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Á¦Ç° ¡í À¯°¡°ø ¡í Ä¡Áî À¯Á¦Ç° - °¡°øÄ¡Áî processed cheese Ãâó : CHEESE: CHEMISTRY , PHYSICS AND MICROBIOLOGY Volume 2 Processed cheese is produced by blending shredded natural cheeses of different types and degrees of maturity with emulsifying agents, and by heating the blend under a partial vacuum with constant agitation until a homogeneous mass is obtained. In addition to natural cheeses, other dairy and non-dairy ingredients may be included in the blend. Processed cheese was initially manufactured without an emulsifying agent; the first attempt was as early as 1895, but only after the introduction of citrates, and especially phosphates, as emulsifying agents did the industrial production of processed cheese become feasible. Production started in Europe on the basis of a Swiss patent, using citrates, issued in 1912. The idea possibly originated from the Swiss national dish, Fondue, for which cheese is heat-treated (melted) in the presence of wine, which contains tartrate that has an emulsifying effect. Processed cheese was developed independently in the USA a few years later (1917) by Kraft, who processed Cheddar cheese with citrates and orthophosphates as emulsifying agents. The newly developed product enabled utilization of natural cheeses which otherwise would be difficult or impossible to utilize, e.g. cheeses with mechanical deformations, localized moulds, trimmings produced during cheese formation, pressing, packaging, etc. It also solved the problem of long-term storage of hard cheeses which otherwise would undergo excessive proteolysis, lipolysis and other detrimental changes, and are thus unsuitable for prolonged storage in their natural form. The assortment was further expanded due to numerous possible combinations of various types of cheese, not only hard varieties, and the inclusion of other dairy and non-dairy components which make it possible to produce processed cheese differing in consistency, flavour, size, and shape. The principal advantages of processed cheese compared to natural cheeses are: (i) reduced refrigeration cost during storage and transport, which are especially important in hot climates; (ii) better keeping quality, with less apparent changes during prolonged storage; (iii) great diversity of type and intensity of flavour, e.g. from mild to sharp, native cheese flavour or specific spices; (iv) adjustable packaging for various usage, economical and imaginative; (v) suitability for home use as well as for snack restaurants, e.g. in cheeseburgers, hot sandwiches, spreads and dips for fast foods. Processed cheeses are characterized essentially by composition, water content and consistency; according to these criteria, three main groups may be distinguished: processed cheese blocks, processed cheese foods and processed cheese spreads (Table I). More recently established sub-types of processed cheeses are: processed cheese slices and smoked processed cheese. The first sub-type belongs to the category of processed cheese blocks, while the second could be either block or spread. In addition, another group of processed cheese products should be mentioned, i.e. processed cheese analogues which are usually based on vegetable fat-casein blends. Finally, the most recent development in cheese processing is processed cheese with a completely new look, i.e. natural cheese-like appearance. Developed in France,4 this product has an open texture, similar to traditional cheeses, with eyes of about O¡¤ 5 mm in diameter. 3 EMULSIFYING AGENTS: TYPES AND ROLE Emulsifying agents (melting salts) are of major importance in processed cheese production where they are used to provide a uniform structure during the melting process, and also of the products. Phosphates, polyphosphates and citrates2,34-37 are most common but sodium potassium tartrate2,36 or complex sodium phosphates of the general formula XNa20,Y AI203,8P20s,ZH20 where X = 6-15, Y = 1,5--4, 5 and Z = 4--40,2 are rarely used. Sodium potassium tartrate, trihydroxyglutaric acid or diglycolic acid are sometimes used. Some characteristics of the most commonly used emulsifying agents are presented in These compounds are not emulsifiers in the strict chemical sense (i.e. they are not surface-active compounds), and since emulsification is not their only purpose, melting salts are conditionally termed 'emulsifying agents'. However, true emulsifiers may be included in commercially produced emulsifying agents, which are usually mixtures of compounds, their composition being protected by the producer. The essential role of emulsifying agents in the manufacture of processed cheese is to supplement the emulsifying capability of cheese proteins. This is accomplished by: (i) removing calcium from the protein system; (ii) peptizing, solubilizing and dispersing the proteins; (iii) hydrating and swelling the proteins; (iv) emulsifying the fat and stabilizing the emulsion; (v) controlling pH and stabilizing it; and (vi) forming an appropriate structure of the product after cooling. The ability to sequester calcium is one of the most important functions of emulsifying agents. The principal caseins in cheese (asl-' a s2-' f3-) have non-polar, lipophilic C-terminal segments, while the N-terminal regions, which contain calcium phosphate, are hydrophilic. This structure allows the casein molecules to function as emulsifiers. 