Effects of highland barley bran extract rich in phenolic acids on the

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Effects of highland barley bran extract rich in phenolic acids on the formation of N#-carboxymethyllysine in a biscuit model Huilin Liu, Xiaomo Chen, Dianwei Zhang, Jing Wang, Shuo Wang, and Baoguo Sun J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b04957 • Publication Date (Web): 07 Feb 2018 Downloaded from http://pubs.acs.org on February 8, 2018

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Journal of Agricultural and Food Chemistry

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Effects of highland barley bran extract rich in phenolic acids on the

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formation of Nε-carboxymethyllysine in a biscuit model

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Huilin Liu1, Xiaomo Chen1, Dianwei Zhang2, Jing Wang1*, Shuo Wang1,3, and

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Baoguo Sun1

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Beijing Engineering and Technology Research Center of Food Additives, Beijing

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Technology and Business University (BTBU), 11 Fucheng Road, Beijing, 100048,

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China.

Beijing Advanced Innovation Center for Food Nutrition and Human Health,

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2

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Tianjin Key Laboratory of Food Nutrition and Safety, Tianjin University of

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Science and Technology, 29 The Thirteenth Road, Tianjin Economy and

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Technology Development Area, Tianjin 300457, China.

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3

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Key Laboratory of Food Nutrition and Safety, Ministry of Education of China,

School of Medicine, Nankai University, Tianjin 300071, China. *Corresponding author: Jing Wang

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Tel: (86 10) 68984545;

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Fax: (86 10) 68985456;

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Email: [email protected]

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*Corresponding author: Shuo Wang

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Tel: (86 22) 6060 1430

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Fax: (86 22) 6060 1332

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Email: [email protected]

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ACS Paragon Plus Environment


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Abstract

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Highland barley, a staple food in northwest China, is a well-known source of

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bioactive phytochemicals, including phenolic compounds. This study evaluated the

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inhibitory effects of highland barley bran extracts (HBBE) on the advanced glycation

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end

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Nε-carboxymethyllysine (CML) contents. CML was detected in all inhibition models

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using HBBE extracted with different solvents. Under optimal conditions, CML

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formation in the heated model system composed of glucose/lysine/linoleic acid was

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effectively inhibited by HBBE. This inhibition effect using extracts from 60% acetone

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solution was 45.58%. Five major phenolic acids from HBBE (ferulic, syringic, sinapic,

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p-coumaric, and caffeic acids) were further tested for their trapping and scavenging

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abilities of glyoxal, a reactive carbonyl species, and a key intermediate compound for

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forming CML. This study has demonstrated that HBBE can potentially control CML

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formation during food processing, so effectively reducing glycation in foods, and

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benefiting those with chronic diseases.

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Keywords: Nε-carboxymethyllysine,

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compounds, inhibition

products

(AGEs)

levels

in

a

biscuit

model,

as

measured

highland barley bran, biscuit,

2


by

phenolic

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Introduction

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The Maillard reaction between reducing sugars and the free amino residues of

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proteins is a complex non-enzymatic browning process that occurs in biological as

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well as in food media (1). The Maillard reaction products (MRPs) contribute to the

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flavor and brown color of some cooked foods, with preservative effects because of

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their anti-oxidative properties (2). However, these MRPs can destroy essential amino

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acids and produce anti-nutritive compounds. Advanced glycation end products (AGEs)

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are a group of stable, complex and heterogeneous compounds formed in the late

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stages of the Maillard reaction by further intramolecular rearrangements (3). Heat

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processing and long-term storage can rapidly accelerate the formation of AGEs (4-7).

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Diet is the major source of exogenously-formed AGEs, because foods are rich in

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reducing sugars, amino acids, peptides, and proteins. The formation and accumulation

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of AGEs increases the potential risk of causing advanced aging and health disorders in

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vivo, such as diabetes, kidney disorders, and Alzheimer’s disease (8-10). Typical

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AGEs contain Nε-carboxymethyllysine (CML), Nε-carboxyethyllysine (CEL),

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Nε-(carboxymethyl)arginine, pyrraline, crossline, and pentosidine (Figure 1) (11),

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CML, the main component of AGEs, has been well-characterized and extensively

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studied (12,13). It is formed on the lysine residue in proteins or free lysine by both

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glycoxidation and lipid peroxidation pathways. Dietary CML may be considered to be

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a chronic risk factor for human health. The concentration of CML, adjusted for age

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and duration of diabetes, has been shown to increase in patients with severe

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complications, Formation and accumulation of CML are suspected to be involved in

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the pathogenesis of advanced aging and several diseases such as diabetes,

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nephropathy (14) , retinopathy (15) and atherosclerosis(16) .

