You are on page 1of 8

Food Hydrocolloids xxx (2017) 1e8

Contents lists available at ScienceDirect

Food Hydrocolloids
journalhomepage:www.elsevier.com/locate/foodhyd

Isolation, characterization and functionalities of bio-fiber gums isolated from


grain processing by-products, agricultural residues and energy crops*

Madhav P. Yadav*, Kevin B. Hicks


Sustainable Biofuels and Co-Products Research Unit, Eastern Regional Research Center, Agricultural Research Service, USDA, 600 East Mermaid Lane, Wyndmoor,
PA 19038, USA

article info abstract

Article history: Potentially valuable water soluble bio-fiber gums (hemicellulose B) were prepared from low-valued grain processing by-
Received 21 December 2016 products, agricultural residues and energy crops by an alkaline extraction followed by ethanol precipitation. The bio-fiber gum
Received in revised form 13 (BFGs) from all these sources are very rich in soluble dietary fiber (87.2e93.6%) except from wheat bran and sugarcane
March 2017 Accepted 7 April
bagasse (only 60.3 and 55.5% respectively) and they are predicted to be non-caloric in human diets qualifying as non-caloric
2017
food ingredient in many products. The sugar composition of these BFGs showed that they were typical arabinoxylans
Available online xxx
containing high molar ratio of arabinose to xylose with some other sugars such as galactose, glucose, galacturonic acid and
glucuronic acid in the side chains. The yield of pure BFG from these plant materials varied from 2.33 (rice fiber) to 25.13%
Keywords:
(corn bran) and they all, except BFG from wheat bran, are very good emulsifiers for stabilizing oil in water emulsions. Their
Soluble dietary fiber
Agricultural processing by-products ORAC values ranged from about 7000 to 29,000 m mole Trolox/ 100 g sample showing that they have the ability to provide
Emulsion stability Emulsifier antioxidant activity in foods, as well as of-fering the other functionalities and health-promoting benefits of dietary fiber. The
ORAC values of BFGs are higher than their respective original plant materials indicating that the antioxidant-rich portions of
Antioxidants the various plant materials can be solubilized and fractionated by the present alkaline extraction process. Published by Elsevier
Ltd.

1. Introduction renewable resource available in a large quantity, can be a good source of


valuable consumer products, as for an example corn fiber gum (Yadav,
The grain processing by-products (corn bran/fiber, wheat bran, rice fiber Johnston, Hotchkiss, & Hicks, 2007a, 2016a, b). These agricultural materials
etc.), agricultural residues (corn stover, wheat straw, sugarcane bagasse etc.) are the source of many bio-based products, which can be used in many food
and lignocellulosic energy crops (switch-grass, miscanthus etc.) are abundant and non-food industries. The fibrous materials from lignocellulosic sources
and often low-valued agri-cultural materials produced in USA and other parts have various appli-cations, such as building materials, particle board, human
of the world. They are natural composites of three major polymeric food, animal feed, cosmetics, medicines and many others (Reddy & Yang,
components: cellulose, hemicelluloses and lignin, which are linked together 2005; Reddy et al., 1989). They are also a very good source of dietary fiber.
via covalent and hydrogen bonds. Along with the three major poly-meric Dietary fibers are complex carbohydrates resistant to diges-tion by human
components, namely cellulose, hemicellulose, and lignin, they may also digestive enzymes. They can be classified into an insoluble group and a
contain other minor components, such as extractives (phenolics, lipids, etc.), soluble group. The soluble dietary fiber (SDF) helps to suppress blood
starch, pectins and proteins (Parajo, Garrote, Cruz, & Dominguez, 2004; cholesterol levels, especially LDL-cholesterol, by binding to bile acids, which
Monlau et al., 2012). Corn fiber/bran, a are made from choles-terol, in the gastrointestinal tract and carrying them out
of the body as waste (Woo & Kim, 2005). It also inhibits lipid absorption in
the digestive tract. In addition, fermentation of SDF in the colon gen-erates
short chain fatty acids (SCFA) which can suppress the syn-thesis of
* cholesterol and maintain a healthy bacterial population. Diets high in fiber-
Mention of trade names or commercial products in this article is solely for the purpose of
providing specific information and does not imply recommendation or endorsement by the U.S. rich carbohydrates can improve glucose and
Department of Agriculture.
* Corresponding author.
E-mail address: madhav.yadav@ars.usda.gov (M.P. Yadav).

http://dx.doi.org/10.1016/j.foodhyd.2017.04.009
0268-005X/Published by Elsevier Ltd.

Please cite this article in press as: Yadav, M. P., & Hicks, K. B., Isolation, characterization and functionalities of bio-fiber gums isolated from grain processing
by-products, agricultural residues and energy crops, Food Hydrocolloids (2017), http://dx.doi.org/10.1016/j.foodhyd.2017.04.009
2 M.P. Yadav, K.B. Hicks / Food Hydrocolloids xxx (2017) 1e8

