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Ice has been suggested to have played a significant role in the origin of life partly owing to its ability to concentrate organic molecules and promote reaction efficiency. However, the techniques for studying organic molecules in ice are absorption‐based, which limits the sensitivity of measurements. Here we introduce an emission‐based method to study organic molecules in water ice: the phosphorescence displays high sensitivity depending on the hydration state of an organic salt probe, acridinium iodide (ADI). The designed ADI aqueous system exhibits phosphorescence that can be severely perturbed when the temperature is higher than 110 K at a concentration of the order of 10−5 M, indicating changes in hydration for ADI. Using the ADI phosphorescent probe, it is found that the microstructures of water ice, i.e., crystalline vs. glassy, can be strongly dictated by a trace amount (as low as 10−5 M) of water‐soluble organic molecules. Consistent with cryoSEM images and temperature‐dependent Raman spectral data, the ADI is dehydrated in more crystalline ice and hydrated in more glassy ice. The current investigation serves as a starting point for using more sensitive spectroscopic techniques for studying water‐organics interactions at a much lower concentration and wider temperature range. [ABSTRACT FROM AUTHOR]

We present a novel deoxygenation method for heterocyclic Noxides utilizing iodide as a catalyst. Iodide acts as a reducing catalyst that is regenerated by formic acid, which also serves as a Brønsted activator and solvent. The method demonstrates high efficiency and excellent selectivity in the reduction of a variety of heterocyclic N-oxides and tertiary amines. Our computational DFT investigation revealed that the reduction mechanism entails a direct interaction between iodide and the oxygen of the N-oxide within a Mg2+/formic acid framework, resulting in the formation of the N-heterocycle and the release of a hypoiodite unit. Additionally, a molecular mechanism for the regeneration of iodide from hypoiodite, facilitated by formic acid, is suggested. This method provides an environmentally friendly approach for the deoxygenation of N-oxides and related species. [ABSTRACT FROM AUTHOR]

Thyroid follicular tumours may take up iodide via the sodium‐iodide symporter. Knowledge of iodide uptake could then allow treatment with I‐131 in dogs with high‐risk tumours. The objective of this study was to determine the relationship between clinically detectable iodide uptake (as determined by scintigraphy and/or thyroxine concentrations) and sodium iodide symporter immunohistochemical labelling on histologically fixed thyroid tumours. Nineteen dogs were identified who were diagnosed with thyroid carcinoma and underwent surgery from November 2017 to July 2021. All had recorded thyroid hormone concentrations and were hyperthyroid and/or underwent preoperative nuclear imaging using planar scintigraphy (technetium‐99m or I‐123), or I‐124 PET‐CT. All dogs subsequently underwent surgery to remove the thyroid mass. Twenty‐two tumours were submitted for histopathologic analysis immediately following surgery, which confirmed a diagnosis of thyroid carcinoma for each tumour. Images and/or thyroid hormone concentrations were reviewed for the included cases, and tumours were sorted into an avid/functional group (group 1) and a non‐avid/functional group (group 2). The tumour tissues were re‐examined histologically using sodium iodide symporter (NIS) immunohistochemistry (IHC). Group 1 contained 15 avid/functional tumours. Twelve of these tumours had membranous NIS IHC labelling. Group 2 contained 7 non‐avid tumours. One of these tumours had membranous NIS IHC labelling. This resulted in an overall sensitivity and specificity for identification of avid/functional tumours with membranous NIS of 80.0% and 85.7%, respectively. NIS IHC may predict ion trapping in canine follicular thyroid tumours. Further studies using iodide‐based imaging are warranted to better determine the clinical utility of this diagnostic modality. [ABSTRACT FROM AUTHOR]

Structures of pyridinium-based ionic liquids containing 1-methylpyridinium [MP]+, 1-ethylpyridinium [EP]+ and 1-propylpyridinium [PP]+ with halide anions (X) where X = Cl−, Br− and I− were studied using density functional theory and the most stable structures of these ionic liquids were compared. Then electronic and structural properties were extracted for the desired liquids. The results show that in the most stable conformers, in these ILs, Cl− and Br− anions prefer to be placed almost in the plane of the pyridinium ring, while I− prefers the position almost vertical to the plane of the pyridinium ring. In order to investigate the hydrogen bonds between molecules by atoms in molecules (AIMs) and natural bonding orbital (NBO) were studied. The calculated thermodynamic functions show that the interaction of the cation–anion pair in ionic liquids containing Cl− and Br− anions is greater than I−, and these interactions decrease with the increase in the atomic weight of the halide. Molecular orbital theory has also been used to calculate quantities related to their stability and activity. Also, ionic liquids containing iodine anion have a high dipole moment compared to ionic liquids containing chloride and bromide. The results of this study show that the properties of Any ILs can be controlled by choosing the appropriate anions. [ABSTRACT FROM AUTHOR]

Exclusive C-donating ligands are rarely used with kinetically labile heavier alkaline earths (Ca, Sr, Ba). We report herein the aptitude of a combination of NHC with fluorenyl connected by a flexible –(CH2)2– linker as a ligand support for heteroleptic Ca– and Sr–N(SiMe3)2 and iodides. The Ca–N(SiMe3)2 complex even catalyzes the intramolecular hydroamination of aminoalkenes to showcase the effectiveness of this ligand framework. [ABSTRACT FROM AUTHOR]

Low‐dimensional hybrid bismuth halide perovskites have recently emerged as a class of non‐toxic alternative to lead perovskites with promising optoelectronic properties. Here, we report three hybrid bismuth(III)‐iodides: 0‐D (H2DAC)2Bi2I10 ⋅ 6H2O (H2DAC_Bi_I), 0‐D (H2DAF)4Bi2I10 ⋅ 2I3 ⋅ 2I ⋅ 6H2O (H2DAF_Bi_I), and 1‐D (H2DAP)BiI5 (H2DAP_Bi_I) (where H2DAC=trans‐1,4‐diammoniumcyclohexane; H2DAF=2,7‐diammoniumfluorene and H2DAP=1,5‐diammoniumpentane). Their synthesis, single‐crystal X‐ray structures, and photophysical properties are reported. The first two compounds comprise edge‐sharing [Bi2I10]4− dimers, while the last compound has cis‐corner‐sharing 1‐D chains of [BiI6]3− octahedra. Intercalation of triiodide (I3−) and iodide (I−) ions enhance electronic coupling between the [Bi2I10]4− of H2DAF_Bi_I, leading to enhanced optical absorption, compared to H2DAC_Bi_I which lacks such intercalants. Furthermore, calorimetric and variable temperature X‐ray diffraction measurements suggest a centrosymmetric to non‐centrosymmetric phase transition (monoclinic P212121↔orthorhombic Pnma) of H2DAP_Bi_I at 448 K (in heating step) and at 443 K (in cooling step). [ABSTRACT FROM AUTHOR]