38-40 When calcium in the Ca-paracaseinate complex of natural cheese is removed during processing by the ion-exchange properties of melting salts, insoluble paracaseinate is solubilized, usually as Na-caseinate. The equation shown earlier10 could be graphically presented as in Fig. 2. The affinity, i.e. sequestering ability, of common emulsifiers for calcium increases in the following order: citrate, NaH2P04, Na2HP04, Na2H2P20 7, Na3HP20 7, Na4P20 7, NaSP30 IO' During processing (prolonged heat treatment with agitation), polyvalent anions from the emulsifying agent become attached to the protein molecules, which increases their hydrophilic properties. The binding of additional quantities of water increases the viscosity of the blend, causing 'creaming'. In order to avoid emulsion destabilization, it is necessary to ensure that there is enough intact casein in the blend (a short, hydrolysed protein structure leads to phase separation). Polyvalent anions (phosphates, citrates) have a high water-adsorption ability They become bound, via calcium, to protein molecules providing them with a negative charge: basic salts also increase the pH of cheese. Both changes, i.e. increased negative charge and pH, result in higher water adsorption by the proteins. The concentrations of Ca and P are about twice as high in the insoluble phase of processed cheese as in the natural cheese from which it was made. The reactivity between the emulsifier and protein is defined by the ratio of insoluble to total proteins in the natural cheese and in the processed cheese.34 The affinity of protein for the cations and anions of melting salts is determined by the valency of the ions.41 Salts consisting of a monovalent cation and a polyvalent anion possess the best emulsifying characteristics. Although some salts have better emulsifying properties than others, they may have inferior calcium-sequestering abilities or may not solubilize and hydrate the protein sufficiently. It is necessary to combine two or more salts to achieve optimal emulsifying and melting characteristics simultaneously and to produce a homogeneous and stable processed cheese. An appropriate pH value is important for several reasons: it affects protein configuration, solubility and the extent to which the emulsifying salts bind calcium.38 The pH of processed cheese varies within the range 5¡¤0-6¡¤5. At pH ~ 5¡¤0, which is near the isoelectric point of the cheese proteins, the texture of the cheese may be crumbly, probably due to weakening of protein-protein interactions, but the incidence of fat emulsion breakage is reduced. At pH ~ 6¡¤ 5, the cheese becomes excessively soft and microbiological problems may be encountered also. The effect of pH on the texture of processed cheese was clearly demonstrated by Karahadian,42 using mono-, di- and trisodium phosphates, the respective pH of 1% solutions of which were 4¡¤2,9¡¤5 and no. Cheese made with NaH2P04 (low pH) was dry and crumbly, whereas cheese made with Na3P04 (high pH) was moist and elastic; the texture of cheese made with Na2HP04 was intermediate. Similar pH-dependent effects apply to other emulsifiers also.38 Some emulsifying agents exhibit bacteriological effects. Monophosphates have a specific bacteriostatic effect which is even more pronounced with higher phosphates and polyphosphates.1,2 Citrates lack such effects and may even be subject to bacterial spoilage. Since the usual heat treatment during processing is relatively mild, processed cheeses are not sterile; although the final product contains no viable bacteria, it may contain viable spores, including Clostridia, which may originate from the natural cheese or from added spices.1. 2,43 Irradiation of spices prior to usage is thus very important. Orthophosphates suppress the germination of Cl. botulinum spores in processed cheese whereas citrates have no effect. 