3.1.3 Enzymatic and chemical changes related to aw values
The relationship between enzymatic and chemical changes in foods as a function of water activity is illustrated in Figure 3.1. With aw at 0.3, the product is most stable with respect to lipid oxidation, non-enzymatic browning, enzyme activity, and of course, the various microbial parameters. As aw increases toward the right, the probability of the food product deteriorating increases.
According to Rahman and Labuza (1999), enzyme-catalyzed reactions can occur in foods with relatively low water contents. The authors summarized two features of these results as follows:
1. The rate of hydrolysis increases with increased water activity but is extremely slow with very low activity.
2. For each instance of water activity there appears to be a maximum amount of hydrolysis, which also increases with water content.
The apparent cessation of the reaction at low moisture cannot be due to the irreversible inactivation of the enzyme, because upon humidification to a higher water activity, hydrolysis resumes at a rate characteristic of the newly attained water activity. Rahman and Labuza(1999) reported the investigation of a model system consisting of avicel, sucrose, and invertase and found that the reaction velocity increased with water activity. Complete conversion of the substrate was observed for water activities greater than or equal to 0.75. For water activities below 0.75, the reaction continued with 100% hydrolysis. In solid media, water activity can affect reactions in two ways: lack of reactant mobility and alternation of active conformation of the substrate and enzymatic protein. The effects of varying the enzyme-to-substrate ratios on reaction velocity and the effect of water activity on the activation energy for the reaction could not be explained by a simple diffusional model, but required postulates that were more complex:
1. The diffusional resistance is localized in a shell adjacent to the enzyme.
2. At low water activity, the reduced hydration produces conformational changes in the enzyme, affecting its catalytic activity.
The relationship between water content and water activity is complex. An increase in aw is usually accompanied by an increase in water content, but in a non-linear fashion. This relationship between water activity and moisture content at a given temperature is called the moisture sorption isotherm. These curves are determined experimentally and constitute the fingerprint of a food system.
3.1.4 Recommended equipment for measuring aw
Many methods and instruments are available for laboratory measurement of water activity in foods. Methods are based on the colligative properties of solutions. Water activity can be estimated by measuring the following:
• Vapour pressure
• Osmotic pressure
• Freezing point depression of a liquid
• Equilibrium relative humidity of a liquid or solid
• Boiling point elevation
• Dew point and wet bulb depression
• Suction potential, or by using the isopiestic method
• Bithermal equilibrium
• Electric hygrometers
• Hair hygrometers
3.1.4.1 Vapour pressure
Water activity is expressed as the ratio of the partial pressure of water in a food to the vapour pressure of pure water with the same temperature as the food. Thus, measuring the vapour pressure of water in a food system is the most direct measure of aw. The food sample measured is allowed to equilibrate, and measurement is taken by using a manometer or transducer device as depicted in Figure 3.2. This method can be affected by sample size, equilibration time, temperature, and volume. This method is not suitable for biological materials with active respiration or materials containing large amounts of volatiles.
Figure 3.2 Vapour pressure manometer.
Adapted from Barbosa-Cánovas and Vega-Mercado, 1996)
3.1.4.2 Freezing point depression and freezing point elevation
This method is accurate for liquids in the high water activity range but is not suitable for solid foods (Barbosa-Cánovas and Vega-Mercado, 1996). The water activity can be estimated using the following two expressions:
Freezing point depression:
-log aw = 0.004207 DTf + 2.1 E-6 DT2f (1)
where DTf is the depression in the freezing temperature of water
Boiling point elevation:
-log aw = 0.01526 DTb - 4.862 E-5 DT2b (2)
where DTb is the elevation in the boiling temperature of water.
