Anal. Chem.

2008, 80, 783-792

APCI Interface for LC- and SEC-MS Analysis of

Synthetic Polymers: Advantages and Limits
Bernard Desmazie`res, William Buchmann,* Peran Terrier, and Jeanine Tortajada

Laboratoire Analyse et Mode lisation pour la Biologie et lEnvironnement, Universite dEvry-Val dEssonne,
CNRS UMR 8587, Ba t. Maupertuis, Bd. F. Mitterrand, 91025 Evry Cedex, France

The main advantage of the APCI interface for the LC-MS

analysis of synthetic polymers resides in its compatibility
with the main chromatographic modes: reversed-phase
liquid chromatography, normal-phase liquid chromatography, and size exclusion chromatography in organic
phase, with the usual flow rates. Moreover, APCI can be
used in positive or negative modes. Representative applications are described to highlight benefits and limitations of the LC-APCI-MS technique with the analysis of
industrial polymers up to molecular masses of 5 kDa:
polyethers; polysiloxanes; and copolymers of siloxanes.
Results are discussed in regard to those obtained by more
classical techniques: SEC and MALDI-MS. The use of an
APCI interface in LC-MS and SEC-MS coupling applied
to synthetic polymers is efficient up to 2000-4500 Da.
The main drawback of the APCI interface is the in-source
decomposition that is observed above m/z ) 2000-3000
and can induce an underestimation of average molecular
weights. However, APCI allows detection on a wide range
of polarity of sample/solvent and appears to be complementary to ESI.
Mass spectrometry (MS), with the introduction and the
development of soft ionization methods such as electrospray
ionization (ESI), by Fenn et al.,1 and matrix-assisted laser desorption/ionization (MALDI), by Tanaka et al.2 and by Karas and
Hillenkamp,3 has been shown to be a very powerful tool for
polymer analysis.4-6 MALDI-MS allows the checking of the nature
of the repeat units and the end groups, estimating the average
molecular weights, the polymerization degrees, and the polydispersity indices when polymers are few disperse. ESI-MS has also
been shown to be a very useful ionization technique also, but ESIMS has been seldom used comparatively to MALDI-MS for
polymer analysis due to the presence of several charge states.
Charge-state distribution overlaps with oligomer chain length
distribution; thus, very complex mass spectra can be obtained with
* To whom correspondence should addressed. E-mail: william.buchmann@
univ-evry.fr.
(1) Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. Science
1989, 246, 64-71.
(2) Tanaka, K. Angew. Chem., Int.l Ed. 2003, 42, 3860-3870.
(3) Karas, M.; Hillenkamp, F. Anal. Chem. 1988, 60, 2299-2301.
(4) Pasch, H.; Shrepp, W. In MALDI-TOF Mass Spectrometry of Synthetic
Polymers; Barth, H. G., Pash, H., Eds.; Springer-Verlag: Berlin, 2003
(5) Montaudo, M. S. Mass Spectrom. Rev. 2002, 21, 108-144.
(6) Montaudo, G.; Lattimer, R. P. In Mass Spectrometry of Polymers; Montaudo,
G., Lattimer, R, P., Eds.; CRC Press: Boca Raton, FA, 2002.
10.1021/ac0715367 CCC: $40.75
Published on Web 12/28/2007

