JOURNAL OF COLLOID AND INTERFACE SCIENCE

ARTICLE NO.

185, 538547 (1997)

CS964637

The Adsorption of Poly(vinyl alcohol) to Biodegradable Microparticles

Studied by X-Ray Photoelectron Spectroscopy (XPS)
KEVIN M. SHAKESHEFF, CARMEN EVORA,1 ISABEL SORIANO,1

AND

ROBERT LANGER2

Department of Chemical Engineering, Massachusetts Institute of Technology, E25-342, 45 Carleton Street, Cambridge, Massachusetts 02139
Received July 15, 1996; accepted October 7, 1996

The design of biodegradable microparticle drug delivery systems

with precisely tailored surface properties requires surface analytical methods that can relate polymer chemistry and fabrication
parameters to the final surface chemistry of the microparticles.
We demonstrate using X-ray photoelectron spectroscopy (XPS)
that it is possible to identify significant variations in the surface
chemistry of microparticles composed of poly(lactic acid) (PLA),
poly(lactide-co-glycolide) (PLGA), or block copolymers of PLA
or PLGA with poly(ethylene glycol) (PEG). These variations are
related to the mechanism by which the microparticle/water interface is stabilized. This, in turn, is controlled by the interfacial
surface tensions of the polymers within aqueous environments.
For PEG containing block copolymers, adsorption of a surfactant,
poly(vinyl alcohol) (PVA), from the aqueous medium onto the
polymer is reduced compared with the PLA and PLGA polymers.
This reduction is achieved because the PEG segments, within the
copolymer structure, stabilize the polymer/water interface. Estimates of the relative amounts of lactide, lactide-co-glycolide, vinyl
alcohol, and ethylene glycol monomer units at the microparticle
surfaces are presented based on curve-fitting analysis of the XPS
data. q 1997 Academic Press
Key Words: Poly(lactic acid) (PLA); poly(lactide-co-glycolide)
(PLGA); poly(ethylene glycol) (PEG); poly(vinyl alcohol) (PVA);
X-ray photoelectron spectroscopy (XPS); microparticles.

INTRODUCTION

There is considerable interest in developing biodegradable

microparticles that can deliver drugs to specific organs or
tissues following intravenous administration or inhalation
(13). A major obstacle to this development is the phagocytosis of microparticles by the reticulo-endothelial system
(RES) of the body. As a consequence of this phagocytosis,
injected microparticles are rapidly removed from the circulation by the mononuclear phagocytosis system (MPS) of the
liver (4) and inhaled microparticles are engulfed by alveolar
macrophages (5).
1
Permanent address: Department of IngenierB a QuB mica y TecnologB a
Farmaceutica, Facultad de Farmacia, Universidad La Laguna, 38200 La
Laguna, Spain.
2
To whom correspondence should be addressed.

538

0021-9797/97 $25.00
Copyright q 1997 by Academic Press
All rights of reproduction in any form reserved.

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Phagocytosis is initiated by protein adsorption to the microparticle surface and it has been proposed that the reduction of this adsorption or the alteration of the composition
of the adsorbed protein layer may provide a general method
of avoiding phagocytosis by the RES. Attention has, therefore, been directed towards methods of engineering microparticle surfaces with the aim of controlling protein adsorption events. A highly successful approach to achieve this
surface engineering is the adsorption of a hydrophilic material to the microparticle surface (69). Early studies in this
field concentrated on the use of poly(ethylene glycol)
(PEG)poly(propylene oxide) (PPO) block copolymers to
coat polystyrene particles (6, 7). For example, Illum et al.
demonstrated the reduction of RES uptake of poloxamine
coated microparticles and, hence, extended residence times
in the vascular compartment (6). Recently, block copolymers
of PEG and poly(lactic acid) (PLA) have been physically
entrapped in poly(lactide-co-glycolide) (PLGA) microparticle surfaces giving these biodegradable microparticles the
same ability to avoid the RES (8, 9). Adsorption of proteins,
such as albumin, to PLGA microparticles also significantly
decreases phagocytosis (10, 11).
An alternative approach to polymer adsorption is the incorporation of hydrophilic block segments into the backbone
structure of the biodegradable polymer used for microparticle fabrication (12, 13). Gref et al. have described the use
of PLAPEG block copolymers to produce nanoparticles
with dramatically altered body distribution as compared to
PLA only particles (12). Encouraging results have also been
reported using these copolymers to produce micelle-forming
delivery systems (13). The two approaches of hydrophilic
material adsorption and chemical incorporation may also be
combined to optimize surface properties (14).
To develop an accurate understanding of the role of surface chemistry in the biodistribution of microparticulate drug
delivery systems there is a need for detailed surface analysis
(15). A number of surface specific techniques are available
for this analysis, including contact angle measurement (16),
static secondary ion mass spectrometry (SSIMS) (17) and
X-ray photoelectron spectroscopy (XPS) (18). The applica-

