DOCSLIB.ORG

Fumaric Acid Fermentation by Rhizopus Oryzae with Integrated Separation Technologies

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Fumaric Acid Fermentation by Rhizopus Oryzae with Integrated Separation Technologies Fumaric Acid Fermentation by Rhizopus oryzae with Integrated Separation Technologies Dissertation Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Kun Zhang, M.S., B.S. Graduate Program in Chemical and Biomolecular Engineering The Ohio State University 2012 Dissertation Committee: Shang-Tian Yang, Advisor Jeffrey J. Chalmers David Wood Copyright by Kun Zhang 2012 ABSTRACT Fumaric acid is a dicarboxylic acid and an indispensible intermediate in the metabolism of many microorganisms. It is used mainly as a food acidulant and as the chemical feedstock for the production of paper resins, unsaturated polyester resins, alkyd resins, plasticizers, and miscellaneous industrial products. Currently, fumaric acid is produced through a petroleum-based chemical method. However, limited deposits of petroleum, increasing production costs and serious environmental repercussions have prompted chemical companies to find an alternative. Fungal fermentation provides a promising solution due to its advantages in environmental friendliness and availability of widespread renewable biomass feedstock. However, conventional fumaric acid fermentation processes suffer from low product yield, low productivity, and high production cost, whereas the competing chemical production methods are currently more economical. Therefore, the goal of this research was to develop effective and economic fermentation and recovery methods for improved fumaric acid production by Rhizopus oryzae. One of the major technical challenges is to control the fungal morphology and physiology for the overproduction of fumaric acid in a sustainable and scalable way. First, an effective fermentation process with good morphology control was developed using soybean meal hydrolysate as the nitrogen source for cell growth and fumaric acid production by R. oryzae. To improve the iii productivity, in situ product recovery by coupling the fermentation with an ion exchange column for fumaric acid adsorption was investigated. In addition, an alternative separation process using adsorption with activated carbon followed with desorption and crystallization with acetone was developed to increase the recovery yield and reduce the production cost. The main results and conclusions are summarized below. First, a simple seed culture medium was developed with soybean meal hydrolysate (SMH) as the nitrogen source for controlling the morphology of R. oryzae ATCC 20344. Uniformly dispersed mycelial clumps with a diameter of ~0.1 mm were formed with enhanced subsequent fumaric acid production. The optimal seed culture conditions were initial pH of 3.0, SMH concentration of 30% (v/v), spore concentration of 8×104/mL and glucose concentration of 10 g/L. With an inoculation size of 25%, the fermentation reached a fumaric acid titer of 50.2 g/L with yield of 0.72 g/g glucose. SMH with a high protein content was a good nitrogen source and the formation of protein precipitate acted as the immobilization carriers for cells. The solid-phase protein also provided a novel method for slow/controlled release that allowed the utilization of the nitrogen source by cells for an extended period without losing cell activity. The fermentation was then studied in a 5-L stirred tank bioreactor (STB) and the results also showed that using SMH as the nitrogen source improved fumaric acid production with increased yield and productivity compared to urea and yeast extract. The effect of CO2 on fumaric acid fermentation was studied. Aeration with air containing 16.7% CO2 increased the productivity by 76% and final product titer by 13%. A product titer of 35.6 g/L, yield of 40% and productivity of 0.4 g/L∙h were obtained in batch fermentation with an initial seeding density of ~5000 mycelial clumps/ml. With CO2 addition, similar iv fumaric acid production in the fermentation was obtained with either CaCO3 or NaOH as the neutralizing agent, indicating that CaCO3 can be replaced with NaOH and CO2 to simplify the downstream process. Separation of fumaric acid from the fermentation broth by adsorption was studied with a strong-basic anion exchange resin IRA900, which was selected because of its high adsorption capacity at the fermentation-favored pH of 5, high selectivity against byproducts (glucose and malic acid) and easy desorption with a high recovery yield. The adsorption isotherm and the mechanism involved in the fumaric acid adsorption onto IRA900 were investigated. The results showed that fumaric acid adsorption onto IRA900 followed the Langmuir isotherm. Also, the adsorption reaction rate between fumaric acid and functional groups of the resin