At both very high and very low water activities, lipid oxidation rates are high compared to the rate at intermediate water activities. What can explain this trend?
Hi Alexxandra Jane Ty
The relationship between rates of lipid oxidation and moisture is complex. The amount of water, the water activity and the state of water in a food, along with other factors, must all be considered.
For most fresh or tissue foods that have moisture contents between 60 - 95% have a water activity very close to 1.T he mode of deterioration at this water activity is generally microbial or enzymatic in nature. Direct lipid oxidation (i.e. not enzyme-mediated) is not an important source of deterioration at this high water activity since other modes of degradation will deteriorate the food first.
Concentration, freezing, and drying are mechanisms by which the water activity of food can be reduced. Such processes may bring the food into the intermediate moisture or low-moisture region where direct lipid oxidation becomes a more important mode of degradation. Also, during dehydration, free radicals can be formed which accelerates lipid oxidation. Freezing can also lead to the acceleration of lipid oxidation rates through the concentration of substrates and catalysts in the unfrozen portion of the system.
On the other hand, Chou et al. (1973) found that water activity primarily affects matrix swelling and thus substrate/reaction site availability as well as catalyst mobility.
Hereinbelow the tow common theories related to the relationship between water activity/content and lipid oxidation are briefly discussed:
Monolayer theory
Unlike most aqueous chemical reactions, the rate of lipid oxidation that takes place in the oil phase is observed to increase as water activity is decreased below the monolayer (i.e. water molecules that are bound tightly to the food surface). This can be explained by considering the role of water in this reaction. It has been suggested that the monolayer of water—or rather, the water saturation of polar groups in lipids—is necessary to cover the surface of the lipid, preventing it from direct exposure to air. This monolayer is essentially “bound” water with limited mobility and is assumed to not participate in chemical reactions. Several studies have found that a variety of foods are most stable to lipid oxidation at a relative humidity or aw consistent with the monolayer.
On the other hand, water can form a hydration sphere around metal catalysts such as Cu, Fe, Co, and Cd. In the dry state, the metal catalysts are most active. As water activity increases, the metals may hydrate which may reduce their catalytic action thus slowing the rate of lipid oxidation.
This monolayer theory, however, cannot be applied universally.
Glass transition theory
According to the glass transition theory, one important function of water is its ability to act as a plasticizing agent. The plasticization of a matrix involves swelling of the polymer matrix when moisture is increased. The resulting increase in free volume might allow for faster diffusion of substrates in the aqueous phase which may lead to faster reaction rates. Plasticization may also increase the contact of the absorbed aqueous phase with the lipid phase. The number of catalytic sites increases such that the rate of lipid oxidation increases.
The above discussion shows that water plays both protective and prooxidative roles in lipid oxidation. In some foods at low aw near the monolayer moisture content, water is protective, presumably because it provides a barrier between the lipid and oxygen.
While the classic food stability map proposed by Labuza et al. (1972) shows lipid oxidation having a U-shaped relationship to aw, no U-shape was also observed; lipid oxidation actually slowed as aw increased as the case of freeze-dried food.
Overall, monolayer and glass transition concepts might not effectively predict lipid oxidation reactions in some foods if oxidation is primarily occurring in the lipid phase and thus would not be significantly impacted by water and the physical state of proteins and carbohydrates. On the other hand, water can play a major role in lipid oxidation chemistry if reactions are primarily promoted by water-soluble prooxidants such as metals. Unfortunately, the causes of lipid oxidation in low-moisture foods are poorly understood, which could be why measurements of water activity, monolayers, and glass transitions do not consistently predict lipid oxidation kinetics.
Sources:
Chapter Relationship Between Water and Lipid Oxidation Rates
https://scholarworks.umass.edu/cgi/viewcontent.cgi?referer=https://www.google.com/&httpsredir=1&article=1159&context=dissertations_2
Lipids undergo oxidation by O2 via radical chain mechanism. The main reactive species are peroxy radicals. In wet organic solvents these radicals form hydrogen bonds with water loosing their reactivity. This explanation is oversimplified.
