CO2-Sourced α-Alkylidene Cyclic Carbonates: A Step Forward in the Quest for Functional Regioregular Poly(urethane)s and Poly(carbonate)s

Article abstract of DOI:10.1002/anie.201704467

Described is a robust platform for the synthesis of a large diversity of novel functional CO₂-sourced polymers by exploiting the regiocontrolled ring-opening of α-alkylidene carbonates by various nucleophiles. The reactivity of α-alkylidene carbonates is dictated by the exocyclic olefinic group. The polyaddition of CO₂-sourced bis(α-alkylidene carbonate)s (bis-αCCs) with primary and secondary diamines provides novel regioregular functional poly(urethane)s. The reactivity of bis-αCCs is also exploited for producing new poly(β-oxo-carbonate)s by organocatalyzed polyaddition with a diol. This synthesis platform provides new functional variants of world-class leading polymer families (polyurethanes, polycarbonates) and valorizes CO₂ as a chemical feedstock.

Full text of DOI:10.1002/anie.201704467

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
International Edition Chemie
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Accepted Article
Title: CO2-sourced α-Alkylidene Cyclic Carbonates: A Step Forward in
the Quest for Functional Regioregular Poly(urethane)s and
Poly(carbonate)s.
Authors: Sandro Gennen, Bruno Grignard, Thierry Tassaing, Christine
Jerome, and Christophe Detrembleur
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201704467
Angew. Chem. 10.1002/ange.201704467
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Angewandte Chemie International Edition
10.1002/anie.201704467
COMMUNICATION
CO -sourced α-Alkylidene Cyclic Carbonates: A Step Forward in
2
the Quest for Functional Regioregular Poly(urethane)s and
Poly(carbonate)s.
!
a
!a
b
a
a
Sandro Gennen, Bruno Grignard, Thierry Tassaing, Christine Jérôme, Christophe Detrembleur*
5
,7
Abstract: We describe a robust platform for the synthesis of a
large diversity of novel functional CO -sourced polymers by
introducing some activating substituents on the 5CC ring
8
2
and/or by employing organocatalysts. Although some of them
exploiting the regio-controlled and site selective ring-opening of α-
alkylidene carbonates by various nucleophiles. The remarkable
reactivity of α-alkylidene carbonates is dictated by the exocyclic
olefinic group that selectively orients the cyclic carbonate ring-
opening with the formation of an enol species. The polyaddition of
were efficient in accelerating the PHU formation, the two
regioisomers were still formed and most of the previous side
reactions are still observed. Moreover, the inertness of 5CC
towards alcohols avoids the preparation of PCs by polyaddition
of bis-5CCs and diols under mild conditions. PCs can only be
prepared by ring-opening polymerization of 5CC in the
2
CO -sourced bis-α-alkylidene carbonates (bis-αCCs) with primary
9
and secondary diamines provides novel regioregular functional
poly(urethane)s. The reactivity of bis-αCCs is also exploited for
producing new poly(β-oxo-carbonate)s by organocatalyzed
polyaddition with a diol. All polyadditions were feasible under
ambient conditions. This synthesis platform provides new
functional variants of world-class leading polymers families
presence of suitable catalysts. Regiocontrol in the ring-
opening is of paramount importance because it affects some
crucial properties of the final polymer, such as their glass and
melting temperatures in polycarbonates and polyesters for
1
0
2
instance. Search for CO -sourced bis-cyclic carbonates that
are able to be copolymerized in a regioselective manner with
both diols and diamines under mild conditions remains an
(
polyurethanes, polycarbonates) and valorises CO
2
as a chemical
feedstock.
important bottleneck for the facile production of advanced CO
sourced polymers.
2
-
2
Making plastics more sustainable by valorizing CO as a
In this paper we engineered a versatile and robust
process to access to a large diversity of novel regioregular
hydroxyl- or oxo-functional polymers by exploiting easily
cheap, inexhaustible and renewable feedstock imposes itself
as a strategic driver for developing future low carbon footprint
materials. Beside its direct copolymerization with epoxides or
customizable
CO
2
-sourced
bis-(α-alkylidene
cyclic
oxetanes that essentially leads to polycarbonates and
carbonate)s (bis-αCCs). Regio-controlled copolymerizations of
these new monomers with diamines or diols are facile and
produce novel families of poly(urethane)s or poly(carbonate)s
under ambient conditions (25°C, ambient atmosphere)
1
poly(ether-co-carbonate) polyols , CO
2
can be converted by
2
transformations into polymerizable building blocks. This
second route is highly seducing as it potentially allows
broadening the scope of polymers that could be produced from
(
Scheme 1).
