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Chlorine Substituted Acetic Acids and Salts. Effect of Salification on Chlorine-35 NQR*
Chlorine Substituted Acetic Acids and Salts. Effect of Salification on Chlorine-35 NQR* Serge David3, Michel Gourdjib, Lucien Guibéb, and Alain Péneaub a Laboratoire de Chimie Organique Multifonctionnelle, Bätiment 420. b Institut d'Electronique Fondamentale, Bätiment 220, Universite Paris-Sud, 91405 ORSAY Cedex, France. Z. Naturforsch. 51a, 611-619 (1996); received October 10, 1995 The NQR of a quadrupolar probe nucleus is often used to investigate the effect of substituent in molecules. The inductive effect, based on a partial charge migration along the molecular skeleton is the only one present in saturated aliphatics, the conjugative effect appearing in conjugated molecules, especially aromatics. As the stepwise charge migration mechanism, formerly used to explain the inductive effect, is now believed obsolete, we have wanted to reexamined the case of chlorine substituted acetic acids and salts. The data in literature was extended by observing reso- nances and determining NQR frequencies in several acids and salts. The present analysis of the salification of mono-, di- and tri-chloroacetic acids, which is equivalent to a deprotonation or the substitution of the acid hydrogen by a negative unit charge, shows that a model based on the polarization of the chlorine atom(s) by the carboxyle group is consistent with experimental results: the polarization energy appears to be proportional to the NQR frequency shifts; experimental data show a correlation between the NQR frequency shifts accompanying salification and the variations of the intrinsic acidity measured in the gas phase; this, in turn shows that there is a proportionality between the polarization energy and the variations in the acid free enthalpy of dissociation. -
Monochloroacetic Acid, Sodium Monochloroacetate
Monochloroacetic acid, sodium monochloroacetate MAK Value Documentation, supplement – Translation of the German version from 2019 A. Hartwig1,* MAK Commission2,* 1 Chair of the Permanent Senate Commission for the Investigation of Health Hazards of Chemical Compounds Keywords: in the Work Area, Deutsche Forschungsgemeinschaft, Institute of Applied Biosciences, Department of Food Chemistry and Toxicology, Karlsruhe Institute of Technology (KIT), Adenauerring 20a, Building 50.41, monochloroacetic acid, sodium 76131 Karlsruhe, Germany monochloroacetate, irritation, 2 Permanent Senate Commission for the Investigation of Health Hazards of Chemical Compounds in the Work oxidative stress, peak limitation, Area, Deutsche Forschungsgemeinschaft, Kennedyallee 40, 53175 Bonn, Germany skin absorption, maximum workplace concentration, MAK * E-Mail: A. Hartwig ([email protected]), MAK Commission ([email protected]) value, prenatal toxicity, hazardous substance Abstract The German Commission for the Investigation of Health Hazards of Chemical Com- pounds in the Work Area has re-evaluated monochloroacetic acid [79-11-8] together with sodium monochloroacetate [3926-62-3] considering all toxicological endpoints. Monochloroacetic acid is a strong acid and dissociates in biological media. Therefore, also data for sodium monochloroacetate are used to evaluate the systemic toxicity. Monochloroacetic acid is corrosive to the eyes but there are no inhalation studies from which a NOAEC for local effects can be derived. Therefore, a maximum con- centration at the workplace (MAK value) of 2 mg/m3 (0.5 ml/m3), which has been set for the better investigated phosphoric acid, is also established for monochloroacetic acid.Asirritationisthecriticaleffect,monochloroaceticacidisclassifiedinPeakLim- Citation Note: itation Category I. By analogy with phosphoric acid, an excursion factor of 2 is set. Hartwig A, MAK Commission. -
APPENDIX G Acid Dissociation Constants