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Therefore, in order to avoid the adverse effects of dietary AGEs or CML upon

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physiological variation of AGE levels, it is desirable to acquire information on the

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prevalence of dietary AGEs or CML in food. Discovering how to inhibit AGEs or

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CML during food processing and storage would reduce the level of dietary AGEs or

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CML. This could offer a potential approach for preventing health disorders caused by

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accumulating dietary CML in vivo. Several studies have investigated the inhibition of

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AGEs or CML. For example, the AGEs inhibitors, aminoguanidine and pyridoxamine,

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have been shown to block CML formation and retard the development of early renal

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disease in streptozotocin-induced diabetic rats (17, 18) . Umadevi et al. have also

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studied the regulatory mechanism of gallic acid against AGEs induced cardiac

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remodeling in experimental rats (19) . Others have reported the inhibitory activities of:

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the edible green alga Capsosiphon fulvescens on rat lens aldose reductase and AGEs

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formation (20); mung bean extract and its constituents, vitexin and isovitexin, on

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the formation of AGEs (21); and olive mill wastewater phenol compounds on reactive

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carbonyl species and AGEs in ultrahigh-temperature-treated milk (22). However, most

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of these studies have covered inhibitory effects in water-soluble systems, but less

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attention has been paid to those in lipid-soluble systems.

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Recently, The highland barley, which is a staple food for people living in

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northwest China (23,24), has also been reported to contain considerable quantities of

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bioactive phytochemicals, including phenolic compounds (25-27). This crop occupies

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the largest area of cultivation with the highest field production because it is the only

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crop that can be grown at high altitudes of 4200–4500 m above sea level (28, 29).

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However, the potential applications of highland barley bran in alleviating or

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preventing chronic disease have rarely been investigated.

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The present study aims to use highland barley bran extract (HBBE) to inhibit

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CML formation in a biscuit model. Biscuit processing baking is particularly prone to

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forming CML because of the relatively high content of sugar and protein ingredients,

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where the condensation of an amino residue of protein and a carbonyl group of a

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sugar lead to a complex cascade of consecutive and parallel reactions. The highland

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barley bran will be are extracted using different solvents, to allow the study of

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phenolic acids which inhibit CML formation. Five major phenolic acids from

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highland barley bran, ferulic acid, syringic acid, sinapic acid p-coumaric acid, and

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caffeic acid, will be are further tested for their trapping abilities of reactive carbonyl

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species, especially glyoxal (GO), a key intermediate compound for the formation of

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CML. This study hopes to provide a useful method of controlling CML formation

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during food processing, which may eventually benefit those with chronic diseases.

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MATERIALS AND METHODS

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Chemicals and Materials. Methanol, acetone, anhydrous sodium sulfite,

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glucose, sodium borate, sodium hydroxide, dinitrosalicylic acid, sodium tartrate, and

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phenol (analytical grade) were purchased from Sinopharm Chemical Reagent Co. Ltd

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(Beijing, China), Folin–Ciocalteu Phenol Reagent (analytical grade) from Source

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Biological Technology Co. Ltd. (Shanghai, China), orthograph β-mercaptoeth

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(analytical grade) from Amresco (Solon, OH, USA), o-phenylenediamine, and

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diphenyl picryl hydrazinyl radical (DPPH) (analytical grade) from J&K Scientific Ltd.

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(Beijing, China). Standards of ferulic acid, syringic acid, sinapic acid, p-coumaric

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acid, and caffeic acid (analytical grade, ≥ 98%) were purchased from Shanghai Tian

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Biotechnology Co. Ltd. (Shanghai, China). Double deionized water (DDW, 18.2 MΩ

112

cm−1) was prepared using a WaterPro water purification system (Labconco Corp.,

113

Kansas City, MO, USA).

