Analysis of acids and sugars in fruit-based drinks by SEC-UV-RI

(1)

(2)

7° Encontro Nacional

de Cromatografia

Grupo de Cromatografia

Sociedade Portuguesa de Quimica

Departamento de Qufmica e Bioqufmica

Faculdade de Ciencias da Universidade do Porta

(3)

Titulo

7Q Encontro Nacional de Cromatografia

Coordena~ao Aquiles Araujo Barros Jose Ant6nio Rodrigues Paulo Joaquim Almeida Luis Ferreira Guido M aria lnes Rocha

Luis Moreira Gon~alves

Manuela Maria Moreira lnes Maria Valente

Daniel Oliveira Carvalho

Jose de Sousa C!mara

Jose Manuel F. Nogueira

Impressao

e

acabamento

Gnlficos Reunidos Rua Alvares Cabral, 22-32 4050-040 Porto

Edi~ao

Sociedade Portuguesa de Qui mica

Uala la11ciro de 2012

Ti•

· agem

275 exemplares ISBN 978-989-97667-0-9

De

p6s

ito

legal

338101/11

(4)

7° Encon

t

ro Nacio

n

a

l

de Croma

t

ografia

in d

i

ce

Comprehensive two-dimensional gas chromatography-mass spectrometry (GCxGC-TOFMS)

.malysis of volatiles in Brazilian Capsicum spp. chili peppers

liP I C-DAD-MS analysis of Tempranillo grape seeds from different geographical origin

Cdfcstol, kahweol and related esters profile in espresso coffee

On the study of historical Arraiolos tapestries- a chromatographic and spectrometric approach

Ci1.11 .1cterization of phenolic and polysaccharidic extracts of Ganoderma lucidum by

cluomalographic techniques

/\ntloxldants in Pinus Pinaster and mycorrhizal fungi during the early steps of symbiosis

< IHomatographic techniques to obtain the biomolecules profile of inedible wild mushrooms

with nnuoxidant value

~1\ISOnal variability of essential oils of Lavandu/a luisieri

/\11 overview of the nutrients and non-nutrients present in the wild mushroom species most .lpprrciated in the Northeast of Portugal

CC MS ilnalysis of Portuguese propel is

<

y({~u~ mu/liflorus: phenolic characterization by HPLC-DAD, ESI-MSn and NMR combined nwthods

Mt·ntha oquat:ica: source of flavanone glycosides

V.lllcl~tion of a NP-HPLC-FLD method for tocopherol analysis in fresh lettuce

( il.11 oKlcri£ation of volatile compounds of passion fruit species of semi-arid region in the 111 o~lill,ln Northeast

Vol.lllk• composition of Portuguese Oak and Portuguese Chestnut wood chips: their relevance lo1 Ot'IIOIO(liC~I purposes

t lilt' dllllf'I"I\IOilal <md comprehensive two-dimensional gas chromatography analysis of chestnut

o~11cl o.1k wood chips with different toasting degrees

Nt•w Ill' I IPI C UV method for the quantification of napthodianthrones from Hypericum species < t..n,11 [Pfll.tllon ol Opuntia /ietts spp. fractions obtained using Sephadex LH-20.

I l•·l!'llllln,Hion of bisphcnol A in mussels using dispersive liquid-liquid microextraction and gas

1 illtHII.IIOfil.iphy nuss spcctromctry

Opliiiii/,IIIOn of In ~ilu clcorivdlilalion dispersive liquid-liquid microextraction for simultaneous

•·XII,I( tln11 ol hhplwnol/\ .md lmpiH•nol 13 in tuna canned followed by gas chromatography

-llc•VI'IOpilH'III ,lflfl v.clld,ltlOII ol .1 •,illlpll' ,111d ~CI1Sitivc I-IPLC/FLD method for N-methyl

I ollll.illlolll'". Jll'"ollrldt'"• "' olllilll.tlll·,•,(ll'", llo~·,(·d 011 cli\J)('IC.iVC' C'Xtrarlion by QuEChERS

121

1

22

123

124

125

126

127

128

129

130

131

1

132

133

134

135

136

137

138

139

140

141 P72.

P73.

P74.

P75.

P76

.

P77.

P78.

P79.

P80.

P81.

P82

.

P83.

P84

.

P85.

P86.

P87.

P88.

P89.

P90.

P91.

P92

.

