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Concept: Hydrogen chloride

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Both nitrate and pentachlorophenol (PCP) are familiar pollutants in aqueous environment. This research is focused on the simultaneous removal of nitrate and PCP from simulated contaminated groundwater using a laboratory-scale denitrification reactor packed with corncob as both carbon source and biofilm support. The reactor could be started up readily, and the removal efficiencies of nitrate and PCP reached up to approximately 98 % and 40-45 % when their initial concentrations were 50 mg N/L and 5 mg/L, respectively, after 15-day continuous operation at 10 h of hydraulic retention time (HRT) and 25 °C. Approximately 91 % of PCP removal efficiency was achieved, with 2.47 mg/L of chloride ion release at 24 h of HRT. Eighty-two percent of chlorine in PCP removed was ionized. The productions of 3-chlorophenol and phenol and chloride ion release indicate that the reductive dechlorination reaction is a major degradation pathway of PCP under the experimental conditions.

Concepts: Concentration, Chemistry, Water pollution, Sodium chloride, Ion, Chlorine, Chloride, Hydrogen chloride

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Ingestion of contaminated soil is one potential internal exposure pathway in areas contaminated by the Fukushima Daiichi Nuclear Power Plant accident. Doses from this pathway can be overestimated if the availability of radioactive nuclides in soils for the gastrointestinal tract is not considered. The concept of bioaccessibility has been adopted to evaluate this availability based on in vitro tests. This study evaluated the bioaccessibility of radioactive cesium from soils via the physiologically-based extraction test (PBET) and the extractability of those via an extraction test with 1 mol/L of hydrochloric acid (HCl). The bioaccessibility obtained in the PBET was 5.3% ± 1%, and the extractability in the tests with HCl was 16% ± 3%. The bioaccessibility was strongly correlated with the extractability. This result indicates the possibility that the extractability in HCl can be used as a good predictor of the bioaccessibility with PBET. In addition, we assessed the doses to children from the ingestion of soil via hand-to-mouth activity based on our PBET results using a probabilistic approach considering the spatial distribution of radioactive cesium in Date City in Fukushima Prefecture and the interindividual differences in the surveyed amounts of soil ingestion in Japan. The results of this assessment indicate that even if children were to routinely ingest a large amount of soil with relatively high contamination, the radiation doses from this pathway are negligible compared with doses from external exposure owing to deposited radionuclides in Fukushima Prefecture.

Concepts: Chernobyl disaster, Digestive system, Chlorine, Nuclear power, Hydrogen chloride, Hydrochloric acid, Fukushima Prefecture, Tōhoku region

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The pressure-temperature phase diagram of ice displays a perplexing variety of structurally distinct phases. In the century-long history of scientific research on ice, the proton-ordered ice phases numbered XIII through XV were discovered only recently. Despite considerable effort, none of the transitions leading from the low-temperature ordered ices VIII, IX, XI, XIII, XIV and XV to their high-temperature disordered counterparts were experimentally found to display the full Pauling entropy. Here we report calorimetric measurements on suitably high-pressure-treated, hydrogen chloride-doped ice XIV that demonstrate just this at the transition to ice XII. Dielectric spectroscopy on undoped and on variously doped ice XII crystals reveals that addition of hydrogen chloride, the agent triggering complete proton order in ice XIV, enhances the precursor dynamics strongest. These discoveries provide new insights into the puzzling observation that different dopants trigger the formation of different proton-ordered ice phases.

Concepts: Crystal, Hydrogen, Ice, Phase, Chlorine, Triple point, Hydrogen chloride, Hydrochloric acid