114

Equipment. Samples were centrifuged using a CR22N high speed refrigerated

115

centrifuge (Hitachi Koki Co. Ltd., Tokyo, Japan). Fluorescence was measured using a

116

multi-functional microplate reader (Biotek Instruments Inc., Winooski, VT, USA).

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CML was analyzed using HPLC-MS/MS with a 1260 diode array detector (DAD)

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(Agilent Technologies Inc., Santa Clara, CA, USA). Samples were dried using an

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R-210 Rotary evaporator (Büchi Labortechnik AG, Flawil, Switzerland).

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Preparation of Biscuit Model System. The model systems were prepared

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using a mass ratio of sugar, lysine, and oil of about 15:13:4 to simulate the mass ratio

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used in biscuit manufacture and consisted of 6 g of glucose and 5 g of lysine in

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phosphate buffer (0.1 M, pH 7.4) to a volume of 200 mL. After adding 2 g of

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Tween-80, the mixtures were stirred constantly for 10 min at room temperature then

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1.6 g of linoleic acid was added. The microemulsion system was then heated by oil

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bath at 190 °C for 8 min.

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Preparation of HBBE. The extract was prepared from highland barley bran (1

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g) using DDW, 60% acetone, and 80% methanol aqueous solution (20 mL) with

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magnetic stirring at 60 °C for 1 h. The extraction was repeated three times then the

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supernatants were combined. The extracts were concentrated under vacuum at 50 °C

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using a rotary evaporator to a volume of 10 mL.(30)

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Inhibitory Effects of HBBE on CML Formation. The inhibitory effects were

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determined by adding HBBE (1 mL) to the biscuit model systems. In order to evaluate

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inhibitory effect, the model systems were identified as a control experiment without

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addition of HBBE.

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Determination of CML. The samples were analyzed using an HPLC-MS/MS

137

system (Agilent). The mobile phase consisted of a mixture of 0.1% trifluoroacetic

138

acid (TFA, v/v) in DDW as solvent A and acetonitrile as solvent B delivered at a flow

139

rate of 0.2 mL/min. The gradient started with 40% (B), decreased linearly to 10% (B)

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in 0.5 min, then increased to 40% (B) in 4 min. The analysis time was 25 min, and the

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injection volume 10 µL. The ESI interface of the MS was operated in positive mode

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with its conditions optimized as follows: capillary voltage, 4 kV; ion source

143

temperature, 300 °C; nebulizer, 15 psi, and gas flow 11 L/min. Tandem MS analyses

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were performed in the multiple reactions monitoring mode (MRM). The specific

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transitions, m/z 205.0 and m/z 84.0, were used for detecting and quantifying CML,

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respectively.

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Determination of Lysine and Reducing Sugars Contents. The contents of

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reducing sugars were measured using a Synergy HT microplate reader (Biotek) as

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described by Meneses et al. with some modification (30). HBBE (100 µL) was added

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to 100 µL dinitrosalicylic acid (DNS) reagent. After boiling for 5 min, the sample was

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cooled quickly and 1 mL of DDW added. The absorbance value was measured at 540

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nm. The DNS reagent was made up as follows: 6.3 g of dinitrosalicylic acid was

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added to 2 M sodium hydroxide (262 mL) then the mixture was added to 500 mL of

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DDW containing 182 g of sodium tartrate. After adding 5 g of phenol and 5 g of

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anhydrous sodium sulfite the mixture was stirred to dissolve the contents then made

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up to a volume of 200 mL with DDW.

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The total lysine content was measured using a Synergy HT microplate reader

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(Biotek) as described by Goodno et al. with some modification (33). HBBE (200 µL)

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was added to 3 mL of o-phthaldialdehyde (OPA) reagent then placed in a dark room at

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room temperature for 5 min for fluorescence detection. The excitation and emission

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wavelengths were set at 340 and 455 nm, respectively. The OPA reagent was made up

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as follows: 100 mL of 0.1 M sodium borate buffer solution (pH 9.5) was mixed with

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0.4 mL β-mercaptoethanol, and o-phenylenediamine (160 mg dissolved in 4 mL

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methanol) then made up to a volume of 200 mL with DDW.

