Halogen Incorporation Research Articles

Exploratory Studies of Effective Inhibitors against the SARS-CoV-2 Main Protease by Halogen Incorporation and Amide Bond Replacement.

In the development of anti-severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) drugs, its main protease (Mpro), which is an essential enzyme for viral replication, is a promising target. To date, the Mpro inhibitors, nirmatrelvir and ensitrelvir, have been clinically developed by Pfizer Inc. and Shionogi & Co., Ltd., respectively, as orally administrable drugs to treat coronavirus disease of 2019 (COVID-19). We have also developed several potent inhibitors of SARS-CoV-2 Mpro that include compounds 4, 5, TKB245 (6), and TKB248 (7), which possesses a 4-fluorobenzothiazole ketone moiety as a reactive warhead. In compounds 5 and TKB248 (7) we have also found that replacement of the P1-P2 amide of compounds 4 and TKB245 (6) with the corresponding thioamide improved their pharmacokinetics (PK) profile in mice. Here, we report the design, synthesis and evaluation of SARS-CoV-2 Mpro inhibitors with replacement of a digestible amide bond by surrogates (9-11, 33, and 34) and introduction of fluorine atoms in a metabolically reactive methyl group on the indole moiety (8). As the results, these compounds showed comparable or less potency compared to the corresponding parent compounds, YH-53/5h (2) and 4. These results should provide useful information for further development of Mpro inhibitors.

High Refractive Index Polymer Thin Films by Charge-Transfer Complexation.

High refractive index polymers are essential in next-generation flexible optical and optoelectronic devices. This paper describes a simple synthetic method to prepare polymeric optical coatings possessing high refractive indexes. Poly(4-vinylpyridine) (P4VP) thin films prepared using initiated chemical vapor deposition are exposed to highly polarizable halogen molecules to form stable charge-transfer complexes: P4VP-IX (X = I, Br, and Cl). Fourier transform infrared spectroscopy was used to confirm the formation of charge-transfer complexes. Characterized by spectroscopic ellipsometry, the maximum refractive index of 2.08 at 587.6 nm is obtained for P4VP-I2. For P4VP-IBr and P4VP-ICl, the maximum refractive indexes are 1.849 and 1.774, respectively. By controlling the concentration of charge-transfer complexes, either through the halogen incorporation step or polymer composition through copolymerization with ethylene glycol dimethacrylate, the refractive indexes of the polymer thin films can be precisely controlled. The feasibility of P4VP-IX materials as optical coatings is also explored. The refractive index and thickness uniformity of a P4VP-I2 film over a 10 mm diameter circular area were characterized, showing standard deviations of 0.0769 and 1.91%, respectively.

Post-synthetic halogen incorporation in Zr-based MOF for enhancement of the catalytic oxidation reactions

BackgroundOne way to convert hydrocarbons to processed products is to use a catalytic oxidation reaction. The oxidation process, unlike hydrogenation, has not grown much in the industry and oxidation of CH bond is important in the production of precursors in the pharmaceutical and agronomical industries. The aim of this work is the study of catalytic properties of alcohol oxidation in the case of post-synthetic modification, as MIP-202 includes large hydrogen-bonding networks that are available to replace chloride with iodide and bromide. MethodThis is the first time that iodide and bromide have been used as active sites on heterogeneous catalysts through post-synthesis modification. These compounds were characterized by X-ray powder diffraction (PXRD), thermal gravimetric analysis (TGA), infrared spectroscopy (FT-IR), N2 gas adsorption-desorption (BET theory), scanning electron microscopes (SEM), and energy dispersive X-ray (EDX) analysis. Significance of findingsUnder ambient temperature, MIP-202-Cl, MIP-202-I, and MIP-202-Br catalyzed the oxidation of alcohols, including benzyl alcohol, with TBHP as the oxidant. Halogens are commonly used in oxidation reactions as oxygen-carrying species, called active catalytic sites. MIP-202-I is introduced as the best catalyst for improving the oxidation of alcohols, and then MIP-202-Br and MIP-202-Cl were introduced as high-efficiency catalysts, respectively.

