Applications of Common Beans in Food and Biobased Materials - ACS

Chapter 22

Applications of Common Beans in Food and Biobased Materials Downloaded by MONASH UNIV on September 20, 2015 | http://pubs.acs.org Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ch022

Atanu Biswas,*,1 William C. Lesch,2 and H. N. Cheng3,* 1National

Center for Agricultural Utilization Research, Agricultural Research Services, U.S. Department of Agriculture, 1815 N. University Street, Peoria, Illinois 61604 2Department of Marketing, University of North Dakota, Grand Forks, North Dakota 58202 3Southern Regional Research Center, Agricultural Research Service, U.S. Department of Agriculture, 1100 Robert E. Lee Blvd., New Orleans, Louisiana 70124 *E-mail: [email protected] (A.B.); [email protected] (H.N.C.)

One of the research trends in recent years is to use natural renewable materials as "green" raw materials for industrial applications. Common beans (Phaseolus vulgaris L.) are well known, widely available, and relatively cheap. They contain polysaccharides, proteins, triglyceride oils, minerals, vitamins, and phenolic antioxidants. Many of these compounds seem to be attractive components for food and biobased products. A review is given here of the more promising approaches for these applications, emphasizing in particular the work done by the authors in the past several years. These include 1) extrusion cooking of whole beans as food products, 2) use of beans as fillers in polymeric blends and composites, 3) extraction of triglyceride oils from whole beans, 4) extraction of phenolic phytochemicals from beans, and 5) conversion of starch in beans to ethanol. These examples illustrate the range of applications possible and the potential value of non-conventional uses of common beans.

© 2013 American Chemical Society In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Downloaded by MONASH UNIV on September 20, 2015 | http://pubs.acs.org Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ch022

Introduction Common beans (Phaseolus vulgaris L.) are significant raw materials for food and are good sources of carbohydrates, proteins, fiber, and micronutrients (1). They are also appreciated for their long storage life, ease of storage and relatively simple preparation as food. The health benefits of beans are well recognized. The U.S. produces about 2.5 billion pounds of dry common beans per year, with a price of about 20 cents per pound (2). The states with the most bean production are North Dakota, Michigan, Nebraska, Colorado, California, and Idaho. Thus far, the leading varieties are pinto beans (42%), navy beans (17%), black beans (11%), and Great Northern beans (5%) (2, 3). Typically common beans (like pinto beans) contain about 64% carbohydrates, 23% proteins, 2% fat, and lower levels of minerals (e.g., iron, potassium, selenium, and molybdenum), vitamins (such as thiamine, vitamin B6, and folic acid), and other bioactive compounds, including flavonoids, polyphenols and phenolics (4). Most of the common beans are currently consumed as food. However, there have been some efforts to find non-food industrial uses for them. Such applications are attractive to the consumers because common beans are natural renewable raw materials that are non-toxic and environmentally friendly and beneficial to the bean growers because they provide added value to the products. Since 2009 there has been a fair amount of work done at USDA to explore new applications of common beans in food and biobased products (5–11). In this article, we aim to review many of these developments. Examples are shown particularly to illustrate the versatility of common beans in different applications. These include the extrusion cooking of beans, the conversion of bean starch to ethanol, the incorporation of beans as fillers in polymer composites, and the possible use of triglyceride oils and phenolic antioxidants as functional additives.

Extrusion Cooking of Common Beans The effects of extrusion cooking on the functional, physiological and nutritional properties of common beans had been reported before (12–20). However, relatively few investigations had been done on whole seed extrudates of common beans (13, 21, 22). It was useful therefore to determine the physicochemical and functional properties of extruded products of four whole common beans including dark red kidney, black, pinto and great northern beans as affected by process variables such as extrusion temperature, feed moisture and screw speed (5). The four common beans were obtained from the Northarvest Bean Growers Association (Frazee, MN). The whole beans were separately ground to particle size less than 0.6 mm using a Retsch mill and defatted using Soxhlet extraction with hexane for 6 h. The % moisture content of defatted ground beans was adjusted by hydrating them with distilled water (to 24% and 28% moisture content) using an electric mixer. The ground beans were fed manually into a single screw Brabender extruder (Brabender Instruments, Inc., South Hackensack, NJ) at constant speed (10 g/min). The process variables included feed moisture (24% and 28%), die end temperature (125, 135, and 160 °C) and screw speed (40, 90 rpm). Bean extrudates 332 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