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Determination of Total Phenolic Compounds in HBBE. The total content of

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phenolic compounds in HBBE were evaluated using the Folin–Ciocalteu method as

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described by Alves et al. with some modification (34). Briefly, 100 µL of HBBE were

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mixed with 400 µL of DDW and 0.25 mL of 1 M Folin–Ciocalteu reagent, then added

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to 1.25 mL of sodium carbonate (7.5 g/100 mL). After reacting for 120 min, the

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absorbance of the mixture was measured at 725 nm.

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Determination of HBBE Antioxidant Activities by Radical-Scavenging

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DPPH and FRAP Assays. The radical-scavenging activity was evaluated using the

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DPPH method as described by Alves et al. with some modification (34). HBBE (150

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µL) was added to 2.85 mL of DPPH (6.6 × 10-5 M), then after mixing fully, it was

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reacted for 2 h in the dark followed by measuring absorbance at 515 nm. The

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inhibition of DPPH was calculated by the following equation, Inhibition rate = 1 - As/Ac × 100

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(1)

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Where, As is the absorbance value of the sample, and Ac is the absorbance value of the

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blank.

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The radical-scavenging activity was also evaluated by the FRAP assay. The S0116

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test kits for measuring total antioxidant capacity (Biyuntian, Shanghai, China) were

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used in the study. Under acidic conditions, ferric tripyridyl triazine TPTZ-Fe(III) is

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reduced to ferrous tripyridyl triazine TPTZ-Fe(II) by antioxidant activity, then the

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concentration of TPTZ-Fe(II) is determined at 593 nm. The total antioxidant capacity

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of HBBE was expressed as millimoles of ferrous equivalent per gram of HBBE (mM

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Fe(II)/g HBBE).

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Determination

of

Scavenging

Phenolic

Acids

on

GO

by

188

HPLC-DAD-MS/MS. The inhibitory effects of polyphenols on protein glycation

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induced by glyoxal (GO), a key reactive intermediate compound formed during the

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Maillard reaction, were studied. A five mM mixture of phenolic compounds (0.5 mL

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each of caffeic acid, syringic acid, p-coumaric acid, ferulic acid, sinapic acid) was

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mixed with 5 mM GO (0.5 mL) then reacted for 8 min at 190 °C then cooled quickly.

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Twenty mM 1,2-diaminobenzene (0.25 mL) and 5 mM internal standard

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(2,3-dimethylquinoxaline, 0.25 mL) were added to the above reaction liquid then the

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reaction continued for 30 min before analysis.

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The analysis system consisted of a 1260 Infinity HPLC (Agilent), an injection

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valve with a 10-µL sample loop, and a DAD detector set at 315 nm. The samples were

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separated using an. Inertsil ODS C18 column (150 × 4.6 mm, 5 µm, C/N 5020-02745,

199

GL Sciences Inc. Japan) at room temperature. The column was stabilized by setting

200

the mobile phase flow rate at 1 mL/min with isocratic elutions at a solvent A: solvent

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B ratio of 50:50. The mass spectra were obtained in full scan mode, with selective ion

202

monitoring at m/z values from 100-1000. The capillary voltage was set at 4000 V and

203

the ionization source at 300 °C.

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Identification of Major Phenolic Acid compounds by 60% Acetone

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Extraction. The phenolic composition was determined using HPLC-VWD-MS/MS as

206

described by Moreira et al. with some modifications (35). The phenolic compounds

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were separated using an Inertsil ODS-SP column (150 mm × 4.6 mm, 4.6 µm). The

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mobile phases, A and B, were 100% methanol and 0.1% formic acid, respectively.

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The gradient was programmed as follows: 90% B at 0 min, from 90% to 0% B in 110

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min, followed by 0% B for 20 min then back to 90% B in 10 min with 10 min of

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reconditioning before the next sample injection. The flow rate was 0.3 mL/min, the

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sample injection volume 20 µL, and the ultraviolet Varian detector was set at 320 nm

213

(SPD-20, Shimadzu, Kyoto, Japan). The mass spectra were acquired under the same

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conditions as for determining the clearance rate of polyphenols.