Crystal chemistry and partitioning of halogens in hydrous silicates

Understanding how halogens are distributed among usual hydrous silicates in the lithosphere is important to constrain their deep geochemical cycle and fluid-rock interactions in subduction zones. This article presents first-principles modelling of halogen (F−, Cl−, Br−) incorporation in hydrous silicates including mica, chlorite, serpentine, amphibole, epidote and carpholite. The approach allows studying the impact of crystal chemistry on halogen partitioning by quantification of the energetic cost of halogen incorporation in minerals. Calculations are carried out in large systems where halogens are in minor to trace concentrations. Estimations show that F-bearing defects must be separated at least 9 Å from one another to reproduce trace element behaviour, this value increasing to at least 10 Å for Cl and Br. Results highlight the competition between the effects of electrostatic interactions and steric hindrance for incorporation of halogens, where steric hindrance has greater importance for heavy halogens, in particular for Br. Interaction with alkalis is a major control for F incorporation, especially in mica. Other parameters such as octahedral site occupancy, Si/Al ratio of tetrahedral sites and the nature of alkalis in amphibole and mica (K or Na) appear to play subordinate roles. Partition coefficients have been estimated in mineral assemblages in an effort to be representative of subduction zone metamorphism. Results show that pargasite, biotite and lizardite are favoured hosts for all three halogens, followed by clinochlore, tremolite and carpholite. The energetic cost of incorporating halogens into dioctahedral phyllosilicates and epidote is comparatively higher, and partitioning is predicted as unfavourable to these minerals. Fractionation between halogens in subduction zones is predicted by the evolution of mineral assemblages and partition coefficients, a consequence of the influence of crystal chemistry over halogen incorporation in hydrous silicates.

Synthesis and Biological Evaluation of Pyrroloindolines as Positive Allosteric Modulators of the α1β2γ2 GABAA Receptor.

γ-Aminobutyric acid type A (GABAA) receptors are key mediators of central inhibitory neurotransmission and have been implicated in several disorders of the central nervous system. Some positive allosteric modulators (PAMs) of this receptor provide great therapeutic benefits to patients. However, adverse effects remain a challenge. Selective targeting of GABAA receptors could mitigate this problem. Here, we describe the synthesis and functional evaluation of a novel series of pyrroloindolines that display significant modulation of the GABAA receptor, acting as PAMs. We found that halogen incorporation at the C5 position greatly increased the PAM potency relative to the parent ligand, while substitutions at other positions generally decreased potency. Mutagenesis studies suggest that the binding site lies at the top of the transmembrane domain.

New insights on Br speciation in volcanic glasses and structural controls on halogen degassing

Abstract The volcanic degassing of halogens, and especially of the heavier Br and I, received increased attention over the last 20 years due to their significant effect on atmospheric chemistry, notably the depletion of stratospheric ozone. While the effect of melt composition on halogen diffusion, solubility, or fluid-melt partitioning in crustal magma chambers has been thoroughly studied, structural controls on halogen incorporation in silicate melts remain poorly known, with only few studies available in simplified borosilicate or haplogranite compositions. Here, we demonstrate that high-energy resolution fluorescence detection X-ray absorption spectroscopy (HERFD-XAS) with a crystal analyzer spectrometer (CAS) is well-suited for the study of Br speciation in natural volcanic glasses which can contain lower Br concentrations than their laboratory analogs. Especially, HERFD-XAS results in sharper and better-resolved XANES and EXAFS features than previously reported and enables detection limits for EXAFS analysis down to 100 ppm when previous studies required Br concentrations above the 1000 ppm level. XANES and EXAFS analyses suggest important structural differences between synthetic haplogranitic glass, where Br is surrounded by Na and next-nearest oxygen neighbors, and natural volcanic glasses of basaltic to rhyodacitic compositions, where Br is incorporated in at least three distinct sites, surrounded by Na, K, or Ca. Similar environments, involving both alkali and alkaline earth metals have already been reported for Cl in Ca-bearing aluminosilicate glass and our study thus underlines that the association of Br with divalent cations (Ca2+) has been underestimated in the past due to the use of simplified laboratory analogs. Overall, similarities in Cl and Br structural environments over a large array of compositions (46–67 wt% SiO2) suggest that melt composition alone may not have a significant effect on halogen degassing and further support the coupled degassing of Cl and Br in volcanic systems.