3.1.4.3 Osmotic pressure
Water activity can be related to the osmotic pressure (p) of a solution with the following equation:
p = RT/Vw ln(aw) (3)
where Vw is the molar volume of water in solution, R the universal gas constant, and T the absolute temperature. Osmotic pressure is defined as the mechanical pressure needed to prevent a net flow of solvent across a semi-permeable membrane. For an ideal solution, Equation (3) can be redefined as:
p = RT/Vw ln(Xw) (4)
where Xw is the molar fraction of water in the solution. For non-ideal solutions, the osmotic pressure expression can be rewritten as:
p = RTfnmb(mwVw) (5)
where n is the number of moles of ions formed from one mole of electrolyte, mw and mb are the molar concentrations of water and the solute, respectively, and f the osmotic coefficient, defined as:
f = -mw ln(aw)/nmb (6)
3.1.4.4 Dew point hygrometer
Vapour pressure can be determined from the dew point of an air-water mixture. The temperature at which the dew point occurs is determined by observing condensation on a smooth, cool surface such as a mirror. This temperature can be related to vapour pressure using a psychrometric chart. The formation of dew is detected photoelectrically, as illustrated in the diagram below:
Figure 3.3 Dew point determination of water activity.
(Adapted from Barbosa-Cánovas and Vega-Mercado, 1996)
3.1.4.5 Thermocouple Psychrometer
Water activity measurement is based on wet bulb temperature depression. A thermocouple is placed in the chamber where the sample is equilibrated. Water is then sprayed over the thermocouple before it is allowed to evaporate, causing a decrease in temperature. The drop in temperature is related to the rate of water evaporation from the surface of the thermocouple, which is a function of the relative humidity in equilibrium with the sample.
3.1.4.6 Isopiestic method
The isopiestic method consists of equilibrating both a sample and a reference material in an evacuated desiccator until equilibrium is reached at 25°C. The moisture content of the reference material is then determined and the aw obtained from the sorption isotherm. Since the sample was in equilibrium with the reference material, the aw of both is the same.
3.1.4.7 Electric hygrometers
Most hygrometers are electrical wires coated with hygroscopic salts or sulfonated polystyrene gel in which conductance or capacitance changes as the coating absorbs moisture from the sample. The major disadvantage of this type of hygrometer is the tendency of the hygroscopic salt to become contaminated with polar compounds, resulting in erroneous aw determinations.
3.1.4.8 Hair hygrometers
Hair hygrometers are based on the stretching of a fibre when exposed to high water activity. They are less sensitive than other instruments at lower levels of activity (<0.03 aw) and the principal disadvantage of these types of meters is the time delay in reaching equilibrium and the tendency to hysteresis.
Today we find many brands of water activity meters in the market. Most of these meters are based on the relationship between ERH and the food system, but differ in their internal components and configuration of software used. One of the water activity meters most used today is the AcquaLab Series 3 Model TE, developed by Decagon Devices, which is based on the chilled-mirror dew point method. This instrument is a temperature controlled water activity meter that allows placement of the sample in a temperature stable environment without the use of an external water bath. The temperature can be selected on the screen and is monitored and controlled with thermoelectric components. Most of the older generations of water activity instruments are based on a temperature-controlled environment. Therefore, a margin of error greater than 5% can be expected due to temperature variations. This equipment is highly recommended for measuring water activity in fruits and vegetables since it measures a wide range of water activity.
The major advantages of the chilled-mirror dew point method are accuracy, speed, ease of use and precision. The AquaLab's range is from 0.030 to 1.000aw, with a resolution of ±0.001aw and accuracy of ±0.003aw. Measurement time is typically less than five minutes. Capacitance sensors have the advantage of being inexpensive, but are not usually as accurate or as fast as the chilled-mirror dew point method. Capacitive instruments measure over the entire water activity range 0 to 1.00 aw, with a resolution of ±0.005aw and accuracy of ±0.015aw. Some commercial instruments can complete measurements in five minutes while other electronic capacitive sensors usually require 30 to 90 minutes to reach equilibrium relative humidity conditions.
3.2 Intermediate Moisture Foods (IMF) concept
Traditional intermediate moisture foods (IMF) can be regarded as one of the oldest foods preserved by man. The mixing of ingredients to achieve a given aw, that allowed safe storage while maintaining enough water for palatability, was only done, however, on an empirical basis. The work done by food scientists approximately three decades ago, in the search for convenient stable products through removal of water, resulted in the so-called modern intermediate moisture foods. These foods rely heavily on the addition of humectants and preservatives to prevent or reduce the growth of microorganisms. Since then, this category of products has been subjected to continuous revision and discussion.
Definitions of IMF in terms of aw values and moisture content vary within wide limits (0.6-0.90 aw, 10-50% moisture), and the addition of preservativ
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