harxxxxx_App-G.qxd 3/8/10 1:34 PM Page AP11 APPENDIX G Acid Dissociation Constants § ϭ 0.1 M 0 ؍ (Ionic strength ( † ‡ † Name Structure* pKa Ka pKa ϫ Ϫ5 Acetic acid CH3CO2H 4.756 1.75 10 4.56 (ethanoic acid) N ϩ H3 ϫ Ϫ3 Alanine CHCH3 2.344 (CO2H) 4.53 10 2.33 ϫ Ϫ10 9.868 (NH3) 1.36 10 9.71 CO2H ϩ Ϫ5 Aminobenzene NH3 4.601 2.51 ϫ 10 4.64 (aniline) ϪO SNϩ Ϫ4 4-Aminobenzenesulfonic acid 3 H3 3.232 5.86 ϫ 10 3.01 (sulfanilic acid) ϩ NH3 ϫ Ϫ3 2-Aminobenzoic acid 2.08 (CO2H) 8.3 10 2.01 ϫ Ϫ5 (anthranilic acid) 4.96 (NH3) 1.10 10 4.78 CO2H ϩ 2-Aminoethanethiol HSCH2CH2NH3 —— 8.21 (SH) (2-mercaptoethylamine) —— 10.73 (NH3) ϩ ϫ Ϫ10 2-Aminoethanol HOCH2CH2NH3 9.498 3.18 10 9.52 (ethanolamine) O H ϫ Ϫ5 4.70 (NH3) (20°) 2.0 10 4.74 2-Aminophenol Ϫ 9.97 (OH) (20°) 1.05 ϫ 10 10 9.87 ϩ NH3 ϩ ϫ Ϫ10 Ammonia NH4 9.245 5.69 10 9.26 N ϩ H3 N ϩ H2 ϫ Ϫ2 1.823 (CO2H) 1.50 10 2.03 CHCH CH CH NHC ϫ Ϫ9 Arginine 2 2 2 8.991 (NH3) 1.02 10 9.00 NH —— (NH2) —— (12.1) CO2H 2 O Ϫ 2.24 5.8 ϫ 10 3 2.15 Ϫ Arsenic acid HO As OH 6.96 1.10 ϫ 10 7 6.65 Ϫ (hydrogen arsenate) (11.50) 3.2 ϫ 10 12 (11.18) OH ϫ Ϫ10 Arsenious acid As(OH)3 9.29 5.1 10 9.14 (hydrogen arsenite) N ϩ O H3 Asparagine CHCH2CNH2 —— —— 2.16 (CO2H) —— —— 8.73 (NH3) CO2H *Each acid is written in its protonated form. -
Evaluating Analytical Methods for Detecting Unknown Chemicals in Recycled Water
PROJECT NO. 4992 Evaluating Analytical Methods for Detecting Unknown Chemicals in Recycled Water Evaluating Analytical Methods for Detecting Unknown Chemicals in Recycled Water Prepared by: Keith A. Maruya Charles S. Wong Southern California Coastal Water Research Project Authority 2020 The Water Research Foundation (WRF) is a nonprofit (501c3) organization which provides a unified source for One Water research and a strong presence in relationships with partner organizations, government and regulatory agencies, and Congress. The foundation conducts research in all areas of drinking water, wastewater, stormwater, and water reuse. The Water Research Foundation’s research portfolio is valued at over $700 million. The Foundation plays an important role in the translation and dissemination of applied research, technology demonstration, and education, through creation of research‐based educational tools and technology exchange opportunities. WRF serves as a leader and model for collaboration across the water industry and its materials are used to inform policymakers and the public on the science, economic value, and environmental benefits of using and recovering resources found in water, as well as the feasibility of implementing new technologies. For more information, contact: The Water Research Foundation Alexandria, VA Office Denver, CO Office 1199 North Fairfax Street, Suite 900 6666 West Quincy Avenue Alexandria, VA 22314‐1445 Denver, Colorado 80235‐3098 Tel: 571.384.2100 Tel: 303.347.6100 www.waterrf.org [email protected] ©Copyright 2020 by The Water Research Foundation. All rights reserved. Permission to copy must be obtained from The Water Research Foundation. WRF ISBN: 978‐1‐60573‐503‐0 WRF Project Number: 4992 This report was prepared by the organization(s) named below as an account of work sponsored by The Water Research Foundation. -
Provisional Peer Reviewed Toxicity Values for Chloroacetic Acid (Casrn 79-11-8)
EPA/690/R-04/004F l Final 11-24-2004 Provisional Peer Reviewed Toxicity Values for Chloroacetic Acid (CASRN 79-11-8) Superfund Health Risk Technical Support Center National Center for Environmental Assessment Office of Research and Development U.S. Environmental Protection Agency Cincinnati, OH 45268 Acronyms bw - body weight cc - cubic centimeters CD - Caesarean Delivered CERCLA - Comprehensive Environmental Response, Compensation, and Liability Act of 1980 CNS - central nervous system cu.m - cubic meter DWEL - Drinking Water Equivalent Level FEL - frank-effect level FIFRA - Federal Insecticide, Fungicide, and Rodenticide Act g - grams GI - gastrointestinal HEC - human equivalent concentration Hgb - hemoglobin i.m. - intramuscular i.p. - intraperitoneal i.v. - intravenous IRIS - Integrated Risk Information System IUR - Inhalation Unit Risk kg - kilogram L - liter LEL - lowest-effect level LOAEL - lowest-observed-adverse-effect level LOAEL(ADJ) - LOAEL adjusted to continuous exposure duration LOAEL(HEC) - LOAEL adjusted for dosimetric differences across species to a human m - meter MCL - maximum contaminant level MCLG - maximum contaminant level goal MF - modifying factor mg - milligram mg/kg - milligrams per kilogram mg/L - milligrams per liter MRL - minimal risk level MTD - maximum tolerated dose i MTL - median threshold limit NAAQS - National Ambient Air Quality Standards NOAEL - no-observed-adverse-effect level NOAEL(ADJ) - NOAEL adjusted to continuous exposure duration NOAEL(HEC) - NOAEL adjusted for dosimetric differences across -
