of Dry-Heated Egg White on Wheat Starch Gel and Gluten Dough

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1 Fd Sci. Technl. Res., 0 (4), , 2004 Eff ect f Dry-Heated Egg White n Wheat Starch Gel and Gluten Dugh M akt SHIMYAMADA, Nrik GAWA2 Kazuhik TACHI Kenjl WATANABEI 3 Ry YAMAUCHI and KJI KAT United Graduate Schl fagricultural Science, Glfu University, - Yanagid, Glfu 50-]93, Japan 2 Faculty fhme Ecnmics, Glfu Wmen's University, 80 Tarmaru, Glfu , Japan 3 Currently Faculty fagriculture, Tky University fagriculture, 737 Funak, Atsuki , Japan Received ctber 27, 2003 ; Accepted July 2, 2004 Characterizatin f the mechanisms f imprvement f Chinese ndles by dry-heated egg white, were estimated by rhelgical and spectrscpic data f the effects f dry-heated egg white n wheat starch gel and gluten dugh. The dry-heated egg white significantly increased breaking stress and elasticity f the starch gel but had little effect n retrgradatin f the gel and distributin f prteins in the gel. n the ther hand, the dry-heated egg white had a negligible effect n creep curves and IR spectra f gluten dugh. Frm these data, imprvement f Chinese ndles by the dry-heated egg white is believed t be due t interactin between the dry-heated egg white prteins and gelatinized starch mlecules rather than gluten prteins. Hwever, the effect f the dry-heated egg white n starch gel was unexpectedly small cmpared t the effect n the ndles. dry-heated egg white, wheat starch, wheat gluten, gelatinizatin Keywrds: Intrductin Egg whites are widely used in fd prcessing because f their excellent prperties f emulsifying, faming and gelling. Further, cntrlled heating in a dry state (fr example, 80'C fr 5- days) was reprted t imprve the functinalities f egg white withut any lss in slubility (Kat et al., 989, 990a, 990b, Mine, 996, 997). Xu et al. (998) reprted the ptential value f dry-heating, which is a heating prcess f fd materials, especially egg white, at ver 00'C fr several hurs with very lw water cntent. The dry-heating allwed egg white pwder t be sluble in water during reheating f slutin f the dry-heated egg white. They als shwed an inhibitry effect n heat-induced cagulatin f fresh egg white t imprve the pasteurizatin f egg white. Watanabe et al. (999) reprted that the dry-heated egg white inhibits heat aggregatin and cagulatin f vtransferrin and lyszyme in freeze-dried egg white resulting in a transparent slutin after reheating (60'C, 5 min). Further study n dry-heating shwed that valbumin frmed sluble aggregates and the aggregates inhibited cagulatin f vtransferrin (Watanabe et al., 2000). Features f the dry-heating recgnized by Xu et al. (998) and Watanabe et al. (999 and 2000) were that the dry-heating allwed mst water t evaprate frm prtein pwder ver 00'C at the first stage and prteins were thermally denatured under very lw water cntent. As fr ther prperties, Tachi et al. (2004) reprted an imprvement in Chinese ndles (Chukamen in Japanese), made frm wheat flur and alkaline slutin (Kansui), by the additin f dry-heated egg white. The dry-heated egg white increased breaking stress, instantaneus elasticity and Abbreviatins: FT-IR. Furier transfrm infrared; NMR, nuclear magnetic resnance tensile strain f the ndles, resulting in greater acceptability. Spray-dried egg white pwder has lng been added t wheat flur t imprve Chinese ndles. Hwever, sprayed egg white has a prblem in that its additin made the ndles shrter as well as firmer than ndles t which there had been n such additin. Additin f the dryheated egg white instead f the spray-dried pwder significantly imprved the Chinese ndles by sensry evaluatin as well as rhelgical prperties. We therefre wanted t clarify the mechanism f imprvement f the ndles by the dry-heated egg white. In this study, we evaluated the effects f the dry-heated egg white n wheat starch gel and gluten dugh and discussed interactins between egg white prtein and starch r gluten. Materials and Methds Materials Cmmercially available wheat starch (special grade, NCA Ryri n Mt K.K., Japan) and gluten (A-Glu SS, Glic Fds C., Ltd., Japan) were used fr this study. Dry-heating f egg white pwder Dry-heated egg white pwder was prepared accrding t previus paper (Xu et al., 998). Namely, the spray-dried egg white pwder was disslved in distilled water and lyphilized. Dried egg white pwder was spread thinly n paper and heated at 20'C fr 6 h uncvered in an ven. The dry-heated egg white was then put in a desiccatr t cl. Preparatin f gluten dugh and starch gel Wheat starch pwder (3 g) and egg white pwder (0.2 g; 4% t starch) was mixed with water (7 g) and put int a casing tube (2 mm i.d.). Bth edges f the tube were fastened and the tube was put in a water bath and first partially gelatinized at 60'C fr 3 min and then cmpletely gelatinized at 00'C fr 30 min (Aman et al., 995). The starch gel was sliced int pieces 0 mm height. Wheat gluten pwder (2.88 g), egg white pwder (spray-

