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Plant foods for human nutrition volume 67 issue 3 2012 doi 10 10072fs11130 012 0301 5 shridhar k sathe harshal h kshirsagar girdhari m sharma solubilization fractionation and electrophore

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2012 Abstract Effects of different solvents, ionic strength, and pH on Inca peanut seed protein solubility were assessed by quantitatively analyzing solubilized proteins using Lowry and

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ORIGINAL PAPER

Solubilization, Fractionation, and Electrophoretic Characterization

Shridhar K Sathe&Harshal H Kshirsagar&

Girdhari M Sharma

Published online: 12 August 2012

# Springer Science+Business Media, Inc 2012

Abstract Effects of different solvents, ionic strength, and

pH on Inca peanut seed protein solubility were assessed by

quantitatively analyzing solubilized proteins using Lowry

and Bradford methods Soluble proteins were fractionated

using Osborne procedure and the polypeptide composition

of solubilized proteins was determined by one dimensional

25 % monomer acrylamide linear gradient SDS-PAGE

Osborne protein fractions were analyzed by the 2D gel

electrophoresis Total seed proteins were efficiently

solubi-lized by 2 M NaCl among the tested solvents The soluble

seed proteins registered a minimum solubility at pH ~4.0

Osborne protein fractions, albumins, globulins, prolamins,

and glutelins accounted for 43.7, 27.3, 3.0, and 31.9 %,

respectively, of the total aqueous soluble proteins Soluble

seed flour proteins are mainly composed of polypeptides in

the MW range of 6–70 kDa of which the predominant

poly-peptides were in the 20–40 kDa range Prolamin fraction was

mainly composed of four polypeptides (MW < 15 kDa)

Glycoprotein staining indicated 32–35 and <14 kDa peptides

to be positive

Keywords Inca peanut Protein Solubility Protein fractions Electrophoresis

Abbreviations β-ME β-mercaptoethanol CBBR Coomassie brilliant blue R CHAPS

3-[(3-Cholamidopropyl)dimethylammonio]-1-propanesulfonate DTT Dithiothreitol EtOH Ethanol IEF Isoelectric focusing kDa Kilodalton

LSD Least significant difference MeOH Methanol

MW Molecular weight PAGE Polyacrylamide gel electrophoresis

pI Isoelectric pH

RT Room temperature SDS Sodium dodecyl sulfate Tris 2-Amino-2-hydroxymethyl-propane-1,3-diol

Introduction Plant foods are important in human and animal nutrition According to FAO [1] statistical data, plant foods [cereals (46.4 %), roots/tubers (5.1 %), vegetable oils (9.6 %), sug-ars/sweeteners (8.1 %), fruits (5.9 %), and pulses (2.1 %)] together provided 77.2 % of the total food energy consumed during 2005–2007 Among plant foods, cereals typically provide the bulk of the calories (range 18.5 % for Burundi and Rwanda to 78.1 % for Bangladesh) Pulses, despite their high protein content, contribute in much smaller portion of global caloric intake (range 0 % for Armenia, Azerbaijan,

S K Sathe ( *):H H Kshirsagar:G M Sharma

Department of Nutrition, Food & Exercise Sciences,

College of Human Sciences, The Florida State University,

402 SAN,

Tallahassee, FL 32306-1493, USA

e-mail: ssathe@fsu.edu

Present Address:

H H Kshirsagar

Roquette America Inc.,

2000 South Batavia Avenue, Suite 400,

Geneva, IL 60134, USA

Present Address:

G M Sharma

Department of Health and Human Services, Public Health Service,

Food and Drug Administration,

Office of Applied Research and Safety Assessment,

Center for Food Safety and Applied Nutrition, U.S FDA,

8301 Muirkirk Road,

Laurel, MD 20708, USA

DOI 10.1007/s11130-012-0301-5

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Belarus, Georgia, Latvia, Samoa, Uzbekistan, and Vanuatu

to 18.7 % for Burundi) Legumes such as beans, peas, and

some oilseeds, make a significant contribution to human and

animal food protein supply [2–5] and therefore are

consid-ered to be valued crops Reviews on legume food and

nutrition [6–13] continue to periodically appear indicating

the global importance and interest in legume research and

utilization

Soybeans, peanuts, peas, and common dry beans are

some of the most widely investigated and utilized legume

crops However, there are many native legume species that

remain under-utilized (e.g., lablab, moth, and Tepary beans)