7° Encontro Nacional de C

r

omatografia

indice

New strategy to enhance the extraction efficiency of polyphenols from dietary vegetables using a modified QuEChERS combined with UHPLC-PDA system

A selective and fast method for the quantitative determination of chloroanisoles in wines using

solid phase microextraction and gas chromatography-quadrupole mass spectrometry Development of a QuEChERS-based extraction method for Ochratoxin A analysis in bread by LC-FLD

GC-FID and GC-MS as a tool to screen the influence of wood ageing technologies in the brandies odourless and odourant compounds

Honey sugars analysis by ion chromatography method with Integrated Pulsed Amperometric Detection (IPAD)

Ocurrence and bioacessibility of nitrates in baby foods

Avalia~ao dos nfveis de contamina~ao cam patulina em diferentes fases do processamento industrial da fruta

Desenvolvimento de urn metodo de analise de melamina em produtos alimentares atraves de MISPE-HPLC-DAD

Quantification of wine ellagitanins by LC-ESI-MS/MS-multiple reaction monitoring Gas-diffusion microextraction: a deeper understanding of the process

Determination of free and total diacetyl in wine by HPLC-UV using gas-diffusion microextraction Determination of pesticide residues in grapes and wine using Quechers and liquid chromatography-diode-array detection

Recovery and analysis by HPLC-DAD of natural antioxidants from brewer's spent-grain Analysis of acids and sugars in fruit-based drinks by SEC-l:JV-RI

Analysis of honey main sugars by size-exclusion chromatography Monitoring malolactic fermentation using HPLC-UV-RI

Determination of chloropropanols in water and food samples using ultrasound-assisted dispersive liquid-liquid microextraction with derivatization and GC-MS detection

Arsenic speciation in rice and fish using HPLC-ICP-MS

Solid-phase extraction followed by dispersive liquid-liquid microextraction for the sensitive determination of ethylphenols species in wine

Fast detection of ~-lactam antibiotics in milk by isocratic HPLC elution

Chromatographic analysis of macro and micronutrients in the most widely appreciated cultivated mushrooms

142

143

144

145

146

147

148

149

150

151

152

153

154

155

156

157

158

159

160

161

162

(5)

7 °

Encon

tro

Nac

i

on

a

l

d

e C

r

o

m

a

tografia

Comunica~oes

em

poster

P85.

Analysis of

acids

and

sugars in

fruit

-

based

drinks by

SEC-UV-RI

Cedric Sequeira

0

_·,*

_{Lufs G. Dias}

_a

_,

_forge

_{Sa Morais}

_a

_{, An}

_a

_{C.A. Veloso}

_b,c

_{, Adt}

_{Hio A.S.C.}

Machado

d··

,

Ant6nio

M. Pere

sa,e,

*

•CIMO-Escola Superior Agn;\ria, lnstituto Politecnico de Bragan~a. Portugal, bOEQB-lnstituto Superior de Engenharia de Coimbra, Coimbra, Portugal, <I BB- Centre of Biological Engineering, University ofMinho,

Braga, Portugal, dLAQUIPAI -Faculdade de Ciencias, Universidade do Porto, Portugal, •LSRE- Laboratory of

Separation and Reaction Engineering- Associate Laboratory LSRE/LCM, ESA-IPB, Portugal

*peres@ipb.pt; ccdric.b.s@hotmail.com

Be

verage

i

nd

u

stry prod

u

ces

a

large

and diverse

range

of

soft drinks,

beverages

con

t

a

i

ni

n

g

f

l

avorings a

n

d/or fruit juices (sodas

and

fru

i

t

juices), of which

t

he

quality and

safet

y

must

be monitored

to protect

and sat

i

sfy customers.

F

r

om

th

e

raw ingredients

to t

h

e f

i

na

l

product,

quality contro

l

is

needed to ensure product

safety

,

quality,

labell

i

ng

,

regu

l

ator

y

compliance

and

consistency.

The

development of

analytical

techniques for sim

ul

taneous

analysis

of

different

compounds

essential to control the

p

roduct

quality, as an alte

rn

at

i

ve

to several

independent traditional

re

fe

rence

methods,

is

of major importance.

