Dithienosilole extended BODIPYs: Synthesis and spectroscopic properties

Article abstract of DOI:10.1142/S1088424619500366

3,/3,5-Dithienosilole-vinyl-BODIPYs were readily synthesized through Knoevenagel condensation reactions. Spectroscopic properties of two dyes in various solvents were investigated. Dyes 1 and 2 show an absorption maxima at 620 and 738 nm with absorption coefficient of 60900 and 77900 M-1· cm-1 in DCM, respectively. Significant red shifts of the main spectral bands are observed relative to that of the parent 1,3,5,7-tetramethyl-BODIPY. TD-DFT calculations reproduce the spectral shifts and experimental spectra.

Full text of DOI:10.1142/S1088424619500366

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2019; 23: 1–7
DOI: 10.1142/S1088424619500366
Published at http://www.worldscinet.com/jpp/
Dithienosilole extended BODIPYs: Synthesis
and spectroscopic properties
Yijuan Sun, Lizhi Gai*,Yitong Wang, Zhirong Qu* and Hua Lu*
Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal
University, Hangzhou 311121, P. R. China
Received 8 December 2018
Accepted 3 March 2019
ABSTRACT: 3,/3,5-Dithienosilole-vinyl-BODIPYs were readily synthesized through Knoevenagel
condensation reactions. Spectroscopic properties of two dyes in various solvents were investigated.
Dyes 1 and 2 show an absorption maxima at 620 and 738 nm with absorption coefficient of 60900 and
-1
77900 M-1 cm in DCM, respectively. Significant red shifts of the main spectral bands are observed
.
relative to that of the parent 1,3,5,7-tetramethyl-BODIPY. TD-DFT calculations reproduce the spectral
shifts and experimental spectra.
KEYWORDS: BODIPY, dyes, spectroscopic properties, DFT calculations.
aza-BODIPY [4–7, 10–11]. In particular, modification
INTRODUCTION
with functional building blocks at the 3,5-positions
can endow them with excellent NIR photophysical
and optoelectronic properties. For examples, our group
developed a novel “turn-on” fluorescent probe based
on a BODIPY fluorophore to detect hypoxia, by
attaching a styryl substituent with a hydroxyl and nitro
group at 3-position of the BODIPY core [12]. Mack
and Nyokong prepared electrospun polystyrene (PS)
nanofibers embedded with thienylvinyl-BODIPY for
the photocatalytic degradation of azo dyes [13]. Dithie-
nosilole (DTS), a silicon-bridged electron-rich planar
tricyclic p system, is a promising electron–donating
building block for efficient donor material, which
possess a s*–p* conjugation between the silicon s
bonds and the bithiophene p system, resulting in a
unique low-lying lowest unoccupied molecular orbital
(LUMO) level [14–16]. It has been widely used as
efficient donor units of conjugated D–A oligomers and
polymers for organic electronic device materials such as
OPVs, OFETs, dye-sensitized solar cells, and organic
light-emitting diodes [15–18].
Fluorophores with absorption and emission
wavelengths in the near-infrared (NIR) region (650–
900 nm, biological window) are especially attractive
for in vivo imaging due to deep tissue penetration of
NIR light and small background autofluorescence
of biomacromolecules in the living systems [1–3].
Among popular chromophores, Boron-dipyrromethene
(4,4-difluoro-4-bora-3a,4a-diaza-sindacene, BDP or
BODIPY) fluorescent dyes, a family of well-known
luminescent compounds, have drawn much attention with
their fascinating structural and attractive photophysical
properties such as high fluorescence quantum yield, large
absorption coefficient, considerably high photostability
and chemical stability and good solubility in common
solvents of different polarity [4–9]. However, the spectral
properties of the common BODIPY dyes are typically
limited to the 470–530 nm region [4–7].
Until now, shifts of the main spectral band into the
red or NIR region have been developed through aryl,
ethynylaryl and styryl substitution at the 1-, 3-, 5-, and/
or 7-positions, aromatic ring fusion, by replacing the
meso-carbon atom with an nitrogen atom to form an
In this paper, 3,/3,5-dithienosilole-vinyl-BODIPYs
are readily synthesized via Knoevenagel condensation
reactions between 1,3,5,7-tetramethyl BODIPY and
dithienosilole-based aromatic aldehyde. The push–pull
interaction is expected to narrow the HOMO–LUMO
gap, resulting in a large red shift of the main spectral
*Correspondence to: Lizhi Gai, email: lizhigai@hznu.edu.cn;
email: Zhirong Qu, quzr@hznu.edu.cn and Hua Lu, email:
hualu@hznu.edu.cn.
Copyright © 2019 World Scientific Publishing Company

