‘3. W. . I. . :97: V 0 1.221 A. .1. 3.3:. Em A ‘ _ ”a ...:o:.fl\!.. t iiiiiiiiiiii ’1’! This is to certify that the thesis entitled EFFECTS OF CHLORINATION 0N FLOUR RHEOLOGICAL PROPERTIES AND ON BAKING QUALITIES 0F HIGH-RATIO AND JAPANESE-SPONGE CAKES presented by Scott Thomas Worthington has been accepted towards fulfillment of the requirements for Masters Food Science degree in MR \Wajo‘gprofessgr Date OCtObe" 14, 1994 0-7639 MS U i: an Affirmative Action/Equal Opportunity Institution LIBRARY Michigan State Unlverslty PLACE ll RETURN BOXtomnauthl-chockouflunyum TO AVOID FINES Mum on or Moro dd. duo. DATE DUE DATE DUE DATE DUE EFFECTS OF CHLORINATION ON FLOUR RHEOLOGICAL PROPERTIES AND ON BAKING QUALITIES OF HIGH-RATIO AND JAPANESE-SPONGE CAKES BY Scott Thomas Worthington A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Food Science and Human Nutrition 1994 .ABSTRACT EFFECTS OF CHLORINATION ON FLOUR RHEOLOGICAL PROPERTIES AND ON BAKING QUALITIES OF HIGH-RATIO AND JAPANESE-SPONGE CAKES BY Scott Thomas Worthington In this study, thirteen soft wheat flour samples were chlorinated to pH 4.8 and pH 4.3, and were analyzed for their rheological preperties and baking potentials. Sedimentation volumes indicated a weakening of the gluten proteins with chlorination, and alkaline water retention capacity (AWRC) tests showed an increase in AWRC (%) with chlorination. Rheological tests were performed on chlorinated and unchlorinated flours. .Alveograph. meaSurements indicated modification to starches and proteins causing increased resistance (P) and stability (P/L), and decreasing extensibility (L) and elasticity (G). Farinograph measurements showed increased.water absorption in chlorinated flours due to modification to starch granules, and increased peak times which also can be attributed to modifications of the proteins and starch granules. Mixograph measurements showed significant decreases in peak time with chlorination which may be attributed to the constant addition of water to treatments with increasing water absorptions. Decreases in peak time may be due to decreases in protein strength as seen in sedimentation volumes. Viscoamylograph measurements indicated significant changes:to the starch components gelling and pasting properties only when the flour was overchlorinated (pH 4.3). The baking potentials of the flours were measured with.high-ratio and.Japanese sponge cake formulas. IHigh-ratio cakes had peak volume and symmetry from cakes baked from the pH 4.8 flours. Japanese-sponge cakes produced optimum volumes from unchlorinated flours but better symmetry was observed from the cakes produced from chlorinated flours. Dedicated to my parents, John and Gayle Worthington, who have made my education possible by their continual love and support. iv ACKNOWLEDGEMENTS Sincere gratitude is expressed to my advisor, Dr. Perry K.W. Ng, for his guidance throughout my research project. I would also like to thank the members of my advisory committee, Drs. Jerry N. Cash, Patrick L. Finney, and William C. Haines for their interest and suggestions. Grateful appreciation is extended to Dr. Christine J. Bergman, Mr. Luis M. Rayas, Dr. Nirmal K. Sinha, and Mr. Hiroshi Yamamoto for their support, guidance and technical expertise with this research. Finally, I would like to thank my parents, sister, and relatives for their continual love and support throughout my education. THUBLE:14.5% moisture) will not store well for more than a week or two due to increased microbial activity. Flours around 13% moisture content have better storage properties under cool dry conditions (Manley 1991) . 27 28 Table 1. Ash, Moisture and Protein Contents of 13 Control Flour Samples Variety Ash" Moisture Protein" (96) (96) (96) lFall 1992 Rely 0.40 12.4 8.2 Crew 0.39 12.0 7.2 Kmor 0.37 12.2 7.8 Lewiain 0.39 12.2 7.9 Dynasty 0.30 12.2 7.5 Excel 0.30 12.4 7.3 Caldwell 0.30 12.4 6.7 Clark 0.36 12.3 7.3 Frankenmuth 0.40 12.2 8.2 IFail 1993 Tres 0.39 13.4 8.7 Lewjain 0.28 13.9 8.1 Dynasty 0.27 13.9 7.9 Frankenmuth 0.29 13.9 6.6 * based on 14% moisture content 29 4.1.4 Alkaline water Retention Capacity The alkaline water retention capacity (AWRC) measures the amount of alkaline water held by flour at 14% moisture basis after centrifugation and is expressed as percent of flour weight (AACC 1990). It is a predictive test of general soft wheat quality. In this study, AWRC of flour samples analyzed ranged from 50.2 to 60.5% (Table 2). Two different trends appear between the 1992 and 1993 crops, however in this study, variations from.chlorine treatment were the focus rather than varietal or environment differences. Yamazaki (1953) tested the cookie-baking potential of soft wheat flours with AWRC values from 40 to 60%. Optimum cookie baking was obtained from flours closer to 50% AWRC. The relation of AWRC to the cake-baking quality of a soft wheat flour has not been studied extensively in the literature. Low water absorption is an important quality factor of soft wheat flour since water absorption affects dough and batter viscosity during baking (Gaines 1986). Results of AWRC demonstrated significant differences (F= 9.68, p<0.05) between the pH 4.3 flour and the other flour treatments (Figure l). The .AWRC ‘values increased.‘with increasing chlorine treatment, indicating that flour pH may have an influence on AWRC. Table 2. Alkaline Water Retention Capacity (AWRC) of Unchlorinated and 30 Chlorinated Flours‘ AWRC (96) Variety Control pH 4.8 pH 4.3 Flour Flour Flour lFall 1992 Rely 53.4 54.8 58.3 Crew 52.2 55.5 58.8 Kmor 55.0 57.9 61.0 Lewjain 55.0 57.9 61.2 Dynasty 54.4 55.1 57.6 Excel 55.3 54.9 56.5 Caldwell 56.2 56.8 61.2 Clark 52.5 55.3 57.3 Frankenmuth 50.2 56.0 56.7 IFall 1993 Tres 60.5 54.2 58.0 Lewjain 58.8 56.5 60.0 Dynasty 57.2 55.6 57.0 Frankenmuth 56.5 55.6 56.6 * based on 14% moisture content mac (s) 31 Control Ill 4.! pH 4.3 Treatment to 1. Eitsotr oi chlorination on slksllns wstor rstsntllon on u FARGIV NC) at ilo rssmplss aver sou oi 13s on p.los) Illsrsnl toilets are slgnlicsntly dliisrsnt. at tho 616v svus. 'rsofly 32 4.1.5 Zeleney Sedimentation Volume The Zeleney sedimentation test measures sedimentation volume (predominantly swollen protein and occluded starch) of flour in dilute acetic acid (AACC 1990). It reflects gluten strength of the tested flours. Values (in m1) vary from three for very'weak wheat to seventy or more for very strong wheat (Halverson and Zeleney 1988) . In this study, sedimentation volumes for flours analyzed ranged from 10.0 to 26.0 ml (Table 3). These values are typical for soft wheat flours (Halverson and Zeleney 1988). Significant differences (F= 6.09, p<0.05) were observed between.the control and.chlorinated flours, but no significant differences were observed between the pH 4.3 and pH 4.8 flours (Figure 2) . The control values were significantly higher than the chlorinated. flour values suggesting that the gluten strengths of the flours were reduced by chlorination. 