ANALYSIS

e N. A. Soyed,M. EL Sukkory,A. Aiod ond W.El-Azab

F r agment at ion
Mechanism
of Alkylmonoglycosides
by MassSpectrometry
Alkylmonoglycosides
with differentalkyl chain lengths(ApCa,
APCe,APCroand APGr4)were preparedby Fisherreactionof
glucosewith fattyalcohols.Excess
alcoholwas usedto increase
the possibilityof producingalkyl monoglycosidesproducts.
Massspectrometry
with chemicalionizationwas used to confirm their structuresas alkyl monoglycosides.
Accordingly.
the
obtainedsignalsat m/z:293., ZO7,221 and 277 corresponds
to their protonatedmolecules.
The baselineswhich are the
most intensive
signalsin eachspectrumat m/z:145, 127,141
and 197representthe mostabundantionsand definethe pathway of theirfragmentation
mechanism.
The mass145for APCg
is generated
from the parention by eliminationof the mass
ROHfollowed by H2O.For this compoundcleavageoccursat
the C-O bond next to the glucosering,while fragmentationof
alkylmonoglycosides
with carbonnumber9, l0 and 14 occurs
at the O-R bond releasing
the alkylcationR of the aglucone
moiety (CnHrn*1)
alongwith largefragmentions characteristic
of the glucosemoiety.

als namely starch and fat or their derivatives according to

their proper application at industrial scale.The use ofglycosidasesto catalyzethe synthesis of alkyl glycosideshas attracted considerableinterest since alkylglycosidesare biodegradablenonionic and nontoxic surfactants[1-31.
Analysis is an essentialrequirement for determining
their composition and structure. So, mass spectrometrywith
its different methodssuch as electronimpact. chemicaiionization, field and spark ionization is an important tool for
identification and structural determination of alg polyglycosides and their derivatives.
Sugar linkage position in glycosides was determined
using ammonia chemical ionization mass spectrometry at
1ow gas pressure. The obtained mass spectrum gave information from both EI as well as CI mass spectrometry in
one step l4]. Determination of APGs as their trimethylsilyle
ethers was performed by Billian and Stan. The substance
can be identified by characteristicmass spectra fragments
such as rnlz 204 and 217 which are the base peaks of pyranosidesand furanosides.The length ofthe alkyl chain could
Keywords: Surfactant,
alkylpolyglycosides,
massspectrometry, be identified in homologousmass series[5]. On the other
aglucone
hand, acetylated B-D-glycopyranosideswere characterized
by GC-MS ahalysis of the prepared tetra acetyl glycosides.
It was found that the resultant fragment ion characteristic
Fragmentierungsmechanismus
von Alkylpolyglycosidenmitof the aglucone moiety was present in all mass specrra,
tels Massenspektrometrie.Alkylmonoglycosidemit unter- along with the fragments obtained from acetylatedglucose