2
Y. SUN ET AL.
band. TD-DFT calculations are performed in order to
explore the effect of DTS moiety and structure–property
correlations.
237 nm for 2 were observed, indicative of the effect of
the greater extent of the p conjugation by incorporation
of DTS moieties. It should be noted that 2 shows intense
absorption peaks at 457 nm, which can be attributed to the
strong S0–S3 and S0–S4 transition and is associated with
the p–p* excited state of DTS moieties. The absorption
maxima do not show any particular trend as a function of
solvent polarity. The emission bands of 1 and 2 exhibit
mirror symmetry with the absorption band. The emission
bands are dependent on solvent polarity and show a
hypsochromic shift of approximately 31 nm (1) and
18 nm (2) with increasing solvent polarity from hexane to
MeCN. 1 exhibits moderate fluorescence, whereas only
very weak emission is observed for 2 in all investigated
solvents, due to double internal conversion probability
induced by more vibrational coupling, which enhances
the rate of intersystem crossing of the dyes [22, 23]. The
fluorescence decay profiles of dyes could be described
by a single-exponential fit (fluorescence lifetime in the
range of 1.29–7.10 ns) in all of the solvents investigated,
similar to the lifetime data of other BODIPY systems
published in the literature [24].
The introduction of vinyl groups at the 3-positions
or 3,5-positions of BODIPY chromophore produces a
greater bathochromic shift, extending the p conjugation
through the 3-positions or 3,5-positions in the reported
literature [7, 10, 25–27]. Compared with the absorption of
classic BODIPY 3, the 3,5-vinyl groups of modification
BODIPY 2a–2c, had larger red shifts with increasing
molar extinction coefficients (Scheme 2), which can be
attributed to a narrowing of the HOMO–LUMO gap due
to enhanced delocalization of the p electrons in vinyl
groups and functional p conjugation rings [7, 10, 25–27].
In addition, dye 2 had low quantum yield related to that
RESULTS AND DISCUSSION
The synthetic route of 1 and 2 is depicted in
Scheme 1. The synthesis of 3,3′-dibromo bithiophene
(6) and the classic BODIPY 3 were reported in the
literature [19]. With 6 as a starting material, after double
Br/Li-exchange, the reaction mixture was reacted with
dichlorobis(2-ethylhexyl)silane to generate 5 in 67%
isolated yield [20]. Compound 4 was synthesized via
Vilsmeier–Haack reaction between 5 and DMF/POCl3 in
moderate yield [21]. Finally, the target dyes 1 and 2 were
readily prepared via Knoevenagel condensation reaction
of the classic BODIPY 3 and 4 under an atmosphere
of p-TSA and piperidine in toluene. The structures of
target products 1 and 2 were characterized by 1H NMR,
13C NMR, 19F NMR, 11B NMR and high resolution mass
spectrometry (HR-MS) (see supporting information).
All compounds are fairly stable under air and moisture
both in solution and in the solid state.
Absorption and emission spectra in different solvents
are presented in Figs 1 and 2, and detailed photophysical
data are collected in Table 1. Dyes 1 and 2 show an
absorption maxima at 620 and 738 nm with maximum
-1
absorption coefficient of 60900 and 77900 M-1 cm in
.
DCM, respectively. In general, the maxima absorption
band can be attributed as typical of a S0→S1 transition
with a shoulder at the high-energy side and owing to the
0–1 vibrational band of the same transition. In contrast to
the absorption spectra of the precursor BODIPY (labs
=
501 nm), dramatic bathochromic shift of 119 nm for 1;
R
R
Si
R
R
Si
Br Br
1) TMEDA/ n-BuLi
-78 °C
DMF/ DCM
POCl3, reflux
CHO
2) SiR2Cl2/THF, r.t
S
S
S
S
S
S
4 (59%)
6
5 (67%)
R = 2-ethylhexyl
+
N
N+
N+
B-
N
B-
4, pTSA/ toluene
F
F
F
F
Piperidine, reflux
N
N
B
F
F
S
S
S
S
R
Si
R
R
2 (22%)
1 (15%)
R
Si R
3
R
Si
S
S
Scheme 1. Synthesis and chemical structures of BODIPY 1–2
Copyright © 2019 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2019; 23: 2–7

