Honey and Syrups: Healthy and Natural Sweeteners with Functional Properties

HONEY AND SYRUPS: HEALTHY AND NATURAL SWEETENERS WITH FUNCTIONAL PROPERTIES

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Ángela-Mariela González-Montemayor*, Adriana C. Flores-Gallegos*, Lilia E. Serrato-Villegas†, Mercedes G. López-Pérez‡, Julio César Montañez-Sáenz*, Raúl Rodríguez-Herrera* *

Food Research Department, School of Chemistry, Autonomous University of Coahuila, Saltillo, Mexico, †Material Science Research Department, School of Chemistry, Autonomous University of Coahuila, Boulevard Venustiano Carranza and Jose Cardenas s/n, Saltillo, Coahuila, Mexico, ‡Biotechnology and Biochemistry Department, Center for Research and Advanced StudiesIPN, Irapuato Unit, Guanajuato, Mexico

6.1 Introduction As part of a human diet, carbohydrates, also named as sugars, have been consumed since long time ago; glucose, fructose, and sucrose are the most important sweet tasting carbohydrates present naturally in foods (Edwards et al., 2016). Glucose is ever-present in the diet and plays an important role in the regulation of human metabolism, it can be consumed in two ways: as free sugar or bonded in polymers (starch, dextrins, and maltodextrins), in addition glucose could be bonded in disaccharides (e.g., fructose bond to glucose is sucrose) (White, 2014). The sugars, besides being a source of energy affect the food texture and color, give its sweetness and also act as preservatives or flavor enhancers (Hinkova et al., 2015). Sugar is an important component of the modern diet, not only by the contribution of fruits and vegetables, but also by the sweeteners added to the processed foods and beverages. If the sweetener contribute to metabolize energy to the diet is a nutritive sweetener and if it not has contribution is a caloric one (White, 2014).

Natural Beverages. https://doi.org/10.1016/B978-0-12-816689-5.00006-7 © 2019 Elsevier Inc. All rights reserved.

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The addition of sugars in many beverages, bakery foods, dairy desserts, and candies plays an important role in the American diet. During the food processing, the added sugars may be all types of syrups, brown sugar, cane sugar, fructose, high-fructose corn syrup (HFCS), honey, molasses and sucrose among others (Bowman, 2016). The oldest sweetener in the world is probably the honey, used by the Egyptians in the 2100 BCE (Erejuwa et  al., 2012), for a long time in human history, honey was an important carbohydrate source and the only available sweetener until the 17th century when the sugar production began (Bogdanov et  al., 2008). Then, in the 17th century, maple syrup was the most popular sweetener used in the United States. Toward the 18th century, with the use of more advanced technologies, it was possible sucrose extraction from sugarcane. Sweeteners obtained through nature like honey (from bees), from plants and tree sap, these last ones denominates syrup because it can be extracted from many different sources such as trees (maple syrup), plants (agave syrup), and fruits and vegetables (corn syrup). Most of the syrups are nutritive and contain high proportion of sugars, proteins, lipids, dietary fiber, and phytochemicals (Clarke, 2003; Edwards et al., 2016). Some of them, also have a lower glycemic potency such as honey and agave, fructose contain may explain this glycemic potency. Extract composition and sensory properties of these natural sweeteners depend on botanical origin, environmental, and production conditions. It is stimulating that so many different compounds have been identified in traditional sweeteners and a number of studies have reported the beneficial effects of these compounds (Mellado-Mojica and López-Pérez, 2013; St-Pierre et  al., 2014; Da Silva et al., 2016). In the following sections, properties, characteristics, composition, and the information related to the obtaining process of the principal honeys and syrups as well as the activities that each one present in the human health.

6.2 Honey Honey has been defined as “the natural sweet substance produced by honey bees from the nectar of plants or from secretions of living parts of plants” (Codex Alimentarius Commission, 2001). Is the only available natural sweetener from the very beginnings of the human population, the relation between man and honey started in the Stone Age (Bogdanov et  al., 2008). Ancient cultures such as the Romans, Greeks, and Egyptians used honey to coat fruits, seeds, and stems of plants to preserve them or to use them like a kind of candies (Chaven, 2014).

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Physical and chemical properties of honeys fluctuate based on the plants from which the bees collect raw material (Rao et al., 2016). The main composition of this valuable food product consists of different sugars, in major part glucose and fructose, and other substances such as amino acids, enzymes, protein, vitamins, minerals, organic acids, and phenol compounds (El Sohaimy et  al., 2015). Also, final honey color, aroma, and flavor depend on processing, manipulation, packing, and storage time (Da Silva et al., 2016). Bee honey is one of the few nonallergic foods, easily assimilated by the human body. It contains nutrients that especially provides energy (El Sohaimy et al., 2015), furthermore, honey is a member of one of the natural compounds that nowadays is considered of high scientific and therapeutic interest (Habib et al., 2014a). In the last two decades, the consumption of honey has increased dramatically because of its nutritional value and healing properties (Wu et al., 2017). There is approximately 20,000 species of bees, being Apis mellifera the primary producer of the sweet product (Chaven, 2014), beyond the production of honey, it produces a variety of valuable products into the beehive, such as pollen, propolis, and royal jelly (Badolato et al., 2017). The varieties of honey may be grouped into mono-­floral when the dominating pollen grain originated from one particular plant, and multi-floral when there is no dominant pollen type in the sample (Erejuwa et al., 2012). Mono-floral honeys are expensive than multi-floral ones (Oroian and Ropciuc, 2017). There is about 320 different varieties of honey originating from various floral sources (Ayoub Meo et al., 2016). In addition to the mono- and multi-floral classification, honey can have two different botanical origins, there are blossom honeys and the honeydew honeys, the first ones are produced by bees from nectar contained in specialized botanical structures (blossoming plants) and the others are obtained from the secretions produced by determined trees and plants (Pita-Calvo and Vázquez, 2017). A particularity of this sweetener is that on average, it is 1–1.5 times sweeter (on a dry weight basis) than sugar (National honey board, 2014), a daily dose of 20 g of honey will cover approximately 3% of the required daily energy (Bogdanov et al., 2008).

6.2.1 Chemical Composition Honey contains about 200 substances. Monosaccharides are about 75% of the sugars found in honey, 10%–15% of disaccharides, and other sugars in small amount. Sugars present in honey are responsible for its energy value and viscosity (Da Silva et al., 2016). Honey can be divided chemically into a major fraction that represents the sugars and the minor fraction that include phenolic

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c­ ompounds, minerals, proteins, free amino acids, enzymes and vitamins, hormones, phenolic compounds, essentials oils, pigments, sterols, and phospholipids (Mahmoodi-Khaledi et  al., 2017). Some components of honey come from plants, some are added by the bees, and other are due to biochemical reactions during honey maturation (Pita-Calvo and Vázquez, 2017). Sugar composition also depends on the botanical origin of the flowers used by bees, geographical origin, climate, and processing storage. Honey, sugars profile include carbohydrates: the monosaccharides glucose and fructose are the most important sugars and the major constituents of the honey (Habib et al., 2014b), there are other in less proportion such as: rhamnose, trehalose, nigerobiose, isomaltose, maltose, maltotetraose, maltotriose, maltulose, meleszitose, melibiose, raffinose, erlose, turanose, laminaribiose, kojibiose, gentibiose, 1-kestose, and others (Khan et  al., 2017; Pita-Calvo and Vázquez, 2017). Honeydew contains more oligosaccharides melezitose and raffinose that blossom honey (Bogdanov et al., 2008). Moisture content is of major importance for honey stability against fermentation and granulation, low moisture decreases microbiological activity (El Sohaimy et  al., 2015). The moisture depends on factor such as sampling, season, climate, and honey processing, but it has been reported that the parameter with high impact is the multiple origin flower (Mahmoodi-Khaledi et  al., 2017). Honey samples from tropical countries have higher moisture content (Chua et al., 2012). Honey protein content may vary according to the honeybee species. Apis cerana honey contains 0.1%–3.3% of protein, while A. mellifera honey contains between 0.2% and 1.6% of proteins. The main source of protein is attributed to pollen, and in less proportion to animal and vegetal sources (Escuredo et al., 2014). One of the most abundant amino acid in honey is proline which represents a total of 50%–85% amino acids, other amino acids present in honey are: glutamic acid, aspartic acid, glutamine, histidine, glycine, threonine, arginine, tyrosine, valine, methionine, cysteine, leucine, lysine, aspargine, and alanine; enzymes are a small fraction of proteins present in honey, some of them are: invertase, α- and β-glucosidase, catalase, distase, and glucose oxidase (Pita-Calvo and Vázquez, 2017). Generally, the pH of honeys is between 3.5 and 5.5 due to the presence of organic acids which in addition give to the honey flavor and protection athwart microbes (Siddiqui et al., 2017). According to many authors, 0.57% of organic acids content in honey causes slight acidity. Its organic acids are derived from sugars by enzymes secreted by honey bees when transforming nectar into honey (Alqarni et al., 2016).

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Complementing the above information, the organic acids are also related with color and honey properties such as electrical conductivity. The predominant acid in honey is gluconic acid, although there are other acids present in honey such as: citric, aspartic, butyric, acetic, formic, fumaric, galacturonic, glutamic, glyoxylic, isocitric, lactic, malic, malonic, propionic, pyruvic, and oxalic acid, among others (Mato et al., 2006). Honey contains small amounts of vitamins, among them: vitamin C which is the most common in honey, other vitamins found are: thiamine, riboflavin, nicotinic acid, pantothenic acid, pyridoxine, biotin, and folic acid; the low pH of honey preserves those vitamins (Kaygusuz et al., 2016). Honey is a valuable source of metals in a daily diet (Wu et al., 2017), in different honey types have detected macro and microelements such as potassium, magnesium, calcium, iron, phosphorus, sodium, manganese iodine, zinc, lithium, cobalt, nickel, cadmium, copper, barium, chromium, selenium, arsenic, and silver (Kadri et al., 2017). In honeys from Malaysia, it have been reported that the principal mineral is potassium followed by sodium, calcium, iron, and magnesium (Chua et al., 2012). The amount of minerals content in honey depends on the botanical origin of the plant where nectar was collected, also minerals content varies from 0.04% to 002% in light and dark honeys, respectively (Da Silva et  al., 2016), in honeys of Nigeria, Pakistan, Bangladesh, Argentina, Spain, and Turkey, the amount of minerals is less than 0.6% (w/w) (Khan et al., 2017). Other chemical group found in honey is that related with polyphenols, they are phytochemicals, a generic term for several thousand plant-based molecules with antioxidant properties (Hossen et al., 2017), some of these compounds found in honey are vanillic acid, caffeic acid, ellagic acid, syringic acid, ferulic acid, p-cumaric acid, benzoic acid, and others; flavonoids such as apigenin, quercetin, pinocembrin, chrysin, galangin, and kaempferol; and antioxidants such as tocopherols, ascorbic acid, superoxide dismutase, and catalase, each constituent has unique nutritional and medicinal properties and this components act synergistically, provided to honey a wide variety of applications (Rao et al., 2016). There are volatile compounds that produce honey flavor, between 400 and 600 of these compounds have been identified in honey (Da Silva et al., 2016; Tahir et  al., 2016), in honey, these molecules come from the nectar of the flowers, for this, is possible to discriminate honeys of different botanical origins (Castro-Vázquez et al., 2009). Also, studies suggest that honeys from arid regions contained higher amounts of polyphenols that the ones that are from non-arid regions (Habib et al., 2014a).