insulin level and also contribute to a decrease in blood lipids for people with Note: This manuscript has been written to honor and celebrate Prof. Glyn
Type II diabetes (Chandalia et al., 2000). However, the levels of fiber required O. Phillipss 90th Birthday for his excellence and invaluable contribution in
to induce these beneficial effects are high (up to 35 g/day) (Franz et al., 2002), the field of hydrocolloids.
which may be difficult for people accustomed to Western diets to achieve. For
this reason, the development of SDF has gained increasing interests (Groop, 2. Materials and methods
Aro, Stenman, & Groop, 1993; Vuksan et al., 1999; Wursch & Pi-Sunyer,
1997). Arabinoxylan-rich fiber (hemicellulose B) has drawn special attention 2.1. Materials
because of its unique acceptability and palatability (Lu, Walker, Muir,
Mascara, & ODea, 2000a; Lu, Gibson, Muir, Fielding, ODea, 2000b, 2004). The plant materials were obtained from various sources as fol-lows: Corn
Arabinoxylan has a beta-1,4-linkage that cannot be hydrolyzed by human bran (Bunge Milling, Inc., St. Louis, MO), Corn stover (Lawrence Shrawder,
digestive enzymes, and thus is a good dietary fiber. a Private Farm, Kempton, PA), Rice fiber (SunOpta Ingredients, Cedar
Rapids, IA), Wheat bran (Deibel Lab-oratories, Bethlehem, PA), Wheat straw
(Hougar Farms LLC, Coat-esville, PA), Switchgrass (ARS lab at University
In addition to above uses, lately lignocellulosic materials are also being Park, PA), Miscanthus (University of Illinois at Urbana-Champaign, Cham-
used for making cellulosic ethanol. Cellulosic biomass con-tains about one paign, IL) and Sugarcane bagasse (Southern Regional Research Center, ARS,
third hemicelluloses A and B (Hoije, Grondahl, Tommeraas, & Gatenholm, USDA, New Orleans, LA). They were oven dried and ground to a 20-mesh
2005), in which Hemicellulose B (Hemi. B) contains mainly carbohydrate particle size using a Wiley mill. Termamyl a-amylase was a gift from
biopolymer arabinoxylan with some other minor components. Arabinoxylan Novozymes, Davis, CA. Medium Chain Triglyceride (MCT) oil was
has a linear 1,4 linked xylan backbone with a-L-arabinose, galactose, purchased from Nestle Nutrition, Min-neapolis, MN. Sodium hydroxide and
glucuronic acid and some other sugars in the side chains. Hemi. B from corn hydrochloric acid were ob-tained from Sigma-Aldrich (St. Louis, MO). All
fiber has been isolated and its structure function relationship is well studied chemicals were reagent grade.
(Doner & Hicks, 1997 and 1998 and Doner & Hicks, 1997; Yadav et al.,
2007a, b, c, d; 2008). Hemi. B from corn fiber (also called corn fiber gum,
CFG) is found to be a very good emul-sifier for the oil-in-water emulsion
system. It contains minor, but functionally significant amounts of protein, 2.2. Standard proximate analyses
phenolic acids and lipids, which contribute towards it emulsifying properties
and may also provide nutraceutical value (Yadav et al., 2007a, b, d and 2008). Protein (N 6.25), ash and moisture contents of all samples were
The insoluble cellulosic residue remaining after hemicellulose sol-ubilization determined using AACC Approved Methods 46-30, 08-01 and 44-19
of corn fiber gum has also been processed and isolated in 25% yield (Doner & respectively (AACC International, 1995). Crude fat content was determined
Johnston, 2001; Yadav, Kale, Hicks, & Hanah, 2017). The functional using the ANKOM XT10 Extractor with hexane as the extracting solvent.
hemicellulose B from barley hulls, several varieties of barley straws and Starch content was determined using a total starch assay kit (Megazyme, Inc.,
several sorghum materials has been isolated, characterized and studied Wicklow, Ireland) based on the use of thermostable a-amylase and
(Yadav & Hicks, 2015, Qiu, Yadav, & Yin, 2017). The effects of CFG on the amyloglucosidase (McCleary, Gibson, & Mugford, 1997).
pasting, thermal and gelatinization behaviors of starch have also been well
studied (Qiu et al., 2015; Qiu et al., 2016).
2.3. Dietary fiber determination

Insoluble dietary fiber (IDF), soluble dietary fiber (SDF), total dietary fiber
In recent years, bioethanol production from lignocellulosic biomass is (TDF) and neutral detergent fiber (NDF) in CAF were determined following
hoped to be a very important alternative to gasoline for transportation as it can the standard A2000 automated fiber analyzer procedure (ANKOM
reduce greenhouse CO2 emissions. Another big advantage using Technology, 2011).
lignocellulosic biomass for biofuel production is that it does not complete
with food supplies. The commercially available biofuel of today is still mostly 2.4. Isolation of hemicelluloses A and B
produced from edible feedstocks, such as corn starch and sugarcane juice,
which can sometimes compete for their food and feed uses. Since lignocellu- The hemicellulose A (Hemi. A) and hemicellulose B (Hemi. B) were
losic materials are non-food biomass they may have less impact on food extracted from the plant material according to the procedure of Yadav, Cooke,
and/or feed markets. These biomasses may have a consider-able amount of Johnston, & Hicks, 2010 with some modification. In brief, the ground plant
alkali soluble, non-cellulosic carbohydrate poly-mers. Such alkali soluble material was boiled at 85 C with efficient mechanical stirring in the presence
carbohydrates are usually polymers of pentoses such as xylose and arabinose of heat stable Termamyl a-amylase at pH 6.8 for 1 h to hydrolyze starch.
which are not easily fer-mented to biofuel in high yield as are sugars such as Then the pH of this suspension was raised to 11.5 by adding 50% NaOH and
glucose, found in the insoluble cellulose-rich fibers. Removal of these alkali the boiling and stirring were continued for additional 30 min. During the re-
soluble polymers from the cellulosic biomass would yield a cellulose-rich action, pH was maintained at 11.5 by adding 50% NaOH and the reaction
(and glucose-rich) feedstock that could be easily hydrolyzed and easily volume was maintained by adding water as needed to compensate water loss
fermented by well-known microorganisms such as brewers yeast, due to evaporation. The hot slurry of the deconstructed material was
Saccharomyces cerevisiae. Thus our current studies are focused on immediately sheared using a high speed Polytron (PT 10/35 GT) equipped
developing valuable uses for these alkali soluble poly-saccharides, so they can with 12 mm probe (Kine-matica Inc., Bohemia, NY) at 10,000 rpm for 30 min
become valuable coproducts of the cellu-losic ethanol process, improving the and cooled to room temperature. The solid residue was separated from the re-
overall economics for cellulosic biofuel production. In this work, we focus on action mixture by centrifugation at 14,000 g for 10 min and discarded. The
food grade hemicellulose B, also called bio-fiber gum (BFG) from grain pro- supernatant was collected in a beaker and its pH was adjusted to 4.0e4.5 by
cessing by-products, agricultural residues and energy crops by treating them adding concentrated HCl to precipitate acid insoluble Hemi. A, which was
with alkali, characterizing them and study their emulsifying and antioxidant collected by centrifugation at 10,000 g for 30 min. Two volumes of ethanol
properties. were gradually added to the supernatant with stirring to precipitate the acid
soluble