Crystallographic and fluid compositional effects on the halogen (Cl, F, Br, I) incorporation in pyromorphite-group minerals

Abstract Pyromorphite-group minerals (PyGM), mainly pyromorphite [Pb5(PO4)3Cl], mimetite [Pb5(AsO4)3Cl], and vanadinite [Pb5(VO4)3Cl], are common phases that form by supergene weathering of galena. Their formation is strongly influenced by processes at the Earth's surface and in the soil overlying a lead deposit, and they incorporate high amounts of halogens, mostly Cl and, in some cases, F. The abundance of Br and I in natural PyGM and their potential as process tracers during surface and sub-surface fluid-rock interaction processes has not been investigated in detail due to analytical difficulties. We, therefore, developed methods for the simultaneous determination of Cl, F, Br, and I in PyGM for (1) powdered bulk samples via combustion ion chromatography (CIC) and (2) compositionally zoned crystals by means of secondary ion mass spectrometry (SIMS). Our study is based on well-characterized samples of pyromorphite (N = 38), mimetite (N = 16), and vanadinite (N = 2) from Schwarzwald (Germany). Natural pyromorphite incorporates more I (up to 26 μg/g) than mimetite (up to 2 μg/g) and vanadinite (up to 1 μg/g), while Br contents are higher in mimetite (up to 20 μg/g) and vanadinite (up to 13 μg/g) compared to pyromorphite (less than 4 μg/g). These results are unexpected, as mimetite and vanadinite have longer As/V-O bonds giving them larger unit cells and larger polyhedral volumes for the Cl site in the Pb26 octahedron than pyromorphite. Accordingly, pyromorphite was expected to preferentially incorporate Br rather than I, but the opposite is observed. Hence, halogen chemistry of PyGM is probably not governed by a crystal-chemical control (alone) but by fluid composition. However, the exact reasons remain enigmatic. This idea is corroborated by spatially resolved SIMS analyses that show that many pyromorphite-group minerals are strongly zoned with respect to their halogen mass ratios (e.g., Br/Cl, Br/I mass ratios). Furthermore, variations in halogen abundance ratios do not correlate with Ca/Pb, P/As, or P/V ratios and therefore may record alternating and season-dependent environmental parameters including biological activity, vegetation density, physico-chemical soil properties, and rainfall rate. We suggest that the zonation reflects multiple single fluid flow episodes and, hence, records surface processes. However, further experiments concerning the fractionation of halogens between fluid and PyGM are needed before halogen ratios in pyromorphite-group minerals can be used as reliable monitors of fluid-driven processes.

Quantum Chemical Examination of the Sequential Halogen Incorporation Scheme for the Modeling of Speciation of I/Br/Cl-Containing Trihalomethanes.

The recently developed three-step ternary halogenation model interprets the incorporation of chlorine, bromine, and iodine ions into natural organic matter (NOM) and formation of iodine-, bromine-, and chlorine-containing trihalomethanes (THMs) based on the competition of iodine, bromine, and chlorine species at each node of the halogenation sequence. This competition is accounted for using the dimensionless ratios (denoted as γ) of kinetic rates of reactions of the initial attack sites or halogenated intermediates with chlorine, bromine, and iodine ions. However, correlations between the model predictions made and mechanistic aspects of the incorporation of halogen species need to be ascertained in more detail. In this study, quantum chemistry calculations were first used to probe the formation mechanism of 10 species of Cl-/Br-/I- THMs. The HOMO energy (EHOMO) of each mono-, bi-, or trihalomethanes were calculated by B3LYP method in Gaussian 09 software. Linear correlations were found to exist between the logarithms of experimentally determined kinetic preference coefficients γ reported in prior research and, on the other hand, differences of EHOMO values between brominated/iodinated and chlorinated halomethanes. One notable exception from this trend was that observed for the incorporation of iodine into mono- and di-iodinated intermediates. These observations confirm the three-step halogen incorporation sequence and the factor γ in the statistical model. The combined use of quantum chemistry calculations and the ternary sequential halogenation model provides a new insight into the microscopic nature of NOM-halogen interactions and the trends seen in the behavior of γ factors incorporated in the THM speciation models.

