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Journal of the American Oil Chemists' Society Volume 70 Issue 6 1993 [Doi 10.1007_bf02545322] Jia Mingyu; Andrew Proctor -- The Effect of Added Solvents on Soy Oil Lutein Adsorption by Silicic Acid-1
The Effect of Added Solvents on Soy Oil Lutein Adsorption
by SUicic Acid Jia Mingyu and Andrew Proctor* Department of Food Science and Technology, The Ohio State University, Columbus, Ohio 43210-1096 I t h a s b e e n r e p o r t e d t h a t a d d i t i o n o f i s o p r o p a n o l t o a s o y oi l mi s c e l l a i nhi bi t s t h e b i n d i n g o f s o y l u t e i n t o a d d e d s i l i c i c a c i d b y c o mp e t i t i v e a d s o r p t i o n . I t w a s s u g g e s t e d t h a t t h e c o mp e t i t i o n w a s b a s e d o n t h e p o l a r i t y o f t h e mi s c e l l a c o ns t i t ue nt s . Thi s i n v e s t i g a t i o n s t udi e d t h e e f f e c t s o f a h o mo l o g o u s s e r i e s o f l o we r a l c o h o l s t o c o mp e t i t i v e l y i nhi bi t l u t e i n bi ndi ng t o s i l i c i c ac i d f r o m a s o y oi l h e x a n e mi s c e l l a . Lu t e i n bi ndi ng i nhi bi t i o n b y mo l e c u l e s o f c a r bo n c hai ns wi t h t h e s a me l e ng t hs , but wi t h di f f e r e nt f unc t i o na l g r o ups , w a s a l s o e x a mi n e d . Mi n o r d i f f e r e n c e s we r e f o u n d b e t we e n me mb e r s o f a h o mo l o g o u s s e r i e s o f a l c o h o l s . A s i mi l a r r e s u l t w a s f o u n d wi t h s h o r t - c h a l n f a t t y ac i ds . Th e abi l i t y o f v a r i o u s f u n c t i o n a l g r o ups t o di s pl a c e l ut e i n f r o m s i l i ci c ac i d w a s de pe nde nt o n t h e mo l e c ul e s ' a bi l i t y t o f o r m h y d r o g e n bo nds , r a t he r t h a n o n po l a r i t y . KEY WORDS: Adsorption, lutein, miscellas, silicic acid, solvents, soy oil. Oil is extracted from soy flakes with hexane, which is then evaporated to produce the crude oil. Crude soy oil contains a number of substances, such as pigments, phospholipids and free fatty acids, which must be removed to produce a bland, light-colored oil that is acceptable to consumers. The commercial removal of pigments is achieved by an adsorp- tion process at 100C on bleaching clays under reduced pressures (1). Soy oil pigment is almost exclusively the carotenoid lutein (2}. Hassler and Hagberg (3) showed that the adsorption of soy oil pigment on bleaching clay occurs according to a Freundlich isothern~ Adsorption of phospholipids (4) and lutein (5) onto silicic acid from soy oil/hexane misceUas also conforms to a Freundlich isotherm. An advantage of this bleaching tech- nique, relative to conventional methods, is that it is con- ducted at ambient temperatures, and the binding of these oil components is modified by the addition of a polar sol- vent to the miscell~ One percent isopropanol in the misceUa promotes adsorption of phospholipid, which presumably oc- curred by removal of triglyceride from adsorption site~ This then facilitates phospholipid binding (4). Free fatty acid ad- sorption to amorphous cristobalite silica was also promoted by isopropanol in a similar system (5). In contrast, iso- propanol inhibited adsorption of lutein to silicic acid (5). This inhibition was explained in terms of competition between misceUa constituents for silanol sites. Polarity was sug- gested to be a basis for competition because of the is~ propanol effect. However, reducing triglyceride concentra- tion promoted lutein adsorption, suggesting that concen- tration and/or molelcular weight of competing species may also be factors that determine adsorption. The objective of this investigation is to study the effect of alcohol molecular weight on lutein binding from a soy oil miscella and the adsorption isotherm. The effect on the *To whom correspondence should be addressed at Department of Food Science, University of Arkansas, 272 Young Avenue, FayetteviUe, AR 72703. lutein isotherm of C3 and C4 compounds with different functional groups was also examined. MATERIALS AND METHODS Oil and sol vent s. Commercially extracted alkali-refined soy oil was stored at 4C and used throughout the in- vestigations. Soy oil miscellas were prepared by diluting soy oil with hexane Water and the following alcohols were added to modify miscella polarity (0.1 M concentration} prior to lutein ad- sorption: