Synthesis, solvatochromic performance, ph sensing, dyeing ability, and antimicrobial activity of novel hydrazone dyestuffs

Article abstract of DOI:10.1155/2019/7814179

New tricyanofuran intramolecular charge transfer dyes comprising the hydrazone group were prepared and fully characterized in order to study their possible solvatochromism, dyeing ability, and antimicrobial activity. The preparation of the hydrazone dyes

Full text of DOI:10.1155/2019/7814179

Hindawi
Journal of Chemistry
Volume 2019, Article ID 7814179, 10 pages
https://doi.org/10.1155/2019/7814179
Research Article
Synthesis, Solvatochromic Performance, pH Sensing, Dyeing
Ability, and Antimicrobial Activity of Novel Hydrazone Dyestuffs
Tawfik A. Khattab ,1 Ahmed A. Allam ,2 Sarah I. Othman ,3 May Bin-Jumah ,3
4
Hanan M. Al-Harbi,3 and Moustafa M. G. Fouda
1Dyeing, Printing and Auxiliaries Department, Textile Industries Research Division, National Research Centre,
33 El-Buhouth Street, Dokki, Cairo 12622, Egypt
2Department of Zoology, Faculty of Science, Beni-Suef University, Beni-Suef 65211, Egypt
3Department of Biology, College of Science, Princess Nourah Bint Abdulrahman University, Riyadh, Saudi Arabia
4Pretreatment and Finishing of Cellulosic-based Fibers Department, Textile Industries Research Division,
National Research Centre, 33 El-Buhouth Street, Dokki, Cairo 12622, Egypt
Correspondence should be addressed to Tawfik A. Khattab; ta.khattab@nrc.sci.eg
Received 18 September 2018; Accepted 4 December 2018; Published 5 February 2019
Academic Editor: Zhen Cheng
Copyright © 2019 Tawfik A. Khattab et al. +is is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
properly cited.
New tricyanofuran intramolecular charge transfer dyes comprising the hydrazone group were prepared and fully characterized in
order to study their possible solvatochromism, dyeing ability, and antimicrobial activity. +e preparation of the hydrazone dyes
was achieved in relatively good yields starting from different aromatic amines. +e hydrazone functional group was presented via
the azo-coupling reaction of the tricyanofuran compound by the properly substituted diazonium chloride. Chemical structures of
the prepared hydrazones were confirmed via nuclear magnetic resonance spectroscopy (1H- and 13C-NMR), Fourier-transform
infrared spectroscopy (FT-IR), and elemental analysis (C, H, and N). +e UV-visible absorption spectra of the produced sensor
colorants displayed interesting solvatochromism in solvents with a different polarity, which was found to be affected by the
substituents bonded to the aromatic hydrazone moiety. +e pH molecular switching was investigated through tuning the
intramolecular charge transfer stimulated by the reversible deprotonation/protonation process in acetonitrile solution showing
color change from yellow to purple. +e produced disperse dyestuffs were employed for dyeing polyester fibers to introduce
acceptable color strength and colorfastness properties. Moreover, the dyes verified a weak to moderate antimicrobial activity
against some selected pathogens, including S. aureus, E. coli, and Candida albicans.
spectra in each solvent. +ere is a variety of solvatochromic
dyes that have been discovered recently, such as pyridinium,
merocyanine, and stilbazolium dyes [9–15].
1. Introduction
Solvatochromic materials attract much interest due to their
potential applicability as sensors in determining solvent
polarity, optical light-emitting diodes, dye sensitized solar
cells, and electro- and photoluminescent materials for laser
purposes, in molecular electronics for the production of
molecular switches, colorimetric chemosensors in detection
of explosives, and volatile organic materials [1–8]. Generally,
a solvatochromic material can be defined as a chemical
substance able to alter its color in solvents of different
polarities due to a variation in its absorption or emission
Hydrazones are originally a Schiff-base group of mate-
rials possessing a secondary amine proton comprising an
important category of compounds in a diversity of research
fields, such as nonlinear optics, sensors, and a variety of
biological and medical applications [16–26]. +us, many
researchers have prepared hydrazone-based materials as
main goal molecular structures and investigated their an-
timicrobial activities. +e widespread use of antimicrobial
agents results in the growth of strongly resistant pathogens.

