526 Biomacromolecules 2001, 2, 526-537

Surface Morphology of
Poly(caprolactone)-b-poly(dimethylsiloxane)-b-poly(caprolactone)
Copolymers: Effects on Protein Adsorption
M. A. Childs, D. D. Matlock, and J. R. Dorgan*
Chemical Engineering Department, Colorado School of Mines, Golden, Colorado 80401
T. R. Ohno
Physics Department, Colorado School of Mines, Golden, Colorado 80401 USA
Received January 2, 2001; Revised Manuscript Received March 5, 2001

Certain triblock copolymer surfaces have beneficial blood contacting properties that remain unexplained
from a mechanistic perspective. In this study, poly(caprolactone-block-dimethylsiloxane-block-caprolactone)
(PCL-b-PDMS-b-PCL) surfaces are characterized by dynamic contact angle analysis, angle-resolved X-ray
photoelectron spectroscopy (XPS), and phase detection imaging atomic force microscopy (AFM). Surface
morphology of films cast from 10 wt % MEK solutions are found to be semicrystalline possessing spherulites
on the micron scale and alternating semicrystalline PCL-rich and amorphous PDMS-rich lamellae on the
nanometer scale. Surface enrichment of the lower surface free energy block, PDMS, is observed using
angle-resolved XPS but the surface composition still consists of both copolymer blocks. Films cast from 1
wt % solutions showed similar morphologies but incomplete surface coverage. Different textural features
of adsorbed fibrinogen layers on coated and uncoated polypropylene are observed. The hypothesis that
patterned block copolymer surfaces can affect protein adsorption and thus influence compatibility is partially
supported by the findings of this study.

Introduction proteins profoundly alter adsorbed protein conformations,

Health complications arise when blood flows external to
its natural environment, the endothelium. Physiological
defense mechanisms include activation of platelets, comple-
ment, intrinsic and extrinsic coagulation systems. Thrombus
formation and positive feedback pathways within these
systems further antagonize the immune system and lead to
what is known as whole body inflammatory response. This
is true in particular, for external cardiopulmonary bypass
(CPB) patients whose blood circulates through vast, hostile
areas there exists the need for surfaces compatible with blood.
The majority of blood-contacting devices utilize polymeric
materials because of their inertness, good mechanical proper-
ties, low cost, and relative biocompatibility. Modification
of these surfaces is perhaps the simplest and most economical
method to further enhance biocompatibility. A novel ap-
proach to inhibit initial activation steps at the blood-
synthetic material interface involves using patterned block
copolymer surfaces.1 This approach exploits the heteroge-
neous structure of a cell membrane whose mobile glyco-
proteins and phospholipids can cluster to form microdomains
that serve to aid in transmembrane communication.2 It also
takes advantage of macromolecular domains of uniform
physicochemical properties, such as wetability and charge,
on the protein. It is hypothesized that microdomain-patterned
synthetic surfaces interacting with these specified areas of
* To whom correspondence should be addressed. e-mail: jdorgan@
mines.edu.
10.1021/bm0100054 CCC: $20.00
Published on Web 04/17/2001
thus disrupting signaling pathways.3
Block copolymers are unique in their ability to demonstrate
a myriad of complex morphologies that are characterized
by variously shaped and sized microdomains. Complex bulk
and surface morphologies arise when block copolymers are
synthesized from thermodynamically incompatible blocks.
Phase separation due to unfavorable monomer contacts or
block crystallization competes with minimization of chain
stretching associated with configurational entropy loss. The
result is a frustrated system from which microdomains arise,
with at least one domain dimension on the nanometer scale.4
Studies of block copolymers have demonstrated improved
biocompatibility through reduced platelet activation, de-
creased surface thrombogenicity, and other factors. Okano
and co-workers studied the copolymer synthesized from
hydroxyethyl methacrylate (HEMA) and dimethylsiloxane
(DMS). They concluded the most effective decrease in
platelet activation occurs when the domain size is roughly
10 nm. Poly(propyleneoxide) (PPO)-b-polyamide copolymers
have also been studied, and it was found, through X-ray
analysis, that domains between 6 and 12 nm were most
effective in decreasing thrombogenicity.5,6 Importantly, it has
even been found that, by optimizing the crystalline state of
pure polypropylene, interlamellar spacings of 11.3 and 10.8
nm minimize adsorption of rabbit serum albumin and rabbit
plasma fibrinogen, respectively.7 In contrast to earlier studies,
this later finding clearly points to the importance of patterning
and domain size as both crystalline and amorphous domains
of polypropylene are hydrophobic.