Characterization and Biochemical Assays of Streptomyces Vanadium-Dependent Chloroperoxidases.

Vanadium-dependent haloperoxidases (VHPOs) are fascinating enzymes that facilitate electrophilic halogen incorporation into electron-rich substrates, simply requiring vanadate, a halide source, and cosubstrate hydrogen peroxide for activity. Initially characterized in fungi and red algae, VHPOs were long believed to have limited regio-, chemo-, and enantioselectivity in the production of halogenated metabolites. However, the recent discovery of homologues in the biosynthetic gene clusters of the stereoselectively halogenated meroterpenoids from marine-derived Streptomyces bacteria has revised this paradigm. Their intriguing transformations have both enhanced and contributed to the fields of synthetic organic and natural product chemistry. We, herein, describe the expression, purification, and chemical assays of two characterized vanadium-dependent chloroperoxidase enzymes (NapH1 and Mcl24), and one homologue devoid of chlorination activity (NapH3), involved in the biosyntheses of halogenated meroterpenoid products.

Quantitative Profiling of the Heavy‐Atom Effect in BODIPY Dyes: Correlating Initial Rates, Atomic Numbers, and 1O2 Quantum Yields

Direct oxidation using molecular oxygen is both attractive and atom‐efficient. However, this process first requires the catalyst‐based activation or electronic reconfiguration of inert O2. The most expedient strategy relies on the generation of singlet oxygen (1O2; a1Δg) from the triplet state (3O2; X3Σg–) by a photosensitizer. In the current arsenal of photosensitizers, boron‐dipyrromethene (BODIPY) cores are considered privileged on account of their unique photophysical characteristics and the ability to tune their behavior through facile structural modifications such as halogen (X) incorporation. Thus, the scaffold has become synonymous with the renowned heavy‐atom effect (HAE), a phenomenon that correlates the increasing atomic number (ZX) of pendant halogen atoms with an enhanced probability of intersystem crossing (S1→T1). Herein, a facile GC‐based method to assess catalyst performance has been developed and validated with a focused set of halogenated BODIPY scaffolds. An initial‐rate approximation was applied to a model transformation and follows the HAE trend (v0,H < v0,Cl < v0,Br < v0,I). This operationally simple approach was corroborated by complementary determinations of absolute singlet oxygen and photoluminescence quantum yields and time‐resolved luminescence decays to evaluate lifetimes. For double logarithmic plots, linear correlations between relative intersystem‐crossing rates kXisc/kYisc and relative atomic numbers ZX/ZY for the respective substituents with corresponding slopes of approximately 4 were obtained, that is, kisc ~ Z4, which also was shown to hold for the fluorescence‐lifetime‐corrected singlet‐oxygen quantum yields as independent measurements. This substantiates theoretical predictions pertaining to the heavy‐atom effect.

Impact of bromide on halogen incorporation into organic moieties in chlorinated drinking water treatment and distribution systems

The impact of elevated bromide concentrations (399 to 750μg/L) on the formation of halogenated disinfection by-products (DBPs), namely trihalomethanes, haloacetic acids, haloacetonitriles, and adsorbable organic halogen (AOX), in two drinking water systems was investigated. Bromine was the main halogen incorporated into all of the DBP classes and into organic carbon, even though chlorine was present in large excess to maintain a disinfectant residual. Due to the higher reactivity of bromine compared to chlorine, brominated DBPs were rapidly formed, followed by a slower increase in chlorinated DBPs. Higher bromine substitution and incorporation factors for individual DBP classes were observed for the chlorinated water from the groundwater source (lower concentration of dissolved organic carbon (DOC)), which contained a higher concentration of bromide, than for the surface water source (higher DOC). The molar distribution of adsorbable organic bromine to chlorine (AOBr/AOCl) for AOX in the groundwater distribution system was 1.5:1 and almost 1:1 for the surface water system. The measured (regulated) DBPs only accounted for 16 to 33% of the total organic halogen, demonstrating that AOX measurements are essential to provide a full understanding of the formation of halogenated DBPs in drinking waters. In addition, the study demonstrated that a significant proportion (up to 94%) of the bromide in source waters can be converted AOBr. An evaluation of AOBr and AOCl through a second groundwater treatment plant that uses conventional treatment processes for DOC removal produced 70% of AOX as AOBr, with 69% of the initial source water bromide converted to AOBr. Exposure to organobromine compounds is suspected to result in greater adverse health consequences than their chlorinated analogues. Therefore, this study highlights the need for improved methods to selectively reduce the bromide content in source waters.

