The viscoelastic properties of processed cheeses depend on their thermal history and fat polymorphism.

Both the composition and the thermal kinetics that are applied to processed cheeses can affect their texture. This study investigated the effect of the storage conditions and thermal history on the viscoelastic properties of processed cheese and the physical properties of the fat phase. The microstructure of processed cheese has been characterized. Using a combination of physical techniques such as rheometry, differential scanning calorimetry, and X-ray diffraction, the partial crystallization of fat and the polymorphism of triacylglycerols (TG; main constituents of milk fat) were related to changes in the elastic modulus and tan δ as a function of temperature. In the small emulsion droplets (<1 µm) dispersed in processed cheeses, the solid fat phase was studied at a molecular level and showed differences as a function of the thermal history. Storage of processed cheese at 4 °C and its equilibration at 25 °C lead to partial crystallization of the fat phase, with the formation of a ß' 2 L (40.9 Å) structure; on cooling at 2 °C min(-1), the formation of an α 3 L (65.8 Å) structure was characterized. The cooling of processed cheese from 60 to -10 °C leads to the formation of a single type of crystal: α 3 L (72 Å). Structural reorganizations of the solid fat phase characterized on heating allowed the interpretation of the elastic modulus evolution of processed cheese. This study evidenced polymorphism of TG in a complex food product such as processed cheese and allowed a better understanding of the viscoelastic properties as a function of the thermal history.

Crystallization and polymorphism of triacylglycerols contribute to the rheological properties of processed cheese.

The thermal, rheological, and structural behaviors of a spreadable processed cheese were studied by complementary techniques including differential scanning calorimetry (DSC), rheology, and X-ray diffraction as a function of temperature. In this product, fat is present as a dispersed phase. Thermal and rheological properties were studied at different cooling rates between 0.5 and 10 degrees C min(-1) from 60 to 3 degrees C. Crystallization properties of fat were monitored at a cooling rate of -2 degrees C min(-1) from 60 to -10 degrees C. Fat triacylglycerols (TGs) crystallized at 15 degrees C in a triple-chain length 3Lalpha (72 A) structure correlated to exothermic events and to the sudden increase in the rheological moduli G' and G''. Upon heating at 2 degrees C min(-1), the polymorphic transition of TGs evidence the melting of the 3Lalpha structure and the formation of a 2Lbeta' (36.7-41.5 A) structure. Melting of the latter follows. These transformations coincide with thermal events observed by DSC and the decrease in two steps of the rheological moduli. The influence of fat crystallization, melting, and polymorphism upon the viscoelastic properties is clearly demonstrated upon both heating and cooling.

Crystallization properties and polymorphism of triacylglycerols in goat's milk fat globules.

The sensorial, functional, and nutritional properties of goat dairy products result from the specific fatty acid composition of goat's milk fat. However, information on the physical and thermal properties of goat's milk fat is scarce. In this study, crystallization of triacylglycerols (TG) in goat's milk fat globules was investigated using polarized light microscopy and the coupling of time-resolved synchrotron radiation X-ray diffraction (XRD) and high-sensitivity differential scanning calorimetry (DSC). The molecular organization of the solid fat phase was characterized for cooling rates between 3 and 0.1 degrees C/min. Quenching of goat's milk fat globules from 50 to -8 degrees C and 4 degrees C was also examined to identify the most unstable polymorphic forms of TG. Then, the melting behavior of fat crystals was studied on subsequent heating at 1 degrees C/min. Triple chain length (3L: 68.6-70 A) and double chain length (2L: 37-45.4 A) structures were characterized and 5 polymorphic forms, alpha, sub-alpha, beta' 1, beta' 2, and beta were identified. Polymorphic transitions were observed within goat's milk fat globules as a function of time after quenching and as a function of temperature on heating. From a technological point of view, this work will contribute to a better understanding of the rheological properties as well as on the flavor evolutions of goat's milk-based products.

Anhydrous goat's milk fat: thermal and structural behaviors studied by coupled differential scanning calorimetry and X-ray diffraction. 2. Influence of cooling rate.