followed the second-order kinetics, indicating a mechanism of two-site-occupancy adsorption reaction between FA2- and resin active sites. However, such a mechanism cannot explain the high adsorption capacity at pH 3 with a high initial fumaric acid concentration. Using an intraparticle diffusion model, it was found that the higher adsorption at pH 3 could be attributed to the higher hydrophobic interaction between neutral fumaric acid molecules and the hydrophobic resin backbone. The separation process using IRA900 ion exchange resin was then scaled up in a fixed bed column with the optimal conditions identified as: the resin in the chloride form, flow rate of 4.10~5.34 ml/min, initial fumaric acid concentration of ~5.0 g/L, and desorption solution of 0.7 mol/L NaCl. It was also found that end product inhibition occurred when the fumaric acid concentration in the medium reached >20 g/L. Therefore, intermittent in situ recovery was used to alleviate the product inhibition and facilitate the subsequent v product separation. A preliminary study showed that fermentation with in situ recovery enhanced product yield by 25% and productivity by 59%. Fermentation produced fumaric acid is usually recovered by precipitation and crystallization of the acid at room temperature. In order to recover the low-concentration fumaric acid (<6.3 g/L) present in the filtrate after crystallization, an integrated separation process was developed for fumaric acid recovery and purification by adsorption with activated carbon followed with desorption and crystallization with acetone. Fumaric acid adsorption on activated carbon was found to be governed by non-electrostatic interactions between the undissociated fumaric acid and the activated carbon. The desorption of fumaric acid from activated carbon was studied using acetone to strip all fumaric acid from activated carbon. After removing acetone by evaporation at 70 oC, fumaric acid crystals were obtained with a high purity and recovery yield. Both activated carbon and acetone can be recovered and reused in the adsorption process. The adsorption and desorption process was then evaluated in a fixed bed column to recover fumaric acid from the fermentation broth, achieving a high recovery yield of 93%. Finally, water sweeping was used to further increase the purity of fumaric acid crystals to >98%. A comparative economic analysis showed that this process could significantly reduce the operational costs and enhance the recovery yield, although it would require additional capital investment. Compared to the conventional recovery process using precipitation, the new process is economically and environmentally favorable with good potential for industrial application. vi DEDICATION Dedicated to my wife and parents vii ACKNOWLEDGEMENTS First, I want to give my special thanks to my advisor, Professor Shang-Tian Yang. Not only his guidance and support throughout my research enabled me to develop a thorough understanding of the subject, but also his patience, understanding and forgiveness taught me how to be a fantastic advisor. It would not have been possible to complete my Ph.D. degree without his invaluable guidance and mentoring. I would like to thank Dr. Jeffrey Chalmers and Dr. David Wood for their time being on my committee and their valuable advices on my research project. I want to give my sincere thanks to all the previous and current laboratory members in our group, especially Dr. Baohua Zhang, Dr. Xiang Zou, Dr. Lijie Zhang for their helpful suggestions and support. Also, I want to thank Ms. Yu Chen for her good job in helping some of my experiments. Financially supports from the United Soybean Board and the Consortium for Plant Biotechnology Research Inc to this project are also acknowledged. Finally, I would like to thank my parents and my parents-in-law for all their support. Special thanks to my wife Qing Zhang as well as our beloved two babies. Without their support, I would have achieved nothing. viii VITA November 1982 ………………………………………………Born-Qingdao, PR China June 2005 ………………………………………………………… B.S. Bioengineering Nanjing University of Technology, Nanjing, PR China June 2008 …………………………………………………………… M.S. Microbiology Nanjing University of Technology, Nanjing, PR China PUBLICATIONS 1. Yang, S.T., Zhang, K., Zhang, B., Huang, H. 2011. Bio-Based Chemicals | Fumaric Acid. In: Murray Moo-Young (ed.), Comprehensive Biotechnology, Second Edition, Volume3, pp.163-177. Elsevier. 2. Zhang, K., Gao, Z., Li, S., Fu, Y., Huang, H., Wei, P., Ji, S. 2008. Multiple target optimizations on the fumaric acid production by Rhizopus oryzae based on Desirability function, China Biotech 28(4): 59-64. 3. Zhang, K., Xu, Q., Li, S., Fu, Y., Gao, Z., Huang, H., 2008. Integrated mutagenesis to screen high fumaric acid producing mutant of Rhizopus oryzae with propylene alcohol resistance.