CO2. To date, five-membered cyclic carbonates (5CCs)
3
prepared by the catalyzed CO
some of the most important CO
production of important polymers,
2
/epoxide coupling represent
2
-sourced synthons for the
mainly poly(β-
hydroxyurethane)s (PHUs) and poly(carbonate)s (PCs). PHUs
are synthesized by the polyaddition of bis-cyclic carbonates
4
(
bis-5CCs) and diamines. Due to the poor reactivity of the five-
membered cyclic carbonate, this aminolysis reaction is
however slow, and suffers from the absence of regiocontrol
that leads to a mixture of regioisomers with primary and
4
d-5
secondary alcohols (Scheme 1).
Moreover, side products
such as urea, oxazolidones or decarboxylated adducts are
most often generated during the polymerization, preventing
high monomer conversion and/or high molar mass PHUs to be
6
easily achieved. Lately, intensive research was devoted to
explore strategies that facilitate the 5CC aminolysis, notably by
2
Scheme 1: Conceptual routes for regioregular functional CO -sourced
[
a]
b]
Center for Education and Research on Macromolecules (CERM),
CESAM Research Unit, Université de Liège, Bâtiment B6a, B-4000
poly(urethane)s and poly(carbonate)s.
LIEGE
(Sart
Tilman),
Belgium
2
We have designed two symmetrical CO -sourced bis-α-
E-mail: christophe.detrembleur@ulg.ac.be
[
Institut des Sciences Moléculaires, UMR 5255 CNRS Université
Bordeaux, 351 Cours de la Libération, F-33405 Talence Cedex,
France.
alkylidene cyclic carbonates (bis-αCCs), one with internal
exocyclic olefins (C1) and the other one, with external ones
(
C2) (Scheme 2). C1 was produced by chemo-selective
palladium/silver promoted Heck coupling of 1,4-diiodobenzene
with CO -sourced 4,4-dimethyl-5-methylene-1,3-dioxolan-2-
!
The authors contributed equally to this work
Supporting information for this article is given via a link at the end
of the document
2
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Angewandte Chemie International Edition
10.1002/anie.201704467
COMMUNICATION
one (DMACC) according to a previously reported procedure
secondary alcohol selectivity of 66:33 attesting for the absence
of regiocontrol (ESI4.1, Fig. S25-S27). The same trend was
observed when comparing the reactivity of DMACC and PrC
with N-methylbutylamine (ESI3.2, Fig. S17-S20 and ESI4.2,
Fig. S28-S29, respectively), although the reactions are slower
in both cases. The acyclic β-oxo-urethane is selectively formed
from DMACC (ESI3.2) whereas only <2mol% PrC are
converted into the corresponding hydroxy-urethane
regioisomers (ESI4.2). Neither PrC nor DMACC reacted with
butane-1-ol at 25°C. However, DMACC was selectively
forming the corresponding acyclic β-oxo-carbonate by reaction
with butane-1-ol in the presence of 2.5mol% DBU as
organocatalyst (reaction complete after 24h), whereas only
1
1
(
see ESI1, Scheme S1). The novel compound C2 was
synthesized by the carboxylative coupling of bis-alkynol with
CO (see ESI2, Scheme S2). The selection of these bis-αCCs
2
was motivated by the presence of exocyclic olefinic groups that
enhance the reactivity of cyclic carbonates against various
nucleophiles (such as amines and alcohols) with the selective
formation of one regioisomer. The driving force for this site-
selective and regio-controlled ring-opening of these cyclic
carbonates relies on the formation of an enol species that
rapidly rearranges into a more stable β-keto tautomer (ESI3,
1
2
Scheme S3).
<
2mol% PrC did react under identical conditions (ESI3.3, Fig.
S21-S24 and ESI4.3, Fig. S30-S31, respectively).
Scheme 2: Structures of the monomers and polymers.
