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Synthesis of Capsicum chinense Citric Acid Esters-Its Methanol Trans-esterification Investigations with hplc Analysis and Its valorization as Gels-Crystals Ca-Salts

Received: 28 November 2021     Accepted: 16 December 2021     Published: 31 December 2021
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Abstract

The esterification between citric acid molecules and raw material-Capsicum chinense organic molecules in excess was carried out at 137°C-410.15°K. The kinetics of the reaction showed that this reaction was second order compared with citric acid and the calculated initial and global speed constant were respectively 1.43×10-1[L2×mol-2×s-1] and 3.84×10-2 [L2×mol-2×s-1]. The synthesized raw material’s-Capsicum chinense’s citric acid esters solutions colors was from light yellow-1.5[mn] to highly orange yellow-60[mn] confirming the esterification between citric acid molecules and the main bioactive molecules constituting the Capsicum chinense including capsaïcine, quercetin and luteolin whose densities were superior to one and explained the high densities of the Capsicum chinense citric acid esters solutions between 0.9825[g/ml] to 1.0636[g/ml]. Then, the alkene concentrations in esters solutions recorded an increase initially and at the middle of the time reaction respectively due to citric acid dehydration and alkenes from the raw material’s-Capsicum chinense’s bioactive molecules. But, the diminution of these alkene concentrations recorded from 900[s] time reaction confirmed their etherification with carboxylic acid and/or alcohol organic functions catalyzed by citric acid’s protonic acid-H+. Second, the trans-esterification mechanisms of the raw materials’ citric acid esters solutions with methanol was explored, inventoried and carried out in order to extract its bioactive molecules and their derivatives synthesized during this trans-esterification reaction where citric acid’s protonic acid-H+ sites functioned as catalyst. Thus, a trans-esterification using reflux-assembly followed by an extraction procedures were established in this manuscript. Indeed, the hplc analysis of the dichloromethane extracts allowed to identify the Capsicum chinense’s bioactive molecules and these derivatives. Third, procedures to synthesize crystals and gel calcium salts of raw material’s citric acid esters solutions was established. An inventory of these gel-crystals structure was done in this manuscript and it was deduced that the first step of these procedures was the esters solution titration with NaOH-0.05N in order to determine the optimum quantities of calcium hydroxide for the synthesis using reflux assembly at 137°C followed by evaporations procedures. Then, once synthesized gel was suffered under thermic treatment until having solid crystals well-structured, both could be characterized by an established EDTA-0.01N and alkene procedures titrations established in this manuscript. Finally, an established titration procedure with NaOH-0.05N allowed to determine their equivalent citric acid molecules concentrations. It was noticed that their citric acid and calcium weight concentration ratio was respectively 4.354/1.67 (≈2/1) which confirmed the well-structured of the product regarding to the exploration salts synthesis-mechanisms figures done in this manuscript.

Published in American Journal of Applied Chemistry (Volume 9, Issue 6)
DOI 10.11648/j.ajac.20210906.16
Page(s) 221-237
Creative Commons

This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2021. Published by Science Publishing Group

Keywords

Capsicum chinense, Citric Acid, Esterification, Methanol, Trans-esterification, hplc, Hexane, Dichloromethane