Load more

Recommended publications
  • Hyperbranched Polyaspartate Esters and a Process for Their Preparation
    Europäisches Patentamt *EP000743335B1* (19) European Patent Office Office européen des brevets (11) EP 0 743 335 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.7: C08G 63/685 of the grant of the patent: 26.09.2001 Bulletin 2001/39 (21) Application number: 96107069.5 (22) Date of filing: 06.05.1996 (54) Hyperbranched polyaspartate esters and a process for their preparation Hyperverzweigte Polyaspartatester und Verfahren zu ihrer Herstellung Ester de polyaspartate hyperramifiés et procédé pour leur préparation (84) Designated Contracting States: (74) Representative: Pettrich, Klaus-Günter, Dr. AT BE CH DE ES FR GB IT LI NL SE c/o Bayer AG, Konzernbereich RP (30) Priority: 18.05.1995 US 443505 Patente und Lizenzen 51368 Leverkusen (DE) (43) Date of publication of application: 20.11.1996 Bulletin 1996/47 (56) References cited: US-A- 5 126 170 (73) Proprietor: Bayer Corporation Pittsburgh, PA 15205-9741 (US) • ISRA L JOURNAL OF CHEMISTRY, vol. 9, 1971, JERUSALEM, pages 105-109, XP000670606 A. (72) Inventors: SINGERMAN ET AL.: "Poly threo-beta-hydroxy • Yeske, Philip E. aspartic acid" Pittsburgh, PA 15228 (US) • Gindin, Lyuba K. Remarks: Pittsburgh, PA 15216 (US) The file contains technical information submitted • Wicks, Douglas A. after the application was filed and not included in this Mt. Lebanon, PA 15228 (US) specification • Jonsson, E. Haakan Coraopolis, PA 15108 (US) Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement.
    [Show full text]
  • Detection and Formation Scenario of Citric Acid, Pyruvic Acid, and Other Possible Metabolism Precursors in Carbonaceous Meteorites
    Detection and formation scenario of citric acid, pyruvic acid, and other possible metabolism precursors in carbonaceous meteorites George Coopera,1, Chris Reeda, Dang Nguyena, Malika Cartera, and Yi Wangb aExobiology Branch, Space Science Division, National Aeronautics and Space Administration-Ames Research Center, Moffett Field, CA 94035; and bDevelopment, Planning, Research, and Analysis/ZymaX Forensics Isotope, 600 South Andreasen Drive, Suite B, Escondido, CA 92029 Edited by David Deamer, University of California, Santa Cruz, CA, and accepted by the Editorial Board July 1, 2011 (received for review April 12, 2011) Carbonaceous meteorites deliver a variety of organic compounds chained three-carbon (3C) pyruvic acid through the eight-carbon to Earth that may have played a role in the origin and/or evolution (8C) 7-oxooctanoic acid and the branched 6C acid, 3-methyl- of biochemical pathways. Some apparently ancient and critical 4-oxopentanoic acid (β-methyl levulinic acid), Fig. 1, Table S1. metabolic processes require several compounds, some of which 2-methyl-4-oxopenanoic acid (α-methyl levulinic acid) is tenta- are relatively labile such as keto acids. Therefore, a prebiotic setting tively identified (i.e., identified by mass spectral interpretation for any such individual process would have required either a only). As a group, these keto acids are relatively unusual in that continuous distant source for the entire suite of intact precursor the ketone carbon is located in a terminal-acetyl group rather molecules and/or an energetic and compact local synthesis, parti- than at the second carbon as in most of the more biologically cularly of the more fragile members.