schiedlichlangenAlkylketten(APG',APce,ApGround ApGla) [6]. Also, alkylglycosideshad been studied by electrosprayiowurden aus Glucoseund Fettalkoholenmittels Fischer-Reak- nization mass spectrometry the effect of the hydrophobic
tion hergestellt.Der Alkohohiberschuss
wurde zur Steigerung and hydrophilic parts of these compounds on the stability
der Ausbeutean Alkylmonoglycosid-Produkt
genutzt.Zur Absi- of (M + Na)* ions had been evaluated[7]. The a and B epi
cherungder Molekrilstrukturen
der Alkylmonoglycoside
wurde mers and ring isomers (pyranosides and furanosides) of
die Massenspektrometrie
mit chemischerlonisationeingesetzt. allgl monoglycosideswere resolved using the alkyl amide
Dieerhaltenen
Verhdltnisse
von Molekiilmasse
zu lonenladung column and isocratic elution I8l. And, the characteristic
m/z:293,3O7,321 und 377 entsprechen
denen der proto- mass fragments of di and tri saicharides obtained by transniertenMolektile.Die Basislinien,
die in jedem Spektrumdie galactosylation reaction had been acquired using GC-MS
stdrksten
Signalebei m/z:145, 127,l4t und 197sind,reprd- spectrometry[9]. Also, fragmentation of D-glucoseand alkylsentierendie am hiiufigsten
vorhandenen
lonen und bestim- monoglycosidesin the presenceof sodium ions in an ionmen den PfadihresFragmentierungsmechanismus.
FrirApGs trap spectrometerwas studiedby Beneito-Cambra
et al. [10].
wurde riber die Abspaltungdes Alkohols ROH und anTherefore, the aim of our study was to determine the
schlieBend
von H2Oaus dem Ausgangsmolek0l
eine Masse molecular masses of the prepared compounds as alkyl
von 145 berechnet.Fi.irdieseVerbindungerfolgtdie Spaltung monoglycosidesproducts (APGs,APGe,APGIS and APGIa)
an der C-O Bindung,die dem Glucosering
am niichstenist, and define the pathway of their fragmentation mechanism.
wiihrenddie Fragmentierung
der Alkylmonoglukoside
mit 9,
l0 und t4 Kohlenstoffatomen
an der C-R-Bindungstattfindet. 2 ExperimentalTechniques
Dabeiwird ein AlkylkationR des Agluconrests(CnH2n*1)
einhergehendmit groBen,fi.irden Glukoserest
charakteristischen In our previous article [11], the synthesis of octyl, nonyl,
lonenfragmenten
abgekist.
decyl and tetradecyl glycosides was performed through
transglycosidationprocessusing p-toluene sulfonic acid as
Stichwiirter:Tensid,Alkylpolyglycoside,
Massensprektrometrie,a catalyst[12-15].
Aglucon
The purity of the productswas determinedby using HPLC
with refractiveindex detector.The structure of the prepared
compoundswas confirmedby FTIR, 1H NMR and ttc NMR.
1 Introduction
Also the molecular mass was confirmed by using mass spectrometry.
Nowadaysallcylmonoglycosidesas nonionic surfactants are
In the present paper detailed mass spectrometry studies
not obscure.They are produced from renewableraw materi
of the synthesizedallcylglycosideswere performed. For this

