Science & Technology Development, Vol 14, No.

K4- 2011

FRIEDEL-CRAFTS ALKYLATION OF ANISOLE AND BENZYL BROMIDE USING ZIF-8 AS

AN EFFICIENT CATALYST

Phan Thanh Son Nam(1), Le Khac Anh Ky(1), Nguyen Thi Hong Nhung(2)
(1) University of Technology, VNU-HCM
(2) Nong Lam University of HCM city
(Manuscript Received on May 13rd 2010, Manuscript Revised October 12nd 2011)

ABSTRACT: A highly porous zeolite imidazolate frameworks (ZIF-8) was synthesized from the reaction of
zinc nitrate hexahydrate and 2-methylimidazole by a solvothermal method in DMF. The ZIF-8 was characterized
using several techniques including X-ray powder diffraction (XRD), scanning electron microscope (SEM),
transmission electron microscope (TEM), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR),
atomic absorption spectrophotometry (AAS), and nitrogen physisorption measurements. Highly crystalline porous
ZIF-8 was achieved with Langmuir surface areas of more than 1700 m2/g being observed. The ZIF-8 could be
effectively used as a solid acid catalyst for the Friedel-Crafts alkylation reaction between anisole and benzyl
bromide with no contribution from homogeneous catalysis of active acid species leaching into reaction solution.
Keywords: ZIF-8, XRD, Friedel-Crafts alkylation reaction.
traditionally catalyzed by more than stoichiometric
1. INTRODUCTION
amounts of anhydrous strong Lewis acids such as
Metal-organic frameworks (MOFs) are currently
AlCl3, TiCl3, FeCl3, or SnCl4 [10]. This method is
receiving significant attention as promising materials
limited by high amounts, toxicity and corrosion of the
for applications involving catalysis, separation, gas
catalysts, generation of a large amount of waste, and
storage, and molecular recognition [1-4]. MOFs are
difficult purification of the desired products [11].
extended porous structures composed of transition
Moreover, these catalysts are highly moisture
metal ions (or clusters) that are linked by organic
sensitive and hence demand moisture-free solvents,
bridges [5]. Zeolite imidazolate frameworks (ZIFs),
reactants and anhydrous catalysts, and also a dry
being classified as a new subclass of MOFs, have
atmosphere for their handling [12]. In this paper, we
emerged as a novel type of highly porous materials,
wish to report for the first time in Viet Nam, to our
combining advantages from both zeolites and
best knowledge, the utilization of a highly porous
conventional MOFs [6,7]. Compared to
zeolite imidazolate frameworks (ZIF-8) as an
conventionally used microporous and mesoporous
efficient heterogeneous catalyst for liquid phase
inorganic materials, these metal-organic structures
Friedel-Crafts alkylation reactions.
have the potential for more flexible rational design,
through control of the architecture and 2. EXPERIMENTAL
functionalization of the pores [8,9].
2.1. Materials and instrumentation
Friedel–Crafts acylation of aromatic compounds
with acid chlorides is an important process in both Chemicals were purchased from Sigma-Aldrich
petroleum and chemical industries. These reaction are and Merck, and used as received without further

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 TAÏP CHÍ PHAÙT TRIEÅN KH&CN, TAÄP 14, SOÁ K4 - 2011