were chopped into pieces and ground to pass through 2-mm sieve using a Thomas mill (5). The results showed that bean type and feed moisture had no significant effect on moisture content of extruded beans, but increasing extrusion temperature led to lower moisture content (5). Bulk density of bean extrudates was not significantly affected by screw speed, bean type, and extrusion temperature. There was, however, a slight trend of decreased bulk density of bean extrudate with increased feed moisture (5). The oil absorption capacity (OAC) showed decreases in three beans (dark red kidney, black, and pinto) after extrusion cooking relative to bean control prior to extrusion (5). Other variables, such as screw speed, bean type, feed moisture and extrusion temperature, did not contribute significantly to change in OAC. Changes in color were also noted after extrusion (5). The bean extrudates were darker and had more redness and yellowness in comparison to the ground beans prior to extrusion.

Table 1. Water absorption index (WAI) of bean extrudates under four extrusion conditions at two different moistures compared to defatted ground bean control WAI (g absorbed water/g dry weight)a Bean

FM %b

Control bean

DK

24

GN

BL

PT

125°C/ 40 rpm

125°C/ 90 rpm

135°C/ 90 rpm

165°C/ 90 rpm

2.62±0.00 2.53±0.01

3.19±0.11

2.81±0.21

3.44±0.07

28

2.47±0.01

2.88±0.07

2.87±0.04

3.77±0.06

24

2.35±0.01 2.69±0.01

3.17±0.04

3.37±0.07

4.15±0.01

28

2.89±0.04

2.85±0.02

2.86±0.03

3.02±0.04

24

2.40±0.03 2.91±0.06

2.97±0.21

2.81±0.26

4.01±0.01

28

2.94±0.04

2.34±0.00

2.35±0.10

3.32±0.03

24

2.21±0.02 2.90±0.06

2.66±0.18

2.99±0.18

4.13±0.02

28

2.72±0.02

2.60±0.07

2.84±0.00

3.71±0.03

a

Data adapted from ref. (5). Values expressed in mean ± standard deviation, DK=Dark red kidney, GN=Great northern, BL=Black, PT=Pinto. b FM= Feed Moisture.

Extrusion strongly influenced the water absorption index (WAI) of bean extrudates. As shown in the data given in Table 1, most WAI values increased upon extrusion. WAI was not significantly affected (at statistical p-value < 0.05) by both screw speed and bean type, but extrusion temperatures and feed moistures had strong influences on WAI. The effect of temperature might be the result of denaturation of protein during extrusion, separation of amylose and amylopectin chains, and swelling of crude fiber in beans. A decrease in WAI was observed when feed moisture went from 24 to 28%. A study of the water solubility

333 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

index (WSI) indicated that it was significantly affected by all process variables, including screw speed, extrusion temperature, and feed moisture (5). It appeared that feed moisture was the most critical factor affecting the extrudate properties including water absorption, water solubility, and color. Screw speed only influenced the moisture and water solubility of final extrudates. Changing extrusion temperature resulted in extrudates that showed differences in moisture, water absorption and solubility (5). The data reported in this work may be useful in process design and product optimization to people who contemplate making commercial products from extruded beans.


Common Bean as Filler in Polymers Whole pinto beans were used as fillers in poly(lactic acid) (PLA) (6), low density polyethylene (LDPE) (4), and poly(vinyl alcohol) (PVOH) (7). For these applications, the pinto beans were first ground into a powder. The scanning electron microscopy (SEM) photomicrographs of pinto bean powder are shown in Figure 1. Elliptically shaped starch granules and irregular particles of protein and other bean components can be observed.