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tion of these techniques in biomaterial research has been

reviewed (1921).
The potential of XPS and SSIMS to record the relationship
between microparticle fabrication parameters and surface
chemistry has been demonstrated. SSIMS can provide qualitative or semi-quantitative data on the molecular species
present on particle surfaces. Examples of the use of SSIMS
in this area include the study of surfactant adsorption to
poly(b-hydroxybutyrate) by Koosha et al. (22) and the identification of immobilized sugar units at the surface of a colloidal system (23). XPS analysis can provide quantifiable
data on biomaterial surface chemistry (24). For example,
Brindley et al. recorded an increase in the contribution of
poly(ethylene oxide) (PEO) chains to the overall surface
chemistry of polystyrenePEO copolymer particles as the
proportion of PEO monomer in the polymerization mixture
was increased (25). Quantification was achieved by comparison of the intensity of the C{O carbon environment (unique
to PEO chains) and C{C/C{H carbon environments
(unique to polystyrene). XPS has also been extensively employed in the analysis of particles composed of copolymers
of methacrylate-based monomer units (26, 27). These studies
have demonstrated the ability of XPS to measure the enrichment of the surface of the particles with one of the constituent monomers, hence providing an insight into the mechanism of surface stabilization during colloid preparation.
The surface chemistry information provided by the XPS
analysis of microparticles is of particular significance as researchers strive to design microparticle surfaces of increased
complexity. In the present study, we use XPS analysis to
measure the degree of surfactant adsorption to PLA, PLGA,
PLAPEG, and PLGAPEG microparticles. The surfactant,
poly(vinyl alcohol), (PVA) is frequently used as a stabilizer
in microparticle fabrication. We are specifically interested
in investigating whether PVA coats the surfaces of the PEGcontaining block copolymers. Ideally, we wish to develop
methods of microparticle fabrication in which particle stabilization is achieved by the PEG segments of the biodegradable polymer. These PEG segments decrease the amount of
phagocytosis of the microparticles more successfully than
adsorbed PVA layers. In addition, by minimizing the extent
of PVA adsorption, we are able to control the surface chemistry of the microparticles via the chemical structure of the
biodegradable polymer rather than the surface chemistry being imposed by the fabrication procedure.
METHODS

Polymer Materials and Synthesis

Lactide was purchased from Aldrich Chemical Company,
Inc. (Milwaukee, WI). Glycolide and poly(vinyl alcohol)
(Mw 25 kDa, degree of hydrolyzation of 88 mol%) were
obtained from Polysciences (Warrington, PA), monometh-

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TABLE 1
Summary of Polymer Molecular Weight
and Microparticle Size Analysis
Particle size analysis (mm)

Sample

Average
molecular
weight (kDa)

10th
percentile

Median

90th
percentile

PLA (small particles)

