Preparation of new biologically active and water soluble dyes: Characterization, aggregation and extraction of metal ions from solutions

Article abstract of DOI:10.14233/ajchem.2019.22048

The synthesis of metallo-phthalocyanines complexes (M = Co, Ni, Cu, Zn) containing azo dye were described in this study. The metallophthalocyanines have been supported by elemental analysis, UV-visible, FT-IR and NMR. The aggregation of phthalocyanine compounds was investigated in different solvents and concentrations. The newly synthesized metallophthalocyanines possess modest antibacterial activity against various Gram-positive and Gram-negative bacteria. Moreover, these complexes have been tested as antioxidant and presented remarkable activities by two different in vitro chemical assays. They were able to reduce DPPH % radical with IC50 values ranging from 3.8 to 7.5 μmol L^-1 and some of them also reduced ABTS % radical cation.

Full text of DOI:10.14233/ajchem.2019.22048

Asian Journal of Chemistry; Vol. 31, No. 6 (2019), 1398-1404
A
SIAN
J
OURNAL OF HEMISTRY
C
https://doi.org/10.14233/ajchem.2019.22048
Preparation of New Biologically Active and Water Soluble Dyes:
Characterization, Aggregation and Extraction of Metal Ions from Solutions
1
2
2,*
NEDRA TOUJ , ABDULLAH SULAIMAN AL-AYED and NACEUR HAMDI
1
Research Laboratory of Environmental Sciences and Technologies (LR16ES09), Higher Institute of Environmental Sciences and Technology,
University of Carthage, Hammam-Lif, Tunisia
2
Department of Chemistry, College of Science and Arts, Qassim University, Al-Rass, Kingdom of Saudi Arabia
*
Corresponding author: E-mail: naceur.hamdi@isste.rnu.tn
Received: 3 March 2019; Accepted: 15 April 2019;
Published online: 29 April 2019;
AJC-19386
The synthesis of metallo-phthalocyanines complexes (M = Co, Ni, Cu, Zn) containing azo dye were described in this study. The metallo-
phthalocyanines have been supported by elemental analysis, UV-visible, FT-IR and NMR. The aggregation of phthalocyanine compounds
was investigated in different solvents and concentrations. The newly synthesized metallophthalocyanines possess modest antibacterial
activity against various Gram-positive and Gram-negative bacteria. Moreover, these complexes have been tested as antioxidant and
presented remarkable activities by two different in vitro chemical assays. They were able to reduce DPPH % radical with IC50 values
-1
ranging from 3.8 to 7.5 µmol L and some of them also reduced ABTS % radical cation.
Keywords: Phthalocyanines, Aggregation, Antibacterial activity, Antioxidant activity.
groups such as crown ethers, alkyl, alkoxy, alkylthio, tertiary
INTRODUCTION
butyl groups and amide groups bound in the peripheral benzene
rings of phthalocyanines structure, solubility of phthalocya-
nines can exceedingly improve in protic or non-protic solvents
Phthalocyanines belong to an immense class of π-conju-
gated metallomacrocycles, which are of great interest due to
their diverse important applications in modern science and
technology [1,2]. Phthalocyanines have an original electronic
structure based on 18-π delocalization, resulting in near-infrared
absorption around 700 nm [3-5]. Subsequent electronic, photo-
physical and photochemical properties are responsible for
many applications [6]. Phthalocyanines are broadly employed
as sensors [7-9], oxidation catalysts [10-12] and photocatalysis
[33,34]. Water-soluble phthalocyanines can be used in PDT
and catalysis. Catalysis of reactions in aqueous media is currently
becoming of major interest. Hence, when designing a phthalo-
cyanines on demand for a specific application, or to get a precisely
targetedproperty, itswater-solubilitymaybearequirement[35-39].
Herein in this study, the synthesis, characterization and
spectroscopic properties of tetrasubstituted metal complexes
[
13] as well as for their nonlinear properties [14-16]. Their use
(
8-11) at the peripheral position with 4-[(4-hydoxyphenyl)azo]-
as photosensitizers of second and third-generation for photo-
dynamic therapy [17] remains a major one. Their applications
depend on their solubility. By introducing electron-withdrawing
such as halogen atoms (-F, -Cl, -Br) and electron-donating
benzene sodium sulfonate group were described. Their Q bands
were appeared at around 613-689 nm. In addition their anti-
microbial and antioxidant activities were also investigated.
EXPERIMENTAL
(
-NH , Ar-S-, RO-, RS-) bulky or long-chain alkyl groups into
2
the peripheral sites on phthalocyanines skeleton, their solubility
can be increased [18-31].
Unfortunately, phthalocyanines don't usually soluble in
common organic solvents and their insolubility causes diffic-
ulties for many applications [32]. When plausible functional
The synthesis of all the compounds and their antimicrobial
activities were done according to the reported procedures [40].
1
5-Nitro-isoindole-1.3-dione (1): White solid (85 %); H
NMR (300 MHz, DMSO-d
(s, 1H), 8.54 (d, J = 6.9 Hz, 1H), 11.76 (s, 1H). C NMR (75
6
): δ 8.00 (d, J = 5.7 Hz, 1H), 8.34
13
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4