DITHIENOSILOLE EXTENDED BODIPYS: SYNTHESIS AND SPECTROSCOPIC PROPERTIES
3
and TD-DFT calculations were performed using the
B3LYP functional and 6-31G (d, p) basis sets of the
Gaussian09 software package [28]. The analysis of the
TD-DFT wave function had S0–S1 transitions mainly
composed of HOMO to LUMO transitions. The HOMO
are almost effectively spread over the entire molecule
(Fig. 3), however, the LUMO mostly localizes on
the BODIPY p system and less on the DTS fragment,
indicating that weak ICT transition occurs from the
donor DTS unit to the BODIPY p system. The DTS
extension stabilizes LUMO and destabilizes HOMO,
thus effectively narrowing the energy gap, leading to
a bathochromic shift compared with the spectral band
position of the parent BODIPY 3. The lowest-energy
excitations of 1 and 2 are predicted to lie at 584 and
725 nm with oscillator strengths of 1.18 and 0.78,
respectively, consistent with the maxima absorption band
(Table 2). The wavelengths of the third/fourth lowest
energy transitions closely match the experimental data
round 400 nm. Therefore, TD-DFT calculations explain
the absorption spectra well (Fig. 4).
In summary, the synthesis, characterization, and
theoretical analysis of dithienosilole-vinyl-BODIPY dyes
have been described. The introduction of dithienosilole-
vinyl groups is clearly promising for designing NIR
Fig. 1. The absorption and emission spectra of 1 and 2 in DCM.
Photographs of 1 and 2 in DCM under visible (left) and excited
at 365 nm using a UV lamp (right)
of 2a–2c, due to the presence of a thiophene group in the
DTS moiety at the 3,5-positions, which increases the rate
of nonradiative decay.
In order to gain deeper insight into the electronic
structures and observed photophysical properties, DFT
Fig. 2. The absorption (left) and emission (right) spectra of 1 and 2 in different solvents
Copyright © 2019 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2019; 23: 3–7

