Analytica Chimica Acta 750 (2012) 48–62

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Analytica Chimica Acta

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Review

Applications of polydimethylsiloxane in analytical chemistry: A review夽

Suresh Seethapathy, Tadeusz Górecki ∗
Department of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1, Canada

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Polydimethylsiloxane (PDMS) has

numerous applications in analytical
chemistry.
 Sorptive properties of PDMS are used
primarily in sampling.
 Partitioning properties are used in
separations.
 Permeability of PDMS forms the basis
for sample introduction and passive
sampling.
 Advantageous mechanical prop-
erties are used in lab-on-a-chip
devices.

a r t i c l e i n f o a b s t r a c t

Article history: Silicones have innumerable applications in many areas of life. Polydimethylsiloxane (PDMS), which
Received 22 February 2012 belongs to the class of silicones, has been extensively used in the field of analytical chemistry owing
Received in revised form 26 April 2012 to its favourable physicochemical properties. The use of PDMS in analytical chemistry gained impor-
Accepted 3 May 2012
tance with its application as a stationary phase in gas chromatographic separations. Since then it has
Available online 11 May 2012
been used in many sample preparation techniques such as solid phase microextraction (SPME), stir bar
sorptive extraction (SBSE), thin-film extraction, permeation passive sampling, etc. Further, it is gain-
Keywords:
ing importance in the manufacturing of lab-on-a-chip devices, which have revolutionized bio-analysis.
Polydimethylsiloxane (PDMS)
Passive sampling
Applications of devices containing PDMS and used in the field of analytical chemistry are reviewed in
Sorption this paper.
Permeability © 2012 Elsevier B.V. All rights reserved.
Extraction

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2. Structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.1. Partitioning properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

Abbreviations: CMV, cytomegalovirus; DNA, deoxyribonucleic acid; ESE, equilibrium sorptive enrichment; GC, gas chromatography; GC–IR-C-MS, gas
chromatography–isotope ratio-combustion-mass spectrometry; GLC, gas liquid chromatography; GADPH, glyceraldehyde 3-phosphate dehydrogenase; GUT, Gdańsk Univer-
sity of Technology; HSSE, headspace sorptive extraction; LOC, lab-on-a-chip; LTPRI, linear temperature-programmed retention index; MESCO, membrane-enclosed sorptive
coating; MESI, membrane extraction with a sorbent interface; MEMS, microelectromechanical system; MIMS, membrane inlet mass spectrometry; MOSFET, metal oxide
semiconductor field effect transistor; NIOSH, National Institute of Standards and Health; OCP, organochlorine pesticides; OSHA, Occupational Safety and Health Administra-
tion; PAH, polyaromatic hydrocarbons; PCB, polychlorinated biphenyls; PCR, polymerase chain reaction; PDMS, polydimethylsiloxane; PTFE, polytetrafluoroethylene; SBSE,
stir bar sorptive extraction; SiSTEx, solvent in silicone tube extraction; SMSE, silicon membrane sorptive extraction; SPME, solid phase microextraction; STE, sorptive tape
extraction; sVOC, semi-volatile organic compound; TWA, time-weighted average; US-EPA, United States Environmental Protection Agency; VOC, volatile organic compound;
WMS, Waterloo Membrane Sampler.
夽 PDMS versatility makes it a perfect material for analytical chemistry.
∗ Corresponding author. Tel.: +1 519 888 4567x35374; fax: +1 519 746 0435.
E-mail address: tgorecki@uwaterloo.ca (T. Górecki).

0003-2670/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.aca.2012.05.004
 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62 49

2.2. Permeability properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

2.2.1. Effect of temperature on the partition coefficient and permeability of PDMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3. Applications utilizing the partitioning properties of PDMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.1. GC columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.2. SPME . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.3. Thin film extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.4. PDMS rod and PDMS tube microextraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.5. SBSE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.6. Integrative and equilibrium sorptive enrichment (ESE) using packed bed PDMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.7. In-tube SPME . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.8. Membrane-enclosed sorptive coating (MESCO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.9. Sorptive tape extraction (STE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4. Applications utilizing the permeability properties of PDMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.1. Permeation passive samplers with PDMS membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.2. Membrane inlet mass spectrometry (MIMS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.3. Membrane extraction with a sorbent interface (MESI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
5. Applications of PDMS in lab-on-a-chip devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
6. Miscellaneous applications of PDMS in the analytical laboratory. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
7. Future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
8. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

Suresh Seethapathy graduated from the University of Tadeusz Górecki is a professor at the Depart-
Waterloo, ON, Canada with a Ph.D. degree in Chem- ment of Chemistry, University of Waterloo (ON).
istry in November 2009 under the supervision of Prof. He obtained his M.Sc. Engineer (1981) and Ph.D.
Tadeusz Górecki. Prior to his studies at Waterloo he (1986) degrees from the Gdansk University of Tech-
worked in analytical chemistry departments of vari- nology, Poland, and the Professor of Chemical Sciences
ous chemical industries including bulk herbal drugs, degree (2009) from the President of the Republic
perfumery raw materials, metal working fluids, poly- of Poland. Prof. Górecki’s scientific interests include
mers and dental pharmaceuticals. Dr. Seethapathy passive sampling, comprehensive two-dimensional
continued his postdoctoral studies in the same group gas chromatography (GC × GC), enhanced extraction
until January 2011. During his tenure at the University techniques, environmental analysis, field analysis,
of Waterloo, his research focused on passive air sam- pyrolysis GC–MS and HPLC. He is an author/co-author
pling, calibration of permeation passive samplers and of 20 books/book chapters, over 130 papers pub-
their applications. The research resulted in successful lished in peer reviewed journals, over 210 conference
commercialization of a polydimethylsiloxane based permeation passive sam- papers/abstracts/short communications (including 36 invited lectures) and 5
pler used for sampling volatile organic compounds from air and soil gas matrices. patents.
Dr. Seethapathy is currently an applications scientist with Thermo Fisher Sci-
entific and is involved in the development of gas chromatography and gas
chromatography–mass spectrometry applications. His other areas of interest
include fast gas chromatography and multidimensional gas chromatography.