370 dried r dry-heated; 0.2 g) and 2 ml f water r alkaline slutin (kansui; 2.5 g f K2HP04,.7 g f Na2HP04 in 00 ml f water) was mixed and stirred fr I min with a glass rd t furnish raw gluten dugh.

2 370 dried r dry-heated; 0.2 g) and 2 ml f water r alkaline slutin (kansui; 2.5 g f K2HP04,.7 g f Na2HP04 in 00 ml f water) was mixed and stirred fr I min with a glass rd t furnish raw gluten dugh. The dugh was put int a casing tube and bth edges tightly fastened and heated in biling water fr 5 min. Rhelgical measurements Rhener RE-3305 (Yamaden C., Ltd., Tky) was used fr measurements f breaking strength and creep behavir f starch gel and gluten dugh cntaining the dry-heated egg white. Stress - strain curves were btained under cnditins as fllws: sample diameter, 2 mm; cmpressive speed,.0 mm/s; and defrmatin rati, 95%. Creep behavir under cmpressin was als analyzed as fllws: sample diameter, 2 mm. Initial speed f the sample plate was set at I. mm/s. Elevatin f the plate was cntinuusly adjusted t prduce a cnstant stress f 60 g-frce by the creep meter (5200 Pa), and the displacement f the gel after the initial stress (60 s) was recrded. The data were stred in a diskette and analyzed using sftware (CA ) designed fr creep analysis (Yamaden C., Ltd.). Furiertransfrm infrared (FT-IR) spectra IR spectra were recrded with a System 2000 FT-IR spectrmeter (Perkin Elmer, Inc.) by Hrizntal ATR methd. 3Cnuclearmagnetic resnance (NMR) spectra 3C NMR spectra were recrded n a Unity Inva 400 spectrmeter (3C at 00 MHz; Varian, Inc.). Relative peak height f each signal f glucse residue t signals f pyridine (an internal standard) was used t characterize the retrgradatin. The peak height derived frm the starch gel immediately after preparatin was set t I and decrease f the relative peak intensity indicated retrgradatin f the starch gel. Distributin fprteins in starch gel Starch gel was fixed with 3.7(~ frmaldehyde slutin (ph 7) fr 24 h, and then sliced by a micrtme (. 5 mm thickness). Each piece f sliced disk was dyed by acrlein Schiff reactin and applied t a BHS ptical micrscpe (lympus ptical C., Ltd.). Results and Discussin Effect f the dry-heated egg white n the starch gel The dry-heated egg white effectively increased breaking stress, instantaneus elasticity, tensile strain and sensry prperties f Chinese ndles cmpared t the spray-dried egg white, as well as the ndles cntaining n egg white (Tachi et al., 2004). In rder t clarify the mechanism, we evaluated the effect f the dry-heated egg white n starch gel. Stress - strain curves f the starch gel cntaining tw kinds f egg white are shwn in Fig.. Breaking stress f the starch gel was increased by additin f the spray-dried egg white pwder, and further increment in the stress was bserved by additin f the dry-heated egg white pwder. The dry-heated egg white shwed mre effective enhancement f the breaking stress, and these data cincided with the previus result (Tachi et al., 2004). Next, the starch gel was applied t a creep experiment (Fig. 2). Creep cmpliance f the starch gels with the 4 ~ CQ3 _ ~ -2 X ~ (D ~ Strain (cmlcm) M. SHIMYAMADA et al. Cntrl 0.8 Fig.. Stress - strain curves f starch gel cntaining dry-heated egg white. Cntrl, N additin f egg white;, additin f spray-dried egg white;, additin f dry-heated egg white. c.5 CL " ~ - x c c5 ~ 0.5 E Cntrl 2 *~~ r' ~ ~ E E ~l E2 n2 ~ n 90 Time (s) Fig. 2. Creep curves f starch gel cntaining dry-heated egg white. Abbreviatins, see Fig. I. Inset, Vigt type six-element mdel. spray-dried egg white was less than that withut the egg white. Further, the dry-heated egg white decreased the cmpliance cmpared with the spray-dried egg white. These data shwed the dry-heated egg white enhanced gel strength f the starch gel mre than the spray-dried, similar t the abve data n breaking stress. Frm these curves, viscelastic mduli were calculated using the sftware (CA , Yamaden C., Ltd.) accrding t a Vigttype mdel (Fig. 2 inset). The starch gel cntaining the spray-dried egg white was well demnstrated by the Vigttype fur-element mdel. Hwever, the gel cntaining n egg white and the dry-heated egg white was calculated by the six-element mdel because the fur-element mdel demnstrated the gel insufficiently. As a result, the mdulus f instantaneus elasticity (E) f the starch gel cntaining the dry-heated egg white was significantly higher than ther samples (Fig. 3 and Table ). Hwever, there was n significant difference in mduli f retarded elasticity. n the ther hand, the mduli f viscsity in steady state (n) and retarded state (n ) varied widely and had n significant differences, s n significant effect was detected (Table ). Hardness and elasticity f the starch gel increased by additin f the dry-heated egg white cmpared with the spray-dry egg white as well as that with n additin. In previus papers (Xu et al., 998, Watanabe et al, 999 and 2000), valbumin mlecules were reprted t frm sluble aggregates during the dry-heating prcess, and the