© 2001 American Chemical Society
Effects on Protein Adsorption
Figure 1. Structure of Tegomer and SMA triblock copolymers.
Siloxane-containing polymers have emerged in biomedical
applications owing to their reputed biocompatibility, low
glass transition temperature (Tg ) -127 °C), and oxidative,
thermal, and ultraviolet stability. An example of a triblock
copolymer in which a central string of amorphous PDMS is
linked to semicrystalline poly(caprolactone) (PCL, Tg ) -70
°C, Tm ) 73 °C) chains is shown in Figure 1; two structural
variations are shown. These are referred to according to their
commercial names of SMA and Tegomer. A previous study
by Lovinger et al. determined the morphology of bulk PCL-
b-PDMS-b-PCL triblock copolymers; crystalline PCL-rich
and amorphous PDMS-rich regions were found using X-ray
diffractometry, small-angle X-ray scattering, polarized optical
micrography, and transmission electron microscopy.8 How-
ever, these techniques reflect bulk properties and lack the
sensitivity required to resolve near-surface characteristics
important in biomedical applications.
In vitro studies indicate that compounding SMA into poly-
(vinyl chloride) (PVC) and coating polypropylene micro-
porous membranes with SMA enhance the biocompatibility
of these base polymers via suspending contact activation and
diminishing coagulation activity in human blood.9 A separate
study reports that this SMA lessens thrombin and fibrinogen
adsorption and platelet binding when blended into PVC. 10
Clinical evaluation involving examination of PVC tubing and
blood after CPB reveals markedly less prothrombin activation
and platelet deposition on the SMA-treated CPB circuit.11
A separate clinical study of CPB circuits prepared with SMA
shows patients’ blood sustaining platelets and resisting both
fibrinolysis and thrombin generation more than patients
undergoing CPB with untreated circuits.12
Results from these clinical studies demonstrate a signifi-
cant improvement in the biocompatibility of materials
modified with PCL-b-PDMS-b-PCL triblock copolymers.
Accordingly, there exists a strong motivation to study these
surfaces for the ultimate goal of achieving a deeper under-
standing of their biocompatibilizing mechanism. The present
study investigates the surface microstructure of SMA and
Tegomer films solution coated onto polypropylene substrates.
Several analytical techniques are employed including dy-
namic contact angle (DCA) analysis, angle-resolved X-ray
photoelectron spectroscopy (AR-XPS), and phase detection
imaging atomic force microscopy (PDI-AFM). All of the
techniques indicate that while the surface composition is
enriched in PDMS, the surface morphology is heterogeneous
and characterized by domains of both blocks.
Materials and Methods
Polypropylene plaques 8 × 3 cm2 in size were injection
molded and used for DCA analysis. Plaques were also cut
Biomacromolecules, Vol. 2, No. 2, 2001 527
into approximately 1 × 1 cm2 pieces, rinsed with deionized
water, and used as substrates.
Polycaprolactone (Aldrich, catalog no. 440752) having an
average molecular weight of 10 000 and poly(dimethyl-
siloxane) homopolymers were dissolved in reagent grade
methyl ethyl ketone (MEK) obtained from Fisher Scientific
(catalog no. M209-20).
Two PCL-b-PDMS-b-PCL triblock copolymers dif-
fering in molecular weight and linker groups were studied.
SMA (Thoratec Laboratories, Berkeley, CA) contains a
3200 PDMS midblock and two 2000 PCL end blocks.
Tegomer (Goldschmidt Chemical Co., Hopewell, VA) has
a 2700 PDMS midblock with 2000 PCL end blocks.
Molecular weights were determined by nuclear magnetic
resonance.