    [Show full text]
  • Profiling Taste and Aroma Compound Metabolism During Apricot Fruit Development and Ripening
    Int. J. Mol. Sci. 2016, 17, 998; doi:10.3390/ijms17070998 S1 of S4 Supplementary Materials: Profiling Taste and Aroma Compound Metabolism during Apricot Fruit Development and Ripening Wanpeng Xi, Huiwen Zheng, Qiuyun Zhang and Wenhui Li Figure S1. Sugars HPLC chromatogram of apricot fruit. Peaks (1) Fructose (2) Glucose (3) Sucrose. (a) sugars mixture standards; (b) sugars for SG peel of S5; (c) sugars for SG pulp of S5. Int. J. Mol. Sci. 2016, 17, 998; doi:10.3390/ijms17070998 S2 of S4 Figure S2. Organic acids HPLC chromatogram of apricot fruit. Peaks (1) oxalic acid (2) tartaric acid (3) quininic acid (4) malic acid (5) citric acid (6) fumaric acid. (a) organic acids mixture standard; (b) organic acid for YC peel of S4; (c) organic acid for YC pulp of S4. Int. J. Mol. Sci. 2016, 17, 998; doi:10.3390/ijms17070998 S3 of S4 Table S1. Chroma values of apricot fruit during development and ripening. L* a* b* C* H Cultivars S1 S2 S3 S4 S5 S1 S2 S3 S4 S5 S1 S2 S3 S4 S5 S1 S2 S3 S4 S5 S1 S2 S3 S4 S5 DX 54.52 57.13 61.56 62.61 55.49 20.28 18.13 14.41 8.87 17.97 39.02 37.67 38.27 39.99 43.83 43.98 42.27 41.06 42.26 47.67 117.46 116.92 110.21 76.26 67.36 HY 54.97 55.83 61.53 65.08 65.11 −16.04 −14.77 −13.30 11.01 12.78 34.44 31.68 32.74 38.82 42.51 37.99 34.84 35.35 52.69 45.14 114.91 114.94 112.05 72.65 72.57 KE 47.02 47.00 48.32 60.11 60.66 −17.08 −17.37 −16.65 −0.36 8.20 30.83 29.09 29.08 48.23 48.48 35.26 33.88 33.51 48.33 49.33 118.94 120.86 119.85 90.67 118.02 AK 50.02 50.90 52.19 68.35 60.28 −21.98 −21.76 −19.02 -4.97 4.04 40.07 39.12 35.71
    [Show full text]
  • Oxaloacetate As the Hill Oxidant in Mesophyll Cells of Plants Possessing
    Proc. Nat. Acad. Sci. USA Vol. 70, No. 12, Part II, pp. 3730-3734, December 1973 Oxaloacetate as the Hill Oxidant in Mesophyll Cells of Plants Possessing the C4-Dicarboxylic Acid Cycle of Leaf Photosynthesis (CO2 fixation/uncoupler/photochemical reactions/electron transport/02 evolution) MARVIN L. SALIN, WILBUR H. CAMPBELL, AND CLANTON C. BLACK, JR. Department of Biochemistry, University of Georgia, Athens, Ga. 30602 Communicated by Harland G. Wood, August 16, 1973 ABSTRACT Isolated mesophyll cells from leaves of NADP+-dependent malic dehydrogenase (10) is in the meso- plants that use the C4 dicarboxylic acid pathway of CO2 fixation have been used to demonstrate that oxaloacetic phyll cells (9, 11). Therefore, one could reason that in meso- acid reduction to malic acid is coupled to the photo- phyll cells the carboxylation of PEP should be coupled to the chemical evolution of oxygen through the presumed pro- reduction of OAA and the required reduced pyridine nucleo- duction ofNADPH. The major acid-stable product oflight- tide should be produced photosynthetically as follows: dependent CO2 fixation is shown to be malic acid. In the presence of phosphoenolpyruvate and bicarbonate the PEP stoichiometry of CO2 fixation into acid-stable products to HC03- + PEP OAA + Pi [1] 02 evolution is shown to be near 1.0. Thus oxaloacetic acid carboxylase acts directly as the Hill oxidant in mesophyll cell chloro- light plasts. The experiments are taken as a firm demonstration that the dicarboxylic acid cycle of photosynthesis is the NADP++H20 NADPH+ 1/202+H+ [2] C4 mesophyll cell major pathway for the fixation of CO2 in mesophyll cells chloroplasts of plants having this pathway.