purification unless otherwise noted. Fourier 2.2. Synthesis of ZIF-8

transform infrared (FT-IR) spectra were obtained on In a typical preparation, a solid mixture of zinc
a Bruker TENSOR37 instrument with samples being nitrate hexahydrate (Zn(NO3)2.6H2O) (1.88 g,
dispersed on potassium bromide pallets. Scanning 6.33mmol) and 2-methylimidazole (H-MeIM) (0.43g,
electron microscope (SEM) studies were performed 5.82mmol) was dissolved in 130 ml of N,N’-
on a JSM 740. Transmission electron microscope dimethylformamide (DMF) in a 10 x 20 ml vials. The
(TEM) studies were performed using a JEOL JEM vial was tightly capped and heated at a rate of 5
1400, in which samples were dispersed on holey o
C/min to 140 oC in a programmable oven and held at
carbon grids for TEM observation. . Elemental this temperature for 24 h, then cooled at a rate of 0.4
analysis with atomic absorption spectrophotometry o
C/min to room temperature. After removal of mother
(AAS) was performed on an AA-6800 Shimadzu. liquor from the mixture, chloroform (20 ml) was
A Netzsch Thermoanalyzer STA 409 was used added to the vial. Colorless polyhedral crystals were
for simultaneous thermal analysis combining collected from the upper chloroform layer, washed
thermogravimetric analysis (TGA) and differential with DMF (3 x 15 ml) for 3 days. After that, the
thermal analysis (DTA) with a heating rate of DMF was exchanged by dichloromethane (DCM) (3
o
10 C/min under a nitrogen atmosphere. X-ray powder x 15 ml) for 3 days. The residual solvents were
diffraction (XRD) patterns were recorded using Cu removed under vacuum at 200 oC for 6h, yielding
Kα radiation source on a D8 Advance Bruker powder 0.26 g of white polyhedral crystals ( 23% based on 2-
diffractometer. Nitrogen physisorption measurements methylimidazole).
were conducted using a Quantachrome Nova 2200e,
2.3. Catalysis studies
in which samples were pretreated by heating under
In a typical reaction, a mixture of anisole (1.94
vacuum at 150 oC for 3 h.
ml, 17.94 mmol), benzyl bromide (0.75 ml, 4.38
Gas chromatographic (GC) analyses were
mmol) and n-dodecane (0.35 ml) as an internal
performed using a Shimadzu GC 17-A equipped with
standard was added into a 50 mL flask containing the
a flame ionization detector (FID) and an DB-5
ZIF-8 catalyst. The catalyst concentration was
column (length = 30 m, inner diameter = 0.25 mm,
calculated with respect to the zinc / benzyl bromide
and film thickness = 0.25 µm). The temperature
molar ratio. The resulting mixture was stirred at the
program for GC analysis heated samples from 60 to
desired temperature for 6 h. Reaction conversion was
140 oC at 10 oC/min and held them at 140 oC for 1
monitored by withdrawing aliquots from the reaction
min; then heated them from 140 to 300 oC at 50
o
mixture at different time intervals, quenching with an
C/min and held them at 300 oC for 3 min. Inlet and
aqueous Na2CO3 solution (1%, 1 ml). The organic
detector temperatures were set constant at 300 oC. n-
components were extracted into diethyl ether (3 x 1
Hexadecane was used as an internal standard to
ml) which was then dried over anhydrous Na2SO4 ,
calculate reaction conversions. GC-MS analyses were
and analyzed by GC with reference to n-dodecane.
performed using a Hewlett Packard GC-MS 5972
The product identity was further confirmed by GC-
with a RTX-5MS column (length = 30 m, inner
MS.
diameter = 0.25 mm, and film thickness = 0. 5 µm).

3. RESULTS AND DISCUSSION

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Science & Technology Development, Vol 14, No.K4- 2011

Figure 1. X-ray powder diffractogram of the ZIF-8

The ZIF-8 was synthesized using zinc nitrate was achieved (Figure 1). Furthermore, the XRD
hexahydrate and 2-methylimidazole by a patterns of the ZIF-8 exhibited a better crystallinity
solvothermal method in DMF, according to a as compared to that of silica-based materials such as
literature procedure [13]. The ZIF-8 was then SBA-15, SBA-16 and MCM-41 where broader peaks
characterized using a variety of different techniques. were normally observed on their diffactograms [14].
Elemental analysis with AAS indicated a zinc loading Indeed, high crystallinity is always expected when
o
of 4.17 mmol/g. A very sharp peak below 10 (with synthesizing MOF-based materials. The overall XRD
2θ of 7.2) was observed on the XRD diffractogram of patterns of the ZIF-8 were in good agreement with
the ZIF-8, indicating that a highly crystalline material the literature [13,15].

