Active Halogen Research Articles

Photothermal-Induced Multimodal Antibacterial Dressing Comprising N-Halamine Hydrogel Loaded with Cow Dung Biochar for Infected Wound Healing.

Disposal of the cow dung pollutants arising from cattle farming threatens the environment and public safety in diverse ways. To date, researchers have worked on developing new pathways to control and manage cattle farming wastes, but most do not involve the reuse of these wastes. Herein, a cow dung biochar-modulated photothermal N-halamine hydrogel (i.e., PAN/CA/CoBC/pMAG-Cl) was designed for converting cow dung into biochar (CoBC), which was then coupled with a 3D interpenetrating hydrogel network to treat infected wounds. The PAN/CA/CoBC/pMAG-Cl hydrogel exhibited excellent synergistic antibacterial performance against 106 CFU·mL-1 Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) within 60 min. The bactericidal effect was multimodal, involving CoBC-based photothermal killing (i.e., temperature as high as 80.5 °C) after 808 nm near-infrared light irradiation for 10 min, contact killing through the strong oxidative characteristic of N-halamine (pMAG-Cl), and release killing via active halogens (i.e., Cl+) reinforced by the photothermal action of CoBC. The S. aureus-infected wound model in vivo demonstrated that the PAN/CA/CoBC/pMAG-Cl hydrogel worked as an ideal wound dressing, capable of resisting bacterial infection, accelerating the healing process, and promoting epithelial regeneration. This proposed strategy could indicate a new way for the disposal of cow dung pollutant and its reuse in antibacterial-associated applications.

Development of the adjoint of the unified tropospheric–stratospheric chemistry extension (UCX) in GEOS-Chem adjoint v36

Abstract. Atmospheric sensitivities (gradients), quantifying the atmospheric response to emissions or other perturbations, can provide meaningful insights on the underlying atmospheric chemistry or transport processes. Atmospheric adjoint modeling enables the calculation of receptor-oriented sensitivities of model outputs of interest to input parameters (e.g., emissions), overcoming the numerical cost of conventional (forward) modeling. The adjoint of the GEOS-Chem atmospheric chemistry-transport model is a widely used such model, but prior to v36 it lacked extensive stratospheric capabilities. Here, we present the development and evaluation of the discrete adjoint of the global chemistry-transport model (CTM) GEOS-Chem unified chemistry extension (UCX) for stratospheric applications, which extends the existing capabilities of the GEOS-Chem adjoint to enable the calculation of sensitivities that include stratospheric chemistry and interactions. This development adds 37 new tracers, 273 kinetic and photolysis reactions, an updated photolysis scheme, treatment of stratospheric aerosols, and all other features described in the original UCX paper. With this development the GEOS-Chem adjoint model is able to capture the spatial, temporal, and speciated variability in stratospheric ozone depletion processes, among other processes. We demonstrate its use by calculating 2-week sensitivities of stratospheric ozone to precursor species and show that the adjoint captures the Antarctic ozone depletion potential of active halogen species, including the chlorine activation and deactivation process. The spatial variations in the sensitivity of stratospheric ozone to NOx emissions are also described. This development expands the scope of research questions that can be addressed by allowing stratospheric interactions and feedbacks to be considered in the tropospheric sensitivity and inversion applications.

Mechanisms underlying the potent antimicrobial effects of plasma-activated seawater (PASW) on fish spoilage bacterium Shewanella putrefaciens

Plasma-activated seawater (PASW) presents a promising approach for marine fish preservation, yet its antimicrobial efficacy and mechanisms remain unclear. This study found that PASW exhibits superior bactericidal properties against the fish spoilage bacterium Shewanella putrefaciens compared to plasma-activated water (PAW), and increased effectiveness in preserving fish fillets. To clarify the mechanisms, a detailed investigation was conducted, including the generation of reactive oxygen/nitrogen species (ROS/RNS) and active halogen species in PASW, and their antimicrobial efficacy. Findings showed greater nitrite and hydrogen peroxide production in PASW relative to PAW, as well as the conversion of chloride/bromide ions into active species, which collectively enhanced PASW's antimicrobial activity. The synergistic action of ROS/RNS and active chlorine/bromine species in PASW promoted the generation of intracellular ROS, causing increased membrane damage, redox imbalance, and consequently higher bacterial mortality. This study enhances our understanding of PASW's antimicrobial effects and highlights its potential applications in the seafood industry.