2
Journal of Chemistry
+erefore, there has been an important concern in the
improvement of diverse inventive collection of pharmaco-
logical agents [27–33]. +ese observations emphasize the
necessity for the preparation of novel hydrazones that gain
diverse biological activities. Arylhydrazones are character-
ized by their simple preparation and worth considering in
the design of novel molecular switches with solvatochromic
and pH sensing performance. A hydrazone functional group
has the ability to operate as a bridge in a donor-acceptor
molecular structure, or it can act itself as an electron donor
moiety, when it is in conjugation with an electron-
withdrawing moiety [34–39].
Herein, we present the synthesis, characterization,
photophysical properties, dyeing behavior, and antimicro-
bial assessment of novel tricyanofuran-hydrazone dyes 1–3,
in which a number of electron-withdrawing and electron-
donating substituents were introduced at the ortho-, meta-,
and para-positions of the aromatic moiety of the diazonium
chloride. +e molecular structures of the novel hydrazone
dyes are presented in Figure 1. +e molecular switching
character of the hydrazone dye was also explored.
arylamine (1.0 mmol) and hydrochloric acid (5.0 mL) in
25 mL glass beaker was stirred on a magnetic stirrer and
cooled to 0–5°C in an ice bath. An aqueous solution of
sodium nitrite (1.0 mmol) in water (3.0 mL) was then
added slowly. +e produced diazonium salt was stirred for
an extra 30 minutes at 0–5°C. In a separate glass beaker,
tricyanofuran (1.0 mmol) was dissolved in acetonitrile
(5.0 mL) and cooled to 0–5°C, and sodium acetate (1.0 g)
was added. +e produced mixture was vigorously stirred in
the ice bath at 0–5°C, while the cold diazonium salt so-
lution was added dropwise. After stirring for an extra two
hours, the crude product was filtered off under vacuum,
washed with distilled water (3 × 5 mL), recrystallized, and
air-dried.
(1) 2-(3-Cyano-5,5-dimethyl-4-((2,4-dinitro-5-fluorophenylhy-
drazono)methyl)furan-2(5H)-ylidene)malononitrile (1). It is
prepared from 2,4-dinitro-5-fluoroaniline (200 mg, 1.0 mmol)
and tricyanofuran (200 mg, 1.0 mmol). +e product was fil-
tered off under vacuum, recrystallized from ethanol, and fi-
nally air-dried to give a red solid (260 mg; yield 63%). mp
226–228°C; 1H-NMR (400 MHz, DMSO-d6) δ (ppm):12.31 (s-
broad, 1H, NH), 8.59 (s-broad, 1H aliphatic, �C-H), 8.44 (d,
J � 8.0 Hz, 1H aromatic), 7.61 (d, J � 8.0 Hz, 1H aromatic), and
1.78 (s, 6H aliphatic). 13C-NMR (400 MHz, DMSO-d6) δ
(ppm): 177.54, 172.92, 158.50, 136.97, 125.05, 118.45, 115.74,
113.61, 113.76, 112.12, 99.83, 98.00, 55.41, 26.73, and 23.91. IR
2. Experimental
2.1. Materials and Methods. Melting points were measured
uncorrected in degree Celsius using Stuart SMP30. FT-IR
spectra were investigated by Fourier-transform infrared
spectrophotometer (Nexus 670, Nicolet, United States) in
−1
(neat, ν/cm ): 3287 (NH), 2206 (CN), 1586 (C�N), and 1507
−1
and 1332 (NO2). MS m/z (%): 410 [M-H]+. Elemental analysis
calculated for C17H10FN7O5 (411.07): C 49.64, H 2.45, F 4.62,
and N 23.84; found: C 49.51, H 2.37, F 4.52, and N 23.96.