Towards reducing DBP formation potential of drinking water by favouring direct ozone over hydroxyl radical reactions during ozonation

When ozonation is employed in advanced water treatment plants to produce drinking water, dissolved organic matter reacts with ozone (O3) and/or hydroxyl radicals (OH) affecting disinfection byproduct (DBP) formation with subsequently used chlorine-based disinfectants. This study presents the effects of varying exposures of O3 and OH on DBP concentrations and their associated toxicity generated after subsequent chlorination. DBP formation potential tests and in vitro bioassays were conducted after batch ozonation experiments of coagulated surface water with and without addition of tertiary butanol (t-BuOH, 10 mM) and hydrogen peroxide (H2O2, 1 mg/mg O3), and at different pH (6–8) and transferred ozone doses (0–1 mg/mg TOC).Although ozonation led to a 24–37% decrease in formation of total trihalomethanes, haloacetic acids, haloacetonitriles, and trihaloacetamides, an increase in formation of total trihalonitromethanes, chloral hydrate, and haloketones was observed. This effect however was less pronounced for samples ozonated at conditions favoring molecular ozone (e.g., pH 6 and in the presence of t-BuOH) over OH reactions (e.g., pH 8 and in the presence of H2O2). Compared to ozonation only, addition of H2O2 consistently enhanced formation of all DBP groups (20–61%) except trihalonitromethanes. This proves that OH-transformed organic matter is more susceptible to halogen incorporation. Analogously, adsorbable organic halogen (AOX) concentrations increased under conditions that favor OH reactions. The ratio of unknown to known AOX, however, was greater at conditions that promote direct O3 reactions. Although significant correlation was found between AOX and genotoxicity with the p53 bioassay, toxicity tests using 4 in vitro bioassays showed relatively low absolute differences between various ozonation conditions.

Effects of pH on the speciation coefficients in models of bromide influence on the formation of trihalomethanes and haloacetic acids

This study investigated effects of pH, bromide and natural organic matter (NOM) level on yields and speciation of trihalomethanes (THMs) and haloacetic acids (HAAs) in chlorinated water. Experimental data were obtained using two water sources, one with a medium (DOC = 1.4 mg/L and SUVA = 2.60 L mg−1 m−1) and the other with higher (DOC = 7.7 mg/L and SUVA = 4.26 L mg−1 m−1) organic carbon level. The experiments employed the simulated distribution system (SDS) procedure at varying bromide concentrations and pH values of 7.0, 8.5 and 10. The speciation of THMs and dihalogenated HAAs (DHAAs) was interpreted based on the modelling of mixed halogenation yields via dimensionless ratios of bromination/chlorination reaction rates at each halogen incorporation node. The approach allowed precise modelling of the speciation of THMs and DHAAs at all examined pHs. In the case of DHAA, the dimensionless ratios of the bromination/chlorination reaction rates were not consistently affected by pH variations. For THMs, increase of pH caused the values of the dimensionless bromination/chlorination reaction rates to decrease in the case of halogenation of the initial reaction sites indicating a decreasing preference toward bromination at this reaction node. A similar trend was observed for the reactivity of dichlorinated reaction intermediate denoted as SCl2 whose formation precedes the release of CHCl3 and CHBrCl2. A similar but less consistent trend was observed for intermediate SBrCl whose halogenation yields both CHBrCl2 and CHBr2Cl. An opposite trend of increasing preference towards bromination at higher pHs was observed monobrominated intermediate SBr and in some extent dibrominated intermediate SBr2. These results help develop detailed DBP speciation models which needed to better understand the generation and potential health effects of THMs and HAAs at varying operating conditions and ultimately to adopt measure to minimize their levels in drinking water systems.

