Source: UNIV OF WISCONSIN submitted to NRP
DEVELOPMENT OF AFFORDABLE, HEALTHY, AND GOOD-TASTING BEVERAGE FORTIFIED WITH DAIRY PROTEIN FOR ENHANCED HUMAN NUTRITION AND WELLNESS AND FOOD SAFETY
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
Reporting Frequency
Annual
Accession No.
1003055
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
(N/A)
Project Start Date
Oct 1, 2014
Project End Date
Dec 31, 2017
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
UNIV OF WISCONSIN
21 N PARK ST STE 6401
MADISON,WI 53715-1218
Performing Department
Food Science
Non Technical Summary
Food insecurity in US frequently corresponds with obesity and under-nourishment of low-income populations. An approach we propose in this project for correcting chronic energy imbalance that poses many health risks is to enable the fortification of beverages with highly-nutritious but under-utilized whey proteins without deteriorating sensory properties. The enhancement of the utilization of whey proteins is also a critical issue for the sustainability of the dairy industry in Wisconsin. The key challenge for utilizing whey proteins in beverage is that the protein tends to denature, aggregate, and precipitate during manufacturing involving thermal processing. Our strategy for preventing the quality loss arising from heat-induced aggregation of whey proteins is to utilize novel polysaccharide stabilizers we have identified in our previous studies. These polysaccharides are expected to bind to the protein surface and form a protective layer that prevents aggregation between proteins. Structures and functionalities of these polysaccharides as well as their correlations with the quality and stability of whey protein fortified beverages will be elucidated based on various physicochemical experiments including atomic force microscopy imaging and force spectroscopy.
Animal Health Component
25%
Research Effort Categories
Basic
50%
Applied
25%
Developmental
25%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
50234702000100%
Knowledge Area
502 - New and Improved Food Products;

Subject Of Investigation
3470 - Other dairy cattle products;