2008 American Chemical Society

higher masses. Amazingly, the use of atmospheric pressure

chemical ionization (APCI) as an ionization method for synthetic
polymer analysis has been scarce whereas singly charged pseudomolecular ions are generally obtained in contrast to ESI. APCI
was initially introduced by Horning et al.7 in the mid-1970s as an
interface between high-performance liquid chromatography (HPLC)
and MS. In APCI, ions are generated at atmospheric pressure,
from the LC effluent through a heated pneumatic nebulizer via
corona discharge ionization. Usually, APCI is preferred over ESI
for the analysis of compounds of low polarity and of low molecular
weights. During the APCI process, the mobile phase acts as a
reactant gas to ensure ionization. APCI is known to be somewhat
less mild than ESI due to the fact that the evaporation of mobile
phase is supported by a heated nebulizer (350-400 C). To our
knowledge, only a few papers deal with the use of APCI for LCMS polymer analysis. Huang and Rood8 showed the advantages
of APCI-MS in the infusion mode over GC/CH4C-MS with various
silylated and unsilylated ethoxylates and carboxylates. Jandera and
co-workers9,10 studied the chromatographic behavior of ethoxylated alcohols and ethylene oxide/propylene oxide copolymers
in normal- and reversed-phase HPLC-MS using APCI-MS as a
detector. Cyclic oligomers of poly(ethylene terephtalate)11-13 and
poly(butylene terephtalate)14 were characterized by reversed-phase
HPLC-APCI MS. In these reports, the use of APCI was always
described in the positive ion mode only and over a limited mass
range (usually <1500 Da). However, packed-column supercritical
fluid chromatography (SFC) with APCI detection was successfully
used in the negative ion mode to analyze phenolic oligomers by
Davidson et al.15 Due to the acidity of the phenolic OH group,
negative-ion APCI was ideal for providing molecular weight
information without extensive fragmentation. Capillary SFC using
APCI-MS as detector was used to characterize siloxane(7) Carroll, D. I.; Dzidic, I.; Stillwell, R. N.; Haegele, K. D.; Horning, E. C. Anal.
Chem. 1975, 47, 2369-2373.
(8) Huang, S. K.; Rood, M. H. Rapid Commun. Mass Spectrom. 1999, 13, 11521158.
(9) Jandera, P.; Holcapek, M.; Theodoridis, G. J. Chromatogr., A 1998, 813,
299-311.
(10) Jandera, P.; Holcapek, M.; Kolarova, L. J. Chromatogr., A 2000, 869, 6584.
(11) Barnes, K. A.; Damant, A. P.; Startin, J. R.; Castle, L. J. Chromatogr., A 1995,
712, 191-199.
(12) Harrison, A. G.; Taylor, M. J.; Scrivens, J. H.; Yates, H. Polymer 1997, 38,
2549-2555.
(13) Bryant, J. J. L.; Semlyen, J. A. Polymer 1997, 38, 2475-2482.
(14) Bryant, J. J. L.; Semlyen, J. A. Polymer 1997, 38, 4531-4537.
(15) Carrott, M. J.; Davidson, G. Analyst 1999, 124, 993-997.

Analytical Chemistry, Vol. 80, No. 3, February 1, 2008 783

Figure 1. APCI mass spectrum (positive mode) of a mixture of surfactants.

polyethylene copolymers.16 Finally, compared to MALDI-MS or

ESI-MS, APCI technique has almost been forgotten by mass
spectrometrists for polymer analysis. The reason is probably that
this ionization method is reputedly efficient for low molecular
weight compounds only, since thermal decompositions are a
common feature of APCI for higher masses. Nevertheless, the
actual mass limits for polymer characterization have not clearly
been addressed due to the very small number of publications in
this field. Recently, new ionization methods have been applied to
polymer analysis: atmospheric pressure MALDI17-20 (AP-MALDI),
desorption/ionization on silicon21,22 (DIOS), and desorptionelectrospray ionization23,24 (DESI). The main advantage of the APMALDI source for polymer analysis resides in its possible coupling
with analyzers enabling MSn experiments.20 With DIOS and DESI
techniques, the sample preparation step is strongly simplified (if
not suppressed). Unfortunately, these new ionization methods
cannot be directly coupled with liquid chromatography, and their
applicability remained limited to low molecular weight polymers
as well. In this paper, various LC-APCI MS couplings are
evaluated; the results are completed by original SEC-APCI MS
experiments. It will be shown from the results that APCI is a very
interesting ionization technique, a serious alternative to the ESI
method for the LC-MS analysis of synthetic polymers. One of
(16) Just, U.; Jones, D. J.; Auerbach, R. H.; Davidson, G.; Kappler, K. J. Biochem.
Biophys. Methods 2000, 43, 209-221.
(17) Doroshenko, V. M.; Laiko, V. V.; Taranenko, N. I.; Berkout, V. D.; Lee, H.
S. Int. J. Mass Spectrom. 2002, 221, 39-58.
(18) Laiko, V. V.; Baldwin, M. A.; Burlingame, A. L. Anal. Chem. 2000, 72, 652657.
(19) Creaser, C. S.; Reynolds, J. C.; Hoteling, A. J.; Nichols, W. F.; Owens, K. G.
Eur. J. Mass Spectrom. 2003, 9, 33-44.
(20) Hanton, S. D.; Parees, D. M.; Zweigenbaum, J. J. Am. Soc. Mass Spectrom.
2006, 17, 453-458.
(21) Lewis, W. G.; Shen, Z. X.; Finn, M. G.; Siuzdak, G. Int. J. Mass Spectrom.
2003, 226, 107-116.
(22) Shen, Z. X.; Thomas, J. J.; Siuzdak, G.; Blackledge, R. D. J. Forensic Sci.
2004, 49, 1028-1035.
(23) Takats, Z.; Wiseman, J. M.; Gologan, B.; Cooks, R. G. Science 2004, 306,
471-473.
(24) Jackson, A. T.; Williams, J. P.; Scrivens, J. H. Rapid Commun. Mass Spectrom.
2006, 20, 2717-2727.