Crystallization and melting properties of triacylglycerols (TGs) in anhydrous goat's milk fat (AGMF) are investigated by X-ray diffraction as a function of temperature (XRDT) coupled with high-sensitivity differential scanning calorimetry (DSC), using synchrotron radiation and Microcalix. The polymorphic behavior of AGMF was monitored by varying the cooling rates between 5 and 1 degrees C/min from 45 to -20 degrees C with their subsequent melting at 1 degrees C/min. Quenching of AGMF at -20 degrees C was also examined to determine the metastable polymorphic form of AGMF. At intermediate cooling rates, TGs in AGMF crystallize, from about 18 degrees C in two different lamellar structures with triple chain length 3Lalpha stacking of 72 A and a double chain length 2Lalpha stacking of 48 A, which are correlated to two overlapped exothermic peaks recorded by DSC. A reversible transition sub alpha <--> alpha was observed. Subsequent heating at 1 degrees C/min shows numerous structural rearrangements before final melting. At fast cooling of AGMF (5 degrees C/min), similar unstable crystalline varieties are formed while three endotherms are recorded. Several new unstable lamellar structures are observed after quenching. All of these data are compared to those previously reported at slow cooling (0.1 degrees C/min) showing a relative stability of the structures formed. In spite of general similitude, the thermal and structural behavior of the goat's milk is more complex than that of the cow's milk.

Milk fat and primary fractions obtained by dry fractionation 1. Chemical composition and crystallisation properties.

The chemical composition and crystallisation properties of milk fat and its primary fractions, obtained by dry fractionation at 21 degrees C, were investigated. The solid fraction (stearin) and the liquid fraction (olein) displayed a different triacylglycerol (TG) composition. Stearin fraction was enriched in long-chain fatty acids, whereas olein fraction was enriched in short-chain and unsaturated fatty acids. Crystallisation properties of milk fat, and both the stearin and olein fractions were studied on cooling at |dT/dt|=1 degrees C min(-1) by differential scanning calorimetry and time-resolved synchrotron X-ray diffraction (XRD) at small and wide angles. Two main types of crystals corresponding to double chain length structures were characterised in the stearin fraction: alpha 2L(1) (47.5 Angstrom) and beta' 2L(2) (41.7 Angstrom). A triple chain length structure was formed in the olein fraction: alpha 3L (72.1 Angstrom). Crystallization of milk fat showed the formation of two 2L (47.3 and 41.6 Angstrom) and one 3L (72.1 Angstrom) lamellar structures with an hexagonal packing (alpha form). A schematic representation of the 3L packing of olein fraction was proposed to explain how a wide diversity of TG can accommodate to form a lamellar structure with a thickness of 72 Angstrom. Furthermore, the sharpness of the small-angle XRD lines associated to the alpha form was explained by the formation of liquid crystals of smectic type.

A long ripple phase in DLPC-decylglucoside mixture evidenced by synchrotron SAXS coupled to DSC.

For the first time, the secondary ripple phase in a system containing dilauroyl phosphatidylcholine (DLPC) is observed by small-angle X-ray diffraction (SAXS). The SAXS profile exhibits many well-resolved peaks. The fast formation of this phase upon cooling from the liquid crystalline lamellar phase L(alpha) is induced by addition of C10G with molar ratio 0.17< or = R = [C10G]/[DLPC]< or = 0.49. For R < 0.17, the primary P(beta') ripple phase is observed. In contrast to the P(beta') phase, which shows a sawtooth shape, the secondary ripple structure is thought to be symmetric. The ripple length (190 angstroms) and the bilayer spacing (74 angstroms) are larger than in the primary ripple phase. Lattice parameters of the new long ripple phase, which are quite insensitive to temperature, vary slightly linearly with R. In this study, structural and thermodynamic changes within the samples were followed as a function of temperature by time-resolved X-ray diffraction coupled to DSC.

Anhydrous goat's milk fat: thermal and structural behavior. 1. Crystalline forms obtained by slow cooling.