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6.2.2 Physical Properties Many constituents may also influence the nutritional quality: granulation, flavor, and texture of honey; is important to measure the physical and chemical parameters of the product given the importance of this sweetener in the industry (Siddiqui et al., 2017). Color is the most important factor determining the import and wholesale prices of honey and is characteristic of the floral source of the honey (Belay et al., 2015), the US Department of Agriculture have classified it into seven categories: water white, extra white, white, extra light amber, light amber, amber, and dark amber (National Honey Board, 2006). Also, a correlation between color and mineral content in the honey has found it applying multivariate statistical techniques (multiple linear regression or linear discriminant analysis) (Pita-Calvo and Vázquez, 2017). Another correlation is the one between the color and flavor; light-colored honey is of slight flavor compared with the darker honey that has stronger flavor. Subject to storage time or heat also changes the color in the honey (Oroian and Ropciuc, 2017). The °Brix concentration (dissolved solid content) in honey is about 76.3–85.3 °Brix is directly related to the sugar content and density, the latter parameter at 20°C is upper than the water density and ranged between 1.3 and 1.4 g/cm3 (Oroian, 2013). Other physical property is the semisolid state that are present in honey named crystallization which occurs when glucose precipitates out of the supersaturated honey solution (Escuredo et al., 2014). The fructose/glucose (F/G) ratio is a factor that determine the crystallization rate of honey as crystallization affects some physical properties of it such as the rheological ones, honeys with a F/G ratio higher than 1.33 do not crystalize (Yilmaz et al., 2014). Furthermore, honey has a freezing point between −5.78°C and −1.42°C, specific heat of 0.54–0.60 cal/g/°C and has a water activity between 0.5 and 0.6 in the 40°C–100°C temperature range (National honey board, 2006). The viscosity (measure of friction forces exerted by the liquid molecules in motion) (Oroian, 2013) depends on the moisture content and temperature, at 24°C and 18.9% moisture, the viscosity of honey is about 9900 cP (Khan et al., 2017). The viscosity takes a part in the rheological properties of honey and these are of great importance given their implications in organoleptic perception and quality control of the raw material (Escriche et al., 2017). The electrical conductivity is closely related to the concentration of mineral and organic acids and shows variability according to the floral origin (Chakir et al., 2016) nowadays is a factor integrated to the International Standards of Honey for the discrimination of honeydew and honey blossom, mixed blossom honeys mostly be in the range of 0.5–0.8 mS/cm (Siddiqui et al., 2017).

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6.2.3  Biological Properties Several studies of honey have confirmed its biological properties such as antioxidant, anti-inflammatory, antibacterial, antiviral, anti-ulcer activities, antihyperlipidemic, antidiabetic, anticancer properties, boosting effect on immune system, and contribution in the wound healing processes (Oryan et al., 2016). In recent years, the pharmaceutical interest in honey has increased due to its well-known health properties (Mahmoodi-Khaledi et  al., 2017). The activity that presents honey probably depends on the grazing ground, the weather conditions, and the natural structure of the blossom nectar (Almasaudi et  al., 2017). Furthermore, each component in honey has a unique nutritional and medicinal property, and these components act synergistically, making able that honey be useful in wide applications (Rao et al., 2016). It has been controversially the incorporation of carbohydrates in the human diet, especially because it has influence in the blood glucose, the importance of carbohydrates is presented in levels of glycemic index (GI), the carbohydrates with maximum values of GI, provide high blood glucose while the ones with minimum GI provide low blood glucose. It has been reported that honey has lower GI, and might be consumed by the diabetic patients (Ayoub Meo et al., 2016). Honey also plays an important role in the improvement of the reproductive system like the concentration of serum testosterone, sperm count, and fertility (Khan et al., 2017). Some enzymes content in honey has a vital role in various activities such as antimicrobial activity, in addition, phenolic compounds, specifically flavonoids have an important role in ameliorating oxidative stress. The term “oxidative stress” refers to the nonequilibrium of the antioxidant systems which translates to a deficiency of the organisms to be protected against oxidation that triggers some chronic diseases (Andrisic et al., 2018), antioxidant activity in honey may play an important role in preventing the initiation and promotion of cancer, several studies evaluate the antitumor activity of honey, depending on its composition, in vitro and in vivo studies show inhibitory effects in breast, gastrointestinal, cervical cancer among others (Badolato et al., 2017). Honey contains 0.3–25 mg/kg of choline and 0.06–5 mg/kg of acetylcholine, the first is essential for cardiovascular and brain function and take a part in the repair of the cellular membrane as long as acetylcholine acts as a neurotransmitter (Bogdanov et al., 2008). The antimicrobial potential of honey has received considerable attention in recent years; this biological activity could be related to its physicochemical and antioxidant properties (Ayoub Meo et al., 2016), is also known that the sugar concentration, low pH, phenolic compounds, protein content, or other unknown components present in

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honey provide antimicrobial activity (Khan et  al., 2017). Substances produced by bees including honey, propolis, wax, and venom have been used in wound management since long time ago. The compositional differences among honey types can influence their medicinal value (Osés et al., 2016). There are reports of the inhibitory activity of honey against 60 Gram-positive and Gram-negative bacteria, it helps in cleaning up wounds, also is a remedy against helminth diseases (Siddiqui et  al., 2017). Tetragonisca angustula honey has significant antimicrobial activity against different bacterial strains such as Bacillus cereus, Pseudomonas aeruginosa, Enterococcus faecali, and Staphylococcus (Sgariglia et al., 2010). Studies in Iranian honeys show the antimicrobial activity against Escherichia coli>Staphylococcus aureus>Pseudomonas aeruginsa>Enterococcus faecalis, this order represents the sensitivity of bacteria to the honey activity (Mahmoodi-Khaledi et al., 2017). Also it is reported that several honeys had an inhibitory effect against the fungus Candida albicans (Almasaudi et  al., 2017). In natural honeys from Pakistan, studies reported that they have antiacanthamoebic (effects against the pathogen Acanthamoeba spp.) properties and possesses superior levels of antioxidants comparing with the marketed honeys (Yousuf et al., 2016). Beside the activity exerted in pathogen microorganisms, honey has a beneficial role in the nonpathogenic gut microbiota, studies show that honey increases the number of Lactobacillus acidophilus, Lactobacillus plantarum, Bifidobacterium bifidum, Streptococcus thermophiles, and Lactobacillus delbrukeii subsp. bulgaricus, this is beneficial because the gut microbiota plays an important role in health and disease, because it exert influence in several functions in organs such as liver and brain (Erejuwa et al., 2012). Some varieties of honey have strong activity against certain viruses such as the rubella virus, herpes simplex virus (HSV), varicella zoster virus, and respiratory syncytial virus (Khan et al., 2017). Tualang honey has been reported to have protective effects in learning and memory, increased the levels of brain-derived neurotrophic factor, and reduced brain oxidative stress (Rao et al., 2016).

6.2.4 Authentication Legal regulations for honey are very strict in the European Union and although the related Codex Alimentarius Standard of Honey is recognized in most of the countries, specific national regulations and control are quite different and not yet harmonized (Elflein, 2015). The elemental profile of honeys not only reflects the environmental condition but also it is an assurance of quality (Chua et al., 2012). The continuously growing demand for honey because of its high nutritional

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value and healing properties in contrast to the stagnating or partly decreasing production volumes worldwide because of climate changes and the impairment of bee health have caused a rise in honey prices, and have made honey an easy target of adulteration (de Ribeiro et al., 2014). Honey can easily be adulterated with cheap sugar-based syrups; the most common adulterants are refined cane sugar, HFCS, beet invert syrup, and maltose syrup. Adulteration has a negative impact on authentic honey producers and consumers. Another way to adulterate honey is to feed the honeybees with products such as the HFCS, the use of the excessive sugar with the intent of producing greater yields affect the sugar content, mineral, content, and proline content in the honey among others (Guler et al., 2017). The authenticity of honey has two important aspects: the origin of the honey and the mode of production, in the origin are included the geographical and botanical origin, while production is related to the harvesting of the hive and processing (Siddiqui et al., 2017). In other perspectives, the honey adulteration involves the public health as the presence of uncontrolled ingredients, the legal concerns as the product will be under the requirements of the Codex Alimentarius and is also remarkable in the economic problems by the competition and destabilization of the markets (Sobrino-Gregorio et al., 2017). Therefore, it is important to develop reliable and quantitative techniques for the detection of adulterants in honey (Li et al., 2017). Honey should be free from any food ingredient, including additives, must be free of organic or inorganic materials, and should be hygienic and pure to preserve its nutritive value (Wu et  al., 2017). Determination of common quality parameters such as sugar spectrum, enzyme activities, hydroxymethylfurfural (HMF), proline content, and pollen spectrum may give hints of possible manipulation of honey, but this food products show a large compositional variations depending on the geographic origin, the botanical type, and environmental factors, that complicate the definition of exact product specifications and distinction between honeys (Elflein, 2015). The common method used to detect adulterated honey is stable carbon isotopic ratio mass spectrometry because it can make a differentiation between plants groups given that the adulterant sometimes has similar composition to honey (Wu et  al., 2017). Other methods than can be used are: chromatography, thermal analysis, nuclear magnetic resonance (NMR), and statistical correlations between sugar composition and honey properties such as moisture, total soluble solids, viscosity, ash, and HMF. In the case of chromatography, through the high-performance anion-exchange ­chromatography-pulsed amperometric detection (HPAEC-PAD) is possible to obtain a fingerprint profile of honey oligosaccharides to differentiate the pure between the adulterated (Wang et  al., 2015).

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The methods mentioned before are effective, most of them are destructive and expensive (Amiry et al., 2017). NMR (LF1H NMR) has gained acceptance in the field of food sciences as a powerful method because the advantages over other techniques and in combination with chemometrical techniques are successfully applied in quality control in some food products (porcine muscle, crude oil, and herbs). LF1H NMR has been used to discriminate pure blossom honey from honey adulterated with HFCS (de Ribeiro et  al., 2014). Nowadays, mid-infrared (MIR), Raman, and near-infrared (NIR) spectroscopy are simple, low cost, and environmental friendly and have been used successfully to determine the honey components and classify botanical and geographical origins of honey (Rybak-Chmielewska, 2007; Li et al., 2017). Also, NIR is more suitable for the authenticity probes especially as a fast screening tool for honey industry and regulatory authorities (Chen et al., 2011). Other technique useful in the authenticity is the multivariate analysis that classifies the data of the samples comparing differences and similarities. One of the most common techniques of multivariate analysis is the principal component analysis (PCA), with this tool physicochemical and rheological data are useful to detect pure and adulterated honeys (Amiry et al., 2017). Rheological properties are useful since the F/G ratio in honey is related to the crystallization, the addition of other adulterants changes the crystal size formed in the product which in turn will change the rheological properties (Yilmaz et al., 2014), but the addition of a moderate amount of invert syrup does not change the F/G, for this, it becomes very difficult to detect the adulteration by conventional analytical methods (Chen et  al., 2011). Also, useful is the physicochemical parameters and phenolic compounds to classify among different honeys and can be used as a chemical marker (Oroian and Ropciuc, 2017). The authentication of honey also could be determined by differential scanning calorimetry (DSC) as the addition of other substances changes the thermal properties of the product (SobrinoGregorio et al., 2017).

6.2.5 Processing As we mentioned earlier, honey is classified into blossom and honeydew. Blossom honey is mainly obtained from the nectar of flowers, whereas bees produce the honeydew honey after collecting the secretions of aphids or other plant sap-sucking insects, which pierce plant cells, ingest plant sap, and then secrete it again (Bradbear, 2009; Santos-Buelga and González-Paramás, 2017). The production of commercial honeys implicates six different phases (extraction, dehumidification, liquefaction and mixture,

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heating, pasteurization, crystallization, and packaging). After the initial harvest, the honeycomb is introduced into the honey extractor, which is a container able to remove honey through a centrifugal force. After extraction, honey is collected and sent to the decanters. Some honeys obtained from peculiar plant species (rape, calluna, and chestnut) may contain high water percentages, which affects its conservation. For this reason, it is necessary a dehumidification step to obtain humidity values lower than 18%–18.5%, to prevent the growth of the naturally occurring yeasts and the subsequent fermentation (Gupta et al., 2016). The temperature must be between 32°C and 35°C and cannot be 38°C to preserve the characteristics of honey (Oliveira, 2010). Sometimes the extracted honey requires a liquefaction step depending on the solidification or stickiness. Nevertheless, because of the low thermostability of certain honey components (enzymes, vitamins, etc.), the temperatures of liquefaction do not exceed 40°C and should be carried out in the shortest possible time. Then, the mixing step is carried out in containers to obtain a uniform final product. The next step of process is the heating, this step can affect severely the organoleptic characteristics of honey and it conduce reactions like browning and the loss of volatile compounds, because of this heating temperatures should not exceed 40°C. Therefore, the most common heating and processing instruments are the traditional hot water bath and hot rooms with forced air circulation, but also commercial trademarks use heat exchangers (Baglio, 2018). Subsequently, the next step is pasteurization where particles such as pollen grains should aggregate themselves around microscopic air bubbles and small crystals acting as aggregation nuclei. The thermal values should be rapidly raised up to 72°C and maintained for about 120 s, after that a rapid cooling is required. Moreover, it should been mentioned that the purpose of pasteurization is not performed for food safety purposes, but with the aim of satisfying the commercial needs (Bogdanov and Martin, 2002). Crystallization is probably the most important physical feature for the characterization of honeys. This process involves the formation of glucose monohydrate crystals in different quantity, shape, and arrangement depending on the processing conditions. The amount of glucose and fructose, and the impurities may affect the complex crystallization phenomenon. The temperatures of crystallization should be recommended in the range 24°C–28°C. Subsequently, the honey is passed in a homogenizer with the aim of separating the crystals. Finally, it is decanted and placed in jars until its consumption. Honey packed for the market must be of high quality, neatly clean packed in, if bottled honey shows signs of granulation it is necessary to replace it (Gupta et al., 2016) (Fig. 6.1).