Effect f Dry-Heated Egg White n Wheat Starch Gel and Gluten Dugh 6 cv ~ L_ 2 - X 8 ~ > ~= c c Di 4 Cntr[ Fig. 3. Elasticity f starch gel cntaining dry-heated egg white and effect f refrigeratin.

3 Effect f Dry-Heated Egg White n Wheat Starch Gel and Gluten Dugh 6 cv ~ L_ 2 - X 8 ~ > ~= c c Di 4 Cntr[ Fig. 3. Elasticity f starch gel cntaining dry-heated egg white and effect f refrigeratin. Abbreviatins, see Fig. I. pen square, Immediately after preparatin; Hatched square, After I day f refrigeratin. resulting aggregates were believed t interact with vtransferrin t inhibit frmatin f insluble aggregates f vtransferrin under thermal denaturatin and t interact with fresh egg white prteins t frm a mre rigid gel structure during re-heating. Cnsidering these reprts, the sluble aggregate f valbumin in the dry-heated egg white is cnsidered t be mre effective fr interactins with starch gel matrix, pssibly because f hydrgen bnding and ther interactins. These imprved interactins may allw the gel netwrk t be dense and tight. Further, the mre rigid structure f prtein aggregate cmpared with the starch gel matrix is prbably respnsible fr high elasiticity f the starch gel cntaining the dry-heated egg white. Then, we evaluated the effect n retrgradatin f the starch gel. Creep cmpliance was measured, because retrgradatin generally allwed the starch gel t be harder (Fig. 3). After I day f refrigeratin at 4'C, the starch gel was applied t a creep experiment. Befre refrigeratin, the elasticity f the dry-heated egg white added gel was significantly higher than bth the cntrl and the spraydried egg white added starch gel. After refrigeratin, the elasticity f each sample increased, but the differences between befre and after refrigeratin were reduced by additin f the dry-heated egg white and there was n significant difference amng 3 kinds f gels despite the egg white additin. Increments f mduli f the elasticity f each starch gel (n additin, spray-dried egg white and dry-heated egg white) frm day t I day were calculated t be.73,.63 and.49, respectively. The dry-heated egg white might have sme suppressive effect n increase f the elasticity by retrgradatin f the starch gel during 37 refrigeratin but there was n clear evidence f retrgradatin f the gel cntaining the dry-heated egg white. T estimate the decrease in gelatinizatin degree f starch mlecules by retrgradatin, the starch gel was applied t 3C-NMR measurements. Kainsh and Ajisaka (978) reprted that glucse residues in starch shwed narrw 3C signals by gelatinizatin. This narrwing f the signals is believed t be caused by higher mbility f glucse residues in gelatinized starch mlecules thrugh the breaking f inter-residual hydrgen bndings by thermal energy. Fuke and Matsuka (984) evaluated the retrgradatin degree f kiwi fruit starch by measuring signal intensities f glucse carbns in starch mlecules. Partial recrystallizatin f starch mlecule during retrgradatin limited the mbility f glucse residues and allwed nly 0w signal intensities. As fr signals assigned t glucse residue in the starch gel, ratis f signal intensities befre and after I day f refrigeratin were calculated n the starch gel, the spray dried egg white added and the dry-heated egg white added gels (Fig. 4), where the intensity immediately after preparatin f the gel was set t I. The starch gel (n additin f egg white) shwed abut 0.68 f relative intensity, while starch gels cntaining the spray-dried egg white r the dry-heated egg white was Additin f the egg white t the starch gel effectively suppressed the decrease f signal intensity, but there was n significant difference between the spray-dried and the dry-heated egg white. Thus, these results shwed n significant differences between the spray-dried and the dry-heated egg whites n the elasticities and 3C NMR signal intensities f the refrigerated gels. ~ > ()._ 08 c:.s; ~ 06 ~as c: 9) Cntrl S D EW Fig. 4. Signal intensity f 3C-NMR spectra f starch gel cntaining dry-heated egg white after refrigeratin. Abbreviatins, see Fig. I. Each signal intensity was relatively shwn against the intensity measured immediately after preparatin f the gel. Table. Creep parameters f starch gel cntaining dry-heated egg white. Nne E x 0~ 5.84 :!: d: :!: 0.86 Nne, ndle with n additin f egg white, spray dried egg white, dry-heated egg white E x :!: :!: :!:.74 E2 X 0-6. :t 0,7.70 :!: 0.6 nl x :!: :!: :t.89 n2 X 0-6 l.63 ~ :~ 4.22 W X 0-8 l.07 ~ :~ 0.70 l.26 :~ 0.2