methanol, ethanol, n-propanol, isopropanol, n- butanol, isobutanol, 2-octanol, 1-nonanol and 1-decanol. The following aldehydes, ketones, acids and esters were also used: propanal, acetone, 2-butanone, acetic acid, pro- pionic acid, n-butyric acid, isobutyric acid, octanoic acid, methyl acetate and ethyl acetate. Ads or bent s . The adsorbent used was silicic acid (Bio- Sil A., 100-200 mesh, Bio-Rad Laboratories, Richmond, CA). Silicic acid was heated in a drying oven to remove moisture and was stored in a desiccator until used. The term "silica" is used as a synonym for silicic acid. Lut e i n meas ur ement . Pigment concentration in the miscellas was measured as lutein by reading optical ab- sorbance at 445 nm, according to the method of Proctor and Snyder (5). Lut e i n i sot herms. Lutein isotherms were determined by preparing 100-mL volumes of 2.5, 5, 10, 20, 30 and 40% (vol/vol) concentrations of soy oil miscellas in hexane The lutein content of each miscella was measured before 0.5 g of silica was added. The misceUas were agitated with a magnetic stirrer in a closed vessel at 22C for 15 min. The concentration of residual lutein remaining unadsorbed was then found, and the amount of lutein adsorbed was calculated by difference Isotherms were plotted as the amount of lutein adsorbed, per gram of silica, vs. the residual concentration of lutein. Duplicate determinations were made. This was the control experiment. Mi scel l a polarity. Isotherms were prepared as described above but with 0.1 M concentration of additional solvent present in the miscella. RESULTS AND DISCUSSION Figure l a shows the effect of adding water and low molecu- lar weight alcohols (C1-C3), to the misceUa on pigment binding. Lutein adsorption followed a Freundlich isotherm, and added solvent reduced lutein adsorption relative to the control in each case There is little difference in the isotherms obtained with ethanol, n-propanol and isopropanol, which were more effective t han water in in- hibiting lutein binding. Methanol was slightly less effec- tive in reducing lutein adsorption. The differences in the results obtained with different solvent systems were best seen at high residual lutein levels. Water was the least effective solvent, but it did signifi- cantly reduce lutein adsorption relative to the control. Water can hydrogen bond to the silica or to other water molecules. In this lipid system it is probably more thermo- Copyright 1993 by the American Oil Chemists' Society JAOCS, Vol. 70, no. 6 (June 1993) 576 J. MINGYU AND A. P ROCTOR O 9 O E v JD O "O c- D 2.50 2. 00 1. 50 1. 00 0, 50 0. 00 a 6 1 2 16 Resi dual l ut ei n ( pM) 2. 50 "~ 2.00 ~ 1 . 5 0 "O . ~ ' 1. 00 C 0 . 5 0 0 . 0 0 0 b I I 6 12 18 Resi dual l ut ei n ( pM) F I G. 1. Lu t e i n i s o t h e r ms we r e o b t a i n e d b y i n c u b a t i n g 0. 5 g o f s i l i c i c a c i d w i t h 100 mL o f 2. 5, 5, 10, 20, 30 a n d 40% ( vol / vol ) a l ka l i - r e f i ne d s o y o i l / h e x a n e mi s c e l l a f o r 15 mi n a t 2 2 C i n t h e p r e s e n c e o f 0. 1 M c o n c e n t r a t i o n o f (a) wa t e r {~,~, me t h a n o l (O), e t h a n o l ( ) , n- pr opanol (A) or i s o p r o p a n o l (A). A c o nt r o l { +) w a s pr e par e d w i t h o u t a dde d s ol - v e n t ; (b) n - b u t a n o l (D), i s o b u t a n o l ( . ) , 2 - o c t a n o l (Y), 1- nonanol { ~ ) a n d 1- decanol ([7). A c ont r ol ( + ) w a s pr e par e d wi t h o u t a dde d s o l v e n t . dynamically stable for water molecules to associate to- gether. The effect of added water in this system may be due to the strength of water/water hydrogen bonding and water's lipophobic nature. To enable water molecules to bind to silica, water hydrogen bonding has to be disrupted, and individual molecules migrate to the adsorption sur- face. This is probably not as energetically favorable as disruption of alcohol hydrogen bonding. Furthermore, an alkane structure would increase solubility in a lipid system and permit binding to an adsorbent. Therefore, competi- tive adsorption would be expected to be improved by ad- 2. 50 .9 ~ 2.00 + O) (D 1. 50 o E " 0 (D 1. 00 O " o c- o. 5o ' $ _1 0. 00 i i I i ~ I I J i I I I I I i I I 6 1 2 Resi dual l ut ei n ( pM) F I G. 2. Lut e i n i s o t h e r ms we r e o b t a i n e d b y i n c u b a t i n g 0. 5 g o f s i l i c i c a c i d w i t h 100 mL o f 2. 