The thermal and structural behaviors of anhydrous goat's milk fat (AGMF) have been determined as a function of temperature using a powerful technique allowing simultaneous time-resolved synchrotron X-ray diffraction as a function of temperature (XRDT) and high-sensivity differential scanning calorimetry (DSC) measurements from the same sample. This first paper, aiming at the characterization of the physical properties of AGMF, we examine crystalline organizations made by triacylglycerols (TG) upon slow cooling at /dT/dt/ = 0.1 degrees C/min from 45 to -20 degrees C in order to approach system equilibrium. Three overlapped exotherms were observed by DSC upon cooling, whereas four endotherms were found on the subsequent heating at 1 degrees C/min. XRDT evidenced that AGMF crystallizes under four different lamellar structures, two with double-chain length packings at 41.5 and 38.2 angstroms and two with triple-chain lengths of 72 and 64.7 angstroms stacking. Simultaneous wide-angle XRDT has shown that initial nucleation mainly occurs in a packing of beta' type from approximately 26 degrees C, although some transient presence of alpha was detected. The absence of polymorphic transition, on heating, until final melting (approximately 40 degrees C) demonstrated the relative stability of the structures formed.

Interaction between artificial membranes and enflurane, a general volatile anesthetic: DPPC-enflurane interaction.

The structural modifications of the dipalmitoylphosphatidylcholine (DPPC) organization induced by increasing concentration of the volatile anesthetic enflurane have been studied by differential scanning calorimetry, small-angle, and wide-angle x-ray scattering. The interaction of enflurane with DPPC depends on at least two factors: the enflurane-to-lipid concentration ratio and the initial organization of the lipids. At 25 degrees C (gel state), the penetration of enflurane within the lipids induces the apparition of two different mixed lipid phases. At low anesthetic-to-lipid molar ratio, the smectic distance increases whereas the direction of the chain tilt changes from a tilt toward next-neighbors to a tilt between next-neighbors creating a new gel phase called L(beta')(2NNN). At high ratio, the smectic distance is much smaller than for the pure L(beta') DPPC phase, i.e., 50 A compared to 65 A, the aliphatic chains are perpendicular to the membrane and the fusion temperature of the phase is 33 degrees C. The electron profile of this phase that has been called L(beta)(i), indicates that the lipids are fully interdigitated. At 45 degrees C (fluid state), a new melted phase, called L(alpha)(2), was found, in which the smectic distance decreased compared to the initial pure L(alpha)(1) DPPC phase. The thermotropic behavior of the mixed phases has also been characterized by simultaneous x-ray scattering and differential scanning calorimetry measurements using the Microcalix calorimeter of our own. Finally, titration curves of enflurane effect in the mixed lipidic phase has been obtained by using the fluorescent lipid probe Laurdan. Measurements as a function of temperature or at constant temperature, i.e., 25 degrees C and 45 degrees C give, for the maximal effect, an enflurane-to-lipid ratio (M/M), within the membrane, of 1 and 2 for the L(alpha)(2) and the L(beta)(i) lamellar phase respectively. All the results taken together allowed to draw a pseudo-binary phase diagram of enflurane-dipalmitoylphosphatidylcholine in excess water.

Characterization of fluorescein isothiocyanate-dextrans used in vesicle permeability studies.

Fluorescein Isothiocyanate-dextrans of various weight average molecular masses (4,400-487,000) were analyzed in buffer solution for pH, osmolarity, fluorescence intensity as a function of the polymer concentration, average molecular masses, and radii of gyration. Labeling of polymers and conformation of the polymers were characterized by high-performance gel exclusion chromatography (HPLC-GEC) and small-angle X-ray scattering. The fluorescence measurements evidence the absence of fluorescence quenching of the FITC chromophores but the existence of an inner filter effect at high polymer concentration. The conformation of the polymers in buffer is very likely of random coil type, as shown by the relationship between the radii of gyration and the weight-average molecular masses of the dextrans (Mw). The medium used to analyze the FITC-dextrans by HPLC-GEC strongly influences their elution behavior. In buffer medium, they are sieved over the TSK G4000 PW column through a single population according to their Mw. whereas in pure water, they are separated into several species by an exclusion mechanism that depends on the number of labeled sites per dextran molecule. A Monte Carlo simulation was used to analyze the distribution of the fluorescent labels. HPLC-GEC in water could interestingly be applied to yield labeled polymers bearing a known number of functionalized groups.