PLA (large particles)
PLGA
PLAPEG
PLGAPEG

100
100
100
84.6
91.7

16.8
47.9
21.2
21.2
26.5

12.1
36.1
10.8
15.1
15.5

5.99
19.7
5.2
4.8
8.1

oxy PEG (20 kDa) from Shearwater Polymers (Huntsville,

AL). Stannous octoate was obtained from Sigma Chemical
Company, Inc. (St. Louis, MO).
PLGA (Resomer RG 506) was purchased from Boehringer Ingelheim (Ingelheim am Rhine, Germany). L-PLA
was purchased from Sigma Chemical Company, Inc. (St.
Louis, MO).
Block copolymers of PLA or PLGA with PEG were synthesized by ring opening polymerization of lactide or lactide
and glycolide (3:1 weight ratio) respectively in the presence
of monomethoxy-PEG (4:1 weight ratio) and stannous octoate as catalyst (12). The PEG segments had molecular
weights of approximately 20 kDa.
Polymer molecular weights were determined by gel permeation chromatography (GPC), the composition by 1HNMR and the relative proportions of block segments were
assessed by 13C-NMR. Molecular weight data is summarized
in the table in Table 1.
Microparticle Preparation
Two sizes of microparticles were prepared by a modified
double emulsion method (28). In brief, large microparticles
(median diameter of 36.1 mm) were prepared by adding 1
ml of water into 2 ml of a methylene chloride solution containing 100 mg of the polymer. The mixture was emulsified
by sonication for 68 seconds at output 3 (Vibra Cell Model
VC-250, Sonics & Materials Inc., Danbury, CT) in an ice
bath to form the first water-in-oil emulsion. This emulsion
was poured into 100 ml of an aqueous PVA solution (1%)
and was mixed by a homogenizer (Silverson L4R) at 6000
rpm for two minutes. This produced the second emulsion
with a composition of (water-in-oil)-in water.
Smaller microparticles (median diameter approximately
12 mm) were prepared by mixing 1 ml of water into 3 ml
of a methylene chloride solution containing 100 mg of the
polymer. The first emulsion was formed by sonication at
output 4 for 10 s in an ice bath. The resulting emulsion was
further emulsified in 4 ml of an aqueous PVA solution (1%)
by sonication at output 4 for 10 s and then diluted in 100

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SHAKESHEFF ET AL.

FIG. 1. C1s regions of XPS data for polymers in powder form: (a) PLA; (b) PLGA; (c) PVA; (d) PEG. Bold solid lines show the original XPS data.
Thin solid lines show the calculated curve from curve fitting. The calculated curve is obscured by the original XPS data curve when a good fit is achieved.
Dotted lines show the curves from individual carbon environments.

ml of an aqueous PVA solution (1%). The diluted suspension

was mixed by homogenization at 8000 rpm for 2 min.
Removal of the methylene chloride occurred by solvent
evaporation whilst the second emulsion was stirred magnetically for 2 h. Microparticles were then collected by centrifugation, washed three times and freeze-dried.
Microparticle size distribution analysis was performed using a Coulter Multisizer II (Coulter Electronic Limited, Luton, U.K.). Microparticles were suspended in isoton II solution (Coulter) using a Coulter type IA nonionic dispersant
and vortex mixing. The suspension was added to 50 ml
isoton II solution until the coincidence of particles was be-

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tween 5 and 10%. Approximately 100,000 particles were

counted. Particle size data is presented in Table 1.
X-Ray Photoelectron Spectroscopy (XPS)
Samples of each polymer, before microparticle fabrication, were analyzed in powder form. Each sample was
ground with a pestle and mortar immediately before XPS
analysis to generate fresh surfaces.
Samples of the microparticles were prepared on glass substrates by drop casting a 10 ml aliquot of a 100 mg/ml aqueous suspension of the microparticles. After approximately
12 h, the suspension had dried leaving a compact bed of