4.2 Rheological Properties of Unchlorinated and Chlorinated Flours 4.2.1 Alveograph Measurements In this study, alveograph measurements for control, pH 4.8, and pH 4.3 flour samples ranged, respectively, as follows: the resistance to deformation values (P) ranged from 21.3 to 44.4 mm, 31.1 to 75.8 mm, and 53.3 to 103.7 mm; the extensibility (L) from 69.5 to 118.1 mm, 46.9 to 87.8 mm, and 22.2 to 47.2 mm; the stability (P/L) from 0.11 to 0.44, 0.36 33 Table 3. Zeleney Sedimentation Volumes of Unchlorinated and Chlorinated FIours‘ Sedimentation Volume (ml) Variety Control pH 4.3 pH 4.8 Flour Flour Flour IFB" 1992 Rely 17.0 14.7 14.7 Crew 12.5 11.7 11.7 Kmor 26.0 16.7 18.4 Lewjain 21.3 16.4 14.7 Dynasty 16.5 9.6 12.0 Excel 16.0 10.0 10.0 Caldwell 16.0 12.7 14.2 Clark 15.3 12.2 12.5 Frankenmuth 21.0 15.6 15.5 Fall 1993 Tres 10.0 9.5 9.5 Lewjain 21.3 14.5 16.5 Dynasty 17.0 10.5 12.5 Frankenmuth 10.5 9.0 9.0 * based on 14% moisture content Ssdlmsnlatlon volalns (uni) 34 Control pH 48 pH 4.8 Trsstmsnt Floors 2. Eiisct oi chlorination on ssllllnsntatlon volumes oi ilour samples (svsrsgs oi 13 ssntplss). Values with dilisrsnt Isttsrs a a significantly diilsrsnt at tho 5% lsvsl. 35 to 1.59, and 1.14 to 3.71; the swelling index (G) from 18.5 to 30.4 ml, 15.2 to 22.7 ml, and 10.8 to 15.5 ml; areas under the curve (S) from 6.5 to 19.1 cmz, 11.4 to 21.0 cm2, and 15.7 to 2.5 cm2; and work of deformation (W) from 42.5 to 127.5, 58.9 to 137.3, and 49.7 to 163.7 Joules. Alveograph measurements for individual flour varieties are listed in Appendix I. Alveograph results indicate significant differences (p<0.05) for P, L, P/L and G values for each flour treatment. These :measurements primarily reflect the effect of chlorination in protein and starch components of flour; There may be oxidation of the sulfhydryl groups of the proteins (Bushuk and Hlynka 1962) and modification of the starch granules (Preston et al 1987). The P values indicated significant differences (F=37.41, p<0.05) among all three flour treatments (Figure 3A), with the P values increasing with the degree of chlorination, indicating an increase in the dough's resistance to deformation with the degree of chlorination. The L values were significantly'different (F=57.33, p<0.05) among all three treatments (Figure 3B) with the L value significantly decreasing as the degree of chlorination increased, indicating a loss in the dough's extensibility as the degree of chlorination increased. This increase in resistance and decrease in extensibility could be attributed to the oxidation of sulfhydryl groups by the chlorine and to modification of the starch. Bushuk and Hlynka (1962) have shown that the 36 Figure 3. Effect of chlorination on alveograph measurements of flour samples (average of 13 samples); A= resistance to deformation (P), B= extensibility (L), C= stability (P/L), D= swelling index (G), E= area (S), F= work of deformation (W); values with the same letter are not significantly different from each other at the 5% level. 37 mgr.“ "”3 emu pli4.8 plus Treatment 3 - 40 ~ 0 . o 2 .. ._l E 1 _ b a o _ cane pli4.8 plus Gum plus plus Trestrnsnt Treatment Carmel pit“ p114: Mel pit“ pH4.8 Treatment Treatment Figure 3 38 addition of an oxidizing agent to hard wheat oxidized the sulfhydryl groups, increasing' the dough's resistance and decreasing its extensibility. Research by Preston and co- workers (1987) has shown that damaged starch, which may be similar to chlorinated starch in structural depolymerization, causes increases in the dough's resistance (P) and decreases in its extensibility (L). The P/L and.G values are indicators of’a dough's stability and swelling index, respectively; The P/L ratios were significantly different (F=54.46, p<0.05) among flour treatments (Figure 3C). This value increased significantly (p<0.05) as the degree of chlorination increased, indicating that the dough's stability increased with chlorine treatment. Preston and co-workers (1987), however, reported that this value decreased with increased starch damage. This discrepancy in the literature may be due to modification of the flour proteins by chlorination which did not occur in Preston and co-workers (1987) damaged starch study. The C values decreased significantly (F=67.16, p<0.05) as the degree of chlorination increased (Figure 3D). The decrease in G values suggests a loss of dough extensibility with chlorination (Kent-Jones and Amos 1967). Preston and co-workers (1987) found. that increased starch damage or decreased water absorption (section 4.2.2) would result in lower' G ‘values; both. of these were seen in results of chlorinated flours in this study. 39 No significant differences (p<0.05) were seen among the flour treatments for S (Figure 3E) and W (Figure 3F) values. Both of these values increased as the degree of chlorination increased. The above results from alveograph measurements indicate that chlorination affected properties of the flour proteins and. starches resulting' in increased. stability, increased resistance and decreased extensibility of cake dough with increased chlorine treatment. 4.2.2 Farinograph Measurements In this study, farinograph measurements for control, pH 4.8, and ij 4.3 flour samples ranged, respectively, as follows: the water absorption from 48.3 to 54.2%, 48.5 to 55.9%, and 49.3 to 57.0%,- the peak time from 0.7 to 2.0 minutes, 0.2 to 1.5 minutes, and 1.0 to 1.5 minutes; the stability from.1.4 to 9.2 minutes, 1.1 to 3.3 minutes, and 1.4 to 2.8 minutes; and.the mixing tolerance index from.100 to 210 BU, 50 to 210 BU, and 75 to 210 BU. Measurements for individual flour varieties are listed in Appendix II. Water absorption values increased significantly (F=14.63, p<0.05) between the control and chlorinated flours (Figure 4A). Farrand (1964) reported that damaged starch can absorb much more water than undamaged starch. It is likely that chlorination affected starch components in a similar way. 40 Figure 4. Effect of chlorination on farinograph measurements of flour samples (average of 13 samples); A: water absorption, B= peak time, C= stability, D= mixing tolerance; values with the same letter are not significantly different from each other at the 5% level. Absorption (96) Stability (minutes) 41 Peak Time (minutes) Control pH 4.3 pH 4.3 °°“"°' P” 4-3 P" 4-3 Treatment Treatment Tolerance (BU) Control 9H 43 PH 43 Control pH 4.8 pH 43 Treatment Treatment Figure 4 42 The results of this study are in agreement with Hoseney (1986) who reported an increase in water uptake by chlorinated starch granules. Pyler (1988) correlated. peak. time values with flour protein strength of a flour . In this study, peak time values were significantly different (F= 2.45, p<0.05) between the control flour and pH 4.3 flour (Figure 4B); the pH 4.8 flour was not significantly different (p<0.05) from the other two treatments. Meredith and Bushuk (1962) observed that oxidizing agents increase the time required to