Study on Gas-Phase Mechanism of Chloroacetic Acid Synthesis by Catalysis and Chlorination of Acetic Acid
Asian Journal of Chemistry; Vol. 26, No. 2 (2014), 475-480 http://dx.doi.org/10.14233/ajchem.2014.15484 Study on Gas-Phase Mechanism of Chloroacetic Acid Synthesis by Catalysis and Chlorination of Acetic Acid * JIAN-WEI XUE , JIAN-PENG ZHANG, BO WU, FU-XIANG LI and ZHI-PING LV Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, Shanxi Province, P.R. China *Corresponding author: Fax: +86 351 6111178; Tel: +86 351 60105503; E-mail: [email protected] Received: 14 March 2013; Accepted: 17 May 2013; Published online: 15 January 2014; AJC-14570 The process of acetic acid catalysis and chlorination for synthesizing chloroacetic acid can exist in not only gas phase but also liquid phase. In this paper, the gas-phase reaction mechanism of the synthesis of chloroacetic acid was studied. Due to the high concentration of acetic acid and the better reaction mass transfer in the liquid-phase reaction, the generation amount of the dichloroacetic acid was higher than that in the gas-phase reaction. Under the solution distillation, the concentration of acetyl chloride, whose boiling point is very low, was very high in the gas phase, sometimes even up to 99 %, which would cause the acetyl chloride to escape rapidly with the hydrogen chloride exhaust, so that the reaction slowed down. Therefore, series reactions occured easily in the gas-phase reaction causing the amount of the dichloroacetic acid to increase. Keywords: Gas phase, Catalysis, Chlorination, Chloroacetic acid, Acetic acid. INTRODUCTION Martikainen et al.3 summed up the reaction mechanism that was consistent with a mechanism found by Sioli according Chloroacetic acid is not only a fine chemical product but to the system condition experiment and systematic theoretical also an important intermediate in organic synthesis. -
Justin Pals.Pdf
MECHANISMS OF MONOHALOGENATED ACETIC ACID INDUCED GENOMIC DNA DAMAGE BY JUSTIN A. PALS DISSERTATION Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Crop Sciences in the Graduate College of the University of Illinois at Urbana-Champaign, 2014 Urbana, Illinois Doctoral Committee: Professor Michael J. Plewa, Chair Professor Benito J. Mariñas Professor A. Layne Rayburn Brian K. Miller, Director of Illinois-Indiana Sea Grant ABSTRACT Disinfection of drinking water stands among the greatest public health achievements in human history. Killing or inactivation of pathogenic microbes by chemical oxidants such as chlorine, chloramine, or ozone have greatly reduced incidence of waterborne diseases. However, the disinfectant also reacts with organic and inorganic matter in the source water and generates a mixture of toxic disinfection byproducts (DBPs) as an unintended consequence. Since they were first discovered in 1974, over 600 individual DBPs have been detected in disinfected water. Exposure to DBPs is associated with increased risks for developing cancers of the colon, rectum, and bladder, and also for adverse pregnancy outcomes including small for gestational age and congenital malformations. While individual DBPs are teratogenic or carcinogenic, because they are formed at low concentrations during disinfection, it is unlikely that any one DBP can account for these increased risks. While genotoxicity and oxidative stress have been suggested, the mechanisms connecting DBP exposures to adverse health and pregnancy outcomes remain unknown. Investigating mechanisms of toxicity for individual, or classes of DBPs will provide a better understanding of how multiple DBPs interact to generate adverse health and pregnancy outcomes. Monohalogenated acetic acids (monoHAAs) iodoacetic acid (IAA), bromoacetic acid (BAA), and chloroacetic acid (CAA) are genotoxic and mutagenic with the consistent rank order of toxicity of IAA > BAA > CAA. -
Preparation and Isolation of the S-Carboxymethy L Derivative Chains of Human Fibrinogen