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Fig. 6.1  Traditional packing of honey in México.

6.2.6 Production Honey is commercially offered in many varieties such as flower, forest, or honeydew honey, and monofloral honey of a certain botanical origin such as acacia, rape sunflower, citrus, lavender, or chestnut. Also, there are specialty and premium honeys such as Manuka honey from New Zealand, which is famous for its natural antibacterial activity (Elflein, 2015). In addition, there are over 300 floral sources for honey at least in the United States such as clover, alfalfa, buckwheat, and orange blossom (National honey board, 2006). The honey produced by Apis mallifera is the most well-known and economically important around the world (El Sohaimy et  al., 2015). During 2008, the annual world production was about 1.2 million tons, which was less than 1% of the total sugar production (Bogdanov et al., 2008). Later, in 2013, China was the first producer of honey with 26.8% of the world production, followed by Turkey with 5.64%, and Iran with 4.44%. The United States was the first importer of honey with 152,000 tons per year (FAOSTAT, 2013). Now, at this year, China is still a large producer and exporter of honey, the annual production is more than 200,000 tons and the 50% of the products are exported to Europe, the United States, and Japan (Wu et  al., 2017). Other export countries of honey are: India, Vietnam, Thailand, New Zealand, Australia, Argentina, Mexico, Brazil, Uruguay, Spain, Hungary, and many others (Elflein, 2015). In Ethiopia, there are approximately 5 million of beehives, and the production is about 45,000 tons per year (Belay et  al., 2015), Mozambique produces around 600 tons of honeys a year but has the potential to produce up to 3600 tons (Escriche et al., 2017).

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6.3  Maple Syrup Acer spp. is one of the most important tree species in North America, there are 160 known species, 6 natives in Canada, which is commercially important. Beyond the beautiful reddish coloration that given to the forest, from these trees is obtained the maple syrup (Abou-Zaid et al., 2008). The maple syrup is a commercially important tree product used as a sweetener with a valuable flavor and other added products (Singh et al., 2014a). This syrup is a natural sweetener produced from concentrated xylem sap collected from some maple species (Sun et al., 2016). Although no one is sure how it was discovered that maple trees sap can be concentrated into a sweet syrup, maple syrup is of a great economic importance in the eastern North American region (Ball, 2007). Compared with the other sweeteners, maple syrup is considered by many to be superior due to its unique flavor, nutrient content, antioxidant potential, and the health benefits that has been presented (Singh et al., 2014a).

6.3.1 Chemical Composition The chemical composition of maple syrup is more than 60% (w/w) of sucrose, followed by traces of glucose (0.43% w/w) and fructose (0.34% w/w) but recent studies suggest a wide range of these concentrations: sucrose is between 511 and 688 mg/g, glucose in a range of 0.94–11.2 mg/g, and fructose between 0.55 and 10 mg/g (MelladoMojica et al., 2016), other components in the syrup are minerals (in total amount of approximately 3638.62 ppm) such as potassium, calcium, magnesium, sodium, manganese, aluminum, zinc, and iron, vitamins such as riboflavin, niacin, and thiamine, amino acids such as arginine, threonine, and proline, and also organic acids (fumaric and malic) (Zhang et al., 2014; Li et al., 2015). In addition, it has a variety of phytochemicals, among which phenolic compounds predominate with high antioxidant activity; chemical analysis showed the concentration of polyphenols of ca. 1494 μg/100 mL; these compounds are responsible for the potential health benefits of maple syrup and are associated with the color and aroma of the syrup (Mellado-Mojica et al., 2016; St-Pierre et al., 2014). More than 50 phenolic compounds have been isolated from the maple syrup among them vanillin, syringaldehyde, coniferaldehyde, cinnamic acid, and benzoic acid as well as flavonoids, lignans, carbonyl compounds, alcohols, furan derivatives, and pyrazines (Li and Seeram, 2010; Sabik et al., 2012; Nahar et al., 2014). In the progression of the sap harvest, there are changes in the component’s sap, in the beginning of the season, sap has the highest pH value and phenolic compounds (e.g., vanillin and syringldehyde) also in the higher concentrations, in the mid-season increase

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the ­mineral concentrations and the sucrose concentrations while at the end of the harvest, there are increments in the microbial counts compared with the beginning (Lagacé et al., 2015). A nutritional aspect of the maple syrup is that a quarter of cup contains 217 calories, but supplies 100% of the Canadian, and the Food and Drugs Administration (FDA) daily recommended value of manganese, riboflavin, zinc, calcium, and potassium (Perkins and van den Berg, 2009).

6.3.2 Physical Properties During the concentration process of the sap, the color becomes darker as the season progress, the Canadian standards graded the maple syrup as extra light (grade AA), light (grade A), medium amber (grade B), and dark (grade C) (Li and Seeram, 2010). In the United States, the color grades are: grades A light amber and medium amber and grades A and B dark amber (Aider et al., 2007). Sensory perceptions are important for producers then the color is a requirement of the product quality (Sabik et al., 2012), the conductivity of the sap has the range of 320–52 μS/cm (Perkins and van den Berg, 2009). Regarding the rheological properties, maple syrup is primarily Newtonian in its flow characteristics, grade, temperature, and density can independently and interactively influence in the apparent viscosity with a range of 0.138–0.160 Ps at 25°C, darker syrups have higher viscosity than the other colored syrups (Perkins and van den Berg, 2009).

6.3.3  Biological Properties For centuries, the aboriginal people consumed the maple sap as a tonic and the goodness of maple products have long been known anecdotally (Yuan et  al., 2013). Biological activities of maple syrup have primarily focused on its diverse phenolic components (Sun et al., 2016). Phenolic-enriched extracts of maple syrup were recently reported to show antiproliferative effects against human lung, colorectal, prostate, and breast tumor cell lines (González-Hernández et al., 2012). In addition, phenolic compounds in maple syrup shown to have α-glucosidase inhibitory activity, suggesting that could limit glucose absorption by the intestine in response to the sweetener ingestion (St-Pierre et al., 2014). Moreover, phenolic-enriched extracts of maple syrup have been reported to show antioxidant activity, antimutagenic, anticancer, anti-inflammatory, and anti-neurodegenerative effects, because, in recent years, this maple syrup has been in the spot as a healthy natural sweetener and consumed as a functional food (Sun et  al., 2016). Phenolic-enriched extracts of maple syrup have shown

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a­ntiproliferative effects against human lung, colorectal, prostate, brain, and breast tumors cell lines (González-Sarrías, Li and Seeram, 2012). As we commented, maple syrup is consumed as a functional food, principally for its phenolic compounds; quebecol is another one founded in the syrup and possesses anti-inflammatory and antiproliferative properties, another phenolic derivatives from maple syrup demonstrated free radical scavenging activity (Sun et al., 2016). Different animal studies suggested that pure maple syrup may have liver-protective effects and ability to reduce plasma glucose levels compared to a sucrose solution alone (Zhang et al., 2014). Recent studies reported inulin-type fructooligosaccharides (FOS) isolated from the maple syrup. These compounds are also present in agave and stevia (Sun et al., 2016). Inulin is considered as a nondigestive polysaccharide, it has interactions with the human lower gastrointestinal tract, principally the colon, promoting Bifidobacterium growth and also has an effect on the triglyceride levels in serum (Shoaib et al., 2016). Furthermore, maple sap contains abscisic acid (ABA), a phytohormone which is involved in the regulation of plant growth, development, dormancy, and stress responses. The ABA has been proposed as a potential antidiabetic molecule, it has a similar structure with thiazolidinediones (antidiabetic drug), and also in recent studies, ABA has been shown to exert protective effects on animal models of type 2 diabetes (St-Pierre et al., 2014). Besides, maple sap contains arabinogalactan, a prebiotic that can selectively improve the growth of some prebiotics and other beneficial bacteria (Lupien-Meilleur et al., 2016). The new knowledge generated on maple syrup properties may boost its use in the human consumption because of its unique flavor and richness of bioactive compounds (carbohydrates, minerals, and phenolic compounds) (Mellado-Mojica et al., 2016).

6.3.4 Authentication Maple syrup is one of the most popular sweeteners consumed worldwide and is of significant cultural an economically important particularly in Canada. The increased knowledge of its chemical constituents would aid for its authentication, characterization, and succeeding detection of intentional adulteration (Li and Seeram, 2010). Maple syrup quality, especially in the commercial value, is defined by its color and flavor, changes in this sensorial properties may be attributed to deterioration caused by microorganisms, and sensory analyses are a decisive way to assure the quality of these properties in the syrup (Filteau et al., 2012). Carbohydrate profile of maple syrup is mainly based on the qualitative and quantitative content of glucose, fructose, and sucrose, although, currently, oligosaccharides are useful molecular markers for

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authenticity, adulterant detection, and quality of natural sweeteners (Mellado-Mojica et al., 2016). The most useful technique to generate oligosaccharides profiles is HPAEC-PAD, which has been used for the identification of adulterants in honey and fruit juices as well for carbohydrate profile characterization of agave syrup and others natural sweeteners (Mellado-Mojica and López, 2015). Besides, Fourier transform infrared (FTIR) spectroscopy has been used in the food and drugs analyses because of its simple, quickly, economical, and nondestructive application. Use of PCA is helpful for exhibiting the clustering pattern of different groups of samples (Rodriguez-Saona and Allendorf, 2011). Combination of these techniques has been successfully applied in many research areas such as differentiation of fruit varieties and determination of honey quality (Rodriguez-Saona and Allendorf, 2011). Optical spectroscopy combined with chemometrics is an useful method to characterize and classify food products as well as fluorescence spectroscopy has been proposed to characterize the properties and adulteration of syrups (Clément et al., 2010).

6.3.5 Processing The raw material for the production of maple syrup is obtained from trees, within the genus Acer the main used species are A. nigrum (black maple), A. rubrum (the red maple), and A. saccharum (sugar maple), with the predominance in use of the latter (Li and Seeram, 2012; Singh et  al., 2014a). The reason why these species are chosen for maple sap collection is essentially its higher content of sugar than other species (commonly 2%–2.5%) and its longer sap production period (Ball, 2007). The sap is obtained from maple trees during the spring months when freeze/thaw cycles cause the sweet sap to rise and flow from the taps made in the tree trunk (Li and Seeram, 2011), as consequence of a combination of physical and osmotic forces (Perkins and van den Berg, 2009). The harvest season occurs between February and April and the next 4 or 6 weeks (Clément et al., 2010) The collection process starts with drilling a hole into trunk in order to get the colorless watery sap, this is composed by approximately 97%–98% water (Abou-Zaid et al., 2008), whereby a concentration process is required to reach a concentered solution with 66–67 °Brix (scale that express grams of sucrose per 100 g of solution) (Singh et al. 2014), this is the right concentration that ensure that sugar do not precipitate from the syrup and microorganism cannot grow on it (Ball, 2007). The two major processes utilized in the aforementioned operation are evaporation by heating and reverse osmosis followed by heating (Perkins and van den Berg, 2009). The maple sap could be seen essentially like a 2% sucrose aqueous solution of which by means of the forcing transport of sap across a membrane in the reverse osmosis

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process it can get a solution of up to 34 °Brix (Bouchard and Lebrun, 1999). During this process, about 75% of water can be removed, however, remaining water must be eliminated by evaporation (Ball, 2007; Abou-Zaid et  al., 2008). It is remarkable that maple sap pre-­ concentration reduces energy and time consumption, leaving intact those substances responsible for maple syrup quality (Bouchard and Lebrun, 1999). In the same way, maple sap is concentered by evaporation, at this step, a dark brown syrup is generated, that concentrates different carbohydrates such as sucrose, and other compounds (i.e., minerals, vitamins, and organic acids) (St-Pierre et al., 2014), where is known that its color becomes darker as the season progresses (Li and Seeram, 2011). Likewise, this is a process which is estimated that 40 L of sap is required to produce 1 L of syrup (Abou-Zaid et al., 2008; Li and Seeram, 2012).