At inflammatory sites, immune cells generate oxidants including H₂O₂. Myeloperoxidase (MPO), released by activated leukocytes employs H₂O₂ and halide/pseudohalides to form hypohalous acids that mediate pathogen killing. Hypochlorous acid (HOCl) is a major species formed. Excessive or misplaced HOCl formation damages host tissues with this linked to multiple inflammatory diseases. Previously (Redox Biology , 2020, 28, 101331) we reported that iodide (I⁻) modulates MPO-mediated protein damage by decreasing HOCl generation with concomitant hypoiodous acid (HOI) formation. HOI may however impact on protein structure, so in this study we examined whether and how HOI, from peroxidase/H₂O₂/I⁻ systems ± Cl⁻, modifies proteins. Experiments employed MPO and lactoperoxidase (LPO) and multiple proteins (serum albumins, anastellin), with both chemical (intact protein and peptide mass mapping, LC-MS) and structural (SDS-PAGE) changes assessed. LC-MS analyses revealed dose-dependent iodination of anastellin and albumins by LPO/H 2 O 2 with increasing I⁻. Incubation of BSA with MPO/H 2 O 2 /Cl⁻ revealed modest chlorination (Tyr286, Tyr475, ∼4 %) and Met modification. Lower levels of these species, and extensive iodination at specific Tyr and His residues (>20 % modification with ≥10 μM I⁻) were detected with increasing I⁻. Anastellin dimerization was inhibited by increasing I⁻, but less marked changes were observed with albumins. These data confirm that I⁻ competes with Cl⁻ for MPO and is an efficient HOCl scavenger. These processes decrease protein chlorination and oxidation, but result in extensive iodination. This is consistent with published data on the presence of iodinated Tyr on neutrophil proteins. The biological implications of protein iodination relative to chlorination require further clarification. [Display omitted] • Peroxidases, such as myeloperoxidase (MPO) damage proteins as sites of inflammation. • Iodide (I−) modulates MPO-induced protein damage and inhibits cross-linking. • Low I− levels cause a dramatic switch from methionine to tyrosine (Tyr) modification. • Hypoiodous acid (HOI) exposure results in selective Tyr and His iodination. • HOI induces only minor gross structural changes but enhances protein hydrophobicity. [ABSTRACT FROM AUTHOR]

The transient electron donor–acceptor (EDA) complex has been an emerging area in the photoinduced organic synthesis field, generating radicals without exogenous transition‐metal or organic dye‐based photoredox catalysts. The catalytic platform to form suitable photoactive EDA complexes for photochemical reduction reactions remains underdeveloped. Herein, a general photoinduced reductive alkylation via the EDA complex strategy is described. A simple yet multifunctional system, triphenylphosphine and iodide salt, promotes the photoinduced decarboxylative hydroalkylation, and reductive defluorinative decarboxylative alkylation of trifluoromethyl alkenes, to access trifluoromethyl alkanes and gem‐difluoroalkenes. Moreover, decarboxylative hydroalkylation can be applied to more kinds of electron‐deficient alkenes as a general Giese addition reaction. [ABSTRACT FROM AUTHOR]

The reaction of 2‐thioxoimidazolidin‐4‐one (thiohydantoin) with aliphatic, aromatic and heteroaromatic α‐iodomethylketones has been investigated in the absence of bases or catalysts. The reaction proceeds as N‐alkylation with subsequent intramolecular dehydrative cyclization. A series of new mono‐ and fused bicyclic iodide and triiodide salts was obtained based on the 5‐oxo‐2‐thioxoimidazolidin‐1‐ium and imidazo[2,1‐b]thiazolium cations. The observed regioselectivity has been rationalized and the mechanism was proposed. [ABSTRACT FROM AUTHOR]

Halide solid electrolytes (SEs) have attracted significant attention due to their competitive ionic conductivity and good electrochemical stability. Among typical halide SEs (chlorides, bromides, and iodides), substantial efforts have been dedicated to chlorides or bromides, with iodide SEs receiving less attention. Nevertheless, compared with chlorides or bromides, iodides have both a softer Li sublattice and lower reduction limit, which enable iodides to possess potentially high ionic conductivity and intrinsic anti‐reduction stability, respectively. Herein, we report a new series of iodide SEs: LixYI3+x (x=2, 3, 4, or 9). Through synchrotron X‐ray/neutron diffraction characterizations and theoretical calculations, we revealed that the LixYI3+x SEs belong to the high‐symmetry cubic structure, and can accommodate abundant vacancies. By manipulating the defects in the iodide structure, balanced Li‐ion concentration and generated vacancies enables an optimized ionic conductivity of 1.04 × 10−3 S cm−1 at 25 °C for Li4YI7. Additionally, the promising Li‐metal compatibility of Li4YI7 is demonstrated via electrochemical characterizations (particularly all‐solid‐state Li‐S batteries) combined with interface molecular dynamics simulations. Our study on iodide SEs provides deep insights into the relation between high‐symmetry halide structures and ionic conduction, which can inspire future efforts to revitalize halide SEs. [ABSTRACT FROM AUTHOR]

Halide solid electrolytes (SEs) have attracted significant attention due to their competitive ionic conductivity and good electrochemical stability. Among typical halide SEs (chlorides, bromides, and iodides), substantial efforts have been dedicated to chlorides or bromides, with iodide SEs receiving less attention. Nevertheless, compared with chlorides or bromides, iodides have both a softer Li sublattice and lower reduction limit, which enable iodides to possess potentially high ionic conductivity and intrinsic anti‐reduction stability, respectively. Herein, we report a new series of iodide SEs: LixYI3+x (x=2, 3, 4, or 9). Through synchrotron X‐ray/neutron diffraction characterizations and theoretical calculations, we revealed that the LixYI3+x SEs belong to the high‐symmetry cubic structure, and can accommodate abundant vacancies. By manipulating the defects in the iodide structure, balanced Li‐ion concentration and generated vacancies enables an optimized ionic conductivity of 1.04 × 10−3 S cm−1 at 25 °C for Li4YI7. Additionally, the promising Li‐metal compatibility of Li4YI7 is demonstrated via electrochemical characterizations (particularly all‐solid‐state Li‐S batteries) combined with interface molecular dynamics simulations. Our study on iodide SEs provides deep insights into the relation between high‐symmetry halide structures and ionic conduction, which can inspire future efforts to revitalize halide SEs. [ABSTRACT FROM AUTHOR]