    [Show full text]
  • Revised Group Additivity Values for Enthalpies of Formation (At 298 K) of Carbon– Hydrogen and Carbon–Hydrogen–Oxygen Compounds
    Revised Group Additivity Values for Enthalpies of Formation (at 298 K) of Carbon– Hydrogen and Carbon–Hydrogen–Oxygen Compounds Cite as: Journal of Physical and Chemical Reference Data 25, 1411 (1996); https://doi.org/10.1063/1.555988 Submitted: 17 January 1996 . Published Online: 15 October 2009 N. Cohen ARTICLES YOU MAY BE INTERESTED IN Additivity Rules for the Estimation of Molecular Properties. Thermodynamic Properties The Journal of Chemical Physics 29, 546 (1958); https://doi.org/10.1063/1.1744539 Critical Evaluation of Thermochemical Properties of C1–C4 Species: Updated Group- Contributions to Estimate Thermochemical Properties Journal of Physical and Chemical Reference Data 44, 013101 (2015); https:// doi.org/10.1063/1.4902535 Estimation of the Thermodynamic Properties of Hydrocarbons at 298.15 K Journal of Physical and Chemical Reference Data 17, 1637 (1988); https:// doi.org/10.1063/1.555814 Journal of Physical and Chemical Reference Data 25, 1411 (1996); https://doi.org/10.1063/1.555988 25, 1411 © 1996 American Institute of Physics for the National Institute of Standards and Technology. Revised Group Additivity Values for Enthalpies of Formation (at 298 K) of Carbon-Hydrogen and Carbon-Hydrogen-Oxygen Compounds N. Cohen Thermochemical Kinetics Research, 6507 SE 31st Avenue, Portland, Oregon 97202-8627 Received January 17, 1996; revised manuscript received September 4, 1996 A program has been undertaken for the evaluation and revision of group additivity values (GAVs) necessary for predicting, by means of Benson's group additivity method, thermochemical properties of organic molecules. This review reports on the portion of that program dealing with GAVs for enthalpies of formation at 298.15 K (hereinafter abbreviated as 298 K) for carbon-hydrogen and carbon-hydrogen-oxygen compounds.