784

Analytical Chemistry, Vol. 80, No. 3, February 1, 2008

its advantages resides in its compatibility with the main chromatographic modes: reversed-phase liquid chromatography
(RPLC), normal-phase liquid chromatography (NPLC), and size
exclusion chromatography (SEC), with the usual flow rates. APCI
operates at flow rates of standard chromatography (typically 1 mL/
min with 4.6-mm-i.d columns). Moreover, APCI can be used in
positive or negative mode. In this work, the performance of the
APCI interface will be investigated in SEC and LC-MS coupling
applied to the analysis of industrial polymers up to molecular
masses of 5 kDa: polyethers; polysiloxanes, and copolymers of
siloxanes. Representative applications will be described to highlight benefits and limitations of the APCI technique.
EXPERIMENTAL SECTION
Materials. Dodecanol ethoxylate C12H25-(OCH2CH2)nOH
(Mn 700 gmol-1), hence described as C12EOn, was purchased
from Sigma-Aldrich (St. Quentin-Fallavier, France). The mixtures
C16/C18EOn and Empilan KM11 and KM25 polymers (Mn 700
and 1500 gmol-1, respectively) were from Marchon (Saint Mihiel,
France), and the mixture C16/C18EOn (Mn 2500 gmol-1) was
from Witco (Greenwich, CT). Hydroxyl-terminated homopolymers
(poly(butylene oxide) Mn 2000 gmol-1 (PTHF), a mixture of
poly(dimethylsiloxane) 5, 10, 20, and 50 cSt, Mn 2500 gmol-1
(PDMS) and linear triblock copolymers, Mn 1900 gmol-1
(PDMS-b-PMS-b-PDMS) containing 33% w/w of poly(methylsiloxane) (PMS) were obtained from Sigma-Aldrich (Saint QuentinFallavier, France). Solutions of polymer (with concentrations
between 10-4 and 10-3 M according to its nature) in the mobile
phase were prepared prior to analysis. No salt was added.
LC and LC-MS Analyses. LC-MS experiments (RPLC,
NPLC, SEC) were carried out using a Merck-Hitachi L6200
chromatograph (Merck, Darmstadt, Germany).
RPLC analyses were carried out using C18 bonded silica
columns (Merck Lichrospher 250 4 mm, dp 5 m, Waters
Symmetry, 150 3.9 mm, dp 4 m). Mobile phases were chosen
depending on the sample: water/acetonitrile or water/methanol
(polyethers); acetonitrile/acetone (polysiloxanes). Flow rates:

Figure 2. RPLC/APCI MS (positive mode) separation of a mixture of surfactants.

0.7-1 mL/min. Injection volumes: 5-20 L. Isocratic mode,

gradient elution or temperature programming were selected
according to the samples analyzed.
NPLC analyses involved several stationary phases: diol bonded
silica (Merck Lichrospher, 250 4.6 mm, dp 5 m); nitrophenyl
bonded silica (Macherey Nagel Nucleosil, 250 3 mm, dp 5 m),
Mobile phases: hexane/dichloromethane/methanol (polyethoxylated surfactants). Flow rate: 0.5-0.8 mL/min. Injection volumes: 5-20 L. gradient elution.
SEC analyses were carried out using one or two columns, 300
8 mm (PL gel, PS/PDVB copolymer); dp 5 m; pore diameter
1000 . Mobile phases were dichloromethane or THF. The
injection volume was 20 L (concentration range 100-500 ppm).
For all chromatographic methods, the detection during the
development of LC methods (before LC-MS coupling) was
carried out by UV and differential refractometry. The connection
of liquid chromatography systems to the mass spectrometer was
ensured by an APCI interface. MS experiments were carried out

