ArticlePublisher preview available

Effect of Solar and Artificial Radiation on Elaidinization and Degradation of Z‐Bixin Extracted from Bixa Orellana Seeds

Wiley
ChemistrySelect
Authors:
Oswaldo Eliecer Cárdenas
Oswaldo Eliecer Cárdenas
Oswaldo Eliecer Cárdenas
  • This person is not on ResearchGate, or hasn't claimed this research yet.
Sarai Vega-Rodríguez at Autonomous University of San Luis Potosí
Sarai Vega-Rodríguez
Agobardo Cárdenas‐Chaparro
Agobardo Cárdenas‐Chaparro
Agobardo Cárdenas‐Chaparro
  • This person is not on ResearchGate, or hasn't claimed this research yet.
Antonio De León-Rodríguez
Antonio De León-Rodríguez
Show all 5 authorsHide
Read publisher preview
Download citation
To read the full-text of this research, you can request a copy directly from the authors.

Abstract and Figures

Z‐bixin is the main metabolite contained in Achiote, which is widely used as a food condiment and pigment. Z‐bixin plays an important role in photosynthesis. It is used to develop artificial solar cells and scavenge radical oxygen and nitrogen species. In this work, the photochemistry of Z‐bixin with solar irradiation and lamps at 365 and 410 nm was determined in solution. The ultraviolet‐visible spectroscopy (UV‐Vis) and Ultra High Performance Liquid Chromatography (UHPLC) analysis showed that elaidinization of Z‐bixin to E‐bixin can be reached under radiation. This is in accordance with the computational evaluation that indicates that the mechanism consists of three bond rotations with an energy requirement of 5.43 and 5.23 kcal/mol for the first and second steps and no energy barriers to the last step. After elaidinization, total degradation was observed through a cascade reaction that generated CO, CO2, H2CO, and HCl.
Figures - available from: ChemistrySelect
This content is subject to copyright. Terms and conditions apply.
A preview of this full-text is provided by Wiley.
Learn more
Content available from ChemistrySelect 
This content is subject to copyright. Terms and conditions apply.
Effect of Solar and Artificial Radiation on Elaidinization and
Degradation of Z-Bixin Extracted from Bixa Orellana Seeds
Oswaldo Eliecer Cárdenas,[a] Sarai Vega-Rodríguez,[a] Agobardo Cárdenas-Chaparro,[b]
Antonio De Leon-Rodriguez,*[c] and Denisse de Loera*[a]
Z-bixin is the main metabolite contained in Achiote, which is
widely used as a food condiment and pigment. Z-bixin plays an
important role in photosynthesis. It is used to develop artificial
solar cells and scavenge radical oxygen and nitrogen species. In
this work, the photochemistry of Z-bixin with solar irradiation
and lamps at 365 and 410 nm was determined in solution. The
ultraviolet-visible spectroscopy (UV-Vis) and Ultra High Perform-
ance Liquid Chromatography (UHPLC) analysis showed that
elaidinization of Z-bixin to E-bixin can be reached under
radiation. This is in accordance with the computational
evaluation that indicates that the mechanism consists of three
bond rotations with an energy requirement of 5.43 and
5.23 kcal/mol for the first and second steps and no energy
barriers to the last step. After elaidinization, total degradation
was observed through a cascade reaction that generated CO,
CO2, H2CO, and HCl.
Introduction
Z-bixin is the main metabolite in annatto, a condiment and
food coloring obtained in the seeds of Bixa orellana Linn,
known as achiote.[1] Annatto is found in margarine, baked
goods, processed meats, and other foods. Z-bixin is used in the
food industry as a natural colorant[2] and additive,[3] but also in
the photovoltaic cell manufacturing,[4] in the development of
drugs to treat inflammatory,[5] infectious diseases,[6,7] and
against the effects of oxidative stress due to its antioxidant
properties,[8–10] among others.
Although natural carotenoids prefer all-E-isomers by ther-
modynamic stability, the Z-isomer of bixin is more stable than
its respective all-E-isomer, Figure 1.[6,11]
It has been reported that methyl bixin is susceptible to
isomeric transformations to form the E-bixin, di-cis isomer, and
other cis-isomers[12] (Figure 2).