Please cite this article in press as: Yadav, M. P., & Hicks, K. B., Isolation, characterization and functionalities of bio-fiber gums isolated from grain processing
by-products, agricultural residues and energy crops, Food Hydrocolloids (2017), http://dx.doi.org/10.1016/j.foodhyd.2017.04.009
M.P. Yadav, K.B. Hicks / Food Hydrocolloids xxx (2017) 1e8 3

Hemi. B (also called bio-fiber gum), which was collected and dried in the molecules. They contain about 0.30e8.97% starch except wheat bran, which
vacuum oven. has 21.87%, indicating that a significant amount of endosperm was not
removed during milling. Since the wheat bran is very rich in starch content, it
2.5. Determination of sugar composition has the lowest percent (41.2%) of insoluble dietary fiber (ISD) in comparison
to all other plant ma-terials studied (84.0e93.1%). They all have very low
Sugars were analyzed by HPAEC-PAD after hydrolyzing Hemi. A and B level of soluble dietary fiber (0.3e3.6%) but their total dietary fiber content is
samples into monosaccharides by methanolysis combined with TFA treatment above 82% except wheat bran (44.8%).
as explained in detail by Yadav, Johnston, & Hicks, 2007b.

3.2. Isolation of Hemi. A and B


2.6. Emulsion preparation and particle size determination
The Hemicelluloses A and B were isolated from grain processing by-
The sample for emulsification (2.5 g) was prepared with 1:4 ratio of products (corn bran, wheat bran and rice fiber), agricultural residues (corn
emulsifier to MCT (octanoic/decanoic acids triglycerides) containing 0.1% stover, wheat straw and sugarcane bagasse) and energy crops (switchgrass
sodium benzoate and 0.3% citric acid. A stock so-lution of emulsifier (27.78 and miscanthus) by an alkali treatment following the scheme shown in Fig. 1.
mg/g solution) containing 0.1% (w/w) sodium benzoate (a preservative) and The percentage yield of Hemi. A and B on dry weight basis is shown in Table
0.3% (w/w) citric acid was prepared for emulsification study by slowly adding 2. The starch asso-ciated with the original plant materials was hydrolyzed to
the calculated amount of Hemi. B, a little at a time with vigorous stirring to a malto-dextrins by treating them with heat stable a-amylase at 85 C to avoid
solution of sodium benzoate and citric acid in water at room tem-perature and the contamination of alkali soluble starch in hemicelluloses and making them
then gently stirring overnight to produce a hydrated, well dissolved and calorie free. In a biofuel process, this hydrolyzed starch could be utilized to
homogeneous solution. The samples for oil-in-water emulsions were prepared produce fuel ethanol.
in triplicate for each sample by taking 2.25 g of above emulsifier stock
solution and 0.25 g of MCT (octanoic/decanoic acids triglycerides) in a glass All these plant materials contain a high percent of acid insoluble
vial. No weighting agent was added during emulsion preparation to avoid the hemicellulose, called Hemi. A (11.20e22.63%) except corn bran, which has
effects of such agent on the emulsification process. The solution was vor- only 3.98% and is comparable to the previous report (Yadav et al., 2007a).
texed and then homogenized using a polytron bench top homog-enizer Hemi. A from these sources has not been well characterized and its functional
equipped with a 12 mm diameter head (Brinkmann, Switzerland, PT 10/35) at properties are not known. It is likely that the Hemi. A fraction contains a
20,000 rpm for 3 min. The above ho-mogenized emulsion was passed through variety of components, not just pure polysaccharide. A full characterization
the EmulsiFlex-B3 high-pressure homogenizer (Avestin Inc., Canada) at and study of its functionality would be needed to determine applications and
20,000 psi ho-mogenization pressure 3 times to prepare the final emulsions. value for this fraction. The corn bran has comparatively more alkali and acid
The particle size distribution of the emulsions was measured using a laser soluble Hemi. B (25.13%) than the other sources (2.33e14.60%). Hemi. B
diffraction particle size analyzer (Horiba LA-950). The volume mean from corn kernels has been shown to have functional properties that are useful
diameter was used for describing particle size of emulsions. The in food applications, such as being a good oil-in-water emulsifier. The
emulsification effectiveness was evaluated on the initial par-ticle size of the structure/function relationship of Hemi. B from corn fiber is well studied and
emulsion at 0 time. The emulsion stability was determined after storing reported (Yadav et al., 2007a, b, c, d, 2008). The corn stover, rice fiber, wheat
emulsions at 60 OoC (acceleration test), (Al-Assaf, et al., 2007) for 3 and 7 straw, switchgrass, miscanthus and sugarcane bagasse do not contain a very
days by measuring their particles size. high percentage of Hemi. B (2.33e8.85%), but if functionally useful, it could
be of considerable importance, especially if it could be obtained as a valuable
co-product during the pre-treatment of these materials prior to their
saccharification and fermentation for fuel ethanol production.

2.7. Antioxidant activity measurement

The antioxidant activity was measured by oxygen radical absorbance 3.3. Proximate composition and dietary fiber analysis of Hemi. A and B
capacity (ORAC) assay following the published pro-cedure (Huang, Ou,
Hampsch-Woodill, Flanagan, & Prior, 2002) with some modification (Ou et
al., 2002). Table 3 shows the proximate composition of Hemi. A isolated from all
eight sources. The ash content in these samples was high ranging from 8.25 to
3. Results and discussion 20.05%. The Hemi.A from corn bran, corn stover and wheat bran are very
rich in protein containing 24.58, 13.51 and 37.85% respectively but the Hemi.
3.1. Compositional analysis of the original plant materials A isolated from the remaining five sources contain only 2.72e4.41% of
protein. Corn bran and wheat bran had 03.91 and 1.43% residual starch but
The compositional analysis of the original plant materials is given in for all other samples the starch content was less than 1%. Their crude fat
Table 1. These samples contain about 1.58e10.27% mois-ture and content varied from 0.65 to 13.30%, except miscanthus (0% fat). The neutral
0.95e11.8% ash (dry weight basis). The protein content varies from 0.63 to detergent fiber (NDF) content in these samples varies from 0 to 0.69%, except
18.33%. The wheat bran contains the highest percent of protein (18.33%). one from corn stover (4.98%). As the Hemi. A from all given sources has
Corn fiber and corn stover have 6.27 and 5.03% of protein respectively, which high level of combined amount of ash, protein and fat, they do not contain
are higher than all remaining materials (0.63e2.16%). Rice fiber has the least very high percent of ISD (1.6e22.5%), SDF (11.2e35.6) and TDF
percent of protein (0.63%) among all the plant materials studied. All of these (15.6e54.0%).
materials contain less than 4% (0.20e3.52%) of extractable lipids (crude fat),
but they have very high levels (80.67e90.40%) of neutral detergent fiber, Table 4 shows the proximate composition of Hemi. B isolated from the
except wheat bran (45.44%), indicating the presence of complex non-starch above mentioned sources. Though they were produced by ethanol
polysaccharides and lignin-type of precipitation, their ash content is still high (2.97e24.39%), showing the
precipitation of some salt with ethanol. Their protein