Due to its widespread use in agriculture, atrazine has entered aquatic environments and thus poses potential risks to public health. Therefore, researchers have done many studies to remove it. Advanced reduction process (ARP) is an emerging technology for degrading organic contaminants from aqueous solutions. This study was aimed at evaluating the degradation of atrazine via sulfite/iodide/UV process. The best performance (96% of atrazine degradation) was observed in the neutral pH at 60 min of reaction time, with atrazine concentration of 10 mg/L and concentration of sulfite and iodide of 1 mM. The kinetic study revealed that the removal of atrazine was matched with the pseudo-first-order model. Results have shown that reduction induced by e aq - and direct photolysis dominated the degradation of atrazine. The presence of anions ( Cl - , CO 3 2 - and SO 4 2 - ) did not have a significant effect on the degradation efficiency. In optimal conditions, COD and TOC removal efficiency were obtained at 32% and 4%, respectively. Atrazine degradation intermediates were generated by de-chlorination, hydroxylation, de-alkylation, and oxidation reactions. Overall, this research illustrated that Sulfite/iodide/UV process could be a promising approach for atrazine removal and similar contaminants from aqueous solutions. [ABSTRACT FROM AUTHOR]

Two compounds, (S)-8-{[(tert-butyldimethylsilyl)oxy]methyl|-1-[(2,2,4,6,7-pentamethyl-2,3-dihydrobenzofuran-5-yl)sulfonyl]-1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidin-1-ium trifluoromethanesulfonate, C27H46N3O4SSi+⋅-CF3O3S-, (1) and (S)-8-(iodomethyl)-1-tosyl-1,3,4,6,7,8-hexahydro-2#-pyri-mido[1,2-α]pyrimidin-1-ium iodide, C15H21IN3O2S⋅+I-, (2), have been synthesized and characterized. They are bicyclic guanidinium salts and were synthesized from N-(tert-butoxycarbonyl)-L-methionine (Boc-L-Met-OH). The guanidine is protected by a 2,2,4,6,7-pentamethyldihydrobenzofuran-5-sulfonyl (Pbf, 1) or a tosyl (2) group. In the crystals of both compounds, the guanidinium group is almost planar and the N-H forms an intramolecular hydrogen bond in a six-membered ring to the oxygen atom of the sulfonamide protecting group. [ABSTRACT FROM AUTHOR]

We performed a systematic review and meta-analysis to evaluate the accuracy of screening cervical cancer tests as alternative standalone methods. The combined estimates of sensitivity of visual inspection with acetic acid, visual inspection with lugol's iodine, conventional pap smear, liquid-based cytology, High risk HPV testing by clinician, High risk HPV testing by self- sampling, cervicography were 64%, 80%, 55%, 70%, 70% and 67% respectively; the combine values of specificity of these screening strategies were 88%, 88%, 96%, 59%, 94%, and 95% respectively. Our findings draw attention to an attractive opinion to facilitate the collection of specimens for DNA HPV by patients in settings where they don't have access to a regular screening programs. [ABSTRACT FROM AUTHOR]

First-principles calculations are carried out to investigate the effect of pressure (up to 40 GPa) on electronic, optical and elastic properties of the scintillator material calcium iodide, CaI2, by using Perdew–Burke–Ernzerh of generalized gradient approximation (PBE-GGA). The electronic band structure reveals an indirect band gap of 3.89 eV and a direct band gap of 4.35 eV for zero pressure. We have also calculated the pressure dependence of optical properties. The elastic constants and elastic moduli increase nonlinearly with pressure. Decreasing Pugh's ratio and increasing hardness with pressure indicate a cross-over from ductile to brittle nature at 5 GPa. Analyses of elastic properties show that CaI2 is mechanically stable up to the applied pressure of 40 GPa. The calculated light yield increases linearly with pressure yielding a pressure coefficient of 1327 ph/MeV per GPa due to the decreasing band gap. Light yield increases as much as 62% at 40 GPa. [ABSTRACT FROM AUTHOR]

The salt metathesis reactions of equimolar amounts of potassium carbazolide Bu4tCarbK (Bu4tCarb is 1,3,6,8-tetra-tert-butylcarbazolyl) with solvent-free rare-earth metal iodides LnI3 (Ln = Y, Dy) in toluene at 100 °C afforded the corresponding half-sandwich carbazolyl iodide complexes [(Bu4tCarb)Ln(μ2-I)2]3. The X-ray diffraction analysis showed that the yttrium compound has a cyclic trinuclear structure that is formed through μ2-bridging iodide ligands connecting Y3+ cations. The metal atom is coordinated by the carbazolyl ligand in a η5 fashion. Under similar conditions, the salt metathesis reaction of Bu4tCarbK with DyI3(THF)3.5 gave the monomeric half-sandwich carbazolyl iodide complex (Bu4tCarb)DyI2(THF)2. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐sulfur (Zn‐S) batteries show great potential for unlocking high energy and safety aqueous batteries. Yet, the sluggish kinetic and poor redox reversibility of the sulfur conversion reaction in aqueous solution challenge the development of Zn‐S batteries. Here, we fabricate a high‐performance Zn‐S battery using highly water‐soluble ZnI2 as an effective catalyst. In situ experimental characterizations and theoretical calculations reveal that the strong interaction between I− and the ZnS nanoparticles (discharge product) leads to the atomic rearrangement of ZnS, weakening the Zn‐S bonding, and thus facilitating the electrochemical oxidation reaction of ZnS to S. The aqueous Zn‐S battery exhibited a high energy density of 742 Wh kg(sulfur)−1 at the power density of 210.8 W kg(sulfur)−1 and good cycling stability over 550 cycles. Our findings provide new insights about the iodide catalytic effect for cathode conversion reaction in Zn‐S batteries, which is conducive to promoting the future development of high‐performance aqueous batteries. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐sulfur (Zn‐S) batteries show great potential for unlocking high energy and safety aqueous batteries. Yet, the sluggish kinetic and poor redox reversibility of the sulfur conversion reaction in aqueous solution challenge the development of Zn‐S batteries. Here, we fabricate a high‐performance Zn‐S battery using highly water‐soluble ZnI2 as an effective catalyst. In situ experimental characterizations and theoretical calculations reveal that the strong interaction between I− and the ZnS nanoparticles (discharge product) leads to the atomic rearrangement of ZnS, weakening the Zn‐S bonding, and thus facilitating the electrochemical oxidation reaction of ZnS to S. The aqueous Zn‐S battery exhibited a high energy density of 742 Wh kg(sulfur)−1 at the power density of 210.8 W kg(sulfur)−1 and good cycling stability over 550 cycles. Our findings provide new insights about the iodide catalytic effect for cathode conversion reaction in Zn‐S batteries, which is conducive to promoting the future development of high‐performance aqueous batteries. [ABSTRACT FROM AUTHOR]