4
Y. SUN ET AL.
Table 1. Spectroscopic and photophysical properties of dyes 1–2 in DCM at 298K
-1
e [M-1 cm ]
lems [nm]
Dvabs-em [cm-1]
t [ns]
FF
Kr [108 s-1] Knr [108 s-1]
.
Dyes
Solvent
labs [nm]
1
Hexane
Toluene
DCM
619
621
620
615
609
610
724
738
738
730
725
727
64100
70100
60900
71500
59900
58000
102400
97500
77900
93400
83300
83700
622
636
653
639
643
653
731
751
760
746
750
749
78
380
815
611
868
1080
132
235
392
294
460
404
1.97
1.82
1.29
2.27
2.01
2.46
6.81
7.10
6.81
5.51
3.27
4.95
0.46
0.47
0.34
0.41
0.24
0.27
0.03
0.02
0.01
0.02
0.01
0.01
2.34
2.58
2.64
1.81
1.19
1.09
0.04
0.03
0.02
0.04
0.03
0.02
2.74
2.91
5.12
2.59
3.78
2.97
1.43
1.38
1.45
1.78
3.03
2.01
THF
MeOH
MeCN
Hexane
Toluene
DCM
2
THF
MeOH
MeCN
N
N
N
N
B
F
B
N
N
F
F
B
F
F
F
2c
2b
2a
EtOOC
COOEt
S
S
CH2Cl2 Φ 0.98
toluene Φ 0.59
abs 629 nm, λem 641 nm
ε=120000 M-1·cm-1
DMF Φ 0.33
λ
abs 593 nm, λem 602 nm
λ
λ
abs 651 nm, λem 663 nm
ε=100000 M-1·cm-1
ε=125000 M-1·cm-1
Scheme 2. The structure and photophysical data of the reported 3,5-divinyleneBODIPY dyes 2a–2c
Fig. 3. The energy level diagram for the frontier p-MOs of the 1–3 using the B3LYP functional with 6-31G(d, p) basis sets. The
angular nodal patterns are shown at an isosurface value of 0.02 a.u.
materials. Density functional calculations on energy-
minimized structures reproduce experimentally observed
data and trends. In this system, s bonds of silicon in a
DTS moiety is not involved in HOMO and LUMO
orbitals, therefore, silicon plays a minor role relating
to the spectral shift. Research on direct orbital interac-
tion between s* of silicon and p*of BODIPY core is
under way.
Copyright © 2019 World Scientific Publishing Company
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DITHIENOSILOLE EXTENDED BODIPYS: SYNTHESIS AND SPECTROSCOPIC PROPERTIES
5
Table 2. Calculated electronic excitation energies, oscillator strengths, and eigenvectors for the
TD-DFT spectra of the dye 1–3 carried out using the B3LYP functional with 6-31G(d, p) basis sets
Statea
Energy (eV)
l (nm)
fb
Orbitals (coefficient)c
3
1
S1
S2
S1
S2
S3
S1
S2
S3
3.03
3.44
2.12
2.74
3.17
1.71
2.22
2.68
409
361
584
452
391
725
560
463
0.47
0.09
1.18
0.07
0.24
0.78
0.13
0.50
H→L (95%)
H-1→L (93%), H→L (7%)
H→L (100%)
H-1→L (55%), H→L+1 (43%)
H-2→L (34%), H-1→L (26%), H→L+1 (38%)
H→L (100%)
2
H-1→L (72%), H→L+1 (27%)
H-2→L (26%), H-1→L (10%),
H→L+1 (31%), H→L+2 (32%)
S4
2.76
450
1.10
H-2→L (23%), H-1→L (16%),
H→L+1 (40%), H→L+2 (18%)
aExcited state. bOscillator strength (<0.01 are not included). cMOs involved in the transitions with H and L denoting
the HOMO and LUMO, respectively.
solvent. HR-MS were recorded on a Bruker Daltonics
microTOF-Q II spectrometer. All the solvents employed
for the spectroscopic measurements were of UV spectro-
scopic grade (Aldrich).
Synthesis and characterization
Synthesis of 3,3′-dibromo-2,2′-bithiophene (6). In
a 150 mL round bottom flask, 3-bromothiophene
(1.45 mL, 15.4 mmol) was taken with anhydrous THF
(30 mL). The solution was cooled to -78°C and lithium
diisopropylamide (LDA (7.5 mL, 2 M solution) was added
dropwise over 30 min. After the addition, the solution
was stirred at same temperature for 1 h and CuCl2 (4.2 g,
31 mmol) was added. The mixture was then allowed to
Fig. 4. Observed and calculated TD-DFT spectra of 1–2 based
on geometry optimizations using the B3LYP functional with
6-31G(d, p) basis sets
stir at -78°C for 1 h and then at room temperature for
4 h. The reaction was quenched with water (20 mL). The
mixturewasextractedwithdichloromethane, washedwith
distilled water (20 mL), dried over anhydrous Na2SO4,
and evaporated in vacuo to obtain a brown solid. The
crude compound was passed through a silica gel column
using (Hex/EA = 98/2) as eluent to yield 6 as a white
EXPERIMENTAL SECTION
1
solid. Yield: 1.4 g (59%), H NMR (400 MHz; CDCl3;
Me4Si) dH, ppm 7.42–7.41 (d, J = 5.2 Hz, 2 H), 7.09–7.08
(d, J = 5.2 Hz, 2 H).
Materials and instrumentation
All reagents were obtained from commercial suppliers
and used without further purification unless otherwise
indicated. All air and moisture-sensitive reactions were
carried out under nitrogen atmosphere. Glassware was
dried in an oven at 100°C and cooled under a stream of
inert gas before use. Dichloromethane and triethylamine
were distilled over calcium hydride. 1H NMR, 13C
NMR, 19F NMR, 11B NMR spectra were recorded on
a Bruker DRX400 and Bruker DRX500 spectrometer
and referenced to the residual proton signals of the
Synthesis of 3,3′-bis(2-ethylhexyl)silylene-2,2′-bith-
iophene (5). At -78°C, a solution of n-BuLi in hexane
(1.6 M, 4.9 mL, 7.8 mmol) was added a solution of
6 (1.25 g, 3.9 mmol) in THF (20 mL). The mixture
was stirred at this temperature for 1 h, then a solution
of dichlorobis(2-ethylhexyl)silane (1.88 g, 5.8 mmol)
in THF (10 mL) was added. This mixture was slowly
allowed to warm to room temperature overnight. The
reaction mixture was then poured into 60 mL water,
extracted with EA (3 × 40 mL), dried over MgSO4,
Copyright © 2019 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2019; 23: 5–7