P2O5-Promoted Cyclization of Di[aryl(hetaryl)methyl] Malonic Acids as a Pathway to Fused Spiro[4.4]nonane-1,6-Diones.

Conventional spiro-linked conjugated materials are attractive for organic optoelectronic applications due to the unique combination of their optical and electronic properties. However, spiro-linked conjugated materials with conjugation extension directed along the main axis of the molecule are still only rare examples among the vast number of spiro-linked conjugated materials. Herein, the synthesis, leading to π-extended spiro-linked conjugated materials─spiro[4.4]nonane-1,6-diones and spiro[5.5]undecane-1,7-diones─has been developed and optimized. The proposed design concept starts from readily available malonic esters and contains several steps: double alkylation of malonic ester with bromomethylaryl(hetaryl)s; conversion of a malonic ester into the corresponding malonic acid; electrophilic spirocyclization of the latter into the annulated spiro[4.4]nonane-1,6-dione or spiro[5.5]undecane-1,7-dione in the presence of phosphorus pentoxide. On the basis of these insights, the developed method yielded spiro-linked conjugated cores fused with benzene, thiophene, and naphthalene, decorated with active halogen atoms. The structures of the synthesized spirocycles were determined by single-crystal X-ray diffraction analysis. Benzene fused spiro[4.4]nonane-1,6-dione decorated with bromine atoms was transformed into V-shape phenylene-thiophene co-oligomer type spirodimers via Stille coupling. The spiro-bis(4-n-dodecylphenyl)-2,2'-bithiophene derivative possessed high photoluminescence properties in both solution and solid state with a photoluminescence quantum yield (PL QY) of 38%.

Multiphase Volatilization of Halogens at the Soil‐Atmosphere Interface on Mars

AbstractThe Martian critical zone, especially its soil‐atmosphere interface, may host an active halogen cycle affecting habitability, as inferred from halogen trends observed in situ at Gusev and Meridiani, along with oxychlorine species detected in situ. However, the sinks and sources of the Martian halogen cycle remain poorly constrained, especially for Br, including the broader geographic significance of halogen volatility in soils. Here, we statistically analyze Br, Cl, and S distribution and associated cations in the soils of Gale Crater and compare the results with soils of Gusev Crater and Meridiani Planum. We further place the overall in situ soil trends in the framework of terrestrial natural evaporative halides and Mars‐analog evaporative experiments. We observe three lines of evidence that support preferential volatilization of Br versus Cl and S in Martian soils: (a) Unlike Cl and S, Br abundance decreases from subsurface to surface. (b) Br and Cl abundances correlate strongly at the relatively dust‐free and freshly exposed surface of the active Bagnold dunes, but Br‐Cl correlations weaken and Br concentrations decrease in less mobile surface soil. (c) Laboratory experiments show preferential Br loss over Cl and S under ultraviolet (UV) irradiation, consistent with the observed Br loss relative to Cl in Martian soil samples. Overall, these findings generally suggest that soil serves as a source for volatilized halogens. Specifically, soil‐atmosphere multiphase reaction pathways constitute a crucial component missing from purely gas‐phase photochemical models of the halogen cycle.

Highly Active Halogen Bonding and Chalcogen Bonding Chloride Transporters with Non-Protonophoric Activity.

Synthetic anion transporters show much promise as potential anti‐cancer agents and therapeutics for diseases associated with mis‐regulation of protein anion channels. In such applications high activity and anion selectivity are crucial to overcome competing proton or hydroxide transport which dissipates cellular pH gradients. Here, highly active bidentate halogen bonding and chalcogen bonding anion carriers based on electron deficient iodo‐ and telluromethyl−triazole derivatives are reported. Anion transport experiments in lipid bilayer vesicles reveal record nanomolar chloride transport activity for the bidentate halogen bonding anion carrier, and remarkably high chloride over proton/hydroxide selectivity for the chalcogen bonding anionophore. Computational studies provide further insight into the role of sigma‐hole mediated anion recognition and desolvation at the membrane interface. Comparison with hydrogen bonding analogues demonstrates the importance of employing sigma‐hole donor motifs in synthetic anionophores for achieving both high transport activity and selectivity.