Figure 1. SEM photomicrographs of pinto bean powder. Left image 190X, right image 1700X. PLA Filler For composite formation, pinto bean powder was mixed with PLA and extruded into ribbons (6). The SEM photomicrographs of the fracture surfaces of PLA and PLA composites are shown in Figure 2. PLA itself had a relatively smooth fracture surface, but the surface of the PLA-bean powder composite was rough and clearly showed the presence of starch granules. The mechanical properties of PLA and PLA-filler composites were reduced by the addition of the filler (6) (Table 2, where TS = tensile strength, E = elongation at breakage, and YM = Young’s modulus). The addition of maleic anhydride (MA) and Lupersol 101 peroxide (L101) caused further reductions in mechanical properties. The main advantage of using bean filler in PLA is to 334 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


decrease cost. The filler perhaps can be used in PLA applications where cost reduction is important and reduced mechanical properties are acceptable. Possible examples are biodegradable and compostable plastics, such as agricultural mulch films, compost bags, and perhaps disposable dinnerware.

Figure 2. SEM photomicrographs of PLA (left) and PLA-pinto bean powder composite, both at 1700X.

Table 2. Mechanical properties of pre-dried PLA and PLA-filler composites formed with pinto bean powder a. Data adapted from ref. (6) PLA:filler:MA:L101

Thickness (mm)

TS (N/mm2)

E (%)

YM (N/mm2)

100:0

1.83±0.08

58.6±0.8

16.7±1.2

493±14

90:10

1.75±0.16

31.5±2.6

9.5±1.8

448±26

80:20

1.72±0.06

23.2±2.3

6.9±0.8

412±42

90:10:2:0.5

1.86±0.15

17.9±3.6

7.8±0.9

314±12

90:10:4:0.5

1.89±0.21

16.3±2.2

8.2±1.1

285±14

80: 20:2:0.5

1.96±0.07

12.0±1.6

5.7±0.9

288±21

80:20:4:0.5

1.93±0.05

14.1±1.3

6.2±1.3

322±30

a PLA and filler were preheated and dried at 50°C for 3 days in an oven.

Standard deviations

are shown after ± signs.

LDPE Filler Powdered pinto bean was mixed with LDPE in an extruder, and the resulting composite was cut into ribbons (6). The SEM photomicrographs of the fracture surfaces of PLA and PLA-bean composite are shown in Figure 3. LPDE had a wrinkled and partly torn surface; the surface of the LDPE-bean composite appeared even more torn, with starch particles clearly evident that gave signs of incompatibility with LDPE. 335 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Figure 3. SEM photomicrographs of LDPE (left) and LDPE-pinto bean powder composite, both at 1700X. The addition of bean powder filler to LDPE had a negative effect on tensile strength and elongation of the composite materials (6) (Table 3). However, the Young’s modulus was enhanced. The addition of MA and L101 negatively impacted tensile strength and elongation, but further enhanced Young’s modulus. Thus, for applications needing a stiffer polyethylene at reduced cost, the use of bean filler might be beneficial.

Table 3. Mechanical properties of pre-dried LDPE and LDPE-filler composites formed with pinto bean powder a. Data adapted from ref. (6) LDPE:filler:MA:L101

Thickness (mm)

TS (N/mm2)

E (%)

YM (N/mm2)

100:0

2.12±0.32

12.4±0.7

241.3±13.2

78±2.1

90:10

2.27±0.21

9.5±0.6

35.2±4.2

83±3.5

80:20

2.28±0.25

7.1±0.6

22.4±2.3

87±4.9

90:10:2:0.5

2.35±0.10

8.7±0.4

20.9±1.6

87±5.8

90:10:4:0.5

2.32±0.29

7.4±0.6

16.8±1.0

86±2.3

80:20:2:0.5

2.27±0.15

6.5±0.5

11.6±1.4

99±5.4

80:20:4:0.5

2.27±0.08

7.0±0.9

12.4±1.8

97±6.8

a PLA and filler were preheated and dried at 50°C for 3 days in an oven.

Standard deviations

are shown after ± signs.