1. Introduction capillary column, on a magnetic stir bar etc.; foams or particles

packed into sorbent tubes, etc. PDMS can be manufactured into the
PDMS belongs to the group of silicones, which are made of sili- required shape and form by processes such as extrusion, coating,
con, carbon, hydrogen and oxygen, and sometimes other elements molding, calendering and soft lithography. Nowadays, it can be eas-
as well. Pioneering work on silicones, and PDMS in particular, was ily fabricated using two-part kits available from various vendors. In
done by both Dow Corning and General Electric Company in the most cases, one of the parts is a pre-polymer (generally a vinyl-
middle of the 20th century, and their development continues to this terminated PDMS), while the other is a cross-linker (dimethyl,
day. A search in the SciFinder Scholar journal database with key- methyl hydrogen siloxane) [1]. By combining the two ingredients
word “polydimethylsiloxane” results in nearly 24,000 hits, which in specific ratios and curing them at specified conditions, PDMS of
illustrates its extensive use in various areas of chemistry, and sci- different properties can be obtained [1]. The structure and physico-
ence in general. The use of the term “PDMS” in analytical chemistry chemical properties of PDMS responsible for its wide applicability
and polymer-related journals only was also researched. With a few in analytical chemistry will first be discussed in this article, fol-
exceptions, the data indicate a steady increase in the number of lowed by their applications in various analytical devices.
research articles related to PDMS since 1981.
The first notable application of PDMS in analytical chemistry 2. Structure and properties
was perhaps its use as stationary phase in gas liquid chromatog-
raphy (GLC). In the past two to three decades, the applications of PDMS (CAS number 63148-62-9) consists of a flexible (Si–O)
PDMS have expanded mainly in the areas of sampling of organic backbone and a repeating (Si(CH3 )2 O) unit [2]. The number of
compounds from air, water and soil gas matrices, as well as manu- the repeating (Si(CH3 )2 O) units generally defines the molecular
facturing of lab-on-a-chip (LOC) devices. PDMS employed in various weight, and consequently many of the viscoelastic properties of
analytical techniques might have many different geometric forms, the material [2]. Based on the application needs, alterations to the
including thin films, tubes and rods; coatings on a fiber, inside a viscoelastic properties can be accomplished by cross-linking the
50 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62
polymer [3] (e.g. vinyl cross-linking), or by adding fillers (e.g. silicon
dioxide) to the polymer network [4].
PDMS is a non-toxic, highly hydrophobic, translucent polymer
that does not bio-accumulate. It has a very low glass transition
temperature of −127 ◦ C [5] and a shear elastic modulus of 250 kPa,
which changes at a very small rate of 1.1 kPa per 1 ◦ C change in tem-
perature [6]. The specific gravity of PDMS is generally within the
range from 0.91 to 1.00. For PDMS with molecular weight varying
from 10,000 to 60,000 g mol−1 , the dielectric constant is very low
and ranges from 2.72 to 2.75 (implying low refractive index) [7].
Further, PDMS is optically transparent down to 300 nm, enabling
its use in some optical measurements [8].
Even though PDMS is non-reactive to many chemicals, it
tends to swell when exposed to hydrophobic solvents. Most
hydrophilic solvents such as water, nitromethane, acetonitrile,
dimethylsulphoxide and ethylene glycol, used frequently in ana-
lytical chemistry, swell the PDMS matrix the least [9]. This makes it
possible to use PDMS to extract analytes from water for quantitative
analysis. On the other hand, most hydrophobic solvents includ-
ing pentane, diisoproylamine, triethylamine and xylene swell the
PDMS the most [9]. This property is often used for extracting the
analytes from the PDMS matrix after the analytes are absorbed in
the polymer. Lee et al. determined the swelling of PDMS in a variety
of polar, moderately polar and non-polar organic solvents gener-
ally used in chemical synthesis and correlated the swelling with
the solubility parameter [9].
In analytical chemistry, the partitioning and permeability prop-
erties of PDMS are by far the most widely used and will be
briefly discussed before their actual use in various applications is
described. Mechanical, electrical and optical properties of PDMS
have been exploited in some applications and will be presented
subsequently.
2.1. Partitioning properties
Whenever there is a difference in the chemical potential of a
species between two phases in contact with each other, there will
always be a net movement of this species in the direction which
tends to bring the system to equilibrium. In the case of PDMS, two
parameters are often used to describe the sorption properties of
the polymer towards a chemical: solubility (S) and partition coef-
ficient (K). These two parameters are thermodynamic properties
and define the relative concentration of an analyte at equilibrium
between PDMS and the matrix in contact with the polymer. Ana-
lyte sorption by PDMS is an absorption phenomenon, where the
analyte molecules diffuse into the bulk of the homogeneous poly-
mer [10]. The term “solubility” is generally used to describe the
sorption property in air, and is defined as the ratio of the analyte
concentration in the membrane (Cm ) to its partial pressure in the
air (p), as shown in Eq. (1). This term is often used in the field of
pervaporation studies.
Cm
S=
p ume) and K is the PDMS-matrix partition coefficient. The general
In analytical chemistry however, the term partition coefficient
(or distribution ratio) is more often used. It is defined as the ratio
of the concentration of the analyte in the vapor or liquid phase to
its concentration in PDMS at equilibrium (Eq. (2)).
Cm
K=
Cg
The two terms are easily convertible using ideal gas law [11].
The partitioning property forms the basis of such techniques as
GLC, solid phase microextraction (SPME), thin film extraction, stir
bar sorptive extraction (SBSE), PDMS rod extraction, PDMS particle
bed extraction, membrane-enclosed sorptive coating (MESCO), etc.
Kinetic region Equilibrium
region
Analyte mass
Time
Fig. 1. Analyte mass accumulation as a function of time.
When PDMS is exposed to the sample matrix, analyte con-
centration in the polymer changes with time as shown in Fig. 1
[12]. The relationship is generally represented by a first-order
one-compartment model described by Eq. (3), where CPDMS is the
analyte concentration in PDMS, Cmedium is the analyte concentra-
tion in the sample matrix, t is the time, and k1 and k2 are the uptake
(into the membrane) and elimination (into the matrix) constants
[12].
k1
CPDMS = Cmedium [1 − e−k2 t ] (3)
k2
For each sampling system based on the partitioning properties
of PDMS, the extraction time profile (or kinetics) at a specific tem-
perature is generally dictated by the volume of the PDMS phase,
its surface-to-volume ratio, sample agitation conditions, partition
coefficient of the analyte of interest, boundary layer conditions, as
well as the analyte’s diffusion coefficient within the PDMS network
[13].
In quantitative applications, the amount of analyte trapped in
PDMS after exposure to a sample is determined, and the concen-
tration in the sample is computed based on which part of the curve
shown in Fig. 1 is used. In the linear region, the analyte mass col-
lected is directly proportional to its concentration in the sample
and the time for which the PDMS is exposed to the sample. The
intermediate region is seldom used, but is currently getting more
popular owing to the introduction of kinetic methods of calibra-
tion [14]. In the equilibrium region, the analyte mass is related to
its concentration through the partition coefficient K as shown in Eq.
(2). Mathematically, it can be shown that the extraction yield R at
equilibrium in a PDMS phase is given by [15];
1
R= (4)
(ˇ/K) + 1
(1) where ˇ is the phase ratio (ratio of sample volume to PDMS vol-
approach is to have high ˇ in order to achieve R greater than the
quantitation limit of the method. Consequently, for a specific ˇ, the
quantitation limits generally decrease with increasing K.
2.2. Permeability properties
(2)
Whenever there is a difference between the concentrations of a
soluble analyte on either side of a polymer membrane, there will
be a net flow of the chemical from one side of the membrane to
the other. This process is termed permeation. For rubbery poly-
mers like PDMS, this process was first described by Graham using
his solution-diffusion model for organic compounds as early as in
 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62
Sample
Analyte concentration at
Concentration
the surface of the
membrane
Analyte
concentration
in air
Fig. 2. Ideal steady state concentration profile when vapor phase concentration is practically zero at the membrane-sorbent interface.
the 1800s [16]. According to this model, the transfer of gas or vapor
across a polymer takes place in three steps: dissolution of the vapor
molecule in the polymer, diffusion of the molecule across the poly-
mer under a concentration gradient, and release of the vapor from
the polymer at the opposite side of the membrane [5]. It can be
shown that the permeability coefficient P of a molecule is the prod-
uct of its diffusion coefficient D in the polymer and its partition
coefficient K.
P = DK
The transport of molecules within the membrane itself is
described mathematically using Fick‘s first law of diffusion, which
states that the flux J of a chemical species across a membrane of
unit area per unit time is proportional to the concentration gradi-
ent between the two surfaces of the membrane. The constant D is
the diffusion coefficient of the chemical in PDMS.
∂C
J = −D
∂x
During the permeation process, the partitioning at the PDMS-
sample interface occurs instantaneously, and the diffusion process
within the membrane determines the kinetics of the analyte trans-
fer (rate determining) [17]. Generally, vapor molecules permeate
faster through rubbery polymers such as PDMS than through
glassy polymers such as Teflon® [5]. In the PDMS structure, the
(–Si–O–Si–) backbone is highly flexible compared to many other
rubbery polymers, and interactions between the individual PDMS
segments are relatively weak. Consequently, PDMS has one of
the lowest glass-transition temperatures for polymers of −127 ◦ C,
which allows long-range segmental motions even at very low tem-
peratures resulting in one of the lowest diffusivity selectivity for
permeation [18]. Because of the low diffusivity selectivity, the dif-
ferences in permeability of vapor molecules through PDMS are
mostly governed by their partition coefficients rather than the dif-
fusivities in the polymer [5].
In practice, concentrations of analytes in the sample matrix can
often change over the duration of the time the PDMS is exposed
to the sample. When such changes occur, there is an intermit-
tent period when steady state concentration profile does not exist
within the membrane. A measure of the time the sampling system
takes to respond to this change in concentrations and reach the
steady state again is quantitatively expressed using various terms
such as residence time [19], relaxation time [20], lag time [21], and
response time [20]. The term “residence time” as applied to passive
sampling was introduced by Tompkins and is defined as the average
51
Membrane
“Zero sink” sorbent
Analyte concentration
at the surface of the
membrane
Distance
residence time of an analyte in the diffusion region at steady-state
conditions [19]:
2
Lm
tr = (7)
2Dr
where tr is the residence time of the analyte with diffusion coeffi-
cient Dr in the PDMS phase, and Lm is the thickness of the phase.
The lower this value is, the shorter is the time required for the
sampler to respond to a change in analyte concentration in the
(5) sample matrix. Response time on the other hand is considered to
be the time taken for the permeation rate to increase from 10% to
90% of the steady state value, and is normally used in the field of
membrane inlet mass spectrometry (MIMS) [22].
An often overlooked factor when comparing results obtained
with PDMS manufactured by different manufacturers or
researchers is the effect of fillers used during the fabrication
process. PDMS is very often fabricated with fillers such as SiO2 (up
to 30%) to increase its mechanical strength [23]. While the filler
was not found to have any effect on the partition coefficients, it
increases the tortuosity of the diffusion path and decreases the
(6)
analytes diffusion coefficient [23]. Consequently, the permeability
of the polymer towards an analyte also decreases in the presence
of a filler.
In practice, the permeability property is used in one of two
major ways. In the first method, the analyte concentration on the
receiving surface is always kept at zero, generally using a strong
sorbent. In such cases, the steady state concentration profile across
the membrane surface can be represented by Fig. 2. In the sec-
ond method, the permeating analytes are swept away from the
membrane surface, typically using a sweep gas or by maintaining
vacuum conditions at the receiving side. If the stripping phase effec-
tively removes the permeated analytes, the concentration profile
will be similar to that shown in Fig. 2, but could often be compli-
cated depending on the partition coefficient of the analytes, the
effectiveness of the stripping process and the boundary layer con-
ditions [24].
Any attempt to use the permeability properties should always
consider the analyte transport mechanism in the phases in contact
with PDMS on its both sides, and necessary corrections in the math-
ematical models should be made. Whenever the fluid flow velocity
at the sampling device’s location is not sufficient to supply analytes
to the sampling surface faster than their rate of transfer into the
sampler, there will always be a region adjacent to the membrane
where the analyte concentration is lower than that in the bulk of
the sample [13]. In the field of passive sampling, this introduces
a negative bias in the analyte concentration determined using the
sampling device, which is said to be due to “starvation effect” [10].
For PDMS-based permeation sampling systems, the magnitude of
52 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62

Table 1
GC column manufacturers and specific codes used for PDMS stationary phases.