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Elsevier - Publisher Connector Volume 14, number 1 FEBSLETTERS April 1971 PREPARATION AND ISOLATION OF THE S-CARBOXYMETHY L DERIVATIVE CHAINS OF HUMAN FIBRINOGEN Genesio MURANO, Bjorn WIMAN, Margareta BLOMBACK and Birger BLOMBACK Dept. of Blood Coagulation Research, Karolinska Institute, Stockholm, Sweden Received 1 March 1971 1. Introduction Amersham, England) Lot No. B 10, specific activity: 50-l 50 mCi/mmole, was diluted appropriately with Fibrinogen is composed of three pairs of polypeptide carrier iodoacetic acid before use. chains: o(A), /3(B), and y [ 1,2] . Fibrinopeptides A 3H-Iodoacetic acid-carrier mixture was prepared and B are cleaved off the a(A) and P(B) chains respecti- fresh by mixing 4 ml of 1 M iodoacetic acid carrier vely by thrombin. The resulting product is fibrin [3,4]. (186 mg/mI of 0.1 N NaOH) with 6 ml of 2-j H-iodo- Sulfitolysis of fibrinogen results in the cleavage of the acetic acid (1 mCi/ml of 0.1 N NaOH). disulfide bridges [5] , and the resulting S-sulfo chain Carboxymethyl cellulose (CM-52) was precycled derivatives have been separated by paper [ 51, starch as recommended by the manufacturer (H. Reeve gel electrophoresis [6] and column chromatography Angel and Co., London, England). [S, 71. More recently, the S-sulfo chain derivatives Radioactivity measurements were performed with from bovine [8] and human [9] fibrinogen have been a Beckman liquid scintillation system (CPM 200). isolated on carboxymethyl cellulose using a stepwise N-Terminal sequence amino acid analysis: The [8] and gradient [9] sodium acetate buffer system. -
Dissociation Constants of Organic Acids and Bases
DISSOCIATION CONSTANTS OF ORGANIC ACIDS AND BASES This table lists the dissociation (ionization) constants of over pKa + pKb = pKwater = 14.00 (at 25°C) 1070 organic acids, bases, and amphoteric compounds. All data apply to dilute aqueous solutions and are presented as values of Compounds are listed by molecular formula in Hill order. pKa, which is defined as the negative of the logarithm of the equi- librium constant K for the reaction a References HA H+ + A- 1. Perrin, D. D., Dissociation Constants of Organic Bases in Aqueous i.e., Solution, Butterworths, London, 1965; Supplement, 1972. 2. Serjeant, E. P., and Dempsey, B., Ionization Constants of Organic Acids + - Ka = [H ][A ]/[HA] in Aqueous Solution, Pergamon, Oxford, 1979. 3. Albert, A., “Ionization Constants of Heterocyclic Substances”, in where [H+], etc. represent the concentrations of the respective Katritzky, A. R., Ed., Physical Methods in Heterocyclic Chemistry, - species in mol/L. It follows that pKa = pH + log[HA] – log[A ], so Academic Press, New York, 1963. 4. Sober, H.A., Ed., CRC Handbook of Biochemistry, CRC Press, Boca that a solution with 50% dissociation has pH equal to the pKa of the acid. Raton, FL, 1968. 5. Perrin, D. D., Dempsey, B., and Serjeant, E. P., pK Prediction for Data for bases are presented as pK values for the conjugate acid, a a Organic Acids and Bases, Chapman and Hall, London, 1981. i.e., for the reaction 6. Albert, A., and Serjeant, E. P., The Determination of Ionization + + Constants, Third Edition, Chapman and Hall, London, 1984. BH H + B 7. Budavari, S., Ed., The Merck Index, Twelth Edition, Merck & Co., Whitehouse Station, NJ, 1996. -
Haloacetic Acids Found As Water Disinfection By-Products
Revised Draft: Report on Carcinogens Monograph on Haloacetic Acids Found as Water Disinfection By-Products October 30, 2017 Office of the Report on Carcinogens Division of the National Toxicology Program National Institute of Environmental Health Sciences U.S. Department of Health and Human Services This information is distributed solely for the purpose of pre-dissemination peer review under applicable information quality guidelines. It has not been formally distributed by the National Toxicology Program. It does not represent and should not be construed to represent any NTP determination or policy. This Page Intentionally Left Blank Revised Draft RoC Monograph on Haloacetic Acids 10/30/17 Foreword The National Toxicology Program (NTP) is an interagency program within the Public Health Service (PHS) of the Department of Health and Human Services (HHS) and is headquartered at the National Institute of Environmental Health Sciences of the National Institutes of Health (NIEHS/NIH). Three agencies contribute resources to the program: NIEHS/NIH, the National Institute for Occupational Safety and Health of the Centers for Disease Control and Prevention (NIOSH/CDC), and the National Center for Toxicological Research of the Food and Drug Administration (NCTR/FDA). Established in 1978, the NTP is charged with coordinating toxicological testing activities, strengthening the science base in toxicology, developing and validating improved testing methods, and providing information about potentially toxic substances to health regulatory and research agencies, scientific and medical communities, and the public. The Report on Carcinogens (RoC) is prepared in response to Section 301 of the Public Health Service Act as amended. The RoC contains a list of identified substances (i) that either are known to be human carcinogens or are reasonably anticipated to be human carcinogens and (ii) to which a significant number of persons residing in the United States are exposed. -
