TRIACYLGLYCER RESULTS AND DISCUSSIONS

C. TRIACYLGLYCER

Cocoa butte gives it its special component is shown Figu There are th and SOS where P Wennermark, 2002 comprising about 2 C18:1, with mino chocolates were d chocolates. The CB chocolates. The chr shown in Figure 6 Chocolate A, B, an milk chocolate is s Chocolate C, F,an white chocolates Ch YCEROL COMPOSITION butter has a very special triacylglycerol composition al texture and sensory properties. The cocoa but hown by its chromatogram in Figure 5. Figure 5. The Chromatogram of Cocoa Butter three dominant triacylglycerols in cocoa butter, P P = palmitic acid, O = oleic acid and S = ste 2002. Cocoa butter has a unique composition, its f 25 palmitic C16, 36 stearic C18 and 35 inor amounts of other fatty acids. In this re s divided into two class: CB chocolates and B chocolates were further divided to dark, milk, hromatogram of Chocolate A which is dark choc 6. This figure i s the representative of dark and H. Also, the chromatogram of chocolate C s shown in Figure 7. that represent the milk c ,and I. The chromatogram of chocolate D that Chocolate D and G are shown in Figure 8. 64 ition, which butter TAGs , POP, POS stearic acid s fatty acids nd 35 oleic e search, the nd non CB k, and white chocolate is rk chocolate C which is k chocolates at represent Figure 6. Th Figure 7. Th Figure 8. Th Based on th chocolates have sim dominated by the thr Chocolate C, D, F, There are many sma This finding implies 10 20 nRIU 10000 20000 30000 40000 50000 RID1 A, Refractive Index Signal 19-03-09 10 20 nRIU 10000 20000 30000 40000 50000 60000 RID1 A, Refractive Index Signal 18-03-09 The Chromatogram of Dark Chocolate, Chocolate The Chromatogram of Milk chocolate, Chocolate The Chromatogram of White Chocolate, Chocolate on the chromatograms, it can be characterized imilar triacylglycerol component with cocoa butte three StUSt; POP, POS, and SOS. Milk and white c F,G, H and I have the same peaks in their chrom mall peaks before POP peak are seen in the chrom ies that since the difference between dark chocola 20 30 40 50 60 19-03-09\RSM-1.D 20 30 40 50 60 18-03-09\TOBW-1.D POP POS SOS POP SOS POS 65 ate A te C ate D d that dark butter which is nd white chocolat e omatogram. omatograms. late to milk min min 66 and white chocolate is the m ilk fat content, it may concluded that the small peaks are the present of the milk fat which is extracted by the solvent. According to Simoneau and German 1996, the milk fat contained triacylglycerol species ranging from C24 to C54. About 35 of the tota l triacylglycerols were long chain C 42. Within these long -chain triacylglycerols, 60 were unsaturated species. The wide range of triacylglycerols in milk fat results in incomplete miscibility in the solid phase. The solid phase behaviour of milk fat has been explained in terms of three fractions high -melting, middle-melting, and low- melting of largely independently -melting solid solutions and is directly related to the molecular composition of milk fat. In this research, the high - melting fraction of milk fat has been included in the triacylglycerol composition of chocolate and the middle -melting fraction of milk fat only partly extracted. The non-CB based chocolates are milk chocolates. Their extract have been analyzed to their triacylglycerol compos ition and surprisingly, the chromatograms of them were quite different with cocoa butter. The chromatogram of Chocolate J that represent the non -CB chocolates Chocolate E, J, K, L, and M is shown in Figure 9. Figure 9. The Chromatogram of Non-CB Chocolate Figure 9 shows that the non-CB chocolates have different chemical composition, triacylglycerol components with cocoa butter. Since there are min 10 20 30 40 50 60 nRIU 10000 20000 30000 40000 50000 60000 70000 80000 RID1 A, Refractive Index Signal 29 -07-09\FON1.D 1 = CaLaLa CLaM 2 = LaLaLa 3 = LaLaM 4 = LaLaO 5 = LaLaPLaMM 6 = LMMLaOM 2 1 3 4 5 6 67 three kind of cocoa butter alternatives that in general term applied to confectionery fats, only two kind of CBA, CBR and CBS that have different triacylglycerol component with cocoa butter. CBR, a non lauric fats with a distribution of fatty acids simila r to that of CB but a completely different triacylglycerol structure; due to this different chemical composition they may be added to cocoa butter only in a small amounts. CBS with some physical similarities but chemically totally different from cocoa butt