Field Of Science
2000 - Chemistry;
Goals / Objectives
The goal of this project is to enable the development of good-tasting and healthy beverages fortified with milk whey proteins. Currently, the pH of acidic beverages fortified with proteins needs to be adjusted to be either lower than 4.3 or higher than 6.5 due to the absence of polysaccharide stabilizers that prevent aggregation and precipitation of proteins in the intermediate pH range, resulting in too much acidity and/or unnatural flavor and taste in certain beverage products. In this project, we attempt to develop two types of novel polysaccharide stabilizers: one is for improving sensory properties of strongly acidic (pH 3.7-4.3) beverages fortified with whey proteins and the other for materializing mildly acidic (pH 5.5-6.5) beverages fortified with whey proteins that are difficult to be found in the current market.Our hypothesis is that interactions between whey proteins and polysaccharide stabilizers are primarily electrostatic. Polysaccharides to be studied in this project carry negatively chargeable groups such as the carboxyl group. Negatively charged groups on polysaccharides are expected to bind to positively charged patches on proteins. Then, the unbound parts of the polysaccharide chain form a brush or hairy layer on the protein surface and physically interfere with the direct contact between proteins and hence aggregation between proteins. On the other hand, polysaccharide molecules remaining in the solution without binding to proteins contribute to an increase in the viscosity of the bulk solution. Such an increase in the viscosity is considered to correlate positively with the molecular size of the polysaccharide stabilizer. We have shown in our previous studies that soybean pectin has a fairly compact molecular structure (e.g., ~100 nm), making it one of the most promising candidates for preventing unfavorable increases in the viscosity of acidic beverages fortified with whey proteins.Conventional polysaccharide stabilizers are unable to bind to proteins and stabilize them in mildly acidic conditions (pH 5.5-6.5). Given that the interaction between protein and polysaccharide is primarily electrostatic, the absence of polysaccharide stabilizers that are capable of binding to proteins in this pH range indicates that both the amount and distribution of negatively charged groups on the polysaccharide chain need to be appropriate relative to those of the positively charged group on the protein surface. In our preliminary investigation, pectin extracted potato tuber was found to prevent heat-induced aggregation of proteins at pH 5.5-6.5. It is therefore critical to elucidate the underlying mechanism of protein stabilization by potato pectin in order to materialize mildly acidic beverages fortified with whey proteins.The specific objectives of the project are:1. To prepare soybean pectin using varied conditions for enabling the fortification of strongly acidic (pH 3-4) beverages using whey proteins without negatively impacting their sensory properties, and characterize molecular properties of the developmental soybean pectin samples;2. To elucidate the molecular mechanism of the interaction between whey proteins and the soybean pectin, and characterize the quality and stability of strongly acidic (pH 3-4) beverages fortified with whey proteins;3. To prepare potato pectin using varied conditions for enabling the development of mildly acidic (pH 5.5-6.5) beverages fortified with whey proteins, and characterize molecular properties of the developmental potato pectin samples; and4. To elucidate the molecular mechanism of the interaction between whey proteins and the potato pectin, and characterize the quality and stability of mildly acidic (pH 5.5-6.5) beverages fortified with whey proteins.
Project Methods
Objective 1. Preparation and characterization of soybean pectin.Preparation of soybean pectinThe residual fibrous material from soy sauce manufacturing will be obtained from a local manufacturer. The material will be suspended in a large quantity of distilled water and stirred at 50°C for 1 hour for removing water soluble impurities. The insoluble residues will be recovered, suspended in water, adjusted to pH 3-5, and autoclaved for extracting pectin. Low-, medium-, and high-molecular weight soybean pectin fractions will be extracted by heating at 120°C and pH 3 for 2 hours, at 120°C and pH 4-5 for 2 hours, and at 130°C and pH 4-5 for 3 hours, respectively. The soybean pectin samples thus prepared will be desalted using electro-dialysis and then freeze-dried.Monosaccharide and amino acid compositions of soybean pectinMonosaccharide and amino acid compositions of the soybean pectin samples will be determined using gas chromatography coupled with mass spectroscopy (GC-MS).Molecular weight distribution of soybean pectinAliquots (50 μL) of sample solutions will be applied to two size exclusion chromatography (SEC) columns connected in series and eluted at room temperature. Elution profiles will be monitored using a multi-angle laser light scattering (MALLS) photometer equipped with a 690 nm helium-neon laser.Molecular structure of soybean pectinCharacterization of individual molecules of soybean pectin will be performed using a BioScope Catalyst atomic force microscope (Bruker, Santa Barbara, CA) located in PI's laboratory. Soybean pectin will be dissolved in an aqueous buffer solution containing 10 mM NH4HCO3 to give a concentration of 1 mg/mL. An aliquot (2 mL) will be drop-deposited onto freshly cleaved mica and allowed to stand in air for 15 minutes. Molecular images