Manufacturer Phase code

Agila Technologies DA-1

Agilent Technologies DB-1, DB-1MS, HP-1, HP-1MS, Ultra-1, HP-101, DB-1ht, SE-30, DB-Petro, DB-PS1, CP-Simdist
Altech AT-1, SE-30, AT-1MS, EC-1
GS-Tek GsBP-1, GsBP-1MS
Machery Nagel Optima 1, Optima 1MS
Ohio Valley OV-1, OV-101
Perkin Elmer PE-1, Velocity-1, Elite-1
Phenomenex ZB-1, ZB-1MS, ZB-1HT
Quadrex 007-1
Restek Rtx-1, MXT-1, MXT-1HT, Rxi-1MS
SGE BP-1, BPX-1
Supelco/Sigma–Aldrich SPB-1, SPB-1MS, Petrocol DH, SPB-1sulfur, Equity-1, SP-210, MDN-1
Thermo Fisher Scientific TR-1, TR-1MS
United States Pharmacopeia G1, G2, G38
Varian/Chrompack VF-1MS, CP-Sil 5CB, CP Sil 5CB-MS

this starvation effect depends on the permeability of PDMS towards
the analyte, the geometry of the sampling system, the fluid flow
velocity and pattern across the surface of the PDMS, and the diffu-
sion coefficient of the analyte in the matrix. Under the absence of
the starvation effect, the uptake rate is polymer-controlled. As the
starvation effect increases, the uptake rate is progressively bound-
ary layer-controlled. Using appropriate models, it is often possible
to estimate the boundary layer thickness for specific analytes, at
which the net analyte transfer rate into the sampling device is
controlled equally by the polymer and the boundary layer [13].
Permeability of PDMS is a function of both the partition and the
diffusion coefficient of the chemical, both of which are temperature
dependent. It is therefore important to consider the thermody-
namic parameters involved in these processes to make necessary
changes in the models used in calculations, as well as take advan-
tage of the effects while using the PDMS for various purposes.
2.2.1. Effect of temperature on the partition coefficient and
permeability of PDMS
The temperature dependence of the partition coefficient of an
analyte between PDMS and air is related through the heat of solu-
tion as shown in Eq. (8), where K0 is the pre-exponential factor, Hs
is the enthalpy difference between analyte sorbed in PDMS and in
its pure phase (heat of solution), R is the gas constant and K is the
partition coefficient at temperature T [18]. The heat of solution for
the partitioning of the majority of volatile organic compounds into
PDMS is negative, indicating that the partition coefficient decreases
with increasing temperature.
 H 
s for GLC separations, and to date it is the most widely used station-
K = K0 exp −
RT
The permeability of PDMS is dependent on both K and D (Eq. (5)).
Consequently, temperature dependence of permeability is decided
by the temperature dependences of both K and D. While the heat
of solution defines the temperature dependence of K (Eq. (8)), the
energy of activation of diffusion defines the temperature depen-
dence of the diffusion coefficient of the analytes within the PDMS
network. This relationship is shown in Eq. (9), where D0 is the
pre-exponential factor and Ed is the energy of activation of dif-
fusion. Ed is positive for most compounds, and consequently the
diffusion coefficients of chemicals in PDMS increase with increase
in temperature [25]. The temperature dependence of permeability
of PDMS can be represented by Eq. (10), where P0 is the standard
permeability and Ep is the energy of activation of permeation.
 E 
d
D = D0 exp −
RT
 E 
P = P0 exp −
p
(10)
RT
Combining the above three equations, it is apparent that Ep is
related to Ed and Hs as shown in Eq. (11). Therefore the direction and
quantitative variation of permeability through PDMS with a change
in temperature is decided based on which of these two parame-
ters defining the activation energy of permeation is dominating.
Many researchers have determined the Ep values for many chemical
species and found them to be negative [25,26]. This shows that for
PDMS, Hs is the dominating factor. In other words, the permeabil-
ity of most gas-phase organic compounds through PDMS decreases
with increasing temperature.
Ep = Ed + Hs (11)
3. Applications utilizing the partitioning properties of
PDMS
Many devices make use of the partitioning properties of PDMS
for various applications. Irrespective of how the PDMS is used, the
challenges in practical applications are not due to the material itself,
but to difficulties with incorporating the environmental effects,
boundary layer effects, uncertainties in quantitation, calibration
data and temperature effects into the models used for quantitative
purposes. Nevertheless, simple mathematical models have been
developed for all the devices discussed in this section for successful
use in quantitative analysis.
3.1. GC columns
PDMS was one of the earliest stationary phase materials tested
(8)
ary phase for GC columns [27]. GC columns coated with PDMS are
available from many manufacturers, each with their own product
code. Examples are listed in Table 1. Many standard methods in
chromatographic analysis published by regulatory agencies such
as US-EPA, NIOSH, OSHA, etc., require the use of PDMS as the sta-
tionary phase for the analysis of specific groups of compounds.
The stationary phases used in GLC have to fulfill many functional
requirements; the popularity of PDMS in this application is due to
the fact that it satisfies most of them [28].
The stationary phase needs to be chemically inert, thermally
stable (low bleed) and handle many temperature cycles during its
usage time. Further, it should be possible to uniformly distribute the
stationary phase inside the column, reproducibly from one batch to
another, during the manufacturing process. Apart from these fun-
damental requirements, the stationary phase should exhibit high
(9) selectivity towards volatile and semi-volatile organic compounds
of interest that need to be analyzed by GC.
The selectivity of PDMS stationary phases arises from the differ-
ences in the partition coefficients of the analytes, hence the use of
 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62
Fig. 3. Decomposition mechanism of PDMS stationary phase (based on reference [39]).
PDMS as the stationary phase falls under the category of partition
gas chromatography techniques [29]. The retention properties of a
compound in such chromatographic separations are the function of
the analyte’s partition coefficient between the carrier gas and the
stationary phase (PDMS in this case). Under isothermal conditions,
the partition coefficient of a solute at a given temperature is related
to the retention time of the solute in the following manner [30],
tr tr − tm Vs
= =K (12)
tm tm Vm
t
where r is the adjusted retention time, tm is the retention time
of an un-retained compound, tr is the retention time of the solute,
K is the partition coefficient of the solute, Vs is the volume of the
stationary phase, and Vm is the volume of the mobile phase.
The differences in the partition coefficients of the analytes can
be explained based on the fundamental molecular interactions
between the analyte and PDMS [31]. Since PDMS is hydropho-
bic, the partition coefficients generally increase with increasing
hydrophobic interactions. Further, the partition coefficients of
homologous series of compounds are simple functions of their
vapor pressure. Consequently, such analytes elute from the col-
umn in the order determined by their vapor pressure, from
high to low. The partition coefficient of an analyte can be easily
manipulated by changing the temperature of the chromatographic
column during sample elution, which is used in temperature-
programmed gas chromatography to overcome the general elution
problem.
Retention times are functions of column dimensions, temper-
ature and linear flow velocity of the carrier gas. To be able to
compare chromatographic results obtained with different columns
and under different conditions, Kovats introduced a system of
retention indices, which are dimensionless numbers obtained by
comparing the retention times of an analyte with those of a
standard set of compounds, such as n-alkanes, under the same
isothermal conditions. Kovats retention indices are determined
using Eq. (13), where tr is the retention time of the analyte, tn is
the retention time of the n-alkane eluting directly before the ana-
lyte, tn+1 is the retention time of the n-alkane eluting directly after
53
the analyte, and n is the number of carbon atoms in the n-alkane
eluting directly before the analyte.
 log(t ) − log(t ) 
r n
I = 100 + 100n (13)
log(tn+1 ) − log(tn )
While Kovats retention indices are based on isothermal gas
chromatographic separation, Van den Dool and Kratz [32] intro-
duced the concept of linear temperature-programmed retention
indices (LTPRI), which involves calculation of the retention indices
while performing the separation under the conditions of linear
temperature programming. LTPRI is defined as:
 t −t 
r n
LTPRI = 100 + 100n (14)
tn+1 − tn
The exact correlation between LTPRI and the partition coef-
ficient is complicated, and involves fluid dynamics inside the
capillary column [33]. However, various researchers working on
determining empirical relationships and/or mathematical approx-
imations have found that LTPRI for a homologous series of
compounds is related to the partition coefficient of the analyte at a
particular temperature as [34]
LTPRI = N ln K + B (15)
where N and B are constants.
The Kovats retention indices and LTPRI values have been deter-
mined for numerous compounds with PDMS stationary phase
and are extensively reported in the literature [35]. The retention
index database published by the National Institute of Standards
and Technology (NIST) is perhaps one of the largest and com-
piles data from numerous literature sources. In addition, many
researchers reported ways to estimate the retention indices based
on structure–property correlations [36–38]. It is therefore possible
to use these retention data to estimate the partition coefficient val-