References
[1] Paulin Merix Raharilaza, Nambinina Richard Randriana, Andry Tahina Rabeharitsara – “Esterification Between Citric acid and Pumpkin Pips’ Organic Molecules – Esters Hydrolysis And Esters Used as Hydrocarbons Additives” - American Journal of Applied Chemistry. Vol. 6, No. 3, 2018, pp. 78-95. doi: 10.11648/j.ajac.20180603.12
[2] Sedraniaina Domoina Marie Esperance, Ny Idealy Elite Randriamanantena, Raïssa Faneva Mampitefa, Nambinina Richard Randriana, Andry Tahina Rabeharitsara – “Esterification Between Citric Acid and Callistemon citrinus, Rice-Husk, Garcinia dulcis Catalysed by Citric Acid’s-H+- Monomers and Polymers Formation Mechanism” - American Journal of Applied Chemistry. Vol. 8, No. 2, 2020, pp. 31-54. doi: 10.11648/j.ajac.20200802.11
[3] Nambinina Richard Randriana, Ernestine Ravomialisoa, Andry Tahina Rabeharitsara – “Washing-Disinfectant Product Synthesis Tested During the Production of the “Speb-Pebe” - Spicy Product Energy Booster Characterized by Established Titration Procedures” - American Journal of Applied Chemistry. Vol. 9, No. 3, 2021, pp. 53-64. doi: 10.11648/j.ajac.20210903.11
[4] DJ Bennett and GW Kirby (1968) Constitution and biosynthesis of capsaicin. Journal of Chemical Society, 442-446.
[5] Département de l'Agriculture des États-Unis, «USDA Database for the Flavonoid Content of Selected Foods» [archive], sur http://www.nal.usda.gov [archive], National Agricultural Library, 2003
[6] Phenol Explorer INRA
[7] Lee Y., Howard L. R., Villalon B. (1995) Flavonoids and antioxidant activity of fresh pepper (Capsicum annuum) cultivars. Journal of Food Science 60:473-476
[8] Howard L. R., Talcott S. T., Brenes C. H., Villalon B. (2000) “Changes in phytochemical and antioxidant activity of selected pepper cultivars (Capsicum species) as influenced by maturity”. Journal of Agricultural and Food Chemistry 48:1713-1720 PubMed (10820084)
[9] J. King, H. Wickes Felter, J. Uri Lloyd (1905) A King's American Dispensatory. Eclectic Medical Publications (ISBN 1888483024)
[10] "Quercetin dihydrate safety sheet". Archived from the original on September 16, 2011.
[11] Chevreul, M. E. (1829). "30e Leçon, Chapitre XI. De la Gaude. [30th lesson. Chapter 11. On Weld (i.e., the plant Reseda luteola, which provides a yellow dye)]". Leçons de Chimie Appliquée à la Teinture [Lessons on Chemistry Applied to Dyeing] (in French). Paris, France: Pichon et Didier. pp. 143–148. Chevreul named luteolin on p. 144: "J'ai fait des recherches sur la composition de la gaude, j'ai obtenu le principe colorant critalisé par sublimation; je l'ai nommé lutéolin." (I have done some research on the composition of weld; I obtained the principal colorant [which I] crystallized via sublimation; I have called it "luteolin".)
[12] Thomson, Thomas (1838). Chemistry of Organic Bodies. Vegetables. London, England: J. B. Baillière. pp. 415–416.
[13] However, Perkin claimed (without citing a source) that Chevreul had isolated luteolin as early as 1814–1815. See: Perkin, Arthur George; Everest, Arthur Ernest (1918). The Natural Organic Colouring Matters. London, England: Longmans, Green and Co. p. 4
[14] Capsaïcine - Chemical Trading Guidchem – Hubei Xin Runde Chemical Co., Ltd - https://www.guidechem.com/trade/capsaicin-cas-404-86-4-id3562256.html
[15] Dihydrocapsaïcine - © 2015 ChemBK.com All Rights Reserved | Build: 20150530002 - https://www.chembk.com/en/chem/dihydrocapsaicin
[16] Mehdi Bagheri Farhoush Kiani Fardad Koohyar Nguyen Truong Khang Fatemeh Zabihi, Department of Chemistry, Faculty of Science, Ayatollah Amoli Branch, Islamic Azad University, Amol, Iran, Division of Computational Physics, Institute for Computational Science, Ton Duc Thang University, Ho Chi Minh City, Vietnam, Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Vietnam, Department of Physics, Ayatollah Amoli Branch, Islamic Azad University, Amol, Iran: “Measurement of refractive index and viscosity for aqueous solution of sodium acetate, sodium carbonate, trisodium citrate, (glycerol + sodium acetate), (glycerol + sodium carbonate), and (glycerol + trisodium citrate) at T = 293.15 to 303.15 K and atmospheric pressure” - https://www.sciencedirect.com/science/article/abs/pii/S0167732219363135