6.3.6 Production At 2009, Canada produced about 9.1 million gallons of maple syrup valued over 353.8 US millions (Sabik et al., 2012). By 2010, maple syrup is still primarily produced in northeastern North America and Canada produces 85% of the world supply (from Quebec), the United States 15% (from New England and New York) (Li and Seeram, 2010). Mostly, Canada is responsible for the major supply of maple syrup, this industry is of great economic importance in the region, with millions of gallons produced every year (Zhang et al., 2014). In 2011, Japan was the second importer of maple syrup, after the United States, with an importation of 2.8 million of kilograms of maple syrup with a value of 24.3 million dollars (International Markets Bureau, 2012).

6.4  Agave Syrup Agave (called Maguey in México) has been used since pre-­ Columbian times as a food and beverage source. Nowadays, the main use of agave is to produce alcoholic beverages such as mescal (species Agave agustrifolia, Agave potatorum, and Agave salmiana), sotol (Agave dasylirion), bacanora (A. angustifolia, A. potatorum, and Agave pacifica), pulque (Agave atrovirens), and the most important the tequila (Agave tequilana) (Fig. 6.2). The agave syrup is a recent Mexican product obtained mostly from different agave species among them: Agave mapisaga, atrovirens, salmiana, Americana, hookeri, and tequilana (Castro and Guerrero, 2013; Muñiz-Márquez et  al., 2015). To produce agave syrup, maguey plant must have an appropriate maturity (Santos-Zea et al., 2012), reached it, a sap from the core of the plant is collected, this edible sap is called “aguamiel” and is one of the raw materials

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Fig. 6.2  Maguey plant from the species A. atrovirens.

to produced syrup (Leal-Díaz et  al., 2016), is important to notice that a single agave plant may have produced up to 1000 L of aguamiel (Olvera Carranza et  al., 2015). On the other hand, the syrup can also be obtained by an enzymatic process, both processes used heat to obtain the product. These processes will be best discussed in the processing section (Willems and Low, 2012). The agave syrup is also called “agave honey,” “agave nectar,” “agave concentrate,” “agave sap,” and “aguamiel concentrate” (Willems and Low, 2012; Olvera Carranza et al., 2015; Leal-Díaz et al., 2016). There are minimal published works about agave syrup, thus it is important to develop knowledge about its chemical composition, its effects on human health, and information for analysis of this syrup authenticity.

6.4.1 Chemical Properties Agave syrup coming from A. tequilana presents sweetness ranged from 65 to 79.5 °Brix, pH from 3.66 to 5.23, also it has a specific carbohydrate profiles, composed mainly of fructose (in 55.6%–90%), FOS, and different oligosaccharide profiles compared with other natural sweeteners (Willems and Low, 2012; MelladoMojica and López, 2015). Studies demonstrated that in the A. tequilana, the fructan content and structure varies, when the plant reaches 5 years, the FOS become larger and more complex (Olvera Carranza et al., 2015). In general, agave syrup has shown the highest F/G ratios comparing with other natural sweeteners; F/G ratio, as we mentioned before, is an indirect measure of sweetening capacity and is employed to evaluate adulteration of honey and syrups, too (Mellado-Mojica and López, 2015).

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Comparing the syrup produced from A. tequilana, the saccharide distribution must be around the concentration of fructose from 71% to 92%, followed by glucose with a concentration from 4% to 15% and sucrose ca. 4%, while when it is produced from A. salmiana, the concentration is >70% fructose, >25% glucose, and >2% sucrose (Santos-Zea et al., 2012; Willems and Low, 2012). In addition, agave syrup has been reported to have a predominating concentration of citric acid. Inositol and mannitol were found in the syrup too, in a range from 0.31% to 0.43% and 0.02% to 2.54%, respectively (Willems and Low, 2012). It also been reported that A. salmiana syrups have a moisture range of 20%–30% and the pH are from 3.5 to 5.2 (Santos-Zea et al., 2016).

6.4.2 Physical Properties Agave syrup has a similar range of color, density, and flavor to honey or maple syrup (Wrobel et al., 2014). Recent studies mentioned that agave syrup has a high sweetening capacity, in fact is reported as sweeter than honey, corn syrup, and sugarcane syrups (MelladoMojica and López, 2015). In syrup obtained directly from fructans of agave the density are 1.49 g/mL, surface tension of 45.3 dinas/cm, and a viscosity of 212 mPa-S (Montañez Soto et al., 2011).

6.4.3  Biological Properties As the agave syrup is a very recent product, there are not much scientific information available about its properties but is widely known for its biological properties that Agave spp. has because of its tradition. Over centuries, the Agave spp. has been used for various culinary and medicinal purposes as it contains phytochemicals (e.g., flavonoids and saponins) considered to be responsible for their anti-­ inflammatory, antiviral, and anticancer activity (Wrobel et al., 2014). Agave generous is a very important commodity in México (Santos-Zea et al., 2012). Some of the FOS found in the syrup are: 1-kestose, inuliotrose, neokestose, and 1-nystose. There is demand for agave syrup as sugar substitute because of the glycemic index, antioxidant capacity, and antibacterial properties that it has. The FOS (also denominated inulin-type fructans) are selectively used and fermented by the human gut, and several studies demonstrated their health benefits as reducers of plasma glucose and lipids (Apolinário et al., 2014; Olvera Carranza et  al., 2015; Márquez-Aguirre et  al., 2016). Prebiotics are defined as nondigestible food ingredients that improve the function of the colon (e.g., inulin) (Hutkins et al., 2016). Also, the fructans decrease the glucose level and serum cholesterol, increasing calcium absorption in bones (Mellado-Mojica and López-Pérez, 2013). Scientific studies on fructans from agave are limited, there are principal studies

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on analyzes of the prebiotic effect that show these fructans (MárquezAguirre et al., 2016). Fructans content in agave syrup is an important factor in the functional food industry. Furthermore, fructans can exert its beneficial effect via direct or indirect mechanisms. Indirect mechanisms involve, as was mentioned before, stimulation of prebiotic bacteria growth and indirect effect was suggested for the inulin-type fructans on lipid profile and as immunomodulatory (Peshev and Van den Ende, 2014). Some of the medicinal effects of agave have been attributed to the presence of saponins, these compounds are characterized by having anticancer, anti-inflammatory, and ulcero-protective activities (Santos-Zea et al., 2016; Sidana et al., 2016). In the case of aguamiel, it has been reported that it contains almost 26 mg/L of ℽ-aminobutyric acid (GABA), amino acid considered to be the main inhibitory neurotransmitter in the adult mammalian brain (Santos-Zea et al., 2012). Also, studies suggest that the presence of steroidal saponins in the agave syrup has been detected, saponins such as kammogenin, manogenin, gentrogenin, and hecogenin, are saponins also capable of decreasing the acute glycemic response (Leal-Díaz et  al., 2016; Sidana et al., 2016). Another recent study showed that agave syrup attenuates the metabolic changes in mice high fat, and reduces the weight, serum glucose, and hepatic lipid levels in those mice (Leal-Díaz et al., 2016). Other benefits that prove the different foods obtained from agave are: antioxidant, mineral absorption, and antidiabetic effects. In addition, agave syrup was tested against Bacillus subtilis and E. coli and presented inhibitory effects to these strains, the content of methylglyoxal (pyruvaldehyde) is possibly responsible of this activity (Wrobel et  al., 2014). In addition, extracts from agave syrup show inhibitory activities against cancer cell and have antioxidant effects (GutierrezUribe and Serna-Saldivar, 2013). In spite of the potential benefits of this syrup, there is also a controversy by the possible adverse effects in the context of obesity and diabetes, when compared with other syrups (Wrobel et al., 2014).

6.4.4 Authentication Because of the increasing popularity of agave syrup as sweetener and as food ingredient, it becomes a target for adulteration. The fact that agave syrup is mainly composed of carbohydrates result in the simple and economically viable adulteration with low-cost sweeteners such as HFCS, cane sucrose, dextrose syrups, and others (Willems and Low, 2012). HPAEC-PAD is recommended for carbohydrate analyses of honey and syrup samples because of its detection limits (Mellado-Mojica and López-Pérez, 2013). In addition, application of NIR and MIR spectroscopy in combination with PCA is useful to iden-

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tify, classify, and discriminate agave syrup from other natural sweeteners and in combination with HPAEC-PAD can establish differences between the oligosaccharides content in agave syrup and other syrups and honey. The carbohydrate profiles of natural syrups have different types of oligosaccharides according to the natural source of the sweetener (Mellado-Mojica and López, 2015).

6.4.5 Processing As we mentioned before, there are two forms to obtain agave syrup, by the heating of aguamiel or heating of agave pines. Some Agave species produce aguamiel, which takes between 8 and 10 years to produce this beverage. Plant stored sugar emits a single flower stalk that could be of 20 ft in height, but this inflorescence must be cut, leaving a concave surface 12–18 in diameter (Fig. 6.3). In addition, agave farmers scratch the cavity to let emanate the sap. Aguamiel is collected twice a day for about 6 months, before agave dies (Nava-Cruz et al., 2015). Then, to produce agave syrup, aguamiel is heated until the desired °Brix is obtained. In the second process to produce agave syrup, the most commonly used specie is A. tequilana Weber var. azul. The process consist in the cut of the agave root base and the sword as leaves are removed from the central stem. To hydrolyze fructans, many trademarks and distributors are using the t­ raditional

Fig. 6.3  Cavity where the aguamiel is stored in the agave.

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method, whole or cut pines are cooked in brick ovens for 36–48 h or in autoclaves for 12 h (González-Hernández et al., 2012), reaching both process temperatures above 100°C. Because the heat transfer is not uniform, the efficiency of hydrolysis is very low, so that some of the carbonized pinecones, while other incomplete hydrolysis. Due to these cooking conditions unfavorable phenomena as the Maillard reactions and the formation of undesired by-products such as phenols, furfural, and HMF are favored from the thermal degradation of pentoses and hexoses. These compounds which may have an impact on the flavor and color of the syrup (MichelCuello et al., 2008). Due to the above conditions and the popularity of agave syrups has led to the development of new strategies to optimize the production by elaborating the syrups through the use of the enzymatic hydrolysis of agave fructans instead of the traditional methods based on thermal or acid hydrolysis (García-Aguirre et  al., 2009; Mellado-Mojica and López, 2015). Therefore, enzymatic hydrolysis based on the use of inulinases constitutes an alternative approach for the production of fructose syrup from Agave plants. Inulinases are β-fructan fructanhydrolases produced mainly by bacteria, fungi, and yeast. The use of exoinulinase (EC 3.2.1.80) and endoinulinase (EC 3.2.1.7) acting either alone or combined has been widely investigated for partial or total inulin hydrolysis. In the particular case of agave fructans, a relatively limited investigation had been carried out so far. Ávila-Fernández et al. (2009) and Waleckx et al. (2011) replace the thermal and chemical treatment, respectively, to hydrolyze the agave fructans during tequila production. Hence, enzymatic hydrolysis for the production of fructose agave syrup might be an alternative for the large-scale production under appropriate conditions of enzyme dosage, temperature, and substrate concentration (Michel-Cuello et al., 2008; Montañez Soto et al., 2011).