will be obtained using peak force tapping (PFT) mode.The effect of pH on the conformation of soybean pectin will be investigated using atomic force microscopy (AFM). Soybean pectin will be dissolved in 1 mM MgCl2 solution to give a concentration of 1 mg/mL and then poured onto freshly cleaved mica or highly oriented pyrolytic graphite (HOPG) placed in the AFM fluid cell. The sample will be left to incubate for 5 min before imaging directly in solution using the PFT mode. After imaging, the fluid cell will be perfused with a buffer solution adjusted to pre-specified pH in order to sequentially decrease pH to be 6.5, 6.0, 5.5, 5.0, 4.5, and 4.0. Molecular images will be obtained at each pH.Objective 2. Mechanism of interactions between soybean pectin and whey protein, and the quality and stability of strongly acidic protein fortified beverage.Preparation of strongly acidic beverage fortified with whey proteinWhey protein isolate having high protein and low carbohydrate levels will be obtained from Davisco Foods International (Eden Prairie, MN). The whey protein will be dissolved to give a protein concentration of 5%, mixed with a 50% w/w sucrose solution, a 3% soybean pectin solution, and distilled water, and adjusted to a pre-specified pH using lactic acid. The final concentrations of protein, sucrose, and soybean pectin will be 1-3% w/w, 5% w/w, and 0.2-0.5% w/w, respectively. The model beverage will be homogenized using a two-stage homogenizer, heat-treated at 141°C for 4 seconds, and stored at 4°C for 2 weeks.Characterization of the simulated beverageThe particle size distribution in the stored beverage will be determined using a Mastersizer 2000 particle size analyzer (Malvern Instruments Inc., Westborough, MA) available in a research laboratory of the Department of Food Science. The zeta potential and viscosity will be also determined using a Zetasizer Nano (Malvern Instruments Inc., Westborough, MA) and a DV-E viscometer (Brookfield Engineering Laboratories, Middleboro, MA), respectively, also available within the Department of Food Science.The morphology of protein particles in the simulated beverage will be studied using AFM. Interaction forces between a single pair of protein particles stabilized by soybean pectin will be investigated using AFM force spectroscopy. An AFM cantilever will be positioned above the center of one of the protein particles immobilized onto the mica surface and driven down onto the target particle until it penetrates the particle. The protein particle thus attached to the cantilever will be detached from the slide simply by retracting the cantilever and positioned over a second particle on the mica surface to determine interaction forces between the pair of protein particles as a function of the separation distance.Objective 3. Preparation and characterization of potato pectin.Preparation of potato pectinPotato tubers will be peeled, sliced, and separated into juice and fiber using a blender. The juice containing starch will be discarded. The fiber will be dried using a vacuum dryer after being washed repeatedly with distilled water to remove any remaining starch. Low-, medium-, and high-molecular weight potato pectin fractions will be extracted from aqueous suspensions of the insoluble residues by heating at 120°C and pH 3 for 2 hours, at 120°C and pH 4-5 for 2 hours, and at 130°C and pH 4-5 for 3 hours, respectively. The potato pectin samples thus obtained will be desalted using electric dialysis and then freeze-dried.A control experiment will be performed to extract potato pectin without the application of heat to clarify whether the heat treatment causes any modifications of the structure and functionality of potato pectin. The potato fiber after removal of starch will be used as the starting material. Potato pectin will be extracted without the application of heat as described under Objective 1.Characterization of potato pectinThe prepared potato pectin samples will be characterized as described under Objective 1. Monosaccharide and amino acid compositions will be determined using GC-MS. The molecular weight distribution will be determined using SEC-MALLS. Molecular morphology and pH-dependent conformational transitions will be investigated using AFM.Objective 4. Mechanism of interactions between potato pectin and whey protein, and the quality and stability of mildly acidic protein fortified beverage.Preparation of mildly acidic beverage fortified with whey proteinWhey proteins (Davisco Foods International, Eden Prairie, MN) will be dissolved to give a protein concentration of 5%, mixed with a 50% w/w sucrose solution, a 3% potato pectin solution, and distilled water, and adjusted to a pre-specified pH using lactic acid. The final concentrations of protein, sucrose, and potato pectin will be 1-3% w/w, 5% w/w, and 0.2-0.5% w/w, respectively. The model beverage will be homogenized using a two-stage homogenizer, heat-treated at 121°C for 30 min, and cool to room temperature before characterization.Characterization of the simulated beverageThe prepared beverages will be characterized as described under Objective 2. Particle size distribution, zeta potential, and viscosity of the simulated mildly acidic beverage will be determined using a Mastersizer 2000 particle size analyzer (Malvern Instruments Inc., Westborough, MA), a Zetasizer Nano (Malvern Instruments Inc., Westborough, MA), and a DV-E viscometer (Brookfield Engineering Laboratories, Middleboro, MA). The morphology of protein particles as well as interaction forces between two protein particles will be evaluated using AFM force spectroscopy.

