Sulfur-containing polymers. VI. Preparation of poly[alkylene bis(oxycarbonyl) disulfides] and related polymers

Poly[alkylene bis(oxycarbonyl) disulfides] have been prepared for the first time by the reductive coupling of alkylene bis(oxycarbonylsulfenyl chlorides). Potassium iodide and a variety of transition metals or their salts were employed as reducing agents. Of these potassium iodide and cuprous chloride gave the best results. Pyrolysis, desulfurization. and thiol-induced fragmentation of the polymers have been studied. Homologous polymers, i.e., monosulfide polymer, trisulfide polymer, and tetrasulfide polymer, have been also synthesized. Monosulfide and disulfide polymers were highly crystalline solids. Trisulfide polymer was a white solid with a low degree of crystallinity. These polymers were soluble in chloroform and dichloromethane. Tetrasulfide polymer was a crystalline yellow solid and was soluble only in HMPA.     

Isolation and spectral characteristics of Ferric Iodide

Ferric iodide is isolated pure for the first time as a dark purple solid when a hexane solution of diiodotetracarbonyliron(II) and diiodine is exposed to actinic radiation. Its identity is confirmed by elemental analysis and quantitative conversion to the known tetraiodoferrate(III) by treatment with tetra-n-butylammonium iodide. Although persistent in the solid state, ferric iodide is readily decomposed in solution to ferrous iodide and 0.5 mol diiodine quantitatively.     

Dual high adhesion surface for water in air and for oil underwater

A new type of dual high surface adhesion both in an oil/water/solid system and in a water/air/solid system is reported. A walnutlike cuprous iodide (CuI) microcrystal surface, which is composed of numerous CuI nanocrystals, shows an amphiphobic, highly adhesive surface for water in air and for oil underwater. The maximum adhesive force is about 120.3 ± 1.6 μN in the air for a water droplet and about 23.8 ± 2.1 μN underwater for an oil droplet. These findings will help us to design novel high adhesive materials in two-phase or multiphase mediums.     

An all-solid-state dye-sensitized solar cell-based poly(N-alkyl-4-vinyl-pyridine iodide) electrolyte with efficiency of 5.64%

Using poly(N-methyl-4-vinyl-pyridine iodide), N-methyl-pyridine iodide and iodine, a solid polymer electrolyte with conductivity of 6.41 mS/cm is prepared. On the basis of a solid polymer electrolyte, a conducting graphite layer, a KI block layer, and a vacuum assembling technique, we achieve an all-solid-state dye-sensitized solar cell with total photoelectric conversion efficiency of 5.64% under AM 1.5 simulated solar light (100 mW/cm2) illumination.     

Evaluation of a new linker system cleaved using samarium(II) iodide. Application in the solid phase synthesis of carbonyl compounds

A new linker design for solid phase synthesis has been developed that is cleaved under mild, neutral conditions using samarium(II) iodide. The feasibility of the linker approach has been illustrated in the solid phase synthesis of ketones and amides using an oxygen linker. Insights into the mechanism of the samarium(II) iodide cleavage reaction are described and the potential of a sequential cleavage carbon-carbon bond forming process is assessed.     

Electron stimulated reactions of methyl iodide coadsorbed with amorphous solid water

The electron stimulated reactions of methyl iodide (MeI) adsorbed on and suspended within amorphous solid water (ice) were studied using a combination of postirradiation temperature programmed desorption and reflection absorption infrared spectroscopy. For MeI adsorbed on top of amorphous solid water (ice), electron beam irradiation is responsible for both structural and chemical transformations within the overlayer. Electron stimulated reactions of MeI result principally in the formation of methyl radicals and solvated iodide anions. The cross section for electron stimulated decomposition of MeI is comparable to the gas phase value and is only weakly dependent upon the local environment. For both adsorbed MeI and suspended MeI, reactions of methyl radicals within MeI clusters lead to the formation of ethane, ethyl iodide, and diiodomethane. In contrast, reactions between the products of methyl iodide and water dissociation are responsible for the formation of methanol and carbon dioxide. Methane, formed as a result of reactions between methyl radicals and either parent MeI molecules or hydrogen atoms, is also observed. The product distribution is found to depend on the film's initial chemical composition as well as the electron fluence. Results from this study highlight the similarities in the carbon-containing products formed when monohalomethanes coadsorbed with amorphous solid water are irradiated by either electrons or photons.     