Therefore conditions of extraction, storage, and light
exposure are important factors to Z-bixin purity and conserva-
tion since it is also isomerized into E-, di-cis, poly-cis, and other
mono cis-isomers.[13]
[a] O. Eliecer Cárdenas, Dr. S. Vega-Rodríguez, Dr. Denisse de Loera
Facultad de Ciencias Químicas
Universidad Autónoma de San Luis Potosí
Av. Dr. Manuel Nava No. 6 Zona Universitaria
78210, Mexico
E-mail: atenea.deloera@uaslp.mx
Homepage: https://investigadores.uaslp.mx/InvestigadorProfile/CDIAAA%
3D%3D
[b] Dr. A. Cárdenas-Chaparro
Escuela de Ciencias Químicas
Universidad Pedagógica y Tecnológica de Colombia
Avenida Central del Norte 39-115, Colombia
[c] Dr. Antonio De Leon-Rodriguez
Instituto Potosino de Investigación Científica y Tecnológica A.C.
Camino a la Presa San José 2055 Col. Lomas 4 sección
78216, Mexico
E-mail: aleonr@ipicyt.edu.mx
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/slct.202201336
Part of the “Organic and Supramolecular Chemistry in Latin America” Spe-
cial Collection.
Figure 1. Z- and E-bixin chemical structures.
Figure 2. Methyl bixin isomers.
ChemistrySelect
www.chemistryselect.org
Research Article
doi.org/10.1002/slct.202201336
ChemistrySelect 2022,7, e202201336 (1 of 7) © 2022 Wiley-VCH GmbH
Wiley VCH Donnerstag, 11.08.2022
2227 - closed* / 258374 [S. 9782/9788] 1
ResearchGate has not been able to resolve any citations for this publication.
Bixin, an apocarotenoid isolated from Bixa orellana L., sensitizes human melanoma cells to dacarbazine-induced apoptosis through ROS-mediated cytotoxicity
Article
Full-text available
  • Feb 2019
  • FOOD CHEM TOXICOL
Cutaneous melanoma has a high capacity to metastasize and significant resistance to conventional therapeutic protocols, which makes its treatment difficult. The combination of conventional drugs with cytostatic molecules of low toxicity has been shown to be an interesting alternative for sensitization of tumor cells to chemotherapy. In this study, we evaluated the effect of bixin, an abundant apocarotenoid present in Bixa orellana, on the sensitization of human melanoma cells (A2058) to dacarbazine treatment, an anticancer agent clinically used for the therapy of metastatic melanoma. UPLC-DAD-MS/MS analyses of bioactive extracts from B. orellana seeds led to the identification of two new apocarotenoids: 6,8′-diapocarotene-6,8′-dioic acid and 6,7′-diapocarotene-6,7′-dioic acid. After being identified as its major compound, bixin (Z-bixin) was evaluated on A2058 cells expressing the oncogenic BRAF VE600 mutation and resistant to dacarbazine treatment. Bixin promoted growth inhibition, reduced cell migration, induced apoptosis and cell cycle arrest in the G2/M phase. When associated with dacarbazine, bixin restored the sensitivity of A2058 cells to chemotherapy, enhancing its antiproliferative, anti-migratory and pro-apoptotic effects. Combined treatment also induced higher ROS (reactive oxygen species) and MDA (malondialdehyde, a lipid peroxidation marker) generation than monotreatment, suggesting that the oxidative stress caused by bixin contributes significantly to its sensitizing effect. Taken together, these data suggest that bixin exerts intrinsic antimelanoma activity by mechanisms complementary to those of dacarbazine, encouraging its use in combined therapy for cutaneous melanoma treatment.
View
Optimization of the Microwave-Assisted Extraction Process of Bioactive Compounds from Annatto Seeds (Bixa orellana L.)
Article
Full-text available
  • Feb 2019
This study deals with the extraction, optimization, and evaluation of the antioxidant and antimicrobial activities of bioactive compounds obtained from the seeds of annatto using microwave-assisted extraction as compared to leaching. Annatto seeds were subjected to a microwave treatment of 2450 MHz and power of 700 watts using a response surface design involving four factors: pH (4–11), solvent concentration (ethanol) (50–96%), solvent-to-seed ratio (2–10), and microwave exposure time (0–5 min). The contents of polyphenol compounds and bixin were taken as response variables. Subsequently, the antioxidant and antimicrobial activities were assessed at the optimal processing conditions predicted by the experimental design. Microwaves, solvent concentration, and the solvent-to-seed ratio showed a statistically significant effect for the extraction of polyphenol compounds and bixin. Thus, microwaves accelerated the extraction of those compounds and the slight increase in temperature caused some degradation of the polyphenol compounds. The microwave-assisted extraction increased the contents of polyphenols and bixin along with their antioxidant activity as compared to leaching extraction. However, this technique does not significantly improve the antimicrobial activity against Bacillus cereus and Staphylococcus aureus.