An extensive report on tropical legumes compiled by the US

National Academy of Sciences over 30 years ago [14] is

particularly informative and useful in this regard In addition

to their use in foods, many legumes are also utilized for

non-food uses (e.g., ornamental uses of several Acacia spp and

production of luxury timbers from Pterocarpus spp.) [14]

Plukenetia L (Euphorbiaceae) is a pantropical genus that

reportedly consists of 19 species belonging to Plukenetieae

(subfamily Acalyphoideae) [15,16] Plukenetia species are

twining vines found in tropical rain forests to seasonally dry

forest or scrub Plukenetia penninervia Muell Arg., a

spe-cies found in rainforests of Mexico is used for basket

weav-ing and other craft activities for several centuries datweav-ing

back to the Mayan period [17] Inca peanut (Plukenetia

volubilis L.), also known as Sacha inchi, is an underutilized

plant that grows wild in the rain forests of the Andean

region This plant belongs to the Euphorbiaceae family

[18] High in oil (54 %, w/w) and protein (27 %) [19], the

plant seeds are typically flat, <2 cm across, and slightly

dome shaped in the middle (Fig.1) The seeds are protected

by a tough, dark outer shell with soft thin tissue layer on the

inside Since the seeds are bitter, they are typically eaten

after suitable processing (e.g., roasting) and are valued as a

significant source of dietary protein by the native people

Unlike soybean, peanut, cottonseed and sunflower oils that

are high in linoleic but low in linolenic acid, Inca peanut oil

contains approximately equal proportions of the essential fatty acids, linoleic- the C18:2, ω-6 (36.8 % w/w) and linolenic-C18:3,ω-3 (45.2 %, w/w) A recent report indi-cates that these two fatty acids accounted for 35.34 and 46.92 % respectively with reported average of the published data of 33.74 and 44.79 %, respectively The quantity of monounsaturated oleic acid (9.6 %, w/w) in Inca peanut lipids is less compared to the corresponding amounts in soybean (22.3 %), peanut (41.3 %), cottonseed (18.7 %), and sunflower (29.3 %) seed oils [19] The Inca peanut seed proteins are soluble in aqueous buffers and a water soluble albumin has been reported to constitute ~25 % (w/w) of the defatted seed flour weight or 31 % of total proteins in the seed This albumin protein is a dimeric, glycosylated [con-tains 4.8 % (w/w) sugar], basic protein (pI~9.4) with an ultracentrifuge sedimentation value of 3S [20] The results

of amino acid composition analyses indicate high levels of cysteine, tyrosine, threonine, and tryptophan and low amounts of phenylalanine in the seed proteins [19, 21] Legume proteins are known to be deficient in sulfur amino acids [6, 22] Inca peanut seed proteins contain high amounts of sulfur amino acids (methionine + cysteine),

37 mg/100 g seed meal protein, as compared to the FAO/ WHO/UNU recommended scoring pattern for these sulfur amino acids—25 mg/100 g protein [1,19] Taken together, Inca peanut seed flour proteins are a valuable source of dietary proteins However, except for some of the reported studies, little is known about the Inca peanut seed proteins Here we report our findings on protein solubility and elec-trophoretic properties of Inca peanut seed proteins

Materials and Methods Materials

The source of seeds used for Fig.1has been reported earlier [19] Hexane defatted seed flours (two separate batches, ~5 kg each) used for the current investigations were a gift from Cristina Thibaut (Cobiosa, Industrias Asociada SL, Madrid, Spain) The defatted flour batches were stored at−20 °C until further use Sources of the reagents and chemicals used have been reported earlier [21,23]