Please cite this article in press as: Yadav, M. P., & Hicks, K. B., Isolation, characterization and functionalities of bio-fiber gums isolated from grain processing
by-products, agricultural residues and energy crops, Food Hydrocolloids (2017), http://dx.doi.org/10.1016/j.foodhyd.2017.04.009
4 M.P. Yadav, K.B. Hicks / Food Hydrocolloids xxx (2017) 1e8

Table 1
Proximate composition and dietary fiber content of original plant materials (all dry weight basis).

Sources Moistureb Ashb Proteina,b Starchb NDFb Crude Fatb ISD SDF TDF
Corn bran 7.87 0.09 0.95 0.04 6.27 0.06 8.97 0.26 80.98 0.69 3.00 0.10 81.9 0.3 82.3
Corn stover 6.24 0.03 5.43 0.18 5.03 0.11 0.67 0.05 80.67 0.47 1.28 0.52 83.5 3.6 87.2
Rice fiber 4.00 0.07 2.41 0.04 0.63 0.06 0.43 0.07 88.54 1.45 0.20 0.07 93.4 3.6 97.1
Wheat bran 10.27 0.02 5.66 0.05 18.33 0.23 21.87 0.73 45.44 0.33 3.52 0.27 41.2 3.6 44.8
Wheat straw 1.58 0.09 6.07 0.10 2.16 0.03 0.60 0.10 85.72 0.42 1.86 0.24 85.2 2.0 87.3
Switchgrass 8.99 0.07 2.38 0.11 2.08 0.01 0.65 0.11 87.06 0.03 0.86 0.17 93.1 1.2 94.3
Miscanthus 2.09 0.17 3.30 0.01 1.31 0.04 1.54 0.14 86.22 1.51 0.72 0.10 87.2 1.6 88.9
Sugarcane bagasse 2.35 0.08 11.80 0.65 1.64 0.06 0.30 0.05 90.40 0.75 1.00 0.19 84.0 1.4 85.4
a Calculated by multiplying nitrogen content by 6.25.
b
Average of triplicates.

Ground Plant Material


Suspended in 85 OC water, pH adjusted to 6.8 and stirred with -
amylase for 1 hr. Then pH raised to 11.5 and stirred at for 30 min.
Slurry of Deconstructed Material

High speed shearing for 1 hr and centrifugation

Supernatant (Alkaline extract) Solid Residue (alkali extracted), Either Discarded or


Used to Cellulosic Arabinoxylan(CAF) Preparation
pH 4.0-4.5

Supernatant (alkali extract)


Hemi. A

2X EtOH

Precipitate-Hemi. B (Bio-Fiber Gum)


Fig. 1. Basic scheme for the isolation of hemicelluloses from corn bran, wheat bran, corn stover, rice fiber, wheat straw, switchgrass, miscanthus and sugarcane bagasse.

Table 2 diets, and should be very useful for making non-caloric food
Hemicellulose A and B from plant materials (% yield, dry weight basis). products.
Sources Hemi. A Hemi. B

Corn bran 3.98 25.13


3.4. Sugar composition of Hemi. A and B
Corn stover 19.82 8.85
Rice fiber 11.20 2.33
Wheat bran 14.85 14.60 Table 5 shows the sugar composition (relative mole percent) of
Wheat straw 22.63 4.80 the Hemi. A isolated from all eight plant materials. The acid insol-
Switchgrass 18.35 5.78 uble Hemi. A from all these sources look like arabinoxylan with
Miscanthus 17.03 2.56
varying Ara to Xyl ratio of 0.0.19 to 0.98 and a few percent of Rha,
Sugarcane bagasse 17.08 3.03
Gal, Glc and acidic sugars. Though there is some similarity in its
sugar composition with Hemi. B, it differs greatly in its solubility
under acidic conditions. Ara to Xyl ratio in Hemi. A from corn bran
content varied from 0 to 1.27% except Hemi. B from wheat bran,
and wheat bran is 0.73 and 0.98 respectively, showing highly
which was rich in protein (8.37%). They all had a little bit of residual
branched structure of their arabinoxylans. But the Ara to Xyl ratio in
starch (0.54e2.43%) and crude fat (0.14e1.37. As expected, these
the Hemi. A from other sources varies from 0.19 to 0.32 showing a
samples had 0 or very low percentage of NDF (0.00e1.92%) and ISD
less branched arabinoxylan structure.
(0.00e3.2%). But they were very rich in SDF varying from 87.2 to
Table 6 shows the sugar composition (relative mole percent) of
93.6% except Hemi. B from wheat bran and sugarcane bagasse,
the Hemi. B isolated from the same eight sources. Hemi. B isolated
which had only 60.3 and 55.5% SDF respectively. It is clear that
from all these sources show a typical arabinoxylan structure with
Hemi. B isolated from most of these sources were almost pure
xylan backbone and Ara in the side chains. The Ara to Xyl ratio of
soluble dietary fiber. They are predicted to be non-caloric in human
Hemi. B from corn bran and wheat bran are high (0.57 and 0.68

Please cite this article in press as: Yadav, M. P., & Hicks, K. B., Isolation, characterization and functionalities of bio-fiber gums isolated from grain processing
by-products, agricultural residues and energy crops, Food Hydrocolloids (2017), http://dx.doi.org/10.1016/j.foodhyd.2017.04.009
M.P. Yadav, K.B. Hicks / Food Hydrocolloids xxx (2017) 1e8 5

Table 3
Proximate composition and dietary fiber content of Hemicellulose A isolated from plant materials (all dry weight basis).