Concurrent atom transfer radical polymerization and nitroxide radical coupling relay polymerization.

Simultaneous atom transfer radical polymerization (ATRP) and nitroxide radical coupling (NRC) seems impossible because the presence of nitroxide radicals would quench the radical polymerization immediately. However, by combining a nitroxide radical and an ATRP active halogen, a halogen group that can initiate one polymer chain by ATRP, into one functional reagent and adding this functional reagent to an ATRP system, concurrent ATRP-NRC relay polymerization was carried out successfully under proper reaction conditions. The key to success was the conjugate radical trapping and re-initiation took place repeatedly, resulting in polymers with inserted alkoxyamine linkages. This novel relay polymerization method provides numerous possibilities for macromolecular architecture/functionality tailoring by using of different functional reagents.

Quinoline-8-olato-chromium catalysts with pseudohalogen effects for the CO2/cyclohexene epoxide copolymerization

Based on our previous studies utilizing CrIII catalysts with trifluoroacetate as labile ligand and an ansa-bis-quinoline-olato ligand as a chemically more robust variant compared to known salen-type N2O2 ligands, we synthesized and investigated a series of structurally similar quinoline-8-olato chromium complexes with different active (pseudo-)halogen ligands X in [(babhq)CrX], (babhq = 2,2′-(butyl-azanediyl)bis(quinolin-8-olate), X = Cl, NCO, and N3. We demonstrate a high activity of these CrIII complexes in the solvent free carbon dioxide/cyclohexene oxide (CHO) copolymerization compared to the state of the art. In much deeper detail than in our previous communication, we altered the labile ligand X and undertook a catalyst screening on the polymerization parameters, such as pressure, temperature, and cocatalyst, i.e. [PPN]N3 (bis(triphenylphosphine)iminiun azide). The activity of the chromium systems was found to much depend on the labile (pseudo-)halogen ligand X and increases in the order Cl < NCO < N3. Especially the azide complex [(babhq)CrN3] displays a high activity, displaying a TOF of 2165 h−1 after 1 h of reaction time along with an induction period of 30 min. At longer reaction times, up to 94% monomer conversion selectively into the respective polycarbonate (pCHC) is observed.

A Review on Adsorption Technologies for Mercury Emission Control.

This study summarized existing adsorption technologies for the removal of elemental mercury in the flue gas. Both carriers (e.g., active carbon (AC), pyrolyzed char, inorganic adsorbents and fly ash) and various modification methods (pore structure improvement, oxygen-containing functional groups addition and new active reagents impregnation) were compared to shed light on the development of future adsorption technology. AC and char possibly performed more mercury adsorption capacity (MAC) compared with fly ash and inorganic adsorbents since carbon atom existence was easier to form the active halogen groups (C-X) and oxygen containing groups. Though both pore structure improvement and chemical group formation improved the MAC of adsorbents, the chemical modification methods (oxygen-containing functional groups addition and new active reagents impregnation) were more effective. The impregnation of halogen, sulfur and metal chloride could distinctly form lots of active sites on the adsorbents and developed high effective mercury adsorbents. In the future, the adsorption researches possibly focus on SO2 and H2O resistance of adsorbents, separable adsorbents, low-cost chemical modification methods, and utilization potential of fly ash.

Improving abrasive tool cutting properties with the use of impregnators that emit chemically active gas media during thermal decomposition

Abstract Impregnation is one of the most commonly used methods of supplying microdoses of lubricant to the cutting zone. The expediency of using substances capable of releasing chemically active gas media, in particular, halogens and chalcogens, during thermal decomposition in the cutting zone as impregnators is substantiated. Application of the recommended compositions as abrasive tool impregnators provides reduction in cutting force components, abrasive tool wear and roughness of the processed surface. The local microprobe analysis demonstrated a reduction in the transfer of abrasive material to the treated surface. Production tests confirmed the effectiveness of the new impregnators.

Metal-Free Halogen(I) Catalysts for the Oxidation of Aryl(heteroaryl)methanes to Ketones or Esters: Selectivity Control by Halogen Bonding.