the range of 400–4000 cm with a spectral resolution of
−1
4.0 cm . Mass spectra were reported on a Shimadzu GCMS-
QP 1000 EX mass spectrometer at 70 eV. Elemental analyses
(C, H, and N) were studied using PerkinElmer 2400 analyzer
(Norwalk, United States). UV-visible absorption spectra
were determined at ambient conditions using UNICAM
UV-visible 300. Nuclear magnetic resonance (NMR) spectra
were measured on a BRUKER AVANCE 400 spectrometer at
400 MHz; chemical shift was given in ppm relatively to an
internal standard TMS at 295°K. +e color strength was
examined using UltraScan PRO Spectrophotometer (light
source D65/10° observer). +e pH values were reported
using a BECKMAN COULTER pHI 340 meter with a
combined glass-calomel electrode.
(2) 2-(3-Cyano-5,5-dimethyl-4-((4-pyridylhydrazono)methyl)fu-
ran-2(5H)-ylidene)malononitrile (2). It is prepared from 4-
aminopyridine (94 mg, 1.0 mmol) and tricyanofuran (200 mg,
1.0 mmol). +e product was filtered off under vacuum,
recrystallized from ethanol, and finally air-dried to give a yellow
solid (160 mg; yield 53%). mp 218–220°C; 1H-NMR (400 MHz,
CD3COCD3) δ (ppm): 12.82 (s-broad, 1H, NH), 8.57 (d,
J � 8.0 Hz, 2H aromatic), 8.31 (s, 1H aliphatic, �C-H), 7.48 (d,
J � 4.0 Hz, 2H aromatic), and 1.84 (s, 6H aliphatic). 13C-NMR
(400 MHz, DMSO-d6) δ (ppm): 176.91, 171.27, 156.37, 134.89,
123.14, 114.01, 113.28, 112.69, 110.71, 99.41, 56.77, 26.91, and
Solvents were purchased from Aldrich and Fluka for
both of the preparation procedures of dyes and spectro-
scopic studies (spectroscopic grade). All reactions were
observed using Merck aluminum thin layer chromatography
plates precoated with silica gel PF254 (20 × 20 mm, 0.25 mm)
and monitored by naked eye under an ultraviolet lamp (254
or 365 nm). +e tricyanofuran moiety and tricyanofuran
hydrazone dyestuffs were prepared according to previously
reported literature [26]. A 100% polyester fabric (149 g/m2)
was supplied by Misr El-Mahalla Spinning and Weaving
Company, El-Mahalla El-Kubra, Egypt. +e fabric was
scoured according to the literature procedure [40, 41].
−1
23.65. IR (neat, ν/cm ): 3248 (NH), 2223 (CN), and 1575
(C�N). MS m/z (%): 303 [M-H]+. Elemental analysis calculated
for C16H12N6O (304.11): C 63.15, H 3.97, and N 27.62; found: C
63.28, H 4.09, and N 27.51.
(3) 2-(3-Cyano-5,5-dimethyl-4-((4-nonylphenylhydrazono)methyl)
furan-2(5H)-ylidene)malononitrile (3). It is prepared from 4-
nonylaniline (220 mg, 1.0 mmol) and tricyanofuran (200 mg,
1.0 mmol). +e product was filtered off under vacuum,
recrystallized from ethanol, and finally air-dried to give an
1
orange solid (370 mg; yield 86%). mp 214–216°C; H-NMR
(400 MHz, CDCl3) δ (ppm): 10.02 (s-broad, 1H, NH), 7.67
(d, J � 8.0 Hz, 2H aromatic), 7.36 (d, J � 8.0 Hz, 2H aromatic),
7.29 (s, 1H aliphatic, �C-H), 2.73 (t, J � 3.2 Hz, 2H aliphatic),
1.81 (s, 6H aliphatic), 1.34 (s, 14H aliphatic), and 0.92
(t, J � 2.2 Hz, 3H aliphatic). 13C-NMR (400 MHz, CDCl3)
2.2. Synthesis of Dyestuffs
2.2.1. General Procedure for the Synthesis of the Hydrazone
Dyes 1–3. A mixture of the appropriate substituted

Journal of Chemistry
3
H
N
NO2
H
N
CN
O
CN
O
CN
CN
CN
CN
N
N
N
O2N
2
1
F
H
N
CN
O
CN
CN
N
3
Figure 1: Hydrazone dyestuffs 1–3.