Sources Moistureb Ashb Proteina,b Starchb NDFb Crude Fatb ISD SDF TDF
Corn bran 1.38 0.16 9.22 0.27 24.58 0.67 3.91 0.48 0.00 10.98 0.82 8.2 19.1 27.3
Corn stover 7.95 0.14 9.60 0.17 13.51 0.48 0.42 0.18 4.98 0.55 3.47 0.37 13.6 26.0 39.4
Rice fiber 2.38 0.17 18.36 0.36 4.30 0.11 0.37 0.15 0.34 0.93 0.68 0.74 19.2 34.8 54.0
Wheat bran 2.66 0.10 8.15 0.18 37.85 0.67 1.43 0.16 0.69 0.19 13.30 0.48 4.3 11.2 15.6
Wheat straw 2.43 0.05 14.35 0.90 4.37 0.35 0.45 0.21 0.00 0 0.79 0.41 2.8 35.6 38.3
Switchgrass 6.39 0.13 13.36 0.47 4.41 0.17 0.60 0.08 0.24 0.08 1.80 0.15 1.6 35.4 37.0
Miscanthus 0.92 0.01 12.42 0.65 2.72 0.06 0.99 0.06 0.00 0.00 9.5 30.4 39.9
Sugarcane bagasse 2.03 0.18 20.05 0.56 3.84 0.02 0.40 0.08 0.00 0.65 0.40 22.5 22.4 44.8
a Calculated by multiplying nitrogen content by 6.25.
b
Average of triplicates.

Table 4
Proximate composition of pure bio-based fiber gums (Hemicellulose B) isolated from plant materials (all dry weight basis).

Sources Moistureb Ashb Proteina,b Starchb NDFb Crude Fatb ISD SDF TDF
Corn bran 3.44 0.21 2.97 0.04 1.20 0.04 1.69 0.14 0.00 0.72 0.12 1.4 93.6 95.1
Corn stover 5.34 0.14 6.92 0.02 1.27 0.14 1.40 0.05 0.26 0.01 0.42 0.17 0.0 87.2 87.3
Rice fiber 7.21 0.32 7.69 0.22 0.43 0.07 0.54 0.11 0.00 ND 1.6 90.3 91.9
Wheat bran 4.21 0.12 4.39 0.09 8.37 0.29 2.36 0.07 1.92 0.52 0.14 0.13 0.6 60.3 61.0
Wheat straw 5.36 0.08 6.21 0.15 0.00 0.59 0.12 0.00 0.80 0.31 0.60 93.1 93.7
Switchgrass 5.02 0.13 5.16 0.02 1.14 0.08 0.90 0.04 0.43 0.29 1.01 0.48 0.7 93.0 93.7
Miscanthus 4.08 0.33 7.10 0.04 0.00 2.43 0.11 0.00 1.37 0.45 3.2 88.0 91.1
Sugarcane bagasse 3.64 0.30 5.98 0.06 0.00 1.98 0.04 0.00 0.44 0.65 1.0 55.5 56.7
a Calculated by multiplying nitrogen content by 6.25.
b
Average of triplicates.

Table 5 3.5. Emulsification study of Hemi. B


Carbohydrate composition of Hemicellulose A isolated from plant materials (relative mole %).

The emulsion stability study was performed at 2.5 g scale and the particles
Sources Rha Ara Gal Glc Xyl GalA GlcA Total (droplets) size (diameter) was measured using a laser diffraction particle size
Corn bran 0.00 35.26 5.29 3.25 48.62 0.0 7.48 100.00 analyzer. Medium chain triglycerides (MCT) (density, 0.95 g/ml at 20 C)
Corn stover 1.65 16.55 7.67 16.71 52.16 1.85 3.40 100.00 were used as the dispersed phase since it is stable to oxidation with no bad
Rice fiber 0.28 14.62 2.40 4.14 77.72 0.03 0.81 100.00 smell or aroma and dissolves many lipophilic substances. The average particle
Wheat bran 0.07 27.32 4.05 36.67 27.86 0.00 4.03 100.00 size of emulsions prepared with Hemi. B from all eight plant materials are
Wheat straw 0.58 14.66 2.76 5.58 74.57 0.74 1.10 100.00
shown in Fig. 2. The emulsification effectiveness was evaluated by measuring
Switchgrass 1.31 15.35 2.69 6.18 73.35 0.00 1.11 100.00
Miscanthus 0.35 14.56 1.67 7.18 75.24 0.21 0.79 100.00 the initial particle size immediately after making emulsions (0 day). The
Sugarcane bagasse 0.41 13.97 2.48 7.23 75.01 0.00 0.91 100.00 emulsion stability was evaluated by storing the emulsions at 60 C (accelerated
Note: Rha, Rhamnose; Ara, Arabinose; Gal, Galactose; Glc, Glucose; Xyl, Xylose; GalA,
temperature stress test) and measuring the particle size after 3 and 7 days. As
Galacuronic acid; GlcA, Glucuronic acid. shown in Fig. 2A, Hemi. B from all sources makes very effective initial
emulsions on 0 day with average particle size of 1 or below 1 mm, except
from wheat bran, whose average particle size was 2.22 mm. The average
particle size of emulsions prepared using Hemi. B from corn stover, rice fiber,
respectively) like their corresponding Hemi.A, showing their highly branched
wheat straw, switchgrass, miscanthus and sugarcane bagasse rose only to
structures. The Hemi. B from other sources have lower Ara to Xyl ratio
showing less branched structures. The Ara to Xyl ratio (branching of AX) of about 1 or a little bit above 1 mm after 3 days storage at accelerated
Hemi. B from corn bran agree with the reported results (Yadav et al., 2007a). temperature conditions. But the average particle size of emulsions prepared
with Hemi. B from corn bran and wheat bran
The other sugars present in the Hemi. B from all these sources are Rha, Gal,
Glc, GalA and GlcA.

Table 6
Carbohydrate composition of Bio-based Fiber Gums (Hemicellulose B) isolated from plant materials (relative mole %).