372 Bth f the spray-dried and dry-heated egg whites were shwn t suppress retrgradatin f starch gel effectively, but there were n significant differences between them.

4 372 Bth f the spray-dried and dry-heated egg whites were shwn t suppress retrgradatin f starch gel effectively, but there were n significant differences between them. Egg white prteins were believed t interact with glucse residues in starch gel matrix after partial breaking f interresidual hydrgen bndings by thermal treatment and t inhibit recrystallizatin f gelatinized starch mlecules by suppressing recnstitutin f inter-residual hydrgen bndings during refrigeratin f the starch gel. But this effect f prtein is likely t be independent f the dispersin state f prteins such as the mlecular mass f prtein aggregates. We characterized distributin f egg white prtein in the starch gel and cmpared the spray-dried and the dry-heated egg white. Sectins f starch gel shwed granules f the prtein and there were n significant differences in prtein distributin (Fig. 5). These data may imply that effect f the dry-heated egg white n the starch gel was nt caused by the distributin f egg white prtein mlecules in the gel, but by interactin between egg white prteins and starch mlecules. Effect f the dry-heated egg white n gluten dugh Then, in rder t identify the interactin between the dryheated egg white and gluten, the effect f the frmer n gluten dugh was evaluated. Creep behavir f the dugh cntaining the dry-heated egg white was cmpared with the dugh cntaining the spray-dried egg white (Fig. 6). There were n differences between these tw samples, and there were als n differences even if the gluten was dispersed in alkaline slutin (Kansui) instead f water (data nt shwn). In rder t evaluate the effect n secndary structure f gluten prtein, the gluten dugh cntaining the dry-heated egg white was subjected t FT-IR spectra and the decnvluted spectra btained are shwn in Fig. 7. Absrbing as _ Lr) ~ = x as ~:~ E M. SHIMYAMADA et al Time (s) Fig. 6. Creep curves f gluten dugh cntaining dry-heated egg white. Fine line, spray-dried egg white; Bld line, dry-heated egg white. peaks ranging frm ca. 700 t 580 cm~ (the amide band I) and frm 580 t 450 cm~ (the amide band II) reflect the secndary structures (e.g., e-helix, P-sheet and randm structures) (Surewicz et al., 993). Additin f egg white allwed the intensity at cal630 cm~ which is assigned t the P-sheet structure (Surewicz et al., 993) t becme rel- c ct: ~2 ō U) L: < Wavenumber (cm~) N additin Fig. 7. Decnvluted FT-IR spectra f gluten dugh cntaining spraydried r dry-heated egg white. Abbreviatins, see Fig, I. S u rface Center Fig. 5. Distributin f prteins in starch gel cntaining dry-heated egg white. - um Abbreviatins, see Fig.