Homopolymer and triblock copolymer surfaces were made
by dip-coating polypropylene plaques into 1 and 10 wt %
solutions of copolymer in MEK. The plaques were dipped
in the appropriate solution for approximately 30 s, then
placed in a vacuum oven to dry for 24 h. Annealed samples
were achieved by placing samples in a vacuum oven at
approximately 55 °C for 24 h (i.e., above the block Tg’s but
below the Tm of the PCL block).
Dynamic contact angle analysis performed in this study
utilized a Cahn model DCA 312 analyzer, equipped with a
Wilhelmy balance. Immersion and withdrawals rates in the
present study were 40 µm/s, with top and bottom dwell times
of 0 s. Contact angles using HPLC grade water were
calculated from the second advancing (immersion) cycle at
room temperature. Five samples of each surface were
measuredseach reported contact angle has error bars span-
ning two standard deviations.
Angle-resolved X-ray photoelectron spectroscopy experi-
ments were performed with a Kratos AXIS HSi imaging
spectrometer. A monochromatic Al KR1,2 source was em-
ployed for all experiments and was operated at 15.0 mA and
14.0 kV. Base pressure was maintained at 5.0 × 10-8 Torr.
Identification of elements present was done by first perform-
ing wide energy range survey scans at high scan rates to
rapidly determine elements present, and then slower scans
were performed over the specific energy ranges for quanti-
fication of individual elements. Survey spectra with a binding
energy ranging from 0 to 1200 eV were collected at a takeoff
angle (measured from the substrate) of 90° and at a pass
energy of 160 eV. High-resolution acquisitions of carbon
1s, silicon 2p, and oxygen 1s regions were conducted at a
pass energy of 40 eV. All high-resolution measurements were
conducted with takeoff angles ranging from 90 to 10° in 10°
increments, which led to sampling depths ranging from 70
to 10 Å.13
Surfaces were imaged using a Nanoscope IIIa Extended
MultiMode AFM (Digital Instruments, Inc., Santa Barbara,
CA) and an AS-130V (“J” vertical) scanner. PDI-AFM was
performed in tapping mode using TESP-10 Nanoprobe SPM
tips, 125 µm in length, with a resonant frequency range of
292-322 kHz. All images were reproducible, acquired at
room temperature, and rastered at 512 × 512 pixels.
528 Biomacromolecules, Vol. 2, No. 2, 2001
Figure 2. DCA results for variously treated polypropylene substrates coated with 1 wt % polymer solutions.
Results and Discussion
The extent of surface enrichment of the PDMS block due
to its low surface free energy is easily investigated by DCA
analysis. If blooming of the PDMS block completely covers
the surface, the contact angles of SMA and Tegomer surfaces
should be the same as that of a PDMS homopolymer surface.
Alternatively, the copolymer values will be intermediate
between those characteristic of PDMS and PCL homopoly-
mer surfaces if blooming does not fill the surface. DCA
analysis performed on annealed samples detects changes in
near surface composition.
Figure 2 shows the contact angles for surfaces made by
solution casting 1 wt % homopolymer and copolymer
solutions; results for both as cast and annealed surfaces are
shown. In addition, measured contact angles for polypro-
pylene control plaques are presented. As expected, PDMS
is more hydrophobic than PCL. The data reveal that contact
angles for copolymer solution-coated substrates lie between
those coated with homopolymer solutions. It is important to
remark, however, that 1 wt % solution coatings do not always
fully cover the polypropylene substrate, as shown in the
PDI-AFM images and by the AR-XPS data presented
below. Interpretation of the DCA data is further complicated
since polypropylene control plaques have contact angles that
also fall intermediate between those coated with homopoly-
mer solutions; contact angle values for 1 wt % copolymer
solution-coated surfaces may be intermediate between the
homopolymer values simply because polypropylene is ex-
posed at the surface.