Metal-free halogen(I) catalysts were used for the selective oxidation of aryl(heteroaryl)methanes [C(sp3 )-H] to ketones [C(sp2 )=O] or esters [C(sp3 )-O]. The synthesis of ketones was performed with a catalytic amount of NBS in DMSO solvent. Experimental studies and density functional theory (DFT) calculations supported the formation of halogen bonding (XB) between the heteroarene and N-bromosuccinimide, which enabled imine-enamine tautomerism of the substrates. No additional activator was required for this crucial step. Isotope-labeling and other supporting experiments suggested that a Kornblum-type oxidation with DMSO and aerobic oxygenation with molecular oxygen took place simultaneously. A background XB-assisted electron transfer between the heteroarenes and halogen(I) catalysts was responsible for the formation of heterobenzylic radicals and, thus, the aerobic oxygenation. For selective acyloxylation (ester formation), a catalytic amount of iodine was employed with tert-butyl hydroperoxide in aliphatic carboxylic acid solvent. Several control reactions, spectroscopic studies, and Time-Dependent Density Functional Theory (TD-DFT) calculations established the presence of acetyl hypoiodite as an active halogen(I) species in the acetoxylation process. With the help of a selectivity study, for the first time we report that the strength of the XB interaction and the frontier orbital mixing between the substrates and acyl hypoiodites determined the extent of the background electron-transfer process and, thus, the selectivity of the reaction.

Evaluation of the Functional Condition of Human Blood Neutrophills Based on the Registrationof Active Halogen Forms Production

The development of adequate methods for monitoring the functional state of neutrophils is an urgent task due to their important role in the development of the inflammatory response. In this study, the functional activity of neutrophils has been assessed using a complex approach, including the registration of generation of ROS by neutrophils as a result of the functioning of the NADPH oxidase complex; degranulation of azurophilic granules; as well as production of AFG, formed in reactions catalyzed by the enzyme azurophilic granules of neutrophils – MPO in the presence of substrates (Н2О2 and halide ions).

Gradient measurements of gaseous elemental mercury (Hg0) in the marine boundary layer of the northwest Sea of Japan (East Sea).

Gaseous elemental mercury (Hg0) is a prolific and persistent contaminant in the atmosphere. Atmospheric concentrations of Hg0 were determined from 17 September to 7 October 2015 in the northwest Sea of Japan aboard the Russian research vessel Professor Gagarinsky. Simultaneous measurements of Hg0 concentrations were performed 2m and 20m above the sea surface using automatic Hg0 analysers RA-915M and RA-915+, respectively. Concentrations ranged from 0.3 to 25.9ng/m3 (n=5207) and from 0.3 to 27.8ng/m3 (n=4415), with medians of 1.7 and 1.6ng/m3, respectively. Elevated Hg0 was observed during three episodes from 19 to 22 September, likely caused by one or more of the following factors: 1) atmospheric transport of Hg0 from the west and south-west (from N. Korea, China, and the Yellow Sea region); 2) Hg0 emission from the sea due to pollution by water from the Tumannaya River; or 3) underwater geological activities. Increased Hg0 concentration was observed during periods when air masses flowed from the south, and low concentrations were observed when air masses came from the north. A daytime increase of Hg0 concentrations at a height of 2m occurred simultaneously with decreasing Hg0 at a height of 20m. These diurnal variations suggest that two contrasting processes occur during the daytime in the marine boundary layer (MBL): Hg0 emission from the sea surface and Hg0 oxidation in the MBL by active halogens formed by photolysis.

Inactivation of microbicidal active halogen compounds by sodium thiosulphate and histidine/methionine for time-kill assays

