Hydrophobicand fibrillar microporous

polyetherurethaneurea prosthesis:
an ESCAstudy on the internal and
external surfaces of explantedgrafts
Marie Therrien, Robert Guidoin,AlainAdnotand Roy&onPaynter*
Biomaterials

Unit,

Quebec

Quebec

City,

(Received

St-Franqois

dAssise

G 1 K 7P4,

13 March

1989;

Hospital

and

Departments

of Surgery

and

Chemical

Engineering,

Lava1 University,

Canada

revised

18 May

1989;

accepted

2 1 June

1989)

The ESCA study gives a good qualitative and quantitative elemental analysis of internal and external
surfaces of foreign materials. Microporous hydrophobic Mitrathane@ (a polyetherurethane urea) grafts
were implanted as blood conduits in dogs for up to 6 month. Surface analysis of explanted grafts
demonstrated the presence of different contaminants: sodium, chlorine, silicon, in patent grafts, i.e. those
implanted for 1 month and less. The sulphur probably comes from the presence of proteins on the surface of
the polymer and the high level of nitrogen is also protein-related. At 6 month implantation, the grafts were
occluded and a decrease of proteins on the surface was observed. The values of N/C and O/C ratios are also
reported. For the virgin material, these ratios correspond to the quantity of hard and soft segments; but, for
the explanted grafts, these parameters are also influenced by the presence of proteins due to the
VersaclearP washing which did not wash away all the proteins on the surface of the polymer. The SEM
photographs showed a certain degradation of polyurethane after 6 month of implantation. However, by
ESCA study, it is difficult to compare the surface of virgin and explanted grafts because it is masked by the
presence of proteins.
Keywords:

Vascular

Textile polyester

prostheses,

success

record

(ePTFE)

vein

diameter.

Possessing

relatively

blood-compatible
have

developed
produced

in

connected;

2PO.

1989

of

and

involved

vessels

<6

vitro

flexible

mm

in

segmented

poly-

the

wall

(Wheat

Ridge,

and hydrophobic
The

control
The

porosity

of

phase

second

one

CO,

of

the

on the opposite,

1 and 2). An X-ray

during

INRS-Energle,

the internal

1020,

The

These

were

were

not
one

spectro-

urethane
from

surfaces

the

vivo
the

polyurethane
for periods

graft in

of up to 6

of explanted

grafts.

City,

METHODS

Quebec

were

fabricated

elastomer

that

polyurethane
provided

on a rotating

previously
were

substitutes

for the following

1 month

implantations
been

implanted
and

were
reported

by

in dogs

as

performed

For each
in duplicate.

elsewhere9

can

be

et

Inc.

of poly-

a method

Annis

prescheduled

month.

grafts

Medica

spinning

mandril,

described

vascular

by Matrix

by electrostatic

prostheses

have
Et Co (Publishers)

in

implanted

on the results of ESCA analysis on

microporous

mandril.

Quebec

of
we

material

in diameter

of the hydrophobic

Varennes,

hydrophobic

aorta substitutes

AND

Hydrophobic

1 wk.
C.P.

prostheses,

and external

5 mm

Canada.
Butterworth

dogs as infrarenal

by

fabricated

photo-electron

understanding

is

to Dr R. Guidoln.

address:

microporous

Synthetic

separation

model

better

been

has

one

hydrophilic
those

USA)

polyetherurethane

of the PEUU on a rotating

has already

model*.

of small

of the first
was

Mitrathane@

of polyurethane

month. This paper focuses

properties,

production

obtain

behaviour
Mitrathane

of the autologous
in

in the

has yet

of hydrophilic

on the hydrophilic

To

and large

graft

study

published

MATERIALS

Inc.

(PEUU).

spinning

Correspondence

been

the

(Figures

*Present

repair

outstanding

hydrophilic

manufacturing6,

were

the

Medica

by

electrostatic

JOL

for

prostheses

pores

scopy

a good

blood conduits3-5.

Matrix
urea

vascular

the performance

saphenous

have

of medium

but no synthetic

been able to challenge

diameter

prostheses

for the replacement

arteries

urethanes

biodegradation

grafts, either woven or knitted and expanded

polytetrafluoroethylene
diameter

ESCA,

adapted
a/.3.