Thermal and structural behavior of milk fat. 3. Influence of cooling rate and droplet size on cream crystallization.

Crystallization of triacylglycerols (TG) within milk fat globules of creams is studied with an instrument coupling time-resolved synchrotron X-ray diffraction (XRDT) at both small and wide angles and high-sensitivity differential scanning calorimetry (DSC) at cooling rates of -3 and -1 degrees C/min from 60 to -10 degrees C and compared to that of the anhydrous milk fat (AMF). Simultaneous thermal analysis permits correlation of the formation of the different crystalline species monitored by XRDT to the DSC events. Under the above cooling conditions, milk fat TG sequentially crystallize, within the globules, from about 19 degrees C, in three different lamellar structures with double-chain length (2L) stackings of 47 and 42 A and a triple-chain length (3L) stacking of 71 A, all of alpha type, which are correlated to two or three overlapped exothermic peaks recorded by DSC. Compared to what is observed for AMF, TG crystallization in emulsion (i) favors sub-alpha formation at low temperature and (ii) induces layer stacking defects in 3L crystals. Subsequent heating at 2 degrees C/min shows numerous structural rearrangements before final melting, confirming that (i) cooling at -1 degrees C/min leads to the formation of unstable crystalline varieties in the dispersed state and (ii) a monotropic transition alpha-->beta' takes place. Similar behavior is observed for cooling at -3 degrees C/min and subsequent heating. An overall comparison of the thermal and structural properties of the crystalline species formed as a function of the cooling rate, between >1000 and 0.15 degrees C/min, and stabilization time at 4 degrees C is given. Depending on the cooling rate, at least five crystalline subcell species are observed at wide angles, alpha and sub-alpha, two beta' and one beta. At small angles, at least six lamellar stackings are identified, three 3L and three 2L. However, a single subcell packing (e.g., alpha) might correspond to several longitudinal chain stackings, demonstrating the usefulness of the small-angle XRD technique. Reconstituted emulsions homogenized under different pressures are used to determine the influence of droplet size on crystallization. The decrease of droplet size induces (i) a higher supercooling/supersaturation and (ii) a higher disorder and/or a smaller size of TG crystals within the emulsion droplets. At the supramolecular scale, polarized light microscopy shows that various cooling rates applied in situ using a temperature-controlled stage directly influence crystal sizes and their type of organization within milk fat globules. The faster the cooling rate, the smaller the size of the crystals within the globules.

Thermal and Structural Behavior of Milk Fat.

Milk fat crystallization was studied using X-ray diffraction as a function of temperature (XRDT) and differential scanning calorimetry (DSC) analysis considering crystals formed during slow cooling of natural milk fat globules of cream. During cooling at |dT/dt|=0.15 degrees C/min from 55 to -8 degrees C, the crystalline varieties formed in fat globules by triacyglycerols (TGs) correspond to two double-chain-length organizations (2L) of 46.5 and 40 Å and to two triple-chain-length stackings (3L) of 71.3 and 65 Å. Nucleation occurs in the alpha form; then the alpha+beta' polymorphic forms coexist until the end of the cooling. The four crystalline varieties start to form within a 10 degrees C range, from about 21 degrees C, preventing separation of overlapped peaks by DSC recording. In a second step, the sample of cream was heated at 2 degrees C/min in the range -8 to +60 degrees C to follow the melting behavior of the crystals. XRDT measurements show the progressive transformations of the crystalline varieties correlated with endotherms and exotherms recorded by DSC. The 40-Å structure takes advantage of the melting of the other species to grow until its melting. The comparison made with anhydrous milk fat behavior under the same conditions shows that crystallization is different in emulsion and in bulk. Copyright 2001 Academic Press.