Methods All experiments were conducted at least in duplicate using separate batches of defatted flours

Protein Solubilization and Extraction Effect of Buffer Proteins were solubilized in the selected solvent and for the indicated extraction time using defatted Fig 1 Inca peanut whole seed and kernel The kernel is packed inside

a dark brown hard shell with an inner soft white tissue lining

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seed flour to solvent ratio of 1:10 (w/v) at room temperature

(RT, ~25 °C) with constant mechanical shaking Aqueous

solvents used for protein solubilization were: A) distilled

deionized water, B) 2 M NaCl, C) 0.1 M Tris-HCl (pH 8.1),

D) 0.05 M Na3PO4buffer (pH 7.5), E) 0.1 M borate saline

buffer (BSB, 0.1 M H3BO3, 0.025 M Na2B4O7, 0.75 M

NaCl, pH 8.45), F) 0.1 M NaOH, G) 0.1 M HCl, H) 2 %

(w/v) sodium dodecyl sulfate (SDS), I) 70 % (v/v) aqueous

ethanol (EtOH), J) 10 % (v/v) acetic acid, K) 0 1 M

NaHCO3, L) 10 % (w/v) Na2SO4. The pH of the slurry

was adjusted using 1 M HCl and 1 M NaOH (pH range

1–12) At the end of the extraction period, the slurry was

centrifuged (12,300g, 15 min, RT), the supernatant collected

and used for further analysis

Effect of Extraction Conditions on Protein Solubility Effects

of ionic strength (0–4 M NaCl), time of extraction (1–5 h,

1 M NaCl), pH (pH range 1–13, 1 M NaCl extraction), and

repeated (five) consecutive extractions in 1 M NaCl on the

protein solubility were determined by extracting 100 mg

defatted flour with the appropriate solvent (1 ml) [e.g., flour

to solvent ratio01:10 (w/v)] at RT with continuous vortexing

at room temperature (RT, ~25 °C) followed by

centrifuga-tion at 16,000 g for 15 min at RT To investigate the effects

of pH on seed flour protein solubility, defatted flours (2 g

each) were first dispersed in either distilled deionized water or

aqueous 1 M NaCl and the pH of the dispersion was adjusted

to the desired value with diluted (0 1 M) NaOH and/or HCl

and continued stirring for 30 min until pH was stabilized

Then, the final flour to solvent ratio 1:10 (w/v) was adjusted

and the soluble proteins were extracted for 1 h with constant

magnetic stirring At the end of extraction, the slurry was

centrifuged (15,000 g, 30 min, 4 °C), the supernatant

collected and analyzed for soluble protein within 48 h

Osborne Fractionation Protein fractionation of the defatted

seed flour proteins was done by the Osborne method [24]

Briefly, the defatted seed flour (100 g) each was sequentially

extracted with 2 M NaCl (albumins + globulins), 70 %

aqueous ethanol (prolamins), and 0.1 M NaOH (glutelins)

at flour to solvent ratio 1:10 (w/v) at room temperature (RT)

for 1 h with constant magnetic stirring The pH of flour

suspensions in distilled water, 2 M NaCl, and 70 % aqueous

EtOh was approximately 6.6–6.7 while in 1 N NaOH the pH

was ~12.6 At the end of each extraction the slurry was

centrifuged (15,000 g, 30 min, 4 °C), the supernatant

col-lected, and the residue was used for next extraction The

residue was discarded after the 0.1 M NaOH extraction step

Each supernatant was filtered through Whatman filter paper

number 4 and dialyzed (molecular weight cut-off of the

dialysis tubing06–8 kDa, Spectra-Por Dialysis, Spectrum

Laboratories, Inc., Rancho Dominguez, CA) against

dis-tilled deionized water for 48 h (4 °C, 10 lit each, six

changes); each dialyzed extract, except for the 2 M NaCl extract, was separately lyophilized True albumins were separated from the true globulins by subjecting the dialyzed 2 M NaCl extract to centrifugation (15,000 g,