6
Y. SUN ET AL.
and evaporated. The residue was purified by silica gel
chromatography (hexane), to give product 5 (0.925 g,
67%). 1H NMR (400 MHz; CDCl3; Me4Si) dH, ppm 7.17
(d, J = 4.0 Hz, 2 H), 7.03 (d, J = 4.0 Hz, 2 H), 1.40–1.38
(m, 2 H), 1.25–1.14 (m, 16 H), 0.94 (t, J = 6.0 Hz, 4 H),
0.81 (t, J = 8.0 Hz, 6 H), 0.76 (t, J = 8.0 Hz, 6 H).
2 H), 6.64 (s, 2 H), 1.46 (s, 6 H), 1.44–1.40 (m, 4 H),
1.25–1.18 (m, 32 H), 1.02 (t, J = 6.0 Hz, 8 H), 0.84 (t, J =
8.0 Hz, 12 H), 0.78 (t, J = 8.0 Hz, 12 H). 13C NMR
(100 MHz; CD2Cl2; Me4Si): dC, ppm 152.29, 149.40,
145.01, 144.96, 144.82, 144.09, 142.36, 135.65, 132.47,
130.59, 129.49, 129.33, 129.17, 127.12, 118.19, 117.38,
36.39, 36.11, 36.08, 32.44, 30.15, 29.34, 29.32, 23.41,
23.12, 18.08, 14.82, 14.36. 11B NMR (128 MHz; CDCl3;
Me4Si) dB, ppm 1.19 (t, BF2) ppm. 19F NMR (376
MHz; CDCl3; Me4Si) dF, ppm -138.74 (q, BF2). UV-vis
(DCM): lmax, nm (log e) 738 (4.89); MS (HRMS-ESI):
m/z 1162.5709 (calcd. for [M–F]+ 1162.5765).
Synthesisof4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,-
5-b′]dithiophene-2-carbaldehyde(4).5(2.0g,4.79mmol)
was dissolved in DCM (20 mL) in a 100 mL round
bottom flask, and then dimethylformamide (349 mg,
4.79 mmol) was added at room temperature. The
resulting reaction solution was cooled to 0°C and then
POCl3 (0.875 mL, 9.55 mmol) was added. The reaction
mixture was refluxed overnight. The reaction mixture
was allowed to cool down and worked up with saturated
sodium acetate solution and extracted using chloroform.
The organic layer was washed with water and dried over
Na2SO4 and purified by column chromatography on silica
(DCM: hexane 2/1) to get 1.3 g (59%) of 4 as a yellow
oil. 1H NMR (400 MHz; CDCl3; Me4Si): dH, ppm 9.86 (s,
1 H), 7.69 (s, 1 H), 7.38 (d, J = 4.0 Hz, 1 H), 7.10 (d, J =
4.0 Hz, 1 H), 1.38–1.37 (m, 2 H), 1.26–1.13 (m, 16 H),
0.99–0.96 (m, 4 H), 0.81–0.73 (m, 12 H).
Spectroscopic measurements
UV-vis absorption spectra were recorded on a
Shimadzu 1800 spectrophotometer. The fluorescence
lifetimes and the absolute quantum yields (FF) of the
samples were determined with a Horiba Jobin Yvon
Fluorolog-3 spectrofluorimeter. Absorption and emission
measurements were carried out in 1 × 1 cm quartz
cuvettes. For all measurements, the temperature was kept
constant at (298 2) K. Dilute solutions with absorbance
of less than 0.05 at the excitation wavelength were used
for the measurement of fluorescence quantum yields.
9,10-Diphenylanthracene was used as the standard ZnPc
(F = 0.28, in DMF)) [29]. The quantum yield, F, was
calculated using equation (1): [30]
Synthesis of DTS-BODIPY 1 and 2. A solution of 3
(162 mg, 0.5 mmol), 4 (335 mg, 0.75 mmol) and a few
crystals of p-TsOH in a mixture of toluene (30 mL) and
piperidine (1.2 mL) was placed in a round bottom flask
equipped with a Dean Stark trap. The mixture was heated
until it evaporated to dryness. After cooling to room
temperature, the resulting mixture was dissolved in DCM
and washed with water three times. The organic phase
was dried over Na2SO4 and the solvent was evaporated
under reduced pressure. The resulting crude residue was
purified by silica gel flash column chromatography (15%
ethyl acetate/hexane) and recrystallized from DCM/
Hexane to provide 1 as a purple solids (59 mg, 15%) and
2 as dark blue solids in 22% yield.
2