reach farinograph peak time in hard wheat. They postulated that the increase was due to the oxidation of sulfhydryl groups by the oxidizing agent. No significant difference (p<0.05) was observed for stability (Figure 4C) and tolerance (Figure 4D) among the flours. However, the stability showed a decreasing trend with increasing chlorination, while the tolerance data showed no trends at all. 4.2.3 Maph Measurements In this study; mixograph measurements for control, pH 4.8, and.pH 4.3 flour samples ranged, respectively, as follows: the peak time from.1.1 to 5.1 minutes, 0.8 to 4.2 minutes, and 0.5 to 4.5 minutes; the peak height from 30 to 50 mm, 31 to 47 mm, and.32 to 44 mm; the stability from 1.4 to 9.2 minutes, 1.1 to 8.0 minutes, and 1.3 to 5.6 minutes; and the tolerance from 3.0 to 10.0 mm, 3.0 to 6.0 mm, and 2.0 to 5.0 mm. Mixograph 43 measurements for individual flour varieties are listed in Appendix III. Mixograph results indicate significant differences (p<0.05) between the control and. chlorinated flours for tolerance, and between control and pH 4.3 flours for peak time. Significant decreases (F=3.320, p<0.05) for peak time between control and pH 4.3 flours were observed, while the pH 4.8 flour was not significantly different (p<0.05) from the other two treatments (Figure 5A). Peak times show a decreasing trend with increasing chlorination. Constant additions of water to flour treatments with increasing farinograph water absorption (see section 4.2.2) may account for the decrease in peak time. If the gluten.proteins are not fully hydrated they do not reach maximum consistency, thus affecting the peak time values (Hoseney 1986). Tolerance measurements show significant differences (F=10.01, p<0.05) between the control and chlorinated flours with no significant difference (p<0.05) seen between the two chlorinated treatments (Figure 5B). This decrease in tolerance may also be due to insufficiently hydrated gluten proteins. No significant difference (p<0.05) among the flours was demonstrated for stability (Figure 5C) or peak height (Figure 5D). Observations of mixograms suggest that the flour components have been modified by chlorination. Further research needs to be done to differentiate between component modifications and water absorption. The results are 44 Figure 5. Effect of chlorination on mixograph measurements of flour samples (average of 13 samples); A= peak time, B= tolerance, C= stability, D= peak height; values with the same letter are not significantly different from each other at the 5% level . Peak Time (minutes) Stability (minutes) Control pH 4.8 pH 4.3 Treatment Gomrol pH 43 pH 43 Treatment 45 Tolerance (mm) Control pH 4.8 pH 4.3 Treatment 8 Peak Height (mm) 3 8 Control pH 4.8 [1114.3 Treatment Figure 5 46 similar to findings from the farinograph studies in section 4.2.2. 4.2.4‘Viscoggylograph Measurements In this study, Viscoamylograph measurements for control, pfli 4.8, and.pui 4.3 flour samples ranged, respectively, as follows: the peak viscosity from 370 to 1090 BU, 375 to 1175 BU, and 1030 to 1390 BU; the break viscosity from 330 to 870 BU, 325 to 875 BU, and 670 to 890 BU; the breakdown from 30 to 280 EU, 30 to 385 BU, and 220 to 675 BU; the setback viscosity from 820 to 1680 BU, 810 to 1820 BU, and 1285 to 1690 BU; the setback from 450 to 790 BU, 435 to 905 BU, and -5 to 390 BU; and the total setback from 490 to 875 BU, 485 to 970 BU, and 470 to 850 BU. Measurements for individual flour varieties are listed in Appendix IV. Contrary to results in this study, Miller and co—workers (1973) found that chlorine treatment of flour results in a drastic decrease in a flour's viscosity. A significant increase in viscosity (p<0.05) between the pH 4.3 and control flours for setback, breakdown viscosity, breakdown, and peak viscosity but no significant increase between the pH 4.8 and control flours was observed. The results are in agreement with Variano-Merston (1985) who reported.that the viscosity’of a flour increases with chlorination, and.Kulp et a1 (1972) who observed that the pasting and gelling properties of chlorinated starch exhibited few changes in their viscoamylograms until starch from heavily chlorinated flour 47 was used. However, Miller and co—workers (1973) reported decrease in viscosity with chlorination. Significant increases (F=22.04, p<0.05) in peak viscosity between the pH 4.3 and the other two treatments were noted, while the control and pH 4.8 treatments were practically identical (Figure:6A). This suggests that in the pH 4.3 flour, the starch was modified to an extent where its viscosity was significantly higher than the other two treatments. Chlorination has been reported to increase the swelling rate of starch (Variano-Marston 1985), but increased swelling does not affect viscosity (Miller et a1 1973). Increased viscosity has been observed to be undetectable in chlorinated flour until it is heavily chlorinated (Kulp et a1 1972). The breakdown viscosities from the pH 4.3 flour were significantly higher than those from the other treatments (F=3.32, p<0.05), with the control and pH 4.8 flours being very similar (Figure 68). This increased viscosity may suggest that the pH 4.3 starch would be more stable (Tipples 1980) during cooking than the other two treatments. ‘Breakdown measurements for the pH 4.3 flour were also significantly higher (F=37.48, p<0.05) than those from. the other two treatment flours, with the pH 4.8 flour being slightly higher than the control flour (Figure 6C). This could suggest that the pH 4.3 flour has better retrogradation properties than the 48 Figure 6. Effect of chlorination on Viscoamylograph measurements of flour samples (average of 13 samples); A: peak viscosity, B= breakdown viscosity, C= breakdown, D= setback, E= setback viscosity, F= total setback; values with the same letter are not significantly different from each other at the 5% level. 49 Breakdown Vbeoslty (BU) Carrel p014.) pllu Treaunsnt “— ". Camel pit“ pl”: Trastaisrl m E . Figure 6 50 other two treatments (Tipples 1980). The oxidizing nature of chlorine could oxidize bulky hydroxyl groups on the starch molecule to less bulky carboxyl or aldehydic groups which can reassociate faster allowing for improved retrogradation properties (Rasper 1980). The setback measurements show a significant (F=27.91, p<0.05) decrease for the pH 4.3 treatment compared to the other two treatments, with no significant difference (p<0.05) seen between the pH 4.8 and control flours (Figure 6D). This may suggest the pH 4.3 flour has a greater stability than the other two treatments which is a reflection of its improved retrogradation.properties. The setback viscosity (Figure 6E) and total setback (Figure 6F) show no significant differences (p<0.05) between flour treatments. Differences in the Viscoamylograph data indicate that the starch in the pH 4.3 chlorinated flour has been modified to a greater extent than the other two treatments, causing differences in the pasting ability of the starch. 