[17] Andry Tahina Rabeharitsara, Behevitra Rovatahianjanahary, Nambinina Richard Randriana, «Pine Wood Powder Treatment to BXH+ Homogeneous Catalyst (H+/H2SO4) Supported on Its Aromatics’ and PNA’ Alkenes – Application in Black Citric Acid Polymer Synthesis», American Journal of Polymer Science and Technology. Vol. 4, No. 1, 2018, pp. 1-27. doi: 10.11648/j.ajpst.20180401.11
[18] Behevitra Rovatahianjanahary - «Traitement De La Poudre Du Bois Du Pin Par De L’acide Sulfurique (H2SO4) Pour Obtenir Le Catalyseur Homogene BxH+ Supporte Sur Les Alcenes Des Aromatiques Et Des Polynucleaires Aromatiques Oxygenes Composant Le Bois- Application Dans La Synthese De Polymere Noire D'acide Citrique» - Mémoire De Fin d’Etudes En Vue De L’obtention Du Diplôme De Master Titre Ingénieur En Génie Des Procédés Chimiques Et Industriels - Ecole Supérieure Polytechnique Antananarivo. Université d’Antananarivo – Promotion 2017.
[19] Phandry Nomena Ndjiva Rabearimihaja, Andry Tahina Rabeharitsara – “Betacarotenes Dosage by Hydrofluoric Acid Solution and Validation of This New Process by SPC”. American Journal of Applied Chemistry. Vol. 4, No. 3, 2016, pp. 91-96. doi: 10.11648/j.ajac.20160403.14
[20] Rabearimihaja Phandry Taryh Nomena Ndjiva - «Valorisation Du Betacarotene Extrait De L’huile De Palme Brute Par De L’acide Acetique Pour La Determination Des Teneurs En Eau De Produits Petroliers (Gazole /Fuel-Oil) Et Dosage Des Teneurs En Betacarotene Par De L’acide Fluorhydrique» - Mémoire de fin d’Etudes en vue de l’obtention du Diplôme de Master Titre Ingénieur en Génie des Procédés chimiques et Industriels - Ecole Supérieure Polytechnique Antananarivo. Université d’Antananarivo – Promotion 2015.
[21] Nambinina Richard Randriana, Raherimandimby Jaochim, Andry Tahina Rabeharitsara: “Trans-Esterification Between Citric Acid and Peanut Oil at Low pH and Ambient Temperature Catalyzed by Citric Acid and Sulfuric Acid Protonic Acid-H+”, American Journal of Applied Chemistry - Volume 8, Issue 4, August 2020, Pages: 100-116- doi: 10.11648/j.ajac.20200804.12 - Chemical Process Engineering Department (E. S. P. A), Antananarivo University, Antananarivo, Madagascar.
[22] George F. Antonious “Capsaicinoids and Vitamins in Hot Pepper and Their Role in Disease Therapy“Submitted: January 16th 2018Reviewed: May 2nd 2018Published: November 5th 2018, DOI: 10.5772/intechopen.78243.
[23] Nambinina Richard Randriana, Ernestine Ravomialisoa, Andry Tahina Rabeharitsara, “Speb-Pebe” - Spicy Product Energy Booster Consumer Test and Its Effects on the Consumers’ Health, American Journal of Applied Chemistry. Vol. 9, No. 6, 2021, pp. 186-201. doi: 10.11648/j.ajac.20210906.12
[24] Masao Bounashita - “HPLC Analysis of Capsaicin and Dihydrocapsaicin in Capsicum” - https://jascoinc.com/applications/analysis-capsaicin-dihydrocapsaicin/
[25] Roxana-Mădălina STOICA, Ovidiu POPA, Liliana-Claudia BLASS, Narcisa BĂBEANU – “Capsaicinoids Extraction From Several Capsicum Species Cultivated In Romania” - Scientific Bulletin. Series F. Biotechnologies, Vol. XIX, 2015 ISSN 2285-1364, CD-ROM ISSN 2285-5521, ISSN Online 2285-1372, ISSN-L 2285-1364 University of Agronomic Sciences and Veterinary Medicine of Bucharest, 59 Mărăşti Blvd, District 1, 011464, Bucharest, Romania - Faculty of Biotechnologies.
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    Nambinina Richard Randriana, Ernestine Ravomialisoa, Andry Tahina Rabeharitsara. (2021). Synthesis of Capsicum chinense Citric Acid Esters-Its Methanol Trans-esterification Investigations with hplc Analysis and Its valorization as Gels-Crystals Ca-Salts. American Journal of Applied Chemistry, 9(6), 221-237. https://doi.org/10.11648/j.ajac.20210906.16