5, 5, 10, 20, 30 a n d 40% ( vol / vol ) a l ka l i - r e f i ne d s o y o i l / he x a ne mi s c e l l a f o r 15 rai n a t 2 2 C i n t h e pr e s e nc e o f 0. 1 M c o n c e n t r a t i o n o f a c e t i c a c i d (A); p r o p i o n i c a c i d (A), n - b u t y r i c a c i d ([7), i s o b u t y r i c a c i d ( B ) a n d o c t a n o i c a c i d (O). A c o n t r o l ( + ) w a s pr e pa r e d w i t h o u t a d d e d s o l v e n t . 18 dition of an alkyl group. Methanol is slightly less effec- tive than ethanol at reducing lutein binding, but the ef- fect of ethanol is similar to that of propanol isomers. Therefore, the methyl groups bound to the hydroxyl car- bon of isopropanol do not sterically hinder adsorption relative to the primary alcohol. Butanol isomers, octanol and nonanol also produced similar isotherms to those obtained wi th propanol (Fig. lb). These data indicate that with lower alcohols there are several small differences in adsorption on the basis of isomerism or molecular weight. Molecular shape and size are reported to be important factors preventing hydrogen bonding to silica due to steric hinderance (6). In studies of long-chain species, Hau and Newar (7) reported that the number of moles adsorbed to silica decreases as chain- length increases. The results of studyi ng the competitive adsorption of lutein suggest that wi th alcohols (C0-C10) (Fig. l a and lb) there is no large change in the isotherm, as alcohol length is increased but small differences are seen. These isotherm studies give indirect evidence that lower alcohols bind largely independently of chainlength. This study is complicated by the presence of triglyceride, which is the major species bound overall (5). Figure 2 shows the effect on lutein adsorption of adding members of a homologous series of fatty acids to the soy oil miscellas. Al though lutein adsorption is reduced rela- tive to the control, there is little difference between iso- therms. Therefore, the ability of free fatty acids to com- pete wi th lutein for binding sites is independent of chainlength. The data conform to Wu and Mead's (8) find- ings that fatty acid adsorption to silica is independent of chainlength. This shows the importance of extracting free fatty acids from soy oil before pigment adsorption. JAOCS, Vol. 70, no. 6 (June 1993) EFFECT OF SOLVENTS ON LUTEIN ADSORPTION 577 2. 50 0 '~ 2 . 0 0 (~ 1. 50 0 E '10 (D 1. 00 , . 0 L., 0 m t = 0, 50 3 . . 1 0. 00 6 12 18 Residual lutein (pM) FI G. 3. Lut e i n i s o t h e r ms were o bt a i ne d b y i nc uba t i ng 0. 5 g o f s i l i ci c a c i d wi t h 100 mL o f 2. 5, 5, 10, 20, 30 a nd 40% (vol / vol ) al kal i - ref i ned s o y oi l / hexane mi s c e l l a f or 15 mi n a t 22 C i n t he pr e s e nc e o f 0. 1 M c o nc e nt r a t i o n o f n- propanol (A), i s o pr o pa no l (A), pr opi oni c a c i d ( I ) , a c e t o ne (C:]), pr opanal ( ) a nd me t h y l a c e t a t e (O). A cont rol ( +) wa s prepared wi t h o u t a dde d s o l v e nt . 2, 50 0 " ~ 2. 00 (D 1. 50 "6 E " O ~D 1 . 0 0 . O 0) " 0 e- 0, 50 _J 0.00 0 6 12 18 Residual lutein (pM) FI G. 4. Lut e i n i s o t he r ms were obt ai ne d by i nc uba t i ng 0. 5 g o f s i l i ci c ac i d w i t h 100 mL o f 2. 5, 5, 10, 20, 30 a nd 40% (vol / vol ) al kal i - ref i ned s o y oi l / he xane mi s c e l l a f or 15 mi n at 22 C i n t h e pr e s e nc e o f 0.1 M c onc e nt r at i on o f n- but anol , ([:]), i s o b u t a n o l ( I ) , n- but yr i c ac i d (A}, i s o but y r i c ac i d (A}, 2- but anone ( } a nd e t h y l a c e t a t e (O). A c ont r ol (Jr) wa s prepared wi t h o u t a dde d s o l v e nt . The effect of an added Ca alcohol, aldehyde, ketone, acid and ester on lutein binding is illustrated in Figure 3. Freundlich isotherms were observed in the presence of each solvent, but there were differences in the solvent' s ability to inhibit lutein binding. The alcohols were the most effective in inhibiting lutein binding, which is prob- ably because they are best able to form hydrogen bonds with silanol groups. Hau and Newar (7) reported t hat the greater the tendency for hydrogen bonding, the stronger the adsorption. This st udy supports t hat premise, with the alcohols being most effective. A silanol hydroxyl is capable of forming two hydrogen bonds with a single alcohol hydroxyl group, or can hydrogen bond to two dif- ferent alcohols (9). Propionic acid was the most effective of the nonalcohol solvents, despite the fact t hat it has a lower polarity