Progress 10/01/14 to 12/31/17

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?We published the results from studies on soybean pectin in Journal of Dairy Science. We submitted the results from the studies on whey protein-alginate conjugate to Journal of Agricultural and Food Chemistry. The results from the studies on citrus pectin has been accepted by Journal of Cereal Science, and will be published soon. The results from the studies on casein-whey protein interaction were published in Food Biophysics. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? We extracted soybean pectin from soy flour at either room temperature or 121°C, and tested their abilities to stabilize milk proteins in acidic conditions. The molar mass of pectin extracted at room temperature was approximately twice that of pectin extracted at 121°C. Particle size distributions in simulated acidified milk drink samples containing 0.2% pectin extracted at either room temperature or 121°C showed monomodal distributions with median diameters of around 1.2 μm at pH 4. The presence of large protein aggregates (~5 μm) was detected at 0.2% pectin extracted at room temperature and pH 3.2, 0.6 to 0.8% pectin extracted at room temperature and pH 4, or 0.2% pectin extracted at 121°C and pH 3.4. The presence of excess polysaccharide molecules unbound to proteins was detected at 0.2% pectin extracted at room temperature and pH 3.2 to 3.4, 0.4 to 0.8% pectin extracted at room temperature and pH 4, 0.2% pectin extracted at 121°C and pH 3.4 to 3.6, and 0.4 to 0.8% pectin extracted at 121°C and pH 4. Due to the higher molar mass, pectin extracted at room temperature provided stronger steric effects to prevent aggregation between milk proteins in acidic conditions than pectin extracted at 121°C, and stabilized acidified milk drinks containing 8.5% milk solids at pH 4 at concentrations as low as 0.2%. Both soybean pectin extracted at room temperature and that extracted at 121°C contained proteinaceous components difficult to dissociate from polysaccharide components using size exclusion chromatography. Additionally, alkaline treatment for breaking O-linkages between amino acid and monosaccharide residues decreased pectin's molar mass by approximately 160 kDa, indicating that they contained naturally occurring conjugates of pectic and proteinaceous moieties. Therefore, soybean pectin is expected to stabilize not only milk proteins at pH around their isoelectric points but also hydrophobic particles suspended in beverage. Inspired by the molecular structure of soybean pectin, we conjugated whey protein and a food grade polysaccharide, alginate, using the Maillard reaction, and found that the whey protein-alginate conjugate was capable of adsorbing to hydrophobic surfaces and forming mechanically stronger interfacial films than unconjugated whey protein. Unconjugated citrus pectin was found to adsorb to an interfacial film of pre-adsorbed protein and strengthen the film. However, such an interfacial film was not as mechanically strong as an interfacial film that the whey protein-polysaccharide conjugate formed. Casein is the major milk protein and is more surface active than whey protein. Therefore, one may assume that casein will displace pre-adsorbed whey protein from an interface. However, we found that casein did not cause a substantial displacement of whey protein but strengthened the interfacial film. We extracted pectin from potato tubers at 121°C and pH 4.5-5.5 and characterize its ability to stabilize milk proteins in acidic conditions was evaluated. Potato pectin prevented the formation of large (>100 μm) aggregates of milk protein at pH 5.5, at which no existing polysaccharide stabilizers are capable of stabilizing milk proteins. Furthermore, we found potato pectin contains a relatively large quantity of acetyl groups. We therefore hypothesize that acetyl groups of potato pectin play a critical role in stabilizing milk proteins at pH 5.5. However, a modified potato pectin sample containing approximately 70% less acetyl groups than unmodified potato pectin showed an even better stability of milk protein at pH 5.5, suggesting that acetyl groups do not play a major role in determining pectin's protein stabilizing ability. Potato pectin stabilized acidified milk drinks containing 8.5% milk solids at pH 5.5, presumably due to a desirable distribution of galacturonic acid residues along the backbone.

Publications

  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Cai, Y., Cai, B., and Ikeda, S. 2017. Stabilization of milk proteins in acidic conditions by pectic polysaccharides extracted from soy flour. Journal of Dairy Science, 100, 7793-7801.
  • Type: Journal Articles Status: Published Year Published: 2017 Citation: Bai, Q., and Ikeda, S. 2017. Caseinate-induced competitive displacement of whey protein from interfaces. Food Biophysics, 12, 462-469.
  • Type: Journal Articles Status: Awaiting Publication Year Published: 2018 Citation: Matsushita, K., and Ikeda, S. 2018. Interactions between gliadin adsorbed to the air-water interface and pectin added to the aqueous phase. Journal of Cereal Science, 79, 201-203.
  • Type: Journal Articles Status: Under Review Year Published: 2017 Citation: Cai, B., Saito, A., Ikeda, S. 2017. Maillard-conjugation of sodium alginate to whey protein for enhanced resistance to surfactant-induced competitive displacement from air-water interfaces.