    [Show full text]
  • Transamination in Tumors, Fetal Tissues, and Regenerating Liver* Philip P
    Transamination in Tumors, Fetal Tissues, and Regenerating Liver* Philip P. Cohen, M.D., and G. Leverne Hekhuis (From the Laboratory o~ Physiological Chemistry, Yale University School of Medicine, New Haven, Connecticut) (Received for publication June 9, I94I) von Euler and co-workers (22), on the basis of TISSUE SOURCES results of essentially qualitative experiments, first re- Tumors.--The mouse tumors employed in this in- ported that the transaminase activity ot~ tumors was vestigation were the following: low. These investigators, using Jensen sarcoma and normal muscle, measured the rate of disappearance of I. United States Public Health Service No. ~7-- oxaloacetic acid in the following reaction: originally described as a neuroepithelioma (20). 1 2. Sarcoma 37 .1 3. Yale No. xuan estrogen-induced ,) 1( + )-glutamic acid + oxaloacetic acid a mammary adenocarcinoma (5). 1 4. No. x5o9I-A - ~'b a-ketoglutaric acid + aspartic acid spontaneous mammary medullary adenocarcinoma In addition to studies of reaction I in tumors, Braun- (6) "1 5- No. 42--glioblastoma multiforme. 2 6. No. stein and Azarkh (2) studied the reaction: i o8--rhabdomyosarcoma. 2 The tumors were transplanted at regular intervals 2) glutamic acid+a-keto acid to insure a uniform supply. a-ketoglutaric acid + amino acid "-b- Fetal, kitten, and adult cat tissues.--Two pregnant cats provided the fetal tissue. The length of the preg- The amino acids investigated in the case of reaction nancy was uncertain, but was estimated to be in the 2b were the d- and l-forms of alanine, valine, leucine, last trimester in both instances. Hemihysterectomies and isoleucine. The rate of reaction za in which both were performed under nembutal anesthesia and 2 d(--)- and l(+)-glutamic acid were used, plus fetuses removed from each animal.
    [Show full text]
  • Oxaloacetic Acid Supplementation As a Mimic of Calorie Restriction Alan Cash*
    22 Open Longevity Science, 2009, 3, 22-27 Open Access Oxaloacetic Acid Supplementation as a Mimic of Calorie Restriction Alan Cash* Terra Biological LLC, San Diego, CA 92130, USA Abstract: The reduction in dietary intake leads to changes in metabolism and gene expression that increase lifespan, re- duce the incidence of heart disease, kidney disease, Alzheimer’s disease, type-2 diabetes and cancer. While all the mo- lecular pathways which result in extended lifespan as a result of calorie restriction are not fully understood, some of these pathways that have resulted in lifespan expansion have been identified. Three molecular pathways activated by calorie re- striction are also shown to be activated by supplementing the diet with the metabolite oxaloacetic acid. Animal studies supplementing oxaloacetic acid show an increase in lifespan and other substantial health benefits including mitochondrial DNA protection, and protection of retinal, neural and pancreatic tissues. Human studies indicate a substantial reduction in fasting glucose levels and improvement in insulin resistance. Supplementation with oxaloacetic acid may be a safer method to mimic calorie restriction than the use of traditional diabetes drugs. INTRODUCTION citric acid cycle, and is found in every cell in the body. Fig. (1) shows a schematic diagram of the citric acid cycle and For over 75 years, scientists have known how to increase the position of oxaloacetate within the cycle. average and maximal lifespan; reduce dietary intake of calo- ries by 25 to 40% over ad libitum baseline values while maintaining adequate nutrition. This reduction in dietary intake leads to changes in metabolism and gene expression Oxaloacetate Citrate that increase lifespan, and also been reported to reduce the incidence of heart disease, kidney disease, Alzheimer’s dis- Malate ease, type-2 diabetes and cancer in animals [1-3].
    [Show full text]
  • 136757A0.Pdf
    NOVEMBER 9, 1935 NATURE 757 quantitatively by the aspartase enzyme, and identified Using the ordinary technique, we have examined qualitatively in the form of the copper salt. Approxi­ specimens of purified l-fructose and l-arabinose, and mately the other half of the nitrogen ( 40-50 per cent) in neither event have we been able to detect the is precipitable by phosphotungstic acid. Since slightest reducing action on Tillmans's reagent. We cystine, arginine, histidine and aromatic amino acids have no explanation to offer of Jonnissian's results, are absent, it is probable that this fraction consists but we thought it might be of interest to publish of lycine. Further work is in progress to determine the above facts, in case that author's statements the nature of the compounds precipitated by phospho­ should lead other workers to under-value what has tungstic acid. come to be recognised as an extremely useful reagent. In an earlier paper1, it was mentioned that aspartic A. L. BACHARACH. acid is not present in the amino acid mixture. This H. E. GLYNN. erroneous conclusion is ascribable to the fact that, Glaxo Laboratories, Ltd., owing to the small amount of material available, the 56 Osnaburgh Street, determination was made from the solution from London, N.W.l. which ammonia had first been distilled off according Oct. 18. to van Slyke, in which process aspartic acid seems to • Proc. 6th Caw,. Cong. Phys. Pharm. Bio., Academy of Sciences be precipitated as a calcium salt. Press, Moscow and Leningrad, 101; 1935. The composition of the excreted amino acid mixture is very interesting in several respects.
