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Chemical and physicochemical properties of the high cohesive silicone gel from
Poly Implant Prothse (PIP) breast prostheses after explantation: A preliminary,
comparative analytical investigation
Giangiacomo Beretta a, , Matteo Malacco b
a
b
Department of Pharmaceutical Sciences, Faculty of Pharmacy, University of Milan, Via Mangiagalli 25, 20133 Milan, Italy
FMH Plastic, Reconstructive and Aesthetic Surgery, Lugano, Switzerland
a r t i c l e
i n f o
Article history:
Received 10 December 2012
Received in revised form 24 January 2013
Accepted 28 January 2013
Available online 10 February 2013
Keywords:
PIP implants
High-cohesive silicone gel
Polydimethylcyclosiloxane
1H NMR
Mass spectrometry
a b s t r a c t
Aim of this work was to gain a deeper insight into the analytical prole of the macromolecular and LMW
fractions of polymeric silicones present in breast implants.
The study was conducted on silicone gel samples from (i) breast prostheses (Poly Implant Prothse,
PIP) explanted from a patient that needed their therapeutical removal, (ii) from a virgin Mc Ghan 410
MX prosthesis and (iii) from a sample of technical-grade non-cohesive silicone. The gels were analysed
using rheological techniques, attenuated total reectance infrared spectroscopy (ATR-FT-IR), nuclear
magnetic resonance (1 H NMR), gas chromatography coupled to mass spectrometry (GCMS) and ow
injection electrospray mass spectrometry (FI-ESI-MS). Our results demonstrate that, compared to the
virgin McGhan gel, the silicone present the PIP prostheses lacks a signicant part of the cross-linking
sites necessary for the high-cohesive properties of the gel, signicant amounts of cholesterol have been
absorbed from the breast tissue by the silicone material, demonstrating the lack of impermeability of its
elastomer shell. The potential implications and consequences of these analytical results are discussed.
2013 Elsevier B.V. All rights reserved.
1. Introduction
High-cohesive silicone gel breast implants (or prostheses) are
medical devices used for breast reconstruction after mastectomy,
to correct congenital defects or for breast augmentation.
They are made by an elastomer silicone shell lled with
a viscous cohesive silicone gel made of a bulk of polymeric
cohesive gel (cross linked polymeric silicones are considered
inert materials due the durability and thermal stability of
their chemical and elastic properties) in which is embedded a
12% of low molecular weight (LMW) silicones among which
hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane
(D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6) and tetradecamethylcycloheptasiloxane (D7) have
been reported (D5-D7 main constituents) [1]. Previous analytical
studies have shown that these LMW silicones can diffuse through
the implant elastomer shell when the implant is in contact with the
lipid media in the breast [1].
Flassbeck et al. reported the identication and quantication of
LMW silicones (from D3 to D6) by GCMS analysis of blood, plasma
and tissues samples from women implanted with breast prostheses
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1H
NMR
G. Beretta, M. Malacco / Journal of Pharmaceutical and Biomedical Analysis 7879 (2013) 7582
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Fig. 1. Optical microscopical examination of (6 magnication) of identier code area (left) and of the elastomer shell (right) of (A) the explanted PIP implant and of (B) the
virgin McGhan implant.
serial number and of its high relief characters, and (ii) an inhomogeneous distribution of its textured elastomer shell, indicating that
the implants were produced under rough manufacturing procedure
and/or that they underwent mechanical and/or chemical erosion
during the implantation period (seven years).
ATR-IR spectroscopic analysis conrmed the polydimethylsiloxane nature of the PIP and Mc Ghan gels (Fig. 2). The spectra were
almost overlapping, with slightly higher absorptions of the PIP gel
at low frequencies ( = 1079.8 cm1 , = 864.0 cm1 , = 700.2 cm1 ,
= 661.4 cm1 ).
Fig. 2. ATR-FT-IR spectra of silicone gels from PIP (dotted line) and McGhan (solid line) silicone gels.
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The rheological evaluation of the of the silicone gel gelproperties showed completely different behaviour (supplementary
data), leading to the rst conclusion that PIP implant ller silicone is
characterized by signicantly reduced viscoelastic properties compared to that of a high-cohesive silicone gel.
The reduced viscosity of the PIP gel may have two origins: (i)
the rst due to its manufacturing procedure: the gel already had
reduced viscosity before implantation, and/or (ii) the silicon gel
viscosity decreased during the seven years of implantation.
3.2.
1H
NMR experiments
G. Beretta, M. Malacco / Journal of Pharmaceutical and Biomedical Analysis 7879 (2013) 7582
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Fig. 4. 1 H NMR spectra (300 MHz, CDCl3 ) of (A) PIP silicone gel and of (B) technical silicone. Expanded spectral windows (0.25 < < 0.60) are in the insets. + 13 C satellites, *
1
H satellites. The 1 H NMR spectrum of McGhan silicone gel was not recorded due to the complete absorption of CDCl3 by the sample (see Fig. 3).
4. Discussion
In March 2010 breasts implants manufactured by Poly Implant
Prosthse (PIP), the same type of prostheses explanted from our
patient, were removed from the market following the discovery
that non medical-grade silicone was used in prostheses implanted
worldwide in at least 300,000 women [28]. The concerning conclusions of recently published clinical studies [21,22], opened a harsh
international discussion about their safety [2931].
Considering the great impact of this issue on the public opinion
and in different elds of the scientic community (from plastic and
reconstructive medicine to analytical chemistry and forensic analysis), it is surprising that since the publication of the rst analytical
studies and controversies on the LMW fraction of cohesive silicone
gels during the decade 19902000 [1-12d], almost no further study
has been focused on the detailed characterization of their chemical
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Fig. 5. GCMS prole of the acetone extracts of (A) PIP silicone gel, (B) McGhan silicone gel and of (C) technical silicone. CH = cholesterol, U = unknown.
experimental spectra/spectral library match, reported in the probability range 950%), on the other hand they highlighted a number
of critical points that we believe of fundamental importance.
It is commonly accepted that polymeric silicone and LMW
silicones are not toxic to living organism and humans and, consequently, that they are of safe use in medical devices such as cohesive
silicone gel breast implants. Studies from the literature or reports
available online have repeatedly shown, using different experimental in vitro or in vivo models, that these materials do not elicit
Fig. 6. Mass spectra of the unknown silicone compounds and cholesterol detected in the GCMS chromatograms of PIP and McGhan silicone gels.
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Fig. 7. Representative FI-ESI-MS spectrum of the acetone extract of PIP silicone gel.
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