Figure 2. SEM (left), and TEM (right) micrographs of the ZIF-8

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 TAÏP CHÍ PHAÙT TRIEÅN KH&CN, TAÄP 14, SOÁ K4 - 2011

The SEM micrograph showed that well-shaped, different from that of conventionally used
high quality polyhedral crystals with crystal sizes microporous and mesoporous inorganic materials.
ranging between approximately 100 and 200 µm Thermal degradation investigations of solid materials
were observed (Figure 2). The SEM images, together are necessary as many applications depend on their
with the XRD patterns showed that the ZIF-8 was thermal stability. In this work, the TGA results
highly crystalline. As expected, the TEM observation showed that the ZIF-8 was stable up to over 400 oC in
revealed that the as-synthesized ZIF-8 possessed a air, ensuring the applicability of the ZIF-8 across a
highly porous structure (Figure 2, right), which was wide temperature range (Figure 3).

Figure 3. TGA result of the ZIF-8

Figure 4. FT-IR spectra of the 2-methylimidazole linker (above) and the ZIF-8 (below)

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Science & Technology Development, Vol 14, No.K4- 2011

FT-IR spectra of the ZIF-8 exhibited a significant was also found at 1843 cm-1, which was identified as
difference as compared to that of 2-methylimidazole the resonance between the N-H…N bending ‘‘out of
(Figure 3, above). In the FT-IR spectra of 2- plane’’ and the N-H stretching vibrations [16]. The
methylimidazole, a strong and broad band, extending disappearance of these absorption bands in the FT-IR
-1
over the frequency range 3400-2200 cm with the spectra of the ZIF-8 (Figure 4, below) indicated that
-1
maximum at approximately 2600 cm was observed, the 2-methylimidazole linkers were fully
indicating the presence of the N-H…N hydrogen deprotonated.
bond. A relatively narrow band of medium intensity

Figure 5. Langmuir surface areas of the ZIF-8

As mentioned earlier, MOF-based materials are observed at around 1000 m2/g [1]. With the invention
currently receiving significant attention as promising of MOFs, the surface areas of crystalline porous
materials for applications involving catalysis, materials could be significantly improved.
separation, and gas storage because of their Interesting, it was found that the ZIF-8 synthesized in
exceptionally high adsorption surface areas [1-5]. this research could afford Langmuir surface areas of
The claim for the highest surface areas of a up to 1705 m2/g (Figure 5). Indeed, several ZIF-8
disordered structure was for activated carbon which samples with surface areas ranging from 1300 m2/g
was around 2000 m2/g, while the largest surface areas to 1810 m2/g were previously synthesized using
of ordered structures such as zeolites or silicas was solvothermal method [6,13].

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 TAÏP CHÍ PHAÙT TRIEÅN KH&CN, TAÄP 14, SOÁ K4 - 2011

OCH3

Br OCH3
OCH3

ZIF-8
+ +

p-isomer o-isomer
Scheme 1. The Friedel-Crafts alkylation reaction between anisole and benzyl bromide using the ZIF-8 catalyst.

The ZIF-8 was assessed for its activity as a solid benzylanisole of 75% was detected in the product
catalyst in the Friedel-Crafts alkylation of anisole mixture. As expected, decreasing the temperature
with benzyl bromide to form p-benzylanisole as the resulted in a drop in reaction rate, with conversions
principal product and o-benzylanisole as the by- of 97% and 27% being observed after 3 h at 90 oC
product (Scheme 1). Effect of temperature on and 80 oC, respectively (Figure 6). However, the
reaction conversion and selectivity was studied in the alkylation reaction could go to completion after 6 h in
o
range of 80 – 100 C, using 5 mol% ZIF-8 catalyst all cases. The selectivity of the p-isomer to the o-
and benzyl bromide molar ratio of 2 : 1. Quantitative isomer remained almost unchanged at different
conversion of benzyl bromide was achieved after 3 h temperature, being around 75% of p-isomer (Figure
o
at the reaction temperature of 100 C without the 7).
need for an inert atmosphere, and a selectivity to p-

100 100

80 80
Conversion (%)