4.3 Baking Results 4.3.1_§igh-Ratio Cakes The high-ratio cake (HRC) formula (AACC 10-90) was designed to measure a flour's cake-baking potential. This formula contains shortening, and higher levels of sugar and water than the Japanese-sponge cake formulation (4.3.2). 51 Cakes of this type yield optimum volumes when.made from flours chlorinated between pH 4.7—4.9 (Hoseney 1986). Nine varieties of the 1992 flour samples were used for baking at SWQL, and subsequently there were inadequate amounts remaining of these samples for baking at Michigan State University (MSU). The four varieties of 1993 flour samples were used for baking at MSU; Due to the differences in.baking location, the results will be statistically analyzed separately. Cake measurements for control, pH 4.8, and pH 4.3 flour samples ranged, respectively, as follows: the volume of cakes baked at Wooster from 801 to 909 ml, 899 to 1006 ml, and 853 to 951 ml; the volumes of cakes baked.at MSU from 915 to 1029 ml, 970 to 1043 m1, and 918 to 980 ml; the volume index for MSU HRCs from 8.15 to 10.4 cm, 10.6 to 12.55 cm, and 9.6 to 10.5 cm; and the symmetry index for MSU’HRCs from 0.55 to 0.35 cm, 0.35 to 0.45 cm, and 0.3 to 7.6 cm. Vblume index and symmetry index measurements were not taken for the HRCs baked at Wooster. Measurements for individual flour varieties are listed in Appendices V and VI. The nine cake samples baked in Wooster demonstrated significant differences (F=3.43, p<0.05) between the pH 4.8 flours and the other flour treatments: the control and.pH 4.3 flours;produced.cakes that.were significantly lower in volumes (p<0.05) (Figure 7A). Peak cake volumes were obtained for the pH 4.8 flours in comparison to the other two treatments. 52 Figure 7. Effect of chlorination on high-ratio cake measurements of flour samples (average of 13 samples); A; volume of cakes baked at SWQL, B= volume of cakes baked at MSU (Michigan State University), C= volume index of cakes baked.at MSU; values with. the same letter are not significantly different from each other at the 5% level. Volume hoax (cm) Moi HI“ ”14.3 Treatment Figure 7 54 Cakes baked from the four flour samples at MSU demonstrated significant differences in volumes (F=3.43, p<0.05) between the pH 4.8 and pH 4.3 flours, while cakes produced from the control flours were not significantly different from cakes produced from the chlorinated flours (Figure 7B). A peak volume was obtained from the pH 4.8 flour, but it was not significantly different from the control flours. A higher volume index was obtained for the cakes baked from chlorinated flours (at MSU) compared to the control flour (Figure 7C). No significant differences were observed between the flour treatments in the symmetry index for MSU baked cakes (data not shown). The control flours produced a cake with lower volume and poorer symmetry (dipped center), while the pH 4.3 flours produced cakes with lower volumes. The pH 4.8 flour produced peak volumes for the HRC's baked at MSU and SWQL, indicating that pH 4.8 is an optimum degree of chlorination for production of AACC 10-90 HRCs with optimum volume and symmetry. These results are in agreement with findings from Montzheimer (1931), Bohn (1934), and Hoseney (1986) that peak volumes were obtained from flour chlorinated to a pH of approximately 4.8. 4 . 3 . 2 Mose-Sponge Cake Japanese—sponge cake (JSC) has a simple formula which consists of a 1:1:1 ratio of sugar, egg, and flour. This 55 formula is similar to ones currently being used in Japan, where the use of chlorinated flour has been discontinued. In this study, cake measurements for control, pH 4.8, and pH 4.3 flour samples ranged, respectively, as follows: the volumes from 1050 to 1205 ml, 965 to 1068 ml, and 958 to 1145 ml; the volume index from 18.8 to 20.5 cm, 17.9 to 19.7 cm, and 17.34 to 20.55 cm; and the symmetry index from 0 to 1.25 cm, 0.7 to 1.7 cm, and 0.9 to 1.3 cm. Measurements for individual flour varieties are listed in Appendix VII. Volumes of Japanese-sponge cakes were significantly different (F=13.58, p<0.05) between the unchlorinated and chlorinated flours. There was no significant difference (p<0.05) between the average cake volumes of pH 4.3 and.pH 4.8 flours (Figure 8A). The volume index shows that the cakes baked from the control flours had significantly higher (F=24.62, p<0.05) volume indices than the cakes baked from.the chlorinated flours (Figure BB). However, the symmetry index showed that the control flour had significantly lower (p<0.05) symmetry than the cakes produced from chlorinated flours (Figure 8C). Peak volumes were obtained for the control flours but better symmetry was obtained from the chlorinated flours. In this study, Japanese-sponge cakes exhibited significant differences (p<0.05) in volume index and symmetry index among the control flours and treated flours at both levels. 56 Figure 8. Effect of chlorination on Japanese sponge cake measurements of flour samples (average of 13 samples); A: volume, B: volume index, C: symmetry index; Values with the same letter are not significantly different at 5% level. 57 Gourd pH 41 pH 4.3 Trestmsrl Figure 8 58 The chlorination appears to have modified the flour so that it constrains the volume of the JSC, yet provides enough internal structure to produce a rounded top in comparison to the flat or dipped peaks of the control flour cakes. The constraints on the volume in the cakes produced from chlorinated flour could. be attributed to the increased resistance in flour proteins and starches which were observed with the alveograph P measurements (Figure 3A). In contrast to high-ratio cakes, Japanese-sponge cakes do not need flour chlorinated to pH 4.8 to bake cakes of optimum volumes, but the symmetry of cakes produced from unchlorinated flour is inferior to cakes baked from the chlorinated flour. An astringent odor was also observed in the JSCs produced from the chlorinated flours. 4.4 Relationship Among Technological and Baking Data 4.4.1 Correlations with volumes of High-Ratio Cakes Baked at SWQL. ' The volumes of high-ratio cakes baked at SWQL correlated significantly with: mixograph peak time (p<0.05, r=0.42); Viscoamylograph break viscosity (p<0.05, r=0.42); and AWRC (p<0.05, r=0.55). Break viscosity is the only measurement that is constant between the HRCs baked at the two different locations (i.e., SWQL and MSU). This may indicate that the 7—1 59 increased retrogradation potential of the starch measured by the break viscosity correlates with the volume of HRCs. Faster retrogradation of the starch may contribute to the increased structural strength observed in cakes baked from chlorinated flour. The correlation of AWRC with volume could be a useful indicator of a soft wheat flour's cake-baking potential. Higher AWRCs enable the flour to produce optimal HRCs. Research needs to be done to establish windows for low (underchlorinated) or high (overchlorinated) .AWRCs that will not produce optimum HRCs. The correlation with mixograph peak time could reflect the different water absorptions of the flour treatments under constant additions of water. 