Two-dimensional tin(II) halide perovskites stand as an environmentally benign alternative to Pb(II) halide perovskites. However, they are often challenging to make due to the oxidation of Sn(II) ion to more stable Sn(IV) ion. Here we report hybrid tin bromide and iodide perovskites: (1,4-BDA)Sn(IV)Br6 and (1,4-BDA)Sn(II)X4 (where X = Br, I; 1,4-BDA = 1,4-diammoniumbutane) with 0D and 2D structures, respectively. Their synthesis, structural characterization and photophysical properties are reported. They show bandgaps in the 1.94–2.70 eV range. [ABSTRACT FROM AUTHOR]

α‐Aryl substituted nitroalkanes are valuable synthetic building blocks that can be easily converted into α‐aryl substituted aldehydes, ketones, carboxylic acids, as well as amines. Herein, an efficient Cu/oxalamide‐catalyzed coupling between nitroalkanes and (hetero)aryl halides (Br, I) was developed to direct access highly diverse α‐aryl substituted nitroalkanes. Compared with the current state of art, this protocol is more environmentally friendly and practical for synthetic chemists. This approach is characterized by a broad substrate scope on both nitroalkane part (primary nitroalkanes and nitromethane) and sp2 halide part ((hetero)aryl bromides/iodides and alkenyl bromides/iodides). The excellent functional group tolerance was observed, which would enable real world synthetic applications. More importantly, TON of current transformation reached to 3640, when some aryl iodides were used as coupling partners. This represents currently the highest catalyst turnover for transition‐metal catalyzed α‐arylation of nitroalkanes. Furthermore, the successful application in late‐stage modification of complex molecules and synthesis of a known retinoid X receptor (RXR) antagonist exemplified its synthetic potential. [ABSTRACT FROM AUTHOR]

α‐Aryl substituted nitroalkanes are valuable synthetic building blocks that can be easily converted into α‐aryl substituted aldehydes, ketones, carboxylic acids, as well as amines. Herein, an efficient Cu/oxalamide‐catalyzed coupling between nitroalkanes and (hetero)aryl halides (Br, I) was developed to direct access highly diverse α‐aryl substituted nitroalkanes. Compared with the current state of art, this protocol is more environmentally friendly and practical for synthetic chemists. This approach is characterized by a broad substrate scope on both nitroalkane part (primary nitroalkanes and nitromethane) and sp2 halide part ((hetero)aryl bromides/iodides and alkenyl bromides/iodides). The excellent functional group tolerance was observed, which would enable real world synthetic applications. More importantly, TON of current transformation reached to 3640, when some aryl iodides were used as coupling partners. This represents currently the highest catalyst turnover for transition‐metal catalyzed α‐arylation of nitroalkanes. Furthermore, the successful application in late‐stage modification of complex molecules and synthesis of a known retinoid X receptor (RXR) antagonist exemplified its synthetic potential. [ABSTRACT FROM AUTHOR]

The thioether-functionalized 2-azabutadiene (iPrS)2C=C(H)-N=CPh2 L ligates to CdI2 and HgI2 to form the chelate compounds [CdI2{(iPrS)2C=C(H)-N=CPh2] (1) and [HgI2(iPrS)2C=C(H)-N=CPh2] (2). Their crystal structures were solved via X-ray diffraction. Both crystallize in the non-centrosymmetric space groups: monoclinic P21 (1) and orthorhombic P212121 (2), respectively. The closed-shell d10 metal centers are four-coordinated (two iodides and S and N coordinating atoms from the ligand L) in both complexes. The geometrical indexes τ indicate that a highly distorted trigonal pyramidal is adopted for 1 and a seesaw geometry for 2. The comparative nature of metal–ligand bonds is discussed on the basis of metric parameters and of QT-AIM (quantum theory of atoms in molecules) calculations. L was also treated with CuI to obtain the dinuclear species [LCu(μ2-I2)CuL] (3), in which the two Cu(I) centers are linked by a short metal–metal bond. The geometric and electronic properties of 3 are compared with those of 1 and 2. [ABSTRACT FROM AUTHOR]

A new catalytic system for reductive С(sp2)–C(sp3) cross-electrophile coupling was designed: PtII iodide complexes in an acetone solution of NaI catalyze the coupling of methyl iodide with vinyl iodide to form propylene. Simultaneously, a small amount of 1,3-butadiene, the product of C(sp2)–C(sp2) coupling, is released. The total yield of the products with respect to the reacted vinyl iodide is almost quantitative. In a large excess of CH3I, the C2H3I consumption is described by the pseudo-first-order kinetics. The cross-coupling occurs as the following sequence of steps: oxidative addition of CH3I to PtII iodide complexes to form a methyl PtIV complex → reduction of the methyl PtIV complex with I– to form the corresponding PtII derivative → oxidative addition of C2H3I to the PtII derivative → reductive elimination of organyl ligands from the intermediate methyl vinyl PtIV complex. [ABSTRACT FROM AUTHOR]