Vol. 31, No. 6 (2019)
Preparation of New Biologically Active and Water Soluble Dyes 1399
MHz, DMSO-d
51.71, 167.61, 167.91.
Phthalamide (2): Yellow solid (95 %); H NMR (300
MHz, DMSO-d ): δ 7.64 (s, 2H), 7.70 (d, J = 8.1 Hz, 1H), 8.02
s, 1H), 8.08 (s, 1H), 8.29 (dd, J = 2.4 Hz, 8.7 Hz, 1H), 8.34
6
): δ 118.16, 124.92, 129.87, 134.42, 137.66,
Nickel phthalocyanine (10): White solid (90 %, 83 mg);
1
m.p.: 285-298 ºC. UV-Vis (νmax, nm): 612, 675, 325. IR (KBr,
1
-1
ν
max, cm ): 3060 (Ar-CH), 1587 (C=C), 1469 (N=N), 1221
6
(Ar-O-Ar), 1183 (O-S-O).Anal. calcd. (found) % for C80
Na Ni·3H O: C, 52.66 (52.71); H, 5.74 (5.76); N, 12.28
(12.40).
H N
44 16
(
(
O
16
S
4
4
2
13
d, J = 2.1 Hz, 1H). C NMR (75 MHz, DMSO-d
1
6
): δ 122.35,
24.38, 129.11, 137.19, 142,65, 147.02, 167.67, 168.67.
-Nitrophthalonitrile (3): White solid (86 %); IR (KBr,
Cobalt phthalocyanine (11):White solid (75 %, 84 mg);
4
m.p.: 295-310 ºC. UV-Vis (νmax, nm): 620, 686, 340. IR (KBr,
-1
-1
ν
max, cm ): 3091 (C-Harom.), 2242 (CN), 1534 (N=Oasym.), 1349
ν
max, cm ): 3060 (Ar-CH), 1588 (C=C), 1469 (N=N), 1220
1
(
N=Osym.), 853 (C-N). H NMR (300 MHz, DMSO-d
6
): δ 8.44
(Ar-O-Ar), 1182 (O-S-O). Anal. calcd. (found) % for
Na Co·3H O: C, 52.65 (52.70); H, 5.74 (5.78);
N, 12.28 (12.30).
(
d, J = 8.7 Hz, 1H), 8.69 (dd, J = 2.1 Hz, 8.4 Hz, 1H), 9.03 (d,
C
80
H
44
N
16
O
16
S
4
4
2
13
J = 2.1 Hz, 1H). C NMR (75 MHz, DMSO-d
1
6
): δ 114.55,
14.86, 116.59, 120.22, 128.52, 128.81, 135.27, 149.69.
Metal free phthalocyanine (7):White solid (80 %); m.p.:
30-335 ºC; UV-Vis (νmax, nm): 620, 690, 345. IR (KBr, νmax
RESULTS AND DISCUSSION
3
,
The first step in the synthetic process of these complexes
(M = Co, Ni, Cu, Zn) was to obtain phthalonitrile (1,2-dicyano-
benzene) derivatives containing 4-[(4-hydoxyphenyl)azo]-
benzene sodiumsulfonate (5). This was accomplished by a base
catalyzed nucleophilic aromatic nitro displacement of 4-nitro-
phthalonitrile with 4-[(4-hydoxyphenyl)azo]benzene sodium
sulfonate (5). The nitration of phthalimide was occurred in
position 4, then the reaction of obtained intermediate with amine
hydroxide, afforded 4-nitrophthalamide (2). The condensation
-1
cm ): 3276 (N-H), 3071 (C-Harom.), 1471 (C-C), 1265 (C-N),
1
MHz, DMSO-d
%
1
602 (C=C), 1208 (C-Olactone), 1725 (C=Olactone). H NMR (300
): δ 8.35-8.45 (m, Harom.). Anal. calcd. (found)
12: C, 70.71 (70.70); H, 2.96 (2.90); N, 9.70
6
for C68
H
34
8
N O
(
9.70).
Zinc phthalocyanine (8): White solid (75 %, 59 mg);
m.p.: 285-290 ºC. UV-Vis (νmax, nm): 617, 688, 340. IR (KBr,
-1
ν
max, cm ): 3060 (Ar-CH), 1646, 1590 (C=C), 1471 (N=N),
1
228 (Ar-O-Ar), 1180 (O-S-O). Anal. calcd. (found) % for
of compound 2 with SOCl in N,N-dimethylformamide gave
2
C
80
H
44
N
16
O
16
S
4
Na
4
Zn·3H
2
O: C, 52.47 (52.53); H, 5.57 (5.50);
dinitrile 3 (Scheme-I). The diazotization process of amino-
benzene sulfonic acid produce stable azo compound 4, which
subsequent reaction with phenol gave 4-[(4-hydoxyphenyl)-
azo]benzene sodium sulfonate (5) (Scheme-II).
Dinitriles 6 were synthesized by reaction of 4-[(4-hydoxy-
phenyl)azo]benzene sodium sulfonate (5) with 4-nitrophthalo-
N, 12.24 (12.26).
Copper phthalocyanine (9): White solid (90 %, 63 mg);
m.p.: 290-295 ºC. UV-Vis (νmax, nm): 604, 678, 328. IR (KBr,
-1
νmax, cm ): 3060 (Ar-CH), 1591 (C=C), 1474 (N=N), 1220
(Ar-O-Ar), 1179 (O-S-O).Anal. calcd. (found) % for C80
H
44
N
16
O
16
S
4
Na
4
Cu·3H
2
O: C, 52.52 (52.57); H, 5.73 (5.74); N, 12. 25
nitrile in the presence of K
2
CO
3
in DMSO at room temperature
(
12.26).
for 48 h (Scheme-III).
O
O
O
HNO , H SO
3
2
4
NH OH 25%
2
NH
NH
O
NH
NH
2
0°C, 5 h
2
O2N
O
1
2
O
CN
DMF, SOCl2
0-2°C , 5h
O N
2
CN
3
Scheme-I: Synthesis of compounds 1-3
OH
(
i)
HO3S
NH2
NaO3S
N N,Cl
NaO3S
N N
OH
4
5
Scheme-II: Synthesis of 4-[(4-hydoxyphenyl)azo]benzene sodium sulfonate (5)