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    Nambinina Richard Randriana; Ernestine Ravomialisoa; Andry Tahina Rabeharitsara. Synthesis of Capsicum chinense Citric Acid Esters-Its Methanol Trans-esterification Investigations with hplc Analysis and Its valorization as Gels-Crystals Ca-Salts. Am. J. Appl. Chem. 2021, 9(6), 221-237. doi: 10.11648/j.ajac.20210906.16

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    Nambinina Richard Randriana, Ernestine Ravomialisoa, Andry Tahina Rabeharitsara. Synthesis of Capsicum chinense Citric Acid Esters-Its Methanol Trans-esterification Investigations with hplc Analysis and Its valorization as Gels-Crystals Ca-Salts. Am J Appl Chem. 2021;9(6):221-237. doi: 10.11648/j.ajac.20210906.16

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  • @article{10.11648/j.ajac.20210906.16,
      author = {Nambinina Richard Randriana and Ernestine Ravomialisoa and Andry Tahina Rabeharitsara},
      title = {Synthesis of Capsicum chinense Citric Acid Esters-Its Methanol Trans-esterification Investigations with hplc Analysis and Its valorization as Gels-Crystals Ca-Salts},
      journal = {American Journal of Applied Chemistry},
      volume = {9},
      number = {6},
      pages = {221-237},
      doi = {10.11648/j.ajac.20210906.16},
      url = {https://doi.org/10.11648/j.ajac.20210906.16},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajac.20210906.16},
      abstract = {The esterification between citric acid molecules and raw material-Capsicum chinense organic molecules in excess was carried out at 137°C-410.15°K. The kinetics of the reaction showed that this reaction was second order compared with citric acid and the calculated initial and global speed constant were respectively 1.43×10-1[L2×mol-2×s-1] and 3.84×10-2 [L2×mol-2×s-1]. The synthesized raw material’s-Capsicum chinense’s citric acid esters solutions colors was from light yellow-1.5[mn] to highly orange yellow-60[mn] confirming the esterification between citric acid molecules and the main bioactive molecules constituting the Capsicum chinense including capsaïcine, quercetin and luteolin whose densities were superior to one and explained the high densities of the Capsicum chinense citric acid esters solutions between 0.9825[g/ml] to 1.0636[g/ml]. Then, the alkene concentrations in esters solutions recorded an increase initially and at the middle of the time reaction respectively due to citric acid dehydration and alkenes from the raw material’s-Capsicum chinense’s bioactive molecules. But, the diminution of these alkene concentrations recorded from 900[s] time reaction confirmed their etherification with carboxylic acid and/or alcohol organic functions catalyzed by citric acid’s protonic acid-H+. Second, the trans-esterification mechanisms of the raw materials’ citric acid esters solutions with methanol was explored, inventoried and carried out in order to extract its bioactive molecules and their derivatives synthesized during this trans-esterification reaction where citric acid’s protonic acid-H+ sites functioned as catalyst. Thus, a trans-esterification using reflux-assembly followed by an extraction procedures were established in this manuscript. Indeed, the hplc analysis of the dichloromethane extracts allowed to identify the Capsicum chinense’s bioactive molecules and these derivatives. Third, procedures to synthesize crystals and gel calcium salts of raw material’s citric acid esters solutions was established. An inventory of these gel-crystals structure was done in this manuscript and it was deduced that the first step of these procedures was the esters solution titration with NaOH-0.05N in order to determine the optimum quantities of calcium hydroxide for the synthesis using reflux assembly at 137°C followed by evaporations procedures. Then, once synthesized gel was suffered under thermic treatment until having solid crystals well-structured, both could be characterized by an established EDTA-0.01N and alkene procedures titrations established in this manuscript. Finally, an established titration procedure with NaOH-0.05N allowed to determine their equivalent citric acid molecules concentrations. It was noticed that their citric acid and calcium weight concentration ratio was respectively 4.354/1.67 (≈2/1) which confirmed the well-structured of the product regarding to the exploration salts synthesis-mechanisms figures done in this manuscript.},
     year = {2021}
    }
    

