salts from the corresponding organic precursors. Recently, thermally stable and highly reactive triflates derived from cyclic hypervalent iodine compounds, benziodoxoles, have been reported and utilized in organic synthesis. The strongest iodine(V) oxidant, IBX-ditriflate, has been prepared from 2-iodoxybenzoic acid (IBX) and triflic acid. IBX-ditriflate can readily oxidize organic substrates that are generally resistant to oxidation.

Atmospheric iodine chemistry can significantly affect the atmospheric oxidation capacity in certain regions. In such processes, particle-phase organic iodine compounds (OICs) are key reservoir species in their loss processes. However, their presence and formation mechanism remain unclear, especially in continental regions. Using gas chromatography and time-of-flight mass spectrometry coupled with both electron capture negative ionization and electron impact sources, this study systematically identified unknown OICs in 2-year samples of ambient fine particulate matter (PM

Cyclic and acyclic diaryliodonium are synthesised by anodic oxidation of iodobiaryls and iodoarene/arene mixtures, respectively, in a simple undivided electrolysis cell in MeCN-HFIP-TfOH without any added electrolyte salts. This atom efficient process does not require chemical oxidants and generates no chemical waste. More than 30 cyclic and acyclic diaryliodonium salts with different substitution patterns were prepared in very good to excellent yields. The reaction was scaled-up to 10 mmol scale giving more than four grams of dibenzo[b,d]iodol-5-ium trifluoromethanesulfonate (>95%) in less than three hours. The solvent mixture of the large-scale experiment was recovered (>97%) and recycled several times without significant reduction in yield.

The results of studying the spectral, integral, and resource characteristics of gas-discharge plasma radiation on multicomponent mixtures (cadmium diiodide with helium and xenon atoms) are presented. The creation of a gasdischarge plasma and the excitation of the components of the working mixture were carried out by a pulse-periodic (pulse repetition rate of 18…20 kHz, pulse duration ~ 150 ns) barrier discharge. Radiation in the visible spectrum of exciplex molecules of cadmium monoiodide, cadmium atoms, xenon was detected. The regularities in changes in the emission characteristics of the plasma are established depending on the repetition rate of the pump pulses, the component and quantitative composition of the mixtures. Research data is of interest for creating a gas-discharge source that radiates simultaneously in the violet, green, red, and infrared spectral ranges.

For a very long time, frequent occurrences of biocrises have wreaked havoc on human beings, animals, and the environment. As a result, it is necessary to develop biocidal agents to destroy or neutralize active agents by releasing large amounts of strong biocides which are obtained upon detonation. Iodine is an efficient biocidal agent for bacteria, fungi, yeasts, viruses, spores, and protozoan parasites, and it is the sole element in the periodic table that can destroy microbes without contaminating the environment. Based on chemical biology, the mechanism of iodine as a bactericide may arise from oxidation and iodination reactions of cellular proteins and nucleic acids. However, because of the high vapor pressure causing elemental iodine to sublime readily at room temperature, it is inconvenient to use this material in its normal solid state directly as a biocidal agent under ambient conditions. Iodine-rich compounds where iodine is firmly bonded in molecules as a C-I or I-O moiety have been observed to be among the most promising energetic biocidal compounds. Gaseous products comprised of large amounts of iodine or iodine-containing components as strong biocides are released in the decomposition or explosion of iodine-rich compounds. Because of the detonation pressure, the iodine species are distributed over a large area greatly improving the efficacy of the system and requiring considerably less effort compared to traditional biocidal methods. The commercially available tetraiodomethane and tetraiodoethene, which possess superb iodine content also have the disadvantages of volatility, light sensitivity, and chemically reactivity, and therefore, are not suitable for use directly as biocidal agents. It is absolutely critical to synthesize new iodine-rich compounds with good thermal and chemical stabilities.In this Account, we describe our strategies for the syntheses of energetic iodine-rich compounds while maintaining the maximum iodine content with concomitant stability and routes for the synthesis of oxygen-containing iodine-rich compounds to improve the oxygen balance and achieve both high-energy and high-iodine content. In the other work, which involves cocrystals, iodine-containing polymers were also summarized. It is hoped that this Account will provide guidelines for the design and syntheses of new iodine-rich compounds and a route for the development of inexpensive, more efficient, and safer iodine-rich antibiological warfare agents of the future.