ues required for the calibration of many sampling devices that will
be presented in the rest of the article.
One of the common problems in GLC is the decomposition of the
stationary phase, often referred to as column bleeding, which tends
to increase the baseline levels affecting the detectability of com-
pounds eluting from the column. While PDMS is generally accepted
as being thermally stable and inert, minor thermal decomposition
54 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62
Fig. 4. Solid phase microextraction device used for TWA sampling (based on Ref. [10]).
is still unavoidable and the detectors of today are sensitive enough
to detect these decomposition products. While using mass spec-
trometry for detection, various decomposition products as shown
in Fig. 3 can be observed, and their mass fragments can be used to
monitor the decomposition. Discernible peaks are generally found
at m/z 207, 281, and 355 [39]. During thermal decomposition, the
PDMS first forms a cyclic trimethylsiloxane trimer, which gives
rise to a peak at m/z 207. The high molecular weight decompo-
sition products are one of the reasons why the ion source in a mass
spectrometer needs to be cleaned regularly for proper functioning.
Many strategies are used to reduce column bleeding, including
polymer cross-linking, chemically bonding PDMS to the column
wall, and carefully avoiding introduction of oxygen into the col-
umn (which tends to increase the decomposition) [40]. Currently,
the use of various methods to reduce the bleeding as described
above makes it relatively easy to increase the column temperature
up to 350 ◦ C and even beyond in some cases.
A successful separation of closely eluting compounds and
quantification using GLC also depends on the column efficiency
(measured through the number of theoretical plates N). Among the
variables described by the van Deemter equation that affect the
efficiency, the diffusion coefficient of the analyte in the stationary
phase is critical [40]. It has been shown that the mass transfer coeffi-
cient in the stationary phase is inversely proportional to the square
of the diffusion coefficient of the analyte [40]. As was discussed in
detail in Section 2.2, the diffusion coefficients of analytes are rela-
tively high in PDMS, which tends to decrease the plate height (or
increase the efficiency).
A specific application of the PDMS stationary phase in chro-
matography is the determination of the distribution of the boiling
points of the components of petroleum fractions (so-called sim-
ulated distillation) [34]. This application is possible owing to the
direct correlation of the retention times determined using PDMS
stationary phase with the boiling points of the generally non-polar
components of these fractions. Recently, PDMS stationary phases in
metal capillary columns were introduced with ladder technology,
which involves systematic cross-bond formation between the indi-
vidual PDMS chains in a stationary phase [41]. Combining this with
effective surface deactivation of the column, simulated distillations
of petroleum fractions containing up to 116 carbon atoms in the
molecules have been performed reproducibly [41]. This also indi-
cated that properly manipulated PDMS stationary phases could be
stable up to 435 ◦ C during a temperature cycle in a chromatographic
run.
Partitioning of analytes into PDMS is an absorptive process;
hence complications such as competitive sorption hardly occur.
However, as the concentration of the analytes increases beyond
its solubility limit, the sorption isotherm deviates from linear-
ity [42]. This phenomenon is observed very easily in partition
chromatography, where high sample loadings result in peak
fronting [42].
3.2. SPME
PDMS was one of the earliest extraction phases tested for use
in SPME. The SPME device consists of an extracting phase such as
PDMS coated on a short fused silica fiber. The coated section of
the fiber is typically 1 cm long [43] and is housed inside a stainless
steel needle. The PDMS-coated fibers are available commercially in
three different thicknesses: 7, 30 and 100 ␮m, as both bonded and
non-bonded phases. The fiber arrangement allows for the extrac-
tion phase to be exposed to the sample matrix by moving the silica
fiber in and out of the needle, as well as for introducing the fiber
into a GC injector for thermal desorption and quantification of the
extracted analytes. When the extraction phase is exposed to the
sample matrix, the analytes partition between the sample matrix
and the PDMS, and the analyte uptake follows the profile illus-
trated in Fig. 2. As illustrated in Fig. 4, the same fiber can be used
for time-weighted average (TWA) concentration measurements by
retracting the fiber into the metal housing to have a well-defined
diffusion distance for the analyte before it can be sorbed. Chen and
Pawliszyn first demonstrated the application of such a system for
the analysis of VOCs in air [44].
Under given fluid flow conditions around the fiber and for a par-
ticular geometry of the sampling device (length and thickness of
the coating), an analyte takes a specific amount of time to equili-
brate between the sample and the PDMS phase. Proper agitation
of the sample and higher diffusion coefficient of an analyte result
in reaching the equilibrium concentration in the PDMS extraction
phase faster.
The amount of analyte extracted by an absorption-type SPME
coating at equilibrium when the extraction phase is in direct con-
tact with the sample matrix (two-phase system) is given by Eq.
(16):
Kfs C0 Vs Vf
n= (16)
Vs + Kfs Vf
where Kfs is the partition coefficient of the analyte between air and
the extraction phase, Vf is the volume of the extraction phase, Vs
is the sample volume and C0 is the concentration of the analyte in
air [43]. When the sample volume is very large compared to the
volume of the extraction phase multiplied by the analyte partition
coefficient, the amount of the analyte (n) collected by the fiber at
equilibrium is given by [43]:
n = Kfs C0 Vf (17)
From the above equation it is clear that under the conditions of
near-infinite sample volume, the equilibrium concentration of an
 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62
analyte in an absorption-type phase (Cf in the case of SPME) is given
by:
n ethanes and ethenes [50]. Bruner et al. found that heavier isotopes
Cf = = Kfs C0 (18)
Vf
Apart from being useful in SPME, this equation forms the basis of
many equilibrium sampling techniques used in sediment and soil
analysis (among others).
Calibration of SPME can be done in many ways as reported in
the literature [45,46]. Of all the methods, kinetic calibration needs
a special mention, as it is well developed and applied for SPME, but
not so widely used for other sampling systems based on the parti-
tioning property of PDMS. The possibility of such calibration arises
as analyte sorption into and desorption out of PDMS is isotropic
[47]. In this method, the PDMS coating is first doped with a known
amount of an isotopic analogue of the analyte of interest and the
extraction process is started. After a certain time (generally less
than the time required to reach equilibrium), the analyte mass
and the isotope analogue mass on the fiber are determined by
chromatography. The knowledge of these masses along with the
knowledge of the amount of isotope analogue originally doped onto
the fiber allows the mass of the analyte that would have been in the
fiber at equilibrium to be calculated. Consequently, analyte con-
centration in the sample can be determined. The isotope analogue
of the analyte is referred to as performance reference compounds
(PRCs). This method is valuable when the partition coefficient of
the analyte is relatively high and the sample agitation conditions
are below optimal, both of which tend to increase the time required
to reach equilibrium.
Variation of the iso-kinetic principle can also be applied for
determining sorption coefficients and quantify analytes in a sam-
ple matrix. In this method, the sorption phase is first loaded with
analyte and allowed to desorb into the sample matrix. This is partic-
ularly useful for highly hydrophobic compounds which take a long
time to reach equilibrium between the sample and the PDMS phase.
For example, Ter Laak et al. used this method to determine sorption
coefficients of PAHs and quantified them in contaminated soil [48].
Kwon et al. have published the theoretical principles behind such a
quantifying method and used it to quickly determine the sorption
coefficients of PAHs in water [49].
It is often not possible to calibrate SPME for each analyte when
a large number of analytes are involved in the analysis of samples
such as gasoline and diesel fuel. For such applications, Martos et al.
introduced a simple method to calibrate SPME with PDMS extrac-
tion phase based on the LTPRI values of the analytes determined
using a capillary column coated with a PDMS stationary phase [34].
This method is possible because the calibration constants for SPME
are a function of the partition coefficients of the analytes between
the PDMS extraction phase and the sample, and so are the retention
indices measured on capillary columns coated with PDMS. Since the
retention index values can be determined with good accuracy, they
can be used to estimate the calibration parameters of SPME. Using
this method, Martos et al. showed that total parameters such as
total petroleum hydrocarbons (TPH) can be determined by SPME.
SPME with a PDMS extraction phase (apart from other extraction
phases) has been widely used as a sample introduction tech-
nique for compound-specific isotope ratio determination using
gas chromatography–isotope ratio-combustion-mass spectrome-
try (GC–IR-C-MS) [50]. In the field of GC–IR-C-MS, it is critical
to avoid any fractionation while sampling so as to determine