4.4.2 Correlations with volumes of High-Ratio Cakes Baked at MSU. The volumes of high-ratio cakes baked at MSU correlated significantly with: alveograph P value (p<0.05, r=0.63), Viscoamylograph peak viscosity (p=0.02, r=0.65), and break viscosity (p<0.05, r=0.38). The viscosity' measurements indicate the gelatinization and pasting properties of chlorinated starch.play'an.important role in the production.of HRCs of optimum volume. The correlation of the alveograph P value also indicates the importance of modified starch and protein in HRC production. 60 4.4.3 Correlations with Vblumes of Japanese-Sponge Cakes The volumes of Japanese sponge cakes correlated significantly with: alveograph P value (p<0.05, r=0.47), L value (p<0.001, r=0.58), P/L value (p<0.01, r=0.42), G value (p<0.001, r=0.57); farinograph water absorption (p<0.05, r=0.34); mixograph tolerance (p=<0.04, r=.04); Viscoamylograph peak viscosity (p<0.01, r=0.48), breakdown viscosity (p<0.05, r=0.38), and breakdown (p<0.05, r=0.44). The alveograph measurements appear to be good indicators of the volume of Japanese-sponge cakes under the given experimental conditions. These values reflect the modifications of the starches and proteins by chlorination and the contribution of these components to JSC 'volume. IFarinograph. water absorption indicates the importance of the hydration of the starch and protein in JSC volume. Viscosity measurements show the importance of the modified starch components to cake volume as was also seen in the HRCs. Positive correlations between mixograph tolerance to JSC were also observed. 5. GENERAL DISCUSSION The purpose of this study was to observe the rheological and baking properties among 13 varieties of unchlorinated and chlorinated (pH 4.8 and 4.3) soft wheat flours. Functional properties of the flours were determined with analytical and rheological tests. Modifications to the flour's components (proteins and starches) account for the differences observed in the results of these tests. Baking potentials of the flours were determined using high-ratio and Japanese-sponge cake formulas, which are markedly different in their formulation, resulting in cakes with different volumes and indices from chlorinated flour in comparison to unchlorinated flours. The properties of the soft wheat flour samples were determined for protein content, ash content, moisture content, alkaline water retention capacity, and Zeleney sedimentation volume. The protein, ash and moisture contents for these flours fell within the acceptable parameters for soft wheat flours used for cake production. Chlorinated flours, because of their high alkaline water retention capacity, would not be suitable for cookie baking (Yamazaki 1953). The relationship between AWRC and cake-baking potential has not been extensively reported in the literature. Sedimentation volumes decreased with chlorination indicating that protein strength decreases with increasing chlorination. This is in agreement 61 62 with Bass (1988) who observed that gluten strength weakened with chlorination. The transfer of gluten proteins to the starch-granule surface of chlorinated starch, causing a 3- to 4-fold increase in the amount of proteins on the starch granule (Seguchi 1993), may contribute to the weakening of the gluten strength evidenced by Zeleney sedimentation volumes. The rheological properties of the flour samples were measured by the alveograph, farinograph, mixograph and Viscoamylograph. Past research using these instruments (Bushuk and Hlynka 1962, Meridith and Bushuk 1962, and Preston et a1 1987) has primarily focused on hard wheat varieties. These studies used.oxidizing agents other than chlorine on the hard wheat samples, but their results are in agreement with the results of this study. Alveograph results indicate significant increases in resistance (P) and extensibility (L) with increasing chlorination. These results are in agreement with Bushuk and Hlynka (1962) who found increases in resistance and decreases in extensibility (an extensograph was used) of hard wheat flours with the addition of an oxidizing agent (N- ethylmaleimide). The increase in resistance indicates an increase in dough strength with chlorination. This discrepancy between results of alveograph and sedimentation measurements may be attributed to the oxidation of sulfhydryl groups by chlorination increasing dough strength. Results similar to this were observed by Tsen and Kulp (1971). By 63 increasing the number of disulfide bonds in the dough the resistance of the dough increased with chlorination. Farinograph. results indicate significant increases in water absorption between control and chlorinated flours, and significant increases in peak height between control and pH 4.3 flours. The increased.water absorption can be attributed to the modification of chlorinated starch (Variano-Marston 1985). This increased water absorption for chlorinated flour may also have an effect on mixograph results where a constant amount of water is added. Increased farinograph peak time from.the control to pH 4.3 flour may be due to similar reasons as the increase in alveograph P value. Mixograph results indicate a significant decrease in peak time between the control and pH 4.3 flours, and in tolerance between control and chlorinated flours. The decrease in peak time contradicts the farinograph peak time measurements. This may be due to the difference in water absorptions between the treatments. 'The chlorinated flour would require higher levels of water for the flour to reach optimum resistance to mixing, but constant additions of water (mixograph) to all treatments may cause a decrease in the peak time values for the chlorinated flours. The decrease in tolerance to mixing with chlorination conflicts with the increased stability in the alveograph (P/L) measurements. This difference may be attributed to the mixograph's lack of sensitivity toward starch, like the alveograph, and may reflect the decreasing 64 protein strength seen from sedimentation volumes. Viscoamylograph results indicated significant differences between the pH 4.3 flours and the other treatments for peak viscosity, breakdown viscosity, breakdown and setback. Kulp and co-workers (1972) found that the pasting and gelation properties were not altered greatly until the flour was heavily chlorinated“ This agrees with our experimental results where significant changes were not observed until the flour was overchlorinated (pH 4.3). Differences between the pH 4.8 and control flours may be detectable if the Viscoamylograph were run in a high sucrose environment similar to a HRC batter» High-ratio cakes (AACC 10-90) can be used as an indicator of baking quality for soft wheat flour. This formula is typical of