60 60
% para

40 40
90 oC 20 80 oC 90 oC 100 oC
20 100 oC
80 oC
0 0
0 1 2 3 4 5 6 1 2 3 4 5 6
Time (h) Time (h)

Figure 6. Effect of temperature on reaction conversion Figure 7. Effect of temperature on reaction selectivity

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Science & Technology Development, Vol 14, No.K4- 2011

100 100

80 80
Conversion (%)

60 60

% para
40 40

5 mol% 3 mol% 1 mol% 5 mol%

20 20
3 mol%
1 mol%
0 0
0 1 2 3 4 5 6 1 2 3 4 5 6
Time (h) Time (h)

Figure 8. Effect of catalyst concentration on reaction Figure 9. Effect of catalyst concentration on reaction
conversion selectivity

With the result in hand, we then decided to ZIF-8, was studied in the range of 1 – 5 mol%
investigate the effect of catalyst concentration on relative to benzyl bromide at a reaction temperature
reaction conversion. It was previously reported that of 90 oC. It was found that quantitative conversion of
Friedel-Crafts alkylation reactions required a large benzyl bromide was achieved after 5 h using 5 mol%
amount of anhydrous AlCl3 catalyst, which could not ZIF-8 catalyst (Figure 8). As expected, decreasing the
be reused because of its instability [10-12]. catalyst loading to 3 mol% resulted in a drop in
Replacement of environmentally unacceptable reaction rate. However the reaction could afford a
anhydrous AlCl3 with solid acids has been shown to conversion of more than 99% at 3 mol% catalyst after
effectively reduce the amount of catalyst for Friedel- 6 h. The catalyst concentrations used in this study
Crafts alkylation reactions, in which the catalyst were therefore comparable to the literature. As
concentrations could vary from less than 0.1 mol% to expected, it was found that the selectivity of the p-
more than 10 mol%, depending on the nature of the isomer remained almost unchanged, being
catalyst as well as the substrate [17-19]. The catalyst approximately 75% in the catalyst concentration
concentration, with respect to the zinc content in the range of 1 – 5 mol% (Figure 9).

100 100

80 80
Conversion (%)

% para

60 60

40 40
(5/1) (5/1) (3/1) (2/1)
20 (3/1) 20
(2/1)
0 0
0 1 2 3 4 5 6 1 2 3 4 5 6
Time (h) Time (h)

Figure 10. Effect of molar ratio on reaction conversion Figure 11. Effect of molar ratio on reaction selectivity

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 TAÏP CHÍ PHAÙT TRIEÅN KH&CN, TAÄP 14, SOÁ K4 - 2011

It should be noted that Friedel-Crafts alkylation found that the reaction rate was decreased if the
reactions are normally carried out under solvent-free toluene : benzyl bromide molar ratio increased from
conditions. A large excess of aromatic hydrocarbon is 2:1 to 5:1 (Figure 10). In a heterogeneous reaction,
usually required in order to achieve high selectivity mass transfer limitation would normally have a
toward monosubstitution. The excess aromatic significant effect on the reaction rate. Therefore,
hydrocarbon also acts as a reaction medium for the increasing the amount of the solvent could lead to a
alkylation process. It was previously reported that the drop in reaction rate. From experimental points of
Friedel-Crafts benzylations of toluene or benzene view, it should be noted that using toluene : benzyl
using solid acid catalysts required a toluene : benzyl bromide molar ratio of less than 2 : 1 could cause
halide or benzene : benzyl halide molar ratio of up to difficulty in stirring the reaction mixture containing
13 : 1 [17,20]. Effect of reactant ratio was therefore the solid catalyst. As expected, the selectivity of the
investigated, having carried out the reaction at 5 p-isomer to the o-isomer remained almost unchanged
o
mol% catalyst at 90 C, using the benzyl bromide at different molar ratio, being around 75% of p-
molar ratio of 2:1, 3:1 and 5:1, respectively. It was isomer (Figure 11).

