Carbohydrate - UNIRIO

Profa. dra. Édira Castello Branco de Andrade Gonçalves

http://www.unirio.br/analisedealimentos

Carbohydrate

Carbohydrate


http://chemistry2.csudh.edu/rpendarvis/hemiacetal.html

Formation

Ketone

http://butane.chem.uiuc.edu/pshapley/GenChem2/B5/2.html

GLUCOSE

Carbohydrate


Formation sucrose


Condensation is the loss of

water in a chemical reaction

aldehyde

ketone

1,2 glycosidic bond

Carbohydrate


Formation maltose

aldehydeCondensation

Lobry de Bruyn–van Ekenstein transformation

pH, T

1,4 glycosidic bond

https://en.wikipedia.org/wiki/Lobry_de_Bruy

n%E2%80%93van_Ekenstein_transformati

on

http://butane.chem.uiuc.edu/pshapley/GenCh

em2/B6/2.html

Carbohydrate


Reactions

Oxidationaldehyde

ketone

Tollen’s reaction

http://academics.wellesley.edu/Chemistry/chem211l

ab/Orgo_Lab_Manual/Appendix/ClassificationTests

/aldehyde_ketone.html#Tollens

Carbohydrate


ReactionsOxidation

aldehyde

cyclic glucose

linear glucose

All five of these isomers are

present in any solution of

this sugar

glucose

Fehling’s reaction

http://butane.chem.uiuc.edu/pshapley/GenChem2

/B6/2.html

Carbohydrate


Reactions


Glucose is a polyprotic acid with 5 OH groups

Acid-Base Properties

Carbohydrate


ReactionsReduction

Polyol pathway

Cataract

Renal damage

Neuropathy

http://www.medbio.info/Horn/Time%205/new_diabe

tes_march_08.htm

Sinthesis of polyols

Carbohydrate


alcohol

ReactionsEsterefication

Proposed mechanism for covalent crosslinking between citric

acid and a polysaccharide

Hemicelluloses were extracted from wheat straw,

were added with citric acid and to produce films

Citric acid acted as a crosslinker, which was

evidenced by its decreasing effects on water solubility

and water vapor permeability, and also as a plasticizer,

which was evident from its effects on tensile propertie

Chatterjee et al. 2015

Carbohydrate


Cross-linking improves some properties of native starch:

thermo-mechanical shearing,

paste stability in acidic medium,

gelatinization temperature

viscosity

Some common

cross-linking

reactions of starch

using different cross-

linking reagents

Chen et al. 2015

Reactions

Carbohydrate


Chatterjee et al. 2015

Reactions

Carbohydrate


Starches

Schematic

representation of

amylose and

amylopectin

Rapidly digestible

starch (RDS), slowly

digestible starch

(SDS) and resistant

starch (RS)

SDS do not

increase the

blood glucose

level compared

to RDS

IG

Horstmann et al. 2017

Carbohydrate


Enzymatic degradation of amylopectin

Food control

IG

Technology


Starches

Carbohydrate


Starches

T0W0, control; T0W1, drought

stress (DS) treatment; T1W0,

HT treatment; T1W1,

combination of HT and DS

treatment

Lu et al. 2014

Scanning electron

micrographs of (A) potato

starch; (B) tapioca starch;

(C) corn starch; (D) rice

starch, (E) wheat starch.


Carbohydrate


Starches

Effective production of resistant starch using pullulanase

immobilized onto magnetic chitosan/Fe3O4 nanoparticles

In this study, pullulanase was firstly immobilized by covalent bonding onto

chitosan/Fe3O4nanoparticles or encapsulation in sol-gel after bonding onto

chitosan/Fe3O4 nanoparticles, and then the immobilized pullulanase was used for

the effective production of resistant starch (RS). The highest RS content (35.1%)

was obtained under the optimized condition of pH 4.4, enzyme concentration of

10 ASPU/g and hydrolysis time of 12 h when debranched by free pullulsanase,

indicating that RS content was significantly (p < 0.05) increased when compared to

native starch (4.3%) and autoclaved starch (12.5%). Under these conditions, the

immobilized pullulanase (10 ASPU/g dry starch) yielded higher RS content

compared to free enzyme (10 ASPU/g dry starch), especially, the pullulanse

immobilized by sol-gel encapsulation yielded the highest RS content (43.4%).