The review summarizes the data on the main chemical and physiological properties of iodine and its capability of complexation with natural and synthetic polymers. Iodine is the best known antiseptic used to prevent and treat microbial infections. Its unique capability of complexation with certain polymers opens wide opportunities for targeted and prolonged delivery to target organs. Polymeric complexes with iodine have another color, other morphology, a higher electrical conductivity, and higher biological activity as compared with initial polymers. The formation of \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\text{I}}_{3}^{ - }$$\end{document} and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\text{I}}_{5}^{ - }$$\end{document} ions is associated with iodine–polymer complexation. Iodine-containing biocompatible adhesive controlled-release formulations are designed as part of research into iodine–polymer complexes. The field is promising in terms of treating certain diseases because tolerance to iodine compounds does not usually develop in microbial cells.

Hypervalent (HV) iodine(III) compounds with fluorine-containing ligands (F, CF3, C6F5CO2, or CF3(CF2)8CO2 (n-C9F19CO2)) reacted, in the presence of iodine or copper salts, with the double bonds in ...

In order to achieve low-cost and high photoelectric conversion efficiency, emerging solar cell technologies have attracted significant attention. The non-toxic and environmentally stable silver bismuth iodine compounds are currently regarded as promising photovoltaic candidates. Herein, we report a new type rudorffite material AgBi3I10 featuring with edge-shared [AgI6] and [BiI6] and an optical band gap of 1.8 eV for solar cell application. A photoelectric conversion efficiency of 2.73% with good air stability under standard illumination test conditions in air can be achieved for a solar cell using AgBi3I10 in combination with a TiO2/Al2O3/NiO/carbon framework. This work highlights new direction for further development of materials for non-toxic and stable photovoltaic applications.

The oxidation of 3-aryl-1H-benzo[f]chromenes with Koser’s reagent in methanol afforded a series of benzoflavylium tosylates. This reaction is the first example of the use of polyvalent iodine compounds to access arene-condensed pyrylium salts.

Four solvent complexes of beryllium iodide were prepared by dissolving BeI2 in N,N-dimethyl formamide (DMF), pyridine (Pyr), N-methyl pyrrolidone (NMP) and 2,6-dimethyl pyridine (2,6-lutidine, Lut). Their crystal structures were established from single crystal X-ray diffraction. For [Be(DMF)4]I2 a new modification is reported (monoclinic, space group P21/c, a = 12.491(2), b = 11.593(2), c = 15.310(3) Å, β = 94.7073(6)°). In [Be(Pyr)4]I2 (monoclinic, space group C2/c, a = 17.8799(13), b = 7.6174(5), c = 18.2611(14) Å, β = 113.508(4)°) and [Be(NMP)4]I2 (orthorhombic, space group Pbca, a = 13.941(5), b = 15.754(3), c = 24.634(7) Å) homoleptic tetrahedral complex cations are formed, while the sterically demanding solvent ligand Lut yields a neutral complex with covalently bound iodine ligands [BeI2(Lut)2] (monoclinic, space group P21/c, a = 7.8492(9), b = 24.265(3), c = 27.037(3) Å, β = 97.076(3)°). Their electrochemical stability with respect to their application as beryllium electrolytes for deposition of beryllium from solution is discussed.

Several novel binaphthyl-based chiral hypervalent iodine(III) reagents have been prepared and structurally analyzed. Various asymmetric oxidative reactions were applied to evaluate the reactivities and stereoselectivities of those reagents. Moderate to excellent yields were observed, however, very low stereoselectivities were obtained. The NMR experiments indicate that these reagents are very easily hydrolyzed in either chloroform or DMSO solvents leading to limited stereoselectivities. It is concluded that the use of chiral ligands is an unsuccessful way to prepare efficient stereoselective iodine(III) reagents.