View
Effects of Cyclohexane/Acetone Ratio on Bixin Extraction Yield by Accelerated Solvent Extraction Method
Article
Full-text available
  • Dec 2015
In this study, accelerated solvent extraction (ASE) was applied to the quantitative extraction of bixin. The effects of cyclohexane/acetone ratios on bixin extraction yield were evaluated. Acetone was used in the process of pigment extraction and also played a major role in its analysis by UV-Vis spectrophotometry. Pure cis-bixin isolated by flash chromatography and characterized by Fourier Transform Infra Red spectrometry was used as a bixin standard for qualitative and quantitative analysis of annatto extracts which were obtained by accelerated solvents extraction. UV-Vis spectrophotometry analysis shows that the extraction using 100 % cyclohexane gives the lowest bixin yield. This is different from the UV-Vis spectra generated with acetone extraction. The difference in percentage of acetone shows significant effects on bixin extraction yields. The use of cyclohexane:acetone (60 % : 40 %) solution at 50 °C for 5 min heating time results the highest total bixin extraction yield (48.00 %) as compared to the other solvent ratios, and to the usual extraction methods using the same solvent (29.14 %). High pressure liquid chromatography analysis shows that bixin extracted by this method has purity degree of 68.16 %.
View
DFT and ENDOR Study of Bixin Radical Cations and Neutral Radicals on Silica–Alumina
Article
Full-text available
  • Oct 2014
Bixin, a carotenoid found in annatto (Bixa orellana), is unique among natural carotenoids by being water-soluble. We stabilized free radicals from bixin on the surface of silica-alumina (Si-Al) and characterized them by pulsed electron-nuclear double resonance (ENDOR). DFT calculations of unpaired electron spin distribution for various bixin radicals predict the EPR hyperfine couplings. Least-square fitting of experimental ENDOR spectra by spectra calculated from DFT hyperfine couplings characterized the radicals trapped on Si-Al. DFT predicts that the trans bixin radical cation is more stable than the cis bixin radical cation by 1.26 kcal/mol. This small energy difference is consistent with the 26% trans and 23% cis radical cations in the ENDOR spectrum. The remainder of the ENDOR spectrum is due to several neutral radicals formed by loss of a H(+) ion from the 9, 9', 13, or 13' methyl group, a common occurrence in all water-insoluble carotenoids previously studied. Although carboxyl groups of bixin strongly affect its solubility relative to other natural carotenoids, they do not alter properties of its free radicals based on DFT calculations and EPR measurements which remain similar to typical water-insoluble carotenoids.
View
Protective effect of bixin on carbon tetrachloride-induced hepatotoxicity in rats
Article
Full-text available
  • Sep 2014
Background The liver is an important organ for its ability to transform xenobiotics, making the liver tissue a prime target for toxic substances. The carotenoid bixin present in annatto is an antioxidant that can protect cells and tissues against the deleterious effects of free radicals. In this study, we evaluated the protective effect of bixin on liver damage induced by carbon tetrachloride (CCl4) in rats. Results The animals were divided into four groups with six rats in each group. CCl4 (0.125 mL kg-1 body wt.) was injected intraperitoneally, and bixin (5.0 mg kg-1 body wt.) was given by gavage 7 days before the CCl4 injection. Bixin prevented the liver damage caused by CCl4, as noted by the significant decrease in serum aminotransferases release. Bixin protected the liver against the oxidizing effects of CCl4 by preventing a decrease in glutathione reductase activity and the levels of reduced glutathione and NADPH. The peroxidation of membrane lipids and histopathological damage of the liver was significantly prevented by bixin treatment. Conclusion Therefore, we can conclude that the protective effect of bixin against hepatotoxicity induced by CCl4 is related to the antioxidant activity of the compound.