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541

FIG. 1Continued

particles that completely covered the substrate. Prior to polymer coating, the glass substrates were cleaned for 24 h in
a 1% solution of RBS 35 Detergent Concentrate (Pierce,
Rockford, Illinois) and rinsed with deionized water.
Spectra were obtained using a Surface Science Laboratories X-100 spectrometer employing a monochromatized
A1 Ka (1486.7 eV) X rays. Photoelectrons were analyzed
by a hemispherical multichannel detector in fixed analyzer
transmission mode. An electron flood gun (energy 5 eV)
was used to compensate for charging during XPS data acquisition. To assist the compensation a nickel mesh in electrical
contact with the spectrometer was placed approximately 1
mm over the samples. For all spectra presented in this paper
the X-ray spot size was 600 mm.
For all samples, a survey spectrum was recorded over a

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binding energy range of 0 to 1000 eV using a pass energy

of 300 eV. In all cases the survey spectra recorded the presence of only oxygen (O1s 533 eV) and carbon (C1s 285 eV)
at the surface. Detailed analysis of the C1s regions of each
sample was recorded over a binding energy range of 280 to
300 eV with a pass energy of 150 eV. Charge referencing
was performed using the C{H peak (285.0 eV) for PLA,
PLGA, and PVA samples. For PLAPEG and PLGAPEG
copolymer samples the position of the C{H peak was not
immediately identifiable and therefore the O{C|O peak
was used for charge referencing using the binding energy
obtained from the PLA data (289.12 eV). The total acquisition time per sample was 15 min. To prove that X-ray induced degradation of the samples did not occur, survey and
C1s spectra from a PVA film, a PLAPEG film and a

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SHAKESHEFF ET AL.

FIG. 2. C1s regions of XPS data for PLA microparticles (average particle diameter 12.1 mm). (a) Comparison of data for PLA powder (thin line)
and microparticles (bold line). (b) Curve fitting using peak labeling introduced in Fig. 1. (c) Extracted PLA components from (b). (d) Extracted PVA
components from (b).

PLGAPEG film were recorded after 30 min. of X-ray exposure. All these spectra were identical to the spectra recorded
after 0 min. X-ray exposure.
Curve fitting was performed using the manufacturer
supplied software. The general procedures for curve fitting have been described by Sherwood (29). A Gaussian
Lorentzian function with an 80% Gaussian component
was applied to all data. No asymmetry component was
introduced. Constraints imposed during curve fitting are

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described in the relevant sections of the Results and Discussion.

Underwater Contact Angle Measurement
Calculation of interfacial tension at the polymer-water interface (gSW) was performed using the methods described in
detail by King et al. (30) and first proposed by Hamilton
(31). In brief, this involves measuring the underwater contact

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angle of octane (saturated with water) (uoct) and air (uair).

Using the method of measurement adopted by King et al.
(30) the contact angle is the external angle of the octane or
air drop. From uoct and uair it is possible to calculate the
polar (gpSV) and dispersive (gdSV) components of the interfacial tension at the polymer-water vapor interface (gSV) using
the equations
gpSV

50.5rKoct
,
50.5 0 Koct

where
Koct

gLWrcos uoct / gWV 0 gLV

4

gLW, the octane/water interfacial tension 50.5 dyn/cm at 257C

gWV, the water/air interfacial tension 72.1 dyn/cm at 257C
gLV, the octane/air interfacial tension 21.6 dyn/cm at 257C

gdSV

gdWVrKair 0 gpSV{gdWVgpWV/(gpSV / gpWV)

,
gdWV 0 Kair / gpSV{gpWV/(gpSV / gpWV)

where
gWV(1 / cos uair)
4

Kair

gdWV 21.6 dyn/cm and gpWV 50.5 dyn/cm.