Moreover, compared to starches hydrolyzed by free pullulanase, starches

hydrolyzed by immobilized pullulanase showed a different saccharide profile of

starch hydrolysate, including a stronger peak C (MW = 5.0 × 103), as well as

exhibited an additional absorption peak around 140 °C. Reusability results

demonstrated that pullulanase immobilized by sol-gel encapsulation had the

advantages of producing higher RS content as well as better operational stability

compared to pullulanase immobilized by cross-linking. The resulting enhanced RS

content generated by the process described in this work could be used as an

adjunct in food processing industries.

Long et al. 2018

Carbohydrate


Starches

Long et al. 2018

Parameter Type

S1 S2 S3 S4 S5

Pasting temp (◦C) 88.00 _ _ _ _

Peak time (min) 5.67 5.87 5.60 4.60 4.67

Peak viscosity (cP) 1375.00 140.00 18.00 19.0022.00

Hold viscosity (cP) 1904.00 136.00 15.00 13.0018.00

Final viscosity (cP) 1249.00 198.00 22.00 22.0024.00

Break down (cP) 281.00 4.00 3.00 6.00 4.00

Set back (cP) 155.00 62.00 7.00 9.00 6.00

Pasting properties of native and debranched starches: pasting temperature (°C), peak time (min), peak viscosity (cP), hold viscosity (cP),

final viscosity (cP), break down (cP) and set back (cP)

S1 corresponds to raw normal maize starch; S2 corresponds to normal

maize starch treated by two autoclaving-cooling cycles; S3 to S5

correspond to normal maize starch hydrolyzed by either free pullulanase,

pullulanase immobilized by covalent bonding, or pullulanase immobilized

by sol-gel encapsulation, respectively, prior to treatment by two

autoclaving-cooling cycles.

Carbohydrate


Reactions Resistant starches

Long et al. 2018

SEM micrographs of native and treated

starches.(A) Typical RVA starch pasting curves of native and treated starches; (B) Differential scanning

calorimetry (DSC) thermograms of native and treated starches; (C) X-ray diffraction patterns (XRD)

of native and treated starches.

Carbohydrate


Gelatinisation, pasting and retrogradation of starch influenced by

heat and time, where AM is amylose and AP amylopectin


Amylose crystallises over a

period of minutes to hours, while

amylopectin retrogrades over

hours or days

process is dependent on the

amylose-amylopectin ratio

Retrogradation

collapse or disruption of

molecular order

irreversible changes in

properties

disrupting hydrogen

bonding between polymer

chains

Gelatinisation/Pasting

Reactions

Carbohydrate


ReactionsEffect of saccharides on sediment formation in green tea concentrate

Reducing sediment in green tea concentrate utilized for tea

production is an important process. In this study, the effect of

saccharides on sediment formation in green tea concentrate was

investigated. The results show that the amount of tea sediment

significantly decreased (31.4%–86.4%) with the addition of

fructose or sucrose and that the ratios of polyphenols and

caffeine in the sediment sharply decreased (24.1%–49.7% and

2.4%–6.2%) while the proportion of total sugars markedly

increased (20.9%–56.5%) in the sediment. Moreover, fructosyl

was found to be a highly effective functional group for preventing

sediment formation, on the basis of experimental results for a

series of sugars with different numbers of fructosyl groups. This

phenomenon was elucidated from the energies of interaction

between typical sugars, polyphenols, and caffeine calculated by

density functional theory method. Our results open new

applications for tea concentrates.

Xu et al. 2017

Carbohydrate


Sugars Concentration of added sugar(g/100 mL)

Catechins concentration in tea sediment (mg/mL)