δ (ppm): 177.68, 172.62, 140.26, 134.04, 130.44, 124.75,
2.5.ColorStrengthMeasurement. +e color strength (K/S) of
115.39, 113.85, 113.19, 111.67, 98.83, 38.21, 29.68, 29.88, 29.73,
the dyed polyester samples was assessed by applying the high
−1
26.71, 25.04, 21.55, and 14.67. IR (neat, ν/cm ): 3386 (NH),
2916 (CH aliphatic), 2846 (CH aromatic), 2217 (CN), and
1577 (C�N). MS m/z (%): 428 [M-H]+. Elemental analysis
calculated for C26H31N5O (429.25): C 72.70, H 7.27, and N,
16.30; found: C 72.83, H 7.19, and N 16.47.
reflectance technique using the Kobelka–Munk equation [K/
S � (1 − R)2/2R − (1 − Ro)2/2Ro], where S is the scattering
coefficient, K is the absorption coefficient, and (R, Ro) are
decimal fractions of the reflectance of both dyed and undyed
polyester samples, respectively [7].
2.3. Dyeing Procedure. +e dyeing process was applied to
the polyester fabric using the high-temperature dyeing
technique according to the literature procedure [4]. +e
dyeing process was carried out using the high-temperature
high-pressure coloration technique according to the lit-
erature procedure [4]. A dispersion of the dyestuff was
prepared by dissolving the proper amount of dye (2 wt.%
relative to the weight of fabric) in 1 mL DMF and then
added gradually with stirring to the dye bath (liquor ratio
50 :1) in presence of sodium lignin sulfonate as a dispersing
agent (2 wt.% relative to the weight of fabric). +e pH of the
dye bath was customized to 4.85 using an aqueous solution
of acetic acid, and the wetted-out polyester fabric was then
added. +e dye-bath temperature was maintained at 130°C
for 180 minutes under pressure in an infrared dyeing
apparatus. +e fabric was then washed and subjected to the
reduction clearing process at 80°C for 45 minutes in an
aqueous bath (1 L) containing sodium hydroxide (2 g) and
sodium hydrosulphite (2 g), followed by soaping using
nonionic detergent (2%). +e fabric was then rinsed in cold
water and neutralized by an aqueous solution of acetic acid
(1 g/L) for 5 minutes at 40°C, followed by rinsing in tap water
and allowed to be air-dried. +e determination of the dye
uptake into polyester fibers was measured applying the ab-
sorption process depending on the Beer-Lambert law. +is
was evaluated by the testing sample from dye bath at different
periods of time (15, 40, 55, 75, 90, 105, 120, 135, 150, 160, 170,
and 180 minutes) while running the dyeing process,
according to the previously reported techniques [4, 7].
2.6. Antimicrobial Evaluation. +e antimicrobial testing of
the obtained hydrazone dyes was performed against S.
aureus (Gram positive), E. coli (Gram negative), and Can-
dida albicans (fungus). +e antimicrobial examination was
made quantitatively using the standard AATCC microbial
count test procedure 100–1999 [42–44].