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A liquid chromatographic-electrospray ionization-time-of-flight/mass spectrometric (LC-ESI-TOF/MS) method was developed and applied for the determination of WKYMVm peptide in rat plasma to support preclinical pharmacokinetics studies. The method consisted of micro-elution solid phase extraction (SPE) for sample preparation and LC-ESI-TOF/MS in the positive ion mode for analysis. Phenanthroline (10mg/mL) was added to rat blood immediately for plasma preparation followed by addition of trace amount of 2M hydrogen chloride (HCl) to plasma before SPE for the stability of WKYMVm peptide. Then, sample preparation using micro-elution SPE was performed with verapamil as an internal standard. A quadratic regression (weighted 1/concentration(2) ), with an equation y=ax(2) +bx+c, was used to fit calibration curves over the concentration range of 3.02~2200 ng/mL for WKYMVm peptide. The quantification run met the acceptance criteria of ±25 % accuracy and precision values. For quality control samples at 15, 165, and 1820 ng/mL from the quantification experiment, the within-run and the between-run accuracy ranged from 92.5 to 123.4 % with precision values ≤15.1 % for WKYMVm peptide from the nominal values. This novel LC-ESI-TOF/MS method was successfully applied to evaluate the pharmacokinetics of WKYMVm peptide in rat plasma.

Concepts: Hydrogen, Ion, Accuracy and precision, Chlorine, Chloride, Hydrogen chloride, Phases of matter, State of matter

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The replacement of mercuric chloride in the production of vinyl chloride monomer, a precursor to PVC, would greatly reduce the environmental impact of this large scale industrial process. The validation of single Au cations supported on carbon as the best catalyst for this reaction at an industrial scale has resulted from nearly 35 years of research. In this feature article we review the development of this catalyst system and address the limitations of a range of characterisation techniques used previously which may induce damage to the fresh catalyst. Following our latest findings using X-ray absorption spectroscopy, we show that under operating conditions the catalyst is atomically dispersed and can be classed as a single site catalyst, we give a perspective on future directions in single atom catalysis.

Concepts: Carbon dioxide, Hydrogen, Atom, X-ray absorption spectroscopy, Absorption spectroscopy, Hydrogen chloride, Polyvinyl chloride, Vinyl chloride

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To determine the amounts and chemical forms of chlorine compounds in elemental chlorine-free (ECF) bleached pulp for sanitary products, a chemical-form-based quantitative analysis flow scheme was created. The scheme involves quantitative determination of compounds eluted in elution tests assuming dermal exposure. The results indicated that most of the chlorine compounds in pulp used for sanitary products were insoluble organically bound chlorine and water-soluble chlorides consisting of chloride ions. The total amount of chlorine obtained by analysis of the total chlorine in the pulp products was close to the sum of the amounts of water-soluble chlorides, residual chlorine, chloroacetic acids, and insoluble organically bound chlorine. Therefore, the balance of chlorine measured by the flow scheme was acceptable. Little residual chlorine was detected in the pulp products, suggesting that the chlorine dioxide used for bleaching was almost completely converted into inactive inorganic chlorides and organic chlorine compounds and that these substances do not affect the health risk posed by pulp products. A risk assessment of the detected chloroacetic acid and dichloroacetic acid revealed that there is no concern about the health risk posed by use of these products.

Concepts: Sodium chloride, Chlorine, Chloride, Hydrogen chloride, Hydrochloric acid, Chloroacetic acids, Trichloroacetic acid, Chloroacetic acid

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Ordered mesostructured TiO2 thin films are employed in diverse applications ranging from catalysis and sensing, to photovoltaic and lithium-ion batteries. Experimentally these mesostructured thin films are fabricated via a sol-gel process coupled with evaporation-induced self-assembly of a supramolecular template, where the concentration of hydrogen chloride (HCl) and water play vital roles. We employ a soft, coarse-grained model of the amphiphilic template Brij58 and spherical particles, representing titanium-oxo clusters, to study the role of HCl and water in the formation of mesostructured TiO2 thin films. The template-cluster and cluster-cluster interactions are reflected in the interaction terms δNBP and εPP, respectively. The results show that a decrease in HCl (increase in εPP) leads to the formation of large mesopores due to the strong attraction between particles, giving rise to a high dispersity index (low order) of the thin films. However, a decrease in water (increase in δNBP) will compensate for the entropic attraction between particles, resulting in thin films with low dispersity index (high order). The variation of the dispersity index in the δNBP-εPP plane provides an intuitive understanding that the slow evaporation of HCl could drive the film towards a uniform mesoporous state, whereas fast evaporation pushes the film through a non-uniform phase. These results indicate that even if the mass proportion of the surfactants Brij58 and titanium precursors is the same in the initial solution, the final mesoporous structures could be diverse, which was confirmed by the controlled experiments. We also confirm the post-processing-towards-order strategy by making the particle rearrangement available by weakening the εPP. The outlined procedure paves the way for soft, coarse-grained models to understand the complex co-assembly of transition metal clusters and amphiphilic surfactants towards the rational design of highly ordered mesoporous structures.