Iodine is an essential micronutrient for humans due to its fundamental role in the biosynthesis of thyroid hormones. As a key parameter to assess health conditions, iodine intake needs to be monitored to ascertain and prevent iodine deficiency. Iodine is available from various food sources (such as seaweed, fish, and seafood, among others) and dietary supplements (multivitamins or mineral supplements). In this work, a microfluidic paper-based analytical device (μPAD) to quantify iodide in seaweed and dietary supplements is described. The developed μPAD is a small microfluidic device that emerges as quite relevant in terms of its analytical capacity. The quantification of iodide is based on the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) by hydrogen peroxide in the presence of iodine, which acts as the catalyst to produce the blue form of TMB. Additionally, powder silica was used to intensify and uniformize the colour of the obtained product. Following optimization, the developed μPAD enabled iodide quantification within the range of 10–100 µM, with a detection limit of 3 µM, and was successfully applied to seaweeds and dietary supplements. The device represents a valuable tool for point-of-care analysis, can be used by untrained personnel at home, and is easily disposable, low-cost, and user-friendly. [ABSTRACT FROM AUTHOR]

This review describes applications of radical reactions developed in the authors' laboratory for the modification of carbohydrates. It focuses on tin‐free variation on the Barton‐McCombie deoxygenation; on reductive de‐iodination; on intermolecular radical additions of xanthates; on allylations and vinylations of xanthates and iodides, with emphasis on allylations using allylic alcohols activated as fluoropyridyl ethers; and, finally, on the synthesis of mercaptosugars. [ABSTRACT FROM AUTHOR]

The nature of the blue color in the iodine–starch reaction (or, in most cases, iodine–iodide-starch reaction, i.e., I2 as well as I− are typically present) has for decades elicited debate. The intensity of the color suggests a clear charge-transfer nature of the band at ~600 nm, and there is consensus regarding the fact that the hydrophobic interior of the amylose helix is the location where iodine binds. Three types of possible sources of charge transfer have been proposed: (1) chains of neutral I2 molecules, (2) chains of poly-iodine anions (complicated by the complex speciation of the I2-I− mixture), or (3) mixtures of I2 molecules and iodide or polyiodide anions. An extended literature review of the topic is provided here. According to the most recent data, the best candidate for the "blue complex" is an I2-I5−-I2 unit, which is expected to occur in a repetitive manner inside the amylose helix. [ABSTRACT FROM AUTHOR]

Polyvinyl alcohol (PVA)/polyvinyl pyrrolidone (PVP) blended polymer loaded with (x) wt. % tetrapropylammonium iodide (TPAI) were fabricated. X-ray diffraction was used to identify the TPAI and crystallinity changes in the blend. TPAI doping's effects on the blends linear and nonlinear optical parameters were examined. The direct and indirect energy gap values of the PVA/PVP blend were reduced from (5, 4.81) eV to (4.77, 4.27) eV and from (4.72, 4.39) eV to (5.11, 4.85) eV as it doped with 25% TPAI in the case of PVA/PVP prepared with distilled water (DW) and dimethylsulfoxide (DMSO), respectively. The value of refractive index at 500 nm was enlarged from 1.32 to 2.3 for the blend doped with TPAI and increased further to 2.67 as it was prepared with DW. A small doping amount of TPAI did not produce a noteworthy alteration in the real part of the dielectric constant (εr) value. By increasing the amount of TPAI (>12.5%), εr increased considerably, with the rate of increase in the blends prepared with DW being higher than that prepared with DMSO. At 500 nm, εr of PVA/PVP increased from 1.8 to 7.11 and 5.34 as it was doped with 31.25%TPAI in the case of the blends prepared with DW and DMSO, respectively. The influences of the solvent, amount of TPAI doping, and excitation wavelength on the fluorescence intensity and emitted colors were also investigated. The maximum DC conductivity (1.89 x10−7 and 1.06 x 10−5 s m−1) was detected at 338 K as the blend was doped with 12.5 wt. % TPAI and prepared with DW and DMSO, respectively. The effects of the amount of TPAI doping and the temperature on the DC conductivity of the various blends were also explored. [ABSTRACT FROM AUTHOR]

In this study, we present the synthesis, characterization and catalytic reactions of a new family of one-component catalysts based on guanidinium salts. The synthesis of cyclic carbonates from epoxides and CO2 at 70–80 °C under 1–5 bar of CO2 pressure is demonstrated using the new one-component guanidinium salts with various substituents. The 1e catalytic system, which has isopropyl-type substituents in its structure, has the best conversion rates; the TON for the synthesis of styrene carbonate was 92. The production of cyclic carbonates from the internal epoxides is another application for these catalytic systems with the conversion of cyclohexane oxide to the respective cyclic carbonate at 86% with 1e catalyst. Finally, ESI-MS was used to examine the interaction of the new organocatalysts with CO2 and epichlorohydrin. These findings led to catalysts made of organic molecules that are suitable for organocatalysis since they do not require a co-catalyst and can operate effectively at moderate pressures and temperatures. [ABSTRACT FROM AUTHOR]

The Cu2O/Cu modified shungite (ShC) absorbent (Cu2O/Cu-ShC) was synthesized by hydrothermal method, benefiting from the mineral backbone and Cu2O/Cu particles, Cu2O/Cu-ShC can remove ~ 96% of I− within 60 min, the batch experiments showed that the I− adsorption process follows pseudo-second-order model and Langmuir model with maximum adsorption capacity of 10.99 mg/g. The high binding affinity between Cu+ and I− contributes effective removal of I− and excellent selectivity at high concentrations of competing ions. This work highlights the feasibility of Cu2O/Cu-ShC for the radioactive iodine separation, and provides a promising sorbent material for large-scale purification of radioactive iodine anions in wastewater. [ABSTRACT FROM AUTHOR]