To Daphnia Magna
H OH metabolites OH Article Targeted Metabolomic Assessment of the Sub-Lethal Toxicity of Halogenated Acetic Acids (HAAs) to Daphnia magna Lisa M. Labine 1,2 and Myrna J. Simpson 1,2,* 1 Department of Chemistry, University of Toronto, 80 St. George St., Toronto, ON M5S 3H6, Canada; [email protected] 2 Environmental NMR Centre and Department of Physical and Environmental Sciences, University of Toronto Scarborough, 1265 Military Trail, Toronto, ON M1C 1A4, Canada * Correspondence: [email protected]; Tel.: +1-416-287-7234 Abstract: Halogenated acetic acids (HAAs) are amongst the most frequently detected disinfection by-products in aquatic environments. Despite this, little is known about their toxicity, especially at the molecular level. The model organism Daphnia magna, which is an indicator species for freshwater ecosystems, was exposed to sub-lethal concentrations of dichloroacetic acid (DCAA), trichloroacetic acid (TCAA) and dibromoacetic acid (DBAA) for 48 h. Polar metabolites extracted from Daphnia were analyzed using liquid chromatography hyphened to a triple quadrupole mass spectrometer (LC-MS/MS). Multivariate analyses identified shifts in the metabolic profile with exposure and pathway analysis was used to identify which metabolites and associated pathways were disrupted. Exposure to all three HAAs led to significant downregulation in the nucleosides: adenosine, guanosine and inosine. Pathway analyses identified perturbations in the citric acid cycle and the purine metabolism pathways. Interestingly, chlorinated and brominated acetic acids demonstrated similar modes of action after sub-lethal acute exposure, suggesting that HAAs cause a Citation: Labine, L.M.; Simpson, M.J. contaminant class-based response which is independent of the type or number of halogens. -
Mechanisms of Monohalogenated Acetic Acid Induced Genomic Dna Damage
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Illinois Digital Environment for Access to Learning and Scholarship Repository MECHANISMS OF MONOHALOGENATED ACETIC ACID INDUCED GENOMIC DNA DAMAGE BY JUSTIN A. PALS DISSERTATION Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Crop Sciences in the Graduate College of the University of Illinois at Urbana-Champaign, 2014 Urbana, Illinois Doctoral Committee: Professor Michael J. Plewa, Chair Professor Benito J. Mariñas Professor A. Layne Rayburn Brian K. Miller, Director of Illinois-Indiana Sea Grant ABSTRACT Disinfection of drinking water stands among the greatest public health achievements in human history. Killing or inactivation of pathogenic microbes by chemical oxidants such as chlorine, chloramine, or ozone have greatly reduced incidence of waterborne diseases. However, the disinfectant also reacts with organic and inorganic matter in the source water and generates a mixture of toxic disinfection byproducts (DBPs) as an unintended consequence. Since they were first discovered in 1974, over 600 individual DBPs have been detected in disinfected water. Exposure to DBPs is associated with increased risks for developing cancers of the colon, rectum, and bladder, and also for adverse pregnancy outcomes including small for gestational age and congenital malformations. While individual DBPs are teratogenic or carcinogenic, because they are formed at low concentrations during disinfection, it is unlikely that any one DBP can account for these increased risks. While genotoxicity and oxidative stress have been suggested, the mechanisms connecting DBP exposures to adverse health and pregnancy outcomes remain unknown. Investigating mechanisms of toxicity for individual, or classes of DBPs will provide a better understanding of how multiple DBPs interact to generate adverse health and pregnancy outcomes.