PVOH Filler The pinto bean was defatted (fat < 0.01%), milled into powder, and passed through a 30-mesh screen (sieve size 0.6 mm) to give the pinto bean flour (PBF) (7). The pinto bean high starch fraction (PBHSF) was obtained from the bean flour through repeated extractions in dilute alkali according to a procedure in the literature (23). 336 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Cold gelatinization (24, 25) was used to make films of PBF and PBHSF with PVA. Initial mechanical testing showed PVOH/PBF film to have better properties than PVOH/PBHSF film; thus, more work was done with the PVA/PBF composite (7). Different amounts of PBF in the composite were used, and mechanical testing carried out along (parallel) and perpendicular (nonparallel) to the direction of film formation. The results obtained for both directions were the same within the limits of experimental error, indicating no strong directional dependence (Table 4). The tensile strength was reduced when PBF was added to PVA, but the elongation actually increased when 20-40% PBF was added to PVA and then decreased at 60% PBF. The Young’s modulus first decreased in the films containing 20-40% PBF but then increased in the film containing 60% PBF.

Table 4. Mechanical properties of films from PVA and PVA/PBF composites at different PBF levels a % PBF

thickness (mm)

TS (N/mm2)

E (%)

YM (N/mm2)

parallel-1

0

0.083

49±3

336±62

652±121

parallel-2

20

0.140

31±1

757±75

31±8

parallel-3

40

0.125

23±0

530±27

55±12

parallel-4

60

0.152

13±1

44±7

184±24

nonparallel-1

0

0.076

57±7

315±59

865±74

nonparallel-2

20

0.131

28±1

706±52

31±5

nonparallel-3

40

0.088

23±1

539±99

66±9

nonparallel-4

60

0.164

13±1

36±12

177±34

sample

a

Data from ref. (7). Standard deviations are shown after ± signs.

Thus, pinto bean appears to be a potentially low-cost filler for PVA with enhanced elongation up to 40% PBF level. Currently PVA-starch composites are being considered for use in agriculture for transportation of plants (26), as film to cover the surface of cultivated fields (26), as fertilizer encapsulant (27), and as water-soluble packaging material (28). Perhaps the PVA/edible bean composites can also be considered for these same applications in the future.

Triglyceride Oils in Common Beans Four common beans (black, kidney, Great Northern, and pinto) were extracted with hexane and found to contain about 2% triacylglycerols (8). The fatty acids in these bean oils were mainly linolenic (41.7–46 wt%), linoleic (24.1–33.4 wt%), palmitic (10.7–12.7 wt%) and oleic (5.2–9.5 wt%). Although the levels of polyunsaturated fatty acids in the bean oils were higher than those in soybean oil, the bean oils exhibited high oxidative stability because of the high amounts of tocopherols present (2,670–2,970 ppm) (8). 337 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Triglycerides are known to be viable alternatives to mineral oils in lubricants. It was reported that the oil extracted from the navy bean hull could be a potential natural antioxidant for use in vegetable oils such as soybean and sunflower oils (29). Since triglycerides are compatible with mineral oils, the bean oils may also be used as antioxidants for other lubricants. In addition, triglycerides have been converted to epoxides, polyols, and dimer products and used as polymer components or additives (such as stabilizers, plasticizers, and surfactants) (30, 31). The bean oils should be able to serve in the same capacities and with improved oxidative stability.


Phenolic Phytochemicals in Common Beans Common beans are known to contain a significant amount of flavonoids, polyphenols, and phenolics. The levels were found to be higher in seed hull than in cotyledon, and higher in dark-colored beans versus light colored beans (9, 32, 33). Recently microwave-assisted extraction at 150°C and 50% ethanol in water was found to be particularly effective in extracting phenolics out of common beans, producing 2-3 times more phenolics than conventional heat extractions (9). The phenolic level ranged from 3 to 11 mg per g bean hull and from 8 to 70 mg per g bean cotyledon (in gallic acid equivalents). Somewhat similar results were obtained from antioxidant assays (10). In view of the high phenolic content and the ease of extraction, the phenolic antioxidants from common beans may perhaps be potential natural additives for use in food polymers or in food-contact packaging materials.