Rapid inactivation of antimicrobial test agents after exact incubation times with microorganisms is required in time-kill assays. Sodium thiosulphate and a combination of methionine and histidine were compared for neutralisation of active halogen compounds.Test oxidants were mixed with surplus sodium thiosulphate (3%–6%) or histidine/methionine (1% each) in phosphate-buffered saline and incubated for different times, followed by addition of Staphylococcus aureus, Escherichia coli, or Pseudomonas aeruginosa at 1000CFU/ml. After further incubation, quantitative cultures were performed.Thiosulphate did not sufficiently inactivate chlorine and bromine compounds, indicated by a 10-fold (S. aureus) up to >100-fold (E. coli, P. aeruginosa) reduction of CFU. This was particularly true for high concentrations of the oxidants of about 50mM, for highly reactive agents (HOCl and bromamine T) more than for chloramine T and N-chlorotaurine, and for short pre-incubation times before addition of the bacteria. By contrast, histidine/methionine proved to be suitable for chloramines and bromamine T and for low concentrations of HOCl (0.07%). HOCl at 0.7% could neither be inactivated completely by thiosulphate nor by histidine/methionine. In contrast to chlorine and bromine compounds, iodine was neutralized by thiosulphate, but not by histidine/methionine.Histidine/methionine is superior to inactivate chlorine and bromine and should replace sodium thiosulphate at least in killing tests with high concentrations of these disinfectants. Inclusion of a short reaction time (maximum one minute) of test oxidant and neutralising substance before addition of bacteria is decisive in inactivation tests to obtain reliable results.

Low-dimensional compounds containing bioactive ligands. Part VIII: DNA interaction, antimicrobial and antitumor activities of ionic 5,7-dihalo-8-quinolinolato palladium(II) complexes with K+ and Cs+ cations

Starting from well-defined NH2(CH3)2[PdCl2(XQ)] complexes, coordination compounds of general formula Cat[PdCl2(XQ)] have been prepared by cationic exchange of NH2(CH3)2+ and Cat cations, where XQ are biologically active halogen derivatives of quinolin-8-ol (5-chloro-7-iodo-quinolin-8-ol (CQ), 5,7-dibromo-quinolin-8-ol (dBrQ) and 5,7-dichloro-quinolin-8-ol (dClQ)) and Cat is K+ or Cs+. The cation exchange of all prepared complexes, K[PdCl2(CQ)] (1), K[PdCl2(dClQ)] (2), K[PdCl2(dBrQ)] (3), Cs[PdCl2(CQ)] (4), Cs[PdCl2(dClQ)] (5) and Cs[PdCl2(dBrQ)] (6) was approved using IR spectroscopy, their structures in DMSO solution were elucidated by one- and two-dimensional NMR experiments, whereas their stability in solution was verified by UV–VIS spectroscopy. Interaction of complexes to ctDNA was investigated using UV–VIS and fluorescence emission spectroscopy. The minimum inhibitory concentration and the minimum microbicidal concentration values were detected against 15 bacterial strains and 4 yeast strains to examine the antimicrobial activity for the complexes. The in vitro antitumor properties of the complexes were studied by testing the complexes on leukemic cell line L1210, ovarian cancer cell line A2780 and non-cancerous cell line HEK293. The majority of the prepared compounds exhibited moderate antimicrobial and very high cytotoxic activity.

A Facile Synthesis and Characterization of Biologically Active Halogen Substituted 1-Acetyl 3, 5-Diphenylpyrazole Derivatives

A Facile Synthesis and Characterization of Biologically Active Halogen Substituted 1-Acetyl 3, 5-Diphenylpyrazole Derivatives

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

Abstract. The springtime depletion of tropospheric ozone in the Arctic is known to be caused by active halogen photochemistry resulting from halogen atom precursors emitted from snow, ice, or aerosol surfaces. The role of bromine in driving ozone depletion events (ODEs) has been generally accepted, but much less is known about the role of chlorine radicals in ozone depletion chemistry. While the potential impact of iodine in the High Arctic is more uncertain, there have been indications of active iodine chemistry through observed enhancements in filterable iodide, probable detection of tropospheric IO, and recently, observation of snowpack photochemical production of I2. Despite decades of research, significant uncertainty remains regarding the chemical mechanisms associated with the bromine-catalyzed depletion of ozone, as well as the complex interactions that occur in the polar boundary layer due to halogen chemistry. To investigate this, we developed a zero-dimensional photochemical model, constrained with measurements from the 2009 OASIS field campaign in Barrow, Alaska. We simulated a 7-day period during late March that included a full ozone depletion event lasting 3 days and subsequent ozone recovery to study the interactions of halogen radicals under these different conditions. In addition, the effects of iodine added to our Base Model were investigated. While bromine atoms were primarily responsible for ODEs, chlorine and iodine were found to enhance the depletion rates and iodine was found to be more efficient per atom at depleting ozone than Br. The interaction between chlorine and bromine is complex, as the presence of chlorine can increase the recycling and production of Br atoms, while also increasing reactive bromine sinks under certain conditions. Chlorine chemistry was also found to have significant impacts on both HO2 and RO2, with organic compounds serving as the primary reaction partner for Cl atoms. The results of this work highlight the need for future studies on the production mechanisms of Br2 and Cl2, as well as on the potential impact of iodine in the High Arctic.