This paper presents our investigation on cesium and iodine revaporization from cesium iodide (CsI) deposits on stainless steel type 304L, which were initiated by boron and/or steam flow. A dedicated basic experimental facility with a thermal gradient tube (TGT) having a temperature range of 1000–400 K was used for simulating the phenomena. In the absence of boron, it was found that the initially deposited CsI at 850 K could be revaporized as CsI vapor/aerosol or reacted with the carrier gas and stainless steel (Cr2O3 layer) to form Cs2CrO4. The latter mechanism consequently released gaseous iodine that was later accumulated downstream. After introducing boron to the steam flow, a severe revaporization occurred. This, in addition to the revaporized CsI vapor/aerosol, was caused by cesium borate (Cs2B4O7 and CsB5O8) formation, which then largely released gaseous iodine that was capable of reaching the TGT outlet (

The mammalian lactoperoxidase system, consisting of lactoperoxidase and the H2O2‐producing enzyme duox, is our first line of defence against airborne microbes. This system catalyses the production of hypoiodite and hypoiodous acid in the presence of sufficient iodine. These products are highly efficient at destroying the H1N1 virus and the respiratory syncytial virus (RSV). Japan has not been affected as much as other nations during the COVID‐19 pandemic (death rate about 10% of the United States), and we think this is due to a diet high in iodine. With this in mind, we suggest four actions to prevent SARS‐CoV‐2 infections. First, health professionals should study the preventative effect of increasing iodine in the diets of the aged, institutionalized, diabetics andsmokers. Second, the recommended daily intake (RDI) for iodine should be significantly increased, to at least double, the current RDI. Governments should encourage the use and distribution of cheap iodized salts, kelp and seaweed. Third, more research should be done around the physiology and the protective effects of the lactoperoxidase system. Finally, the degradation products of the SARS‐CoV‐2 viral particle by hypoiodite and hypoiodous acid should be characterized; portions of the damaged particle are likely to elicit stronger immunity and better vaccines.

X-ray computed tomography (CT) imaging can produce three-dimensional and high-resolution anatomical images without invasion, which is extremely useful for disease diagnosis in the clinic. However, its applications are still severely limited by the intrinsic drawbacks of contrast media (mainly iodinated water-soluble molecules), such as rapid clearance, serious toxicity, inefficient targetability and poor sensitivity. Due to their high biocompatibility, flexibility in preparation and modification and simplicity for drug loading, organic nanoparticles (NPs), including liposomes, nanoemulsions, micelles, polymersomes, dendrimers, polymer conjugates and polymeric particles, have demonstrated tremendous potential for use in the efficient delivery of iodinated contrast media (ICMs). Herein, we comprehensively summarized the strategies and applications of organic NPs, especially polymer-based NPs, for the delivery of ICMs in CT imaging. We mainly focused on the use of polymeric nanoplatforms to prolong circulation time, reduce toxicity and enhance the targetability of ICMs. The emergence of some new technologies, such as theragnostic NPs and multimodal imaging and their clinical translations, are also discussed.

The reactivity of hydrogen peroxide and catalytic hydroiodic acid toward 3,6-dimethoxy-2-(cycloamino)anilines is tunable to give ring-fused benzimidazoles or 1,4,6,9-tetramethoxyphenazine in high yield. Mechanisms via a detected nitroso-intermediate are proposed for oxidative cyclization and the unexpected intermolecular displacement of the oxazine. An aqueous solution of molecular iodine is capable of the same transformations. Oxidative demethylation gave targeted benzimidazolequinones, including without cleavage of the incorporated oxetane.

Hypervalent iodine compounds formally feature expanded valence shells at iodine. These reagents are broadly used in synthetic chemistry due to the ability to participate in well-defined oxidation-reduction processes and because the ligand-exchange chemistry intrinsic to the hypervalent center allows hypervalent iodine compounds to be applied to a broad array of oxidative substrate functionalization reactions. We recently developed methods to generate these compounds from O

An efficient protocol for C–H condensation of hypervalent iodine compounds toward arenes in fluoroalcohols has been applied to the recyclable preparation of mesityl iodonium(III) salts. The electrophilicities of [hydroxy(tosyloxy)iodo]mesitylene (MesI(OH)OTs) and iodomesitylene diacetate (MesI(OAc)2) are suitably enhanced in 2,2,2-trifluoroethanol. A series of nucleophilic aromatic compounds react smoothly with MesI(OH)OTs and MesI(OAc)2 or in situ hypervalent iodine(III) species, generated from iodomesitylene, to provide the target mesityl iodonium(III) salts in good yields at room temperature with broad functional group tolerance. This C–H condensation strategy merits high para-regioselectivities during the diaryliodonium(III) salt formation, but the major limitation in the case of low-reactive aromatic substrates is byproduct formation resulting from the self-condensation of the nucleophilic mesitylene ring in MesI(OH)OTs and MesI(OAc)2.