Sources Fuc Rha Ara Gal Glc Xyl GalA GlcA Total

Corn bran 0.19 0.43 27.41 12.06 4.27 48.43 1.02 6.20 100.00
Corn stover 0.84 1.32 17.99 10.85 9.58 52.25 1.75 5.42 100.00
Rice fiber 0.20 0.97 18.12 8.06 3.64 65.36 1.57 2.07 100.00
Wheat bran 0.00 0.55 31.10 5.27 14.00 46.03 0.83 2.21 100.00
Wheat straw 0.28 2.50 19.67 11.67 7.25 54.46 1.69 2.50 100.00
Switchgrass 0.33 1.12 19.04 7.25 6.33 61.69 1.67 2.57 100.00
Miscanthus 0.31 1.00 18.46 7.99 10.17 57.89 1.90 2.28 100.00
Sugarcane bagasse 0.19 1.28 17.12 6.37 12.38 58.39 2.16 2.11 100.00

Note: Fuc, Fucose; Rha, Rhamnose; Ara, Arabinose; Gal, Galactose; Glc, Glucose; Xyl, Xylose; GalA, Galacturonic acid; GlcA, Glucuronic acid.

Please cite this article in press as: Yadav, M. P., & Hicks, K. B., Isolation, characterization and functionalities of bio-fiber gums isolated from grain processing
by-products, agricultural residues and energy crops, Food Hydrocolloids (2017), http://dx.doi.org/10.1016/j.foodhyd.2017.04.009
6 M.P. Yadav, K.B. Hicks / Food Hydrocolloids xxx (2017) 1e8

Fig. 2. Average particle size of emulsions prepared with biofiber gum from corn bran, corn stover, rice fiber, wheat bran, wheat straw, switchgrass, miscanthus and sugarcane bagasse. Lower particle

size is an indication of greater emulsion stability. Each plotted point is an average of three trials SD. A 0 day, B 3 days and C 7 days.

rose to 2.80 and 14.88 respectively during 3 days storage at the accelerated (Fig. 2B). After 7 days storage at the same temperature, the average particle
temperature (60 C) showing that they made a less stable emulsions in size of Hemi. B from wheat bran increased drastically above 40 mm, showing
comparison to Hemi. B from other six sources very unstable emulsions, which could be due to

Please cite this article in press as: Yadav, M. P., & Hicks, K. B., Isolation, characterization and functionalities of bio-fiber gums isolated from grain processing
by-products, agricultural residues and energy crops, Food Hydrocolloids (2017), http://dx.doi.org/10.1016/j.foodhyd.2017.04.009
M.P. Yadav, K.B. Hicks / Food Hydrocolloids xxx (2017) 1e8 7

35,000

30,000
Whole Material, Hemicellulose-B
25,000

20,000

15,000

10,000

5,000

Fig. 3. ORAC values of the whole biomass and the Hemicellulose-B (BFG) isolated from them.

very high content of ash (24.39) in this sample. The particle size of the transfer. The higher the ORAC score is an indication of a greater the
emulsion prepared with Hemi. B from corn bran was about 9 mm, showing materials antioxidant capacity. There is great need of compounds that can
an intermediate stability as reported previously (Yadav et al., 2007a). But the serve to protect foods and non-food products against oxidative damage due to
particle size of emulsion prepared with Hemi. B from all remaining six free radicals, oxygen, ozone, and other deleterious environmental agents. It
sources stayed below 3 mm, indicating that they were very good emulsifiers has been reported that the free and bound phenolic residues associated with
and make stable emulsions. The emulsion stability of these samples did not the plant poly-saccharides, like spruce galactoglucomannans,
correlate well with their protein content showing that their emulsifying carboxymethylated spruce galactoglucomannans, gum arabic and corn fiber
properties were not just based on the protein content but some other structural gum effi-ciently inhibited and altered the pathways of lipid oxidation of
features were responsible for their emulsifying properties. rapeseed oil in its water emulsion in the presence of each of the above
polysaccharides (Lehtonen et al., 2016). BFGs, which have ability to
emulsify, encapsulate, or form a protective film on the products that are
sensitive to oxidation, such as vitamins, omega-3 polyunsaturated fatty acids,
fish oils, medicines, paint pigments, and the like, should be useful for
3.6. Antioxidant properties of BFG and its source material protecting these sensitive mate-rials (Yadav et al., 2016a, b). BFGs isolated
from these eight plant sources do not only have the ability to emulsify,
By normal cellular processes in the body, UV irradiation and encapsulate, and form films on these sensitive oxidation-prone materials, but
environmental stresses, highly reactive molecules like free radicals and also have the ability to prevent oxidation due to their antioxidant properties.
reactive oxygen species are generated. These reactive mole-cules react with The hydrophilic ORAC values of pure BFGs (Hemi. B) isolated from corn
cellular components damaging DNA, carbohy-drates, proteins and lipids bran, wheat bran, corn stover, rice fiber, wheat straw, switchgrass,
causing injury to cells and tissues. Excess production of such reactive species miscanthus, and sugarcane bagasse are higher than their respective original
can cause several diseases including cancer, diabetes and atherosclerosis etc. biomasses (Fig. 3) indicating that more antioxidant containing BFG products
Most organisms have antioxidant systems to protect themselves from can be solubilized and made available by the present alkaline extraction
oxidative stress, however an excess free radical and/or reactive oxygen spe- process. Our re-sults clearly indicate that all these BFGs, especially those
cies can cause severe damage. One way to measure the antioxidant power of from wheat bran, corn stover, switchgrass and miscanthus, are very rich in
compositions, foods, and plant phytochemicals is to determine the Oxygen antioxidant (ORAC Value, above 7000 mmol TE/100 g), which is higher than
Radical Absorbance Capacity (ORAC) value of the composition (Graf, 1992; the original materials they were prepared from. In addition to being very
Ohta, Yamasaki, Egashira, & Sanada, 1994). The ORAC antioxidant assay powerful antioxidants, these BFGs are very rich (over 80%) in soluble dietary
measures the loss of fluorescein fluorescence over time due to peroxyl-radical fiber (Table 4). Human con-sumption of such materials could be beneficial for
formation by the breakdown of 2,2-azobis-2-methyl-propanimidamide, prevention of heart disease.
dihydro-chloride (AAPH). Trolox, which is a water soluble vitamin E analog,
serves as a positive control inhibiting fluorescein decay in a dose dependent
manner. The ORAC assay is a kinetic assay measuring fluorescent decay and
antioxidant protection over time. The anti-oxidant activity can be normalized
to equivalent Trolox units to quantify the composite antioxidant activity
present. This assay measures the materials antioxidant activity by hydrogen
atom 4. Conclusion