The

infrarenal

aorta

periods:

24 h,

period

of time,

Results

which

summarized

as

Ltd. 0142-9612/89/080517-04$03.00

Biomatenals

1989,

Vol

10 October

517

ESCA analysis on explanted grafts: M. Therrien et al.

follows: at death, all but the two grafts implanted for 6

month were patent. After 1 month implantation, all PEUU
grafts were yellow stained on both internal and external
surfaces and 6 month after implantation, the yellow
colouration was more evident (Figure 3), but proteins were
less abundant than at 1 month. Washing was sufficient to
remove most of the proteins.

Graft processing
The explanted samples were washed in Versaclean@ (Fisher
Scientific, Montreal, Quebec, Canada), a colloidal laboratory
detergent, after a first washing in a physiological saline
solution (30 min), then in distilled water (three 5 min
washes). This was followed by a 16 h wash in 5%
Versaclean, a 7 min distilled water wash and a 1 h wash in
12.5% Versaclean. Before going through the graded alcohol
series and critical point drying, the samples were again
rinsed in distilled water for 90 min (four changes).

ESCA study
Virgin samples were investigated in a SSX-100 spectrometer
(Surface Science Laboratories, Mountain View, CA, USA) at
Surface Science Western University of the University of
Western Ontario Canada. This instrument features a focused
monochromatic AlKa X-ray beam which is aligned with a
specific area of the sample surface using a fixed-focus
microscope. The explanted prostheses were evaluated on a
VG ESCA Lab MK2 (VG Scientific, East Grinstead, West
Figure 1 The SEM photographs of external surface (a) and transverse cut
(b) of virgin hydrophilic Mitrathane? Note that the microporous structure is
achieved by closed ceiled pores.

Figure 2
The SEM photographs of external surface (a) and transverse cut
(b) of virgin hydrophobic Mitrathane? The porosity is visible and the pores
communicate.

518

Biomaterials

1989, Vol 10 October

Figure 3
The macroscopic photographs
of explanted
hydrophobic
Mitrathane@ after I month (a) and 6 month (b) implantation. The yellow
staining is more evident after 6 month of implantation.

ESCA

Sussex, UK) which

University.

features

a MgKa

beam

at Lava1

RESULTS
In Table 1, the values for the apparent surface composition of
the prostheses are reported. Carbon, nitrogen and oxygen
are the major components of the polyurethane and sodium,
chlorine, silicon and sulphur are the minor elements
deposited on the surfaces. These components are due to
contamination during the preparation of the grafts and/or to
implantation.
The N/C and O/C ratios were calculated. The values
for the virgin and explanted polyurethane are presented in
Table 2.
In Tab/e 3, the estimated compositions of reference
proteins are reported. The percentage of carbon, nitrogen,
oxygen and sulphur are presented for a comparison with the
values of polyurethane.

DISCUSSION
Blood polyurethane interactions are affected by the surface

Table

Apparent

surface

composition

of prostheses

Time of
implantation

Surface

Na

Cl

SI

Internal
External

80
79

2
2

24 h

Internal
External

71
70

1 wk

Internal
External

1 month

6 month

17
19

1
P

8
10

20
19

0.1
-

0.5
0.4

73

19

0.2

0.2

Internal
External

69
75

10
6

20
19

0.2
0.2

0.1
-

0.1

0.2
0.2

Internal
External

76
74

4
6

19
20

0.2

*Present
Table 2

Results

of N/C

and

O/C

ratios

of prostheses

Time of
Implantation

Surface

Internal
External

80
79

24 h

Internal
External

71
70

1 wk

Internal
External

73

1 month

Internal
External

69
75

6 month

Internal
External

76
74

4
6

Table 3

Estimated

composition

N/C

o/c

2
2

17
19

0.03
0.03

0.21
0.24

8
10

20
19

0.1 1
0.14

0.28
0.27

19

0.10

0.26

10
6

20
19

0.14
0.08

0.29
0.25

19
20

0.05
0.08

0.25
0.27

of reference

materials

(proteinsJ

Protein

AlbumIn
Haemoglobin
Fibrinogen
y-globulin

65
65
67
63

14
14
12
14

18
18
20
23

2
3
1
ND

ND: no data.

analysis

on explanted

grafts:

M.