An efficient and simple protocol for the synthesis of trifluoromethylated quinazolines has been described by I2-/KI-promoted oxidative C(sp3)-C(sp2) bond under the optimal oxidative cyclization reaction conditions. The required 2,2,2-trifluoro-N-benzyl-N'-arylacetimidamides are readily prepared from the corresponding acetimidoyl chlorides and benzylamines under a nucleophilic substitution reaction in the form of in situ. The merits of this protocol are the use of inexpensive molecular iodine, metal-free oxidative coupling and good to excellent yields.

Iodine is an essential micronutrient for human health; phytofortification is a means of improving humans’ nutritional iodine status. However, knowledge of iodine uptake and translocation in plants remains limited. In this paper, plant uptake mechanisms were assessed in short-term experiments (24 h) using labelled radioisotopes; the speciation of iodine present in apoplastic and symplastic root solutions was determined by (HPLC)-ICP-QQQ-MS. Iodine storage was investigated in spinach (Spinacia oleracea L.) treated with I− and IO3−. Finally, translocation through the phloem to younger leaves was also investigated using a radioiodine (129I−) label. During uptake, spinach roots demonstrated the ability to reduce IO3− to I−. Once absorbed, iodine was present as org-I or I− with significantly greater concentrations in the apoplast than the symplast. Plants were shown to absorb similar concentrations of iodine applied as I− or IO3−, via the roots, grown in an inert growth substrate. We found that whilst leaves were capable of absorbing radioactively labelled iodine applied to a single leaf, less than 2% was transferred through the phloem to younger leaves. In this paper, we show that iodine uptake is predominantly passive (approximately two-thirds of total uptake); however, I- can be absorbed actively through the symplast. Spinach leaves can absorb iodine via foliar fertilisation, but translocation is severely limited. As such, foliar application is unlikely to significantly increase the iodine content, via phloem translocation, of fruits, grains or tubers.

The detection of wastewater impact on stream chemistry is often hindered by high background concentrations of ubiquitous solutes. In the present study we tested the applicability of artificial sweeteners (AS) and iodinated X-ray contrast media (ICM) as tracers to detect this impact by examining wastewater treatment plant (WWTP) effluents and surface water samples. The developed direct injection LC-MS/MS method enabled the detection of these anthropogenic micropollutants in aqueous samples down to trace level concentrations. The 2-h-composite sampling of WWTP effluent revealed fluctuating ICM concentrations between and within days with highest concentrations at the end of the week. Diatrizoic acid (DTZ) and iopromide (IOP) were the predominant ICM with concentrations up to 7 μg/L. Concentrations of the AS acesulfame (ACE) fluctuated between 0.5 μg/L and 1 μg/L. Concentrations of AS and ICM in surface water were both associated with wastewater impact. DTZ contamination was more widespread whereas some sampling points exhibited a more pronounced contamination with non-ionic ICM. Surface water was frequently contaminated with AS. Particularly ACE was detected in every surface water sample indicating that it is chemically stable and that inputs to the aquatic environment via WWTP effluents are widespread. The broad application of ACE as food additive enables its application as a tracer throughout Germany. Furthermore, the developed LC-MS/MS method enables rapid detection of ACE down to the low ng/L-range. Nonetheless, DTZ or IOP could be used in addition to ACE to verify anthropogenic influences on natural waters.

1,3-Diamines are an important class of compounds that are broadly found in natural products and are also widely used as building blocks in organic synthesis. Although the intramolecular C-H amination of N-alkylsulfamide derivatives is a reliable method for the construction of 1,3-diamine structures, the majority of these methods involve the use of a transition-metal catalyst. We herein report on a new transition-metal-free method using tert-butyl hypoiodite (t-BuOI) or N-iodosuccinimide (NIS), enabling secondary non-benzylic and tertiary C-H amination reactions to proceed. The cyclic sulfamide products can be easily transformed into 1,3-diamines. Mechanistic investigations revealed that amination reactions using t-BuOI or NIS each proceed via different pathways.