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Statistical Analysis. The results were expressed as means ± standard deviation

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from three independent determinations. Analysis of variance was used to establish any

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significant differences (p < 0.05) between the applied treatments using the SPSS

218

software package (version 17.0, SPSS Inc, Chicago, IL, USA).

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RESULTS AND DISCUSSION

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Effect of Different Extraction Solvents on the Total Content of Phenolic

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Compounds in HBBE. Effect of Solvents on Total Phenolic Contents of HBBE.

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The total content of phenolic compounds in HBBE were detected was evaluated by

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gallic acid (GA), with different extraction solvents, DDW, 60% acetone, and 80%

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methanol. Table 1 shows that the total content of phenolic compounds was highest in

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HBBE from the 60% acetone extraction (407.52 mg GA/100 g HBBE), followed by

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DDW (192.10 mg GA/100 g HBBE), and 80% methanol (190.21 mg GA/100 g

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HBBE). Acetone has also been reported as more effective than other organic solvents

228

for extracting polyphenols from other sources, such as grapes (36), mango seeds(37),

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banana peels(38) and some plants (30). The content of acetone and water in the

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solvents were more than 50%, so the extraction rate of phenolic compounds was

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relatively good, especially in the matrix containing protein, because acetone has been

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shown to degrade the polyphenol-protein complex effectively The extraction rate of

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phenolic compounds was relatively good, when the acetone and water in the solvents

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were more than 50%, especially in the matrix containing protein. The acetone has

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been shown to degrade the polyphenol-protein complex effectively (39).

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Effect of Different Extraction Solvents Effect of Solvents on Contents of

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Lysine and Reducing Sugars in HBBE. The contents of lysine and reducing sugars

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are shown in Table 1. The content of lysine was higher in HBBE using DDW as an

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extraction solvent (56.52 µg/g) and using 60% acetone (64.32 µg/g). The content of

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reducing sugars (49.69 mg/g) was higher using DDW than the other solvents possibly

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because the extraction conditions were not suitable for the full release of reducing

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sugars. Carvalheiro et al. have also reported that using water as a solvent was

243

beneficial for releasing reducing sugars (40).

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Effect of Different Extraction Solvents on the Antioxidant Activity of HBBE.

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The antioxidant activity of HBBE was evaluated using DPPH and FRAP assays. The

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stable radical, DPPH, can be reduced to its non-radical form, DPPH-H, in the

247

presence of a hydrogen-donating antioxidant. Figure 2A shows that the scavenging

248

rate of DPPH using the 60% acetone and 80% methanol solvents, at 81.22% and

249

81.29%, respectively, was higher than using DDW at less than 35%. The total

250

antioxidant capacity was also evaluated by the FRAP assay (Figure 2B). The

251

antioxidant capacity of HBBE from 60% acetone and 80% methanol extractions, were

252

7.82 and 4.63 mg FE(II)/g HBBE, respectively.

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The Effect of Different Extraction Solvents on the Inhibitory Effect of

254

HBBE on CML formation. The effect of extraction solvents (DDW, 60% acetone

255

and 80% methanol) on the inhibitory effects of HBBE was investigated. Figure 3

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shows that HBBE displayed an obvious inhibitory effect of 45.58% on CML

257

formation using 60% acetone as the extraction solvent. The inhibitory rates for DDW

258

and 80% methanol extractions were 12.62% and 2.71%, respectively. The HBBE from

259

60% acetone extractions contained several phenolic compounds possessing dicarbonyl

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scavenging capacities which can affect CML formation in systems composed of

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glucose and lysine (41). Phenolic compounds were also present in HBBE extracted

262

using DDW and 80% methanol, but they had a low inhibitory effect on CML

263

formation. The reducing sugars and available lysine, the precursors to CML, were

264

extracted well by DDW (49.69 mg/g, and 56.52 µg/g, respectively, Table 1). Therefore,

265

this method of extraction could lead to CML formation.