These unique characteristics of α-alkylidene carbonates were
ascertained by comparative kinetic studies of model reactions
between a model α-alkylidene cyclic carbonate, DMACC, or a
conventional 5CC, propylene carbonate (PrC), with a primary
(
1-heptylamine) or secondary amine (N-methylbutylamine), or
a primary alcohol (butane-1-ol) (Figure 1a). DMACC was
formed by the catalyzed coupling of CO with 2-methyl-3-
Figure 1: a) Time-conversion curves of 4,4-dimethyl-5-methylene-1,3-
dioxolan-2-one (DMACC) or propylene carbonate (PrC) with 1-heptylamine,
N-methylbutylamine or butan-1-ol in DMF (1M) under ambient conditions,
with or without DBU as catalyst (2.5mol%) (inset: zoom for the reaction
profiles for PrC with 1-heptylamine, N-methylbutylamine and butan-1-ol (the
latter with DBU); b) Reaction schemes and products formed under ambient
conditions in DMF without DBU.
2
1
3
butyn-2-ol according to a reported procedure (ES1, Scheme
S1). Figure 1 compares all results of kinetics of reactions
carried out in dimethylformamide under ambient conditions.
When reacted with 1-heptylamine, DMACC was rapidly
converted and selectively produced the corresponding
hydroxy-oxazolidone with a conversion of 90% within 45 min.
This product results from the ring-opening by the primary
amine with the formation of the enol species that rapidly
rearranged into the more stable β-keto tautomer (β-oxo-
urethane), followed by an intramolecular cyclization (Figure 1b).
Based on these regioselective reactions on model
DMACC, we first considered the polyaddition of bis-αCCs with
equimolar amount of a secondary diamine, N,N’-dimethyl-1,6-
1
13
hexanediamine (N1, Scheme 2) in equimolar amount in CHCl
[bis-αCCs] and [N1] = 0.5 M) under ambient conditions.
3
The structure of the product was confirmed by H- and C-
NMR analyses of the product collected at the end of the
reaction (ESI3.1, Fig. S13-S16), and the selectivity of the
reaction was demonstrated by the absence of any other side
product. Under identical conditions, less than 5% of PrC was
reacted, and only 10% of PrC was converted after 2h of
reaction into two β-hydroxy-regioisomers with a primary to
(
Poly(β-oxo-urethane)s with carbonyl groups within the main
polymeric backbone are expected to be formed from bis-αCCs
bearing internal exocyclic olefin (C1) whereas poly(β-oxo-
urethane)s with pendent β-oxo groups should be formed from
bis-αCCs bearing external exocyclic olefin (C2) (Scheme 2).
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COMMUNICATION
C1 copolymerized with N1 with the formation of poly(oxo-
urethane)s with weight average molar mass (Mw) of 5600 and
exclusion chromatography (SEC) analysis were carried out on
crude products in order to avoid any fractionation of the
polymer during precipitation that would increase further the
molar mass. SEC chromatograms of polymers produced in
9
2
500 g/mol after 3 h and 24 h, respectively (Table 1, entries 1-
). Under similar experimental conditions, no polymer was
collected from C2 and N1 after 3h and only oligomers with a
molar mass of 4300 g/mol were obtained after 24 h (Table 1,
CHCl
3
, DMF or in DMF with DBU are shown in ESI5, Fig. S32-
, and
36. The activation of the polymerization by DMF vs CHCl
3
entries 7-8). Importantly, the substitution of CHCl
3
for DMF as
by DBU was also evidenced on the model reactions (Figure 1)
with no noticeable influence on the selectivity of the reactions.
All these results also suggest that C1 is more reactive than C2
due to the conjugation of the exocyclic olefin to the aromatic
ring that further increases its reactivity.
solvent strongly accelerated the polymerization with a clear
increase of the molar mass between 3 and 24 h of reaction
(
Table 1, entries 3-4, 9-10) and the formation of a high molar
mass polymer from C1 (Mw = 40000 g/mol) after 24h. An
unprecedented high molar mass polymer (Mw = 87000 g/mol)
was collected from C1 after only 3h by adding DBU to boost
the reaction (Table 1, entry 5).