Iodine-based contrasting agents for computed tomography (CT) have been used for decades in medicine. Agents like Lugol's iodine enhance the contrasts between soft tissues and mineralized (skeletal) tissues. Because a recent study on extant avian heads showed that iodine-ethanol (I2 E) is a better contrast enhancer overall than the standard Lugol's iodine, here, we tested if I2 E could also enhance the CT contrasts of two fossilized skeletal tissues: bone and calcified cartilage. For this, we used a partial ankle joint from an extinct pheasant from the Late Miocene of Northwest China (Linxia Basin). The pre-staining CT scans showed no microstructural details of the sample. After being immersed into a solution of 1% I2 E for 8 days and scanned a second time, the contrasts were drastically enhanced between the mineralized tissues (bony trabeculae and calcified cartilage) and the sediments and minerals inside vascular spaces. After three other staining-scanning cycles in 2%, 3%, and 6% I2 E solutions, the best contrasts were obtained after immersion in 6% I2 E for 7 days. Energy Dispersive Spectroscopy showed that iodine was preferentially absorbed by the mineralized tissues and the minerals in the vascular spaces, but not by the sediments. This method not only effectively increased the contrasts of two different fossilized skeletal tissues, it was also non-destructive and reversible because part of the fossil was successfully de-stained after a few days in pure ethanol. These preliminary results indicate that iodine-ethanol has the potential to be used widely in vertebrate paleontology to improve CT imaging of fossilized tissues.

The heat formation of 33 molecules for the iodine compounds were performed using the functional density theory (DFT) (B3LYP, M06-2X and WB97XD), and the basis sets (6-311G (d, p) and cc-pVQZ + d). The best agreement with experimental data was achieved by using B3LYP/cc-pVQZ+d, WB97XD/6-311G (d,p) and MP2/6-311G (d,p).

Objectives Dual-energy computed tomography allows for an accurate and reliable quantification of iodine. However, data on physiological distribution of iodine concentration (IC) is still sparse. This study aims to establish guidance for IC in abdominal organs and important anatomical landmarks using a large cohort of individuals without radiological tumor burden. Methods Five hundred seventy-one oncologic, portal venous phase dual-layer spectral detector CT studies of the chest and abdomen without tumor burden at time point of imaging confirmed by > 3-month follow-up were included. ROI were placed in parenchymatous organs (n = 25), lymph nodes (n = 6), and vessels (n = 3) with a minimum of two measurements per landmark. ROI were placed on conventional images and pasted to iodine maps to retrieve absolute IC. Normalization to the abdominal aorta was conducted to obtain iodine perfusion ratios. Bivariate regression analysis, t tests, and ANOVA with Tukey-Kramer post hoc test were used for statistical analysis. Results Absolute IC showed a broad scatter and varied with body mass index, between different age groups and between the sexes in parenchymatous organs, lymph nodes, and vessels (range 0.0 ± 0.0 mg/ml–6.6 ± 1.3 mg/ml). Unlike absolute IC, iodine perfusion ratios did not show dependency on body mass index; however, significant differences between the sexes and age groups persisted, showing a tendency towards decreased perfusion ratios in elderly patients (e.g., liver 18–44 years/≥ 64 years: 0.50 ± 0.11/0.43 ± 0.10, p ≤ 0.05). Conclusions Distribution of IC obtained from a large-scale cohort is provided. As significant differences between sexes and age groups were found, this should be taken into account when obtaining quantitative iodine concentrations and applying iodine thresholds. Key Points • Absolute iodine concentration showed a broad variation and differed between body mass index, age groups, and between the sexes in parenchymatous organs, lymph nodes, and vessels. • The iodine perfusion ratios did not show dependency on body mass index while significant differences between sexes and age groups persisted. • Provided guidance values may serve as reference when aiming to differentiate healthy and abnormal tissue based on iodine perfusion ratios.