Annealing of the 1 wt % solution-coated surfaces results
in contact angles within the standard deviations of the
respective untreated samples. This indicates that all surfaces
are stable and remain unaltered throughout the annealing
process. It should be noted that the large standard deviations
observed for untreated substrates coated with PCL solutions
are likely due to surface roughness. Nonhomogeneous
coatings of this semicrystalline polymer produce a large
amount of visible surface roughness, a factor that strongly
Childs et al.
reduces the reproducibility of DCA data. Annealing may
serve to decrease this variability.
A more convincing understanding of surface morphology
is obtained from the 10 wt % polymer solution-coated
surfaces. AFM shows that full coverage is achieved at this
concentration. Figure 3 shows results for untreated and
annealed 10 wt % homopolymer and copolymer solution-
coated surfaces. Values for the polypropylene control plaques
are also shown. Data for the annealed 10 wt % PCL solution-
coated surfaces are not available, because upon heating these
coatings dewet and bead up, making DCA analysis impos-
sible. These results imply that it is PDMS, and not PCL,
that wets the polypropylene substrate.
Figure 3 shows that contact angles for the Tegomer
surfaces are lower than those for the SMA surfaces indicating
a greater amount of PDMS at the SMA solution-coated
surface. This result agrees with stoichiometric calculations
of mass percentages of PDMS in the copolymer based on
AR-XPS that give 43 and 38 wt % PDMS for SMA and
Tegomer, respectively. XPS demonstrates that PDMS is
enhanced at the air-copolymer interface and this enhance-
ment is apparent in the simple DCA experiments.
A crucial finding from the DCA data is that both blocks
appear to be present at the surface in both the 1 and 10 wt
% solution coatings. This is consistent with the existence of
a microdomain structure at the copolymer interface. Certainly
conditions exist that permit, for example, the PDMS block
to cover the entire surface while still producing a micro-
domained structure in the bulk. However, crystallization of
one of the blocks in block copolymers is known to lead to
the rapid formation of robust microstructure (one in the so-
called strong segregation regime).14 The block copolymer
samples did not change upon annealing significantly above
the Tg’s of both blocks thus indicating considerable stability
as a result of the PCL crystallinity.
AR-XPS is an effective method to measure depth profiles
of atomic composition. This type of analysis is germane for
block copolymer systems since they can produce a dissimilar
Effects on Protein Adsorption Biomacromolecules, Vol. 2, No. 2, 2001 529

Figure 3. DCA results for variously treated polypropylene substrates coated with 10 wt % polymer solutions.

elemental makeup as a function of depth from the interface.

For example, Jalbert et al. utilized AR-XPS to study
alkylamine terminal groups attached to a PDMS backbone.13
As a result of the lower surface energy of the PDMS
backbone, the experimental atomic percentages of nitrogen
from the higher surface energy alkylamine groups showed a
depletion in the surface region compared with stoichiometric
predictions if no enhancement occurred. Gorelova et al.
employed AR-XPS to demonstrate phase segregation of
PDMS to the air-surface interface from blends of poly-
(methyl methacrylate) (PMMA)/PDMS graft copolymers in
poly(vinyl chloride).15 Similarly, Chen et al. employed the
technique to study surface composition and migration
phenomenon of different molecular weights, concentrations,
and architectures of AB block copolymers blended into
A-type homopolymers.16 These previous studies conclusively
demonstrate that AR-XPS provides surface composition data
as a function of depth, from the top few angstroms of a
polymer surface to approximately 100 Å below.
XPS is a particularly beneficial technique for the present
SMA and Tegomer copolymers because it permits quanti- Figure 4. Representative wide energy XPS scan for polypropylene
fication of the surface composition. Figure 4 shows a substrates coated with triblock copolymer solutions.
representative wide energy range survey scan for a triblock starting at around 44 Å, further indicating that compositions
copolymer surface. As expected, only carbon, oxygen, and below this depth correspond to the bulk phase. Enhancement
silicon are detected. Figure 5 compares the mass % of PDMS of PDMS is evident as concentrations rise to 55 wt % at the
for 1 and 10 wt % SMA solution-coated surfaces between near-surface. These results agree with DCA analysis, showing
depths of 10 and 70 Å. Mass % PDMS calculations are based the surfaces are not completely covered by the lower surface
upon silicon mass % detected by the XPS measurements and energy PDMS block. Interpretation of the 1 wt % SMA
the stoichiometry of the polymer structure. Because silicon solution-coated surfaces is not straightforward since detection
is present only in the PDMS block, concentrations can be of carbon from the exposed polypropylene substrates influ-
calculated directly from measured silicon concentrations and ences the measurements.