The structure and regioregularity of the poly(oxo-
1
13
urethane)s were investigated by
H
and
C-NMR
spectroscopies on purified products, and all assignments were
in agreement with the polymer structures. For the polymer
1
Table 1: Poly(ß-oxo-urethane)s, poly(ß-hydroxy-2-oxazolidone)s, and
poly(ß-oxo-carbonate)s prepared under ambient conditions: reaction
conditions and molecular characteristics.
produced from C1, H NMR spectrum (Figure 2b) shows a
peak characteristic of a methylene in α position of both an
1
3
aromatic ring and a ketone group (δ = 3.75 ppm) and C NMR
spectrum highlights new resonances of the β-oxo group at 207
ppm and the urethane carbonyl group at 155 ppm (ESI5, Fig.
S37b). Identical observations pervade for poly(β-oxo-
Poly(ß-oxo-urethane)s
Conv.
CC
[%b ]
M
n
M
w
Entr
y
Cat.
t
a
Polymer
Solvent
d
[g/mol] [g/mol]
Đ
[h]
a
a
1
urethane)s synthesized from C2. H-NMR characterizations
1
2
3
4
5
6
7
8
9
P(C1-N1)
P(C1-N1)
P(C1-N1)
P(C1-N1)
P(C1-N1)
P(C1-N1)
P(C2-N1)
P(C2-N1)
P(C2-N1)
P(C2-N1)
P(C2-N1)
P(C2-N1)
CHCl
CHCl
3
3
-
3
3400
5600 N.d. 1.64
9500 92.6 1.90
confirmed the formation of only one type of regioregular chains
with pendant oxo groups by the presence of a singlet at 2.11
ppm typical of a methyl group in α position of a ketone (ESI5,
-
24 5000
DMF
DMF
DMF
DMF
-
-
3
4500 11000 92.0 2.45
24 13500 40000 97.2 2.96
20000 87000 97.7 4.35
1
3
Fig. S38b). C NMR analysis evidenced resonance of the
carbonyl groups of urethane linkage at 154 ppm and oxo group
at 207 ppm (ESI5, Fig. S39b). Interestingly, whatever the
chemical structure of bis-αCC, no evidence of structural
defects such as β-hydroxy urethanes are observed at least
within the limit of NMR, in agreement with the selectivity noted
on model reactions (ESI3).
DBU
3
DBU 24 25000 73000 99.0 2.92
CHCl
CHCl
3
-
3
-
-
N.d.
-
3
-
24 2700
2000
24 5000
5000
4300 91.9 1.59
3000 85.4 1.50
7000 95.5 1.40
7500 98.3 1.50
DMF
DMF
DMF
DMF
-
-
3
1
1
1
0
1
2
DBU
3
DBU 24 11000 16000 99.0 1.45
Poly(ß-hydroxy-2-oxazolidone)s
Conv.
CC
t
M
n
M
w
Polymer
Solvent Cat.
Đ
[
h] [g/mol] [g/mol]
[
%]
1
1
1
1
3
4
5
6
P(C1-N2)
P(C1-N2)
P(C2-N2)
P(C2-N2)
DMF
DMF
DMF
DMF
-
-
-
-
3
22000 77000 99.0 3.50
24
3
-
-
-
-
11000 15000 N.d. 1.37
24 21500 31000 97.8 1.44
Poly(ß-oxo-carbonate)s
Solvent Cat. t [h]
Polymer
M
n
M
w
Conv
g/mol] [g/mol] . CC
%]
Đ
[
[
1
1
1
2
7
8
9
0
P(C1-N3)
P(C1-N3)
P(C2-N3)
P(C2-N3)
CHCl
3
DBU 24
DBU 24
DBU 24
DBU 24
3000
5500 90.8 1.83
c
c
DMF
-
-
70.0
-
CHCl
3
13000 17500 96.1 1.35
17000 25000 99.2 1.47
DMF
a
determined by SEC in DMF/LiBr eluent using PMMA standards for
calibration. Representative SEC chromatograms are in ESI5 (Fig. S32-S36)
conversion in cyclic carbonate determined by H NMR in CDCl
b
1
3
or DMF-d
7
C
d
M
n
and M
w
values are out of calibration. 5 mol% of DBU. N.d. not
determined.
By analogy with the DBU catalyzed aminolysis of 5CC
8
b
with amines, DBU is expected to act as an hydrogen bond
acceptor that activates the secondary amine and facilitates the
ring-opening of bis-αCCs. The same accelerating effect was
also noted for C2 but in a lesser extent (Table 1, entries 11-12).