30 min, 4 °C) The separated true albumins (superna-tant) and the true globulins (residue) were separately lyophilized The lyophilized protein fractions were stored at −20 °C in plastic screw-capped bottles until further use

Gel Electrophoresis SDS-PAGE Sodium dodecyl sulfate polyacrilamide gel elec-trophoresis (SDS-PAGE) was run by the method of Fling and Gregerson [25] as described in Sharma et al [26] Appropriate protein samples were loaded on 8–25 % linear acrylamide gradient separating gel and 4 % monomer acryl-amide stacking gel The gel was typically run at 10 mA/gel until the tracking dye migrated to the gel edge (typically

20 h) The gels were stained with Coomassie Brilliant Blue

R (CBBR) or silver stain followed by appropriate destaining

as described earlier [23]

2D Gel Electrophoresis were conducted as described below (a) SDS-PAGE gels without the reducing agent [2 %v/v mercaptoethanol (β-ME)] were run in the first dimen-sion followed by SDS-PAGE in the presence of the reducing agent Gels were typically run at a constant current (10 mA/gel) with tap water cooling provided during the gel run The gels were stained with Coo-massie Brilliant Blue R and appropriate lanes were excised for 2D analysis The excised gel strips were soaked in SDS-PAGE sample buffer [0.05MTris-HCl,

pH 6.8; 0.1 % (w/v) SDS; 0.01 % (w/v) bromophenol blue; 30 % (v/v) glycerol] containing 2 % (v/v)β-ME and heat-denatured (~100 °C) in a microwave oven (Kenmore, model 565.68301790, Sears, Hoffman Estates, IL) for 30 s at 1,000 W The strips were then cooled to RT, turned 90º counterclockwise, laid on top

of the 4 % stacking gel with a 8–25 % linear monomer acrylamide gradient SDS-PAGE separating gel, and electrophoresed as indicated above The gels were then stained (CBBR) and destained as described by Sathe et

al [23] Briefly, the gels were stained overnight with 0

25 % Brilliant blue R (B0149-100 G, Sigma-Aldrich)

in 50 % methanol and 10 % acetic acid The gels were destained with destain solution (50 % methanol and

10 % acetic acid) once followed by diluted destaining solution (~1:1 with water) until the background was clear

(b) IEF-SDS-PAGE Fractionated proteins were subjected

to 2D gel separations using isoelectric focusing (IEF)

in the first dimension followed by SDS-PAGE as de-scribed by Sharma et al [26] About 1.1–1.4 mg of

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freeze-dried protein fractions were suspended in 500μl

rehydration buffer [8 M urea, 2 %w/v

3-[(3-Cholami-dopropyl)dimethylammonio]-1-propanesulfonate

(CHAPS), 0.002 % bromophenol blue, 0.5 % carrier

ampholyte, and 20 mM dithiothreitol (DTT)] for 1 h at

room temperature followed by centrifugation at

16,000 g for 15 min An appropriate amount (30–

50μl) of the supernatant was mixed with the

rehydra-tion buffer to a final volume of 250μl and was used to

rehydrate pH 3-10NL 13 cm IPG strips (17-6001-15,

GE healthcare) overnight (thus loading the protein

sample on the strips) The strips were covered with

mineral oil to prevent evaporation The rehydrated

strips (containing the protein samples) were used for

IEF as per manufacturer’s recommendation (IEF100,

Hoefer Scientific Co., CA) using following conditions:

1- gradient volt, 1,000 V, 1 h; 2- gradient volt,

12,000 V, 1 h; 3- constant volt, 12,000 V, 25,000 V,

1 h; 4- constant volt, 1,000 V, 1 h For the 2nd

dimension, the focused strips were incubated

15 min in equilibration buffer (6 M urea, 75 mM

Tris-HCl pH 8.8, 29.3 % glycerol, 2 % SDS,

0.002 % bromophenol blue) containing 10 mg/ml

DTT, followed by 15 min in equilibration buffer

containing 25 mg/ml iodoacetamide The IPG strips

were then horizontally placed on a 8–25 % gradient

monomer linear acrylamide gel and sealed with 1 %

(w/v) agarose An appropriate amount (10 μl) of

same supernatants and protein markers were loaded

on the either side of the gel, and run overnight at

constant current of 10 mA/gel followed by 20 mA/

gel next day, until the tracking dye reached gel

edge The gels were then stained (CBBR) and

destained as described by Sathe et al [23])

Glycoprotein Staining

Glycoprotein staining was done on SDS-PAGE gels using the

Gelcode glycoprotein staining (Pierce Chemical Co.,

Rock-ford, IL) procedure following manufacturer’s instructions

Proximate Composition

Moisture An accurately weighed sample (0.1 g) was placed in

an aluminum pan and was dried in a previously heated

vacu-um oven (Barnstead Lab-Line, Melrose Park, IL; model

3608-5; 95-100 °C, 25 in of Hg) to a constant weight AOAC

Official Method 925.40 [27]

Protein AOAC Official Method 950.48 [27] The

micro-Kjeldahl method was used to determine total proteins using

0.1 g sample Sample nitrogen content was calculated using

the formula: Protein %ð Þ ¼ total N %ð Þ  5:7

Soluble Protein Soluble protein was determined using the methods of Lowry et al [28] and Bradford [29] Each sam-ple was typically suitably diluted and analyzed in duplicate Tannins A known weight of the sample (0.1 g) was extracted for 1 h in absolute methanol (MeOH) and acidified (1 % HCl, v/v) MeOH with continuous vortexing followed

by centrifugation (15,000 g, 10 min, RT) Aliquots of the supernatant were immediately analyzed for tannin using a

4 % (w/v) vanillin assay [30] A catechin standard curve (0–

1 mg/ml) was prepared simultaneously Tannin content was expressed as catechin equivalents

Statistical Analysis All statistical analyses were performed using SPSS statistical software (version 15; Chicago, IL) All experiments were conducted at least in duplicate, and data are expressed as the mean ± standard deviation (SD) One-way ANOVA and Fish-er’s least significant difference (LSD) test as described by Ott [31] were used to determine statistical significance, and results were considered to be significant if the differences between the two means exceeded the LSD value (p00.05)

Results and Discussion Defatted Flour

Three samples from each of the two defatted flours batches (n06) were analyzed for proximate composition The average percent protein (%N x 5.7), moisture, ash, and soluble carbo-hydrate content of the defatted flours were 59.1±3.3, 8.32± 0.11, 6.46±0.05 and 1.03±0.06, respectively The average total soluble phenolics in the defatted flours were 0.117± 0.021 and 0.112±0.016 g/100 g flour when extracted with

Fig 2 Seed flour protein solubility in a Distilled deionized water, b

2 M NaCl, c 0 1 M Tris –HCl (pH 8.5), d 0.05 M Sodium phosphate buffer (pH 7.5), e 0.1 M BSB (pH 8.45), f 0.1 M NaOH, g 0.1 M HCl,

h 2 % (w/v) SDS, i 70 % (v/v) EtOH, j 10 % (v/v) acetic acid, k 0.1 M NaHCO 3 , l 10 % (w/v) Na 2 SO 4 LSD (p 00.05) is 7.76 (Lowry) and 0.97 (Bradford), n 06 for both

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methanol and acidified methanol, respectively, indicating the

phenolics both solvents The chemical composition of the

defatted flour found in the current investigation is consistent

with soybean [32], peanut [33], sesame [34], and lupin [35,36]

seed flours The protein content of the defatted flour found in

the current investigation is comparable to the reported

protein content (53 %) for the defatted flour from inca

peanut grown in Peru [19]