Te n si deS ur f .Det .47 ( 2 O 1 O)4

@ C a rlH a n s e rP u b l i sher,
Muni ch

217 W
/

N aglaA . S ay edet a l .: F ra g me n ta ti om
n e c h a n i s mof al kyl monogl ycosi des
by massspectrometry

purpose_theSSQ 7000 mass spectrometerfrom Finnigan

was useo.
Analysis of the allglglycosides was performed by direct
insertion probe using chemical ionization technique with

methane as reagent gas. MS condition: ionization voltage

70eV, temperature 100'C increased at lO0'C/minute to
350'C, mass rangewas 50-6700 mass units.

P+
6g
a" Pi

aQo

A P G8
g9

40

5B

2Q
E6 q
3L9

lllt

E+

auo

A P G9

OE

*. +5

4E
.2

eo

66

ao

BO

4a
.3

F F T - n,

4rH.*l

E+ eg
4.63

4 96

APG10
EO

60

{0

=o

-4

.4- Z i L- 5

+.z _e.-

-?

5F - e

E+ 0g
il .4#

ro6

5A

ao

=o

Figure I

218

Massspectraof the preparedAPCs

TensideSurf.Det. 47 (2O1O)4

Na g laA ' S ay edet al .: F ra g m e n ta ti om

n e c h a n i s mo f al kyl monogl ycosi des
by massspectrometry

Resultsand Discussion

o The second fragmentation mechanism can be seen

from scheme2 and 3, APGeand Apclo havevery simAlkylmonoglycosides with different hydrocarbon chain
ilar fragmentationpathwaywhich takes place by elimIengths (APGs,APGe, APG16and ApGla) were characterination of one moleculeof water mlz:18 and four
ized^byMS analysis.The mass spectraof such compounds
protonsto generatethe positiveions at mlz=285 and
confirm their structures,and the obtained signals sfredligtrt
mlz:299, followedby eliminationof C,H2, and oxyon the mechanism of their fragmentation palhway.
gen moleculeto give the ions at mlz: 127.Moreover,
In general, glucose is a common factor in the prepared
may ariseby cleavage
of the glycosidicring.
-mlz:85
compounds.As it can be seenfrom Fig. 1, the expectedmo(c) Molecular
ion peakatmlz = 377representihe massof piolecular ion peak of glucosewas not recbrded,moit probably
tonatedmoleculeof tetradecylmonoglycoside(ApG1a).The
due to the low volatility of glucose which has seveial polai
basepeak occursat mlz = I97 correspondsto its alkyl ion.
groups 1161.
o Fragmentions witll large massei characteristicof the
glucosemoiety arernf z = 31,3,285 and 2I3 generated
(a) Mass spectrum of APGgwas compatiblewith its structurby elimination of [(CH2)3,(HzO), 2Hr], 27H2 and
al formula. The molecularion peak at mlz=293 coryeC5H12respectively.Basically,it has the same fragspondsto protonatedmoleculesbf octylmonoglycoside.
mentation mechanismas ApGe and ApGro, but with
o The tallestline alrnf z: 145is its basepeik. It represlight difference of its fragmentation steps as shown
sents the most comment fragment ion to be formed.
in scheme4.
This value defines its fragmentation pathway which
occurs at the C-O bond
next to glucose ring, and
)the positive charge tend
to stay with the ring fragment {scheme1).
o The intensive sienal at the
mass mfz:163 is generated by elimination of the
ROH molecule from the
parentions followedby successivereleaseof a warer
moleculeto givethe masses
mlz : 1,45andmlz = 127.
Fragment ion CaH5O2at
mlz:85 originatesfrom
cleavageof the glycosidic
nng.
-i
-;
i':r'
:
-'" : .t- tOther signals present in
+ lr -i-. -"
;- li I .i.t;
-r
the spectrum may be gen+- -* i -i- -+--i* *-i- ierated from alkyldiglycoi - r.1
r 4
I r
*+
f'
side and impurities since
+
+
+ * -J--,* -r )
+
+
the purity of the prepared
tL-Lj*1t'-fr'r
APG8 compound was
around92%lL7l.
(b) Mass spectra of APGe and
APGI6 are shown in Fig. 1. It
is apparent that the signal
peaks at mlz=307 and ml
z:321 representsthe parent
ions which confirm their
structures mainly as nonylmonoglycoside and decylmonoglycoside. Two fragmentation mechanisms can be
found for APGeand APG16.
o The observedbaselines at
m lz = 127 f or Ap Ge a n d
mlz: t41for APG16represents the alkyl chains lost
in fragmentation. The results obtained define the
main pathway of their
\
\
fragmentation mechanism
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Te n si d eS ur f .Det .47 (2 O 1 O)4

219

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Na g laA . S ay edet a l .: F ra g m e n ta ti om
n e c h a n i s mof al kyl monogl ycosi des
by massspectrometry

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Proposedfragmentationmechanismof APGS

Scheme 3

m,"*5

Proposedfragmentationmechanismof APCI0

H2OH

-o
CII'

?HroH^

*r'"Pi
I

I .r*t

J>.",L/'.
tffi=H:'l'*
H

TI'-\?*.
OFI
mlzZW

OII

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I
I

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mlzl59

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*

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I-

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),

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olr

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|"rLr/t

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nlz243

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a'
i

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-cH2co
---------'-"+
mlzl27

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t, ---. f 1
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lt
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HOHHOH
mJz,I??
Scheme 4

+
*

rn/z 85

Proposedfragmentationmechanismof APCI4

Tenside
Surf.Det.47 (2o1o)4

N a g l aA . S ay edet al. : F ra g m e n ta ti ome

n c h a n i s mo f al kyl monogl ycosi des
by massspectrometry

References

Figure2 Cleavageof the C-O bond for APC' and the O-R bond for the
APCe,A P C r oa n d A P C I a

Beyondthe baseline, other intensive signals CoHz.*r

(mlz: I41, t27) and C.H2a_1(mlz:11L,97 and 83)
originate from the aglucone part by successivereIeaseof methylene group.