    [Show full text]
  • Strecker Degradation Products of Aspartic and Glutamic Acids and Their Amides
    Czech J. Food Sci. Vol. 19, No. 2: 41–45 Strecker Degradation Products of Aspartic and Glutamic Acids and their Amides JAN RÖSSNER, JAN VELÍEK, FRANTIEK PUDIL and JIØÍ DAVÍDEK Institute of Chemical Technology Department of Food Chemistry and Analysis, Prague, Czech Republic Abstract RÖSSNER J., VELÍEK J., PUDIL F., DAVÍDEK J. (2001): Strecker degradation products of aspartic and glutamic acids and their amides. Czech J. Food Sci., 19: 4145. Aspartic and glutamic acids, asparagine and glutamine were oxidised with either potassium peroxodisulphate or glyoxal. Non- volatile products were derivatised and analysed by GC/FID and GC/MS. Volatile reaction products were isolated and analysed by the same methods. It was found that the degradation reactions of amino acids are complex. Amino acids are principally degraded via the corresponding α-keto acids to Strecker aldehydes (aspartic acid to oxalacetic and 3-oxopropionic acids and glutamic acid to α-ketoglutaric and 4-oxobutyric acids), which are unstable and decomposed by decarboxylation to the corresponding alde- hydes. Aspartic acid also eliminates ammonia and yields fumaric acid whereas glutamic acid gives rise to an imine, pyroglutamic acid. A recombination of free radicals leads to dicarboxylic acids (succinic acid from aspartic acid, succinic, glutaric and adipic acids from glutamic acid). The major volatile products (besides the aldehydes) are lower carboxylic acids (acetic acid from aspartic acid and propionic acid acid from glutamic acid) that can at least partly arise by radical reactions. In both quality and quantity terms, a higher amount of degradation products arises by oxidation of amino acids by peroxodisulphate. Keywords: Strecker degradation; Strecker aldehydes; amino acids; glyoxal; sodium peroxodisulphate; aspartic acid; glutamic acid; asparagine; glutamine; radicals The reaction of an α-amino acid with an oxidation re- asparagine (Asn) and glutamine (Gln).