T

herefore

,

the

present

work

reports

the ap

plica

t

i

on of

size exc

lu

sion ch

r

o

matograph

y

(SE

C),

wh

i

c

h

al

l

ows

ca

r

ry

i

ng out ana

l

ysis free of orga

n

ic

solvents,

using

two detectors co

u

p

l

ed

i

n

ser

i

es

-

Ult

rav

i

o

l

et (UV) and

Re

fractive

In

dex

(R

I)

- fo

r

t

he

simultaneous

analysis

of

ac

i

d

i

f

i

ers

(citric, tartaric,

l

actic,

acetic

,

malic

and ascorbic

acids,

by

UV),

and

swee

ten

ers

(

sucrose,

glucose and

fructos

e

by R

I

),

in

commerc

ial

non-a

l

coho

l

i

c

beverages

w

i

th different

l

e

v

els

o

f

added

fr

u

it

j

uice.

Asco

rb

ic aci

d

i

s

used as

a stab

i

lizer in

the

soft

drinks,

impro

v

i

ng t

h

e

beverage

she

lf

-

l

if

e stabi

li

ty

due to its antioxidant propert

i

es.

The r

esu

lt

s s

ho

wed

that

the s

i

multaneous calibrations for acid

compounds

(U

V)

and for

glucose (RI)

were straight-forward.

On

the other

hand,

for sucrose and fructose

simultaneous

ana

l

ysis,

the calibrations

(RI) were more complex since

the

predict

iv

e

mode

l

s established

had to take

into account malic and tartaric

acids

in

ter

f

e

r

ences

,

regardless the

good resolution

between

t

he peaks of sucrose

and fructose.

Finally,

the

results

f

o

r

sample

anal

ysis

showed that a

ll

the sugars evalua

ted

were prese

n

t

i

n

t

he juice

d

rinks

as

we

ll

as the

citr

i

c, ta

r

taric, malic and ascorb

i

c acids

.

In a

ll

sa

m

ples

,

l

act

ic

a

nd

acet

ic

acids w

ere

no

t

detected

.

(6)

Analysis of acids and sugars

i

n

f

ruit-based drinks by SEC-UV-RI

Ctklric Sequeira'· •• Luis

G

.

Oias~

Jo

rge

S8

Mo

rais',

Ana

C.A.

Veioso", AcJeNo

AS

.

C

.

Machaclo~ Ant6nio

M.

Peres'-~

·

~CIMO • Escola SuperlOt AgtiM, 11\slib.lto Po1tect!leo de BragMCS. POI'Iugal, t0E08 -tlsti'IUIO SuperlOt de Engerh&'la de Colmbm, Com:r'a, Porh.gat

<ea -

CMtte 01 8101ogk:al E0!1neeMg, Ut\l...etSty 01 Mhho. Bmga. Portugal, 11_1.A.()..ApAI_{• Faculda}_de_de_Clr!ncias_{, U}_li'let'Sda_d_e_do_{Porto. Potrugal}_._"l.SSIE_-labotatory_o_r_Se_p_nt!O_n_and_Aeactlo_n_{EngineefiiYJ •}_A_sSOCi_at_e_Labor'atcry

LSAEILCM, ESA·IPB. POI'Iugal

•peres>tl!pb.pc; cedrlc.b.~hottn&ll..ccm

Introduction

Objectives

From the ('('ffllngmc::henls to the nnar pi"OCilCl, be\'erage lnduslf'Y needslo enSUte: prodi.Ct salety:

To appl)' siZe exeliSion chromat~ {SEC) "ilh two d!lt:ectors cOI.flled h ser~&s • UtraVIOie! (I.JI/,I and Aetrac:tl\<e hdex ~) • 10r the Simu1!Meous ~s 01:

""""y:

labehlg;

.-egulatoty ~lanO&:

conset~r~cy.

New green ana~<flcal mectn:folo!1es lOt SimJI!anoous an~Sis ol dlllerenl cornpoi.ll'ds

are essential to controllhe be\•erages qual.ly: as an anernatfve to se\«81 f'ldependent Uad'rtlonal mterence mettn:rs.

Samples

CommerCial non-aJOOhoic ~ wl!h ditterel'l'! levels 01 ackJed htit ).lloe: htit dMkS wlh addt.on Of ln.it j!Joe aboVe 30%:

ltUt dri'lkS wlh added lru1t J,~lee between 14% and 30%:

gasilledJ,~ICes wl!h a petOeOtage ollrult J,~lee betv~ 6% and 10%; iCe tea d(IOkS "ithadditloo or le!ls lhan 4% 01tnll1juiCe.