Bio-fiber gum (BFG), also called Hemicellulose B is a highly

Please cite this article in press as: Yadav, M. P., & Hicks, K. B., Isolation, characterization and functionalities of bio-fiber gums isolated from grain processing
by-products, agricultural residues and energy crops, Food Hydrocolloids (2017), http://dx.doi.org/10.1016/j.foodhyd.2017.04.009
8 M.P. Yadav, K.B. Hicks / Food Hydrocolloids xxx (2017) 1e8

functional value-added product that can be prepared with the yield varying fiber from the by-product of wheat flour processing behaves physiologically like a soluble,
from 2.33 to 25.13% from many low value grain processing by-products, fermentable fiber in the large bowel of rats. Journal of Nutrition, 130, 1984e1990.

agricultural residues and energy crops. The BFG con-sisted almost entirely of Lu, Z. X., Walker, K. Z., Muir, J. G., Mascara, T., & ODea, K. (2000a). Arabinoxylan fibre, a
soluble dietary fiber, making them suitable as non-caloric bulking and by-product of wheat flour processing, reduces the postprandial glucose in normoglycaemic
texturizing agents in many food prod-ucts providing them with potential subjects. The American Journal of Clinical Nutrition, 71, 1123e1128.

health benefits like blood cholesterol level lowering and prebiotic activities in Lu, Z. X., Walker, K. Z., Muir, J. G., & ODea, K. (2004). Arabinoxylan fiber improves
the human gut. All these materials contained a high percentage of acid metabolic control in people with Type II diabetes. The European Journal of Clinical
insoluble Hemi. A (3.98e22.63%), which needs more study to determine Nutrition, 58, 621e628.
McCleary, B. V., Gibson, T. S., & Mugford, D. C. (1997). Measurement of total starch in cereal
functionality and potential new industrial applications. Corn and wheat bran products by amyloglucosidase - a-amylase method: Collaborative study. Journal of AOAC
contained comparatively more Hemi. B (25.13 and 14.60% respectively) than International, 80, 571e579.
other sources (2.33e8.85%) and Hemi. B from all these sources has a typical Monlau, F., Sambusiti, C., Barakat, A., Guo, X. M., Latrille, E., Trably, E., et al. (2012).
Predictive models of biohydrogen and biomethane production based on the compositional
cereal arabinoxylan structure with xylan backbone and Ara in the side chains. and structural features of lignocellulosic materials. Environ-mental Science and
A low percent of Gal, Glc and acidic sugars was also detected and more likely Technology, 46(21), 12217e12225.
they are present in the side chains. They have highly branched structure. Ohta, T., Yamasaki, S., Egashira, Y., & Sanada, H. (1994). Antioxidative activity of corn bran
hemicellulose fragments. Journal of Agricultural Food Chemistry, 42, 653e656.
Hemi. B from all these sources are very good emulsifiers except the Hemi. B
from wheat bran and they are very good antioxidant with high ORAC. Owing Ou, B., Huang, D., Hampsch-Woodill, M., Flanagan, J. A., & Deemer, E. K. (2002). Analysis
to their high functionality and non-caloric na-ture, BFGs produced from these of antioxidant activities of common vegetables. Journal of Agricultural Food Chemistry,
50, 3122e3128.
low-valued agricultural by-products are very interesting and should be
Parajo, J. C., Garrote, G., Cruz, J. M., & Dominguez, H. (2004). Production of xyloo-
commercially valu-able health-promoting, soluble dietary fiber based bulking ligosaccharides by autohydrolysis of lignocellulosic materials. Trends in Food Science &
agents, viscosifiers and texturizing agents for use in the food industry and Technology, 15(3), 115e120.
Qiu, S., Yadav, M. P., Chen, H., Liu, Y., Tatsumi, E., & Yin, L. (2015). Effects of corn fiber
beyond.
gum (CFG) on the pasting and thermal behaviors of maize starch. Carbohydrate Polymers,
115, 246e252.
Qiu, S., Yadav, M. P., & Yin, L. (2017). Characterization and functionalities study of
hemicellulose and cellulose components isolated from sorghum bran, bagasse and biomass.
Food Chemistry, 230, 225e233.
Qiu, S., Yadav, M. P., Liu, Y., Chen, H., Tatsumi, E., & Yin, L. (2016). Effects of corn fiber
Acknowledgements gum with different molecular weights on the gelatinization behaviors of corn and wheat
starch. Food Hydrocolloids, 53, 180e186.
Reddy, B. S., Engle, A., Katsifis, S., Simi, B., Bartram, H. P., Perrino, P., et al. (1989).
We would like to acknowledge Stefanie Simon for her excellent technical Biochemical epidemiology of colon cancer: Effect of types of dietary fibre on fecal
assistance in preparing these BFGs and charactering and doing their mutagens, acid and neutral sterols in healthy subjects. Cancer Res., 49, 4629e4635.
functionalities test.
Reddy, N., & Yang, Y. (2005). Biofibers from agricultural byproducts for industrial appli-
cations. Trends in Biotechnology, 23, 22e27.
References Vuksan, V., Jenkins, D. J., Spadafora, P., Sievenpiper, J. L., Owen, R., Vidgen, E., et al. (1999).
Konjac-mannan (glucomannan) improves glycemia and other associ-ated risk factors for
Al-Assaf, A., Phillips, G. O., Aoki, H., & Sasaki, Y. (2007). Characterization and properties of coronary heart disease in type 2 diabetes. A randomized controlled metabolic trial. Diabetes
Acacia senegal (L.) Willd. var. Senegal with enhanced properties (Acacia (sen) SUPER Care, 22, 913e919.