The structures of 16 phosphane chalcogenide complexes of gold(I) halides, with the general formula R¹ 3-nR² nPEAuX (R¹ = t-butyl; R² = isopropyl; n = 0 to 3; E = S or Se; X = Cl, Br or I), are presented. The eight possible chlorido derivatives are: 1a, n = 3, E = S; 2a, n = 2, E = S; 3a, n = 1, E = S; 4a, n = 0, E = S; 5a, n = 3, E = Se; 6a, n = 2, E = Se; 7a, n = 1, E = Se; and 8a, n = 0, E = Se, and the corresponding bromido derivatives are 1b-8b in the same order. However, 2a and 2b were badly disordered and 8a was not obtained. The iodido derivatives are 2c, 6c and 7c (numbered as for the series a and b). All structures are solventfree and all have Z' = 1 except for 6b and 6c (Z' = 2). All molecules show the expected linear geometry at gold and approximately tetrahedral angles P--E--Au. The presence of bulky ligands forces some short intramolecular contacts, in particular H. . .Au and H. . .E. The Au--E bond lengths have a slight but consistent tendency to be longer when trans to a softer X ligand, and vice versa. The five compounds 1a, 5a, 6a, 1b and 5b form an isotypic set, despite the different alkyl groups in 6a. Compounds 3a/3b, 4b/8b and 6b/6c form isotypic pairs. The crystal packing can be analysed in terms of various types of secondary interactions, of which the most frequent are 'weak' hydrogen bonds from methine hydrogen atoms to the halogenido ligands. For the structure type 1a, H. . .X and H. . .E contacts combine to form a layer structure. For 3a/3b, the packing is almost featureless, but can be described in terms of a double-layer structure involving borderline H. . .Cl/Br and H. . .S contacts. In 4a and 4b/8b, which lack methine groups, Cmethyl--H. . .X contacts combine to form layer structures. In 7a/7b, short C--H. . .X interactions form chains of molecules that are further linked by association of short Au. . .Se contacts to form a layer structure. The packing of compound 6b/6c can conveniently be analysed for each independent molecule separately, because they occupy different regions of the cell. Molecule 1 forms chains in which the molecules are linked by a Cmethine. . .Au contact. The molecules 2 associate via a short Se. . .Se contact and a short H. . .X contact to form a layer structure. The packing of compound 2c can be described in terms of two short Cmethine--H. . .I contacts, which combine to form a corrugated ribbon structure. Compound 7c is the only compound in this paper to feature Au. . .Au contacts, which lead to twofold-symmetric dimers. Apart from this, the packing is almost featureless, consisting of layers with only translation symmetry except for two very borderline Au. . .H contacts. [ABSTRACT FROM AUTHOR]

A new methodology using various aryl(alkyl)iodides and CaC2 as coupling partners has been developed for the successful preparation of 2,5-disubstituted furans in good to excellent yields. The broad substrate range makes this method a practical and versatile approach for the preparation of (hetero)aryl- and alkyl-substituted furans, which are valuable building blocks in many biologically active compounds and functional materials. [ABSTRACT FROM AUTHOR]

"Perovskite/carbon" interface is a bottle‐neck for hole‐conductor‐free, carbon‐electrode basing perovskite solar cells due to the energy mismatch and concentrated defects. In this article, in‐situ healing strategy is proposed by doping octylammonium iodide into carbon paste that used to prepare carbon‐electrode on perovskite layer. This strategy is found to strengthen interfacial contact and reduce interfacial defects on one hand, and slightly elevate the work function of the carbon‐electrode on other hand. Due to this effect, charge extraction is accelerated, while recombination is obviously reduced. Accordingly, power conversion efficiency of the hole‐conductor‐free, planar perovskite solar cells is upgraded by ≈50%, or from 11.65 (± 1.59) % to 17.97 (± 0.32) % (AM1.5G, 100 mW cm−2). The optimized device shows efficiency of 19.42% and open‐circuit voltage of 1.11 V. Meanwhile, moisture‐stability is tested by keeping the unsealed devices in closed chamber with relative humidity of 85%. The "in‐situ healing" strategy helps to obtain T80 time of >450 h for the carbon‐electrode basing devices, which is four times of the reference ones. Thus, a kind of "internal encapsulation effect" has also been reached. The "in situ healing" strategy facilitates the fabrication of efficient and stable hole‐conductor‐free devices basing on carbon‐electrode. [ABSTRACT FROM AUTHOR]

We report the synthesis of cross‐linked pseudopeptides through a palladium‐catalyzed carbonylative cross‐coupling reaction. The reaction involves the coupling of α‐amino acid iodides with α‐amino acid esters via in situ CO insertion to give pseudopeptides linked by the side chain of the electrophilic counterpart. The key features are the use of a sustainable in situ CO surrogate, simple non‐inert conditions, short reaction time, and broad substrate scope. Both amino acids and peptide iodides were utilized as coupling partners. [ABSTRACT FROM AUTHOR]

Alkenyl iodide, as an essential precursor and structural unit in organic synthesis, has been widely used in the synthesis of natural products, pharmaceutical pesticides and functional materials. The high reactivity of the Csp2−I bond enables the formation of a C−M bond through oxidative addition, followed by subsequent transformations of the C−M bond to create new chemical bonds. A variety of valuable scaffolds, in particular the cyclic motifs, could be achieved via designing and synthesis the corresponding alkenyl iodide, which makes this strategy to be a hot topic in synthetic chemistry. In this paper, the recent progresses of transition metal‐catalyzed cyclizationof alkenyl iodides are summarized, and the possible mechanisms for most transformations are described in detail. [ABSTRACT FROM AUTHOR]

Leiomyosarcoma (LMS) has been challenging to diagnose because of limitations in clinical and radiographic predictors, as well as the lack of reliable serum or urinary biomarkers. Most uterine masses consist of benign leiomyoma (LM). However, it is currently a significant challenge in gynecology practice to differentiate LMS from LM. This inability poses grave consequences for patients, leading to a high number of unnecessary hysterectomies, infertility, and other major morbidities and possible mortalities. This study aimed to evaluate the use of Survivin-Sodium iodide symporter (Ad-Sur-NIS) as a reporter gene biomarker to differentiate malignant LMS from benign LM by using an F18-NaBF4 PET/CT scan. The PET/CT scan images showed a significantly increased radiotracer uptake and a decreased radiotracer decay attributable to the higher abundance of Ad-Sur-NIS in the LMS tumors compared to LM (p < 0.05). An excellent safety profile was observed, with no pathological or metabolic differences detected in Ad-Sur-NIS-treated animal versus the vehicle control. Ad-Sur-NIS as a PET scan reporter is a promising imaging biomarker that can differentiate uterine LMS from LM using F18-NaBF4 as a radiotracer. As a new diagnostic method, the F18 NaBF4 PET/CT scan can provide a much-needed tool in clinical practices to effectively triage women with suspicious uterine masses and avoid unnecessary invasive interventions. [ABSTRACT FROM AUTHOR]