I
n
sample 



sample 



Astd
Φsample = Φstd
(1)


Istd
A
nstd


sample 



where the sample and std subscripts denote the sample and
standard, respectively, I is the integrated emission intensity,
A stands for the absorbance, and n is refractive index.
DFT calculations
1
1: H NMR (400 MHz; CDCl3; Me4Si): dH, ppm
The G09W software package was used to carry out
DFT geometry optimization using the B3LYP functional
with 6-31G (d, p) basis sets [28]. The same approach was
used to calculate the absorption properties based on the
time-dependent (TD-DFT) method.
7.49–7.48 (m, 3 H), 7.39 (s, 1 H), 7.36 (s, 1 H), 7.32–
7.30 (m, 2 H), 7.25 (s, 1 H), 7.05 (d, J = 4.0 Hz, 1 H),
7.05 (d, J = 4.0 Hz, 1 H), 6.56 (s, 1 H), 5.99 (s, 1 H),
2.60 (s, 3 H), 1.43 (s, 2 H), 1.42 (s, 3 H), 1.39 (s, 3 H),
1.26–1.15 (m, 16 H), 0.96 (t, J = 6.0 Hz, 4 H), 0.83 (t,
J = 8.0 Hz, 6 H), 0.77 (t, J = 8.0 Hz, 6 H). 13C NMR
(100 MHz; CD2Cl2; Me4Si): dC, ppm 152.77, 143.19,
143.03, 135.46, 133.55, 132.55, 131.84, 130.63, 129.78,
129.52, 128.80, 128.64, 127.00, 125.84, 125.15, 124.37,
121.53, 119.39, 117.95, 117.23, 36.34, 36.04, 34.54,
31.58, 30.56, 30.11, 29.26, 23.35, 23.12, 18.02, 14.53,
14.29, 10.95. 11B NMR (128 MHz; CDCl3; Me4Si) dB,
ppm 0.97 (t, BF2) ppm. 19F NMR (376 MHz; CDCl3;
Acknowledgments
Financial support was provided by the National Natural
Science Foundation of China (Nos. 21801057, 21871072,
21501073). Research funding project of Hangzhou
Normal University (2018PYXML009, 2018QDL002,
2018YLXK16). Theoretical calculations were carried out
at the Computational Center for Molecular Design of
Organosilicon Compounds, Hangzhou Normal University.
Me4Si) dF, ppm -142.43 (q, BF2). UV-vis (DCM): lmax
,
nm (log e) 620 (4.78); MS (HRMS-ESI): m/z 775.3541
(calcd. for [M + H]+ 775.3537).
Supporting information
2: 1H NMR (400 MHz; CDCl3; Me4Si): dH, ppm 7.55–
7.51 (m, 3 H), 7.43–7.41 (m, 3 H), 7.38–7.36 (m, 3 H),
7.33–7.30 (m, 2 H), 7.24 (s, 2 H), 7.13 (d, J = 4.0 Hz,
1H NMR, 13C NMR, 19F NMR, 11B NMR and HR-MS
spectra are given in the supplementary material. This
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DITHIENOSILOLE EXTENDED BODIPYS: SYNTHESIS AND SPECTROSCOPIC PROPERTIES
7
material is available free of charge via the Internet at
http://www.worldscinet.com/jpp/jpp.shtml.
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