1
400 Touj et al.
Asian J. Chem.
NC
NC
NO2
CN
NaO S
N N
OH
3
(ii)
5
NaO3S
N N
O
CN
6
Scheme-III: Synthesis of dinitriles (6)
1
13
13
The dinitriles 6 were characterized by H NMR, C NMR
supporting the proposed structure. In the C NMR spectrum
of compound 6, aromatic carbon atoms were observed at the
range of 117.3-161.8 ppm whereas carbon atom CN was
observed at 160.1 ppm.
and FT-IR. In the IR spectrum of dinitrile 6, -OH vibration of
compound 5 disappeared. The characteristic vibrations corres-
ponding to aromatic CH stretching was observed at 3080 cm .
-1
1
In H NMR spectrum, the aromatic protons of compound 6
The self-heating of dinitrile 6 in the presence of 1,8-diaza-
bicyclo[5.4.0]undec-7-ene (DBU) for 24 h at 150 ºC under N
1
3
appearred between 7.45 and 8.20 ppm. The C NMR spectrum
2
of nitrile compound 6 showed 14 carbon resonance signals,
atmosphere gave compound 7 (Scheme-IV). The metal free
CN
NaO S
N N
O
CN
3
6
SO3Na
N
N
DBU, DMAE, 24 h
O
N
N
N
N
N
O
N
N
SO3Na
NaO3S
N
N
O
N
N
N
O
N
N
SO3Na
7
Scheme-IV: Synthesis of metal-free phthalocyanine compound 7