Acid!ieta compounds In samples were analysed ditec:lty.

Sog:n OOI'I'fXlUOd!lln samples were ana)j'Sled aflet dilltloo (1: I

ot.

Results

SEC·UV albm:d to analyse directfy

aJ lhe acdllers ,... S9fll)les

:;

LN a

n

alysis

• cl!f'IC add • tat&'k-.9LXJ • aSCOrbic acid ·malic add ·lactc acid

· aoet.c

acid I·Otoc;o:_, 2·Tiir~llo!ol !l·t.\'l.eiKitl 4. J\foOOft)itab:j s.l.aait aa.:a

o-

1\oelc;;o:.,

}-

_"

;:,

1-::==:==:::;::~~

_!"

_•o

U

::;~=~·;

A

~==

_

;:::::=:::::

_

'OJ

~

""' -HccQIIIO\ llrno, mn

SEC-AI arowed to analysa directly OtYy tt)Q sucrose in sam~s.

}

A

ll

cal

ib

rations

:

R>:0

,

9997

Glucose

analys

i

s

Overl..,Pr.g

p

OOI<S

(SEC-RI):

GluCOSQ + tartaric acid

Fructosa -+ malic acid

• t\t.lttiple calibration: glucose v.ith cartallc add

"

!

..

,.,

..

•..

_•

fiweel"'oea-comoot!!'ldS•

• SL..::I'06e • tructose ·giUCOie

H

PLC equipment

var

.

an

Prosw 220 P~~np Viltian 0050 lN (\...tttaviOiet d!lt:ectOI) VMan Al·4 (fetr'ac:lh.<e fldex deleClOI)

Ph~ 77251 manualln,ec:lor v.ith Loop ol 20 11 L

Sonware Slat Chr"Oma!ograptry wori<Sialloo. ''ef'Sicrl 6.4

Jones 1981 ch!'OI'I"'fftography COILmn 0\>en COLUMN

SupeiC:ogGI C-610H d& 30Cm x 7 .SIM'I 01

H

PLC conditions

C01imn temperalure: 30"C

Ellent compOSIIIon: 1% Of ~00:: add aqueous SOlutiOn

Ellent el!Uon: ISOCratiC

Flux: 0.5 «Umln

Ellent temperalure: 40"C

RI analysis

I·SU0:-2·0~•1oltllflcatid

3·~~·mU:1II;icl

• Sinple calibration: g._.oose wihOtlt cattarje aCid Pt:akAN!a = 2.064Xl04 X (GiuelX'e)-+ 1.04XIO.-.

Pt:akAN!a = 2.0SXIO' X IGlu~ I-+ 2.00xto' X !Tartaric acid I+ t.S1XIOs

!

:

=L_

-

· .

-

_.

.

'

...

.

('(ol((fl!nl1 ... ,~~.

F

ruc

t

ose

analys

i

s

• Slo~e calibtatlon: rructose wllhout mati<: acid Pt:akArea = t.94BxtQ'I X IFruttu:~el-2.70XJO"

·.

.

Coon.,on•i•.e'l.

..

·.

--·--,_

_t•_p_._...._.._{. .}_._{. ""'}

\

•

• Mutbple call!aiUoo: lructose with mak aCid

Peak Are;~.= 1~94X 10"' X 1Fru«O$t!)-+ IA9x1Q'I X IM:.Iit;~.ddl-6.62XI01

• -.

~

~==~~.--=c=

• :'"'

....

..

.

""'

Conclus

i

ons

Ouanlillcalloo Of -;~ucose or 1ruc1ose was a COI'Jl)lex task

(0-.'el'lapped peakS \\ilh aci:JS):

.. oo::MII.<e S4QflaiS trcm tartaric or maliC add pteSenoe wer-e oblaoed:

.. pt'edc:tll.<e models ee!abliShed mUSl lake lnlo aocO!IIt I8Jt8I1C-or maliC aod !Otertetar"W::e .

..

,he

lh(ee wg:neomllaled

were

ptesent in a11he jUICe

""""

'

.. Citrlc, t$1811C. male end ascorbc acids. were pfesel'l'! 10

oo-..-ageL

. . No scaii.Stlea! d11erl!noes ~ cbtel\<e'<! 1or ~

•18\les cbtaioed lOt glloose Or1f\IC1ose b:ltwoon Simple

M:J mul!ip~ calb'allon mcde'S ·~-;..0.321.