    [Show full text]
  • Supplementary File 1 (PDF, 650 Kib)
    Preliminary Zinc and boscalid sub lethal concentrations Zinc and boscalid sub lethal concentrations were determined by running preliminary 72‐hour LC50 exposures. A range of concentrations, resulting in 100% survival to 100% mortality was run for both chemicals in water only exposures. Filtered seawater was used as a control and to dilute stock concentrations of zinc and boscalid. Six treatments with three replicates were run for both chemicals including a control (seawater only). The zinc chloride (ZnCl2) exposure concentrations were: 62mg/L; 125mg/L; 250mg/L; 500mg/L and 1000mg/L. The commercial fungicide Filan® has 500g/kg active ingredient of boscalid, concentrations of 100mg/L; 250mg/L; 500mg/L; 750mg/L and 1000mg/L. Acid‐ rinsed 600ml glass beakers were randomly placed in a temperature‐controlled incubator at 20oC (+/‐ 1oC) with added aeration and a one ply sheet of ethanol rinsed toilet paper in each beaker as substratum. No food was added; the average pH of the water was 7.5 across treatments. The dissolved oxygen remained between 70‐100%. Zinc chloride LC50 = 125mg/L and boscalid LC50 = 750mg/L. Table S1. –Concentrations of boscalid and zinc at 0 h and one week. Measured concentrations of boscalid and zinc detected in estuaries in Victoria, Australia. Exposure at Control Exposure at 0 hr Environmental dose 1 week Boscalid 0 N/A 75 mg/L 3.3 mg/L (Vu et al. 2016) Zinc 0.026 – 0.034 mg/L 12.5 mg/L 3.4 mg/L (Long et al. 2015) Table S2. Water Quality Parameters. Date Sample Dissolved oxygen (%) pH Conductivity (µS/cm) Ammonia 15/05/17 Control 98.36 8.44 59464.4 0.25 15/05/17 Zinc 99.10 8.31 59379.1 0.25 15/05/17 Boscalid 99.18 8.28 59656.8 0.25 15/05/17 Mixture 94.81 8.25 59386.0 0.25 30/05/17 Control 101.90 8.16 59332.4 0.5 30/05/17 Zinc 102.47 8.11 59536.7 0.5 30/05/17 Boscalid 92.17 8.15 59489.3 0.5 30/05/17 Mixture 101.57 8.14 59593.2 0.5 Supplementary Material .
    [Show full text]
  • 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.
    [Show full text]
  • The Protective Role of Alpha-Ketoglutaric Acid on the Growth and Bone Development of Experimentally Induced Perinatal Growth-Retarded Piglets
    animals Article The Protective Role of Alpha-Ketoglutaric Acid on the Growth and Bone Development of Experimentally Induced Perinatal Growth-Retarded Piglets Ewa Tomaszewska 1,* , Natalia Burma ´nczuk 1, Piotr Dobrowolski 2 , Małgorzata Swi´ ˛atkiewicz 3 , Janine Donaldson 4, Artur Burma ´nczuk 5, Maria Mielnik-Błaszczak 6, Damian Kuc 6, Szymon Milewski 7 and Siemowit Muszy ´nski 7 1 Department of Animal Physiology, Faculty of Veterinary Medicine, University of Life Sciences in Lublin, Akademicka St. 12, 20-950 Lublin, Poland; [email protected] 2 Department of Functional Anatomy and Cytobiology, Faculty of Biology and Biotechnology, Maria Curie-Sklodowska University, Akademicka St. 19, 20-033 Lublin, Poland; [email protected] 3 Department of Animal Nutrition and Feed Science, National Research Institute of Animal Production, Krakowska St. 1, 32-083 Balice, Poland; [email protected] 4 Faculty of Health Sciences, School of Physiology, University of the Witwatersrand, 7 York Road, Parktown, Johannesburg 2193, South Africa; [email protected] 5 Faculty of Veterinary Medicine, Institute of Preclinical Veterinary Sciences, University of Life Sciences in Lublin, Akademicka St. 12, 20-950 Lublin, Poland; [email protected] 6 Department of Developmental Dentistry, Medical University of Lublin, 7 Karmelicka St., 20-081 Lublin, Poland; [email protected] (M.M.-B.); [email protected] (D.K.) 7 Department of Biophysics, Faculty of Environmental Biology, University of Life Sciences in Lublin, Citation: Tomaszewska, E.; Akademicka St. 13, 20-950 Lublin, Poland; [email protected] (S.M.); [email protected] (S.M.) Burma´nczuk,N.; Dobrowolski, P.; * Correspondence: [email protected] Swi´ ˛atkiewicz,M.; Donaldson, J.; Burma´nczuk,A.; Mielnik-Błaszczak, Simple Summary: Perinatal growth restriction is a significant health issue that predisposes to M.; Kuc, D.; Milewski, S.; Muszy´nski, S.
    [Show full text]