a knowledge of the structure and molecular weight of the Achievement of stoichiometric values of mass % PDMS
PDMS block in the triblock copolymer. For substrates coated at depths less than approximately 10 Å from the surface for
with a 10 wt % SMA solution, PDMS concentrations at the 1 wt % SMA solution-coated surfaces may be compared
depths of 70 Å essentially agree with stoichiometric calcula- with the 10 wt % samples that achieve stoichiometric PDMS
tions (an experimental value of 40 wt % compared to 43 wt concentrations at a depth of 70 Å. The 1 wt % SMA solution
% calculated), indicating that bulk phase composition is coatings only partially cover the polypropylene substrate (see
nearly achieved at such depths. In addition, average mass AFM results below), so when only the very near surface of
concentrations of PDMS only change significantly with depth the sample is probed, no polypropylene substrate is detected.
530 Biomacromolecules, Vol. 2, No. 2, 2001
Figure 5. AR-XPS results for 1 and 10 wt % SMA solution-coated substrates.
Figure 6. AR-XPS results for 1 and 10 wt % Tegomer solution-coated surfaces.
Under these conditions, only SMA that rests above the
substrate is examined. This explains why at grazing takeoff
angles the amount of silicon detected corresponds to the
stoichiometric mass concentration of PDMS. As larger and
larger depths are probed, more of the polypropylene substrate
is examined, thus detecting additional carbon.
Enhancement of PDMS at the interface is also observed
in polypropylene substrates coated with Tegomer solutions;
this effect is shown in Figure 6. The 10 wt % Tegomer
solution-coated surfaces show that PDMS mass concentra-
tions are somewhat higher (44 wt %) at the deepest depths
probed than the calculated stoichiometric values (38 wt %).
However, it should be remembered that the XPS technique
does sample all of the material within the sampling depth.
Accordingly, the PDMS enriched surface does influence the
reported values at a “depth” of 70 Å. This effect is further
indicated in Figure 6 where 10 wt % Tegomer solution-
coated surfaces are not shown to reach a plateau value of
mass % PDMS at any depth. Enhancement of PDMS appears
to occur from more than 70 Å below the surface, reaching
mass PDMS concentrations of 65 wt % at the copolymer-
Childs et al.
air interface. The greater surface enrichment found with this
copolymer produces a thicker surface region of nonhomo-
geneous composition. The 1 wt % Tegomer solution-coated
surfaces show similar enhancement phenomena.
Certainly observation of PDMS enhancement by AR-XPS
provides strong evidence of a block copolymer system in
which the lower surface free energy blocks are preferentially
driven to the interface. However, the XPS data do not support
the hypothesis that only PDMS is present on the surface (the
surface composition never reaches 100% PDMS even at the
shallowest depths). A related XPS study of PDMS containing
triblock copolymers also finds that the near surface is not
saturated with PDMS, even upon annealing.17 For the present
investigation, it is easy to rationalize the lack of a PDMS
overlayer based on the crystalline block anchoring the
morphology and preventing complete blooming.
Atomic force microscopy (AFM) is a powerful and
versatile scanning probe technique that revolutionized surface
characterization for an extremely wide variety of materials.
Application of AFM techniques has been shown to be
especially appropriate for studying various polymer sys-
Effects on Protein Adsorption
Figure 7. Series of low magnification height (left) and phase (right) PDI-AFM images of a 10 wt % SMA solution-coated surface: (a) 50.0 µm;
(b) 13.0 µm; (c) 5.00 µm.