100

80
Conversion (%)

60

40
5 mol%
20 Leaching test

0
0 1 2 3 4 5 6
Time (h)

Figure 12. Leaching test indicated no contribution from homogeneous catalysis

When using a solid catalyst, a crucial issue is the rather than the solid ZIF-8 catalyst. The organic
possibility that some of active sites could migrate phase was separated from the solid catalyst after 2 h
from the solid support to the liquid phase and that reaction time by simple centrifugation, having used 5
these leached species could become responsible for a mol% fresh ZIF-8 catalyst. The reaction solution was
significant part of the catalytic activity. In order to transferred to a new reactor vessel, and stirred for an
determine if leaching was a problem for the Friedel- additional 4 h at 90 oC with aliquots being sampled at
Crafts alkylation reaction using the ZIF-8 catalyst, an different time intervals, and analyzed by GC. The
experiment was performed to estimate the data from GC determinations gave quantitative
contribution of leached active species to the catalytic information about residual, catalytically active acid in
activity by performing a simple centrifugation during solution. Within experimental error, no further
the course of the reaction to remove the solid reaction was observed, proving there to be no
catalyst. If the catalytic reaction continued this would contribution from leached active species and
indicate that the active species was leached acid

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Science & Technology Development, Vol 14, No.K4- 2011

conversion only being possible in the presence of the achieved with Langmuir surface areas of more than
solid ZIF-8 catalyst (Figure 12). 1700 m2/g. The ZIF-8 could be effectively used as a
solid catalyst for the Friedel-Crafts alkylation
4. CONCLUSION reaction between toluene and benzyl bromide. It was
In summary, a highly porous zeolite imidazolate apparent that the ZIF-8 catalyst exhibited advantages
frameworks (ZIF-8) was synthesized from the over conventional Lewis acid catalysts such as AlCl3,
reaction of zinc nitrate hexahydrate and 2- FeCl3, and ZnCl2 in the Friedel-Crafts alkylation
methylimidazole by a solvothermal method in DMF. reaction. Our results here demonstrated the feasibility
The ZIF-8 were characterized using several of employing MOF-based materials as heterogeneous
techniques including XRD, SEM, TEM, TGA, FT- catalysts for several organic transformations. Further
IR, AAS and nitrogen physisorption measurements, exploration on applications of MOF-based materials
and the analysis results were in good agreement with in catalysis appears warranted, and is the focus of on-
the literature. Highly crystalline porous ZIF-8 was going investigation.

NGHIÊN CỨU SỬ DỤNG ZIF-8 LÀM XÚC TÁC CHO PHẢN ỨNG ALKYL HÓA THEO
FRIEDEL-CRAFTS CỦA ANISOLE VỚI BENZYL BROMIDE

Phan Thanh Sơn Nam, Lê Khắc Anh Kỳ, Nguyễn Thị Hồng Nhung
Trường ðại học Bách Khoa, ðHQG-HCM

TÓM TẮT: Vật liệu khung hữu cơ – kim loại với cấu trúc tương tự như zeolite (ZIF-8) ñã ñược tổng hợp
theo phương pháp kết hợp nhiệt ñộ và dung môi từ phản ứng giữa zinc nitrate hexahydrate và 2-methylimidazole.
Xúc tác ñược phân tích bằng những phương pháp như nhiễu xạ tia X (XRD), hiển vi ñiện tử quét (SEM), hiển vi ñiện
tử truyền qua (TEM), phân tích nhiệt trọng lượng (TGA), phổ hồng ngoại (FT-IR), quang phổ hấp thu nguyên tử
(AAS) và ño bề mặt riêng Langmuir. ZIF-8 ñược tổng hợp với bề mặt riêng Langmuir trên 1700 m2/g. Xúc tác ZIF-8
thể hiện hoạt tính tốt trong phản ứng alkyl hóa theo Friedel-Crafts giữa anisole với benzyl bromide mà không cần
môi trường khi trơ cũng như các hóa chất khan nước. Kết quả nghiên cứu còn cho thấy phản ứng alkyl hóa trên xúc
tác ZIF-8 xảy ra dị thể mà không có ñóng góp của phần xúc tác hòa tan vào dung dịch phản ứng.

molecules in crystals Nature, 427, 523

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