1.1 Introduction
The discovery of bioactive compounds present in natural matrices has gained an increasing amount of attention during the past two decades. In addition to this fact, the awareness of the health benefits of eating healthy foods, as well as the development of analytical instruments, has contributed to the study of pepper fruits and their by-products as sources of bioactive compounds (Baenas, et al. 2019).
Pepper became so important in the Middle Ages that spice traders were dubbed âPepperersâ in England, âPoivriersâ in France, and âPfeffersackeâ in Germany (Govindarajan and Stahl, 2009). Oleoresin can be obtained from different plants such as basil, capsicum (paprika), cardamom, celery seed, cinnamon bark and clove bud. Pepper (Capsicum annuum L.) is appreciated as a food additive, a pigment for its physiological and pharmaceutical uses due to its high level of antioxidants. Pepper spray has been widely used for decades by government agencies or military forces worldwide to combat interpersonal violence or civil unrest, law enforcement, criminal incapacitation, personal defence and sometimes even in controlling wild animals. Oleoresins are semi-solid extracts made up of resin and essential fatty oil that are obtained by evaporating the solvents used to make them (King, 2006). Naturally occurring oleoresins are referred to as Balsams. Oleoresin, often known as spice drops, includes all of the pungency and flavour components of pepper (Ravindran and Kallupurackal, 2012). The oleoresin, which is made up of volatile and non-volatile components, can be separated by squeezing the herb or using a solvent mixture to extract the volatile and non-volatile components (Peter, 2012).
1.2 Economic Importance
In the Mexican culture, the wild chilli pepper that is also known as chile piquin (C. annuum var glabriusculum) plays a very significant role, serving as a staple food since prehistoric times. There are a variety of ways of preparing cilantro, whether fresh green, dried, used in dust, brine, sauces, salads, moles, stuffed chilli, sweet candies and other applications (Garcia et al., 2017). In Mexico, the chile is used for a variety of purposes, including Curanderos utilize it in various ceremonies, such as âcleansing,â which refers to avoiding bad vibrations and is widely employed as an evil eye remedy. Prehispanic ethnic cultures, for example, were known to use medicinal plants (MartĂnez-Ăvalos et al., 2018). The Aztecs employed them to treat toothaches, ear infections, constipation and labour pains, and the early Spaniards in America praised their use. It is used to treat dyspepsia in the digestive system, as well as toothaches, diarrhoea, ear pain, cough and fever because capsaicin promotes blood circulation. Some medicines have been made from oleoresins from Capsicum spp., and they act on the mucosa to relieve respiratory problems. Chilli with meals may be the most popular hangover treatment. Capsicum is an ornamental plant in Mexican culture, and it is used as an adornment in plates, altars, religious gatherings and amulets, among other things (Kunnumakkara et al., 2009). Chilli is also used in cosmetics, paintings, and meals, and it is used in industry to obtain oleoresins, from which capsaicin is made, and it is utilized in human and animal foods, such as birds, and even in personal defence (Baenas et al., 2019).
1.3 Geographic Distribution and Ecology
C. annuum var glabriusculumâs distribution extends throughout Mexico, Central America, Colombia and down into several regions of Peru (MartĂnez-Ăvalos et al., 2018). Mexico has registered this species in all 34 states, and it can be found in the coastal zone from Sonora to Chiapas on the Pacific, and from Tabasco to YucatĂĄn and Quintana Roo on the Gulf of Mexico. Northeastern Mexico is typically found from sea level to approximately 1200 m and is particularly accessible to disturbed zones of small deciduous and thorny forest. However, a recent study on potential distribution modelling is being investigated. The temperature could be one of the key environmental variables affecting its spread from 18.3 Co, according to Martnez-valos and Venegas-Barrera (MartĂnez-Ăvalos et al., 2018; Smith et al., 1957; kraft et al., 2014; AguilarâMelĂ©ndez).