The Integral Method, a new approach to quantify bactericidal activity

The bactericidal activity (BA) of antimicrobial agents is generally derived from the results of killing assays. A reliable quantitative characterization and particularly a comparison of these substances, however, are impossible with this information. We here propose a new method that takes into account the course of the complete killing curve for assaying BA and that allows a clear-cut quantitative comparison of antimicrobial agents with only one number.The new Integral Method, based on the reciprocal area below the killing curve, reliably calculates an average BA [log10CFU/min] and, by implementation of the agent's concentration C, the average specific bactericidal activity SBA=BA/C [log10CFU/min/mM].Based on experimental killing data, the pertaining BA and SBA values of exemplary active halogen compounds were established, allowing quantitative assertions. N-chlorotaurine (NCT), chloramine T (CAT), monochloramine (NH2Cl), and iodine (I2) showed extremely diverging SBA values of 0.0020±0.0005, 1.11±0.15, 3.49±0.22, and 291±137log10CFU/min/mM, respectively, against Staphylococcus aureus. This immediately demonstrates an approximately 550-fold stronger activity of CAT, 1730-fold of NH2Cl, and 150,000-fold of I2 compared to NCT.The inferred quantitative assertions and conclusions prove the new method suitable for characterizing bactericidal activity. Its application comprises the effect of defined agents on various bacteria, the consequence of temperature shifts, the influence of varying drug structure, dose–effect relationships, ranking of isosteric agents, comparison of competing commercial antimicrobial formulations, and the effect of additives.

Fluorinated azobenzenes with highly strained geometries for halogen bond-driven self-assembly in the solid state

Attempted cocrystallisation of brominated and iodinated octafluoroazobenzene derivatives with morpholine led to the exhaustive replacement of fluorine substituents that are in ortho-positions to the azobenzene with sterically demanding morpholine groups. The resulting molecules exhibit a highly unusual strained conformation of the azobenzene unit, in which the terminal phenyl rings adopt a mutually nearly completely orthogonal orientation. Substitution of ortho-fluorine groups with N-morpholine fragments provides molecules with active halogen bond donor and acceptor sites that guide the molecular self-assembly in the solid state towards the formation of polymeric halogen-bonded chains.

Nitrate postdeposition processes in Svalbard surface snow

AbstractThe snowpack acts as a sink for atmospheric reactive nitrogen, but several postdeposition pathways have been reported to alter the concentration and isotopic composition of snow nitrate with implications for atmospheric boundary layer chemistry, ice core records, and terrestrial ecology following snow melt. Careful daily sampling of surface snow during winter (11–15 February 2010) and springtime (9 April to 5 May 2010) near Ny‐Ålesund, Svalbard reveals a complex pattern of processes within the snowpack. Dry deposition was found to dominate over postdeposition losses, with a net nitrate deposition rate of (0.6 ± 0.2) µmol m−2 d−1 to homogeneous surface snow. At Ny‐Ålesund, such surface dry deposition can either solely result from long‐range atmospheric transport of oxidized nitrogen or include the redeposition of photolytic/bacterial emission originating from deeper snow layers. Our data further confirm that polar basin air masses bring 15N‐depleted nitrate to Svalbard, while high nitrate δ(18O) values only occur in connection with ozone‐depleted air, and show that these signatures are reflected in the deposited nitrate. Such ozone‐depleted air is attributed to active halogen chemistry in the air masses advected to the site. However, here the Ny‐Ålesund surface snow was shown to have an active role in the halogen dynamics for this region, as indicated by declining bromide concentrations and increasing nitrate δ(18O), during high BrO (low‐ozone) events. The data also indicate that the snowpack BrO‐NOx cycling continued in postevent periods, when ambient ozone and BrO levels recovered.