Vol. 31, No. 6 (2019)
Preparation of New Biologically Active and Water Soluble Dyes 1401
-
1
compound 7 were characterized by spectroscopic methods
such as FT-IR, H NMR and UV-visible techniques.
the major strong -CN band at 2227 cm of compound 6
disappeared after conversion to metallophthalocyanines (8-11).
A very weak band in all metallophthalocyanines above 3000
1
The disappearance of C≡N stretching vibrational band at
-1
-1
2
225 cm confirmed the proposed structure 7. In addition, C-
cm is due to aromatic C-H stretching.
-
1
O-C stretching vibration was observed at 1207 cm . The
aromatic protons appeared between 8.35 and 8.45 ppm. In
addition, they were broader because their higher numbers and
aggregation [35]. Several researchers [36-39,41] generally used
substituted phthalonitriles or 1,3-diimino-1H-isoindoles as
starting materials for synthesis of phthalocyanines.
The UV-visible absorption spectra of metallophthalo-
cyanines 8-11 (M = Co, Ni, Cu, Zn) in DMSO were observed
in the intense Q absorption at 688, 678, 675 and 686 nm,
respectively. In addition, intense B band absorptions were
observed at 340 nm for compound 8, 328 nm for compound
9, 325 for compound 10 and 340 nm for compound 11 in
DMSO (Table-1).
The reflux reaction of dinitrile 6 with metal chloride salts
under N
2
atmosphere in dimethylaminoethanol (DMAE) for
The aggregation behaviours of water-soluble phthalo-
cyanines containing azo dye 8-11 were investigated in DMSO.
The metallophthalocyanines 8-11 did not show any aggregation
in DMSO. The aggregation behaviours of metallophthalocyanines
2
4 h gave metallophthalocyanines 8-11 (Scheme-V).
1
13
H NMR and C NMR spectra of the complexes (M =
Cu, Co) because of paramagnetic metal atom. In FT-IR spectra,
CN
NaO S
N N
O
CN
3
6
SO Na
3
Metal salts,
1
70°C,
DMAE,
4 h
N
N
2
O
N
N
N
O
N N
SO3Na
NaO S
N N
O
N M
N
3
N
N
N
O
8
:
M = Zn
M = Cu
N
N
9
:
1
1
0 : M = Ni
1 : M = Co
SO Na
3
8
-11
Scheme-V: Protocol synthesis of complexes 8-11