Addition of gpSV and gdSV gives the interfacial tension between

the polymer and water saturated air (gSV). This value is then
substituted into the harmonic mean equation, shown below,
to give an estimate of gSW, the polymerwater interfacial
tension:

gSW gSV / gWV 0 4

d
SV
d
SV

D S

g gdWV
gpSVgpWV
04 p
.
d
g / gWV
gSV / gpWV

Underwater contact angles were measured using a VCA

2000 Video Contact Angle System (Advanced Surface Technology, Inc., MA). Samples were prepared by dip coating a
glass slide in a 10 mg/ml chloroform solution of the polymer.
Polymer films were dried for 1 h under laboratory conditions.
Angles were recorded after the polymer film had been exposed to water for 30 min. Three samples of each polymer
were studied and five contact angles were measured per
sample.
RESULTS AND DISCUSSION

PLGA and PLA Microparticles

As a first step in the XPS analysis we consider the carbon
(C1s) regions of the four basic polymer structures encoun-

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543

tered in this study; PLA, PLGA, PVA, and PEG. The C1s
spectra of these polymers are presented in Fig. 1, along with
their chemical structures. All four spectra are in agreement
with previously published work (32). The tables in Fig. 1
summarize the peak assignments and shows the theoretical
and experimental relative percentage of each carbon environment. The numbers assigned to each peak will be used to
identify the presence of these carbon environments in the
analysis of data for the microparticles.
For PLA, we observed the expected three peaks of near
equal area corresponding to the ester group (peak 1, 289.12
eV), the methine group (peak 2, 287.05 eV), and the methyl
group (peak 3, 285.00 eV). These three peaks are again
present in the spectrum of PLGA with peak 3 having the
lowest relative area due to the glycolide monomer possessing
only ester and methylene groups. The XPS spectrum of PVA
shows the expected presence of three carbon environments
with 95.0% of the peak area contributed by the methine a
to the hydroxy (peak 5, 286.4 eV) and methylene (peak 6,
285.00 eV) groups. The remaining 5.0% of the C1s region
is derived from the nonhydrolyzed acetate groups (peak 4,
289.12 eV). The poly(vinyl acetate) groups present in the
PVA are important because they increased the surface activity of the material. The XPS data for PEG shows one peak
from the ether carbons (peak 7, 286.4 eV). It is noticeable
that the methine groups of PLA and the methylene groups
of PLGA (peak 2) are shifted /0.6 eV compared to the
methine a to the hydroxy group of PVA (peak 5) and the
ether group of PEG (peak 7) due to the secondary shift from
the adjacent ester.
The analysis of PVA adsorption during microparticle formation by XPS is complex due to the PVA C1s spectra
sharing a number of peaks with the PLA, PLGA, and PEG
C1s spectra. However, with careful curve fitting, it is possible to estimate the relative contribution of the different polymers to the microparticle surface chemistry. The first example, the analysis of PLA microparticles with median diameters of 12.1 mm, will be described in detail to explain the
curve-fitting procedure.
The data in Fig. 2a compares the carbon regions of the
PLA microparticles and the original powder. From this data,
without curve fitting, it is possible to make a number of
qualitative statements about the differences in surface chemistry between the samples. The curve for the microparticles
displays a significantly increased intensity in a region from
285.00 to 286.5 eV as compared to the PLA microparticles.
This suggests that PVA adsorption has occurred to stabilize
the polymer/water interface during microparticle preparation
because the presence of PVA adds intensity at binding energies of 285.00 and 286.4 eV.
Based on this initial assessment, curve fitting was performed using the peaks expected for PLA and PVA; peaks
1 to 3 for PLA and peaks 4 to 6 for PVA. Although peaks
1 and 4, and 3 and 6, are found at identical binding energies

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SHAKESHEFF ET AL.

carbon region XPS data. An example of this data is shown

in Fig. 4. These microparticles had a median diameter of
10.8 mm, a similar diameter to that of the smaller PLA
microparticles. The XPS analysis revealed the presence of
approximately 50% vinyl alcohol monomer units to 50%
lactic acid monomer units at the surface. In comparison with
the values obtained for the 12.1 mm median diameter PLA
particles, the PLGA microparticles have adsorbed less PVA.
This may be expected from the slight increase in hydrophilicity of the PLGA over PLA.
PLGAPEG and PLAPEG Block Copolymer
Microparticles

FIG. 3. C1s regions of XPS data for PLA microparticles (average particle diameter 36.1 mm).