A Solid‐State Reference Electrode Based on a Self‐Referencing Pulstrode

The design of solid‐state reference electrodes without a liquid junction is important to allow miniature and cost‐effective electrochemical sensors. To address this, a pulse control is proposed using an Ag/AgI element as reliable solid‐state reference electrode. It involves the local release of iodide by a cathodic current that is immediately followed by an electromotive force (EMF) measurement that serves as the reference potential. The recapture of iodide ions is achieved by potentiostatic control. This results in intermittent potential values that are reproducible to less than one millivolt (SD=0.27 mV, n=50). The ionic strength is shown to influence the activity coefficient of released iodide in accordance with the extended Debye–Hückel equation, resulting in a predictable change of the potential reading. The principle is applied to potentiometric potassium detection with a valinomycin‐based ion‐selective electrode (ISE), demonstrating a completely solid‐state sensor configuration.     

Formation of complexes of crown ethers in the absence of solvent observed by differential thermal analysis

Differential thermal analysis was employed as a new method to observe the formation of complexes of dibenzo-18-crown-6 polyether and macrocyclic nitro derivatives with potassium iodide. DTA thermograms of polyethers, of solid complexes, and mixtures of polyether and potassium iodide were obtained in an atmosphere of dry nitrogen.     

固相配位化学反应——ⅩⅩⅩ.室温下铁氰化钾的固相反应

本文首次报道了铁氰化钾在室温下与碘化钾、硫化钾的固相氧化还原反应,实验发现在固相下铁氰化钾与碘化钾混合后,生成单质碘和亚铁氰化钾,而在溶液中该反应是反方向进行的.实验还发现,在固相下铁氰化钾与还原剂硼氢化钠不反应,而在溶液中,该反应却能进行.对反应机制进行了初步探讨.     

Surface segregation of dissolved salt ions

Surface segregation of iodide, but not of fluoride or cesium ions, is observed by a combination of metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy (UPS(HeI)) of amorphous solid water exposed to CsI or CsF vapor. The same surface ionic behavior is also derived from molecular dynamics (MD) simulations of the corresponding aqueous salt solutions. The MIES results show the propensity of iodide, but not fluoride, for the surface of the amorphous solid water film, providing thus strong evidence for the suggested presence of heavier halides (iodide, bromide, and to a lesser extent chloride) at the topmost layer of aqueous surfaces. In contrast, no appreciable surface segregation of ions is observed in methanol, neither in the experiment nor in the simulation. Furthermore, the present results indicate that, as far as the thermodynamic aspects of solvation of alkali halides are concerned, amorphous solid water and methanol surfaces behave similarly as surfaces of the corresponding liquids.     

固相配位化学反应——ⅩⅩⅩ.室温下铁氰化钾的固相反应

本文首次报道了铁氰化钾在室温下与碘化钾、硫化钾的固相氧化还原反应,实验发现在固相下铁氰化钾与碘化钾混合后,生成单质碘和亚铁氰化钾,而在溶液中该反应是反方向进行的.实验还发现,在固相下铁氰化钾与还原剂硼氢化钠不反应,而在溶液中,该反应却能进行.对反应机制进行了初步探讨.     

Determination of trace iodide in iodised table salt on silver sulfate-modified carbon paste electrode by differential pulse voltammetry with electrochemical solid phase nano-extraction

Electrochemical solid phase nano-extraction, a novel sample preparation technique, was used for the determination of trace iodide in iodised table salt based on the silver sulfate nanoparticle-modified carbon paste electrode. Electrochemical solid phase nano-extraction was realized in the exchange between the sulfate anion in nanoparticles and an iodide anion from aqueous solution. The released silver cation serves as the electrochemical probe for the determination of iodide. The extraction follows a Freundlich adsorption isotherm, and can be used in the detection of iodide in the concentration range 5.0 × 10⁻¹²-4.0 × 10⁻⁹ M. The amount of iodide in iodised table salt was determined as 0.875 ± 0.002 μg/g, which is about 2.5% of the addition amount of iodate with a relative deviation of 5.92% and a standard addition recovery of 90-110%. The large amounts of chloride and iodate did not interfere with the detection.     

含中氮茚环的二甲川菁的合成

硫代甲酰基中氮茚;碘化二甲基喹啉鎓盐;荧光;含中氮茚环的二甲川菁的合成     

Anionic Lead Complexes on the Solid Phase of Fibrous Filled Materials in the Reaction with 4(2-Pyridylazo)resorcinol

The influence of the nature of anions (iodide, bromide, thiosulfate, pyrophosphate, tartrate, and acetate) in the anionic lead complex adsorbed on a solid phase of a fibrous sorbent filled with the AV-17 anion exchanger on the color reaction between lead and 4-(2-pyridylazo)resorcinol (PAR) was studied by diffuse reflectance spectrometry. The influence of anions on the complexation of lead with PAR on the solid phase was discussed for different types of the color reaction. It was demonstrated that the reactions with iodide at pH 5–10 and with thiosulfate at pH 10 are significant in the determination of lead as three-component complexes on the support. In the presence of other anions, lead ions do not react with PAR on the AV-17 solid phase.     