tems.18 Regarding copolymers, Magonov and Heaton em-
ployed PDI-AFM to verify TEM and XPS studies of
poly(styrene)-b-poly(butadiene)-b-poly(styrene) (PS-b-PBD-
b-PS) triblock copolymers that showed an enhancement of
lower surface energy PBD blocks at the surface.19 AFM not
only was able to verify the previous studies, but also was
able to generate more detailed information about this
copolymer system, revealing a wormlike pattern of stiff PS
within an amorphous sea of PBD. Many others have taken
Biomacromolecules, Vol. 2, No. 2, 2001 531
advantage of such a powerful mode of analysis to reveal the
wide variety of surface morphologies and properties dem-
onstrated by block copolymer systems.16,20-22
The existence of phase-separated triblock copolymer
surfaces is directly revealed with PDI-AFM. Height and
phase images of a 10 wt % SMA solution-coated surface
are shown for one sample at low magnification in Figure 7
and another sample at high magnification in Figure 8; the
morphologies shown are typical of 10 wt % SMA solution-
532 Biomacromolecules, Vol. 2, No. 2, 2001 Childs et al.

Figure 8. Series of high magnification height (left) and phase (right) PDI-AFM images of a 10 wt % SMA solution-coated surface: (a) 1.88 µm;
(b) 1.00 µm.
coated surfaces. Bright areas in the height images presumably
indicate elevated regions and dark regions represent de-
pressed material. However, as discussed in ref 19, height
images of block copolymer morphology in tapping mode are
not reliable because the relative contrast of the blocks
depends sensitively on the driving frequency in height
images. For this reason, no scale is provided. Such sensitivity
does not exist in phase images, and the contrast between
rubbery PDMS-rich and crystalline PCL-rich areas is excel-
lent. However assignment of each phase to a particular
contrast cannot be definitively stated. The low magnification
scans reveal semicrystalline spherulites on the order of 5-10
µm. Such spherulitic morphology is consistent with the
studies by Lovinger et al. of PCL-b-PDMS-b-PCL triblock Figure 9. Schematic models of possible molecular arrangements in
copolymers with similar molecular weights and linker the lamellar crystals of SMA and Tegomer copolymers (after Lov-
inger): (a) extended-type PCL blocks and (b) once-folded PCL blocks.
groups.8 High magnification shows a lamellar morphology
is present in which fibrous, PCL-rich semicrystalline spheru- the conclusion that PCL chains are either folded once within
lites are seen to be completely space filling with amorphous the semicrystalline core or not folded at all, as shown in
PDMS located in the interlamellar regions. Exact evaluation Figure 9. A once-folded conformation corresponds to a
of interlayer thicknesses are made difficult by the lack of semicrystalline thickness of approximately 5 nm, whereas
distinct, sharp boundaries that separate such layers; however, extended PCL chains are plausible for a 10 nm lamellar
thicknesses measured using a ruler overlaid on the 1.00 µm thickness. This is again in agreement with Lovinger et al.
phase image are estimated to be between 5 and 10 nm for who found, by estimating crystallinity from X-ray diffrac-
bright regions and between 5 and 15 nm for dark regions. tometry and assuming the density of amorphous phase to be
Assigning a value to the fully extended PCL chain length 0.85 times that of the crystalline phase, a semicrystalline
of 15 nm and to the fully extended PDMS of 13 nm leads to thickness of 6 nm corresponding to a once-folded PCL
Effects on Protein Adsorption
Figure 10. Series of low magnification height (left) and phase (right) PDI-AFM images of a 10 wt % Tegomer solution-coated surface: (a) 50.0
µm; (b) 15.0 µm; (c) 7.73 µm.
morphology. It is again worth emphasizing that the rapid
crystallization of the PCL block must lead to a pinning of
the PDMS thus preventing the formation of an overlayer.
A series of height and phase PDI-AFM images of a 10
wt % Tegomer solution-coated surface, shown in Figures
10 (low magnification) and 11 (high magnification), dem-
onstrate spherulitic structures similar to those revealed in
10 wt % SMA solution-coated surfaces. However Tegomer
spherulites range from approximately 5 to 25 µm. No other
significant differences are observed in images of 10 wt %
Tegomer solution-coated surfaces compared to those of
Biomacromolecules, Vol. 2, No. 2, 2001 533
SMA. Measurement by hand of lamellar thicknesses result
in approximately 10 nm for bright regions and range from 5
to 20 nm for the dark regions.
