Научная статья на тему 'Preparation and Characterization of Renewable Bio-Polyol from the Edible Seed Oil'

Preparation and Characterization of Renewable Bio-Polyol from the Edible Seed Oil Текст научной статьи по специальности «Биологические науки»

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Ключевые слова
Salvia hispanica oil / polyol / FTIR / NMR / antimicrobial / bio-polymers

Аннотация научной статьи по биологическим наукам, автор научной работы — J.L. Jebisha, S. Begila David

Polyol is an organic compound containing multiple hydroxyl groups. This study looked at the possibility of using an edible oil extract from Salvia hispanica seeds as a sustainable source for polyols and, eventually, biodiesel or polyurethane. For this, a combination of hydrogen peroxide and acetic acid was used to create new polyol from the aforementioned oil in one-step synthesis. Standard techniques such as physicochemical analysis, phytochemical and basic radical identification, FTIR and NMR were used to characterize the polyol derivative that was extracted from the oil. Antimicrobial activity of both oil and polyol were tested against certain bacteria and fungi. Spectral analysis demonstrated the formation of polyol and this result indicated the possible of using Salvia hispanica polyol as a raw material for the preparation of bio-polymers.

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Текст научной работы на тему «Preparation and Characterization of Renewable Bio-Polyol from the Edible Seed Oil»

Journal of Stress Physiology & Biochemistry, Vol. 20, No. 3, 2024, pp. 29-36 ISSN 1997-0838 Original Text Copyright © 2024 by Jebisha and Begila David

ORIGINAL ARTICLE

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Preparation and Characterization of Renewable Bio-Polyol

from the Edible Seed Oil

1 Research scholar (Reg no:21213162032019), Department of Chemistry and research Centre, Scott Christian college (autonomous), Nagercoil-629 003, Tamil Nadu, India.

(Affiliated to Manonmaniam Sunderanar University, Tirunelveli-627 012, Tamil Nadu, India)

2 Research supervisor & Associate professor, Department of Chemistry & research Centre, Scott Christian college (autonomous), Nagercoil-629 003, Tamil Nadu, India.

(Affiliated to Manonmaniam Sunderanar University, Tirunelveli-627 012, Tamil Nadu, India)

*E-Mail: begilarobinfagmail. com

Polyol is an organic compound containing multiple hydroxyl groups. This study looked at the possibility of using an edible oil extract from Salvia hispanica seeds as a sustainable source for polyols and, eventually, biodiesel or polyurethane. For this, a combination of hydrogen peroxide and acetic acid was used to create new polyol from the aforementioned oil in one-step synthesis. Standard techniques such as physicochemical analysis, phytochemical and basic radical identification, FTIR and NMR were used to characterize the polyol derivative that was extracted from the oil. Antimicrobial activity of both oil and polyol were tested against certain bacteria and fungi. Spectral analysis demonstrated the formation of polyol and this result indicated the possible of using Salvia hispanica polyol as a raw material for the preparation of bio-polymers.

Key words: Salvia hispanica oil, polyol, FTIR, NMR, antimicrobial, bio-polymers

J.L. Jebisha 1, S. Begila David

2

Received March 13, 2024

The chemical industry has been prompted to explore for new sources of renewable resources as raw materials by the strong demand for products with petrochemical origins, as well as their unfavorable environmental effects and the growing scarcity of these non-renewable resources. Due to nature's enormous synthetic potential and many green chemistry principles, these raw materials have significantly aided the plastics industry's sustainable development (Eissen et al., 2002; Tian et al., 2012). Due to their availability, low toxicity, biodegradability, natural fluidity, and affordability, vegetable oils are among the most popular alternatives (Biermann et al., 2000; Guner et al., 2006; de Espinosa, et al., 2011). To create polyols, a number of vegetable oil molecules must undergo a chemical transformation. These bio-polyols are then used, among other things, to create polyurethanes (Zhang et al., 2015), polyesters (Chaudhari. et al., 2015), and epoxy (Fernandes et al., 2017). Vegetable oil polyols are fascinating substances with applications as corrosion inhibitors (Kosari et al., 2014; Yoo et al., 2012), tensioactive agents or organogelators (Stan et al., 2008), and useful monomers for the production of diverse macromolecular compounds (Ji et al., 2015). Polyols have been created using natural oils like castor (Ugarte et al., 2014), soybean (Ji et al., 2015), camelina (Balanuca et al., 2015), palm kernel (Septevani et al., 2015), jatropha (Saalah et al., 2015), and rapeseed (Zieleniewska et al., 2015; Kuranska et al., 2015).