Conversion of Bean Starch to Ethanol Eight common beans, from Northarvest Bean Growers Association, were evaluated for potential conversion of starch to ethanol (11). Enzymes were supplied by Genencor International (Beloit, WI). The beans were assayed in a laboratory-scaled process based upon the commercial corn dry grind fermentation process (34, 35). The beans were ground and added to 100 mL distilled water in 500 mL Corning bottles and adjusted to pH 6.0-6.5 with Ca(OH)2. α-Amylase (8 units/g beans) was added, and the mixtures heated to 90°C and then autoclaved for 15 min. Additional α-amylase (16 units/g beans) was added, and the mixture was incubated at 95°C for 60 min. They were cooled on ice, and the pH of mixtures adjusted to 4.0-4.5 with phosphoric acid. Glucoamylase (0.4 units/g), 0.03% (w/v) (NH4)2SO4 and 4×10−4% Antifoam 289 (Sigma, St. Louis, MO) were added, followed by inoculation with an overnight preculture of S. cerevisiae Y-2034 to OD 550 = 1.0 (1-cm path-length; DU640 spectro-photometer, Beckman Coulter, Fullerton, CA). Fermentations were carried out at 32°C and mixed by shaking at 100 rpm (Innova 4230 incubator shaker, New Brunswick Scientific, Edison, NJ). At 72 h, fermentation supernatants were sampled for product analysis. More details were given in the original reference (11). The starch content of the beans used was around 40% (Table 5). Ethanol yield was 0.43–0.51 g ethanol/g glucose (0.19–0.23 g ethanol/g beans). The average 338 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

ethanol yield for the eight bean types was 92% of maximum theoretical yield, demonstrating that starch from beans could be efficiently converted to ethanol. Ethanol concentration obtained from 20% (w/w) solids loading was 3.5–4.4% (w/ v). The residual fermentation solids contained, on a dry basis, 37.1–43.6% crude protein, 10.8–15.1% acid detergent fiber and 19.1–31.3% neutral detergent fiber. Thus, this work showed that bean starch could be readily converted to ethanol, using the same process and enzymes applied to corn.


Table 5. Starch present in beans and ethanola derived from fermentation. Data adapted from ref. (11) Bean type

Starch (% db)

Final ethanol (% w/v)

Ethanol yield (g g−1 glucose)

Efficiency (% of theoretical)

Black

40.9

4.09 ± 0.33

0.46 ± 0.04

88.3

Pinto

42.2

4.39 ± 0.44

0.48 ± 0.04

94.0

Dark red kidney

39.5

3.54 ± 0.45

0.48 ± 0.01

92.6

Light red kidney

42.1

3.92 ± 0.12

0.46 ± 0.01

90.3

Pink

40.8

3.67 ± 0.02

0.43 ± 0.01

83.5

Navy

40.0

4.22 ± 0.06

0.50 ± 0.01

97.6

Great northern

39.8

4.29 ± 0.24

0.51 ± 0.04

100

Small red

44.0

4.22 ± 0.55

0.46 ± 0.06

90.4

a

Average values reported ± standard deviation; each experiment was carried out at least twice, in triplicate.

Conclusions In this work, several examples from the authors’ work are given to illustrate the potential applications of common beans in food and biobased products. The use of common beans as fillers in polymers is perhaps unconventional, but in all three polymers (PLA, LDPE, and PVOH) the bean fillers seem to be useful; at the very least the bean fillers reduce the cost of the polymeric composites. The rather extensive data on extrusion cooking of beans may be of use to food technologists interested in the product development of extruded beans. The results of triglycerides and phenolic phytochemicals demonstrate the ease of extraction and the potential value of these materials. The ethanol yield obtained from bean starch suggests that the ethanol may be considered a coproduct, and together with bean triglycerides and phytochemicals they may provide added value to the common beans. 339 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Acknowledgments


The USDA work cited in this review was supported by a grant from Northarvest Bean Growers Association. The authors thank N. Sutivisedsak, M.A. Cotta, B.S. Dien, R.L. Evangelista, V. L. Finkenstadt, C. Hall, S. Liu, B. R. Moser, N. N. Nichols, B. K. Sharma, M. Singh and J. L. Willett for fruitful collaborations. Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture. USDA is an equal opportunity provider and employer.

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341 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Applications of Common Beans in Food and Biobased Materials - ACS

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