266

Isolation and Identification of Major Phenolic Acids using HBBE Extracted

267

with 60% Acetone. Cereals contain many antioxidants, mainly phenolic compounds

268

such as ferulic acid, vanillic acid, caffeic acid, clove acid, fenugreek acid, anthocyanin,

269

quinine, flavones, flavanone, and aminophenol compounds. Five major phenolic acids

270

were determined in HBBE in the present study. The HPLC chromatograms of the

271

phenolic acids in HBBE detected at a UV detection wavelength of 320 nm are shown

272

in Figure 4. Peaks 1-5 with an m/z of 387 were isomers of dimer ferulic acid; peak 6,

273

caffeic acid; peak 7, syringic acid; peak 8, p-coumaric acid; peak 9, ferulic acid; peak

274

10, sinapic acid; peak 11, sinapic acid polymers; and peaks 12-15 with an m/z of 579,

275

isomers of trimer ferulic acid. The contents of five major phenolic acids in highland

276

barley bran extracts are shown in Table 2. The syringic acid content was highest at

277

18.29 mg/kg, with ferulic acid, caffeic acid, and sinapic acid at levels of 3.11, 2.78,

278

and 2.43 mg/kg, respectively. The content of p-coumaric acid was lowest at 0.81

279

mg/kg. A recovery study on the samples evaluated the accuracy of the phenolic acids

280

determination using HPLC-MS/MS. The recoveries, ranging from 90.5% to 103.7%,

281

confirmed the ability of this method to provide an accurate quantification of phenolic

13



282

acids.

283

Inhibition of CML formation by HBBE from 60% acetone extraction.

284

Figure 5 shows that the five major phenolic acids in HBBE from the 60% acetone

285

extraction had a good inhibitory effect on CML formation. The effects were

286

investigated using extract concentrations of 0.1, 0.2, and 0.4 mg/mL. The best

287

inhibition effect using HBBE from 60% acetone extraction was exhibited at

288

concentrations of 0.2, and 0.4 mg/mL, with inhibition values of 60.70% and 60.5%,

289

respectively. Figure 5 shows that the five major phenolic acids, including phenolic

290

acids, ferulic acid, syringic acid, sinapic acid, p-coumaric acid, and caffeic acid in

291

HBBE from the 60% acetone extraction had a good inhibitory effect on CML

292

formation. The five major phenolic acids, ferulic acid, syringic acid, sinapic acid,

293

p-coumaric acid, and caffeic acid in HBBE from 60% acetone extraction, significantly

294

inhibited CML formation. At a concentration of 0.4 mg/mL, the inhibition rates for

295

caffeic acid, syringic acid and ferulic acid were 55.5%, 56.5%, and 43.3%,

296

respectively. The inhibition effect of caffeic acid, syringic acid and ferulic acid at

297

three concentrations on biscuit model systems, showed that the increase in the

298

concentration of inhibitors increased the CML inhibitory effect. When the

299

concentration of HBBE was 0.1 mg/mL, both p-coumaric acid and sinapic acid still

300

had good inhibitory effects on CML formation of 41.1% and 44.0%, respectively. But

301

the increase in the concentration of p-coumaric acid and sinapic acid had an opposite

302

trend of CML inhibitory effect. The concentration of HBBE was 0.1 mg/mL, both

303

p-coumaric acid and sinapic acid still had good inhibitory effects on CML formation

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of 41.1% and 44.0%, respectively.

305

Complex chemical reactions can occur as a result of heat treatments such as

306

baking. These reactions may cause a reduction in the nutritional value of foods and

307

form an Amadori product such as GO, which is degraded during prolonged heating

308

into a wide range of CML compounds which can be formed in heat-treated biscuits.

309

Table 2 shows that The caffeic acid, syringic acid, p-coumaric acid, ferulic acid, and

310

sinapic acid at a concentration of 5 mM exhibited a significant inhibitory effect on

311

CML formation induced by GO. Excess GO can degrade into 1,4-quinoxaline (31, 32),

312

which can be used as the target compound for detecting GO. The GO clearance rates

313

were 55%, 50%, 60%, 62%, 51%, for caffeic acid, syringic acid, p-coumaric acid,

314

ferulic acid, and sinapic acid, respectively, indicating a good radical GO scavenging

315

capacity (Table 2). The direct GO trapping capacity was investigated using the biscuit

316

model system. However, using HPLC-MS/MS, HBBE only showed a slight ability to

317

trap GO therefore GO might be removed by other chemical reactions, or HBBE might

318

be inhibited by other intermediate compounds from forming CML.