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  • TY  - JOUR
    T1  - Synthesis of Capsicum chinense Citric Acid Esters-Its Methanol Trans-esterification Investigations with hplc Analysis and Its valorization as Gels-Crystals Ca-Salts
    AU  - Nambinina Richard Randriana
    AU  - Ernestine Ravomialisoa
    AU  - Andry Tahina Rabeharitsara
    Y1  - 2021/12/31
    PY  - 2021
    N1  - https://doi.org/10.11648/j.ajac.20210906.16
    DO  - 10.11648/j.ajac.20210906.16
    T2  - American Journal of Applied Chemistry
    JF  - American Journal of Applied Chemistry
    JO  - American Journal of Applied Chemistry
    SP  - 221
    EP  - 237
    PB  - Science Publishing Group
    SN  - 2330-8745
    UR  - https://doi.org/10.11648/j.ajac.20210906.16
    AB  - The esterification between citric acid molecules and raw material-Capsicum chinense organic molecules in excess was carried out at 137°C-410.15°K. The kinetics of the reaction showed that this reaction was second order compared with citric acid and the calculated initial and global speed constant were respectively 1.43×10-1[L2×mol-2×s-1] and 3.84×10-2 [L2×mol-2×s-1]. The synthesized raw material’s-Capsicum chinense’s citric acid esters solutions colors was from light yellow-1.5[mn] to highly orange yellow-60[mn] confirming the esterification between citric acid molecules and the main bioactive molecules constituting the Capsicum chinense including capsaïcine, quercetin and luteolin whose densities were superior to one and explained the high densities of the Capsicum chinense citric acid esters solutions between 0.9825[g/ml] to 1.0636[g/ml]. Then, the alkene concentrations in esters solutions recorded an increase initially and at the middle of the time reaction respectively due to citric acid dehydration and alkenes from the raw material’s-Capsicum chinense’s bioactive molecules. But, the diminution of these alkene concentrations recorded from 900[s] time reaction confirmed their etherification with carboxylic acid and/or alcohol organic functions catalyzed by citric acid’s protonic acid-H+. Second, the trans-esterification mechanisms of the raw materials’ citric acid esters solutions with methanol was explored, inventoried and carried out in order to extract its bioactive molecules and their derivatives synthesized during this trans-esterification reaction where citric acid’s protonic acid-H+ sites functioned as catalyst. Thus, a trans-esterification using reflux-assembly followed by an extraction procedures were established in this manuscript. Indeed, the hplc analysis of the dichloromethane extracts allowed to identify the Capsicum chinense’s bioactive molecules and these derivatives. Third, procedures to synthesize crystals and gel calcium salts of raw material’s citric acid esters solutions was established. An inventory of these gel-crystals structure was done in this manuscript and it was deduced that the first step of these procedures was the esters solution titration with NaOH-0.05N in order to determine the optimum quantities of calcium hydroxide for the synthesis using reflux assembly at 137°C followed by evaporations procedures. Then, once synthesized gel was suffered under thermic treatment until having solid crystals well-structured, both could be characterized by an established EDTA-0.01N and alkene procedures titrations established in this manuscript. Finally, an established titration procedure with NaOH-0.05N allowed to determine their equivalent citric acid molecules concentrations. It was noticed that their citric acid and calcium weight concentration ratio was respectively 4.354/1.67 (≈2/1) which confirmed the well-structured of the product regarding to the exploration salts synthesis-mechanisms figures done in this manuscript.
    VL  - 9
    IS  - 6
    ER  - 

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Author Information
  • Chemical Process Engineering Department (E. S. P. A), Antananarivo University, Antananarivo, Madagascar

  • Chemical Process Engineering Department (E. S. P. A), Antananarivo University, Antananarivo, Madagascar

  • Chemical Process Engineering Department (E. S. P. A), Antananarivo University, Antananarivo, Madagascar

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