Experimental partitioning of halogens and other trace elements between olivine, pyroxenes, amphibole and aqueous fluid at 2GPa and 900-1,300°C.

We present new partition coefficients for various trace elements including Cl between olivine, pyroxenes, amphibole and coexisting chlorine-bearing aqueous fluid in a series of high-pressure experiments at 2 GPa between 900 and 1,300 °C in natural and synthetic systems. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA–ICP–MS. The chlorine and fluorine contents in mantle minerals were measured by electron microprobe, and the nature of OH defects was investigated by infrared spectroscopy. Furthermore, a fluorine-rich olivine from one selected sample was investigated by TEM. Results reveal average Cl concentrations in olivine and pyroxenes around 20 ppm and up to 900 ppm F in olivine, making olivine an important repository of halogens in the mantle. Chlorine is always incompatible with Cl partition coefficients D Clolivine/fluid varying between 10−5 and 10−3, whereas D Clorthopyroxene/fluid and D Clclinopyroxene/fluid are ~10−4 and D Clamphibole/fluid is ~5 × 10−3. Furthermore, partitioning results for incompatible trace element show that compatibilities of trace elements are generally ordered as D amph/fluid ≈ D cpx/fluid > D opx/fluid > D ol/fluid but that D mineral/fluid for Li and P is very similar for all observed silicate phases. Infrared spectra of olivine synthesized in a F-free Ti-bearing system show absorption bands at 3,525 and ~3,570 cm−1. In F ± TiO2-bearing systems, additional absorption bands appear at ~3,535, ~3,595, 3,640 and 3,670 cm−1. Absorption bands at ~3,530 and ~3,570 cm−1, previously assigned to humite-like point defects, profit from low synthesis temperatures and the presence of F. The presence of planar defects could not be proved by TEM investigations, but dislocations in the olivine lattice were observed and are suggested to be an important site for halogen incorporation in olivine.Electronic supplementary materialThe online version of this article (doi:10.1007/s00410-013-0902-5) contains supplementary material, which is available to authorized users.

Formation and Speciation Characteristics of Brominated Trihalomethanes in Seawater Chlorination

Formation character of brominated-trihalomethanes (Br-THMs) in chlorinated seawater and its dependence on applied chlorine dose, reaction time, and temperature were investigated in the laboratory. Seawater was collected from the east coast of India and a chlorine dose of 1, 3, 5, and 10 ppm was each applied at a temperature of 20, 30, and 40 degrees C to investigate the yield and kinetics of Br-THMs formation. Qualitative and quantitative estimation of THM formation at various intervals of time ranging from 5 min to 168 h was determined by a gas chromatograph equipped with an electron capture detector (GC-ECD). Chlorine dose, chlorine contact time, and reaction temperature positively affected the load of THMs. The ratio of chlorine dose to halogen incorporation decreased from 12% to 5% with increasing applied chlorine dose from 1 to 10 ppm. Significant levels of THMs were found to be formed within 0.5 h of reaction, followed by a very slow rate of formation. Elevated temperature favored both increased rate of formation and overall THM yield. The formation order of different trihalomethane species at all studied temperatures was observed to be bromodichloromethane (CHCl2Br) < dibromochloromethane (CHClBr2) < bromoform (CHBr3). Formation of chloroform was not observed, and bromoform was the dominant (96% to 98%) among the three THM species formed.