It has to be noted that all molar mass determinations by size
1
Figure 2. Stacked H NMR spectra of P(C1-N2) (Table 1, entry 13) in DMF-
d
7
, P(C1-N1) (Table 1, entry 4) in CDCl
CDCl (after purification by precipitation).
3
and P(C1-N3) (Table 1, entry 17) in
3
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Angewandte Chemie International Edition
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COMMUNICATION
Next, the polyaddition of bis-αCCs with a primary diamine,
never obtained by polyaddition of di-cyclic carbonates with
diols at 25°C. SEC chromatograms for P(C2-N3) produced at
1
,8-octadiamine (N2), was considered in DMF ([bis-αCCs] and
N2] 0.5 M). Under ambient conditions, C1 rapidly
copolymerized with N2 with the formation of a polymer of
7000 g/mol after only 3 h of reaction and did not require the
[
=
25°C with 5 mol% DBU in CHCl
S36.
3
or in DMF are shown in Fig.
1
13
7
H- and C-NMR analyses confirmed the structures of
addition of DBU (Table 1, entry 13; ESI5, Fig. S34 for SEC).
The primary diamine is more reactive than the secondary one,
in line with model reactions (Figure 1a; ESI3.1). A swollen-jelly
product was collected after 24h and revealed to be insoluble in
most common organic solvents, probably as the result of its
high molar mass (Table 1, entry 14). Under identical
experimental conditions, the polymer formed from C2
remained soluble after 24h, with a molar mass increase from
the poly(β-oxo-carbonate)s, one bearing keto groups within the
main polymer backbone, and the other one with pendant
ketone groups (Figure 2c; ESI 5, Fig. S37c, S38C, S39C, S42).
The regioselectivity in the ring-opening of the cyclic carbonate
is evidenced by the absence of any peak of defects such as β-
hydroxyl carbonates or ether links that would result from
different αCCs ring-opening pathways. To the best of our
knowledge, this synthesis approach provides the first example
of the preparation of polycarbonates of high molar mass by
polyaddition of 5-membered bis-cyclic carbonates with diols
under ambient conditions.
1
5000 to 31000 g/mol after 3h and 24h, respectively (Table 1,
entries 15-16; ESI5, Fig. S35 for SEC), in the absence of any
catalyst.
1
13
As confirmed by H-, C- and COSY NMR analyses,
poly(ß-hydroxy-2-oxazolidone)s were formed (Figure 2a; ESI5,
Fig. S37a, S38a, S39a, S43-S44) as the result of the
regioselective ring-opening of bis-αCCs with primary amine,
followed by an intramolecular cyclization (Scheme S3).
Importantly, by working at low temperature (25°C), no
dehydration was observed, affording selectively novel
regioregular poly(ß-hydroxy-2-oxazolidone)s. This reaction
pathway doesn’t only enable a facile access to functional
polymers but it also provides the first alternative and safer
route to conventional poly(oxazolidone)s that are currently
produced from nasty di-isocyanates and di- or polyepoxides at
In conclusion, we have demonstrated for the first time
that CO
αCCs) are suitable building-blocks for the facile synthesis of a
large diversity of unprecedented regioregular CO -sourced
2
-sourced bis-α-alkylidene cyclic carbonates (bis-
2
polymers under mild experimental conditions (25°C, ambient
atmosphere, no purification/drying of the co-reagents). The
remarkable reactivity of bis-αCCs towards primary/secondary
amines and primary alcohols is dictated by the exocyclic
olefinic group that selectively orients the cyclic carbonate ring-
opening with the formation of an enol species. Novel
regioregular
poly(β-oxo-urethane)s,
poly(ß-hydroxy-2-
1
4
oxazolidone)s and poly(β-oxo-carbonate)s are therefore
accessible by copolymerizing a single bis-αCCs with a
secondary diamine, primary diamine or diol, respectively. This
robust synthesis platform provides new functional variants of
world-class leading polymers families (polyurethanes,
high temperature (> 160°C).
Some of the poly(b-oxo-urethane)s (P(C1-N1; Table 1,
entries 4-6) and poly(b-hydroxy-oxazolidone)s (P(C1-N2);
Table 1, entry 13) were characterized by a high dispersity (Đ=
2
.9-4.3) that is much higher than the value expected for a
1
5
polycarbonates) while valorising CO as a chemical feedstock.