Therrien

et al.

properties of the polymer. ESCA studies allow a surface

analysis of virgin and explanted samples; their depth of
analysis is between 1 and 10 nm. The basis of the surface
analysis of polyurethanes is that the surface properties of a
polyurethane represent the sum of the effects of all the
chemical groups on the surface.
An ESCA study gives a good qualitative and quantitative
elemental analysis of the internal and external surfaces of
polyurethane grafts. In Tab/e 1, the percentage of elements
is reported. The first columns (C, N and 0) represent
concentrations of major elements and other columns
(Na
.S) show concentrations of minor components
calculated from survey scans. Sodium and chlorine are
common contaminants on many biomaterials. Silicon may
originate from polysiloxane, a mould-release agent used
during the manufacturing of the graft. The presence of
sulphur probably comes from the proteins on the surface of
the prosthesis. If we compare the percentages of sulphur on
virgin and explanted hydrophobic Mitrathane, we see some
differences that indicate the possible presence of proteins.
Furthermore, the concentration of nitrogen is higher for
explanted polyurethane than for virgin polyurethane and
sulphur seems more abundant on explanted grafts. Also, it
can be seen that the silicon found as a contaminant on the
virgin material is masked by adsorbed proteins on the
surfaceof explanted polyurethane. Finally, uponexamination
of Tab/e 3, we can conclude that the values for plasma
proteins are near the values of explanted Mitrathane.
For a period of 6 month implantation, a diminution of
proteins on the surface was observed. Parallel histological
studies9 showed fibrin and infiltration of blood elements into
the Mitrathane graft at 24 h, and at 1 wk. At 1 month, a thin
internal capsule was present on the graft flow surface of the
prosthesis. However, at 6 month, a complete occlusion
occurred. Most thrombi were anchored to the anastomoses
and were found to be non-adherent to the graft surface. This
is an explanation for the diminution of proteins.
Polyurethane is composed of soft and hard segments.
Soft segments come from polyether groups and hard
segments from urethane-urea groups. Biocompatibility of
biomaterials is due in part to alternation of soft and hard
segments. If the polymer has a lot of soft segments, its
surface is exposed to adsorption of proteins and conformational variations of fibrinogen and to a degradation of the
polymer. On the other hand, if a polymer has more hard
segments, the biocompatibility is much better because the
secondary amide groups, present in hard segments, form
reversible hydrogen bonds with peptide bonds in fibrinogen.
In Tab/e 2, the values for N/C and O/C ratios are
reported. For the virgin sample, the N/C ratio corresponds to
quantity of hard segments and the O/C ratio to the quantity
of soft segments. The soft segment concentration is high for
the virgin Mitrathane graft and the flow surface (internal) of
the prosthesis has more hard segments. Now, thecomparison
of these values (O/C and N/C) for the virgin and explanted
grafts is difficult because, for the explanted polyurethane
grafts, these results correspond rather to the presence of
proteins. For this reason, it is not yet possible to comment on
the increase or decrease of soft and hard segments on the
surface of explanted polyurethane grafts because the protein
layer masks the surface of the polymer.

CONCLUSION
The use of ESCA appeared to be the most appropriate
method for analysis of the internal and external surfaces of

Biomaterials

7989,

Vol

10 October

519

ESCA analysis on explanted grafts: M. Therrien er al.

polymer and allow a better understanding of the phenomenon

of degradation.

ACKNOWLEDGEMENTS
This work was supported by the Medical Research Council of
Canada (Grant MA 9429). The authors are indebted to
K. Horth and Y. Marois for their collaboration. The grafts
were kindly provided by Matrix Medica Inc.

REFERENCES
1
Figure 4
The SEM photograph of external surface of hydrophobic
Mitrarhane after 6 monrh of implantation. Nora the presence of biological
debris on the flow surface and some broken fibriis in the PU srrucrure.

vascular grafts because the penetration is only l-l 0 nm.

The results for the virgin and explanted hydrophobic
Mitrathane confirmed that these prostheses were submitted
to a surface degradation and/or an adsorption of proteins
during the implantation (Figure 4). The Versaclean washing
seems to be the best detergent for removal of most of the
proteins without changing the surface of polymer. The
scanning electron microscopy (SEM) photographs showed a
certain degradation of polyurethane after 6 month implantation. However, by ESCA study, it is difficult to compare the
surface of virgin and explanted grafts because it is masked
by the presence of proteins. To complete these findings,
other possible experimentation and analysis would be
necessary such as Fourier Transform Infrared-Attenuated
Total Reflectance (FTIR-ATR) (a surface analysis method
with a depth of 1000 nm) to see the infrared bands of
proteins and polymer. Differential Scanning Calorimetry
(DSC) could also be used to determine the glass transition
temperatures and melting temperatures of virgin and
explanted polyurethane which would characterize the

520

Biomaterials

1989, Vol 10 October

10

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