Concepts: Water, Hydrogen, Interaction, Experiment, Chlorine, Chloride, Hydrogen chloride, Hydrochloric acid

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Catalytic asymmetric cycloadditions of reactive ketene intermediates provide new opportunities for the production of chiral heterocyclic molecules. Though known for over 100 years, ketenes still remain underexplored in the field of transition-metal ™-catalyzed asymmetric cycloadditions because (1) ketenes, as highly electron-deficient species, are possibly unstable to low-valance TMs (i.e., decarbonylation or aggregation) and (2) the conventional thermal synthesis of ketenes from acyl chlorides and amines may be incompatible with TM catalysis (i.e., reactive acyl chloride and amine-hydrochloride by-products). Herein, we detail the unprecedented asymmetric [4+2] cycloaddition of vinyl benzoxazinanones with a variety of ketene intermediates via sequential visible-light photoactivation and palladium catalysis. It is well demonstrated that, the traceless and transient generation of ketenes from α-diazoketones through visible-light-induced Wolff rearrangement is important for the success of present cycloaddition. Furthermore, chiral palladium catalysts with a new, chiral hybrid P, S ligand enable the asymmetric cycloaddition with high reaction selectivity and enantiocontrol.

Concepts: Amine, Chemical reaction, Catalysis, Hydrogenation, Catalytic converter, Cycloaddition, Hydrogen chloride, Ketene

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The adsorptions of tryptophan (Trp) on silver or gold surfaces were investigated by surface-enhanced Raman scattering (SERS) measurements. In addition, peptides with Trp in different chain positions were studied and the adsorption sites were determined based on marker bands. The indole ring was the main group responsible for the interactions with gold nanoparticles (AuNPs). In the presence of HCl, the SERS spectra suggested that the anchoring of such peptides on AuNPs was reinforced by ionic pair interactions between protonated amine and chloride ions. The adsorptions of Trp and its derivatives on silver nanoparticles (AgNPs) show some variability in the spectral patterns, even though the enhanced carboxilate and amino features were ever ascribed as preferable adsorption site. Based on DFT calculations the vibrational assignment allows the reinterpretation of previous published works. The investigations showed that both the high affinity of indole moiety for the AuNP surfaces make these substrates adequate for studying the adsorption of peptides containing Trp and the proposed SERS assignments could be helpful for further studies of more complex structures.

Concepts: Sodium chloride, Adsorption, Ion, Gold, Tryptophan, Chloride, Hydrogen chloride, Reactions on surfaces

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Graphitic carbon nitride (GCN) nanosheets with unique physicochemical properties have received increasing attention in the area of photocatalysis, yet tunable thickness for the straightforward production of this graphite-like two-dimensional (2D) nanomaterial remains a challenge. In this work, GCN nanosheets with different thicknesses were firstly prepared by a direct calcination of melamine supramolecular aggregates (MSA) obtained from a hydrochloric acid (HCl)-induced hydrothermal assembly approach. The resultant nanosheets over nanometer scale thickness could be precisely controlled via simply adjusting the HCl concentration. Compared to the bulk GCN (BGCN), the thinner nanosheets possessed a high specific surface area, a large electronic-band structure, and fast charge separation ability. The thinnest nanosheets with a thickness of approximately 4 nm exhibited excellent visible-light-driven photocatalytic water splitting performance in hydrogen evolution (524 μmol h(-1) g(-1)), which is over 9-fold higher than the BGCN powder. This work provides a thickness-dependent strategy for the preparation of metal-free GCN nanosheets and develops a promising 2D photocatalyst for application in solar energy conversion.

Concepts: Sun, Hydrogen, Photoelectrochemical cell, Chlorine, Photocatalysis, Photocatalytic water splitting, Hydrogen chloride, Hydrochloric acid