An herbaceous plant called chia has opposing, serrated leaves that range in size from 1.5 to 3 inches long and 1 to 2 inches wide. Oval in shape, seeds are roughly 2 mm (0.08 inches) in length and 1 mm (0.04 inches) in width. The lustrous seeds contain darker irregular marks or specks on them and their coat can range in hue from cream to charcoal grey. An annual herb called chia (Salvia hispanica L.) blooms in the summer. It is about a meter tall and has opposite, petiolate, serrated leaves that range in length from 4 to 8 cm a width of 3 to 5 cm (Ayerza et al., 2010).

Therefore, this study concentrates in the obtention of new bio-based polyol from the edible oil extract from the seeds of the Salvia hispanica and also to test the

phytochemicals and basic radicals present in the oil extract. In addition, we characterize the prepared polyols using various physical properties and spectroscopic methods. The application of the prepared polyol against certain microbes were also tested.

MATERIALS AND METHODS

OIL EXTRACTION:

The extraction of oil was carried out using AOAC technique Am2-93 (Official Methods and Recommended Practices of the American Oil Chemists' Society; AOCS Press: Champaign, IL, USA, 1995). In a Soxhlet device, 5g of Salvia hispanica L. seeds were extracted with 100 ml of n-hexane as the extraction solvent. Following an 8hour period, the n-hexane was eliminated at 40°C and low pressure. After obtained, the Salvia hispanica L. oil (SHO) was kept in a refrigerator till additional research was conducted. SYNTHESIS OF POLYOL:

The synthesis of the polyols was done in accordance with the approach outlined by Monteavaro et al. (2005). 5g (5.6 mmol) of oil 9.30 mL (0.162 mol) of glacial acetic acid in 20 mL of toluene, together with a few drops of sulfuric acid, were combined in a three-necked flask that was fitted with an isobaric funnel, reflux condenser, and mechanical stirrer. At room temperature, the mixture was mechanically agitated until it was completely homogenized. Subsequently, 5.30 mL of a 30% H2O2, solution was added gradually while maintaining the temperature. Following the addition of H2O2, the mixture was heated for 12 hours to 60°C. After bringing the reaction mixture down to room temperature, surplus peroxide was removed by stirring it for 20 minutes while adding a 10% (w/v) sodium bisulfide solution. Following that, the mixture was mixed with 50 mL of ethyl ether, and the organic phase was repeatedly washed to a pH of neutral using a 10% (w/v) sodium carbonate solution. In order to extract Salvia hispanica L. (SHP), the organic phase was lastly dried over sodium sulphate and concentrated under vacuum to remove the ethyl ether. CHARACTERISATION OF OIL AND POLYOL: PHYSICO CHEMICAL ANALYSIS:

The acid value of SHP was determined by the volumetric titration method according to ASTM D1980-

87. The known quantity of sample is dissolved in neutral butanol-toluene mixture and 3-4 drop of phenolphthalein indicator added, swirling gently and titrated against the 0.1 N alcoholic KOH solution. Equation (1) was used to determine the acid value of SHP.

Acid value=RX N X 56.1 (1)

W

where B = Burette reading (ml), N = Normality of alcoholic KOH solution, W = weight of sample (g).

The hydroxyl value of SHP was determined by acetic anhydride-pyridine method according to ASTM D4274-16. The calculation of hydroxyl value was done by using Equation (2).