Protein Solubility

Among the tested solvents, 0.1 N NaOH and 2 M NaCl were

the most effective solvents for solubilizing the flour proteins

(Fig.2) Since the albumin fraction constitutes a significant

portion of the total seed proteins, a good solubility was

expected in aqueous solvents [21] Although 0.1 M NaOH

was the most effective protein solubilizer, the exposure to

alkali is known to alter proteins through amino acid

deamida-tion and may therefore alter protein properties [37,38] Alkali

exposure may also cause destruction of some of the essential

amino acids, such as lysine, thereby decreasing the nutritive

value of the solubilized proteins For these reasons, 2 M NaCl

was considered to be the best solvent to solubilize the Inca

seed flour proteins in this investigation When soluble proteins

were analyzed by Lowry et al [28] and Bradford [29]

meth-ods, the latter method consistently registered lower protein

content (Fig 2), regardless of the solvent used Bradford

method is reportedly ~4× more sensitive than the Lowry

method and susceptible to interference by 1 % SDS, 1 %

Triton X-100, and to a lesser extent by 1 % hemosol, 2 M

Tris, acetone, and 5 % phenol Lowry protein assay is

susceptible to a number of reagents and chemicals commonly found in biological samples Among these, amino acid these, glycine (at 0.5%) is known to decrease color with protein by

50 % Glycine, at 118 mg/g protein, is the second most abundant amino acid, behind glutamic acid (133 mg/g pro-tein), in Inca peanut flour proteins [19] A lower color yield and lower protein content would be expected, all provided glycine was in free amino acid form when Lowry method was used It is unlikely that all glycine residues in Inca peanut seeds would be in the free amino acid form Solvents used for protein solubilization are also unlikely to contain significant amounts of glycine The lower protein content (Bradford method) of 0.1 M Tris-HCl (pH 8.1) extracted protein samples although possible, is not likely due to the interference by Tris

as the final Tris concentration in the assay (≤0.1 mM) was far less than the reported 2 M Tris interfering in the Bradford assay The consistent lower protein estimation by Bradford

Fig 4 Seed flour protein solubility in distilled deionized water at the indicated pH (Lowry method) Note the minimum protein solubility at

pH 4 LSD (p 00.05)01.26, n06

Fig 3 Effects of a indicated

NaCl concentration, b

extraction time, c consecutive

extraction (1 h each) in aqueous

2 M NaCl, and d pH on seed

flour protein solubility For b

and d, aqueous 1 M NaCl was

used for protein extractions.

The LSD (p = 0.05) values for

Lowry method were 2.81, 6.8,

4.46, and 8.18 respectively for

a, b, c, and d LSD (p = 0.05)

values for the Bradford method

were 1.52, 1.76, 0.82, and 1.26,

respectively for a, b, c, and d,

n = 6 for both

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assay [28] as compared to Lowry procedure [27], in all tested