2
polyaddition at full conversion (Đ=2). These large dispersities
are observed for the polymers of high molar masses, and seem
thus to be linked to the high viscosity of the reaction medium.
It gives access to families of functional polymers that are not
accessible by any other techniques. These novel conceptual
routes will considerably diversify the range of functional
polymers via the presence of the hydroxyl- or oxo- groups in
the polymer backbone or by their post-modification. Our
strategy opens avenues to new applications and novel
The enhanced reactivity of bis-αCCs vs bis-5CCs was
then exploited to produce novel regioregular poly(β-oxo-
carbonate)s by reacting C1 or C2 with 1,4-butanediol in CHCl
[bis-αCCs] and [N3] = 0.5 M). As primary alcohols are less
3
2
research perspectives in the field of CO transformation. The
(
protocols for the synthesis of bis-αCCs have now to be
optimized in order to facilitate the synthesis of the regioregular
polymers at a large scale and at a competitive cost.
reactive than amines, copolymerizations were performed using
DBU as organocatalyst (5 mol%), no reaction being observed
without catalyst, in line with the model reactions. By analogy
with the ring-opening polymerization of cyclic esters, the
catalytic activity of DBU probably arises from a complex
interplay between the alcohol activation via H-bonding and
nucleophilic activation of the cyclic carbonate, which facilitates
Experimental Section
1
6
the polyaddition of the diol onto bis-αCCs. After 24h under
ambient conditions, a polymer with a molar mass of 17500
g/mol was collected from C2, whereas it was lower from C1
Materials, experimental protocols and additional characterizations
1
13
(
SEC, H-NMR, C-NMR, COSY, HRMS) and schemes.
(
Table 1, entries 19 and 17). When carried out in DMF, only
Acknowledgements
oligomers of low molar mass (out of SEC calibration) were
formed from C1. This result contrasts with polymerizations
involving diamines that were faster in DMF. This experiment is
however reproducible and further experiments would be
required to understand this observation. Importantly, under
identical conditions, the polymer collected from C2 showed a
molar mass as high as 25000 g/mol (Table 1, entry 20), a value
The authors of Liège thank the “Region Wallonne” in the frame
of the CO Green and Flycoat projects, the "Belgian Science
2
Policy" in the frame of the "Interuniversity Attraction Poles
Programme (IAP VII/5) – Functional Supramolecular Systems"
and the "Fonds National pour la Recherche Scientifique”
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COMMUNICATION
(
F.R.S.-FNRS) for financial supports. C.D. is Research
[5]
A. Cornille, M. Blain, R. Auvergne, B. Andrioletti, B. Boutevin, S.
Director by F.R.S.-FNRS.
Caillol, Polym. Chem., 2017, 8, 592-604
6] V. Besse, F. Camara, F. Mechin, E. Fleury, S. Caillol, J.-P. Pascault,
B. Boutevin, Eur. Polym. J., 2015, 71, 1-11
7] O. Lamarzelle, P.-L. Durand, A.-L. Wirotius, G. Chollet, E. Grau, H.
Cramail, Polym. Chem., 2016, 7, 1439-1451
8] a) M. Blain, H. Yau, L. Jean-Gerard, R. Auvergne, D. Benazet, P.
[
Keywords: polymerization • regioselectivity • carbon dioxide •
[
polyurethane • polycarbonate
[
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This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201704467
COMMUNICATION
COMMUNICATION
The regio-selective ring-opening and high reactivity of bis(α-alkylidene carbonate)s
with diamines and diols is exploited to provide a broad scope of functional
regioregular polymers under ambient conditions. This robust synthesis platform
provides new functional variants of world-class leading polymers families
Sandro Gennen, Bruno Grignard,
Thierry Tassaing, Christine Jerome,
Christophe Detrembleur*
(
2
polyurethanes and polycarbonates) and valorizes CO as a chemical feedstock.
Page No. – Page No.
CO
2
-sourced
a
-alkylidene
cyclic
carbonates: a step forward in the
quest for functional regioregular
poly(urethane)s and poly(carbonate)s
This article is protected by copyright. All rights reserved.