using a quadrupole time-of-flight mass spectrometer (Applied

Biosystems Q-Star Pulsar, Foster City, CA) equipped with an APCI
Ionization source (Applied Biosystems). The heater temperature
was 300-400 C, needle current 2-3 A. Focusing potential was
265 V, declustering potentials 1 and 2 were respectively (1) 5085 and (2) 15-20 V, gas pressures (1) 80 and (2) 15 psi, and
curtain gas 45 psi. N2 was used as collision gas with a 3 psi
pressure. Data acquisition was from m/z 200 to 500 up to 2500 to
5000 according to samples in the TOF-MS mode only.
MALDI-TOF MS. Experiments were performed using a Perseptive Biosystems Voyager-DE Pro STR MALDI-TOF mass
spectrometer (Applied Biosystems/MDS Sciex, Foster City, CA).
This instrument was equipped with a nitrogen laser ( ) 337 nm).
The mass spectrometer was operated in the positive ion reflectron
mode with an accelerating potential of +20 kV. Mass spectra were
recorded with the laser intensity set just above the ionization
threshold (2500-3000 in arbitrary units, on our instrument) to
avoid fragmentation and to maximize the resolution (pulse width
Analytical Chemistry, Vol. 80, No. 3, February 1, 2008

785

Figure 3. NPLC/APCI MS (positive mode) separation of a C16EO25 surfactant.

3 ns). Typically, 10 acquisitions corresponding to 50 shots each

were summed for each deposit to obtain representative mass
spectra. External calibration using a mixture of two poly(ethylene
glycol) standards (M
h n )1000 and M
h n ) 2000) was performed with
the same 2,5-dihydroxybenzoic acid (DHB) matrix as in the
experiment. DHB matrix was purchased from Aldrich Chemical
and used without further purification. For all experiments, equal
volumes of polymer solution (10-3 M in THF) and of matrix
solution (10-1 M in THF) were mixed. About 1 L of the resulting
mixture was spotted onto the sample plate and allowed to air-dry
at room temperature just before MALDI analysis.
RESULTS AND DISCUSSION
Analysis of a Mixture of Polyoxyethylenic Surfactants
(C12/C16/C18EOn, Sample I) by RPLC/APCI MS Coupling.
The first example of polymer analysis by LC-MS using an APCI
interface concerns a mixture of three poly(ethylene oxides)
bearing alkyl chains of different lengths C12H25O(CH2CH2O)nH,
786 Analytical Chemistry, Vol. 80, No. 3, February 1, 2008

C16H33O(CH2CH2O)nH, and C18H37O(CH2CH2O)nH. The sample

was in fact a 1/1 mixture of polydodecanol (C12EO9) and of KM11
(described as a C16/C18EO11 mixture by the supplier with about
2/3 of C18 chains). These compounds belong to linear alcohol
ethoxylates (R-(OCH2CH2)mOH), which are widely used as industrial nonionic surfactants.25 Commercial formulations are complex
mixtures of oligomers depending on the distribution of both
ethylene oxides (EO) and alkyl end groups (R). Since the
physicochemical properties of these polymers largely depend on
the ratio of the length of the hydrophobic (R) to the hydrophilic
(EO) segments, efficient characterization techniques are required.
Various chromatographic methods have been described to analyze
this class of compounds and other polyether derivatives by
Rissler,26 Trathnigg,27 and Di Corcia.28 Different techniques (two(25) Thetford, D. Applications of oligomeric surfactants in polymer systems. In
Surfactants in Polymers, Coatings, Inks and Adhesives; Karsa, D. R., Ed.; CRC
Press: Boca Raton, FL, 2003.
(26) Rissler, K. J. Chromatogr., A 1996, 742, 1-54.