the compound-specific isotope ratios of the analyte in the sam-
ple with sufficient accuracy. Since sampling with SPME involves
phase transfer (from liquid or air to the PDMS phase), and phase
transfer phenomena involve isotopic fractionation, care has to be
taken while interpreting data based on this technique. Hunkeler
and Aravena determined such isotopic fractionation effects for
55
PDMS-coated SPME and found very small isotopic effects relative
to experimental error for chlorinated methanes and chlorinated
were generally retained less (except at low temperatures) when
using a GC column with a PDMS stationary phase by determin-
ing the retention behaviors of CH4 –CD4 , C2 H6 –C2 D6 , C2 H4 –C2 D4
and C7 H8 –C7 D8 [51]. Bermejo et al. observed similar results when
chlorinated products of (1 H10 )1,4-dimethylbenzene and (2 H10 ) 1,4-
dimethylbenzene were analysed using PDMS stationary phase. The
observation was generally attributed to the higher vapor pressure
of the heavier isotope analogues (isotope vapor pressure effect)
[52].
Even though PDMS is biocompatible, its use in in vivo sampling
of biological fluids is not preferred mainly because of the non-
specific adsorption of proteins to the hydrophobic surface of the
polymer [53]. Therefore, surface or chemical modification of PDMS
is often necessary for its use in sampling biological fluids.
The use of SPME (not restricted to PDMS phase alone) has been
extensively studied, reviewed and reported. Consequently, rather
than referring to individual journal research articles, the readers
are directed to the many review articles specifically published on
the calibration, development and applications of SPME [54–76].
3.3. Thin film extraction
In this technique, a thin film of PDMS is used for the extraction
and pre-concentration of analytes from air, water or soil matrices.
Compared to an SPME or SBSE device, thin films have larger sur-
face and hence mass uptake is faster [67,77]. Further, since the total
volume of the thin film PDMS is generally higher than that in SPME
(and possibly also SBSE), larger analyte amount can be extracted
leading to higher sensitivity of the sampling method without com-
promising the time required for the extraction [78]. Analytes from
the PDMS film can either be solvent-extracted and analyzed by
conventional liquid injection GC analysis, or they can be thermally
desorbed directly into the GC inlet for higher sensitivity.
Qin et al. used such thin films for the extraction and analysis
of five polycyclic aromatic hydrocarbons (PAHs) from water. They
also showed that thin PDMS films could be used to mimic the bioac-
cumulation of PAHs by black worms owing to the hydrophobicity
of the polymer [78]. Similar studies were done by Bragg et al. for
the quantitation of PAHs in the Meuse River in the Netherlands and
Hamilton Harbour in Ontario, Canada [79]. Jahnke et al. studied
the applicability of thin PDMS films for the in-tissue extraction of
PCBs from fish [80] and found that equilibration of PCBs into PDMS
was rapid for lipid-rich fish, but slow for low lipid-containing fish.
Kinetic calibration is possible with thin film extractions just like
with SPME, as was demonstrated by Bragg et al. [79]. Thin films
can also be coated on the inside of containers (e.g. vials, beakers,
jars, etc.), and the sample (soil, sediment, water) equilibrated with
the PDMS layer. For example, Maenpaa et al. coated PDMS on the
inside surface of 20 and 120 mL vials and jars, respectively, for the
sampling and analysis (by solvent desorption) of PCB-contaminated
soil and sediments [81]. This method is also sometimes referred to
as the immobilised liquid extraction (ILE).
3.4. PDMS rod and PDMS tube microextraction
An excellent review of the applications of PDMS rods and PDMS
tubes for sample preparation was recently published by van Pinx-
teren et al. [82]. The ultimate goal of these devices is to increase the
sensitivity of extraction by increasing the PDMS volume. The review
indicated that studies to date used PDMS phase volumes ranging
from 8 to 635 ␮L in the form of tubes or rods for the extraction
of analytes from various matrices such as air, water, milk and tea.
The analytes of interests extracted from these matrices included
56 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62
many common pollutants, such as PAHs, PCBs, chlorobenzenes,
polybrominated diphenyl ethers, halogenated anisoles, pesticides,
and other VOCs and sVOCs. PDMS tubes can be used both as par-
tition sampling devices, as well as permeation sampling devices.
In the latter case, the outside of the tubes serve as the sampling
surface, and the analytes permeating to the inside of the tube are
stripped using a solvent or gas for further analysis [83,84].
Ouyang et al. compared SPME operated in the TWA mode by
retracting the fiber into the needle housing, PDMS rod and thin film
for the extraction of PAHs in Hamilton Harbour (Ontario, Canada).
The PDMS rod used in the study was 1 cm long with a diameter of
1 mm (volume of about 7.85 ␮L), while the 127 ␮m thick PDMS film
corresponded to a volume of 63.5 ␮L. As expected, they found that
the passive sampling rate increased in the order thin film > PDMS
rod > SPME (in TWA mode). The comparatively large surface area-
to-volume ratio of thin films was responsible for this observation
[85]. Zhao et al. described the theory of PDMS rod extraction from
aqueous solutions for the kinetic calibration method and applied it
to the quantification of PAHs [86].
3.5. SBSE
Introduced in 1999 for analyte pre-concentration from aqueous
samples, SBSE is now commercially available from Gerstel GmbH
(Germany). The SBSE device consists of a magnetic stir bar, a coating
of extraction phase on the outside, and a thin glass layer between
the two (to avoid metal-catalyzed decomposition of PDMS) [87].
For the extraction, the bar is allowed to stir the sample solution
to speed up the partitioning of the analytes between the matrix
and the coating. Once the extraction process is finished, the SBSE
device is usually thermally desorbed, and the analytes are intro-
duced into a GC column for quantitation. Unlike SPME fiber, which
can be desorbed directly in the injector of a GC, the SBSE device
requires a separate module for desorption and re-focusing, as it
takes a considerably longer time for analyte release from the much
larger volume of PDMS (which leads to severe peak broadening if no
re-focusing is applied). SPME fiber contains about 0.5 ␮L of PDMS as
opposed to 25–125 ␮L for the SBSE device. The desorption module
commercially available from Gerstel GmbH (Germany) is designed
to allow cryogenic re-focusing of the analytes before their release
into the GC column for separation.
The main application of SBSE to-date has been direct extrac-
tion of analytes from aqueous samples, but it can also be used
for sampling analytes from sample headspace (headspace sorptive
extraction, HSSE) [87] or from the air [88]. In SBSE, an analyte’s
PDMS–water partition coefficient required for quantitative pur-
poses can be determined through calibration or can be easily
estimated based on the analyte’s octanol–water partition coeffi-
cient (Kow ) [89]. Because the Kow values are widely available in
the literature, development of applications for various analytes in
aqueous solutions is relatively easy.
While many researchers experimented with different coatings
on the stir bars, only PDMS and PDMS/ethylene glycol phases have
been available commercially at the time of writing of this paper
[90]. Yun Nie and Kleine-Benne studied the use of a mixture of
ethylene glycol (EG) and PDMS, as well as polyacrylate (PA) alone
as extraction phases for SBSE [91]. Their experiments indicated
that EG-PDMS phase had better extraction efficiency than 100%
PDMS and 100% PA phases for phenols, furans, acids and alcohols
in matrices such as whisky, multivitamin drinks and white wine.
However, the temperature limits at which the SBSE could be des-
orbed were comparatively lower for the EG-PDMS phase. Further,
the EG-PDMS phase absorbed larger quantities of water because
of its polar nature, which is disadvantageous when working with
mass spectrometric detectors.
A recent review article on SBSE by Lancas et al. described the
theoretical aspects of the technique and covered a wide range
of applications developed for pharmaceutical, biomedical, envi-
ronmental, and food analysis [92]. Prieto et al. reviewed the
applications of SBSE with special emphasis on method optimiza-
tion, novel applications and limitations, and offered insight into
potential solutions for commonly observed problems [93]. While
initially SBSE was used almost exclusively in combination with
GC–MS, many applications involving solvent desorption followed
by liquid chromatography or liquid chromatography–mass spec-
trometry analysis were published recently [94–98].
3.6. Integrative and equilibrium sorptive enrichment (ESE) using
packed bed PDMS
The integrative and ESE techniques were devised to overcome
some of the challenges normally encountered using adsorptive sor-
bents in sorbent bed tubes [99]. Some of those problems include
adsorbent breakdown at high desorption temperatures, competi-
tive sorption effects and analyte reactivity with the sorbent [99].
Owing to the advantages of PDMS discussed earlier, PDMS was
researched as an alternative sorption material for use in sorbent
bed tubes.
Baltussen et al. first reported the use of packed bed PDMS for the
extraction of PAHs and organochlorine pesticides (OCPs) in water
in 1997 [100]. They prepared PDMS particles by crushing PDMS
under liquid nitrogen and packed 0.325 g of it in a tube with a total
bed length of 5.8 cm. The PDMS particles were held in place using
quartz wool plugs. The sample was drawn through the tube for
enrichment, and the tube was subsequently dried using inert gas,