319

In conclusion, highland barley bran extract contains several phenolic acids, such

320

as caffeic acid, syringic acid, p-coumaric acid, ferulic acid, and sinapic acid, which

321

possess obvious inhibitory effects on CML formation. In the study, the main phenolic

322

acids from HBBE have better GO scavenging capacity to inhibit the CML formation.

323

Sources of HBBE are rich in China and available at a low cost, thus providing a wide

324

and feasible application for use in foods to inhibit CML formation, which was largely

325

attributed to both its antioxidant activities and radical scavenging capacities. HBBE

15



326

also holds promise for future application in the inhibition of other dietary AGEs and

327

so prevent chronic diseases.

328 329

Acknowledgements

330

This work was supported by the National Natural Science Foundation of China (No.

331

31571940, and No. 31501559), the Outstanding Young Talents of High-level

332

Innovation and Entrepreneurs Support Program (2017000026833ZK28), Beijing

333

Excellent Talents Funding for Youth Scientist Innovation Team (2016000026833TD01)

334

and Support Project of High-level Teachers in Beijing Municipal Universities

335

(IDHT20180506).

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336

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468

2005, 21, 233-243 %@ 1520-6033.

469

41. Peng, X.; Cheng, K.-W.; Ma, J.; Chen, B.; Ho, C.-T.; Lo, C.; Chen, F.; Wang, M.,

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471

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chemistry 2008, 56, 1907-1911.

23



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473

Table 1. The Effect of Different Extraction Solvents (DDW, 60% Acetone, and

474

80% Methanol) on the Contents of Total Phenolic Compounds, Available Lysine,

475

and Reducing Sugars in HBBE Solvents (%,V/V) DDW 60% acetone 80% methanol

Composition Total phenolic compounds (mgAGE/100gHBBE)

Available lysine (µg/gHBBE)

Reducing sugar (mg/gHBBE)

192.10±6.11b 407.52±37.89a 190.21±3.63b

56.52±6.09a 64.32±3.23a 5.11±0.56b

49.69±3.41a 5.99±0.24b 1.88±0.08c

476

24


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477

Table 2. The Contents of Five Major Phenolic Acids in HBBE

Polyphenols

Retention time

Content(mg/kgHBBE)

Rate of recovery(%)

Clearance rate(%)

caffeic acid syringic acid p-coumaric acid ferulic acid sinapic acid

35.269 38.146 44.626 47.505 50.905

2.784±0.200 18.289±0.829 0.812±0.044 3.111±0.194 2.434±0.078

100.2±0.16 103.7±0.71 90.5±0.67 97.9±0.15 101.5±0.48

55 50 60 62 51

478

25



479

Figure captions

480

Figure 1. The chemical structures of typical advanced glycation end products

481

(AGEs).

482

Figure 2. The effect of 3 different extraction solvents (DDW, 60% acetone, 80%

483

methanol).on the FRAP and DPPH scavenging activity of HBBE.

484

Figure 3. The effect of HBBE on CML inhibition using 3 different extraction solvents

485

(DDW, 60% acetone, 80% methanol).

486

Figure 4. The HPLC chromatograms showing the phenolic acid profile of HBBE.

487

Peaks 1-5, isomers of dimer ferulic acid; 6, caffeic acid; 7, syringic acid; 8,

488

p-coumaric acid; 9, ferulic acid; 10, sinapic acid; 11, sinapic acid polymers; 12-15,

489

isomers of trimer ferulic acid.

490

Figure 5. The effect of HBBE from 60% acetone extraction at concentrations of 0.1,

491

0.2, and 0.4 mg/mL on the inhibition of CML formation.

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27x19mm (600 x 600 DPI)



16x6mm (600 x 600 DPI)


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27x19mm (600 x 600 DPI)



27x19mm (600 x 600 DPI)


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27x19mm (600 x 600 DPI)



21x14mm (300 x 300 DPI)


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Effects of highland barley bran extract rich in phenolic acids on the

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