Hi Alexxandra Jane Ty
The relationship between rates of lipid oxidation and moisture is complex. The amount of water, the water activity and the state of water in a food, along with other factors, must all be considered.
For most fresh or tissue foods that have moisture contents between 60 - 95% have a water activity very close to 1.T he mode of deterioration at this water activity is generally microbial or enzymatic in nature. Direct lipid oxidation (i.e. not enzyme-mediated) is not an important source of deterioration at this high water activity since other modes of degradation will deteriorate the food first.
Concentration, freezing, and drying are mechanisms by which the water activity of food can be reduced. Such processes may bring the food into the intermediate moisture or low-moisture region where direct lipid oxidation becomes a more important mode of degradation. Also, during dehydration, free radicals can be formed which accelerates lipid oxidation. Freezing can also lead to the acceleration of lipid oxidation rates through the concentration of substrates and catalysts in the unfrozen portion of the system.
On the other hand, Chou et al. (1973) found that water activity primarily affects matrix swelling and thus substrate/reaction site availability as well as catalyst mobility.
Hereinbelow the tow common theories related to the relationship between water activity/content and lipid oxidation are briefly discussed:
Monolayer theory
Unlike most aqueous chemical reactions, the rate of lipid oxidation that takes place in the oil phase is observed to increase as water activity is decreased below the monolayer (i.e. water molecules that are bound tightly to the food surface). This can be explained by considering the role of water in this reaction. It has been suggested that the monolayer of water—or rather, the water saturation of polar groups in lipids—is necessary to cover the surface of the lipid, preventing it from direct exposure to air. This monolayer is essentially “bound” water with limited mobility and is assumed to not participate in chemical reactions. Several studies have found that a variety of foods are most stable to lipid oxidation at a relative humidity or aw consistent with the monolayer.
On the other hand, water can form a hydration sphere around metal catalysts such as Cu, Fe, Co, and Cd. In the dry state, the metal catalysts are most active. As water activity increases, the metals may hydrate which may reduce their catalytic action thus slowing the rate of lipid oxidation.
This monolayer theory, however, cannot be applied universally.
Glass transition theory
According to the glass transition theory, one important function of water is its ability to act as a plasticizing agent. The plasticization of a matrix involves swelling of the polymer matrix when moisture is increased. The resulting increase in free volume might allow for faster diffusion of substrates in the aqueous phase which may lead to faster reaction rates. Plasticization may also increase the contact of the absorbed aqueous phase with the lipid phase. The number of catalytic sites increases such that the rate of lipid oxidation increases.
The above discussion shows that water plays both protective and prooxidative roles in lipid oxidation. In some foods at low aw near the monolayer moisture content, water is protective, presumably because it provides a barrier between the lipid and oxygen.
While the classic food stability map proposed by Labuza et al. (1972) shows lipid oxidation having a U-shaped relationship to aw, no U-shape was also observed; lipid oxidation actually slowed as aw increased as the case of freeze-dried food.
Overall, monolayer and glass transition concepts might not effectively predict lipid oxidation reactions in some foods if oxidation is primarily occurring in the lipid phase and thus would not be significantly impacted by water and the physical state of proteins and carbohydrates. On the other hand, water can play a major role in lipid oxidation chemistry if reactions are primarily promoted by water-soluble prooxidants such as metals. Unfortunately, the causes of lipid oxidation in low-moisture foods are poorly understood, which could be why measurements of water activity, monolayers, and glass transitions do not consistently predict lipid oxidation kinetics.
Sources:
Chapter Relationship Between Water and Lipid Oxidation Rates
https://scholarworks.umass.edu/cgi/viewcontent.cgi?referer=https://www.google.com/&httpsredir=1&article=1159&context=dissertations_2
lipids undergo accoriding to yurii v gelettii sir by 02 via radical chain mechanism. the main reactive species are proxy radicals .but the property water and its oxidation and mosture is totally done accourding to the dencity and humidiaty of water
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