followed by thermal desorption into GC for quantification. Except
for naphthalene and acenaphthene, the method showed very good
reproducibility. Such traps packed with PDMS were further evalu-
ated by Baltussen et al. for use in environmental sampling [101].
When used in the ESE mode, the sample is continuously passed
through the tube until equilibrium is reached between the sample
matrix and PDMS. The advantage of the method over integrative
collection with PDMS is that the maximum possible amount of the
analyte (determined by its partitioning coefficient) can be collected,
which lowers the quantitation limits. Further, analytes with low
breakthrough volume can be sampled without any problem. The
disadvantage, however, is that the partition coefficients of the ana-
lytes need to be known in order to quantify the concentrations, and,
more importantly, the analyte concentration in the sample matrix
needs to remain constant throughout the sampling period. The
application of the device was demonstrated for compounds such as
benzene, toluene and p-xylene [99]. Aguilar et al. reported perform-
ing online ESE-chromatography to determine benzene, toluene and
p-xylene in environmental wastewater samples [102]. Baltussen
et al. showed the use of the technique for high molecular weight
compounds such as benzo (a) pyrenes, which are very difficult or
not possible to thermally desorb from adsorbents [100].
3.7. In-tube SPME
In in-tube SPME, sampling is performed in a fashion similar to
that described for sorbent bed above, but a hollow column with
coating on the inside wall is used for the extraction. This technique
is also referred to as ESE by some researchers. In this technique,
sample (gas or liquid) is first allowed to equilibrate with the extrac-
tion phase by repeated draw/eject cycles. Once the extraction
step is complete, the analytes are either desorbed thermally and
introduced into a GC, or are desorbed with a stronger solvent for
introduction into an LC column for separation. The method is gener-
ally automated by using a series of valves to perform the draw/eject
cycles for extraction and desorption automatically [103]. Most of
 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62
the articles published in peer reviewed journals indicate that the
technique is more widely used for sampling from aqueous phase
combined with solvent desorption and liquid chromatography.
Analysis of the published articles indicates that PDMS is not as
widely used for this technique as for some others described in this
article.
Pham Tuan et al. described the theoretical aspects of this pre-
concentration technique and demonstrated its applicability for the
analysis of VOCs in air [104,105]. Bagheri and Salemi used this tech-
nique to analyse PAHs in water in an offline-mode and detected the
analytes at concentrations as low as 0.001–0.006 ␮g L−1 [106]. Glo-
big and Weickhardt used a fully automated in-tube SPME device to
quantify PAHs in river water [107]. Wang et al. used a 5 m, 0.53 mm
internal diameter column with a 1.2 ␮m thick PDMS film to analyze
PAHs and chlorinated pesticides, and observed that analyte recov-
ery was 50 times higher than that seen with an SPME fiber, even
though the volume of PDMS in the in-tube setup was only 10 times
higher [108]. Several other applications of in-tube SPME with PDMS
have been described in the literature [109–111].
3.8. Membrane-enclosed sorptive coating (MESCO)
The MESCO device is made by enclosing a certain amount of
PDMS (e.g. coated on an SBSE stir-bar) in a water-filled dialysis
membrane bag made of regenerated cellulose [112]. The whole
assembly is introduced into the sample matrix and analyte con-
centration in the PDMS occurs by mass transfer through a series
of compartments: sample, dialysis membrane, water and PDMS
receiving phase. The analyte mass collected in the PDMS phase was
found to be linear with the exposure time and was described by
Eq. (19), where MS is the mass accumulated in PDMS over time t,
Mo is the mass of analyte in the sampler prior to deployment, Cw
is the analyte concentration in water during deployment, KSW is
the partition coefficient between PDMS and water, Vs is the vol-
ume of PDMS, kov is the overall mass transfer coefficient, A is the
membrane surface area exposed to water, and ˛ is the membrane
porosity [113]. The calibration of the MESCO sampler can either be
done using standard sample solutions, or by using kinetic methods
where a PRC is added to the PDMS phase immediately prior to the
sampler deployment [113].
  k A˛  
ov
MS (t) = Mo + (CW KSW VS − Mo ) 1 − exp − t (19)
KSW VS
Many applications of MESCO devices have been reported in
the literature, and their use is gaining popularity. Vrana et al.
demonstrated the applicability of MESCO for sampling of various
persistent organic pollutants in water by comparing the results
with traditional spot sampling [113]. Further, they showed that
desorption of PRCs from the PDMS phase was isotropic to the ana-
lyte accumulation, and hence kinetic methods could be used for
calibration. The MESCO device has been used for many other appli-
cations, examples of which are provided in references [114–119].
3.9. Sorptive tape extraction (STE)
The STE method is similar to thin film extraction described
above, but was devised specifically to sample organic compounds
released from the skin. STE is performed with a PDMS tape with
typical dimensions of 15 mm × 4 mm for thermal desorption, and
15 mm × 12 mm for liquid desorption; the tape thickness is 0.5 mm
[120]. One side of the tape is in direct contact with skin, while the
other is sealed by an adhesive tape which holds the PDMS in place.
The amounts of analytes collected by the tape at equilibrium are
determined by their PDMS-skin partition coefficients. Sisali et al.
demonstrated the applicability of STE for the extraction of sebum
from skin surface and quantified it by a gravimetric method [120].
57
Sgorbini et al. evaluated the method for the analysis of cosmetically
important chemicals such as citronellol, Z-citral (neral), geran-
iol, cinnamaldehyde, anisyl alcohol, cinnamyl alcohol, eugenol,
methyleugenol, coumarin, isoeugenol, ␣-isomethylionone, 2-(4-
tert-butylbenzyl)propionaldehyde (lilial), ␣-amylcinnamaldehyde
and ␣-hexylcinnamaldehyde [121]. Bicchi et al. studied volatile
organic compounds permeating out of the skin when perfume is
applied to different parts of the body [122]. They used the same
method for the analysis of chemicals released from the surface of
vegetables and fruits (pulp and surface). This technique is promis-
ing for its use in the cosmetic industry, as well as in healthcare
studies related to allergens and biomarkers in skin.
4. Applications utilizing the permeability properties of
PDMS
4.1. Permeation passive samplers with PDMS membranes
Permeation passive samplers are based on analyte transfer from
the sampled medium (air or water) to a collecting phase (generally
a sorbent) through a polymer membrane [123]. This type of sam-
pler can be used for sampling organic compounds from both air
and water. In the authors’ laboratory, a simple permeation-type
passive sampler based on a GC autosampler vial was developed for
sampling of volatile organic compounds from the air. It is available
commercially as a so-called Waterloo Membrane Sampler (WMS)
[31]. A PDMS membrane (100 ␮m nominal thickness) fabricated
in the laboratory using the spin coating technique is first cut to
fit the top of a 2 mL crimp-top autosampler vial. A suitable sor-
bent depending on the analyte of interest (generally Anasorb 747®
or Carbopack B® ) is then added to the vial. The rubber septum
normally accompanying the aluminum crimp cap is removed, the
PDMS membrane is placed on top of the vial as shown in Fig. 5
and crimped. During deployment, the sampler is turned upside
down so that the membrane is in direct contact with the sorbent
on one side, and the sample matrix on the other. Since the sor-
bent adsorbs all the analytes reaching the inner membrane surface
instantaneously, the analyte concentration inside the vial is main-
tained at zero all the time for continuous permeation of analytes
across the membrane.
When there is no starvation effect (practically zero boundary
layer width), the analyte uptake can be easily described by Eq. (20),
where C0 is the analyte concentration in air, M is the amount of
analyte collected in time t by the sampler, and k is the calibration
constant of the sampler towards a particular analyte. The parameter
k is dependent on the geometry of the sampler and fundamental
transport properties of the membrane towards the specific analyte.
It is given by Eq. (21), where D is the diffusion coefficient of the
analyte in the membrane, A is the surface area of the membrane,
and Lm is the membrane thickness.
kM
C0 = (20)
t
Lm
k= (21)
DKA
The calibration constants of the WMS sampler have been deter-
mined for over 40 volatile organic compounds including primary
and secondary alcohols, chlorinated ethanes and ethenes, aromatic
hydrocarbons, alkanes, and esters [31]. Based on Eq. (21), the per-
meability of PDMS for the analytes was also reported.
The research also showed that the calibration constant k (and
hence the permeability) can be easily estimated based on the LTPRI
of the analytes due to the interesting properties of PDMS described
in Section 3.1. Since the partition coefficient of an analyte is pro-
portional to the LTPRI determined using a capillary column with
a PDMS stationary phase, LTPRI could be used to estimate the
58 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62
Fig. 5. (a) Components of the WMS sampler and (b) WMS sampler deployment configuration.
calibration constant of an analyte in the sampler. Consequently,
the method could be used to determine parameters such as TPH