Figure 4. SEC/APCI MS (negative mode) separation of a mixture of surfactants C18/C16EO25.

dimensional LC, MALDI-TOF, ESI-MS, and LC-ESI-MS) have been

recently compared.29 Among these techniques, LC-ESI-MS coupling allowed a faster analysis than two-dimensional LC (4 min
versus 2 h). Moreover, compared to MALDI-TOF MS and ESIMS alone, LC-ESI-MS experiments prevent overlaps of isobaric
ions and permit byproduct identification more easily. Figure 1
shows the APCI-TOF mass spectrum of a mixture of C12/C16/C18
EOn recorded in the positive ion mode. For the sake of comparison, Figure 2 displays the separation of the same mixture by
RPLC/APCI-TOF MS (positive ion mode). In Figure 1, the overlap
of some isotopic patterns makes uneasy the assignments of ions
and the accurate determination of their relative abundances. For
example, in the expanded region of Figure 1, m/z 715 and 716
can respectively correspond to (C12 EO12 + H)+ and (C14 EO11 +
NH4)+, but a part of m/z 716 can also correspond to the isotopic
contribution M + 1 from (C12 EO12 + H)+. The ions at m/z 727
and 728 can arise from (C16 EO11 + H)+ and (C18 EO10 + NH4)+,
m/z 699 and 700 from (C14 EO11 + H)+ and (C16 EO10 + NH4)+,
but overlaps can also occur. The advantage of a chromatographic
separation before MS analysis is clear: spectra are simplified; the
separation prevents possible overlaps of isotopic patterns (or of
(27) Trathnigg, B. J. Chromatogr., A 2001, 915, 155-166.
(28) Di Corcia, A. J. Chromatogr., A 1998, 794, 165-185.
(29) Buchmann, W.; Nguyen, H. A.; Cheradame, H.; Morizur, J. P.; Desmazieres,
B. Chromatographia 2002, 55, 483-489.

isobaric ions) and can reduce spectral suppression effects. For

the most complex mixtures, the separation step becomes extremely useful. For the RPLC/APCI-TOF MS coupling experiment
shown in Figure 2, a C18 bonded silica column was used with
methanol as the mobile phase. Under these conditions, the
separation follows the length of fatty chains; the selectivity for
the polyoxyethylenic part is suppressed. The APCI mass spectra
recorded on-line corresponding to four fractions (A, B, C, D)
exhibit two main series for each fraction: (M + H)+ and (M +
NH4)+ ions as shown in Figure 2. The four fractions correspond
respectively to C12/C14/C16/C18 EOn, where C14EOn is an impurity.
Average molecular weights and polymerization degrees were
deduced from the sum of the abundances (M + H)+ + (M +
NH4)+. The four polyethers C12/C14/C16/C18 EOn present a similar
DPn 13 (M
h n 750-850 gmol-1). If it is assumed that the four
polymers are ionized with the same efficiency independently of
the alkyl chain length, then their relative proportions are respectively 43, 12, 21, and 24%. These results appear in good agreement
with the expected values: 50, 0, 17, and 33%.
Analysis of the Surfactant C16EOn (Sample II) by NPLC/
APCI MS Coupling. Figure 3 is an example of the specific
interest of APCI versus ESI. The ESI process needs the use of a
polar solvent or polar solvent mixture (typically water/methanol
or water/acetonitrile) for an efficient ionization process; thus, ESI
Analytical Chemistry, Vol. 80, No. 3, February 1, 2008