Hydroxyl value = (B - S) x N x 56.1 (2)

W

where B = Burette reading for blank (ml), S = Burette reading for sample (ml), N = Normality of alcoholic KOH solution, W = weight of sample (g). PHYTOCHEMICAL AND BASIC RADICAL IDENTIFICATION:

Phytochemical screening and basic radical identification were performed to asses the qualitative chemical composition of different samples of crude extracts using commonly employed precipitation and colouration reactions to identify the major and secondary metabolites. FTIR ANALYSIS:

The chemical structure of the SHO and SHP were identified by FTIR on a Bruker ATR spectrophotometer. The spectra were observed in the 600 - 4000 cm-1 wavelength range. 1H NMR SPECTROSCOPY:

The supportive confirmation of chemical structure was given by 1H nuclear magnetic resonance (NMR)spectroscopy. 1H spectra of the product were analyzed using Bruker DPX 400 MHz spectrophotometer with CDCls as solvent. ANTIMICROBIAL ACTIVITY:

Antimicrobial activity was examined using "The Kirby-Bauer Method" against the number of pathogens including both gram-positive and gram-negative bacteria and also certain fungi. The zone of inhibition of both SHO and SHP were examined against certain pathogens.

RESULTS AND DISCUSSION

PHYSICO CHEMICAL ANALYSIS:

The acid number is expressed as the number of milligrams of KOH required to neutralize the acidity of sample. The OH number is the amount of available reactive hydroxyl groups on polyol molecules. The viscosity was measured using Brookfield viscometer and the density of the polyol were also analysed. The SHP is well dissolved in Chloroform. The results of the certain physico chemical analysis were mentioned in the Table 1.

PHYTOCHEMICAL SCREENING:

The preliminary phytochemical study reveals the presence of glycosides, reducing sugars, phenolic compounds and saponins (Table 2) in the SHO. The color change in the extract were also listed in the table. BASIC RADICAL IDENTIFICATION:

Basic radical test shows the presence of bismuth, barium calcium and magnesium in the SHO were listed in the Table 3. FTIR:

The successful conversion of SHO to SHP was confirmed qualitatively by FT-IR spectroscopy. Fig. 1 and Fig. 2 shows the FTIR spectra of SHO and SHP respectively. The SHP spectra shows a broad band at 3562 cm-1 which were assigned to the presence of a hydroxyl (-OH) stretching vibration. A strong band at 3181 cm-1 was attributed to the presence of aromatic -CH-stretching and bands at 1644 cm-1 and 1400 cm-1 were assigned to the presence of amide band from protein carbonyl stretches and C-O-H bending vibrations. The appearance of new peak at 3562 cm-1 in SHP spectra confirms the formation of polyol. 1-H NMR spectra:

Fig. 3 and Fig. 4 gives the 1-H NMR spectra of the SHO and SHP respectively. The methylene protons of the aliphatic chains may be responsible for the signal seen as a triplet between 1.63 to 1.67 ppm (3H) in Fig. 4. The proton of the hydroxyl group is represented by the sharp singlet peak at 2.731 ppm (6H); the electronegative influence of the oxygen atom is responsible for the absorption shift towards the downfield. The multiplet signal at 3.8 ppm (2H) is indicative of the protons next to the acid's carbonyl

32 Preparation and Characterization of Renewable Bio-Polyol...

group. The peak shift downwards as a result of the present in the range of 5.3 to 5.3 ppm (Fig. 3) in SHO

carbonyl group's electronegative action, which de-shield vanished, indicating that the SHP structures were

the area (Dai et al., 2005). The signals corresponding to essentially unsaturated. Lastly, the hydroxylation

the toluene structure were found at 7.5-7.6ppm as reaction was verified by the lack of signals in the range

multiplet (Fig. 4). This evidence confirmed that the of 2.8 to 3.3ppm in relation to the epoxide groups (-

elimination of toluene was ineffective. Furthermore, the CH(O)CH-).

olefinic hydrogen (-CH=CH-) signal that had been

Table 1: Physico chemical analysis of polyol

Parameters Chia based polyol

Acid number (mg KOH/g) 5.386

OH number (mg KOH/g) 166.54

Density (g/cm3) 0.868

Viscosity (cps) 464

Solubility Chloroform

Table 2: Phytochemical screening of SHO

EXPERIMENT OBSERVATION INFERENCE

NaOH test No blue green color obtained Absence of anthocyanin

Extract + 2ml of NaOH

Bromine water test: Pale yellow color obtained Presence of glycosides

Extract + bromine water

1ml of + lead acetate solution No precipitate obtained Absence of phenol

5 ml of extract + 2ml of CHCls + 3 ml of conc. H2SO4 No reddish-brown precipitate obtained Absence of terpenoids