using the sampler, which is a formidable task with any other pas-
sive sampler currently in use [31]. A similar approach could be used
for other permeation-based techniques described in the remainder
of the section, though.
Actual permeability of PDMS towards various analytes can also
be determined experimentally using various methods. One such
method is based on the use of the concept of inverse gas chro-
matographic techniques (IGC) to determine not only the partition
coefficients, but also the diffusion coefficients of the analytes in the
membrane. The method of determining the diffusion coefficients is
based on the fact that the chromatographic retention time and the
profile of the eluting peaks are functions of the partition coefficient
of the analyte between the carrier gas and the stationary phase and
the diffusion coefficients of the analytes in the stationary phase
and the mobile phase among many other variables [124]. Cankur-
taran and Yilmaz determined the enthalpy and entropy parameters
for selected n-alkanes in PDMS, a method which could be useful
when determining the variations of the calibration constants of
PDMS-based sampling techniques with temperature [125]. Zhao
et al. demonstrated the applicability of IGC for the determina-
tion of the diffusion coefficients of various n-alkanes in crosslinked
PDMS [126]. Kloskowski et al. determined the partition coefficients
of many environmentally important volatile organic compounds
using this method [127].
The research into the WMS sampler described earlier also indi-
cated that the permeability of PDMS followed Arrhenius-type
relationship as discussed in Section 2.4 [25]. Further, because of
the hydrophobicity of PDMS, it was also shown that the permeabil-
ity was mostly independent of the humidity of the gaseous sample
[25].
A different configuration of a PDMS-based permeation passive
sampler developed at the Gdansk University of Technology (GUT)
was used extensively for sampling various volatile organic com-
pounds from indoor and outdoor air. The applications of the GUT
sampler were reported in various publications [128–131]. Bicchi
et al. introduced a modified SBSE device (called dual-phase SBSE)
which contained a small cavity between the magnetic stir bar and
the PDMS phase [132]. The cavity could be filled with different
types of sorbent and the device then functions very similar to the
WMS or the GUT sampler as a permeation passive sampler. While
the WMS, GUT and the dual-phase SBSE devices use a sorbent as
the receiving phase to maintain the concentration gradient across
the PDMS membrane, Janska et al. used acetonitrile sealed in a
PDMS tube as the receiving phase (termed by them as “solvent in
silicone tube extraction” (SiSTEx)) [133]. In this method, analytes
first permeate from the aqueous phase through the PDMS walls
of the tubing and partition into acetonitrile. Janska et al. used this
method to quantify various organophosphorous and organochlo-
rine pesticides in fruits and vegetables using GC/pulsed flame
photometric and halogen specific detectors [133]. It is important to
realize that the solvent in the tube permeates out of the tube and
its presence alters the solubility property of the PDMS walls allow-
ing extraction of relatively polar analytes [134]. A similar design,
but termed as “silicon membrane sorptive extraction (SMSE)” was
employed by Van Hoeck and co-workers who used ethyl acetate as
the PDMS polarity modifier. They demonstrated its applicability for
the quantification of atrazine and its three metabolites [134].
4.2. Membrane inlet mass spectrometry (MIMS)
PDMS is perhaps the most widely used material in membrane
inlet mass spectrometry (MIMS). In MIMS, a membrane is used as an
interface between the sample and the mass spectrometer. Sample
introduction into the instrument is achieved by permeation occur-
ring continuously through the polymer membrane. The device was
pioneered by Hoch and Kok in 1963 [135]. Generally, a vapor or
liquid phase sample is passed across one side of the membrane
continuously, and the permeating analytes are introduced either
directly into the ion source of the mass spectrometer, or indirectly
with a secondary sweep gas flowing into the ion source [136]. As
opposed to other techniques described thus far in the article, MIMS
can be used for continuous (online) monitoring of organic com-
pounds in the sample, or in offline mode. PDMS-based MIMS has
been used for the analysis of various compounds in air, water and
other matrices. A brief summary (not intended to be exhaustive) is
presented in Table 2.
A recent application of MIMS using PDMS was reported by
Tremblay et al. for on-line determination of compound-specific
isotope ratio in environmental analysis [151]. The ability of the
gas chromatography–isotope ratio-combustion-mass spectrome-
try (GC–IR-C-MS) used for the purpose to accurately determine
the isotope ratio in a sample is critical, and hence it is important
to determine any isotope fractionation happening in the perme-
ation process involved in MIMS. Tremblay et al. found that there
was no statistically differentiable isotopic fractionation for CO2 ,
but the permeated formaldehyde had a C13 enrichment resulting
in an increase in ı13 C by 1.0026 ± 0.0003‰. Since GC–IR-C-MS is
a highly promising technique and PDMS is one of the most widely
used materials for sample preparation, it is perhaps critical for more
 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62
Table 2
Applications of MIMS with PDMS membranes.
Description
Selected aromatic hydrocarbons, alcohols, and ketones in
air
Toluene, phenol, chloroform and chlorobenzene and
selected primary and secondary alcohols in aqueous
solutions
Benzene, toluene, ethylbenzene, m-xylene and other
volatile organic compounds in water and sewage from a
chemical plant
Methanol, H2 S, dimethylsulphide, benzene, chloroform,
1,4-dioxan, toluene and other gases in water
Benzaldehyde and 1,1-dichloroethylene in aqueous
solution
Benzene and selected alkyl substituted benzenes,
halobenzenes, and iodoalkanes in air
Flavour components such as methyl salicylate and
3-phenyl-2-propenal in human breath
Butane in air
Oxygen and carbon dioxide respiration rates of minimally
processed potato and broccoli
Online monitoring of the fermentation process: ethanol,
H2 and CO2 in the liquid phase, and H2 and CO2 in the
gas phase
Volatile organic compounds in air including halogenated
and aromatic hydrocarbons
Quantitation of anti-depressants, pain relievers, epileptic
medicine and anti-histamines in tablets
Volatile organic compounds in air
Volatile organic compounds in sea water
Enzyme modified PDMS for low volatility and hydrophilic
esters
Methanethiol, di-Me sulfide, carboxylic acids,
4-methylphenol, aldehydes, indole, and skatole from
biological livestock ventilation system
research to be done in the area of determining isotopic fractionation
accompanying partitioning and permeability processes.
4.3. Membrane extraction with a sorbent interface (MESI)
When MIMS was first introduced, the system was designed in
such a way that the permeated analytes entered the ion source
directly because of the vacuum conditions inside the instru-
ment [135]. The MESI technique developed by Pawliszyn and
co-workers allowed membrane introduction to be used on-line
with GC equipped with arbitrary detectors. In MESI, analytes
passing through a membrane connected in line with a gas chro-
matograph are swept by the carrier gas to a suitable trap, where
they are enriched. This can be done by cryogenic focusing or by
trapping the analytes with a thermally desorbable sorbent [152].
In either case, the focused analytes are introduced periodically into
the GC column by rapidly heating the segment containing the pre-
concentrated analytes. The use of PDMS for extraction was retained
in this method. Both flat PDMS membranes and PDMS tubing were
used for the purpose [152,153].
Yang et al. described a detailed kinetic model for the extraction
of organic compounds from headspace using MESI with PDMS tub-
ing and showed that it was in agreement with the experimental
results obtained for the extraction of benzene from water [154].
Guo and Mitra provided a theoretical analysis of non-steady-state,
pulse introduction MESI which included boundary layer effects
involved in the permeation process [155]. Since the permeation
rate is dependent on the velocity of the stripping phase and tem-
perature of the PDMS membrane, Liu et al. devised a method to
account for this variation [24]. In this method, they used a calibrant
in the stripping gas which permeated out into the sample matrix;
the amount permeated depended on the stripping gas velocity and
membrane temperature. The non-permeated calibrant was sorbed
59
Table 3
Applications of PDMS-equipped MESI techniques.
Reference Application Reference
[26] Benzene in the headspace of aqueous solution [154]
Ethylene in human breath using online technique [24]
[137] Organochlorine and aromatic hydrocarbons in water [156]
Acetone in human breath [157]
Semi-volatile organic compounds (PAHs) in air using [158]
[138] MESI-ion mobility spectrometry
Pheromones in water by MESI-ion mobility spectrometry [159]
Analysis of methane and ethane in human breath [160]
[139] Biogenic volatile organic compounds emissions (including [161]
␣-pinene, eucalyptol and ␥-terpinene) from eucalyptus
[140] dunnii
Thermooxidative degradation products of polystyrene [162]
[22] Benzene, toluene and xylenes in aqueous solutions and [153]
chloroform in tap water
[141]
[142]
in the sorbent interface, and its amount (along with the knowl-
[143]
edge of the original concentration in the stripping phase) could be
[144] used to correct for the variation in permeation rate due to temper-
ature and flow effects. Selected applications of MESI using PDMS
are listed in Table 3.
[145]
[146] 5. Applications of PDMS in lab-on-a-chip devices