Studies On The Use Of Halide Ion Selective Electordes In Salt Media And The Extension Of The Generalized Standard Addition method To Determine The Concentration Of Halide Ions In Geothermal Brins

Abstract

The effect of chloride on the bromide and iodide solid state precipitate electrodes is studied and selectivity constants calculated. The use of multiple linear regression analysis to determine the initial concentration of halide ions in solutions is studied and the resulting technique is used to determine fluoride, iodide and bromide in a geothermal-geopressured brine.     

Highly sensitive determination of iodide by ion chromatography with amperometric detection at a silver-based carbon paste electrode

A silver-based solid carbon paste electrode was developed for use as a detector in ion chromatography (IC) for the sensitive determination of iodide in real samples. Micro- and nano-particles of silver were investigated for the fabrication of different electrodes. The iodide assay was based on IC with amperometric detection (IC-AD) at a silver composite electrode polarized at +0.080 V versus Ag/AgCl. Free iodide and organoiodide compounds were studied. The detection process was characterized by studying the redox behavior of iodide ions at both silver and silver composite electrodes by cyclic voltammetry (CV). The presence of iodide ions in solution was found to considerably facilitate metallic silver oxidation, with response currents directly related to iodide concentration. The calibration curve at the selected silver carbon paste electrode was linear in the concentration range comprised between 0.635 microg/L and 63.5 microg/L iodide. The relative standard deviation (R.S.D.) for successive injections was below 3% for all iodide standard solutions investigated. The limit of detection (LOD) was 0.47 microg/L (3.7 nmol/L) for an injection volume of 20 microL, i.e. 74 fmol injected. The IC-AD method was successfully applied to the determination of iodide in complex real samples such as table salts, sea products and iodide bound drug compounds. The analytical accuracy was verified by the assay of iodide in milk powder from an iodide certified reference material (CRM) Community Bureau of Reference (BCR) 150.     

Highly Luminescent Inks: Aggregation‐Induced Emission of Copper–Iodine Hybrid Clusters

Aggregation‐induced emission (AIE) is an attractive phenomenon in which materials display strong luminescence in the aggregated solid states rather than in the conventional dissolved molecular states. However, highly luminescent inks based on AIE are hard to be obtained because of the difficulty in finely controlling the crystallinity of AIE materials at nanoscale. Herein, we report the preparation of highly luminescent inks via oil‐in‐water microemulsion induced aggregation of Cu–I hybrid clusters based on the highly soluble copper iodide‐tris(3‐methylphenyl)phosphine (Cu₄I₄(P‐(m‐Tol)₃)₄) hybrid. Furthermore, we can synthesize a series of AIE inks with different light‐emission colors to cover the whole visible spectrum range via a facile ligand exchange processes. The assemblies of Cu–I hybrid clusters with AIE characteristics will pave the way to fabricate low‐cost highly luminescent inks.     

The Reduction of Sulfoxide by Iodide/Organic Acid System in the Solid State

A novel solid state reduction of sulfoxides including methionine sulfoxide to the corresponding sulfides by iodide/organic acid system is described.     

Enzyme electrode for glucose based on an iodide membrane sensor

The construction of a new type of enzyme electrode for the potentiometric determination of glucose is reported. The electrode response is based on the enzymecatalyzed reactions: The highly selective iodide sensor monitors the local decrease in the iodide activity at the electrode surface. The properties of the above reactions were examined kinetically, with flow-stream techniques and potentiometric detection. The glucose electrode constructed and the use of flow-stream experiments with two iodide sensors provided accurate and convenient glucose determinations in the absence of some oxidizing and reducing agents.     

S-(Trimethoxysilylmethyl)- and S-(Silatranylmethyl)isothiuronium Halides and Their N-Substituted Derivatives

Previously unknown S-(trimethoxysilylmethyl)- and S-(silatranylmethyl)isothiuronium halides and their N-substituted derivatives were prepared. According to the IR and UV spectra, these compounds exist in the solid state and in methanol and acetonitrile solutions in the form of two equilibrium salt structures: those with the positively charged nitrogen and carbon atoms, or predominantly in one of these. In solutions of the iodides in highly polar acetonitrile, the first salt structure can occur in an equilibrium with its dissociation products, S-organylisothiourea (or its N-substituted derivative) and hydrogen iodide.