Peculiarities of Er3+ photoluminescence in halogen-doped amorphous silica

The spectra and photoluminescence kinetics of Er3+ ions embedded in amorphous fluorine- and chlorine-doped silica matrices synthesized by surface-plasma chemical vapor deposition were investigated at 27–300 K. Luminescence was excited with an Ar+ laser at a wavelength of 514.5 nm and with a diode laser at a wavelength of 975 nm. Narrow and well-expressed components of Stark sublevels with a small contribution of inhomogeneous broadening intrinsic to Er3+ ions in crystalline rather than amorphous matrices were revealed and identified in photoluminescence spectra. The structure of Stark sublevels was well-resolved at low temperatures. The presence of the well-resolved Stark structure in spectra was indicative of stable anion complex formation in Er3+ environment presumably associated with halogen incorporation. This environment was formed at a stage of the low-temperature plasma-chemical synthesis and was destroyed at glass fusion.

DBP formation in drinking water: kinetics and linear modelling

An original approach for modelling disinfection by-products formation in chlorinated water is proposed. Assuming a multi-step formation mechanism, and introducing partition coefficients to differentiate the various compounds formed as a consequence of halogen incorporation and oxidation reactions, a system of linear differential equations is obtained and solved in explicit terms. Two sets of solutions are derived: the first one assuming that the reaction rate is the same for all species included in the model, as a consequence of steady state approximation; the second one assuming that the reaction rate is different from one species to another. Experimental data, obtained varying reaction time and chlorine dose, are used to calibrate the two models. Statistic tests are also performed to compare the two sets of solutions and validate the assumed hypotheses.

Bromide Oxidation and Formation of Dihaloacetic Acids in Chloraminated Water

A comprehensive reaction model was developed that incorporates the effect of bromide on monochloramine loss and formation of bromine and chlorine containing dihaloacetic acids (DHAAs) in the presence of natural organic matter (NOM). Reaction pathways accounted for the oxidation of bromide to active bromine (Br(l)) species, catalyzed monochloramine autodecomposition, NOM oxidation, and halogen incorporation into DHAAs. The reaction scheme incorporates a simplified reaction pathway describing the formation and termination of Br(l). In the absence of NOM, the model adequately predicted bromide catalyzed monochloramine autodecomposition. The Br(l) reaction rate coefficients are 4 orders of magnitude greater than HOCl for the same NOM sources under chloramination conditions. Surprisingly, the rate of NOM oxidation by Br(l) was faster than bromide catalyzed monochloramine autodecomposition by Br(l) so that the latter reactions could largely be ignored in the presence of NOM. Incorporation of bromine and chlorine into DHAAs was proportional to the amount of NOM oxidized by each halogen and modeled using simple bromine (alpha(Br)) and chlorine (alpha(Cl)) incorporation coefficients. Both coefficients were found to be independent of each other and alpha(Br) was one-half the value of alpha(Cl). This indicates that chlorine incorporates itself into DHAA precursors more effectivelythan bromine. Model predictions compared well with DHAA measurements in the presence of increasing bromide concentrations and is attributable to the increased rate of NOM oxidation, which is rate limited by the oxidation of bromide ion in chloraminated systems.

Oxyhalide silicate glasses

The data available in the literature on the properties and structure of silicate glasses containing halides are reviewed. The results of measurements of thermal, electrical, and chemical characteristics that illustrate effects associated with the incorporation of halogens (fluorine, chlorine) into the silicate glass matrix are summarized. Different concepts regarding the mechanisms of halogen incorporation are analyzed, and the structural role of halogens in glasses is discussed. The factors responsible for the volatilization of halogens in the course of synthesis and specific features of their dissolution in silicate melts are considered.

Synthesis and photoinitiated polymerization of diacrylate derivates of halobenzoates

The synthesis, characterization, mesomorphism and photoinitiated polymerization of new thermotropic derivatives of bis{4-[6-(acryloyloxy)hexyloxy]halobenzoate}-1,4-phenylene were studied. Halogen incorporation in the mesogenic unit decreases the stability of the mesophases of monomers containing three aromatic rings. The monomer MIII exhibits a nematic phase which has been macroscopically oriented by surface pre-treatment and fixed by photopolymerization in situ, yielding a uniaxially crosslinked network. The molecular ordering of liquid crystalline diacrylate films was visualized by examining the fracture surface by scanning electron microscopy. These films exhibit a fine texture, illustrating the presence of an oriented layered structure.