44 Differences in processing conditions, e.g. type of emulsifier, pH and moisture level, also affect spore germination. The characteristics of individually melting salts and their mixtures have been studied extensively,l,43,44-55 3.1 Phosphates Two types of phosphates are used: (i) Monophosphates (orthophosphates), e.g. NaH2P04, Na2HP04 and Na3P04 and (ii) condensed polyphosphates: (a) poly-phosphates, (b) metaphosphates - rings, e.g. Na3P30 9 and Na4P40 12 and (c) condensed phosphates - rings with chains and branches. The ability to sequester calcium is closely related to the ability to solubilize protein. According to von der Heide,56 the solubilization of fat-free rennet casein was 30% with orthophosphate, 45% with pyrophosphate and 85% with polyphosphate. Similar findings were made by DaclinY The concentration of soluble nitrogen increased with the concentration of polyphosphates added in the range of 1_3%.58 Hydrolysis of polyphosphates to orthophosphates in processed cheese was evident after cooling. The calcium-sequestering ability of sodium meta phosphate is markedly lower than that of sodium tetrametaphosphate; a smooth homogeneous processed cheese is obtained with the latter salt. 59,60 Differences in depolymerization of casein and changes in the flow properties of processed cheese are related to differences in calcium complexation between mono- and tetrapolyphosphates. Melting rate, ultrafiltratable calcium concentration and textural properties (stress/relaxation, hardness, gumminess and elasticity) of processed cheese are affected more by varying the condensed phosphate than the polyphosphate concentrations,62 Sharpf 63 suggested that the emulsifying effect of chain phosphates is associated with their interaction with paracasein in such a way that phosphate anions form bridges between protein molecules. Newly developed phosphate/polyphosphate emulsifying agents, KSS-4 (pH = 4) and KSS-11 (pH = 11), were examined in four processed cheese plants; all the processed cheese blocks obtained, including smoked, were of excellent physicochemical, microbial and organoleptic quality.55 Processed cheese of good quality can be produced using 1 % of surface-active mono glyceride preparation in combination with 50% of the usual amount of phosphate.64 A processed cheese with improved rheological properties and storage stability can be produced using an emulsifier consisting of tripolyphosphate and monoglycerides.65 Addition of monoglycerides to the cheese blend increases the hydrophilic properties of the cheese immediately after processing, as well as during storage.66 All condensed polyphosphates hydrolyse in aqueous solutions; hydrolysis also occurs during melting and afterwards. The degradation of polyphosphates increases with the duration of processing, irrespective of the rate of stirring and the temperature usedY About 50% of the polyphosphates added are hydrolysed during the melting procedure and the remainder is hydrolysed after 7 to 10 weeks of storage.68 The hydrolysis of phosphates and polyphosphates in 1 % solution, as influenced by temperature, is shown graphically in a recently published book. 3.2 Citrates Of the many citrates available, only trisodium citrate, alone or in combination with other salts, is used as an emulsifying agent in processed cheese production, although citric acid may be used to correct the pH of the cheese. Potassium citrate imparts a bitter taste to the finished product. Monosodium citrate is reported2 to cause emulsion breakdown during cheese melting because of its high acidity, while disodium citrate leads to water separation during solidification of the melt, also because of high acidity. Comparison of the effects of sodium citrate, sodium citro-phosphate and sodium potassium tartrate on chemical changes in processed cheese showed35 that the highest and the lowest acidity were obtained with citro-phosphate and tartrate, respectively. Soluble nitrogen was higher in all three processed cheeses than in the initial natural cheese and was highest when Na citrate was used as emulsifier. Trisodium citrate and NaH2P04 have similar effects on cheese consistency and yield softer cheeses than several polyphosphates; the effect of the latter on cheese firmness increases with the degree of phosphate condensation.69 The effect of citrate, orthophosphate, pyrophosphate, tripolyphosphate and Graham's salt [(NaP03)n.HP] on the physicochemical properties of processed cheese were examined by Kairyukshtene et af.34 The pH values of 3% solutions of these salts were 8¡¤16, 8¡¤89, 6¡¤61, 9¡¤31 and 5-49, respectively. Soluble protein contents in processed cheese were increased and the water-binding capacity and plasticity of the cheese blends during processing were markedly improved by the use of alkaline salts. The finest fat dispersions were obtained with citrate, tripolyphosphate or orthophosphate in the processing of fresh curds or green cheese and by using citrate or Graham's salt with well-ripened cheese. Addition of citrate, orthophosphate, pyrophosphate or sodium potassium tartrate, all at 3%, to curds obtained from concentrated milk led to products with