1.4 Production
The production of chilli fruits in Mexico is one of the largest in the world, with the country growing 2.2 million tons of them each year from a surface area of 149,000 ha at a participation rate of 12,000 producers each year. Considering these facts, chilli is a significant commercial and social export product, with over 600,000 tonnes of green chilli produced each year, and its global consumption is growing every year. People from 9 cities in the states of Coahuila, Nuevo LeĂłn and Tamaulipas favour the types jalapeno chilli (37.3%), piquin (29.6%) and serrano (24.0%), while the cities of Linares and Ciudad Victoria are the largest consumers of the variety âpiquin.â Harvesting wild chilli Capsicum annum var glabriusculum fruits by people living in rural areas is a popular activity in some Northern (Coahuila, Nuevo LeĂłn, San Luis Potosi and Tamaulipas) and Northwestern (Baja California Sur, Sonora, Chihuahua and Sinaloa) Mexican states, as the price is always high and they are commercialized in both Mexico and the United States (MartĂnez-Ăvalos et al., 2018; Govindrajan and Salzer, 1986).
1.5 Extraction Techniques
1.5.1 Supercritical CO2 Extraction
Extraction of supercritical CO2 was either done in duplicate or using a dynamic extraction method consisting of an extracting column that is continuously supplied with solvent through a fixed solid bed (De Aguiar et al., 2013).
1.5.1.1 Global Yield (X0)
In order to determine X0, experiments were conducted in a dynamic extraction device (Applied Separations, Speed, Allentown, PA). In this experiment, 4.0 g of sample for the fixed bed was put in a stainless steel column with a volume of 5.6 mL. The effect of pressure and temperature on X0 was studied using a factorial design by repeating 2 Ă 32 = 18 experiments, each with three levels and two variables. The pressures and temperatures were 15, 25 and 35 MPa and 40°C, 50°C and 60°C, respectively. It was determined that pressure ranges below 15 MPa can reduce extraction rate and yield, while pressures over 35 MPa result in unfeasible costs compression. To avoid thermal degradation in the extract, levels of temperature were chosen over the critical temperature of CO2 (31.1°C) and over 60°C, the upper limit. A flow rate of 1.98 10â4 kg/s was selected for the solvent flow. The extraction period was set at 320 minutes after initially testing. Using the chosen solvent flow rate showed that all of the immediately accessible solutes had been removed by convection. Glass flasks were used to collect the extracts, which were then weighed on an analytical balance (De Aguiar et al., 2013).
1.5.1.2 Kinetic Experiments
For kinetics, frozen and oven-dried pepper samples were used with the similar extraction unit used for global yield experiments, at pressures and temperatures that yielded the highest capsaicinoids yield and the conditions evaluated during the design of the experiment. The sample used for the assay constituted approximately 4.0 g, the quantity of which was fixed inside of a 5.6 mL column of stainless steel. Carbon dioxide (CO2) was injected at a flow rate of 1.98 10â4 kg/s, and the average particle size of dry materials was 0.88 (*0.06) mm and 0.51 (*0.01) mm, respectively, for a freeze-dried and oven-dried sample. A curve showing the extraction flow was derived by measuring the mass of the extracted extract based on the time. According to the methodology presented, capsaicinoids were determined in the extract (De Aguiar et al., 2013).
1.5.2 Soxhlet Extraction
During the study, approximately 5 kg of fresh peppers were dried under the air circulation oven for 20 hours at approximately 70°C and lyophilized for 72 hours at approximately â40°C (highest capsaicinoids). As part of the extraction process, the samples were ground in a knife mill after drying; homogenization is important for them as it reduces resistance to mass transfer. An extraction technique suitable for Soxhlet extraction was selected, using hexane as a solvent. The extraction apparatus was packed with filter paper, and 5.0 g of freeze-dried sample was put in at a time. The system was heated to boiling (69°C) with hexane (0.15 L) added. The reflux was maintained for 6 hours, after which the solvent was evaporated under vacuum (at 25°C), and the recovered extract was weighed and stored for further analysis at â18°C (De Aguiar et al., 2013).
1.5.3 Microwave Reflux Extraction
Five grams of sieved samples were combined with solvents such as acetone andwater hexane, and stirred with a magnetic stirrer. Soaking and stirring were performed to ensure that the sample and solvent were properly hydrate...