Selenocysteine selenenic acids (Sec–SeOHs) and selenocysteine selenenyl iodides (Sec–SeIs) have long been recognized as crucial intermediates in the catalytic cycle of glutathione peroxidase (GPx) and iodothyronine deiodinase (Dio), respectively. However, the observation of these reactive species remained elusive until our recent study, where we successfully stabilized Sec–SeOHs and Sec–SeIs using a protective molecular cradle. Here, we report the first demonstration of the chemical transformation from a Sec–SeI to a Sec–SeOH through alkaline hydrolysis. A stable Sec–SeI derived from a selenocysteine methyl ester was synthesized using the protective cradle, and its structure was determined by crystallographic analysis. The alkaline hydrolysis of the Sec–SeI at −50 °C yielded the corresponding Sec–SeOH in an 89% NMR yield, the formation of which was further confirmed by its reaction with dimedone. The facile and nearly quantitative conversion of the Sec–SeI to the Sec–SeOH not only validates the potential involvement of this process in the catalytic mechanism of Dio, but also highlights its utility as a method for producing a Sec–SeOH. [ABSTRACT FROM AUTHOR]

Monovalent thulium iodide TmI, formed by the reaction of thulium with iodine at 680°C, does not dissolve in isopropylamine (IPA), but quickly disproportionates to form finely dispersed thulium metal and TmI2(IPA)2. Similar transformations are observed in dimethoxyethane, but disproportionation proceeds significantly slower. It is impossible to isolate the powdered thulium formed in this case. The observed transformations are the first example of disproportionation of a monovalent lanthanide salt. [ABSTRACT FROM AUTHOR]

Despite having been known for a long time, quaternary 4,4′-bipyridinium salts, or viologens, are still a highly inspiring class of compounds, thanks to their peculiar redox and charge transfer properties. However, more complex structures containing multiple pyridinium rings, also interspaced by conjugated moieties, allow an even wider synthetic variability and tunability of their characteristics. The compound described herein is a star-shaped, fully conjugated molecule with three methylated pyridinium rings connected by a triple bond spacer to a central benzene core, which was synthesized from readily available building blocks, representing a quite simple model of multi-pyridyl extended viologen; its UV–visible absorption and fluorescence spectra have also been investigated. [ABSTRACT FROM AUTHOR]

Viologens are a highly advantageous class of compounds for the synthesis of functional materials. Owing to their versatile structure, they can embed additional conjugated moieties, thus representing a convenient platform, for example for organic semiconductors and other energy-related uses. A straightforward synthesis of an extended viologen containing a bithiophene is described here, together with its UV-visible absorption and fluorescence spectroscopy, showing multiple absorption and emission bands. Thanks to its ease of synthesis and optical properties, this organic salt appears to be of potential interest for various optoelectronic applications. [ABSTRACT FROM AUTHOR]

A number of β-iodovinyl sulfones were synthesized by direct difunctionalization of internal alkynes with arenesulfonyl iodides under irradiation with red light (λmax 625 nm) generated by an economical LED source. The products were obtained in high yields (68–99%) from equimolar amounts of the reactants. The reaction of sulfonyl iodides with internal alkynes follows a radical mechanism and provides a regioselective method of synthesis of β-iodovinyl sulfones. [ABSTRACT FROM AUTHOR]

Natural activities and industrial emissions can lead to high bromide and iodide concentrations in surface water, and potentially pollute drinking water sources. During drinking water disinfection process, bromide and iodide can transform into brominated disinfection by-products (Br-DBPs) and iodinated disinfection by-products (I-DBPs), which are more toxic than chlorinated disinfection by-products (Cl-DBPs). Therefore, studying bromide and iodide removal from water is of great significance to the ecological environment, human health and resource recovery. In this work, we reviewed the techniques for bromide and iodide removal from water and unprecedently classified the techniques into four types: membrane techniques, adsorption techniques, electrochemical techniques and chemical oxidation techniques. It is worth mentioning that chemical oxidation is not covered in other reviews before. The halide removal performance, mechanism, applications, merit and demerit of each technique were discussed and compared. Finally, we proposed research priorities in the context of existing and future halide removal from water. Most of these methods have been studied in depth, but still have some problems and challenges. Electrolysis and chemical oxidation are mostly used in the field of bromine and iodine production, and less attention is paid to the remaining bromide and iodide in water. The research on electrolysis and chemical oxidation for halide removal is potential but lacking. It is hoped that this review will provide theoretical support and guidance for the development of new halide removal technologies and decision-making of environmental management. [ABSTRACT FROM AUTHOR]

The prediction of the metal cluster within a coordination polymer or complex, as well as the dimensionality of the resulting polymer or complex (i.e., 0D, 1D, 2D, or 3D), is often challenging. This is the case for Ph2P(CH2)mPPh2 ligands (1 ≤ m ≤ 8) and CuX salts, particularly for X = I. This work endeavors a systematic statistical analysis combining studies in the literature and new data, mapping the nature of the resulting CuI aggregates with eight different diphoshphines in 2:1, 3:2, 1:1, 2:3, and 1:2 CuI:Ph2P(CH2)mPPh2 molar ratios as a function of m, which lead to either pure products or mixtures. Several trends are made relating stoichiometry and chain length to the CuI cluster formed (i.e., globular vs. quasi-planar). Four new X-ray structures were determined: [Cu3I2(L1)3]I, Cu3I3(L2)2, Cu2I2(L6)2, and Cu4I4(L8)2, where m is, respectively, 1, 2, 6, and 8, in which the CuxIy central aggregates adopt triangular bipyramid, diamond, rhomboid, and cubane shaped motifs, respectively. Photophysical measurements assisted the establishment of trends considering the paucity of the crystallographic structures. During this study, it was also found that the 0D-complex Cu2I2(Ph2P(CH2)5PPh2)2 exhibits thermally activated delayed fluorescence. [ABSTRACT FROM AUTHOR]

An atomically precise Cu(I) macrocyclic complex Cu8I was developed for chemodynamic therapy (CDT) research. The {Cu8} macrocyclic skeleton gradually forms with the selective recognition of iodide ions, and the monitoring of intermediate fragments during Cu8I formation using time-dependent electrospray ionization mass spectrometry indicates the following possible formation process: [Cu1] → [Cu2] → [Cu3] → [Cu4] → [Cu5I] → [Cu6I] → [Cu7I] → [Cu8I] when recognized by iodide ions. Furthermore, the Cu(I)-mediated Fenton-like reaction in Cu8I catalyzes the production of toxic ˙OH from H2O2, which results in efficient tumor suppression. [ABSTRACT FROM AUTHOR]