6.4.6 Production Reports of the Secretariat of Agriculture in México of 2009 showed that at least in Jalisco, the state with major production of agave, the production was of 6000 tons by this year (Nava-Cruz et al., 2015). By 2012, about 90% of the agave harvest goes toward the production of beverages such as tequila and mescal, the remaining is being used for agave syrup production (Montañez Soto et al., 2011; Willems and Low, 2012). Later, the large number of trademarks and distributors of agave syrup from A. tequilana reflect the increase in production and acceptance as a sweetener in México and other countries (Mellado-Mojica and López-Pérez, 2013). Nowadays, there are a planted area of 100,000 ha of agave that produces an ­annual

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entrance of more than 1600 million of Mexican pesos (Servicio de Información Agroalimentaria y Pesquera, 2016).

6.5  High-Fructose Corn Syrup Corn is the most dominant crop, the most profitable and its cultivation is highly subsidized by the US government. Corn is the primary source of high-fructose syrup or the denominated HFCS by its origin (Parker et al., 2010). Even though the high-fructose syrup can also be obtained from potato, rice, sorghum, wheat, Jerusalem artichoke, dahlias, chicory, and cassava (Johnson et al., 2009; Bode et al., 2014). HFCS is used as a major sweetener in processed carbonated and non-carbonated beverages, juices, cereals, bread, canned fruits, jams, jellies, condiments, and prepared desserts (Ferder et  al., 2010; Babacanoglu et  al., 2013). The HFCS is also named isoglucose in Europe and dextrose/fructose in other parts of the world (Bode et al., 2014). The advantages of this syrup are because it is cheaper than sucrose and more easy to handle than crystalline sucrose (Gensberger et al., 2012). The development of this relatively low-cost syrup has made possible for it to become a viable alternative to sucrose and other sugars. HFCS represents ca. 40% of all added caloric sweeteners in the US diet (Ferder et al. 2010). Something to notice is that the HFCS name implies that has high amount of fructose in comparison with other sweeteners, but it is really not, moreover, it has similarity composition with sucrose (White and Nicklas, 2016).

6.5.1 Chemical Properties HFCS is primarily constituted of the monosaccharides glucose and fructose in the free or unbonded state (White and Nicklas, 2016) is made by chemical and enzymatic hydrolysis of corn starch which contains amylose and amylopectin transformed those into corn syrup which contain mostly glucose followed by isomerization of glucose into fructose (Singh et al., 2014b). HFCS contains amounts of riboflavin, niacin, pantothenic acid, folic acid, vitamin C, calcium, iron, magnesium, phosphorus, potassium, sodium, and zinc (Parker et al., 2010). The moisture content of this syrup is between 23% and 29% (White, 2014). HFCS is not significantly different in composition or metabolism from other fructose/glucose sweeteners as sucrose, honey, and fruit juice concentrates (Singh et  al. 2014b). There are three categories of HFCS, the HFCS-90 with 90% of fructose and the rest of glucose, HFCS-42 with 42% of fructose, and HFSC-55 with 55% of fructose (Parker et al., 2010).

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6.5.2 Physical Properties The HFCS has been categorized as a high-quality liquid sweetener because it is highly soluble and noncrystalline in nature with increased shelf life (Johnson et al., 2009), also it has an equal sweetness to sucrose and a caloric value of 3.6 kcal/g and is similar with sucrose and fructose (White, 2014).

6.5.3  Biological Properties With the extensive use of HFCS since the 1970s, there are reported some consequences of high consumption of HFCS, as it has a higher content of fructose, this sugar changes the presence of free or bound glucose, and some studies showed that exists a parallel increase in the consumption of HFCS and prevalence of obesity (Babacanoglu et al., 2013). Other studies have demonstrated the metabolic equivalence of HFCS and sucrose, so sucrose has an implicated role in promoting obesity (Yu et al., 2013), in addition, there are studies that found the consumption of beverages sweetened with fructose, HFCS, or glucose makes no difference effects on low-chronic system inflammation (associated with type 2 diabetes) (Kuzma et al., 2016). Moreover, a study on 30 nonobese women study mentioned that HFCS and sucrose result in similar circulating glucose, insulin, and leptin (Melanson et  al., 2007). Other study performed using rats has exposed an alternative sweetener, rare sugar syrup for HFCS that contains bioactive rare sugars. HFCS was dissolved in NaOH solution, isomerized, neutralized, desalinated, and concentrated by standards methods and resulted in the rare sugar syrup. In the same study also found that this rare syrup suppresses abdominal fat deposition as compared with starch and HFCS diets (Iida et al., 2013). There is experimental and clinical evidence that suggest the association between the consumption of HFCS and the obesity and other injury processes (Ferder et al., 2010), moreover, other studies claims that there is a link between the HFCS consumption with chronic bronchitis and asthma (DeChristopher et al., 2017).

6.5.4 Authentication Unfortunately in matter or authentication, the HFCS is the principal sweetener added to another syrups and honey for adulteration. There are studies that with carbon isotope ratio, it is successfully detected the adulteration by HFCS in honeys, since honey is the most commonly adulterated food product, is the principal target for adulteration by the addition of sugars and HFCS is one of the cheaper sweeteners (Çinar et al., 2014). Also, with Raman spectroscopy, it was possible to detect the adulteration in honey produced by HFCS as with chromatography, thermal analysis, and NMR (Li et al., 2012).

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Nevertheless, there are studies on the use of ultraviolet-C (UV-C) light, making efficient the reducing number of microorganism in the HFCS, it is not a manner of authentication but is a topic of quality, although its high osmotic pressure, low water content and high temperatures is unusual in bacterial spoilage, some yeast and spores may survive, the UV-C treatment contributes as purification technology (Ros-Polski et al., 2016).

6.5.5 Processing The production of HFCS involves a multipurpose process called corn wet milling, in which starch from corn is obtained together with other corn products (i.e., corn oil, fiber, and gluten). During HFCS production, raw material is harvested and shipped to continue with the aforementioned corn wet milling process (White, 2014). The latter concisely comprises a cleaning step, with a subsequent steep process, in which corn is soaked in water for a certain time, with a later addition of SO2. Sulfur dioxide helps in pH, color changes, and microbial growth control, additionally increase hull softening for its posterior removing, as well as in gluten denaturation to release the starch granules. Posterior processes such as grind, mill, centrifuge, and wash are required to obtain high-purity starch. Enzymatic transformations take place in HFCS production, this conversions are carried out by a multienzymatic hydrolysis of starch and can be divided in three steps: liquefaction, saccharification, and isomerization. In the first step, corn starch is hydrolyzed by thermostable α- or β-amylase (EC 3.2.1.1) to produce oligosaccharides. During this process, many factors have to be controlled such as temperature, pH, solids, and calcium concentration. The solids level is recommended to keep between 30% and 35%, meanwhile pH has to be controlled to 5.8–6.5. Likewise, calcium is used as a cofactor to enhance amylase thermostability. The chosen temperature for treatment must be selected in base of enzyme source (e.g., Bacillus licheniformis amylase is very thermostable and is used at temperature above 100°C) (Singh et al. 2017). The process of saccharification occurs with the enzyme glucoamylase (EC 3.2.1.3) which depolymerize oligomers to produce dextrose. Saccharified hydrolysate is then clarified and purified by carbon refine, ion-exchange, and evaporation. The dextrose-enriched hydrolysate is then used in the third-step enzymatic conversion (White, 2014). Isomerization of dextrose to fructose is carried out by the enzyme glucose isomerase (EC 5.3.1.5). This process was made economically viable by Yoshiyuki Takasaki and Osamu Tanabe, with the use of an immobilized glucose isomerase (Takasaki and Tanabe 1971). After a partial purification that is carried out by carbon and ion-exchange treatments, the commercial product HFCS-42 (containing ≥42% of fructose)

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is obtained (Singh et  al. 2017). Much of these enzymatic processes could be replaced and/or combined with acid or alkaline treatments, taking into account the modifications in product quality. Later, purifications are usually made, based on better fructose affinity than glucose for strong acid cation exchange resins in the calcium salt form. From this process, an enriched fructose syrup (≥90%) is produced, which can be used by its addition to HFCS-42 in the formulation of HFCS-55 (Eggleston et al. 2017). The latter is used to emulate sweetness of sucrose, this is used as a reference with a relative sweetness in a 10% solution of 100, while HFCS-42 has lower value of 90 ± 2, HFCS-55 gets a relative sweetness of 99 (White and Nicklas, 2016). Innovations have been made to technologies implied in HFCS production, such as in clarification process with the use of microfiltration technology in ceramic membranes instead of the processes of precipitation, centrifugation and/or diatomaceous earth filtration, as well as rotary vacuum or pressure leaf filtration (Almandoz et al. 2010). Enzymatic technology as well has gone through improvements, especially in isomerization of dextrose. The direct conversion of dextrose to fructose was limited to HFCS-42, since a higher ratio of fructose in final product requires a higher temperature and lower pH for reaction equilibrium of isomerization and commercially available isomerases have a relative poor thermostability (Jin et al. 2017). Efforts have been made in protein engineering, especially in order to increase enzyme thermostability for its usage in the one-step production of HFCS-55. The glucose isomerase from Thermoanaerobacter ethanolicus expressed in the recombinant strain of E. coli TEGI-W139F/V186T was efficiently used to produce HFCS-55 at 90°C by Liu et al. (2015), and later was immobilized in order to increase the enzyme activity recover, as well as the range of pH and temperature stability (Jin et al. 2017). Likewise recombinant thermostable glucose isomerase mined from Thermus oshimai was used at 85°C, reaching a 52.16% of fructose (Jia et al. 2017), producing in this way new perspective for increased producing operations.

6.5.6 Production The annual per capita intake of HFCS from 1967 to 2006 increased from 0.03 to 58.2 lbs, whereas sucrose decreased from 98.5 to 62.3 lbs (Le et al., 2012). In the United States consumes approximately the 40% of the production of HFCS (Singh et al., 2014b)

6.6  Future Trends Although honey and maple syrup are widely known, it is still necessary for more investigation around the authentication and biological mechanisms of these syrups. In terms of agave syrup, it is

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necessary to generate knowledge about its composition and its biological mechanisms as well as on its authentication, since it has the potential as a prebiotic. Also, it is important to known well the implication of the HFCS in the increase of obesity. One more information on these syrups will be found, more opportunities about sweeteners options, may open, which will be a great contribution to the food industry.

6.7 Conclusions There is lot of available information about the honey bee, its composition, biological properties, production, but because of source and environment have effect on honey quality is necessary more studies on each type of honey. Still, this sweetener is the most popular for its antibacterial, anti-inflammatory, antiviral effects, its content of vitamins, minerals, and antioxidants. Maple syrup becomes really popular in recent times, also because of its antioxidant activity and the inulin-type fructooligosaccharides that also are found in agave syrup. The agave syrup is proposed as a prebiotic because of its FOS and its possible anticancer and anti-inflammatory activities by its saponins content. In spite of this increased popularity, HFCS is one of the sweeteners that is used for adulteration of honey, maple syrup, and agave syrup, nowadays is considered one cause of obesity increase for being the principal ingredients of beverages and some foods.

Acknowledgment AMGM thanks the National Council of Science and Technology of Mexico (CONACyT) for the financial support during her postgraduate studies under the scholarship agreement number 773959.

Conflict of Interest Authors declare no conflict of interest.

References Abou-Zaid, M.M., Nozzolillo, C., Tonon, A., Coppens, M., Lombardo, D.A., 2008. Highperformance liquid chromatography characterization and identification of antioxidant polyphenols in maple syrup. Pharm. Biol. 46 (1–2), 117–125. https://doi. org/10.1080/13880200701735031. Aider, M., de Halleux, D., Belkacemi, K., 2007. Production of granulated sugar from maple syrup with high content of inverted sugar. J. Food Eng. 80 (3), 791–797. https:// doi.org/10.1016/j.jfoodeng.2006.07.008.