an American high-ratio cake which contains higher levels of sugar, shortening and water than Japanese-sponge cake. The advent of chlorination allowed for the development of these types of cakes, and chlorination is necessary to produce high-ratio cakes of optimum volume and symmetry; Past research by Montzheimer (1931) confirms experimental results that optimum volumes and symmetry were obtained from the pH 4.8 flour; ZModification.of the flour proteins and starches as indicated by the sedimentation and rheological tests contribute to this improvement causing increased swelling and interactions among the flour components (Kulp et al 1972). Japanese-sponge cake formula, with its low levels of sugar 65 and no shortening added, allow this cake formula to produce optimum cake volumes from unchlorinated flour or possibly a flour chlorinated to a lesser degree than in this study; This formula contains a high proportion of eggs in comparison to high-ratio cakes. The additional amount of eggs may form a stabilizing network when the eggs are coagulated during baking (Guy and Pithawala 1981), lending structural support to the cake and helping to maintain its volume. This support along with lower amounts of shortening and sugar in comparison to high-ratio cakes allow the Japanese-sponge cake to produce optimum volumes from unchlorinated flours. Unchlorinated flours produced optimum volumes with this formula but the symmetry of cakes produced from the unchlorinated flours were inferior to cakes baked from chlorinated flours. Unchlorinated cakes had flat tops and some were even slightly dipped in comparison to the dome shaped cakes produced from the chlorinated flours. Chlorination appeared to constrain cake volume but also allows for a stronger internal cake structure which may be due to increasing resistance from the proteins, and interactions of the modified starch granule surface with the other flour components. 6. SUMMARY Sedimentation volumes indicate a weakening of the gluten proteins with chlorination. Chlorination appears to oxidize the gluten proteins possibly allowing them to associate with the starch-granule surface. Alkaline water retention capacity (%) increased with chlorination. This increase correlated with the volumes of high-ratio cakes (HRCs). Currently the relationship between AWRC (%) and.cake volume has not.been extensively reported in the literature. Alveograph measurements indicated modification to starches and proteins causing increased resistance (P) and stability (P/L), and decreasing extensibility (L) and elasticity (G). These trends are consistent with other researchers who studied the effect of other oxidizing agents on these properties in hard wheat and the effect of starch damage on hard wheat. Farinograph measurements showed increased water absorption and increased. peak times in chlorinated flours. The increase in water absorption is most likely due to modification of the starch granules. Increased 66 67 water absorption with chlorination was in agreement with previously reported findings. Increased peak times may be attributed to modifications to the starch and protein components of chlorinated flours. Mixograph measurements showed significant decreases in peak time and tolerance with chlorination. The decrease in peak time which conflicts with farinograph peak times may be attributed to the constant addition of water to treatments with increasing water absorptions which prevented complete hydration of the flour proteins. The decrease in tolerance may be due to decreases in the protein strength that were seen in the sedimentation volumes. ‘Viscoamylograph. measurements indicated significant changes in the starch components gelling and pasting properties of the pH 4.3 flour. These results are in agreement with past research which observed significant changes in a starch's gelling and pasting properties when it was overchlorinated. High-ratio cakes had.peak volume and symmetry when baked from the pH 4.8 flours. These results are in agreement with past research which found optimum HRCs were baked from flour chlorinated to about pH 4.8. 68 Japanese-sponge cakes (JSCs) produced optimum volumes from unchlorinated flours but better symmetry was observed for the cakes produced from chlorinated flours. The lower sugar, shortening and water levels and higher egg content in comparison to the HRC formula allow unchlorinated flours to produce optimum JSC volumes. However, differences in formulations do not allow unchlorinated flours to maintain optimum symmetry in their cakes as was seen for the chlorinated flours. 7. Future Studies Future studies should look into viable alternatives to chlorine treatment because of its potential carcinogenic effect. Chlorine treatment has a profound effect on the starch component of a flour. Chlorination results in increased surface hydrophobicity of the starch granule and increased water absorption via depolymerization of the granule. Creating a modified starch with these properties and substituting the starch from an unchlorinated flour with this modified starch would.be a study of interest. Reformulation of high-ratio cake (HRC) is also an area where future research can be focused. Modification of HRC formula ingredients which weaken the internal structure of the HRC (e.g. shortening and sugar) along with the addition of strengthening agents (e.g. egg whites and gums) would be another way to replace chlorinated flour. The use of different ingredients may allow the HRC to maintain its volume, symmetry and internal structure, imparted by chlorinated flour. 69 8. BIBLIOGRAPHY AACC (American Association of Cereal Chemists). 1990 Approved methods of AACC Vol. 1 and 2. The association, St. Paul, MN. Annual Report, 1970. Flour Milling and Baking Research Association, Chorleywood, England. Ash, D.J. and Colmey, K. 1973. The role of pH in cake baking. Bakers Digest. Feb:36-48. Barret, F.F. and Sollars, W.F. 1961. High pH level and chlorine requirement of Pacific Northwest soft wheat flours. Cereal Sci. Today. 10:151-154. Bass, E.J. 1988. Wheat Flour Milling. In wheat chemistry and technology. Y. Pomeranz ed. AACC St. Paul, MN p 31. Bennett, R. and Devlin, J.J. 1954. Evaluation of cake flours. Food Manuf. 29(12):479-481. Bohn, L. J. 1934. Some factors in influencing the quality of cake flours. Cereal Chem. 11:598-604. Buntoku, Y. 1969. How to think about food sanitation. Tokyo, Japan. 186—190. Bushuk, W. and Hlynka, I. 1962. The effect of Iodate and N- ethylmaleimide on extensograph properties of dough. Cereal Chem. 39:189-195. Chopin, M. 1927. Determination of baking value of wheat by measure of specific energy of deformation of dough. Cereal Chem. 4:1-13. Clements, R.L. and Donelson, J.R. 1982. Role of free flour lipids in batter expansion in layer cake.I. Effects of aging. Cereal Chem. 59:121-125. Conforti, F.D. and Johnson, J.M. 1992. Use of farinograph in predicting baking quality of unchlorinated and unchlorinated 70 71 flour. Journal of Food Quality. 