Toxic and odorous iodinated disinfection byproducts (I-DBPs) could form in the chemical oxidation of iodine-containing water. A critical step for controlling the hazardous I-DBPs is to convert the iodine species into stable and harmless iodate (IO3−) while inhibiting the accumulation of highly reactive hypoiodous acid (HOI). Herein, the oxidation of I− and HOI with ferrate was investigated, and the formation profile of HOI was determined based on 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) coloring method through a stopped-flow spectrophotometer. The second-order rate constants (kapp) of ferrate with HOI decreased from 1.6 × 105 M−1s−1 to 8.3 × 102 M−1s−1 as the solution pH varied from 5.3 to 10.3, which were 7.5, 7.2 and 13.8 times higher than that of ferrate with I− at pH 6.0, 7.0 and 8.0, respectively. Compared with other oxidants such as ozone, hypochlorous acid, chloramine and potassium permanganate, ferrate would swiftly oxidize HOI formed in the I− oxidation process. For the ferrate oxidation of I-containing water, HOI was swiftly oxidized to IO3− from pH 5.0 to 9.0. Phosphate buffer promoted the oxidation of I− while inhibited the oxidation of HOI with ferrate. When 5 mgC/L of humic acids (HA) existed in the solution, no formation of iodoform and monoiodoacetic acid (MIAA) was observed in the oxidation of iodide (20 μM) with ferrate (from 10 μM to 80 μM). These results suggested that ferrate oxidation could be an effective method for the control of I-DBPs in iodine-containing water treatment.

In this work, we have investigated the crystalline-size dependence of optical absorption and photoluminescence emission of CH3NH3PbI3 films, which is necessary to identify the potential practical applications of the gadgets based on perovskite films. This study was carried out at low temperatures to minimize the extra complexity induced by thermal effects. The purpose was to clarify the origin of the dual emission peak previously reported in the literature. We found that the grain size is responsible for the appearance or disappearance of this dual emission on CH3NH3PbI3 at low temperatures, whereas we have inferred that the thickness of the perovskite layer is a much more important factor than the size of the grains in the location of the energy of the band gap. Moreover, the increase in the grain size allows slowing down the phase transition. Additionally, we evidence a decrease in the effective Rydberg energy of the exciton in several samples, from 23–25 meV at 7 K to 12–13 meV at 165 K, by fitting to Elliott–Toyozawa theory. We have extracted other important physical parameters of perovskites from the photoluminescence-data deconvolution, such as the band gap, exciton–phonon interaction, and exciton binding energy. A new phase transition at 45.5 K was determined by the temperature dependence of full width at half-maximum and the integrated intensity of the photoluminescence, and it was confirmed by the radiative lifetime obtained from the time-resolved photoluminescence emission by means of time-correlated single-photon counting at different temperatures, excitation fluencies, and emission energies.

Background and Purpose— The aim of the study was to investigate the utility of iodine contrast agent leakage (the iodine sign) analyzed by Gemstone spectral imaging in early hematoma formation compared with that of the spot sign for predicting early hematoma expansion (HE) and poor functional outcomes. Methods— From 2014 to 2017, 91 patients with spontaneous intracerebral hemorrhage who underwent spectral computed tomography angiography within 6 hours of spontaneous intracerebral hemorrhage onset were prospectively included in our study. We defined a positive iodine sign as tiny enhancing foci within the hematoma on Gemstone spectral imaging and an iodine concentration inside the foci of >7.82 (100 µg/mL). Univariate and multivariate logistical regression analyses were performed to assess risk factors for HE, and the predictive value of HE was analyzed. Results— Positive spot and iodine signs were present in 38.5% (35/91) and 57.1% (52/91) of the patients, respectively. Using multivariate analysis, the iodine sign independently predicted HE (odds ratio, 53.67; 95% CI, 11.88–242.42; P 2 =29.97; P Conclusions— The iodine sign is a reliable and sensitive marker for predicting HE and poor functional outcomes. Clinical Trial Registration— URL: https://www.clinicaltrials.gov . Unique identifier: NCT02625948.