787

is not compatible with NPLC. On the contrary, the APCI source

can work whatever the polarity of the solvent. Thus, APCI can be
used in NPLC with nonpolar mobile phases. In Figure 3, a sample
of C16EO25 was analyzed by NPLC-APCI MS in the positive ion
mode using a diol bonded silica column with a mixture of hexane/
dichloromethane/methanol as mobile phase with gradient elution
(from 92/4/4 to 76/12/12 in 40 min). The main ions consist of
(M + H)+ ions. The resolution was somewhat low but sufficient
to identify the components and determine the average values:
DPn ) 23.1, M
h n ) 1258 gmol-1. The average molecular weight
and polymerization degree were calculated from the (M + H)+
ions by making a sum of the mass spectra over the entire elution.
Analysis of the Surfactant C18EOn (Samples III) by SEC/
APCI MS Coupling. Size exclusion chromatography is certainly
the most widely used chromatographic method by polymer
specialists in order to determine the average molecular weights
of polymers. This technique is rarely used in combination with
MS. Figure 4 depicts SEC separation with APCI-TOF MS detection
of a C18EO25 surfactant performed using a PL Gel (1000 ) column
with dichloromethane as mobile phase. In the negative mode, (M
+ Cl)- ions were typically detected up to m/z ) 2200. At the
beginning of the elution (fraction A), another distribution appeared
in the 700-1200 mass range. This unexpected series of ions
disappeared progressively during the experiment when lighter
oligomers were eluted. These ions were assigned to thermal
decompositions in the source since the phenomenon was growing
with the temperature increase of the APCI heater. Another
distribution appeared in the fractions B and C corresponding to
a C16EOn byproduct. From the APCI-MS data and assuming
identical ionization efficiencies, the polymer mixture would be
composed of 85% C18 EOn (DPn ) 22.6, M
h n ) 1264 gmol-1) and
15% C16 EOn (DPn ) 15.4, M
h n ) 921 gmol-1).
Analysis of the Surfactant Witco Cetalox C16/C18EOn
(Sample IV) by SEC/APCI MS Coupling. Under the same
conditions, a similar sample but with a higher average molecular
weight (C18/C16EO50) was analyzed in order to assess the upper
limit of mass detection with the APCI interface. The results are
given in Figure 5. A total of 55% of the (M + Cl)- ions correspond
to C18 EOn (DPn ) 23.4, M
h n ) 1301 gmol-1) and 45% corresponds to C16 EOn (DPn ) 20.9, M
h n ) 1163 gmol-1). (M + Cl)ions were detected up to m/z ) 2500 (see fraction A), but
decomposition remained important for higher masses. Under our
conditions, 2500 atomic mass units (amu) seemed to be the upper
detection limit. The extent of decomposition can depend on many
factors such as the following: nature of mobile phase, source
temperature, source pressure, and needle current. Since the
quality of the separation is related to the composition of the mobile
phase, the latter was not modified. However, in order to prevent
thermal decomposition of the oligomers in the source, the source
temperature was decreased from 400 to 300 C. Unfortunately,
this did not efficiently limit the decomposition but rather reduced
ionization efficiency. The source heater temperature was set to
an optimal value of 350 C. The effect of source pressure was
explored also. This pressure increases with the chromatographic
flow rate but can be controlled by opening the exhaust. Unfortunately, the main consequence obtained by modifying this parameter was a deterioration of the chromatographic resolution when
moving away from the optimal value of the exhaust. Last, the
788 Analytical Chemistry, Vol. 80, No. 3, February 1, 2008

Figure 5. SEC/APCI MS (negative mode) separation of a mixture

of surfactants C18/C16EO50.

thermal decomposition can depend on the nature of repeat unit

of the oligomers. As it will be shown, some oligomers can be more
fragile than others.
Analysis of the Poly(tetrahydrofuran) (Sample V) by
RPLC/APCI MS Coupling. Poly(tetrahydrofuran) is a linear,
saturated, diol polyether derived from the polymerization of
tetrahydrofuran. While soluble in almost all conventional organic
solvents, it is barely soluble in water. Poly(tetrahydrofuran) is
typically used as soft segment for thermoplastic elastomers and
cross-linked elastomers. The LC analysis of poly(tetrahydrofuran)
was optimized by Rissler et al.30 This method was adapted, THF
was replaced by acetone in the mobile phase. Figure 6 depicts
the RPLC separation of a poly(tetrahydrofuran) APCI-MS detection. The separation was achieved using two C18 columns with
elution gradient, from 18% acetone in acetonitrile to 100% acetone.
Mass spectra of various selected fractions are also given in Figure
6. Two kinds of ionic species are detected: (M + H)+ and (M +
NH4)+ adducts. From A to D, isotopic patterns are more and more
spread due to the isotopic contribution of carbon. However,
monoisotopic ions remain easily assignable. Based on the peak
intensity of the total ion current, the estimation of the average
molecular weight and of the polymerization degree gave DPn )
27.5 and M
h n ) 1995 gmol-1. From the total ion current and the
various assignments A-D, it is clear that mass detection limit is
higher than in the previous experiment. The upper mass limit is
above 3000 amu. Clearly, this limit depends on the nature of the
oligomers and of the mobile-phase composition.
(30) Rissler, K. Chromatographia 2004, 59, 669-675.

Figure 6. RPLC/APCI MS (positive mode) separation of a poly(tetrahydrofuran).