15:333-347. Donelson, J. R. 1988. The contribution of high-protein fractions from cake and cookies flours to baking performance. Cereal Chem. 65(5):389-391. Donelson, J.R. Yamazaki, W.T. and Kissell, L.T. 1984. Functionality in white layer cake of lipids from untreated and chlorinated patent flour.II. Flour fraction interchange study. Cereal Chem. 61(2):88-91. Ewart, J.A.D. 1968. Action of glutaraldehyde, nitrous acid, or chlorine on wheat proteins. J. Food Agric. 19:371-374. Faridi, H and RaSper, V.F. 1987. The alveograph handbook. AACC. St Paul, Mn. Farrand, E.A. 1964. Flour properties in relation to modern bread process in the United Kingdom with special reference to alpha amylase and starch damage. Cereal Chem. 41:98—108. Finney, K.F. and Yamazaki, W.T. 1967. Wheat and wheat improvement. Quisenberry, K.S. Reitz, L.P. Ed. Am. Soc. Agron. Madison,WI. Fisher, N. Hutchinson, J.B. Berry, R. Hardy, J. Ginocchio, AJV. 1983. Long term toxic and carcinogenicity studies in cake made from chlorinated flour. 1. Studies in rats. Food Chem Toxicol. 21(4):427-434. Gaines, C. S. 1986. Alkaline water retention capacity-AACC method 56-10. Cereal Foods World. 31:837-838. Gracza, R. 1959. The subseive— size fractions of a soft wheat flour produced by air classification. Cereal Chem. 36:465-487. Ginocchio, AJV. Hardy, J. 1983. Long term toxic and carcinogenicity studies in cake made from chlorinated flour. 2. Studies in mice. Food Chem Toxicol. 21(4):435-439. 72 Gough, B.M. Whitehouse, M.E. and Greenwood, C.T. 1978. The role and function of chlorine in the preparation of high ratio cake flour. CRC Critical Reviews in Food Sci. and Nut. 11:91-113. Greenwell, P. Evers, A.D. Gough, B.M. and Russel, P.L. 1985. Amyloglucosidase- catalyzed erosion of native surface modified and chlorine treated wheat starch granules. The influence of surface protein. Journal of Cereal Sci. 3:279- 293. Guy, R.C.E. and Pithawala, H.R. 1981. Rheological studies of high ratio cake batters to investigate the mechanism of improvement of flours by chlorination or heat treatment. J. Fd. Technol. 16:153-166. Halverson, J. and Zeleny, L. 1988. Criteria of wheat quality. In wheat chemistry and technology. Y. Pomeranz ed. AACC St. Paul, MN p 15. Haung, G. Finn, J.W. and Variano—Marston, E. 1982. Flour chlorination I. Chlorine location and quantification in air classified fractions. Cereal Chem. 59:496-502. Hanson, W.H. 1932. Effects of the amount and kind of bleach used on flour in relation to its aging. Cereal Chem. 9:358- 377. Haung, G. Finn, J.W. and Variano-Marston, E. 1982. Flour chlorination I. chlorine location and quantification in air classified fractions. Cereal Chem. 59:496-500. Hoseney, R.C. 1986. Principles of Cereal Science and Technology American Association of Cereal Chemists, Inc. St. Paul, MN. Hoseney, R.C. Wade, P. and Finley, J.W. 1988. Soft wheat products. In wheat chemistry and technology. Y. Pomeranz ed. AACC St. Paul, MN p 407. Hlynka, I. and Barth, F.W. 1955. Chopin alveograph studies. I. Dough resistance at a constant sample deformation. Cereal Chem. 32:463-471. 73 Johnson, J.A. and Swanson, C.O. 1946. Effect of flour proteins on mixograph patterns. Bakers Dig. 20: 15-19. Kent-Jones, D.W. and Amos, A.J. 1967. Modern Cereal Chemistry, 6th ed., Food Trades Press Ltd. London. p 323. Kissell, L.T. 1959. A.1ean-formula cake method for varietal evaluation and research. Cereal Chem. 36: 168-175. Kissell, L.T. and Marshall, B.D. 1972. Design and construction of a reactor for gaseous treatment of flour. Cereal Sci. Today 12:245-248. Kissell, L.T. and Yamazaki. W.T. 1974. Reaction of batter expansion and contraction to cake volume (abstract). Cereal Sci. Today. 19:400. Kissell, L.T. Donelson, J.R. and Clements, R.L. 1977. Functionality in white layer cake of lipids from untreated and chlorinated patent flour (abstract). Cereal Foods World 22:476. Kissell, L.T. Donelson, J.R. and Clements, R.L. 1979. Functionality in white layer cake of lipids from untreated and chlorinated patent flour.I. Effects of free lipids, Cereal Chem. 56(1):11-14. Kulp, K. Tsen, C.C. and Daly, W.T. 1972. Effect of chlorine on starch component of soft wheat flour. Cereal Chem. 49:194-200. Manley, D. 1991. Technology of bisquit, crackers and cookies 2nd edition. Ellis Horwood, New York. p 88. Markley, M.C. Bailey, C.H. and Harrington, F.L. 1939. The colloidal behavior of flour dough. IV. Dough formation of flours of diverse types. Cereal Chem. 16:271-279. Meredith, P. and Bushuk, W. 1962. The effect of iodate, N- ethylmaleimide, and oxygen on the mixing tolerance of dough. Cereal Chem. 39:411-426. 74 Miller, B.S. Derby, R.I. and Trimbo, H.B. 1973. A pictorial explanation for the increase in viscosity of a heated wheat starch-water suspension. Cereal Chem. 50:271-280. Montzheimer, J. W. 1931. A study of methods for testing cake flour. Cereal Chem. 8:510-514. Nemeth, L.J. 1993..A comparative study of Canadian and international soft wheats. Master Thesis. Food Science Department, University of Manitoba, Winnipeg. Nagao, S. Imai, S. Sato, T. Kaneko, Y. and Otsubo, H. 1976. Quality characteristics of soft wheats and their use in Japan. I. Methods of assessing wheat suitability for Japanese products.Cereal Chem. 53: 988-997. Ngo. W. Hoseney, R.C. and Moore, W.R. 1985. Dynamic rheological properties of cake batter made from chlorine treated and untreated flour. J. of Food Sci. 50:1338-1341. Pomeranz, Y. 1987. Modern cereal science and technology. VCH Publishing, Inc. New York. Preston, K.R. Kilborn, R.H. and Dexter, J.E. 1987. Effects of starch damage and water absorption on the alveograph properties of Canadian hard red spring wheats. Can. Inst. Food Sci. Technol. J. 20:75-80. Pyler, E.J. 1988. Baking Science and technology, Vol II. Sosland Publishing Co. Merriam, KS p 854-857. Rasper, V. 1980. Theoretical aspects of amylographology. 1g The amylograph handbook. Shuey W.C. and Tipples, K.H. eds. AACC. St. Paul, MN. Russo, J.V. and Doe, C.A. 1970. Heat Treatment of flour as an alternative to chlorination. J. Food Technol. 5:363-374. Seguchi, M. 1985. Model experiments on hydrophobicity of chlorinated surface proteins. Cereal Chem. 62(3):166-169. 