An aminoquinolate diarylboron (AQDAB) and tetrabutylammonium iodide (TBAI) co-catalyzed photoredox process for N-functionalization of NH-sulfoximines/sulfonimidamides has been successfully developed. This protocol can afford the corresponding N-sulfenylated and N-phosphonylated products in good to excellent yields under conditions without metallic (photo)catalysts, external oxidants, or acidic/basic additives. A wide range of functional groups are tolerated, and the N-phosphonylated products of NH-sulfonimidamides have been reported for the first time. [ABSTRACT FROM AUTHOR]

The first examples of [2]catenanes capable of selective anion transport across a lipid bilayer are reported. The neutral halogen bonding (XB) [2]catenanes were prepared via a chloride template‐directed strategy in an unprecedented demonstration of using XB⋅⋅⋅anion interactions to direct catenane assembly from all‐neutral components. Anion binding experiments in aqueous‐organic solvent media revealed strong halide over oxoanion selectivity, and a marked enhancement in the chloride and bromide affinities of the catenanes relative to their constituent macrocycles. The catenanes additionally displayed an anti‐Hofmeister binding preference for bromide over the larger iodide anion, illustrating the efficacy of employing sigma‐hole interactions in conjunction with the mechanical bond effect to tune receptor selectivity. Transmembrane anion transport studies conducted in POPC LUVs revealed that the catenanes were more effective anion transporters than the constituent macrocycles, with high chloride over hydroxide selectivity, which is critical to potential therapeutic applications of anionophores. Remarkably these outperform existing acyclic halogen bonding anionophores with regards to this selectivity. Record chloride over nitrate anion transport selectivity was also observed. This represents a rare example of the direct translation of intrinsic anion binding affinities to anion transport behaviour, and demonstrates the key role of the catenane mechanical bond effect for enhanced anion transport selectivity. [ABSTRACT FROM AUTHOR]

The first examples of [2]catenanes capable of selective anion transport across a lipid bilayer are reported. The neutral halogen bonding (XB) [2]catenanes were prepared via a chloride template‐directed strategy in an unprecedented demonstration of using XB⋅⋅⋅anion interactions to direct catenane assembly from all‐neutral components. Anion binding experiments in aqueous‐organic solvent media revealed strong halide over oxoanion selectivity, and a marked enhancement in the chloride and bromide affinities of the catenanes relative to their constituent macrocycles. The catenanes additionally displayed an anti‐Hofmeister binding preference for bromide over the larger iodide anion, illustrating the efficacy of employing sigma‐hole interactions in conjunction with the mechanical bond effect to tune receptor selectivity. Transmembrane anion transport studies conducted in POPC LUVs revealed that the catenanes were more effective anion transporters than the constituent macrocycles, with high chloride over hydroxide selectivity, which is critical to potential therapeutic applications of anionophores. Remarkably these outperform existing acyclic halogen bonding anionophores with regards to this selectivity. Record chloride over nitrate anion transport selectivity was also observed. This represents a rare example of the direct translation of intrinsic anion binding affinities to anion transport behaviour, and demonstrates the key role of the catenane mechanical bond effect for enhanced anion transport selectivity. [ABSTRACT FROM AUTHOR]

Novel pyrido[1',2';2,3]imidazo[5,1‐a]isoquinolinium iodides independently substituted at their 5‐ and 6‐position were prepared from 5‐iodopyrido[1',2';2,3]imidazo[5,1‐a]isoquinolinium iodides using Suzuki‐Miyaura cross‐coupling reaction. The desired coupling products had cationic extended π‐conjugated skeletons and fluoresced strongly in the 420–460 nm region in methanol. In cell staining assay, the 5‐styryl‐substituted compounds, which showed lower fluorescence quantum yields in methanol, emitted high fluorescence in the intracellular environment and were specifically distributed to the endoplasmic reticulum. [ABSTRACT FROM AUTHOR]

In this study, the Lengyel-Epstein system is under investigation analytically. This is the reaction–diffusion system leading to the concentration of the inhibitor chlorite and the activator iodide, respectively. These concentrations of the inhibitor chlorite and the activator iodide are shown in the form of wave solutions. This is a reaction†"diffusion model which considered for the first time analytically to explore the different abundant families of solitary wave structures. These exact solitary wave solutions are obtained by applying the generalized Riccati equation mapping method. The single and combined wave solutions are observed in shock, complex solitary-shock, shock singular, and periodic-singular forms. The rational solutions also emerged during the derivation. In the Lengyel-Epstein system, solitary waves can propagate at various rates. The harmony of the system's diffusive and reactive effects frequently governs the speed of a single wave. Solitary waves can move at a variety of speeds depending on the factors and reaction kinetics. To show their physical behavior, the 3D and their corresponding contour plots are drawn for the different values of constants. [ABSTRACT FROM AUTHOR]

1,3,4‐Trisubstituted 1,2,3‐triazolium salts having either aliphatic or benzylic substituents at the N‐1 and N‐3 positions were synthesized in two steps involving: i) copper(I) catalyzed azide‐alkyne 1,3‐dipolar cycloaddition (CuAAC), and ii)N‐alkylation of the 1,2,3‐triazole intermediates. Trans‐N‐alkylation reactions in bulk and in the presence of excess methyl iodide were monitored by 1H NMR spectroscopy for each 1,2,3‐triazolium molecular model. By assigning the different formed species and their respective evolution with time, it was possible to conclude that trans‐N‐alkylation exchange reactions are significantly faster for benzylic substituents than for aliphatic ones. Furthermore, the exchange reactions are noticeably faster at the N‐3 position than at the N‐1 position most likely due to the steric hindrance induced by the neighboring C‐4 substituent. The kinetics of trans‐N‐alkylation reactions are thus influenced by both the chemical nature of the N‐1 and N‐3 substituents and the regiochemistry of the 1,2,3‐triazolium group. This provides important structural design rules to improve the properties of thermosetting covalent adaptable networks involving trans‐N‐alkylation of 1,2,3‐triazolium salts. [ABSTRACT FROM AUTHOR]