Montmorillonite (Mt) is the major clay mineral of bentonite, which is the candidate buffer material in the engineered barrier system for geological disposal of high level waste (HLW). The alteration of Mt due to its interaction with carbon steel (overpack) can produce Fe–Mt. In order to understand the basic properties of Fe–Mt, the sorption studies using Eu(III) are reported here. For this, Fe(III)–Mt was prepared by conventional cation exchange method using FeCl3 with Na–Mt. The obtained Fe(III)–Mt was then reduced to Fe(II)–Mt using ascorbic acid. Both the samples were characterized based on their X-ray diffraction, Fourier transform infrared spectra, cation exchange capacity and specific surface area. The batch sorption studies of Eu(III) were conducted for both Fe(III)–Mt and Fe(II)–Mt as a function of pH (3–10), ionic strength (0.001 M–1 M) and Eu(III) concentration (10−8–10−3 M). The distribution coefficient (Kd) was found to be higher for Fe(III)–Mt compared to Fe(II)–Mt and Na–Mt. The sudden increase in sorption in the pH range 4.5–6 and remaining constant beyond it indicates ion exchange mechanism at pH4.5. This is further corroborated by ionic strength dependent sorption data which shows decrease in sorption capacity of Fe–Mt with increasing ionic strength at low pH, but remaining more or less unchanged at higher pH. Eu(III) adsorption isotherm on Fe–Mt increased linearly with [Eu(III)] reaching saturation at 10−5 M and 10−4 M for Fe(III)–Mt and Fe(II)–Mt, respectively. The amount of iron released from Fe–Mt and Fe(II)/Fetotal during sorption were estimated to understand the effect on Eu(III) sorption behaviour by release of interlayer iron in Fe–Mt.

Optimal conditions for the microextraction concentration and spectrophotometric determination of iodine (I, V, VII) forms as ionic associates of triiodide anions with the cation of astrazone brilliant red 4G dye have been found. A new procedure for the spectrophotometric determination of the total iodine content in drinking and mineral waters with the detection limit of 8.9 μg/dm3 was developed and tested. This procedure is combined with microextraction concentration and meets the requirements of “green” chemistry.

This article presents an overview of recent advancements in the field of uranium chemistry, paying special attention to the preparation of starting materials and to the chemistry of uranium halides in liquid ammonia. Where suitable, insights into the chemistry of thorium are also presented. Herein, we report upon the crystal structures of several ammine complexes as well as their deprotonation products. Specific examples of hydrolysis products in liquid ammonia are showcased. Additionally, advancements in the preparation of uranium cyanides are presented.

This work investigated impacts of iodide (I−) on the transformation of the widely used phenolic preservative methylparaben (MeP) as well as 11 other phenolic compounds by potassium permanganate (KMnO4). It was found that KMnO4 showed a low reactivity towards MeP in the absence of I− with apparent second-order rate constants (kapp) ranging from 0.065 ± 0.0071 to 1.0 ± 0.1 M−1s−1 over the pH range of 5–9. The presence of I− remarkably enhanced the transformation rates of MeP by KMnO4 via the contribution of hypoiodous acid (HOI) in situ formed, which displayed several orders of magnitude higher reactivity towards MeP than KMnO4. This enhancing effect of I− was greatly influenced by solution conditions (e.g., I− or KMnO4 concentration or pH), which could be well simulated by a kinetic model involving competition reactions (i.e., KMnO4 with I−, KMnO4 with MeP, HOI with KMnO4, and HOI with MeP). Similar enhancing effect of I− on the transformation kinetics of 5 other selected phenols (i.e., p-hydroxybenzoic acid, phenol, and bromophenols) at pH 7 was also observed, but not in the cases of bisphenol A, triclosan, 4-n-nonylphenol, and cresols. This discrepancy could be well explained by the relative reactivity of KMnO4 towards phenols vs I−. Liquid chromatography-tandem mass spectrometry analysis showed that iodinated aromatic products and/or iodinated quinone-like product were generated in the cases where I− enhancing effect was observed. Evolution of iodinated aromatic products generated from MeP (10 μM) treated by KMnO4 (50-150 μM) in the presence of I− (5-15 μM) suggested that higher I− or moderate KMnO4 concentration or neutral pH promoted their formation. A similar enhancing effect of I− (1 μM) on the transformation of MeP (1 μM) by KMnO4 (12.6 μM) and formation of iodinated aromatic products were also observed in natural water. This work demonstrates an important role of I− in the transformation kinetics and product formation of phenolic compounds by KMnO4, which has great implications for future applications of KMnO4 in treatment of I−-containing water.