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Almasaudi, S.B., Al-Nahari, A.A.M., Abd El-Ghany, E.S.M., Barbour, E., Al Muhayawi, S.M., Al-Jaouni, S., Azhar, E., Qari, M., Qari, Y.A., Harakeh, S.A.M., Al-Nahari, A., Sayed, M., Abd El-Ghany, E., Barbour, E., Al Muhayawi, S.M., Al-Jaouni, S., Azhar, E., Qari, M., Qari, Y.A., Harakeh, S., 2017. Antimicrobial effect of different types of honey on Staphylococcus aureus. Saudi J. Biol. Sci. 24 (6), 1255–1261. https://doi. org/10.1016/j.sjbs.2016.08.007. Alqarni, A.S., Owayss, A.A., Mahmoud, A.A., 2016. Physicochemical characteristics, total phenols and pigments of national and international honeys in Saudi Arabia. Arab. J. Chem. 9 (1), 114–120. https://doi.org/10.1016/j.arabjc.2012.11.013. Amiry, S., Esmaiili, M., Alizadeh, M., 2017. Classification of adulterated honeys by multivariate analysis. Food Chem. 224, 390–397. https://doi.org/10.1016/ j.foodchem.2016.12.025. Andrisic, L., Dudzik, D., Barbas, C., Milkovic, L., Grune, T., Zarkovic, N., 2018. Short overview on metabolomics approach to study pathophysiology of oxidative stress in cancer. Redox Biol. 14, 47–58. https://doi.org/10.1016/j.redox.2017.08.009. July 2017. Apolinário, A.C., De Lima Damasceno, B.P.G., De Macedo Beltrão, N.E., Pessoa, A., Converti, A., Da Silva, J.A., 2014. Inulin-type fructans: a review on different aspects of biochemical and pharmaceutical technology. Carbohydr. Polym. 101 (1), 368–378. https://doi.org/10.1016/j.carbpol.2013.09.081. Ávila-Fernández, Á., Rendón-Poujol, X., Olvera, C., González, F., Capella, S., PeñaAlvarez, A., López-Munguía, A., 2009. Enzymatic hydrolysis of fructans in the tequila production process. J. Agric. Food Chem. 57 (12), 5578–5585. https://doi. org/10.1021/jf900691r. Ayoub Meo, S., Ahmad Al-Asiri, S., Latief Mahesar, A., Javed Ansari, M., 2016. Role of honey in modern medicine. Saudi J. Biol. Sci. https://doi.org/10.1016/j.sjbs.2016.12.010. Babacanoglu, C., Yildirim, N., Sadi, G., Pektas, M.B., Akar, F., 2013. Resveratrol prevents high-fructose corn syrup-induced vascular insulin resistance and dysfunction in rats. Food Chem. Toxicol. 60, 160–167. https://doi.org/10.1016/j.fct.2013.07.026. Badolato, M., Carullo, G., Cione, E., Aiello, F., Caroleo, M.C., 2017. From the hive: honey, a novel weapon against cancer. Eur. J. Med. Chem. https://doi.org/10.1016/ j.ejmech.2017.07.064. Baglio, E., 2018. Honey: processing techniques and treatment. In: Baglio, E. (Ed.), Chemistry and Technology of Honey Production. Springer, Catania, pp. 15–23. https://doi.org/10.1007/978-3-319-65751-6_2. Ball, D.W., 2007. The chemical composition of maple syrup. J. Chem. Educ. 84 (10), 1647. https://doi.org/10.1021/ed084p1647. Belay, A., Solomon, W.K., Bultossa, G., Adgaba, N., Melaku, S., 2015. Botanical origin, colour, granulation, and sensory properties of the Harenna forest honey, Bale, Ethiopia. Food Chem. 167, 213–219. https://doi.org/10.1016/j.foodchem.2014.06.080. Bode, J.W., Empie, M.W., Brenner, K.D., 2014. Evolution of high fructose corn syrup within the sweeteners industry. In: Rippe, J.M. (Ed.), Fructose, High Fructose Corn Syrup, Sucrose and Health. Springer, New York, pp. 277–291. https://doi. org/10.1007/978-1-4899-8077-9. Bogdanov, S., Jurendic, T., Sieber, R., Gallmann, P., 2008. Honey for nutrition and health: a review. J. Am. Coll. Nutr. 27 (6), 677–689. https://doi.org/10.1080/07315724.2008.10719745. Bogdanov, S., Martin, P., 2002. Honey authenticity: a review. Mitt. Lebensm. Hyg. 1–20. Available from: http://www.bee-hexagon.net/files/file/fileE/Honey/ AuthenticityRevue_Internet.pdf. Bouchard, C.R., Lebrun, R.E., 1999. Concentration polarization modelling in the maple sap. Int. J. Food Sci. Technol. 1993, 217–228. https://doi. org/10.1046/j.1365-2621.1999.00252.x. Bowman, S.A., 2017. Added sugars: definition and estimation in the USDA Food Patterns Equivalents Databases. J. Food Compos. Anal. https://doi.org/10.1016/ j.jfca.2017.07.013. October 2016.

Chapter 6  Honey and Syrups: Healthy and Natural Sweeteners With Functional Properties   171

Bees and their Role in Forest Livelihoods. In: Bradbear, N. (Ed.), 2009. Food and Agriculture Organization of the United Nations, Rome. Castro, A., Guerrero, J., 2013. El agave y sus productos. Temas Selectos de Ingeniería de Alimentos 7 (2), 53–61. Castro-Vázquez, L., Díaz-Maroto, M.C., González-Viñas, M.A., Pérez-Coello, M.S., 2009. Differentiation of monofloral citrus, rosemary, eucalyptus, lavender, thyme and heather honeys based on volatile composition and sensory descriptive analysis. Food Chem. 112 (4), 1022–1030. https://doi.org/10.1016/j. foodchem.2008.06.036. Chakir, A., Romane, A., Marcazzan, G.L., Ferrazzi, P., 2016. Physicochemical properties of some honeys produced from different plants in Morocco. Arab. J. Chem 9, S946–S954. https://doi.org/10.1016/j.arabjc.2011.10.013. Chaven, S., 2014. Honey, confectionery and bakery products. In: Motarjemi, J., Lelieveld, H. (Eds.), Food Safety Management: A Practical Guide for the Food Industry. Elsevier, London, pp. 283–299. https://doi.org/10.1016/B978-0-12-381504-0.00011-1. Chen, L., Xue, X., Ye, Z., Zhou, J., Chen, F., Zhao, J., 2011. Determination of Chinese honey adulterated with high fructose corn syrup by near infrared spectroscopy. Food Chem. 128 (4), 1110–1114. https://doi.org/10.1016/j. foodchem.2010.10.027. Chua, L.S., Abdul-Rahaman, N.L., Sarmidi, M.R., Aziz, R., 2012. Multi-elemental composition and physical properties of honey samples from Malaysia. Food Chem 135 (3), 880–887. https://doi.org/10.1016/j.foodchem.2012.05.106. Çinar, S.B., Ekşi, A., Coşkun, I., 2014. Carbon isotope ratio (13C/12C) of pine honey and detection of HFCS adulteration. Food Chem. 157, 10–13. https://doi.org/10.1016/ j.foodchem.2014.02.006. Clarke, M.A., 2003. Syrups. In: Caballero, B., Finglas, P., Toldra, F. (Eds.), Encyclopedia of Food Sciences and Nutrition. second ed. Academic Press, Maryland, pp. 5711–5717. https://doi.org/10.1016/B0-12-227055-X/01175-5. Clément, A., Lagacé, L., Panneton, B., 2010. Assessment of maple syrup physico-­ chemistry and typicity by means of fluorescence spectroscopy. J. Food Eng. 97 (1), 17–23. https://doi.org/10.1016/j.jfoodeng.2009.08.029. Codex Alimentarius Commission, 2001. Codex standard of honey. Codex Stan 12-1981, 1–8. Da Silva, P.M., Gauche, C., Gonzaga, L.V., Costa, A.C.O., Fett, R., 2016. Honey: Chemical composition, stability and authenticity. Food Chem 196, 309–323. https://doi. org/10.1016/j.foodchem.2015.09.051. de Ribeiro, R.O.R., Mársico, E.T., Carneiro, C.S., Monteiro, M.L.G., Júnior, C.C., de Jesus, E.F.O., 2014. Detection of honey adulteration of high fructose corn syrup by Low Field Nuclear Magnetic Resonance (LF 1H NMR). J. Food Eng 135, 39–43. https:// doi.org/10.1016/j.jfoodeng.2014.03.009. DeChristopher, L.R., Uribarri, J., Tucker, K.L., 2017. Intake of high fructose corn syrup sweetened soft drinks, fruit drinks and apple juice is associated with prevalent coronary heart disease, in U.S. adults, ages 45–59 y. BMC Nutr. Nutr. J. 3 (1), 51. https:// doi.org/10.1186/s40795-017-0168-9. Edwards, C.H., Rossi, M., Corpe, C.P., Butterworth, P.J., Ellis, P.R., 2016. The role of sugars and sweeteners in food, diet and health: alternatives for the future. Trends Food Sci. Technol. 56, 158–166. https://doi.org/10.1016/j.tifs.2016.07.008. El Sohaimy, S.A.A., Masry, S.H.D.H.D., Shehata, M.G.G., 2015. Physicochemical characteristics of honey from different origins. Ann. Agric. Sci. 60 (2), 279–287. https://doi. org/10.1016/j.aoas.2015.10.015. Elflein, L., 2015. Authenticity of honey. Food Lab Int. 259–303. https://doi. org/10.1007/978-1-4613-1119-5_8. Erejuwa, O.O., Sulaiman, S.A., Ab Wahab, M.S., 2012. Honey—a novel antidiabetic agent. Int. J. Biol. Sci. 8 (6), 913–934. https://doi.org/10.7150/ijbs.3697.

172  Chapter 6  Honey and Syrups: Healthy and Natural Sweeteners With Functional Properties

Escriche, I., Tanleque-Alberto, F., Visquert, M., Oroian, M., 2017. Physicochemical and rheological characterization of honey from Mozambique. LWT Food Sci. Technol. 86, 108–115. https://doi.org/10.1016/j.lwt.2017.07.053. Escuredo, O., Dobre, I., Fernández-González, M. and Seijo, M. C. (2014) Contribution of botanical origin and sugar composition of honeys on the crystallization phenomenon, Food Chem. 149, pp. 84–90. doi: https://doi.org/10.1016/ j.foodchem.2013.10.097. FAOSTAT (2013) Food and agriculture organization of the United Nations, commodity balances- livestock and fish primary equivalent. Available from: http://www.fao. org/faostat. Ferder, L., Ferder, M.D., Inserra, F., 2010. The role of high-fructose corn syrup in metabolic syndrome and hypertension. Curr. Hypertens. Rep. 12 (2), 105–112. https:// doi.org/10.1007/s11906-010-0097-3. Filteau, M., Lagacé, L., LaPointe, G., Roy, D., 2012. Maple sap predominant microbial contaminants are correlated with the physicochemical and sensorial properties of maple syrup. Int. J. Food Microbiol 154 (1–2), 30–36. https://doi.org/10.1016/ j.ijfoodmicro.2011.12.007. García-Aguirre, M., Sáenz-ÁLVARO, V.A., Rodríguez-Soto, M.A., Vicente-Magueyal, F.J., Botello-ÁLVAREZ, E., Jiménez-Islas, H., Marcela, C.M., Rico-MARTÍNEZ, R., Navarrete-BOLAÑOS, J.L., 2009. Strategy for biotechnological process design applied to the enzymatic hydrolysis of agave fructo-oligosaccharides to obtain fructose-rich syrups. J. Agric. Food Chem. 57 (21), 10205–10210. https://doi.org/10.1021/jf902855q. Gensberger, S., Mittelmaier, S., Glomb, M.A., Pischetsrieder, M., 2012. Identification and quantification of six major α-dicarbonyl process contaminants in high-fructose corn syrup. Anal. Bioanal. Chem. 403 (10), 2923–2931. https://doi.org/10.1007/ s00216-012-5817-x. González-Hernández, J.C., Pérez, E., Damián, R.M., Chávez-Parga, M.C., 2012. Isolation, molecular and fermentative characterization of a yeast used in ethanol production during mezcal elaboration. Rev. Mex. Ing. Quím. 11, 389–400. Available from: http:// www.redalyc.org/articulo.oa?id=62026894004. Guler, A., Garipoglu, A.V., Onder, H., Biyik, S., Kocaokutgen, H., Ekinci, D., 2017. Comparing biochemical properties of pure and adulterated honeys produced by feeding honeybees (Apis mellifera L.) colonies with different levels of industrial commercial sugars. Kafkas Univ. Vet. Fak. Der. 23 (January), 259–268. https://doi. org/10.9775/kvfd.2016.16373. Gupta, R.K., Reybroeck, W., De Waele, M., Bouters, A., 2016. Bee products: production and processing. In: Gupta, R.K., Reybroeck, W., Van Veen, J.W., Gupta, A. (Eds.), Beekeeping for Poverty Alleviation and Livelihood Security Technological Aspects of Beekeeping. vol. 1. Springer, New York, pp. 670. Gutierrez-Uribe, J.-A. and Serna-Saldivar, S. (2013) Agave syrup extract having anticancer activity. Habib, H.M., Al Meqbali, F.T., Kamal, H., Souka, U.D., Ibrahim, W.H., 2014a. Bioactive components, antioxidant and DNA damage inhibitory activities of honeys from arid regions. Food Chem. 153, 28–34. https://doi.org/10.1016/j.foodchem.2013.12.044. Habib, H.M., Al Meqbali, F.T., Kamal, H., Souka, U.D., Ibrahim, W.H., 2014b. Physicochemical and biochemical properties of honeys from arid regions. Food Chem. 153, 35–43. https://doi.org/10.1016/j.foodchem.2013.12.048. Hinkova, A., Bubnil, S., Kadlec, P., 2015. Chemical composition of sugar. In: Cheung, P.C.K., Mehta, B.M. (Eds.), Handbook of Food Chemistry. Springer, Berlin, pp. 586– 624. https://doi.org/10.1007/978-3-642-36605-5. Hossen, M.S., Ali, M.Y., Jahurul, M.H.A., Abdel-Daim, M.M., Gan, S.H., Khalil, M.I., 2017. Beneficial roles of honey polyphenols against some human degenerative diseases: a review. Pharmacol. Rep. https://doi.org/10.1016/j.pharep.2017.07.002. Institute of Pharmacology, Polish Academy of Sciences.