er; due to this they are suitable only for whole replacement of CB Spangenberg, 2001. The triacylglycerol component of the non-CB chocolates reflects similar to the palm kernel and coconut oil triacylglycerol components which are dominated by lauric bas ed fats Noor Lida et. al., 2002. As the matter of fact that CBA, which is made from modification hydrogenated or fractionation of palm kernel and coconut oil is CBS, it may be concluded that the non-CB chocolates are wholy consisting of CBS lauric ba sed fats. In this research, the triacylglycerol components are determined by using the triacylglycerol standard that have been done by Renata 200 9. The triacylglycerol standard is the mixture of single standard PPP, OOO, OOS, SSS, OOP with cocoa butte r POP, POS, SOS, SOA, fully hydrogenated soybean oil PPS, PS, palm kernel oil and refining bleaching deodorized palm oil CaLaLa, CaLaM, LaLaLa, LaLaM, LaLaO, LaLaPLaMM, MLL, MMLLaOM, MMMLaPM, LMO LaOO, MPLLaOPMMO, LaPPMMP, PLO, PPL. The chroma togram of triacylglycerol standard is given in Appendix X . The retention time of each tri acylglycerol component is used as the standard to identify the tri acylglycerol in chocolate samples. The retention time of each standard is given in Table 9. The perc entage of TAGs are defined by their area of each component per total area of TAGs. 68 Table 9. Retention Time of Triacylglycerol Standard Peak Retention Time Triacylglycerol Component Peak Retention Time Triacylglycerol Component 1 11.161 CaLaLa 15 29.418 OOO 2 12.338 CaLaM 16 30.705 POO 3 13.660 LaLaLa 17 31.501 PLS 4 15.535 LaLaM 18 32.097 POP 5 17.247 LaLaO 19 34.073 PPP 6 17.865 LaLaPLaMM 20 36.642 SOO 7 18.787 MLL 21 37.497 SLS 8 19.853 MMLLaOM 22 38.197 POS 9 20.701 MMMLaPM 23 40.608 PPS 10 22.165 LMOLaOO 24 45.766 SOS 11 23.060 MPLLaOPMMO 25 48.388 PSS 12 24.212 LaPPMMP 26 55.186 SOA 13 25.635 PLO 27 58.079 SSS 14 26.731 PLP Ca = caprilic acid; La = lauric acis; M = mirystic acid; P = palmitic acid; S = stearic acid; O = oleic acid; L = linoleic acid; Ln = linolenic acid; A = arachidic acid. Moreover, the triacylglycerol component identification can not be determined by using the triacylglycerol standard itself because the retention time of each samples is different due to its composition and area. The higher of area in TAGs will result in different retention time. In addition, the triacylglycerol identification can be achieved by using additional datas such as triacylglycerol component of cocoa butter and CBS that have been analyzed by other researchers. Chocolate triacylglycerol components are determined using combination of triacylglycerol standard and cocoa butter triacylglycerol component according to Lipp and Anklam 1998 b. Although the chocolates have the same triacylglycerol components, they can be differentiated by its composition. Each chocolate has different triacylglycerol composition that can affect to its p hysical properties. Three main TAGs composition is given in Figure 10. Figure 10. The Dark chocola POP, POS, and POS to have higher cont which only contain a its fat based has lea the other hand, Cho lower POS and SOS vegetable fat in it tha Moreover, ac 3 chocolates that ha are Chocolate F, H, chocolate F, with chocolate POS co respectively. The pr manufacturer are CB Chocolate H and I, 3 triacylglycerol comp This study suits to t the pure and comm C52 POS contents 15 15.7 39.8 41 28.5 5 10 15 20 25 30 35 40 45 CB A T A G a re a Area of TAGs: POP, POS, and SOS of CB -cho olates, chocolate A and B seemed to have the mor OS composition to cocoa butter. T he POP and ontent than milk chocolates. The fact that dark c n a little amount of milk powder and mostly cocoa ead to the similarity TAG composition to cocoa but hocolate I, which is also dark chocolate, have hig OS than other dark chocolates. This is due to the a that might have different composition with cocoa but according to the in formation label of the products have any vegetable fat addition besides cocoa but H, and I. Based on the triacylglycerols component h POS 38.2 has no big difference to the ot composition, Chocolate C and D, 37.7 and product s’ label inform that the vegetable fat us CBEs, which are Palm, Illipe, and Shea. On the I, 30.7 and 24.0 respectively, have significant omponent POS to the whole cocoa butter milk o the Bohacenko et. al. ’s 2005 study, which dem mercially produced cocoa butter equivalents show nts than genuine CBs. Surprisingly, Chocolate