poor sensory attributes, although citrate at 2% gave satisfactory results.36 3.3 Salt Combinations As already mentioned, salt mixtures are used to combine the best effects of their individual components.43,45-47,49-53,55 Some early results49.5' seem to favour citrate in melting salt combinations, but more recent studies emphasize the desirable effects of phosphates. According to Shubin,49 a combination of sodium citrate, trihydroxyglutarate and Na2HP04 gave the best results in the manufacture of processed cheese. Earlier work5' showed that orthophosphates and pyrophosphates were generally unsatisfactory, whether used alone or in a combination, but citrate was useful to a limited extent; polyphosphates were satisfactory in every respect. Thomas et al.52 produced processed cheeses with a 3% addition of disodium phosphate, tetrasodium diphosphate, pentasodium triphosphate or trisodium citrate or equal quantities of sodium polyphosphate and tetrasodium phosphate. The general acceptability of all cheeses was about the same, but cheeses made with disodium phosphate, tetrasodium diphosphate or pentasodium triphosphate had elevated contents of water-soluble nitrogen compared to other cheeses. When the melting salts were used at 2 or 4%, no differences were detected in the levels of water-soluble nitrogen in any of the processed cheeses or in their stickiness, crumbliness, sliceability or general acceptability. In general, polyphosphates yield processed cheese with superior structure and better keeping quality than other emulsifying agents,45 apparently due to their ability to solubilize calcium paracaseinate because of their high calciumsequestering capacity. Pyrophosphates and, in particular, orthophosphates contribute undesirable sensory attributes to processed cheese and although citrates are as efficient as emulsifiers as polyphosphates, they lack their bacteriostatic effect. Sood & Kosikowski53 investigated the possibility of replacing cheese solids with untreated or enzyme-modified skim milk retentates in the manufacture of processed Cheddar cheese. Casein in the retentates was largely insoluble and therefore the retentates cannot be used alone for processing. However, cheese containing up to 60% of retentate solids (treated with fungal protease and lipase preparations) had better sensory attributes than the reference cheese; a combination of sodium citrate (2¡¤7%) and citric acid (0¡¤3%) was the best emulsifier for retentate-containing cheese. Increasing the retentate content to 80% resulted in an unacceptable product with a hard, long-grained texture. Effects of heating/shearing cheese (protein) Heating (to temperatures applied to processed cheese manufacture) and shearing of natural cheese usually results in the formation of a heterogeneous, gummy, pudding-like mass that undergoes extensive oiling-off and moisture exudation during manufacture and on cooling. These defects arise from the following. • Further dehydration/aggregation and shrinkage of the para-casein/casein matrix as affected by (a) increased hydrophobic interactions as induced by the relatively low pH of cheese (for most cheeses, ¡4.6–5.6) and high temperature applied during processing, (b) the precipitation of soluble (serum) calcium and phosphate, leading to further calcium/phosphate-mediated interactions between the para-casein molecules (especially in rennet-curd cheeses), and (c) the consequential decline in pH and negative charge. • Destabilisation of the native milk fat emulsion, formation of non-globular fat, and lique faction and coalescence of the latter, due to physical damage to, and removal of, the NMFGM. • The absence of an active emulsifying agent to re-emulsify the free fat. The above effects may be considered as a more extreme form of the shearing/heating applied to the curd during the manufacture of ¡®pasta-filata¡¯ cheeses where the heating conditions (e.g. heating at 57–60◦C while kneading/stretching with screw type augers or baffles) of the curd at the desired pH (5.3–5.8, depending on the calcium-to-casein ratio) are applied to provide a controlled aggregation of the curd protein to form fibres and limited coalescence of fat to impart the desired stringiness and free oil when the finished cheese (e.g. Mozzarella, pizza cheese, string cheese) is subsequently cooked on pizza (Guinee, 2003; Kindstedt et al., 2004). Indeed, the effect of heating as a means of providing controlled protein destabilisation and moisture expulsion are exploited in several areas of dairy product/ingredient manufacture (e.g. protein recovery from milk in the form of casein powders, moisture regulation in cheese), while shearing of native fat globules is the basis of fat recovery from cream as butter or anhydrous butteroil. |
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