The only significant compositional difference between the
copolymers is that the middle block has a molecular weight
of 2700 in Tegomer as opposed to 3200 in SMA. Lamellar
thickness measurements of 10 wt % Tegomer solution-coated
surfaces do not elucidate the conformation of the PCL chains
since it is not known if the crystalline regions are bright or
dark in the phase images. If the dark regions represented
PCL-rich material, they would allow for both extended and
534 Biomacromolecules, Vol. 2, No. 2, 2001
Figure 11. Series of high magnification height (left) and phase (right) PDI-AFM images of a 10 wt % Tegomer solution-coated surface: (a)
3.78 µm; (b) 1.42 µm. The lamellar spacings of the domains are plainly visible in the high magnification PDI-AFM scans.
once-folded arrangements since they measure 5-20 nm wide.
If, however, the bright regions corresponded to PCL-rich
material, the measured thickness of 10 nm would indicate
extended PCL chains with chain ends incorporated into the
amorphous PDMS-rich region.
Image analysis tools may be used to find the lamellar
spacing from the AFM results. Power spectrum density
analysis calculates an average spacing, or a length defined
as one-half the length of the repeating unit (a repeating unit
in the present case corresponds to the lamellar spacing). If
one considers the present system as a clumpy mixture in
which the repeating structures are statistically similar in
shape, yet have no regular arrangement, then the linear scale
of segregation, SL, can be calculated as the average spacing.23
The 10 wt % SMA solution-coated surfaces are not analyzed
because the high magnification images do not have sharp
enough boundaries between bright and dark regions. How-
ever, a 10 wt % Tegomer solution-coated surface is easily
analyzed by this method, and the average spacing is
calculated to be approximately 8 nm corresponding to a
lamellar spacing of 16 nm. Utilizing a Fourier transform
method, the average lamellar spacing (distance from one
bright domain to the next) is calculated to be approximately
18 nm. Lovinger et al. determined average lamellar spacings
of 15 and 18 nm by analysis of TEM micrographs and by
Childs et al.
SAXS, respectively.8 Clearly the present results are in
excellent agreement with these previous findings for bulk
spacings.
AFM demonstrates that the 1 wt % SMA and Tegomer
solution-coated surfaces exhibit a variety of morphologies
as a result of different surface coverages. A small fraction
of 1 wt % copolymer solution-coated surfaces analyzed have
morphologies identical to those coated with 10 wt %
copolymer solutions, demonstrating the same characteristic
space-filling crystalline spherulites at low magnification and
fibrous lamellar phase separation at higher magnification.
However, most 1 wt % copolymer solution-coated surfaces
analyzed exhibit some exposed polypropylene regions. Figure
12 is a series of height and phase images of a 1 wt % SMA
solution-coated surface in which semicrystalline spherulitic
structures are evident in low magnification scans, yet
randomly located copolymer-deficient areas are observed at
higher magnification. These areas, indicated in the height
images as dark spots, are consistent with low copolymer
solution concentrations forming films that are too thin. In
light of the AR-XPS data and the additional AFM results
not presented, it is evident that full surface coverage is not
guaranteed using a 1 wt % copolymer solution dip coating.
Similar observations were made for the Tegomer triblock.
Effects on Protein Adsorption Biomacromolecules, Vol. 2, No. 2, 2001 535

Figure 12. Series of height (left) and phase (right) PDI-AFM images of a 1 wt % SMA solution-coated surface: (a) 10.0 µm; (b) 4.11 µm; (c)
1.27 µm. Incomplete coverage is evident in the form of small elongated voids.

These findings may have important consequences for indus-
trial coating processes utilizing such triblock copolymers.