Non-Gallatedcatechins

Gallated catechins Total catechins

Maltose 0 5.32 ± 1.18a 11.10 ± 1.35a 16.42 ± 2.47a

20 2.81 ± 0.65b 5.99 ± 0.72b 8.80 ± 1.24b

30 1.59 ± 0.14c 4.43 ± 0.31c 6.02 ± 0.43c

40 1.26 ± 0.11d 2.86 ± 0.53d 4.12 ± 0.65d

50 0.89 ± 0.15e 1.88 ± 0.21e 2.77 ± 0.36e

Glucose 20 2.15 ± 0.14b 6.87 ± 0.47b 9.02 ± 0.65b

30 1.63 ± 0.20c 5.11 ± 0.36c 6.73 ± 0.58c

40 1.24 ± 0.11d 3.82 ± 0.10d 5.06 ± 0.25d

50 1.13 ± 0.09d 3.55 ± 0.13d 4.67 ± 0.24d

Sucrose 20 1.11 ± 0.21b 2.82 ± 0.14b 3.93 ± 0.36b

30 0.51 ± 0.12c 1.00 ± 0.18c 1.51 ± 0.32c

40 0.18 ± 0.05d 0.28 ± 0.04d 0.46 ± 0.13d

50 0.21 ± 0.06d 0.30 ± 0.06d 0.51 ± 0.11d

Fructose 20 0.62 ± 0.08b 1.90 ± 0.12b 2.52 ± 0.23b

30 0.43 ± 0.05c 0.66 ± 0.10c 1.10 ± 0.14c

40 0.30 ± 0.06c 0.55 ± 0.04c 0.85 ± 0.10c

50 0.31 ± 0.04c 0.57 ± 0.05c 0.88 ± 0.11c

Catechin concentrations in tea sediment from tea concentrates with various

added sugars (sterilized at 90 °C for 6 min, stored at 4 °C for 14 days)

Xu et al. 2017

Sugars competitively prevent catechins from participating in tea sediment

formation and that sugars with the fructosyl group (sucrose and fructose)

inhibit participation of gallated catechins.

Reactions

Carbohydrate


Xu et al. 2017

Energies of glucose/fructose and EGCG/caffeine interactions.

☻Fructose dominates glucose in the competitive interaction with EGCG

or caffeine, which reduces sediment formation or turbidity.

☻ Fructose and sucrose with fructosyl are more effective at reducing the

amount of tea sediment than are maltose and glucose, with the fructosyl unit

in the sugar being a key functional group.

Reactions

Carbohydrate


Caramelization

Caramelization

involves both

sugar

isomerization and

sugar degradation

reactions.

Isomerization of

monosaccharides

generally starts

with enolization,

namely Lobry de

Bruyn-Alberda van

Ekenstein

transformation

reaction, followed

by sugar

degradation

reactions

General Mechanism for Thermal and Acid

Promoted Caramelization of Sucrosea

Di-D-fructose

dianhydrides

(DFAs)

Su Rez-Pereira et al. 2010

Carbohydrate


Maillard Reaction

http://www.photobiology.com/photoiupac2000/koldunov/

Typically, the Maillard reaction involved three stages :

the initial (condensation), the intermediate

(degradation), and the final (polymerization)


Carbohydrate Maillard Reaction

Proposed pathways and precursors of furan (toxicity)

Nie et al. 2013

Effect of pH, temperature and

heating time on the formation

of furan in sugar–glycine

model systems

Carbohydrate


Maillard Reaction

Mechanism for the Maillard reaction and caramelization during

hazelnut roasting. SUC, sucrose; GLC, glucose; FRU, fructose;

FFC, fructofuranosyl cation; 1,2-ED, 1,2-enediol; AP, Amadori

product; HP, Heyns product; 1-DG, 1-deoxyglucosone; 3-DG, 3-

deoxyglucosone 3,4-DG, 3,4-dideoxyglucosone; GO, glyoxal; MGO,

methylglyoxal; DMG, dimethylglyoxal; HMF, 5-hydroxymethyl-2-

furfural; AA, total amino acids; P, products.

Tas & Gökmen 2017

Carbohydrate


Zhang et al. 2013

In this research, we evaluated the impacts of six types of dietary polyphenols

on both physical and chemical characteristics of fructose caramel prepared

at either neutral or alkaline pH. Besides the potential of increasing the

browning intensity and antioxidant capacity of caramel, dietary polyphenols

were capable of influencing the amount of furfurals in caramel and most

importantly, rosmarinic acid was revealed to be a promising polyphenol to

reduce the level of harmful HMF. Chemical reactions amoung fructose,

dietary polyphenols and their thermal transformation products were found to

play an important role in the production of brown polymeric pigments and

heated-induced antioxidants in caramel. The reactions include formation of

adducts of polyphenol with sugar fragments. The findings based on the

chemical model used in this study imply interests of future research exploring

the thermal interaction between sugar and polyphenols in food systems and

how the interaction affects the sensory property and nutritional composition

of food products.

Impacts of selected dietary polyphenols on caramelization

in model systems

Carbohydrate


(A and B)

Comparison of

browning

intensity

amoung caramel

prepared with or

without

polyphenol

addition (CP),

polyphenol

equivalent

solution after

thermal

treatment (PE)

and calculated

sum of fructose

caramel control

and heated

polyphenol

equivalent

solution

(FE + PE)

Zhang et al. 2013

C and D Effects of sugar reactivity towards caramelization on the difference

of browning intensity between caramel prepared with polyphenol addition

and calculated sum of sugar caramel control and heated polyphenol

equivalent solution [(C) phloretin; (D) rosmarinic acid].