Analysis of a Poly(dimethylsiloxane) (Sample VI) by

RPLC/APCI MS Coupling. A further example is given in Figure
7 with the RPLC separation of a mixture of poly(dimethylsiloxane).
This polymer is composed of straight chains terminated with two
trimethylsilyl groups. Siloxane polymers (silicones) are known to
occur in various forms (fluids, gels, etc.) for a wide variety of
applications.31 An efficient separation was achieved using two
Merck C18 columns and applying an elution gradient, from 80%
acetone in acetonitrile to 100% acetone. Mass spectra recorded
during elution show the presence of (M + NH4)+ adducts mainly.
Isotopic patterns are strongly affected by the presence of silicium.
Intact oligomer chains are detected here above 3500 amu. DPn
and M
h n values were estimated from the (M + NH4)+ ions by
making a sum of the mass spectra over the entire elution and by
taking into account the isotopic patterns (DPn ) 30.3, M
hn )
2403).
Analysis of a Block Copolymer of Methyl- and Dimethylsiloxanes (Sample VII) by RPLC/APCI MS. The last example
(31) Kendrick, T. C.; Parbhoo, B.; White, J. W. In Siloxane Polymers and
Copolymers, The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; John Wiley: Chichester, 1989.

concerns a block copolymer of methyl- and dimethylsiloxanes.

Figure 8 shows the RPLC/APCI(+) separation obtained using two
C18 bonded silica columns. The structure of such a copolymer is
described at the top of Figure 8. The separation was achieved in
the isocratic mode with acetonitrile/acetone 66/34 as mobilephase composition. However, columns were set in an oven with
a programmed temperature (from 25 to 80 C, 1 C /min). (M +
NH4)+ ions were detected as main series. Each chromatographic
peak consists of overlapping of combinations of methyl and
dimethyl polysiloxanes with a constant number of methyl groups
within the chain. For example, with a retention time of 20 min,
oligomers contain a total of 25 methyl groups ((x + y) 2 + z )
25). When considering the x, y, z contributions of methyl and
dimethyl siloxanes, it can correspond to various (x + z)/y ratios:
12/1, 11/3, 10/5, or 9/7. A contour plot (Figure 9) deduced from
the RPLC/APCI-TOF separation was produced by means of a
method described in detail elsewhere.32 This 2D plot reports the
ion intensities of the various oligomers as a function of the number
of methylsiloxane and dimethylsiloxane units. Only ions with m/z
(32) Terrier, P.; Buchmann, W.; Cheguillaume, G.; Desmazieres, B.; Tortajada,
J. Anal. Chem. 2005, 77, 3292-3300.

Analytical Chemistry, Vol. 80, No. 3, February 1, 2008

789

Figure 7. RPLC/APCI MS (positive mode) separation of a poly(dimethylsiloxane).

Table 1. Average Molecular Weights (Mn), Average Degrees of Polymerization (DPn), and Polydispersity Indexes (Ip)
Deduced from SEC, MALDI-MS, and LC-APCI MS
SEC dataa

I
II
III
IV
V
VI
VII

sample

Mn

C12EOn
C16EOn
C18EOn
C16EOn
C18EOn
C16EOn
C18EOn
PTHF
PDMS
PDMS-b-PMS-b-PDMS

529
917c

DPn

MALDI-TOF MS+datab

LC-APCI-MS data

Ip

Mn

DPn

Ip

mode

Mn

DPn

Ip

7.8
15c

1.17
1.09c

29.6
33.1
42.6c

1.06
1.07
1.07c

2506
2430
1437

34.5
32.8
N/A

1.98
1.48
1.77

12
18.9
18.7
30.8
27.3
45
45
12.4
13.04
11.8
5

1.08
1.06
1.06
1.02
1.03
1.03
1.03
1.29
1.04
1.17
1.53

RPLC +

1545
1726
2132c

716
1073
1095
1596
1473
2225
2253
909
1127
(DMS) 873
(MS) 298

745
805
825
1258
1264
1163
1301
1995
2403
1107
322

12.7
12.8
12.6
23.1
22.6
20.9
23.4
27.5
30.3
14.9
5.4

1.02
1.03
1.03
1.04
1.07
1.07
1.11
1.3
1.1
1.08
1.17

NPLC +
SEC SEC RPLC +
RPLC +
RPLC +

a Refractometric detection. Poly(ethylene oxides) were used as standards. b 2,5-Dihydroxybenzoic acid was used as MALDI matrix. c These
data are an average measurement of C16EOn + C18EOn.