1
402 Touj et al.
Asian J. Chem.
TABLE-1
Antibacterial activity: The water-soluble metallophthalo-
cyanines containing azo dyes 8-11 were evaluated for their
antimicrobial activities as indicated in previous studies [50].
The antimicrobials results are presented in Table-2. The inhibi-
tion zones of these compounds were ranged between 14-25
mm with different patterns. Also, the active compounds were
analyzed in order to determine the lowest concentration (MIC)
capable of inhibiting visible bacterial growth. The MIC values
revealed that complex 11 had promising antimicrobial profile
against LB14110.
UV-VISIBLE SPECTRAL DATA FOR METALLO
PHTHALOCYANINES (Pcs) 8-11 IN DIFFERENT SOLVENTS
DMSO, DMF AND THF) AT A CONCENTRATION OF 10 M
–
5
(
Bandes (Q),
λmax (nm) (log ε)
B-Band,
Solvent
MPcs
λmax (nm) (log ε)
340 (4.780)
328 (4.000)
325 (4.770)
340 (4.760)
336 (5.044)
335 (4.918)
342 (4.946)
333 (4.881)
340 (5.100)
342 (5.010)
350 (4.950)
342 (4.790)
8
9
617 (4.38); 688 (5.08)
604 (4.187); 678 (4.878)
612 (4.28); 675 (4.95)
620 (4.40); 686 (4.78)
611 (4.642); 678 (5.197)
619 (4.593); 675 (5.150)
628 (4.706); 668 (5.060)
616 (4.507); 675 (5.020)
634 (4.89); 679 (5.22)
630 (4.78); 675 (5.16)
612 (4.55); 679 (5.24)
626 (4.67); 672 (5.07)
DMSO
DMF
THF
1
1
0
1
8
9
Free radical scavenging activity: The in vitro antioxidant
activities of complexes 8-11 were evaluated in a series of assays
involving DPPH scavenging [51]. It was found that water-soluble
metallophthalocyanines containing azo dye 8-11 possess higher
activity than Trolox with EC50 value of 4.8, 5, 3.8 and 4.2
10
11
8
9
10
-1
11
µmol L , respectively (Table-3).
ABTS radical cation decolorization assay: The potential
of complexes 8-11 to scavenge free radicals was also assessed
8
-11 in DMSO were also investigated at different concentra-
+•
tions for determination of the aggregation depending on concen-
tration [42-49] (Fig. 1). These metallophthalocyanines 8-11
did not show any aggregation in the concentration ranges
between 1 × 10 M and 6 × 10 M. The intensity of absorption
of Q band also increased in parallel and no new bands (normally
blue-shifted), which might be attributed to aggregated species
were observed.
by their ability to quench ABTS [52]. Fig. 2 depicted the
•
+
concentration dependent decolorization of ABTS while the
EC50 values exhibited by water-soluble metallophthalocyanines
containing azo dye 8-11 are summarized in Table-3.
−
6
−6
Henceforth, the water-soluble metallophthalocyanines
containing azo dye 8-11 were shown to be efficient to fix free
+•
radicals DPPH and ABTS .
1
1
.6
.4
1
1
1
1
0
0
0
0
.6
.4
.2
.0
.8
.6
.4
.2
0
2
.0
.5
2
.0
1.5
.0
1
1
0.5
0
1.0
y = 76200x + 0.399
R² = 0.999
y = 10050x + 0.127
0.5
2
R
= 0.994
1.4×10
Concentration (M)
–6
–6
–5
0
1.2
.0
4×10
9×10
1.4×10
–6
–6
–5
4×10
9×10
Concentration (M)
1
(b)
(
a)
–6
0.8
0.6
0.4
6×10–
M
M
6
–6
8
×10
6×10
M
M
M
M
M
–
6
–6
10×10–
M
M
M
8
×10
6
–6
1
1
2×10–
10×10
12×10
4×10
6
–6
4×10
–6
1
0
.2
0
3
00
400
500
600
700
800
3
00
400
500
600
700
800
Wavelength (nm)
Wavelength (nm)
1
1
1
1
1
0
0
0
0
.8
1.4
1.2
1.0
2
1
1
0
.0
.5
.0
.5
0
1.5
1.0
.6
.4
.2
.0
.8
.6
.4
.2
0
y = 10000x + 0.278
R² = 0.992
0.5
0
y = 89037x + 0.030
R² = 0.996
4×10–6
9×10–6
1.4×10–5
–6
–6
–5
4
×10
9×10
1.4×10
Concentration (M)
Concentration (M)
0
.8
(c)
(d)
–
6
6
×10
M
M
M
M
M
–6
–6
8×10
0.6
0.4
6×10
8×10
M
M
–
6
–6
1
0×10–6
12×10–6
4×10
–6
10×10
12×10
4×10
M
M
M
–6
1
–6
1
0
.2
0
3
00
400
500
Wavelength (nm)
Fig. 1. Aggregation behaviour of phthalocyanine 8 (a), 9 (b), 10 (c) and 11 (d) in DMSO
600
700
800
300
400
500
600
700
800
Wavelength (nm)

Vol. 31, No. 6 (2019)
Compounds
Preparation of New Biologically Active and Water Soluble Dyes 1403
TABLE-2
ANTIBACTERIAL ACTIVITY OF THE SYNTHESIZED COMPOUNDS 6-11
Inhibition zone (mm)
MIC (mg/mL)
LB14110
ATCC6835
15 ± 0.4
15 ± 0.3
14 ± 0.2
16 ± 0.2
14 ± 0.3
17 ± 1.1
–
ATCC19117 ATCC14028 ATCC49189
LB14110
1.6
ATCC19117 ATCC14028
6
7
8
9
16 ± 0.4
17 ± 0.3
15 ± 0.2
18 ± 0.4
14 ± 0.4
19 ± 0.5
–
16 ± 0.4
17 ± 0.3
15 ± 0.2
14 ± 0.4
15 ± 0.5
22 ± 0.4
–
17 ± 0.5
22 ± 0.2
19 ± 0.1
20 ± 0.3
18 ± 0.5
21 ± 0.4
–
18 ± 0.5
19 ± 0.2
18 ± 0.1
21 ± 0.3
19 ± 0.5
24 ± 0.1
–
2.2
2.4
2.7
2.4
1.5
1.4
1.5
1.6
1.2
0.0195
2.5
2.3
1.9
2.2
10
2
2.5
11
1.26
0.039
2.6
0.625
Ampicillin
TABLE-3
THE EC VALUES EXHIBITED BY WATER-SOLUBLE
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50
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+
•
Free radical scavenging
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50
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-1
-1
IC (µmol L )
IC (g L )
50
8
9
4.8
5
3.8
4.2
7.5
0.72
0.98
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1.17
0.549
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