samples, remains unresolved and therefore warrants further

investigations to determine the cause(s) for this difference

At NaCl concentration≥0.5 M protein solubility increased

significantly≥ 0.05NaCl concentration (Fig.3a) Extraction

time of 15–30 min was considered adequate to maximally

solubilize the flour proteins in 2 M NaCl (Fig.3b) and two

consecutive extractions were able to solubilize the majority

of the flour proteins (Fig 3c) Bradford assay once again

registered lower protein readings than the Lowry assay when

procedure the NaCl solubilized samples were analyzed

(Fig.3a, b, and c) In the presence of 1 M NaCl the influence

of pH on protein solubility (Fig.3d), as determined by Lowry

method [27], was statistically not significant as indicated by

the narrow range (40.93 to 47.00 g solubilized protein/100 g

deffated flour at pH 1 and 12, respectively) The difference in

protein solubility was less than the LSD08.18 (p00.05) for

this tested pH range (1-13) Protein solubility of these

sam-ples, determined by Bradford method, exhibited a narrow

range [8.42 to 13.38 g solubilized protein/100 g deffated flour

at pH 4;] With the exception of solubility at pH 3, protein

solubility as determined by Bradford method, significantly

decreased at pH 4 The low protein solubility in the pH range

3–5 was further confirmed when the influence of pH on protein

solubility in distilled water, i.e in the absence of 2 M NaCl,

was determined (Fig 4) The observed pH dependence of

protein solubility is consistent with the reported dominance

of acidic amino acids in the make-up of the seed flour

proteins [19] Taken together, protein solubility results

in-dicate the importance of ionic strength in solubilizing Inca

peanut seed proteins

Osborne Protein Fractionation and Electrophoresis

With the exception of 70 % aqueous EtOH, solubilized

proteins exhibited a consistent polypeptide pattern,

regard-less of the solvent used (Fig.5) The soluble seed proteins

were characterized by polypeptides in the 10–70 kDa range The soluble seed flour proteins are mainly composed of two molecular species (32–35 kDa and ~60–62 kDa) Electro-phoretic profiles in the absence of the reducing agentβ-ME (Fig 5a) also indicated that seed proteins contained disul-fide bond-linked polypeptides Upon reduction, the electro-phoresis profile (Fig 5b) indicated that the 60–62 kDa polypeptide is composed of a disulfide bond linked dimer

of 32–35 kDa and a 60–62 kDa monomeric polypeptide Although disulfide bond reduction facilitated a significant disappearance of the 60–62 kDa polypeptides, it did not allow their elimination (e.g., compare the band width and intensity of these bands in lanes J, K, and L in Fig 5a versus

Fig 6 Two dimensional SDS-PAGE of BSB (0.1 M, pH 8.45) soluble proteins First dimension (top gel) was run in the absence of a reducing agent (2 % (v/v) β-ME) Protein (100 μg load) migration was from left to right Second dimension gel was run by the presence of a reducing agent (2 % (v/v) β-ME) using soluble protein (50 μg) in the left reference lane and molecular weight markers in the right reference lane Protein migra-tion was from top to bottom

Fig 5 SDS-PAGE (8 –25 % linear monomer acrylamide gradient)

analysis of total seed flour soluble proteins using silver a, b and

glycoprotein c staining in indicated solvents (A-L, same as in Fig 2 )

in the absence a and presence b, c of a reducing agent (2 %v/v β ME).

Protein load in each lane was 10 μg a, b, and 40 μg c This figure is a composite of 3 different gels (15 wells each) Protein (S) and polypep-tide (P) standards used are indicated by their molecular weights (kDa)

on the left

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5b) Comparison of the corresponding lanes of Fig.5a and b

demonstrate the increased concentration and number of

poly-peptides with MW<30 kDa indicating the importance of

disulfide bonds in the seed protein organization These results

indicate the presence of two different types of 60–62 kDa

proteins A 2D analysis of the aqueous 2 M NaCl soluble

proteins in SDS-PAGE (Fig.6) further confirmed the presence

of two different types of 60–62 kDa proteins The polypep-tides solubilized by 70 % (v/v) aqueous EtOH stained poorly usnig silver staining (lane I, Fig 5a and b) Glycoprotein staining (Fig.5c) of the solubilized proteins demonstrated that the 32–35 kDa polypeptides are glycosylated The glycopro-tein staining also revealed that the 70 % (v/v) aqueous EtOH soluble polypeptides (range 10–30 kDa) that were poorly stained in silver staining were readily recognized (Fig 5c, track I)

Of the total soluble proteins, true albumin, globulin, and glutelin were the major fractions in the seed flour soluble proteins with prolamin contributing in a small proportion (Fig 7b) Typically, over 90 % of the seed flour proteins could be solubilized by the aqueous solvents used for pro-tein fractionation One dimensional SDS-PAGE analysis of the Osborne fractions (Fig.7) indicates (judged qualitatively based on band width and intensity) that the major polypep-tides (30–40 kDa range) that constitute the albumin fraction also appear to be the major polypeptides in globulin and glutelin fractions The main difference between the albumin and globulin fraction was the distinctly different polypep-tides present in the globulin fraction (indicated by an * next