View
Bixin attenuates mechanical allodynia, anxious and depressive-like behaviors associated with experimental diabetes counteracting oxidative stress and glycated hemoglobin
Article
  • Jun 2021
  • BRAIN RES
Neuropathic pain, depression, and anxiety are common comorbidities in diabetic patients, whose pathophysiology involves hyperglycemia-induced increased oxidative stress. Bixin (BIX), an apocarotenoid extracted from the seeds of Bixa orellana, has been used in traditional medicine to treat diabetes and has been recognized by its antioxidant profile. We aimed to investigate the effect of the BIX over the mechanical allodynia, depressive, and anxious-like behaviors associated with experimental diabetes, along with its involved mechanisms. Streptozotocin-induced diabetic rats were treated for 17 days (starting 14 days after diabetes induction) with the corresponding vehicle, BIX (10, 30 or 90 mg/kg; p.o), or INS (6 IU; s.c.). Mechanical allodynia, depressive, and anxious-like behavior were assessed by electronic Von Frey, forced swimming, and elevated plus-maze tests, respectively. Locomotor activity was assessed by the open field test. Blood glycated hemoglobin (HbA1) and the levels of lipid peroxidation (LPO) and reduced glutathione (GSH) were evaluated on the hippocampus, pre-frontal cortex, lumbar spinal cord, and sciatic nerve. Diabetic animals developed mechanical allodynia, depressive and anxious-like behavior, increased plasma HbA1, increased LPO, and decreased GSH levels in tissues analyzed. Repeated BIX-treatment (at all tested doses) significantly attenuated mechanical allodynia, the depressive (30 and 90 mg/kg) and, anxious-like behaviors (all doses) in diabetic rats, without changing the locomotor performance. BIX (at all tested doses) restored the oxidative parameters in tissues analyzed and reduced the plasma HbA1. Thereby, bixin may represent an alternative for the treatment of comorbidities associated with diabetes, counteracting oxidative stress and plasma HbA1.
View
TiO2-based dye-sensitized solar cells prepared with bixin and norbixin natural dyes: Effect of 2,2’-bipyridine additive on the current and voltage
Article
  • Jul 2020
  • OPTIK
In this paper, we discovered that the 2,2'-bipyridine (bipy) was able to increase the voltage and short circuit current of dye-sensitized solar cells (DSSCs) prepared using bixin and norbixin natural dyes that are environmentally friendly. Titanium oxide (TiO2) film was deposited on FTO-glass. Morphological analysis revealed that the film was porous and consisted of almost spherical particle with an average size of 35 nm. The photoelectric behavior of the DSSCs was evaluated under polychromatic radiation adjusted to 1.5 AM standard. The analysis revealed that the presence of bipy in the electrolyte significantly increased the open circuit voltage (VOC) values from 299 to 519 mV for the DSSCs prepared using bixin dye, whereas the VOC values increased from 293 to 311 mV for the DSSCs prepared using norbixin dye. Also, it was observed that the bipy additive positively influenced the short-circuit current (JSC) values of these devices. The simultaneous increase in VOC and JSC rendered this bipyridinic compound a good additive candidate for TiO2 nanoparticles-based DSSC using natural dyes.
View
Achiote (Bixa orellana L.): a natural source of pigment and vitamin E
Article
  • Mar 2017
Commercialization of agricultural products, including seeds and its derived products, represents an important economic source for developing countries. Natural colorants obtained from the seeds of achiote plant (annatto) have been used since pre-Hispanic times. Also, production of this crop has been important for Mayan cuisine. Annual world production of achiote seeds is approximately 14,500 tons (dry weight). Two thirds of the production is commercialized as dried seeds and the rest as colorant. Latin America produces 60% of the total world production, followed by Africa (27%) and Asia (12%). The main producers in Latin America are Peru, Brazil and Mexico. The purpose of the present paper is to review the most recent literature on Bixa orellana L. focusing on bixin, norbixin, tocotrienols and tocopherols biosynthesis, use and industrial applications of annatto extracts, as well as its nutraceutical potential and its benefits for human health.
View
Evaluation of stability of bixin in nanocapsules in model systems of photosensitization and heating
Article
  • Jan 2014
  • LWT-FOOD SCI TECHNOL
Bixin is a good quencher of singlet oxygen, but is unstable at high temperatures and has low solubility in water. The aim of this study was to evaluate the stability of bixin in lipid-core nanocapsules (BIX-LNC) during photosensitization (5–25 °C) and heating (65–95 °C) in model systems of ethanol:water (2:8). The BIX-LNC were prepared by the technique of interfacial deposition of preformed polymer, with a mean diameter (D4,3) of 195 ± 27 nm. During photosensitization in air-saturated conditions, free bixin and BIX-LNC exhibited activation energies of 7.09 and 11.48 kcal/mol, respectively, and in the absence of oxygen exhibited activation energies of 8.96 and 16.31 kcal/mol, respectively. During heating, free bixin and BIX-LNC showed activation energies of 15.06 and 23.81 kcal/mol, respectively. The activation energies for BIX-LNC were superior to those of free bixin in both the photosensitization and heating experiments, suggesting that encapsulation increased the stability of bixin.
View
Combining Synchronous Transit and Quasi‐Newton Methods to Find Transition States
Article
  • Jan 1993
AbstractA linear synchronous transit or quadratic synchronous transit approach is used to get closer to the quadratic region of the transition state and then quasi‐newton or eigenvector following methods are used to complete the optimization. With an empirical estimate of the hessian, these methods converge efficiently for a variety of transition states from a range of starting structures.
View