3. Results and Discussion
3.1. Synthesis of Hydrazone Dyestuffs. +e highly electron-
deficient tricyanofuran moiety was prepared according to a
previously described literature procedure by applying
Knoevenagel condensation between 3-methylacetoin and
malononitrile in presence of absolute ethanol as a solvent
and sodium ethoxide as a strong base [26]. Knoevenagel
condensation reaction is an interesting reaction for the
synthesis of electron-deficient substances, such as the highly
electron-deficient oxygen-containing tricyanofuran hetero-
cycle. +e strongly electron-withdrawing CN groups on the
tricyanofuran moiety are useful for the stabilization of the
tricyanofuran carbanion obtained by proton abstraction
from the active methyl substituent in presence on sodium
acetate as a weak base [2]. +e tricyanofuran carbanion was
then subjected to azo coupling by the appropriate aryldia-
zonium salt to produce the consequent unstable azo dyes
that were converted directly into the stable hydrazone dyes
1–3 as shown in Scheme 1.
+e molecular structures of prepared hydrazone dyes
were verified according to their spectroscopic data. FT-IR
spectra displayed absorption peaks at 3287, 3248, and
2.4. Colorfastness Properties. Colorfastness to perspiration
(ISO105-E04 :1989), washing (ISO105-C02 :1989), rubbing
(ISO105-X12 :1987), and light (ISO105-B02 :1988) was
tested according to AATCC standard test methods. Col-
orfastness to light was assessed employing the blue scale
(1–8; where 1 is very poor and 8 is excellent), while col-
orfastness to washing, perspiration, and rubbing was eval-
uated according to the grey scale (1–5; where 1 is very poor
and 5 is excellent) [7].
−1
3386 cm which are assigned to the hydrazone NH group,
−1
whilst the peaks at 1586, 1575, and 1577 cm are due to
C�N stretch of the hydrazone functional group for dyes 1, 2,
1
and 3, respectively. +e H-NMR spectra showed singlet
peaks at 12.31, 12.82, and 10.02 ppm which are assigned to
the proton of the hydrazone NH group of dyes 1, 2, and 3,
respectively. +e 1H-NMR spectra of dyes 1–3 displayed also
a singlet peak around 8.59, 8.31, and 7.29 ppm, respectively,

4
Journal of Chemistry
CN
CN
H2
C
CH3CN
CH3COONa
H2C
CN
CN
CN
CN
H
Cl
Ar N N
Diazonium salt
+
O
O
Tricyanofuran
carbanion
Tricyanofuran
0–5°C
H
H
N
CN
CN
Ar
N
CN
CN
N
Ar
CN
CN
N
1–3
O
O
Hydrazone form
Azo form
Ar =
H
N
NO2
H
N
H
N
N
O2N
3
F
2
1
C9H19
Scheme 1: Synthesis of hydrazone dyes 1–3.
due to the aliphatic vinyl proton (�C-H). +e downfield
shifting of such singlet signal is a result of the strong impact
of the electron-withdrawing tricyanofuran moiety.
Table 1: UV-visible absorption maxima of dyestuffs 1–3 in dif-
ferent solvents.
λmax (nm)
Solvent
1
2
3
Methanol
525
530
540
538
455
455
455
455
460
485
480
497
485
480
485
485
475
485
480
480
480
480
475
485
485
475
485
3.2. Solvatochromic Measurements. +e UV-visible ab-
sorption bands were monitored in the wavelengths ranges
455–540, 475–497, and 475–485 nm for dyes 1, 2, and 3,
respectively (Table 1 and Figure 2). +ey exhibited colors
between yellow and purple in various pure solvents of
different polarities. +e type of substituents on the aryl-
hydrazone moiety was found to affect on the UV-visible
absorption maximum band. A distinctive solvatochromic
behavior of all dyestuffs in both of protic and aprotic
solvents was monitored. Protic environment was antici-
pated to exhibit partial protonation to the hydrazone
dyestuffs via hydrogen bonding of the OH proton of the
protic solvent to the lone pair of electrons on the hydra-
zone NH functional group [2]. +is leads to reduced charge
on the hydrazone NH group to result in the hypsochromic
shift. In both of nonpolar and aprotic environment,
nonetheless, this phenomenon was negligible and we had
to change our thought to other contributions for salvation,
such as the dipolar nature of solvents. Solvatochromism
monitored in our hydrazone dyes arises from changes in
the contribution degree of the lone pair of electrons on the
nitrogen atom of the NH functional group, which can
partially function as a bridge among partially electron-rich
hydrazone donor and highly electron-deficient tricyano-
furan acceptor fragment in a semi-donor-acceptor mo-
lecular system. +is can simply be described as an extended
inductive effect as demonstrated in Scheme 2. +is results
in an interesting positive solvatochromic behavior owing
to the generated partial extended conjugation [4]. +ere-
fore, the polarizability due to the donor or acceptor
substituents on the arylhydrazone moiety certainly in-
fluences the solvatochromic performance of the prepared
hydrazone dyes.