> 600 Da were taken into account in order to avoid the

contribution of low-mass ions coming from in-source decompositions. The estimation of the average polymerization degrees gave
for each sort of repeat unit: DPn (DMS) ) 14.9, DPn (MS) ) 5.4.
790 Analytical Chemistry, Vol. 80, No. 3, February 1, 2008

Comparison of LC-APCI MS Results with SEC and MALDI

MS Data. Finally, average molecular weights deduced from the
LC-APCI MS experiments were compared with those obtained
by SEC and MALDI MS (see Table 1). First, MALDI MS and

Figure 8. RPLC/APCI MS (positive mode) separation of a methylsiloxane/dimethylsiloxane triblock copolymer.

Figure 9. Contour plot deduced from a RPLC/APCI MS (positive

mode) separation of a methylsiloxane/dimethylsiloxane triblock copolymer (ion intensities reported as a function of the number of
methylsiloxane and dimethylsiloxane units).

LC-APCI MS provide much more information than SEC. For

example, SEC gives only one average molecular weight value for
the mixture C16/C18EOn (samples I, IV) whereas MALDI MS and
LC-APCI MS can give one value of Mn and DPn for each polymer
as a function of the fatty chain length. In the case of sample VII,
SEC cannot determine the composition of the copolymer. Second,
the results concerning the molecular weights depend on the
polymer. With poly(ethylene oxides) (samples I-IV), lower
molecular weight values were obtained from LC-APCI MS than
from SEC or MALDI MS analyses (except for C12EOn). Average
molecular weights deduced from LC-APCI-MS for sample IV seem
strongly underestimated. Fragmentations of the heavier chains
can explain the strong differences in the estimation of polymerization degrees. For the poly(tetrahydrofuran) (V), the PDMS (VI),

the values deduced from LC-APCI MS were higher than those

from MALDI-MS but slightly lower than SEC values. This can be
partially explained by a lack of desorption-ionization efficiency in
MALDI-MS with the heaviest oligomers. The copolymer PDMSb-PMS-b-PDMS (VII) leads to similar results by both MALDI-MS
and LC-APCI-MS. As already mentioned, SEC does not seem to
be the most appropriate method in this case because this
technique is not able to distinguish the different repeat units of
the copolymer. Concerning the polydispersity indexes, except for
sample I, they roughly decrease in the following order: SEC >
LC-APCI MS > MALDI-MS probably because the detection of
the heaviest chains is limited in both MALDI-MS and APCI-MS
analyses. It must be emphasized that even if LC-APCI MS can
lead to an underestimation of the average molecular weights; the
accuracy of the quantitative results depends on the polymer.
Owing to the separation step before mass analysis, LC-APCI MS
coupling provides the best qualitative data.
To conclude, the use of APCI interface in LC-MS and SECMS coupling applied to synthetic polymers is efficient up to 20004500 Da, pseudomolecular ions are easily detected both in normaland in reversed-phase LC conditions, as well as in organic-phase
SEC (whatever the ion mode: positive or negative). The main
results are that the analysis of polyethers is possible in RPLC,
NPLC, or SEC APCI-MS coupling up to m/z ) 2500 at least. The
analysis of polysiloxanes is easy up to at least m/z ) 4500 in RPLC
or SEC/APCI MS, in the positive or negative ion modes. The main
drawback of the APCI interface is the in-source decomposition,
Analytical Chemistry, Vol. 80, No. 3, February 1, 2008

791

which is observed above m/z ) 2000-3000 and can result in

underestimation of molecular weights. However, APCI allows
detection on a wide range of polarity of sample/solvent and
appears to be complementary to ESI. Fundamental studies of the
chemical ionization process and a comparison with the newly
developed atmospheric pressure photoionization33,34 could permit

the extension of the range of detectable molecular weights by

optimizing source parameters.

(33) Raffaelli, A.; Saba, A. Mass Spectrom. Rev. 2003, 22, 318-331.

(34) Robb, D. B.; Covey, T. R.; Bruins, A. P. Anal. Chem. 2000, 72, 3653-3659.

792

Analytical Chemistry, Vol. 80, No. 3, February 1, 2008

Received for review July 20, 2007. Accepted October 29,

2007.
AC0715367