LEAD ACETATE TEST: No red precipitate Absence of tannins

Extract + 1ml of lead acetate

Extract + CHCl3 + conc. H2SO4 No purple color obtained Absence of steroids

Extract + Molisch's reagent Purple color is obtained Presence of reducing sugars

Extract + 2N HCl and remove the No white precipitate obtained Absence of alkaloids

aqueous layer and add Mayer's reagent

Alcohol + extract + ferric chloride Intense color Presence of phenolic compounds

Extract + water + shake well Foamy lather is obtained Presence of saponins

Alcohol + extract + Mg ribbon + No color change Absence of flavonoids

Conc. HCl

Alcohol + Conc. HNO3 + NH3 No reddish orange color is obtained Absence of xanthoproteins

Table 3: Basic radicals' identification

EXPERIMENT OBSERVATIONS INFERENCE

Extract + KI No golden spangles Absence of lead

Extract + NH4OH white precipitate Presence of bismuth

Extract + cupron reagent + NaOH No green color obtained Absence of copper

Extract + potassium ferrocyanide No white precipitate obtained Absence of zinc

Extract + dil. HCl + water + H2S No yellow precipitate Absence of cadmium

Extract + potassium thiocyanate No red or blue color Absence of ferric and cobalt

Extract + dil. HCl + aluminon reagent + (NH4)2CO3 No bright red precipitate is obtained Absence of aluminum

Extract + conc. HNO3 + sodium bismuthate + No pink color Absence of manganese

water

Extract + dimethyl glyoxime + NH4OH No scarlet red precipitate Absence of nickel

Extract + potassium chromate Pale yellow precipitate Presence of barium

Extract + NH4OH + ammonium oxalate White precipitate Presence of calcium

Extract + Magneson reagent + NaOH Blue precipitate Presence of magnesium

Extract +NaOH + Nesseler's reagent No reddish-brown precipitate Absence of ammonium

Table 4: Shows the zone of inhibition against certain microbes

Bacteria Zone of inhibition

SHO SHP Control (Amikacin)

Proteus mirabilis 12 mm 11 mm 18 mm

Salmonella ttypi 13 mm 14 mm 19 mm

Fungi Zone of inhibition

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SHO SHP Control (nystatin)

Aspergillus niger 10 mm 8 mm 15 mm

C. tropicalis 15 mm 14 mm 13 mm

Figure 1. FTIR spectra of SHO

Figure 2. FTIR spectra of SHP

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Figure 3. 1-H NMR spectra of SHO

Figure 4. 1-H NMR spectra of SHP

Figure 5. Zone of Inhibition against fungi

Figure 6. Zone of Inhibition against bacteria

Antifungal property

16 14

12 10

8 &

4

2 о

Aspergillus niger С.Tropicalis

■ SHO ■ SHP ■ Control (Nystatin)

Antibacterial property

20 18 16 14 12 10 8 6 4 2 о

Proteus mirabilis Salmonella typi

■ SHO BSHP ■ Control (Amikacin)

Figure 7. Comparative study

APPLICATION: ANTIMICROBIAL ACTIVITY:

Two bacterial cultures (Fig. 6) including Proteus mirabilis (gram positive), Salmonella typi (gram negative) and two fungal cultures (Fig. 5) including Aspergillus niger and C. tropicalis were used to check the antimicrobial potential of both SHO and SHP. Amikacin was used as a control against bacterial cultures while Nystatin was used as a control against fungal cultures. The zone of inhibition against both bacteria and fungi were listed in the Table 4. The bar graph shows the comparative study of SHO and SHP against certain microbes (Fig. 7).

CONCLUSION

We can infer from the results above that SHP was successfully prepared from the hexane extract of Salvia Hispanica and it was characterized by using FTIR and 1H NMR spectroscopy. The physico-chemical analysis of the SHP and phytochemical screening and basic radical identification of SHO were examined. The antimicrobial potential of the prepared polyol and the oil were tested against certain bacteria and fungi. Thus, the prepared bio-polyol can be used as an alternative for organic polyols which can be effectively use for the preparation of certain bio- polymers.

CONFLICTS OF INTEREST

The authors declare that they have no potential

conflicts of interest.

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