Ethanol
DMSO
DMF
Acetonitrile
Dichloromethane
Tetrahydrofuran
1,4-Dioxane
Toluene
3.3. Assessment of pH Sensing Effect. +e electron-
withdrawing functional group on arylhydrazone generates
an acidic NH hydrazone proton able to create a conjugate
base, or so called an arylhydrazone anion, with an electron-
donating ability. +is arylhydrazone anion acts as an
electron-donating moiety in conjugation with the strong
electron-deficient tricyanofuran moiety leading to an in-
teresting spectral switch of a donor-acceptor molecular
system under pH stimulus [24]. Figure 3 displays the UV-
visible absorption spectra and color changes of dye 1 dis-
−1
−5 mol·L ), under the
solved in acetonitrile (ca. 2.3 ×10
deprotonation and protonation reversible process. Upon
−1
addition of 1.0 mol·L of methanolic solution of tetrabu-
tylammonium hydroxide (TBAH) to compound 1 dissolved
in acetonitrile to raise the pH value, the maximum ab-
sorption wavelength at 451 nm was bathochromically shifted
−1
to 538 nm. On the contrary, the addition of 1.0 mol·L
methanolic solution of trifluoroacetic acid (TFAA) resulted
in the maximum absorption band at 451 nm to reappear,
while reducing the pH value.
+e existence of an isosbestic point at 489 nm verifies
that there are two different molecular species: hydrazone and
hydrazone anion that coexist together in equilibrium with

Journal of Chemistry
5
1.0
0.8
1.0
0.8
0.6
0.4
0.2
0.0
0.6
0.4
0.2
0.0
–0.2
350
400
450
500
550
600
650
400
450
500
550
600
Wavelength (nm)
Wavelength (nm)
Methanol
Ethanol
DMSO
DMF
CH3CN
CH2Cl2
THF
Dioxane
Toluene
Methanol
Ethanol
DMSO
DMF
CH3CN
CH2Cl2
THF
Dioxane
Toluene
(a)
(b)
1.0
0.8
0.6
0.4
0.2
0.0
350
400
450
500
550
600
Wavelength (nm)
Methanol
Ethanol
DMSO
DMF
THF
Dioxane
Toluene
CH3CN
CH2Cl2
(c)
Figure 2: UV-visible absorption spectra of dyestuffs 1 (a), 2 (b), and 3 (c) in solvents of different polarities.
each others and that the spectral changes are attributed to
the acidity of the hydrazone NH. Considering this hydra-
zone NH prevented resonance among arylhydrazone and
tricyanofuran, this proposes that a negatively charged
arylhydrazone anion was formed in alkaline environment
leading to a considerable increment of the internal charge
transfer that can be described as an extended resonance
effect (Scheme 3).
were recorded, and the results are displayed in Figure 4. It
was obvious that this procedure was highly reversible
demonstrating that compound 1 was stable at different pH
values.