G th 15.7 15.1 12.2 12.8 13.4 13.4 15.9 41 41.4 37.7 38.6 38.2 35.6 31 27.9 30.1 29.7 30.5 29.2 31.1 A B C D F G H Chocolate 69 chocolates ore similar nd POS tends k chocolate, coa butter in a butter. On higher POP, addition of a butter. oducts, there are butter . They ent of them, other milk nd 38.6 used by the the contrary, ant different k chocolate. demonstrated show lower G that has no 15.9 16.6 31 36.5 30.7 24 H I POP POS SOS any vegetable fat ad Chocolate C and D. Triacylglyce consist of POP, POS such as POO, SOO, of it. The TAGs ha triacylglycerols St triacylglycerols StU2 StStSt such as PLP in Figure 11. Fi Figure 12 85.1 70.0 75.0 80.0 85.0 90.0 CB T A G a re a 1.5 1.1 8.1 9.7 1.9 1.5 0.0 2.0 4.0 6.0 8.0 10.0 12.0 CB A T A G a re a addition mentioned in the label has lower POS, 35. . cerols composition such a complex system that POS, and SOS. Cocoa butter also consists of othe OO, SOA, and others that also contribute to the cha have been summarized to some groups: monouns StUSt such as POP, POS, SOS, PLO; diuns StU2 such as POO, SOO; and saturated triacy LP, SSS, PSS, and PSS. The StUSt of chocolate Figure 11 . The StUSt of CB-chocolates 12 . The StStSt, StU2, and U3 of CB Chocolates 85.1 86.3 88.2 81.2 83.6 82.6 81.7 79.5 CB A B C D F G H Chocolate StUSt 1.2 2.4 2.1 2.1 2.1 2.7 1.6 9.7 8.3 7.5 7.2 7.7 7.6 6.9 11.2 1.5 0.9 2.0 1.5 1.7 1.8 1.3 A B C D F G H Chocolate 70 35.6 than hat not only other TAGs haracteristic onounsaturated diunsaturated cylglycerols ates is given tes 79.5 78.4 H I 1.6 11.2 2.4 I StStSt StU2 U3 71 Based on Figure 12, Chocolate B has the highest StUSt, 88.2 followed by Chocolate A and cocoa butter, 86.3 and 85.1 respectively. Chocolate H has the lowest amount of StUSt, 78.4. A study literature from Shukla 1995 implies that the higher monounsaturated triacylglycerol will result in the higher hardness and melting profiles. In addition, although saturated, diunsaturated, and polyunsaturated triacylglycerols only contained in small amount, they also contribut e to the melting properties of chocolates. Higher saturated TAG can give higher melting property because of its saturated and long chain triacylglycerols make them harder to be melt. In contrast, the higher diunsaturated and polyunsaturated could give lower melting properties to the chocolates due to the presence of double bond in the TAGS. Table 10 gives the triacylglycerol composition of CBS chocolates, Chocolate E, J, K, L, and M. According to Noor Lida et. al. 2002 cocoa butter substitute CBS is dominated by palm kernel oil TAGs composition, LaLaLa, LaLaM, CaLaLa, CLaLa, LaLaPLaMM, and LaLaO. Table 10. The Triacylglycerol Composition of non CB Chocolates TAGs area M J E K L CaLaLa CLaM 14.4 13.5 12.8 13.9 12.3 LaLaLa 19.8 20.3 18.7 20.5 11.9 LaLaM 16.1 17.8 16.3 16.8 9.1 LaLaO 12.4 14.2 13.4 12.7 11.5 LaLaPLaMM 8.6 9.7 9.9 8.4 11.4 LMMLaOM 6.3 6.7 7.9 5.7 11.5 MMM LaPM 5.9 5.5 7.4 5.0 13.6 LMO LaOO 1.9 1.4 0.5 2.1 1.2 LPMLaOPMMO 2.7 2.5 3.5 2.3 5.0 LaPPMMP 1.6 1.0 0.5 1.9 1.0 Others 10.1 7.5 9.1 10.5 10.8 Ca: Capric; La: Lauric; M: Myristic; L: Linoleic; P: Palmitic; O: Oleic The triacylglycerol compositions definitely explain that Chocolate E, J, K, L, and M are made from CBS or lauric type -fat. Lauric-type specialty fats are produced from oils containing mainly of triacylglycerols of lauric and 72 myristic acids. For instance, hydrogenation of palm kernel oil produces a range of lauric-type fats with slip melting point SMP varying from 32 to 41°C. This study suits to those chocolates that have higher slip melting point than others. The high SMP of chocolates is due to the presence of saturated acid, lauric acids and myristic acids. Based on the international regulation about permitted vegetable fa t addition to chocolate, Chocolate E, J, K, L, and M should not be claimed as a chocolate. Surprisingly, Chocolate E that involved in middle -price chocolate also is a non CB chocolate. It should be noted that all the chocolate samples taken were the produc ts renowned manufacturers, expected to observe the directive to give a real chocolate product to the consumer. Chocolate E, J, K, L, and M still could be called milk chocolate according to SNI 01 -4293-1996 since there is no any requirement about cocoa butt er using. Consequently, these products cannot be sold in other countries especially U.K, Canada, Europe, and U.S which have a strict regulation about chocolate.

D. SOLID FAT CONTENT