Progress 10/01/15 to 09/30/16

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?The results were disseminated through one journal article as seen under products. What do you plan to do during the next reporting period to accomplish the goals?Preparation of potato pectin Potato tubers will be peeled, sliced, and separated into juice and fiber using a blender. The juice containing starch will be discarded. The fiber will be dried using a vacuum dryer after being washed repeatedly with distilled water to remove any remaining starch. Low-, medium-, and high-molecular weight potato pectin fractions will be extracted from aqueous suspensions of the insoluble residues by heating at 120°C and pH 3 for 2 hours, at 120°C and pH 4-5 for 2 hours, and at 130°C and pH 4-5 for 3 hours, respectively. The potato pectin samples thus obtained will be desalted using electric dialysis and then freeze-dried. A control experiment will be performed to extract potato pectin without the application of heat to clarify whether the heat treatment causes any modifications of the structure and functionality of potato pectin. The potato fiber after removal of starch will be used as the starting material. Potato pectin will be extracted without the application of heat. Characterization of potato pectin Monosaccharide and amino acid compositions will be determined using GC-MS. The molecular weight distribution will be determined using SEC-MALLS. Molecular morphology and pH-dependent conformational transitions will be investigated using AFM. Preparation of mildly acidic beverage fortified with whey protein Whey proteins (Davisco Foods International, Eden Prairie, MN) will be dissolved to give a protein concentration of 5%, mixed with a 50% w/w sucrose solution, a 3% potato pectin solution, and distilled water, and adjusted to a pre-specified pH using lactic acid. The final concentrations of protein, sucrose, and potato pectin will be 1-3% w/w, 5% w/w, and 0.2-0.5% w/w, respectively. The model beverage will be homogenized using a two-stage homogenizer, heat-treated at 121°C for 30 min, and cool to room temperature before characterization. Characterization of the simulated beverage Particle size distribution, zeta potential, and viscosity of the simulated mildly acidic beverage will be determined using a Mastersizer 2000 particle size analyzer (Malvern Instruments Inc., Westborough, MA), a Zetasizer Nano (Malvern Instruments Inc., Westborough, MA), and a DV-E viscometer (Brookfield Engineering Laboratories, Middleboro, MA). The morphology of protein particles as well as interaction forces between two protein particles will be evaluated using AFM force spectroscopy.

Impacts
What was accomplished under these goals? We extracted pectic polysaccharides from soy flour either at room temperature (SPRT) or 121 °C (SPH) and evaluated their abilities to stabilize milk proteins in acidic conditions. Both SPRT and SPH contain proteinaceous components that were difficult to dissociate from polysaccharide components using size exclusion chromatography, while the molar mass of the former was approximately twice that of the latter. Due to higher molar mass, SPRT was expected to provide stronger steric effects to prevent aggregation between milk proteins in acidic conditions than SPH. Alkaline treatment of SPRT for breaking O-linkages between amino acid and monosaccharide residues decreased its molar mass by ca. 160 kDa, indicating they contained naturally occurring conjugates of pectic and proteinaceous moieties. Particle size distributions in simulated acidified milk drink samples containing 0.2% SPRT or SPH showed monomodal distributions with median diameters of around 1.2 μm at pH 4. The presence of large protein aggregates (~5 μm) was detected at 0.2% SPRT and pH 3.2, 0.6-0.8% SPRT and pH 4, or 0.2% SPH and pH 3.4. We detected the presence of excess polysaccharide molecules unbound to proteins at 0.2% SPRT and pH 3.2-3.4, 0.4-0.8% SPRT and pH 4, 0.2% SPH and pH 3.4-3.6, or 0.4-0.8% SPH and pH 4. The present results suggest that molecular characteristics of pectic polysaccharides vary depending on extraction conditions and hence their functional behavior.

Publications

  • Type: Journal Articles Status: Published Year Published: 2016 Citation: Cai, B. and Ikeda, S. 2016. Effects of the conjugation of whey proteins with gellan polysaccharides on surfactant-induced competitive displacement from the air-water interface. Journal of Dairy Science, 99, 6026-6035.


Progress 10/01/14 to 09/30/15

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals?We plan to conduct a week-long shelf life study comparing the stability of acidified milk beverages containing soybean pectins prepared using different extraction methods. We will also conduct single molecule studies of soybean pectin using atomic force microscopy in order to clarify the molecular mechanism of interactions between soybean pectin and milk protein. The extraction and characterization of potato pectin have been initated and will be another focus of our studies in the next reporting period.

Impacts
What was accomplished under these goals? We extracted soybean pectin samples by heating at 120 ºC under three different pH conditions (pH 3, 4.6 and 6.7) and also at room temperature and pH 4.5, and analyzed their chemical compositions, molar masses, pH-dependent charge profiles, and abilities to stabilize milk proteins in acidic conditions. The molar mass of the sample prepared by extraction at room temperature (1830 kg/mol) was determined to be approximately twice those of the other samples prepared by the application of heat at 120 ºC (970 kg/mol). UV and refractive index profiles obtained by size exclusion chromatography revealed that the majority of polypeptides carried over to the sample extracted at room temperature was covalently linked to polysaccharide molecules. The sample extracted at room temperature had a slightly lower galacturonic acid content and hence less charged in the pH range from 3 to 5 than the other samples prepared by the application of heat at 120 ºC, while there were no significant differences between these samples in their abilities to stabilize milk proteins at pH 4.

Publications