3.4. Evaluation of Dyes Uptake. Polyester fabrics are de-
scribed by their high affinity toward disperse colorants. +e
prepared hydrazone colorants are characterized by their
nonionic small molecular structures with low solubility in the
aqueous medium. +us, they can be described as disperse
dyestuffs with the capability to be applied on hydrophobic
fabrics, such as polyester. +e prepared dyes 1–3 were applied
To inspect the reversibility and stability of such pH
−1
sensing changes, methanolic solutions (1.0 mol·L ) of
TBAH and TFAA were employed to exchange the pH among
∼6.62 and ∼6.93. +e ratios of UV-visible absorption values
at 451 nm (∼0.8327) and at 538 nm (∼0.6650) of compound 1

6
Journal of Chemistry
H
N
NO2
CN
CN
CN
N
+
O
O
N
O
O
F
H
NO2
CN
O
N
-
CN
CN
N
O
N
O
O
F
Scheme 2: An extended inductive effect afforded a semi-donor-acceptor molecular system.
H+
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
OH–
350
400
450
500
550
600
650
700
Wavelength (nm)
pH 6.62
pH 6.73
pH 6.78
pH 6.85
pH 6.93
(a)
(b)
Figure 3: UV-Vis absorption spectra (a) and the corresponding color variations (b) of the hydrazone dye 1 in acetonitrile (ca.
2.3 ×10−5 mol·L−1) at a range of pH values (6.62–6.93).
–
H
N
–
CN
CN
CN
N
N
–
CN
CN
CN
CN
CN
CN
N
N
N
OH
R
R
R
+
O
O
O
H
Hydrazone
(yellow)
Hydrazone anion
Extended resonance
(purple)
Scheme 3: Suggested pH sensing mechanism.
by the high-temperature and -pressure approach at 130°C on
polyester samples at 2% shade to afford dyed polyester
substrates from yellow, orange, and orange-red. All dyes
demonstrated excellent uptake into polyester substrates as
displayed in Figure 5. +is fact is an indication of their high
penetrations through the polyester chains. In addition, the
high dye uptake can be attributed to the fabric affinity as a
result of the small and planar molecular structures of the
prepared hydrazone colorants. +us, the dyed polyester
fabrics showed excellent colorfastness to washing and rub-
bing. +e shades, color strength, and colorfastness properties
of dyestuffs 1–3 are displayed in Table 2. +e colorfastness
against light of the prepared dyes 1–3 was found to rely on the
substituent type on the hydrazone moiety. +ese substituents
are able to change the electron density over the entire mo-
lecular structure of the dye. +us, all dyes displayed good

Journal of Chemistry
7
0.65
0.60
0.55
0.50
0.45
0.40
0.35
(pH 6.93 at 538nm)
(pH 6.62 at 451nm)
1
2
3
4
5
6
7
8
9
10 11 12 13 14 15
Number of cycles
Figure 4: Variations in the ratio of the absorbances at 451 and 538 nm of 1 in acetonitrile (ca. 2.3 ×10−5 mol·L−1) while shifting pH values
back and forth between 6.62 and ∼6.93.
100
90
80
70
60
50
40
30
20
10
0
0
15 30 45 60 75 90 105 120 135 150 165 180
Dyeing time (minutes)
Dye 1
Dye 2
Dye 3
Figure 5: Uptake of the prepared dyestuffs 1–4 on polyester fabrics.
colorfastness to light except for dye 1, which contains highly
summarized in Table 3. Dyestuff 1, comprising higher
electron-withdrawing substituents, demonstrated low in-
hibition effect on the reduction percentages due to poor
antimicrobial resistance, while dyestuffs 2 and 3 with
electron-donating substituents showed moderate antimi-
crobial resistance.
electron-withdrawing nitrosubstituents. On the contrary, dye
1 showed a better color strength than dyes 2 and 3, which is in
agreement with electron-withdrawing nitrosubstituents with
the ability to increase the depth of color on dye 1. +e shades
of the dyed polyester substrates were in accordance with the
monitored absorption maximum wavelength of the prepared
dyes in solution.