Knowing the intimate details of the surface morphology
is a first step in understanding the mechanistic functioning
of such surfaces in improving biocompatibility. Figure 13
shows an AFM result for a block copolymer surface that
has been exposed to a 0.1 mg/mL human fibrinogen surface
for 30 s. Again height and phase mode images are presented
and it is seen that for this short exposure time, incomplete
surface coverage is obtained. Particularly in the phase mode
image, it can be seen that the underlying lamellar morphology
appears to template the adsorption of the fibrinogen. That
is, the fibrinogen molecules or clusters lie with their long
axis along the lamellae (see the upper right quadrant of the
phase image). This finding supports the idea that protein
adsorption can be mediated, in a conformational sense,
through the interaction with block copolymers. However, this
image represents scant experimental evidence for such an
effect. Dewetting effects during sample drying could influ-
ence fibrinogen deposition. An in situ AFM experiment at
536 Biomacromolecules, Vol. 2, No. 2, 2001 Childs et al.

Figure 13. Height (left) and phase (right) PDI-AFM images of a 1 µm2 area of a 10 wt % SMA solution-coated surface exposed to a 0.1 mg/mL
human fibrinogen solution for 30 s. The fibrinogen adsorbs along the lamellae, showing a templating action of the surface on adsorption.

Figure 14. Comparison of the morphology of adsorbed fibrinogen layers over a 100 µm2 area. The sample on the left is untreated polypropylene,
and the one to the right is polypropylene coated with block copolymer; both surfaces are covered with a layer of fibrinogen protein but exhibit
different textures (see text).

the copolymer liquid interface is needed but facilities for
such an experiment were not available to the authors.
Further evidence of the effects of the block copolymer
surface on protein adsorption is presented in Figure 14. Here,
phase mode images of polypropylene surfaces exposed to a
0.1 mg/mL fibrinogen solution for 24 h at 37 °C are shown.
The surface to the right is coated with a 10 wt % SMA
solution. The morphologies of the two fully established
fibrinogen layers are distinct; the copolymer treated surface
exhibits a finer, grained texture. The untreated surface
possesses coarser features (a morphology reminiscent of
cauliflower blooms). These findings more directly support
the premise that some type of templating action may exist.
An alternative explanation is that the exposure of both
copolymer blocks at the surface simply produces an inter-
mediate contact angle. Given the combined findings of the
present study and those of other groups,7,17 this interpretation
appears to be a rather simplistic view of the action of these
block copolymer compatibilizers. Certainly, changes brought
about by micropatterning lead to surfaces possessing fun-
damentally different blood contacting properties.
Conclusions
This study investigates the surface morphology of triblock
copolymer solution coatings on polypropylene substrates and
its affect on the adsorption of fibrinogen. DCA analysis
shows that copolymer solution-coated surfaces have contact
angles that lie within the range of the respective homopoly-
mers and provides perhaps the most compelling indication
of the presence of both PDMS and PCL at the surfaces. AR-
XPS studies show enhancement of the lower surface free
Effects on Protein Adsorption
energy block, PDMS, at the interface. However, AR-XPS
results also indicate the presence of both blocks at the surface.
PDI-AFM images are also revealing, showing completely
space-filling semicrystalline spherulites for all 10 wt %
solution-coated surfaces. On the nanometer scale, such
spherulites show alternating bright and dark lamellae cor-
responding to semicrystalline PCL-rich domains and amor-
phous PDMS-rich regions. The 1 wt % copolymer solution-
coated surfaces vary in morphology but commonly show
semicrystalline weblike fibers. Utilization of the present
powerful suite of analytical tools provides a detailed picture
of the intimate nature of the surface morphology formed from
solvent casting such films.
Observation of the effects of the surface morphology on
protein adsorption supports a novel approach to understand-
ing the mechanism of improved blood compatibility on block
copolymer surfaces. Namely, that microdomain patterned
synthetic surfaces profoundly alter the nature of the adsorbed
protein layer. This study reports some evidence for such
effects by showing modified adsorbed protein morphology
brought about by the micropatterned copolymer coating.
Future design of biomedical materials should include a direct
recognition of the surface as a two-dimensional object in
which lateral compositional variations are of significant
importance.
Acknowledgment. This work was supported by the U.S.
National Science Foundation, Division of Biological and
Environmental Sciences, through Grant BES 9709959. The
authors are grateful to the reviewers for a number of
suggestions leading to the improvement of the presentation
of the findings and for pointing out an error in the original
treatment of the XPS data.
References and Notes
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