Chapter 6  Honey and Syrups: Healthy and Natural Sweeteners With Functional Properties   173

Hutkins, R.W., Krumbeck, J.A., Bindels, L.B., Cani, P.D., Fahey, G., Goh, Y.J., Hamaker, B., Martens, E.C., Mills, D.A., Rastal, R.A., Vaughan, E., Sanders, M.E., 2016. Prebiotics: why definitions matter. Curr. Opin. Biotechnol. 37, 1–7. https://doi.org/10.1016/ j.copbio.2015.09.001. Iida, T., Yamada, T., Hayashi, N., Okuma, K., Izumori, K., Ishii, R., Matsuo, T., 2013. Reduction of abdominal fat accumulation in rats by 8-week ingestion of a newly developed sweetener made from high fructose corn syrup. Food Chem. 138 (2–3), 781–785. https://doi.org/10.1016/j.foodchem.2012.11.017. International Markets Bureau, 2012. Consumer Trends: Honey and Maple Syrup in Japan. International Markets Bureau, Canada. Johnson, R., Padmaja, G., Moorthy, S.N., 2009. Comparative production of glucose and high fructose syrup from cassava and sweet potato roots by direct conversion techniques. Innovative Food Sci. Emerg. Technol. 10 (4), 616–620. https://doi. org/10.1016/j.ifset.2009.04.001. Kadri, S.M., Zaluski, R., Orsi, R. de O., 2017. Nutritional and mineral contents of honey extracted by centrifugation and pressed processes. Food Chem. 218, 237–241. https://doi.org/10.1016/j.foodchem.2016.09.071. Kaygusuz, H., Tezcan, F., Bedia Erim, F., Yildiz, O., Sahin, H., Can, Z., Kolayli, S., 2016. Characterization of Anatolian honeys based on minerals, bioactive components and principal component analysis. LWT Food Sci. Technol. 68, 273–279. https://doi. org/10.1016/j.lwt.2015.12.005. Khan, S.U., Anjum, S.I., Rahman, K., Ansari, M.J., Khan, W.U., Kamal, S., Khattak, B., Muhammad, A., Khan, H.U., 2017. Honey: single food stuff comprises many drugs. Saudi J. Biol. Sci. https://doi.org/10.1016/j.sjbs.2017.08.004. Kuzma, J.N., Cromer, G., Hagman, D.K., Breymeyer, K.L., Roth, C.L., Foster-Schubert, K.E., Holte, S.E., Weigle, D.S., Kratz, M., 2016. No differential effect of beverages sweetened with fructose, high-fructose corn syrup, or glucose on systemic or adipose tissue inflammation in normal-weight to obese adults: a randomized controlled trial. Am. J. Clin. Nutr. 104 (2), 306–314. https://doi.org/10.3945/ ajcn.115.129650. Lagacé, L., Leclerc, S., Charron, C., Sadiki, M., 2015. Biochemical composition of maple sap and relationships among constituents. J. Food Compos. Anal. 41, 129–136. https://doi.org/10.1016/j.jfca.2014.12.030. Le, M.T., Frye, R.F., Rivard, C.J., Cheng, J., McFann, K.K., Segal, M.S., Johnson, R.J., Johnson, J.A., 2012. Effects of high-fructose corn syrup and sucrose on the pharmacokinetics of fructose and acute metabolic and hemodynamic responses in healthy subjects. Metab. Clin. Exp. 61 (5), 641–651. https://doi.org/10.1016/ j.metabol.2011.09.013. Leal-Díaz, A.M., Noriega, L.G., Torre-Villalvazo, I., Torres, N., Alemán-Escondrillas, G., López-Romero, P., Sánchez-Tapia, M., Aguilar-López, M., Furuzawa-Carballeda, J., Velázquez-Villegas, L.A., Avila-Nava, A., Ordáz, G., G ­utiérrez-Uribe, J.A., ­Serna-Saldivar, S.O., Tovar, A.R., 2016. Aguamiel concentrate from Agave salmiana and its extracted saponins attenuated obesity and hepatic steatosis and increased Akkermansia muciniphila in C57BL6 mice. Sci. Rep. 6 (September), 34242. https://doi.org/10.1038/srep34242. Li, L., Seeram, N.P., 2010. Maple syrup phytochemicals include lignans, coumarins, a stilbene, and other previously unreported antioxidant phenolic compounds. J. Agric. Food Chem. 58 (22), 11673–11679. https://doi.org/10.1021/jf1033398. Li, L., Seeram, N.P., 2011. Quebecol, a novel phenolic compound isolated from Canadian maple syrup. J. Funct. Foods 3 (125–128), 4. https://doi.org/10.1016/ j.jff.2011.02.004. Li, L., Seeram, N.P., 2012. Chemical composition and biological effects of maple syrup. In: Emerging Trends in Dietary Components for Preventing and Combating Disease, pp. 443–461. https://doi.org/10.1021/bk-2012-1093.

174  Chapter 6  Honey and Syrups: Healthy and Natural Sweeteners With Functional Properties

Li, M., Seo, S., Karboune, S., 2015. Bacillus amyloliquefaciens levansucrase-catalyzed the synthesis of fructooligosaccharides, oligolevan and levan in maple syrup-based reaction systems. Carbohydr. Polym 133, 203–212. https://doi.org/10.1016/j.carbpol.2015.07.010. Li, S., Shan, Y., Zhu, X., Zhang, X., Ling, G., 2012. Detection of honey adulteration by high fructose corn syrup and maltose syrup using Raman spectroscopy. J. Food Compos. Anal 28 (1), 69–74. https://doi.org/10.1016/j.jfca.2012.07.006. Li, S., Zhang, X., Shan, Y., Su, D., Ma, Q., Wen, R., Li, J., 2017. Qualitative and quantitative detection of honey adulterated with high-fructose corn syrup and maltose syrup by using near-infrared spectroscopy. Food Chem. 218, 231–236. https://doi. org/10.1016/j.foodchem.2016.08.105. Lupien-Meilleur, J., Roy, D., Lagacé, L., 2016. Viability of probiotic bacteria in a maple sap beverage during refrigerated storage. LWT Food Sci. Technol. 74, 160–167. https://doi.org/10.1016/j.lwt.2016.07.045. Mahmoodi-Khaledi, E., Lozano-Sánchez, J., Bakhouche, A., Habibi-Rezaei, M., Sadeghian, I. and Segura-Carretero, A. (2017) Physicochemical properties and biological activities of honeys from different geographical and botanical origins in Iran, Eur. Food Res. Technol. 243(6), pp. 1019–1030. doi: https://doi.org/10.1007/ s00217-016-2811-0. Márquez-Aguirre, A.L., Camacho-Ruíz, R.M., Gutiérrez-Mercado, Y.K., PadillaCamberos, E., González-Avila, M., Gálvez-Gastélum, F.J., Díaz-Martínez, N.E., Ortuño-Sahagún, D., 2016. Fructans from agave tequilana with a lower degree of polymerization prevent weight gain, hyperglycemia and liver steatosis in highfat diet-induced obese mice. Plant Foods Hum. Nutr. 71 (4), 416–421. https://doi. org/10.1007/s11130-016-0578-x. Mato, I., Huidobro, J.F.J.F., Simal-Lozano, J., Teresa Sancho, M., Sancho, M.T., 2006. Rapid determination of nonaromatic organic acids in honey by capillary zone electrophoresis with direct ultraviolet detection. J. Agric. Food Chem. 54 (5), 1541–1550. https://doi.org/10.1021/jf051757i. Melanson, K.J., Zukley, L., Lowndes, J., Nguyen, V., Angelopoulos, T.J., Rippe, J.M., 2007. Effects of high-fructose corn syrup and sucrose consumption on circulating glucose, insulin, leptin, and ghrelin and on appetite in normal-weight women. Nutrition 23 (2), 103–112. https://doi.org/10.1016/j.nut.2006.11.001. Mellado-Mojica, E., López, M.G., 2015. Identification, classification, and discrimination of agave syrups from natural sweeteners by infrared spectroscopy and HPAEC-PAD. Food Chem. 167, 349–357. https://doi.org/10.1016/j.foodchem.2014.06.111. Mellado-Mojica, E., López-Pérez, M.G., 2013. Comparative analysis between blue agave syrup (Agave tequilana Weber var. azul) and other natural syrups. Agrociencia 47 (3), 233–244. Mellado-Mojica, E., Seeram, N.P., López, M.G., 2016. Comparative analysis of maple syrups and natural sweeteners: carbohydrates composition and classification (differentiation) by HPAEC-PAD and FTIR spectroscopy-chemometrics. J. Food Compos. Anal 52, 1–8. https://doi.org/10.1016/j.jfca.2016.07.001. Michel-Cuello, C., Juárez-Flores, B.I., Aguirre-Rivera, J.R., Pinos-Rodríguez, J.M., 2008. Quantitative characterization of nonstructural carbohydrates of mezcal agave (Agave salmiana Otto ex Salm-Dick). J. Agric. Food Chem. 56 (14), 5753–5757. https://doi.org/10.1021/jf800158p. Montañez Soto, J.L., Venegas González, J., Bernardino Nicanor, A., Ramos Ramírez, E.G., 2011. Enzymatic production of high fructose syrup from Agave tequilana fructans and its physicochemical characterization. Afr. J. Biotechnol. 10 (82), 19137–19143. https://doi.org/10.5897/AJB11.2704. Muñiz-Márquez, D.B., Contreras, J.C., Rodríguez, R., Mussatto, S.I., Wong-Paz, J.E., Teixeira, J.A., Aguilar, C.N., 2015. Influence of thermal effect on sugars composition of Mexican Agave syrup. CyTA—J. Food 13 (4), 1–6. https://doi.org/10.1080/194763 37.2015.1028452.