Carbohydrate


Comparison of antioxidant capacity amoung caramel prepared with

or without polyphenol addition (CP), polyphenol equivalent solution

after thermal treatment (PE) and calculated sum of fructose caramel

control and heated polyphenol equivalent solution (FE + PE) [(A)

pH = 7; (B) pH = 10

Zhang et al. 2013


Carbohydrate

Jiang et al. 2008

Impact of caramelisation on the glass transition temperature of several

caramelized sugars. Part I: Chemical analyses.

This study investigated the impacts of six dietary polyphenols (phloretin,

naringenin, quercetin, epicatechin, chlorogenic acid and rosmarinic acid) on

fructose caramelization in thermal model systems at either neutral or alkaline

pH. These polyphenols were found to increase the browning intensity and

antioxidant capacity of caramel. The chemical reactions in the system of sugar

and polyphenol, which include formation of polyphenol-sugar adducts, were

found to be partially responsible for the formation of brown pigments and heat-

induced antioxidants based on instrumental analysis. In addition, rosmarinic

acid was demonstrated to significantly inhibit the formation of 5-

hydroxymethylfurfural (HMF). Thus this research added to the efforts of

controlling caramelization by dietary polyphenols under thermal condition, and

provided some evidence to propose dietary polyphenols as functional

ingredients to modify the caramel colour and bioactivity as well as to lower the

amount of heat-induced contaminants such as 5-hydroxymethylfurfural (HMF).


Carbohydrate

Change of Tg with different holding time.

Jiang et al. 2008

Carbohydrate


PHONGKANPAI et al. 2006

Antioxidative activity and other characteristics of caramelization products

(CPs) from fructose or glucose solutions prepared at pHs ranging from

7.0 to 12.0 with heating at 100C for various times (0–180 min) were

investigated.ThedegradationofbothsugarsincreasedwithincreasingpHlevel

sand heatingtime(P 0.05). The intermediate degradation products and

browning intensity also increased when pH and heating time increased (P

0.05) as evidenced by the increase in A270,A285 and A420,

respectively. The reducing power and 2–2-diphenyl-1-picrylhydrazyl

radical scavenging activity of CPs were coincidental with the browning

development and the intermediate formation. Generally, CPs from

fructose showed greater antioxidative activity as shown by the higher

reducing power and scavenging effect than CPs from glucose. Therefore,

CPs from both sugars with pronounced antioxidative activity can be

prepared by heating fructose or glucose solutions at very alkaline pH for

an extended time.

Effect oh pH on antioxidative activity and other

characteristics of caramelization products

Carbohydrate


CHANGES IN THE REDUCING

SUGAR CONTENT OF

CARAMELIZATION PRODUCTS

FROM FRUCTOSE (A) AND

GLUCOSE (B) WITH DIFFERENT pHS

DURING HEATING AT 100C FOR

VARIOUS TIMES

(□) pH 7.0,

(▪) pH 8.0,

(▵) pH 9.0,

(▵) pH 10.0,

(○) pH 11.0 and

(●) pH 12.0.

PHONGKANPAI et al. 2006


Carbohydrate

Advanced glycation end products (AGEs)

The Maillard reaction

(non-enzymatic reactions

of reducing sugars with

amines) in vivo is

associated with long term

complications of diabetes,

uremia, atherosclerosis,

and Alzheimer disease

Henning et al. 2011

Degradation reactions

Carbohydrate


Kinetic model of acrylamide formation and elimination for mimicking Maillard reactions



Carbohydrate

Formation pathways of acrylamide from

asparagine. a: α-hydroxycabonyl compound

Liu et al. 2015)vvvv


Carbohydrate


Possible reactions polyphenols might be involved in [marked

as (1)–(7)]. Arrows pointing to polyphenols mean the reactions

steps increase acrylamide formation; arrows pointing to

intermediates mean the reaction steps reduce acrylamide

formation.

Liu et al. 2015)

Degradation reactions Role of plant polyphenols in acrylamide formation and elimination

Carbohydrate


Reactive carbonyl pool from various carbonyl

sources and possible reactions positions for

antioxidants (marked as (1)–(7)).

Jin et al. 2013

Relationship between antioxidants and acrylamide formation


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