we have kept these peaks separate to highlight the presence

of two different monomer units at the surface. The relative
areas of peaks 1 to 3 were constrained to the same values
recorded for the PLA powder (see Fig. 1) and, similarly,
peaks 4 to 6 were constrained based on the relative areas of
the peaks in the C1s regions of the PVA powder (see Fig.
1). Initially, the full width at half maximum values (FWHM)
(i.e., the peak widths) were fixed for all peaks based on
the XPS data of the powders. Using these constraints, the
curve fitting procedure involved varying the relative proportion of PLA and PVA components. After the best fit had
been calculated, the FWHM values were allowed to vary by
{0.2 eV.
The data in Fig. 2b shows the curve fit for the PLA microparticles and to clarify the relative importance of the PLA
and PVA components their corresponding peaks have been
plotted separately in Figs. 2c and 2d. This analysis reveals
that the surface of these microparticles is composed of approximately 44% lactide monomers and 56% vinyl alcohol
monomers.
An identical curve fitting procedure was performed on the
C1s region data of the PLA microparticles of 36.1 mm median diameter. This data is shown in Fig. 3. Analysis of the
area under the curves of the PLA and PVA components
gives an estimate of the relative percentage of lactide and
vinyl alcohol monomer units at the microparticle surface to
be 55% lactide to 45% vinyl alcohol. Therefore, using XPS
analysis it has been possible to directly measure the increased adsorption of the PVA surfactant to the PLA surface
resulting from the decrease in microparticle average size.
This PVA adsorption increase is driven by the formation of
a larger surface area during small microparticle formation.
The presence of PVA on PLGA microparticle surfaces
can also be clearly identified by careful curve fitting of the

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It was anticipated that the presence of the hydrophilic

PEG block in the copolymer structure would strongly influence the surface chemistry changes occurring as a result of
stabilization of the polymerwater interface during microparticle formation. There are two possible routes of stabilization for these block copolymers. The first possible route of
stabilization would be PVA adsorption from the aqueous
phase, as was recorded for the PLA and PLGA microparticles. Secondly, stabilization could be inherent in the surface
properties of the microparticles due to the presence of the
PEG blocks at the polymerwater interface.
As with the analysis of the PLA and PLGA microparticles,
we first consider the XPS data of the block copolymers in
powder form. The XPS data of the C1s regions of the PLA
PEG and PLGAPEG block copolymers are presented in
Fig. 5. Both sets of data reveal the presence of four peaks.
Peaks 1 to 3 result from the PLA or PLGA block. The other
peak, centered at approximately 286.3 eV and labeled peak
7, results from the PEG block. The summary data in Fig. 5
shows that the experimentally calculated percentages of
PLA, PLGA and PEG components are very close to the
theoretical values based on all the carbon environments being present in their stoichiometric ratios.

FIG. 4. C1s regions of XPS data for PLGA microparticles.

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545

FIG. 5. C1s regions of XPS data for (a) PLAPEG and (b) PLGAPEG powders.

The XPS data of the C1s region of the PLAPEG microparticles is shown with the data from the original powder in
Fig. 6a. It is noticeable that the two curves are similar.
The only significant deviation occurs at a binding energy of
approximately 286.3 eV, where the microparticle surface
generates a higher intensity indicating an increase in the
contribution of PEG. Based on this comparison, we first
attempted to curve fit by assuming an increase in peak 7,
i.e., more contribution to the surface from the PEG, while
maintaining the same area ratios between peaks 1 to 3. This
means that we assume that none of the three carbon environments of PLA can enrich the polymer surface independently.
We believe this assumption to be reasonable given the short
separation between the carbon groups in the PLA structure.
We found that curve fitting based on only PEG surface enrichment, gave an excellent fit to the experimental data for
binding energies of 286 to 290 eV. However, the curve fit