5 Effect f Dry-Heated Egg White n Wheat Starch Gel and Gluten Dugh atively larger. These changes are thught t be respnsible fr differences in structures between gluten and egg white prteins. Cmparing the spray-dried and dry-heated egg whites, the decnvluted spectra had almst equal patterns with nly a slight difference in peak tp psitin f amide band I f each sample, namely 639 cm~ (spraydry egg white) and 936 cm~ (dry-heated egg white). S these data may shw that bth egg whites have almst the same effects n the gluten prtein structures. There may be n differences in interactins between egg white and wheat prteins, even if we use the spray-dried r the dry-heated egg whites. These data suggest that the dry-heated egg white prtein interact with starch mlecules and/r the starch gel netwrk mre than wheat prteins, and there were sme differences in interactins between the spray-dried and the dry-heated egg whites. Hwever, Tachi et al. (2004) reprted much greater imprvement f rhelgical and sensry prperties f Chinese ndle. These data seem t shw that the dry-heated egg white prteins affect the interactin between starch and gluten and the effect brings abut an imprvement in the rhe- 0gical prperty f the ndles. Acknwledgement This study was funded by the lijima Memrial Fundatin fr the Prmtin f Fd Science and Technlgy. Ref erences Aman, T., Hayashi, A., Miura, M., Ishida, K. and hshima, K. (995). Creep bahavir f starch gels at the earlier retrgradatin stage. y Tshitsu Kagaku, 42, (in Japanese). Fuke, Y, and Matsuka, H. (984). Studies n the physical and chemical prperties f kiwi fruit starch. J. Fd Sci., 49, , 627. Kainsh, M. and Ajisaka, K. (978). Carbn-3 nuclear magnetic resnance spectra f grss plant tissues cntaining starch. Tetrahedrn Lett., 8, Kainuma, K. (986). Gelatinizatin and Retrgradatin, In "Seibutsukagaku Jikkenhu 9 Experimental Methds in Starch and Related Sugars," eds. by M. Nakamura and K. Kainuma. Gakkai Shuppan Senta, Tky, pp Kat, A., Ibrahim, H.R., Watanabe, H., Hnma, K. and Kbayashi, K. (989). New apprach t imprve the gelling and surface functinal prperties f dried egg white by heating in dry state. J. Agric. Fd Chem., 37, Kat, A., Ibrahim, H.R., Watanabe, H., Hnma, K. and Kbayashi, K. (990a). Structural and gelling prperties f dry-heated egg white prteins. J. Agric. Fd Chem., 38, Kat, A., Ibrahim, H.R., Takagi, T. and Kbayashi, K. (990b). Excellent gelatin f egg white preheated in the dry state is due t the decreasing degree f aggregatin. J. Agric. Fd Chem., 38, Mine, Y. (996). Effect f ph during the dry heating n the gelling prperties f egg white prteins. Fd Res. Int., 29, 55=6. Mine, Y. (997). Effect f dry heat and milk alkaline treatment n functinal prperties f egg white prteins. J. Agric. Fd Chem., 45, Surewicz, W.K., Mantsch, H.H. and Chapman, D. (993). Determinatin f prtein secndary structure by Furier Transfer Infrared Spectrscpy: A critical assessment. Bichemistry, 32, Tachi, K., gawa, N., Shimyamada, M., Watanabe, K. and Kath, K. (2004). Effects f dry-heated egg white n rhelgical prperties and structure f Chinese type ndles. Nippn Shkuhin Kagaku Kgaku Kaishi, 5, (in Japanese). Watanabe, K., Xu, J.Q. and Shimyamada, M. (999). Inhibiting effects f egg white dry-heated at 20'C n heat aggregatin and cagulatin f egg white and characteristics f dry-heated egg white. J. Agric. Fd Chem., 47, Watanabe, K., Nakamura, Y., Xu, J.Q, and Shimyamada, M. (2000). Inhibitin against heat cagulatin f vtransferrin by valbumin dry-heated at 20'C. J. Agric. Fd Chem., 48, Xu, J.Q., Shimyamada, M. and Watanabe, K. (998). Heat aggregatin f dry-heated egg white and its inhibiting effect n heat cagulatin f fresh egg white. J. Agric. Fd Chem., 46,

19 th INTERNATIONAL CONGRESS ON ACOUSTICS MADRID, 2-7 SEPTEMBER 2007 NARROW TUBES ACOUSTIC IMPEDANCE CHARACTERIZATION USING FINITE ELEMENT BASED TOOLS

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