A general concept can be deducted from the obtained results. The probability of cleavageof a particular bond is related to the bond strength. Accordingly, the diflerence between the mechanism of fragmentation pathway for APG3
and that of APGe, APGI6 and APGIa may be attributed to
the inductive eflect of the methyt group. It is well known
that the inductive effect of methyl group increasesthe electron density on oxygen atom and thus strengthen the O-R
bond and hinders the breaking of the O-R bond. Consequently, for APG3 cleavageoccurs between the oxygen arom
and the glycosidiccarbon atom forming the intensive signal
at the mass mlz: 163.On the other hand, as the alkyl chain
increases beyond Cs, the inductive eflect of the methyl
group dies out (since it is significant only over a short distance) and the induced energy can overcomethe O-R bond
strength releasing the all1ylfragments ions (mlz = I27, t4L
and 1,97,Figure 2).
4

Conclusion

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2. VonRontvvijk,
F.,Woudenberg-Von
Oosterom,M. andSheldon,R ,4.;J.Mol.
C atalB. . E nzym6 (1999)5l l -552.
3. Lindhorslf K: Essentials
of carbohydrate
chemistry
and biochemistry
WileyVCH,New York.2000.
4. Reznicek,C. andMotho,M.: Carbohydrates
Research
293 (1996) t3j- t3Z
5. Billion,P..andSton,H.J.: Tenside,Surf.Det.35(3) (199S) t8t - i84.
6. Jerkovic,L andMostelic,J.: Croat.Chem. Acta77(3) (2OO4)529-535.
7. Zembrzusko,J.,Zgolo-Crzeskowio(A. and Fronsko,M.: Tenside,Surf. Det.
42(4) (2005) 226-228.
8. Beneito-Combro,M., Bernobe-Zofon,V.,Herrero-A,4ortinez,
J. M. and RomisRomos,C.'.Talanta
74 (2007) 65-it.
9. Cordelle-Cobos,A, Maiinez-Villoluengo, C.,Sonz,M. L. andMontillo, A.:Food
Chemistry114(2009) 1099- 1105.
10. Beneito-Combro,M., Bernobe-Zofon,V, Herrero-Mortinez,J. M. and RomisRomo9G.:Analytical
LetIeB42 (2009) 907-921.
|. El-Sukkary,M. M. A., Soyed,N. A., lsmoil, A. andEl-Azob,W L M: J. Surt.
D eterg.
// QOOS )t29-131.
12. Hill, K. andRhode,O: Fett/Lipidt0t (1999) 25-33.
I3. Sowodo,H.: (1990)lpn Pa[.02,264,789(1990)CA t24950b,il4.
t4. Cruexke,J. andSchmidt,5.: (1996) Cer Offen DE 4, 431,953.
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R.M, Torrill,.T.C. andBossler,C: Spectroscopic
ldentificationof
OrganicCompounds;
4'n lohn Wiley& Sons,NewYork.
11. WoleedEl-Azob:
MSc.Thesis,Petroleum
Research
Institute,
200i.
Received:
09.12.2009
R evi sed:
16.02.2010
*

Conespondence to
Dr. NaglaSayedAli
EgyptianPetroleumResearchlnstituteNearJeevan
Evaluation
andAnalysis
NasrCity
C ai o,11727
EgYPt
E-Mail
: naglaalisayed@yahoo.com

The authorsof this paper

Mohommed El-Sukkory
is Professorof OrganicChemistryat the Petrochemical
depanmenl.
AsmoilAiod is Professorof OrganicChemistryat Petrochemical
department.

A seriesof alkylmonoglycosideswith alkyl chain lengths (8,

9, 10 and 14) were synthesized using transglycosidation
method. Characterization of these compounds -was performed by MS analysis. It was observedthat fragmentation
pathway of octyl monoglycosideoccursat the C-O bond next
to the glucose ring, while for APGe, APGI6 and ApG14,
cleavageoccurs at the O-R bond.

Te n si d eS ur f .Det .47 (2 O 1 O)4

WoleedEl-Azobis a researcher
in OrganicChemistryat the Evaluationand Analysis
department.

You will find the article and additional material by entering the document number T5110069 on our website at
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221 W