[147]
One of the growing areas in analytical chemistry is the develop-
[148]
[149] ment of lab-on-a-chip (LOC) devices which utilize a combination
of mechanical, optical and electrical properties of PDMS [8]. Even
[150] though silicon was used successfully during the initial periods of
development of LOCs, alternatives were researched because of high
demand, bio-compatibility requirements, lower production costs,
and optical characteristics. PDMS is optically transparent down to
300 nm, isotropic and homogeneous, and is easily processed using
soft lithography techniques. Consequently, PDMS is one of the most
widely used polymers for the fabrication of the LOC devices and
microelectromechanical systems (MEMS). LOCs found numerous
applications in the bio-analytical field, especially in genomics and
proteomics. The disadvantages of PDMS for some applications have
also been recognized. For example, filling microchannels with a
hydrophilic aqueous solution is difficult due to the hydrophobicity
of the PDMS surface, and its use in electrophoresis is not practical
because of the uncharged surface [163].
LOCs are generally micro-channel systems connected to liquid
reservoirs and designed to allow chemical species and solvents to
pass through them. Various analytical steps including sampling,
pre-concentration, filtering, mixing, separation, isolation and anal-
ysis can be performed with them. Rondelez et al. used LOCs to
study femtoliters of a sample solution to measure the activity of
single molecules of ␤-galactosidase and horseradish peroxidase
and showed the technique’s usefulness in ultra-sensitive bioassays
[164]. Quake and Scherer used PDMS-based LOC to directly measure
fluorescence and sort DNA molecules [165]. Viriyatanavirote et al.
demonstrated the use of PDMS microchip capillary electrophoresis
for the determination of thiol compounds using a pulsed amper-
ometric detection system [166]. Abram and Clague used a PDMS
microchip for pre-treatment of a bovine serum sample prior to
detecting biomarkers of interest [167]. Yang et al. reported the use
of PDMS-quartz microchip-based capillary electrophoresis method
for qualitative and quantitative analysis of protein–DNA interac-
tion using electrokinetic sample injection method [168]. Cho et al.
reported the development of a low-cost biochip to perform DNA
polymerase chain reaction (PCR) and successfully performed PCR
analyses of the sex-determining Y chromosomes (SRY) gene and
mouse glyceraldehyde 3-phosphate dehydrogenase (GAPDH) gene
in less than 54 min [169]. Liu et al. incorporated an optical fiber
for fluorescence detection in a PDMS electrophoresis micro chip
60 S. Seethapathy, T. Górecki / Analytica Chimica Acta 750 (2012) 48–62
and showed its use in the separation of most segments of test
DNA markers [170]. A MOSFET-type biosensor was incorporated
on a PDMS micro-fluidic channel by Shin et al. for the detection of
biomolecules and was tested using thiols as test compounds [171].
The same group also developed a PDMS micro-chip for performing
PCR [172]. Schoening et al. used PDMS/glass capillary electrophore-
sis combined with amperometric detection for the analysis of
catecholamines and dopamine [173]. Ros et al. demonstrated the
application of a PDMS microdevice to detect as low as 100 fmol
of fluorescein. They also showed that the device could be used for
the detection of a single DNA molecule [174]. Huang et al. used a
chemiluminescence detection system combined with PDMS/glass
micro-chip electrophoresis and showed that it could detect as low
as 5 × 10−11 mol L−1 of cobalt (II), which at that time was four orders
of magnitude lower than any known method reported in the liter-
ature [175]. With their model of hybrid PDMS/glass micro-chip,
Sanders et al. demonstrated the molecular diagnostic analysis of a
variety of DNA samples for Duschenne Muscular Dystrophy and
cytomegalovirus (CMV) infection [176]. Development of LOCs is
happening rapidly and will likely continue at the same or higher
rate in future.
A combination of partitioning and optical properties of PDMS
has also been exploited for its use as sensors in spectroscopic tech-
niques. An investigation of the near infrared spectrum of PDMS
indicates intense absorption bands at 1184, 1402 and 1690 nm
(contributed by the methyl groups of PDMS) and provides oppor-
tunities for use of some of the remaining NIR region for various
purposes [177]. Albuquerque et al. used this property to devise a
PDMS-based sensor for sampling BTEX in water, which was quan-
tified using the CH stretching absorption bands (1140–1150 nm) in
the aromatic hydrocarbons [177]. Similarly, Lima et al. used PDMS
rods for sampling and quantitation of benzene, toluene and xylenes
in water using the NIR region for absorption measurements com-
bined with multivariate calibration techniques [178]. Howley et al.
established that PDMS has a suitable spectral window in the mid-
infrared region and used this property to develop a PDMS-coated
sapphire fiber sensor for the quantification of aliphatic and aro-
matic hydrocarbons in water [179].
6. Miscellaneous applications of PDMS in the analytical
laboratory
Highly cross-linked PDMS (along with modifiers) is very stable
at high temperatures and hence has been used widely for the man-
ufacturing of septa used in gas chromatography inlets. Since the
process of sample injection in GC involves coring of the septum,
it is sometimes unavoidable that PDMS particles are introduced
into the liner. When such coring happens, the PDMS particles in
the liner often result in non-ideal chromatography, manifested by
tailing peaks.
Chromatographic vials typically use septa made of PDMS and
modifiers. This allows for easy puncturing of the septum with a
syringe needle to draw the sample contained in the vial. How-
ever, since PDMS readily sorbs various analytes, septa coated with
a thin film of PTFE are normally used to avoid such sorption issues.
In many cases, a single puncture of the PTFE-lined septum while
taking a sample with a syringe exposes the PDMS to the sample
vapor, which might affect the analyte concentration in the sample
contained in the vial. The best practice is therefore to change the
septum whenever the sample requires prolonged storage for future
use.
High molecular weight silicone grease (containing PDMS as one
of the components) is used widely for sealing mass spectrometry
analyzer chambers in many models. High molecular weight frac-
tion with very low vapor pressure is used to ensure that little to
no vapors are present, as they could produce artifacts in the mass
spectrum. At the same time, the highly homogenous and viscous
material aids in proper sealing of the chambers.
In many laboratories, heating glass flasks for purposes such as
distillation is often done by immersing them in PDMS-based sil-
icone fluid. Because of the high heat stability of silicone oils, no
offensive off-gassing occurs while heating the flasks for various
purposes. Gloves made of silicone or PDMS are widely use for han-
dling hot materials.
7. Future perspectives
The prerequisites for the application of polymeric materials such
as PDMS are the knowledge of their fundamental properties, as
well as cost-effective, reliable manufacturing. PDMS can be man-
ufactured today in a highly reproducible manner, hence it is not a
challenge anymore for reproducibility in quantitative work. In the
last decade, extensive fundamental studies have been carried out
ranging from simple measurements of sorption and permeability
properties to complicated neural network modeling to understand
the structure–property relationship between a chemical species
of interest and PDMS. More such studies need to be done as they
have the ability to predict the applicability of PDMS for analytical
purposes.
To the best of our knowledge, only the hydrophobic properties of
PDMS have been exploited in the field of sample preparation and
chromatographic separation. Many surface treatment procedures
such as oxygen plasma, ultraviolet light, corona discharge etc., have
the ability to render the surface of PDMS hydrophilic and could
potentially open new avenues in sampling and sample prepara-
tion of hydrophilic compounds as well [180]. Hydrophilic surfaces
have also been modified permanently by attaching polar chemical
groups to further obtain selective sorption properties [171]. Nev-
ertheless, the dominant trend in dealing with analytes that are not
easily handled using PDMS is to use alternative polymeric mate-
rials. As an example, the use of various membrane materials in
sampling has been reviewed by Seethapathy et al. [10].
In the field of PDMS fabrication, equipment such as spin coaters
required for the manufacturing of membranes with reproducible
and accurate geometric parameters is available at affordable prices.
This might not only allow researchers to obtain reliable data, but
also reduce the time and money involved in the research. Fabri-
cation based on soft lithography has matured, hence PDMS-based
LOCs will likely dominate the development of the field in the next
decade.
8. Summary
PDMS has been used extensively for various purposes in
analytical chemistry since its invention. Its main uses include
chromatographic separations and sample preparation for organic
analytes in various matrices such as air, soil and water. Owing to its
favorable properties, the use of PDMS in LOC devices is increasing
very fast, and various groundbreaking accomplishments have been
reported in this area. Fundamental properties of PDMS are being
researched aggressively, which will likely result in further uses of
PDMS in many analytical applications.
Acknowledgements
The authors wish to thank MITACS elevate postdoctoral schol-
arship and NSERC Canada for financial assistance.
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