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data slightly underestimated the experimental intensity at

approximately 285 eV to 286 eV. This suggests the need to
consider some degree of PVA adsorption. The curve fitting
data assuming both PEG enrichment and PVA adsorption is
shown in Fig. 6b. We obtained excellent agreement between
experimental and curve fit data based on relative monomer
concentrations at the microparticle surfaces of 58% lactide:
30% ethylene glycol:12% vinyl alcohol. This equals a lactide:ethylene glycol ratio of 1.9:1 compared to a ratio of
2.1:1 for the powder, indicating a slight enrichment of the
surface with PEG over PLA. Although, precise quantification of the XPS data is difficult due to the large number of
peaks required to consider the presence of the three different
polymers, we believe that the data strongly suggests that the
presence PEG chains at the polymerwater interface reduces
the extent of PVA adsorption.
Applying the same curve fitting procedure to the PLGA

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FIG. 6. C1s regions of XPS data for PLAPEG microparticles. (a) Comparison of data for PLAPEG powder (thin line) and microparticles (bold
line). (b) Curve fitting using peak labeling introduced in Fig. 1. (c) Extracted PLA components from (b). (d) Extracted PEG component from (b). (e)
Extracted PVA components from (b).

PEG microparticle data we obtained the graphs in Fig. 7.

Again, we were unable to fit the experimental data unless a
small contribution was made by the PVA curves. Calculating
the relative monomer concentration at the microparticle surfaces gave estimates of 56% lactide:32% ethylene glycol:11% vinyl alcohol. In agreement with the data from the
PLAPEG microparticles, these relative monomer contributions indicate a slight surface enrichment of PEG over PLGA
and a reduction of PVA adsorption of approximately 38%
compared to the PLGA microparticles.
Therefore, XPS analysis of PLA, PLGA, PLAPEG, and
PLGAPEG microparticles has revealed significantly different surface chemistries which appear to be explained by the
stabilization of the polymer/water interface by PEG segments in the copolymers. This stabilization decreases the

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FIG. 7. C1s regions of XPS data for PLGAPEG microparticles.

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TABLE 2
Contact Angle Data and Surface Tension Calculations
for PLA, PLGA, PLAPEG, and PLGAPEG Films

uoct
gpSW (dyn/cm)
uair
gdsw (dyn/cm)
gsv (dyn/cm)
gsw (dyn/cm)

PLA

PLGA

PLAPEG

PLGAPEG

817
20.5
667
21.3
41.8
12.6

647
28.4
477
27.6
55.9
6.9

297
44.5
247
21.6
66.0
0.4

167
48.6
157
20.9
69.5
0.1

need for PVA adsorption. This hypothesis is supported by

measurement of the interfacial surface tensions of thin films
of the polymers made within an aqueous environment. The
surface tension data is shown in Table 2. The data shows that
the PLAPEG and PLGAPEG block copolymer surfaces
display highly hydrophilic character with interfacial tension
values at the polymerwater interface of 0.4 and 0.1 dyn/
cm, respectively.
CONCLUSIONS

These studies show that XPS analysis provides a method

of differentiating the presence of PVA, PEG, and PLA
PLGA on microparticle surfaces. For PLA and PLGA microparticles, relatively high surface contributions from PVA
were evident. Comparison of the percentage areas of the
carbon environments in the XPS data enabled estimates of
the surface contribution from vinyl alcohol and lactide/lactide-co-glycolide monomers to be calculated.
For the block copolymers of PLA or PLGA with PEG
segments, the presence of PEG at the polymerwater interface during microparticle formation reduced the requirement
for PVA adsorption to achieve stabilization. This resulted
in a decrease in the contribution of vinyl alcohol monomers
from approximately 50% for the PLA/PLGA polymers to
approximately 11% for the block copolymers.
ACKNOWLEDGMENTS
This work was supported by NIH Grant HD29125. Kevin Shakesheff
acknowledges the support of the NATO Science Fellowship to North
America. Individual support was provided to Carmen Evora by the Spanish
Science and Education Ministry (reference no. R1-P3300) and to Isabel
Soriano by the Direccion General de Universidades del Gobierno Autonomo
de Canarias.

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