Chapter 6  Honey and Syrups: Healthy and Natural Sweeteners With Functional Properties   175

Nahar, P.P., Driscoll, M.V., Li, L., Slitt, A.L., Seeram, N.P., 2014. Phenolic mediated a­ nti-inflammatory properties of a maple syrup extract in RAW 264.7 murine macrophages. J. Funct. Foods 6 (1), 126–136. https://doi.org/10.1016/j. jff.2013.09.026. National Honey Board, 2006. Honey: A Reference Guide to Nature’s Sweetener. National Honey Board, Firestone, CO. Retrieved from www.honey.com. National Honey Board (2014) Carbohydrates and the Sweetness of Honey, National Honey Board. Available from: www.honey.com. Nava-Cruz, N.Y., Medina-Morales, M.A., Martinez, J.L., Rodriguez, R., Aguilar, C.N., 2015. Agave biotechnology: an overview. Crit. Rev. Biotechnol. 35 (4), 546–559. https://doi.org/10.3109/07388551.2014.923813. Oliveira, J.V., 2010. Dehumidification or Dehydration Unit for Apicultural Use. US Patent US20100275621A1. Olvera Carranza, C., Ávila Fernández, Á., Bustillo Armendáriz, G.R., López-Munguía, A., 2015. Processing of Fructans and oligosaccharides from agave plants. In: Preedy, V.R. (Ed.), Processing and Impact on Active Components in Food. first ed Elsevier, London, pp. 146–154. https://doi.org/10.1016/B978-0-12-404699-3.01002-7. Oroian, M., 2013. Measurement, prediction and correlation of density, viscosity, surface tension and ultrasonic velocity of different honey types at different temperatures. J. Food Eng. 119 (1), 167–172. https://doi.org/10.1016/j.jfoodeng.2013.05.029. Oroian, M., Ropciuc, S., 2017. Honey authentication based on physicochemical parameters and phenolic compounds. Comput. Electron. Agric 138, 148–156. https://doi. org/10.1016/j.compag.2017.04.020. Oryan, A., Alemzadeh, E., Moshiri, A., 2016. Biological properties and therapeutic activities of honey in wound healing: a narrative review and meta-analysis. J. Tiss. Viab 25 (2), 98–118. https://doi.org/10.1016/j.jtv.2015.12.002. Osés, S.M., Pascual-Maté, A., Fernández-Muiño, M.A., López-Díaz, T.M., Sancho, M.T., 2016. Bioactive properties of honey with propolis. Food Chem. 196, 1215–1223. https://doi.org/10.1016/j.foodchem.2015.10.050. Parker, K., Salas, M., Nwosu, V.C., 2010. High fructose corn syrup: production, uses and public health concerns. Biotechnol. Mol. Biol. Rev. 5 (5), 71–78. https://doi.org/ 10.1080/17441692.2012.736257. December. Perkins, T.D., van den Berg, A.K., 2009. Maple syrup-production, composition, chemistry, and sensory characteristics. In: Taylor, S.L. (Ed.), Advances in Food and Nutrition Research. first ed vol. 56. Elsevier, Vermont, pp. 101–143. https://doi. org/10.1016/S1043-4526(08)00604-9. Peshev, D., Van den Ende, W., 2014. Fructans: prebiotics and immunomodulators. J. Funct. Foods 8 (1), 348–357. https://doi.org/10.1016/j.jff.2014.04.005. Pita-Calvo, C., Vázquez, M., 2017. Differences between honeydew and blossom honeys: a review. Trends Food Sci. Technol 59, 79–87. https://doi.org/10.1016/j. tifs.2016.11.015. Rao, P.V., Krishnan, K.T., Salleh, N., Gan, S.H., 2016. Biological and therapeutic effects of honey produced by honey bees and stingless bees: a comparative review. Braz. J. Pharm. 26 (5), 657–664. https://doi.org/10.1016/j.bjp.2016.01.012. Rodriguez-Saona, L.E., Allendorf, M.E., 2011. Use of FTIR for rapid authentication and detection of adulteration of food. Annu. Rev. Food Sci. Technol. 2 (1), 467–483. https://doi.org/10.1146/annurev-food-022510-133750. Ros-Polski, V., Popović, V., Koutchma, T., 2016. Effect of ultraviolet-C light treatment on Hydroxymethylfurfural (5-HMF) content in high fructose corn syrup (HFCS) and model syrups. J. Food Eng. 179, 78–87. https://doi.org/10.1016/ j.jfoodeng.2016.01.027. Rybak-Chmielewska, H. (2007) High performance liquid chromatography (Hplc) study of sugar composition in some kinds of natural honey and winter stores processed by bees from starch syrup, J. Apicultural Sci., 14.02.2007, 51(1), pp. 23–38.

176  Chapter 6  Honey and Syrups: Healthy and Natural Sweeteners With Functional Properties

Sabik, H., Fortin, J., Martin, N., 2012. Identification of pyrazine derivatives in a typical  maple syrup using headspace solid-phase microextraction with gas ­chromatography-mass spectrometry. Food Chem. 133 (3), 1006–1010. https://doi. org/10.1016/j.foodchem.2011.07.132. Santos-Buelga, C., González-Paramás, A.M., 2017. Chemical composition of honey. In: Alvarez-Suarez, J.M. (Ed.), Bee Products-Chemical and Biological Properties. Springer, Quito, pp. 301. https://doi.org/10.1007/978-3-319-59689-1. Santos-Zea, L., Leal-Diaz, A., Cortes-Ceballos, E., Gutierrez- Uribe, J., 2012. Agave (Agave spp.) and its traditional products as a source of bioactive compounds. Curr. Bioact. Comp. 8 (3), 218–231. https://doi.org/10.2174/157340712802762410. Santos-Zea, L., Leal-Díaz, A.M., Jacobo-Velázquez, D.A., Rodríguez-Rodríguez, J., García-Lara, S., Gutiérrez-Uribe, J.A., 2016. Characterization of concentrated agave saps and storage effects on browning, antioxidant capacity and amino acid content. J. Food Compos. Anal. 45, 113–120. https://doi.org/10.1016/j. jfca.2015.10.005. Servicio de Información Agroalimentaria y Pesquera, 2016. Atlas Agroalimentario. . México. Sgariglia, M.A., Vattuone, M.A., Sampietro-Vattuone, M.M., Soberón, J.R., Sampietro, D.A., 2010. Properties of honey from Tetragonisca angustula fiebrigi and Plebeia wittmanni of Argentina. Apidologie 41 (6), 667–675. https://doi.org/10.1051/ apido/2010028. Shoaib, M., Shehzad, A., Omar, M., Rakha, A., Raza, H., Sharif, H.R., Shakeel, A., Ansari, A., Niazi, S., 2016. Inulin: properties, health benefits and food applications. Carbohydr. Polym. 147, 444–454. https://doi.org/10.1016/j.carbpol.2016.04.020. Sidana, J., Singh, B., Sharma, O.P., 2016. Saponins of Agave: chemistry and bioactivity. Phytochemistry 130, 22–46. https://doi.org/10.1016/j.phytochem.2016.06.010. Siddiqui, A.J., Musharraf, S.G., Choudhary, M.I., Rahman, A. ur, 2017. Application of analytical methods in authentication and adulteration of honey. Food Chem 217, 687–698. https://doi.org/10.1016/j.foodchem.2016.09.001. Singh, A.S., Jones, A.M.P., Saxena, P.K., 2014a. Variation and correlation of properties in different grades of maple syrup. Plant Foods Hum. Nutr. 69 (1), 50–56. https://doi. org/10.1007/s11130-013-0401-x. Singh, I., Langyan, S., Yadava, P., 2014b. Sweet corn and corn-based sweeteners. Sugar Tech 16 (2), 144–149. https://doi.org/10.1007/s12355-014-0305-6. Sobrino-Gregorio, L., Vargas, M., Chiralt, A., Escriche, I., 2017. Thermal properties of honey as affected by the addition of sugar syrup. J. Food Eng. 213, 69–75. https://doi. org/10.1016/j.jfoodeng.2017.02.014. St-Pierre, P., Pilon, G., Dumais, V., Dion, C., Dubois, M.J., Dubé, P., Desjardins, Y., Marette, A., 2014. Comparative analysis of maple syrup to other natural sweeteners and evaluation of their metabolic responses in healthy rats. J. Funct. Foods 11 (C), 460–471. https://doi.org/10.1016/j.jff.2014.10.001. Sun, J., Ma, H., Seeram, N.P., Rowley, D.C., 2016. Detection of inulin, a prebiotic polysaccharide in maple syrup. J. Agric. Food Chem. 64 (38). https://doi.org/10.1021/ acs.jafc.6b03139. Tahir, H.E., Xiaobo, Z., Xiaowei, H., Jiyong, S., Mariod, A.A., 2016. Discrimination of honeys using colorimetric sensor arrays, sensory analysis and gas chromatography techniques. Food Chem. 206, 37–43. https://doi.org/10.1016/j.foodchem.2016.03.032. Waleckx, E., Mateos-Diaz, J.C., Gschaedler, A., Colonna-Ceccaldi, B., Brin, N., GarcíaQuezada, G., Villanueva-Rodríguez, S., Monsan, P., 2011. Use of inulinases to improve fermentable carbohydrate recovery during tequila production. Food Chem 124 (4), 1533–1542. https://doi.org/10.1016/j.foodchem.2010.08.007. Wang, S., Guo, Q., Wang, L., Lin, L., Shi, H., Cao, H., Cao, B., 2015. Detection of honey adulteration with starch syrup by high performance liquid chromatography. Food Chem 172, 669–674. https://doi.org/10.1016/j.foodchem.2014.09.044.

Chapter 6  Honey and Syrups: Healthy and Natural Sweeteners With Functional Properties   177

White, J.S., 2014. Sucrose, HFCS, and fructose: history, manufacture, composition, applications and production. In: Rippe, J.M. (Ed.), Fructose, High Fructose Corn Syrup, Sucrose and Health. Springer, New York, pp. 277–291. https://doi. org/10.1007/978-1-4899-8077-9. White, J.S., Nicklas, T.A., 2016. High-fructose corn syrup in beverages: composition, manufacturing, properties, consumption and health effects. In: Wilson, T., Temple, N.J. (Eds.), Beverage Impacts on Health and Nutrition. Springer, Switzerland, pp. 49–67. https://doi.org/10.1007/978-3-319-23672-8. Willems, J.L., Low, N.H., 2012. Major carbohydrate, polyol, and oligosaccharide profiles of agave syrup. Application of this data to authenticity analysis. J. Agric. Food Chem. 60 (35), 8745–8754. https://doi.org/10.1021/jf3027342. Wrobel, K., Corrales Escobosa, A.R., Gomez Ojeda, A., Wrobel, K., Magana, A.A., 2014. Methylglyoxal is associated with bacteriostatic activity of high fructose agave syrups. Food Chem. 165, 444–450. https://doi.org/10.1016/j.foodchem.2014.05.140. Wu, L., Du, B., Vander Heyden, Y., Chen, L., Zhao, L., Wang, M., Xue, X., 2017. Recent advancements in detecting sugar-based adulterants in honey—a challenge. TrAC— Trends in Analyt. Chem. 86, 25–38. https://doi.org/10.1016/j.trac.2016.10.013. Yilmaz, M.T., Tatlisu, N.B., Toker, O.S., Karaman, S., Dertli, E., Sagdic, O., Arici, M., 2014. Steady, dynamic and creep rheological analysis as a novel approach to detect honey adulteration by fructose and saccharose syrups: correlations with HPLC-RID results. Food Res. Int 64, 634–646. https://doi.org/10.1016/j.foodres.2014.07.009. Yousuf, F.A., Mehmood, M.H., Malik, A., Siddiqui, R., Khan, N.A., 2016. Antiacanthamoebic properties of natural and marketed honey in Pakistan. Asian Pacific J. Trop. Biomed. 6 (11), 967–972. https://doi.org/10.1016/j.apjtb.2016.05.010. Yu, Z., Lowndes, J., Rippe, J., 2013. High-fructose corn syrup and sucrose have equivalent effects on energy-regulating hormones at normal human consumption levels. Nutr. Res 33 (12), 1043–1052. https://doi.org/10.1016/j.nutres.2013.07.020. Yuan, T., Li, L., Zhang, Y., Seeram, N.P., 2013. Pasteurized and sterilized maple sap as functional beverages: chemical composition and antioxidant activities. J. Funct. Foods 5 (4), 1582–1590. https://doi.org/10.1016/j.jff.2013.06.009. Zhang, Y., Yuan, T., Li, L., Nahar, P., Slitt, A., Seeram, N.P., 2014. Chemical compositional, biological, and safety studies of a novel maple syrup derived extract for nutraceutical applications. J. Agric. Food Chem. 62 (28), 6687–6698. https://doi.org/10.1021/ jf501924y.

Further Reading González-Sarrías, A., Li, L., Seeram, N.P., 2012. Anticancer effects of maple syrup phenolics and extracts on proliferation, apoptosis, and cell cycle arrest of human colon cells. J. Funct. Foods 4 (1), 185–196. https://doi.org/10.1016/j.jff.2011.10.004.