GUM TM): Part 1-control maturation of Acacia senegal var. senegal to increase Woo, D. H., and Kim, J. K.. (2005). Method for preparing soluble dietary fiber from corn hull.
viscoelasticity, produce a hydrogel form and convert a poor into a good emulsifier. Food U.S. Patent NO. 6,838,099.
Hydrocolloids, 21, 319e328. Wursch, P., & Pi-Sunyer, F. X. (1997). The role of viscous soluble fiber in the meta-bolic
American Association of Cereal Chemists. (1995). Approved Methods of the AACC (9th ed.). control of diabetes. A review with special emphasis on cereals rich in beta-glucan. Diabetes
St. Paul, MN: The Association. Methods 08-01, 44e15A and 46-30. Care, 20, 1774e1780.
ANKOM Technology. (2011). A2000 automated fiber analyzer. NY: Ankom Technol-ogy, Yadav, M. P., Hicks, K. B., Johnston, D. B., Hanah, K., and Shukla, T. P. (2016b). Bio-based
Macedon. http://www.ankom.com/media/documents/Method_6_NDF_ fiber gums (BFGs) and processes for producing BFGS. US Patent No. 9,434,788 B2.
4013011_A200,A200I.pdf.
Chandalia, M., Grag, A., Luthohann, D., Bergman, K. V., Grundy, S. M., & Brinkley, L. J. Yadav, M. P., Cooke, P., Johnston, D. B., & Hicks, K. B. (2010). Importance of protein rich
(2000). Beneficial effects of a high dietary fiber intake in patients with type 2 diabetes components on the emulsifying properties of corn fiber gum. Cereal Chemistry, 87(2),
mellitus. The New England Journal of Medicine, 342, 1392e1398. 89e94.
Doner, L. W., Chau, H. K., Fishman, M. L., & Hicks, K. B. (1998). An improved process for Yadav, M. P., Fishman, M. L., Chau, H. K., Johnston, D. B., & Hicks, K. B. (2007c). Molecular
isolation of corn fiber gum. Cereal Chemistry, 75(4), 408e411. characteristics of corn fiber gum and their influence on its emulsi-fying properties. Cereal
Doner, L. W., & Hicks, K. B. (1997). Isolation of hemicellulose from corn fiber by alkaline Chemistry, 84(2), 175e180.
hydrogen peroxide extraction. Cereal Chemistry, 74(2), 176e181. Yadav, M. P., & Hicks, K. B. (2015). Isolation of barley hulls and straws constituents and study
Doner, L. W., & Johnston, D. B. (2001). Isolation and characterization of cellulose/ of emulsifying properties of their arabinoxylans. Carbohydrate Poly-mer, 132, 529e536.
arabinoxylan residual mixtures from corn fiber gum processes. Cereal Chemistry, 18(2),
200e204. Yadav, M. P., Hicks, K. B., Johnston, D. B., Hotchkiss, A. R., Jr., Chau, H. K., & Hanah, K.
Franz, M. J., Bantle, J. P., Beebe, C. A., Brunzell, J. D., Chiasson, J. L., Garg, A., et al. (2002). (2016a). Production of bio-based fiber gums from the waste streams resulting from the
a. Evidence-based nutrition principles for the treatment and prevention of diabetes and commercial processing of corn bran and oat hulls. Food Hydrocolloids, 53, 125e133.
related complications. Diabetes Care, 25, 148e198.
Graf, E. (1992). Antioxidant potential of ferulic acid. Free Radical Biology and Med-icine, Yadav, M. P., Johnston, D. B., & Hicks, K. B. (2007b). Structural characterization of corn fiber
13435e13448. gum from coarse and fine corn fiber and a study of their emulsifying properties. Journal of
Groop, P. H., Aro, A., Stenman, S., & Groop, L. (1993). Long-term effects of guar gum in Agricultural Food Chemistry, 55, 6366e6371.
subjects with non-insulin-dependent diabetes mellitus. The American Journal of Clinical Yadav, M. P., Johnston, D. B., & Hicks, K. B. (2008). Fractionation, characterization and study
Nutrition, 58, 513e518. of emulsifying properties of corn fiber gum. Journal of Agricultural Food Chemistry, 56,
Hoije, A., Grondahl, M., Tommeraas, K., & Gatenholm, P. (2005). Isolation and 4181e4187.
characterization of physicochemical and material properties of arabinoxylans from barley Yadav, M. P., Johnston, D. B., Hotchkiss, A. T., & Hicks, K. B. (2007a). Corn fiber gum: A
husks. Carbohydrate Polymers, 61, 266e275. potential gum Arabic replacer for beverage flavor emulsion. Food Hydrocol-loids, 21,
Huang, D., Ou, B., Hampsch-Woodill, M., Flanagan, J. A., & Prior, R. L. (2002). High- 1022e1030.
throughput assay of oxygen radical absorbance capacity (ORAC) using a multichannel Yadav, M. P., Kale, M., Hicks, K. B., & Hanah, K. (2017). Isolation, characterization and the
liquid handling system coupled with a microplate fluorescence reader in 9 ewell format. functional properties of cellulosic arabinoxylan fiber isolated from agri-cultural processing
Journal of Agriculture and Food Chemistry, 50, 1815e1821. by-products, agricultural residues and energy crops. Food Hydrocolloids, 63, 545e551.

Lehtonen, M., Teraslahti, S., Xu, C., Yadav, M. P., Lamp, A.-M., & Mikkonen, K. S. (2016). Yadav, M. P., Moreau, R. A., & Hicks, K. B. (2007d). Phenolic acids, lipids, and proteins
Spruce galactoglucomannans inhibit the lipid oxidation in the rapeseed oil-in-water associated with purified corn fiber arabinoxylans. Journal of Agricultural Food Chemistry,
emulsions. Food Hydrocolloids, 58, 255e266. 55, 943e947.
Lu, Z. X., Gibson, P. R., Muir, J. G., Fielding, M., & ODea, K. (2000b). Arabinoxylan

Please cite this article in press as: Yadav, M. P., & Hicks, K. B., Isolation, characterization and functionalities of bio-fiber gums isolated from grain processing
by-products, agricultural residues and energy crops, Food Hydrocolloids (2017), http://dx.doi.org/10.1016/j.foodhyd.2017.04.009