than the aldehydes and ketones used. This is most likely due to its ability to hydrogen bond. Each molecule is capable of forming two hydrogen bonds to a silanol group (9). Organic acids are not bound to silica to the same degree as alcohols, but the acid binding strength is greater (7). At low miscella residual concentrations (<9 ~M), the lu- tein isotherm, obtained with the remaining solvents, did not differ from the control or from each other. However, differences were evident in the 40% miscella. Acetone reduced lutein binding slightly more than propanal, prob- ably because of the greater polarity in a similar system (10). The isotherm obtained with methyl acetate was similar to t hat of the control. This indicates t hat this ester was not any more effective t han triglyceride esters in com- peting with lutein for adsorption sites. This could be because the amount of added ester is negligible compared to the amount of triglyceride esters in the system. In any case, the position of the carbonyl group on an ester may make hydrogen bonding to a surface sterically difficult. Nevertheless, in this system triglyceride is the major oil component, and therefore, concentration is the overriding consideration (5). The nonalcohol solvents were practically ineffective at reducing lutein binding at most miscella concentrations. Therefore, ability to hydrogen bond is more important t han polarity in determining a molecule's ability to com- pete with lutein for adsorption sites. The effectiveness of the solvents as competitors for lu- tein adsorption was alcohol > acid > ketone > aldehyde > ester. This is supported by Hau and Newar (7}, who found t hat when comparing different classes of com- pounds of the same chalnlength, the amount adsorbed was alcohol > acid > ester. Figure 4 shows the effect of selected C4 compounds on lutein adsorption by silic& The pat t ern of adsorption was similar to t hat obtained with C3 compounds, i . e . , alcohol > acid > ketone > ester. In contrast to the isotherms ob- tained with C8 compounds, at all residual lutein levels, ketones and acids produced isotherms t hat were dissimilar from the control but similar to each other. In summary, alcohols can compete more effectively with lutein for adsorption sites on silica t han other solvents because of their ability to form hydrogen bonds, rather t han their polarity. Water is not as effective as alcohols because of the energy needed to overcome hydrogen bond- ing between water molecules in a hydrophobic environ- ment. There is little difference between isotherms obtained within a homologous series of small molecular weight alcohols or fat t y acid. Functional groups, other than alc~ hols, inhibit lutein binding to a lesser extent, even if polarity is greater t han the corresponding alcohol. JAOCS, Vol. 70, no. 6 (June 1993) 578 J. MI NGYU AND A. PROCTOR ACKNOWLEDGMENTS Sal ari es and research suppor t provi ded by st at e and federal f unds appr opr i at ed t o t he Ohio Agr i cul t ur al Research and Devel opment Center, The Ohio St at e Uni versi t y, were gr eat l y appreci at ed. Thi s is J our nal Ar t i cl e number 64-93. Thanks is expressed t o Dr. J ohn Lowbri dge for his useful comment s on t he data. REFERENCES 1. Brekke, O.L., in Handbook of Soybean Processing and Utiliza- tion, edi t ed by D.R. Eri ekson, E. H. Pryde, O.L. Brekke, T.L. Mount s and R.A. Falb, Ameri can Soybean Associatior~ St. Louis, and Amer i can Oil Chemi st s' Society, Champai gn, 1980, pp. 71-88. 2. Vogel, P.V., Fette Seifen Anstrichm. 79.97 (1977). 3. Hassler, J.W., and R.A. Hagber g, Oil and Soap 16:188 (1946). 4. Brown, H.G., and H. E. Snyder, J. Am. Oil Chem. Soa 62:753 (1985). 5. Proctor, A. , and H. E. Snyder, Ibid. 64:1163 (1987). 6. Iler, R.K., in The Chemistry of Silica, Chapt er 6, J ohn Wiley & Sons Co., New York, 1979. 7. Hau, L.-B., and W~. Nawar, J. Am. Oil Chem. Soa 62:1596 (1985). 8. Wu, G.S., and J.F. Mead, Lipids 12:965 (1977). 9. Marshall, K., and C.H. Rochester, J. Chem. Soc. Faraday Trans. I 71:1754 (1975). 10. McClellan, A.L., Tables of Experimental Dipole Moments, W.H. Fr eeman and Co., San Fr anci sco and London, 1963. [Received November 5, 1992; accept ed Apr i l 8, 1993] JAOCS, Vol. 70, no. 6 ( June 1993)
XXIVth International Congress of Pure and Applied Chemistry: Plenary and Main Section Lectures Presented at Hamburg, Federal Republic of Germany, 2–8 September 1973