75 Seguchi, M. 1987. Effect of chlorination on the hydrophobicity of wheat starch. Cereal Chem. 64(4):281-282. Seguchi, M. 1990. Study of wheat starch starch-granule surface proteins from chlorinated wheat flour.. Cereal Chem. 63:258-260 Seguchi, M. 1993. Effect of wheat flour aging on starch- granule surface proteins. Cereal Chem. 70:362-364. Shuey, W.C. 1984a. Physical factors influencing farinograms. In The Farinograph Handbook. D'Appolonia, B.L. and Kunerth, eds. W.H. AACC. St Paul, Mn. Shuey, W.C. 1984b. Interpretation of farinograms. In The Farinograph Handbook. D'Appolonia, B.L. and Kunerth, eds. W.H. AACC. St Paul, Mn. Sulaiman, B.D. and Morrison, W.D. 1990. Proteins associated with the surface of starch granules purified by centrifuging through caesium chloride. Journal of Cereal Sci. 12:53-61. Terada, M. Minami, J. and Yamamoto, T. 1982. Characteristics of bread and sponge cake baked from wheat flour exposed to gaseous ammonia, Cereal Chem. 60(1):90-92. Tipples, K.H. 1980. Uses and Applications. In The amylograph handbook. Shuey W.C. and Tipples, K.H. ed. AACC. St. PauI, MN. Tomie, H. and Okubu, K. 1984. Sudachi (porous gel) in cooking (part 2). the correlation of formation between bubble and air dissolved from solution and "Su" during gelation of eggs. J. Home Econ. 35:760-765. Tsen, C.C. and Kulp, K. 1971. Effects of chlorine on flour proteins, dough properties, and cake qualities. Cereal Chem. 48:247-255. Uchino, N. and Whistler, R.L. 1962. Oxidation of wheat starch with chlorine. Cereal Chem. 39:477-482. 76 Variano-Marston, E. 1985. Flour Chlorination: New thoughts on an old topic. Cereal Foods World. 30(5):339-342. Wei, C.L. Ghanbari, H.A. Wheeler, W.B. and Kirk, J.R. 1984. J. Food Sci. 49:1136-1153. Yamazaki, W.T. 1953. An alkaline water retention capacity test for the evaluation of cookie baking potentials of soft wheat flours. Cereal Chem. 30:242-246. Yamazaki, W.T. and Kissell, L.T. 1978. Cake flour and baking research. Cereal Foods World. 23(3):114-118. 9 . Appendices .52. me In um... .52. a... In «no .52. .858 «0 >926 u>> do... «w SSE»)... no $5.an add $53.22.... n._ 6265.82. 2 8:238. «n. 77 as... v... .5. mm. ..«|« 4.8 r..." R. 3 M... e.» .3. .8. 3. 4.3 58...? 48 m..«..m.«c mas. .o..« .3 .3. .«.m. 1...... 4... .8... .23 .«.«« as. .08 on... ....n .n..« 65m a..« o.«« on n... .... a.» e. A an .2. 3... 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[51L l I I :‘ -’ . I i ' l U '1 k \ : i l ‘ W \_ 1 '2 '~ 1 \ \ x "\ T\\\\\\\\L1 .XlllX\\\\\\)ll\\V\\j “M u” m" o I "I “he.“ I” / fill/I'll 71/! /l]/l-’l-’l./ljlll/L I l v ..111--I\l. i‘x" “\\ W \‘W \ \l m\MMMM \ \Y\ \ A ,7 /// II?%%$8/l /// // T/I/ lf/I/lf/I’w/lf/l/l/J Til ] l/ll MIIIIIIIIL I ..« 4“ I f l g I . i l '- 81 Farinograms of unchlorinated and chlorinated flours from Clark 1992 variety: 1) Control, 2) pH 4.8, 3) pH 4.3. manual: I” ///£/7///7”/1 /.I=///;'/ /// [ I ’ / / [1.7/:1;17/’1.//I "15 f 1' I I I . I = I I 2 . 1 . . . l \\ \ x f“ [—31; ‘ \. A E Qz\;\\[=\x\x\gV\'\ \1 1...: Mn): \ \ -. \* I I MW 77/72/77 I’l/[///////1/] lIlfl/[7lT/IIIIJII/ 1 l 3 i I 7 I I i ' {I J 1 I Li )4) 2 7 7 I: -\«.‘\;\7\‘-.‘\Tj\:li\- ‘ LL)...‘ L433: \....‘.-...\..‘2.}. T [:f/ / [:7 --/ /I’ [l/ / / W1? a. a . 3 \k)\j {if J_A \A"\A \\ \ \ \ ‘ gY \ ‘\ \ 82 Farinograms of unchlorinated and chlorinated flours from Crew 1992 variety: 1) Control, 2) pH 4. 8, 3) pH 4.3. “In.“ no l/I/ [/j 7 //1 0:er I/I/ Ill/fl 11 I Ill 1]" 1 NJ! [I]!!! l 1 I! 11 l/ 1 l/ l, l f I j I l I I l ! l i. t, . 1 Li ‘\ \\ \1:\\X\TX\\H\\\ “A \X\\\\\'L\\\\\T\\ “ma-0“ “who. 83 Farinograms of unchlorinated and chlorinated flours from Dynasty 1992 variety: 1) Control, 2) pH 4. 8, 3) pH 4.3. ”It.“ a. fiTl’r/I/f/fI/l I 111/111 111/111 1111111111111 1 a 1 . 3 i j : I i 2 j A '42! Y ‘ 1 \t 1 1 z ~‘\\\\\ \‘1111 1 X l \‘Tj\\\\ll‘\‘\j X nun-awn -~~~ mm “ an.“ . ////1/j/1//[/L1/1//// 11171111111111 111111711111 “\F \q ‘1‘ “Oh“ i. 111 1/ / 1 / / f r 111/ 11/1/1/1/1. 1' I I : . y ‘ i I . ' . £ 3 3 84 Farinograms of unchlorinated and chlorinated flours from Dynasty 1993 variety: 1) Control, 2) pH 4. 8, 3) pH 4.3. 0.0...“ an II III/I II I/If/I I II I IIII II “III III' IDI1I II IIIIIII III’ I I 1 f I I I I ; I ~ : I ' I/ I I ZEEE?;¥%¥IIIIIIIJII j I 1 IIIT/I/IIL IIIIIIIIIIIIIIIII] 1 I I I I) I _ \ 1\\111\1\\1\\\\\ \\\\\\\\1\\\1\11 m..- """f? .. “Oh.“ u II/IIIIIIIII] II/I/IIIIIIII IIIHIII1I LIIIIIIIIII I i l I 3 I I \X I 1 1 47 17‘ I I1 ____1..L_.1 \ \\A\\ x \W\ \\ :\1 \ \_X \ 85 Farinograms of unchlorinated and chlorinated flours from Excel 1992 variety: 1) Control, 2) pH 4. 8, 3) pH 4.3. /7/7///1//"7r/m/“7 / 11 »/ [III/(Ill L / Li I 111/ [TILL-IL I I 1 3 . ,I’ ; I :‘ J I I Io i ‘ I i111: ‘ \ —I I I l o 2 - x I \ \m \ m: $—BJL\L\ V\\1\1\\\VFC W '/L/] III/[1' Nilj/ /;'1]/J 1.;I/lfl/I" I I ’ i I I [I I a I I I I I 'Ii— '1 AWN \ \1411 -_T1;T \ \__\ \ \ \ 86 Farinograms of unchlorinated and chlorinated flours from Frankenmuth 1992 variety: 1) Control, 2) pH 4.8, 3) pH 4.3. 1111/ 11117111117 7 IIII/J1ls'71/ [ [/r I’ [I/ L11_1111111111111;1 I I , 1 I 1 I I 1 I I '1‘ . , I I I I I i 1 I . g I [\1 _\1 _ ‘1\\\L\\l\_\"1\;\\\2.\ \\T\W\a\ :YL\\\1l-~Lll\\\ “tun-o Juan-no.5 “ 2 /_.~/ [1/17k/uu»: LIL/Ill’l [ll /1 1/77 III/II'I'I’ ,Il, jL I I 1 I I I - 1+1“) ‘ 1 I— 3 —L ‘ ‘ ‘ I‘ : 1 87 Farinograms of unchlorinated and chlorinated flours from Frankenmuth 1993 variety: 1) Control, 2) pH 4.8, 3) pH 4.3. “km . ITIJJI /1FIF/ / / / / / 11111171111 11 L? I‘ I]; If I’d I III II [I 11" '4 :' '51 1 1 I L J“ 1\:\\1‘1\: 1. 1 1 \11\g\1 \\\ L31\\ \\ALU‘Y‘\ \\\‘ ~ ‘W -“uu “a.“ on! II I’ll/11 1 II III II // I1 II III IIILIIIIT [I Will I 88 Farinograms of unchlorinated and chlorinated flours from Kmor 1992 variety: 1) Control, 2) pH 4. 8, 3) pH 4.3. when: no J/7 FI/I LI////// “/1 /1 111111 11111111 1L,1; 1'71;;11;11111 1111- 1' j -- 11111;1111111;’ 1 I u... i‘- N l\"7\\l\\i‘31\1' \xut\\\\\\1\ \ 3.. sun—- mm a. m “onus-cu- IWIIIWHEIJ/f1/ll/l/l/l ll] '/1/ [/7'l1l/l FIIll/l lI/;IJ1’/l ;/LIJIJ; .11 1'1 '\ fir L . | ——v> 89 Farinograms of unchlorinated and chlorinated flours from Lewjain 1992 variety: 1) Control, 2) pH 4.8, 3) pH 4.3. ...-... ”0'1“!” [ll/f1/j7f/ll Jill/[Ill]! [I'll/1]]7l1/Jg ' ! 1 A 1 -'*—<~1 -- ~11“ p.— -<>-——-<»-~ 1 N ~«~\ NW L“ x N HT? 1.1: p- 1’, yd 1" F’Jfi’l /./‘ §//” 1 i// 4- P - r' '- 11 “Ohm!” --ou 411111111r 111111111 1111111 1 ”In“ an 90 2) pH 4. 8, Farinograms of unchlorinated and chlorinated flours from Lewjain 1993 variety: 1) Control, 3) pH 4.3. ////////]7/[ l/////// /.'1/ lfl/ [1 L51! [UPI/1111' 711111 1 1 1 1' 11.1 '1 I11 a 1l 4‘. 1 ‘ 1 ,_ ‘\\ \ \‘1 “\1_1__ \1\ \1\"\\:.\111‘T\ 1\\1\\\\X\L 2 1 WT \ \\\1\\\\\\T ......b..\...\\‘1\‘\ \ L111-..) - 1'1/-1'"7//////// 4/1/1/1/’ / 71’ l/J/l 1111;111111[311/1]! L1111'1’1'1'1rl 11YJ1111.11 1 '1 i 1 3 .‘1. ‘1 1. _. _\'_ ‘ 411\\ V \ \xi\‘\\ 91 Farinograms of unchlorinated and chlorinated flours from Rely 1992 variety: 1) Control, 2) pH 4. 8, 3) pH 4.3. "/ 111157717111 11111-111111 #1le [1111/1L1111 1' l 1 I I b. ~‘ ! I! H Y O l I l 1 ,. -—-n——..“ _ -.. 1 I 1 11 \ \ AA \ \A \1 fit. \\ 1...); 1 1 1 \ \ \“L ‘2 \ ‘ \ \ \; \\ f/// //////7 //// ///T W] // «ll/[[1/[If/l/ 1 /1 l l.// 7— 11/1!/! {1] 1 fl 1‘: 1. 1\1\‘\‘\ \\‘\\\\\T I 1 I w \ , --.- —-—.»- 4.. 92 Farinograms of unchlorinated and chlorinated flours from Tres 1993 variety: 1) Controhn 3);}! 4. 8, 3) pH 4.3. /'/I I/ ’ / I / / I 17" I I T7 I I] II [III I .I I i A I t I I O I I i I I I ‘— ‘ I I T\\\\ __\\‘x \\\ W \\I‘\\\: uncanny-um“ “flu“ IJ/I'II/I IJl/ll/I'Il/ J I I I mun-c an L/l/lwI/ /’ .0. ' -_..,-.‘ 4 —-..I //////// li/I/I/IIII/I/I‘I/7 [III/ll/I/I‘Il/lI/HHT I 1 \L \ \_ \ I 7 I I j III I I I /' // II I II I I I I ’1/7 I [T/ / II IT? 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