to the polypeptide on the right of the globulin track) Glob-ulin and glutelin fractions had comparable polypeptide com-position with the glutelin fraction exhibiting higher proportion of polypeptide marked by the arrow (right side

of the glutelin track) Prolamin fraction was mostly

Fig 7 SDS-PAGE (8-25% linear monomer acrylamide gradient) in the

presence of a reducing agent ( 2 % (v/v) β-ME) for Osborne protein

fractions Protein load, except for the standards, was 75 μg each Note

the different polypeptides in globulin (*) compared to the albumin

fraction profile The polypeptide marked ( ←) in the alkali glutelin

fraction profile was distinctly different when compared with globulin

fraction polypeptide profile

Fig 8 2D (IEF top gel left to

right- pH range 3 –10 followed

by SDS-PAGE- top to bottom)

gel electrophoretic analysis of

the fractionated proteins

pre-pared from the defatted seed

flour Protein load was ~60 μg

each in both directions

Molec-ular weights (kDa) of the

stan-dard proteins are indicated in

each gel on the left The protein

fractions in the second

dimen-sion gel are in the

corresponding gel (right lane)

indicated as A albumin, Gb

Glubulin, P Prolamin, and Gn

Alkali Glutelin

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composed of four polypeptides in the molecular weight

range 6–12 kDa Two dimensional gel electrophoresis of

the protein solubility fractions (IEF in the first dimension

followed by the SDS-PAGE in the presence of β-ME

(Fig 8) further confirmed that the seed flour proteins

were mainly composed of two types of polypeptides

with estimated molecular weights in the range 32–

35 kDa that were linked together by disulfide bonds

These results also demonstrated that the glutelin fraction

is different than the globulin fraction (compare the

globulin profile to that of the profile for glutelin

frac-tion in Fig 8), mainly with respect to the isoelectric pH

of individual polypeptides A closer examination

indi-cates that the globulin fraction contained polypeptides

that are slightly more basic (judged based on their

mobility in the first dimension) than those in the

glu-telin fraction although the molecular weight, indicated

by their mobility in the second dimension, appear to be

similar Although alkali exposure of the insoluble

glob-ulin polypeptides during glutelin fraction preparation

may possibly cause deamidation resulting in the

forma-tion of acidic polypeptides, it does not explain why the

globulin polypeptides were not solubilized during 2 M

NaCl extraction (the first step) during seed flour protein

fractionation especially since the flour to solvent ratio

of 1:10 (w/v) provided more than sufficient amount of

solvent It is possible that when albumins and globulins

are present together, their collective behavior, as

op-posed to their individual behavior, may differ

signifi-cantly, an observation similar to the one reported earlier

in the Great Northern bean (Phaseolus vulgaris L.)

proteins [39] One possible reason of the different

be-havior between albumins and globulins, when present

together, is, the protein-protein interactions These

protein-protein interactions are facilitated by dfferent

bonding forces (e.g., ionic, hydrogen, hydrophobic, and

disulfide) depending on the environmental conditions

permitted by the experimental conditions used (e.g.,

pH, ionic strength, and temperature) Such protein-protein

interactions may lead to formation of large protein complexes

(soluble and insoluble) thereby affecting their solubility If

globulin solubility is limited due to the presence of albumins,

the insoluble globulins would then be extracted as the

glute-lins solubilized by alkali solution Note the appearance of new

polypeptides [>56 kDa and <72 kDa and several polypeptides

in >26 and ~34 kDa range)] in the second dimension that were

not part of the globulin fraction The >26 kDa and ~34 kDa

polypeptides have more acidic pIs compared to pIs of

the original globulin fraction Since alkali solubilization

would possibly deamidate susceptible globulin

polypep-tides, they may appear as part of the glutelin fraction

(Fig 8) Further investigations in understanding the

molecular, nutritional, and functional properties of Inca

peanut seed proteins would be helpful in utilizing this protein source for a variety of purposes and are there-fore underway

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