4. Conclusions
Some novel tricyanofuran hydrazone derivatives were
prepared and applied on polyester fibers as disperse dyes
with a variety of substituents at ortho-, meta-, and para-
positions of the arylhydrazone moiety. +ey were prepared
using a simple approach via azo coupling of the tricya-
nofuran starting material with the appropriate diazonium
3.5.AntimicrobialActivity. +e produced dyestuffs 1–3 were
independently examined against Escherichia coli, Staphylo-
coccus aureus, and Candida albicans, using the plate agar
counting as the standard procedure. +e antimicrobial re-
duction percentages stimulated by the prepared dyes are

8
Journal of Chemistry
Table 2: Colorfastness, shade, and tinctorial strength of dyed polyester substrates.
Perspiration Rubbing
Wash
Alt.∗
Dyes
Acidic
Alt.∗
Basic
Alt.∗
Light
Shade
K/S
λmax (nm)
St.∗
Dry
Wet
St.∗
St.∗
1
2
3
4
4-5
4-5
4
4-5
4-5
4
4-5
4-5
4
4-5
4-5
3-4
4-5
4
3-4
4-5
4
3-4
4-5
4
3-4
4-5
4
5
6-7
6-7
Orange-red
Yellow
Orange
11.79
8.05
5.43
485
478
463
∗Alt. � alteration in color; St. � staining on cotton.
Table 3: Antimicrobial properties of dyestuffs 1–3.
upon dyeing polyester fabric. Satisfactory antimicrobial
activity of the hydrazone dyes was monitored.
Antibacterial
Antifungal
(bacterial reduction %)
Dyes
(fungal reduction %)
Conflicts of Interest
Candida albicans
E. coli
1.3
S. aureus
1
2
3
9
10 1.4
17 1.8
25 1.5
0
0
+e authors declare that there are no conflicts of interest
regarding the publication of this paper.
12 1.6
19 1.1
8
1.3
Acknowledgments
chloride. +e molecular structures of dyes were verified by
1H-NMR and 13C-NMR spectra, elemental analysis, and
FT-IR spectra. A positive solvatochromism was recorded
by UV-visible absorption spectra in a variety of solvents
with different polarities. +e pH molecular switching ef-
fect, accompanied by reversible color changes, was mon-
itored by UV-visible spectra as a result of the variation of
the pH value leading to the production of charge de-
localization on the hydrazone dye resulting in extended
conjugation through a quinoid form. +is stimulated
planarity of hydrazone dye resulted from the electron-
withdrawing substituents on the arylhydrazone moiety
producing higher conjugation extent of the hydrazone
anion dye than that of the hydrazone dye. +us, the pH
sensory is displayed via modulating the intramolecular
charge transfer changed by deprotonation/protonation
processing. +e prepared dyestuffs were applied on
polyester substrates by the high-temperature and -pressure
technique to give good depths of shades from yellow,
orange, and orange-red. +e studied dyestuffs displayed
mostly satisfactory colorfastness properties. We also ex-
plored the application of the hydrazone dyes as potential
substances with antimicrobial efficiency against some
pathogenic species. Dyes comprising electron-donating
groups on the arylhydrazone moiety demonstrated mod-
erate antimicrobial activities, while dyes with highly
electron-withdrawing groups on the arylhydrazone dis-
played weaker antimicrobial activities.
Technical support from National Research Centre, Cairo,
Egypt, is gratefully acknowledged. +is work was funded by
the Deanship of Scientific Research at Princess Nourah Bint
Abdulrahman University through the Research Groups
Program (Grant no. RGP-1440-0002).
Supplementary Materials
Novel solvatochromic and pH sensory molecular switching
tricyanofuran hydrazone disperse dyes with antimicrobial
activity were prepared to introduce a satisfactory color-
fastness on polyester fabric. (Supplementary Materials)
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