Dyes and Pigments 161 (2019) 147–154

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Dyes and Pigments

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An optical sensor of acidity in fuels based on a porphyrin derivative T

a,b,c a a a
Placido G. Mineo , Fabiana Vento , Antonio Abbadessa , Emilio Scamporrino ,
Angelo Nicosiaa,∗
a
Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria, 6, 95125, Catania, Italy
b
CNR-IPCB Istituto per i Polimeri, Compositi e Biomateriali, Via P. Gaifami 18, I-95126, Catania, Italy
c
CNR-IPCF Istituto per i Processi Chimico-Fisici, Viale F. Stagno d’Alcontres 37, I-98158, Messina, Italy

A R T I C LE I N FO A B S T R A C T

Keywords: The measure of the acid concentration in an organic media is a common issue in chemistry. With the aim to
Porphyrin overcome this problem in a facile and inexpensive way, the spectroscopic properties of a PEGylate porphyrin
Fuel derivative, the 5,10,15,20-p-(ω-methoxypolyethyleneoxyphenyl) porphyrin (P), as an acidity sensor were tested.
Organic solvents Its behaviour was analysed in toluene and several fuels through acid titration experiments. In each case,
Acidity optical sensor
examining UV–vis and fluorescence spectroscopic data, the disappearance of the free-base porphyrin derivative
Jet fuel
Uv–vis signals (B- and Q-bands) and the increasing of new bands, as a consequence of the added acid, was
monitored.
On the basis of these data it was possible to evaluate the presence of acid in several organic media as toluene,
gasoline, diesel, and jet fuel, using our porphyrin derivative in very low amount (about 3 ppm).
Finally, in order to exclude the risk of a negative contribution of P in ash formation, the complete oxidation of
the porphyrin compound under common engine's combustion conditions was also ascertained.

1. Introduction
Fossil fuels are the most diffuse energy source for engines from
automotive to air transport. The acidity of a fuel is an important issue
because of possible interactions with metallic or polymeric moieties of
the engines. In general, gasoline does not suffer from acidity problems
for the absence of sulphur and acidic additives which could turn into
acid compounds during the combustion reactions [1]. Nevertheless, the
accidental presence of acidic substances could decrease the engine
performance until it is damaging.
The acidity in diesel and jet fuels is due to organic acids present in
the native hydrocarbon mixtures or formed during the refining pro-
cesses [1]. It is evaluated by several methods [2–4] and defined with
the Total Acid Number (TAN), i.e. the number of milligrams of po-
tassium hydroxide necessary to neutralize the organic and/or inorganic
acids contained in 1 g of petroleum product.
In principle, presence, in moderate amounts, of organic acids and
esters in diesel and jet fuels, beyond acting as an energy supply, can also
exert a lubricating function [5]. Anyways, a fuel with a high TAN value
could be a cause of additional corrosive wear to the engines [6].
Moreover, as a consequence of environmental sustainability, a more
intense use of biodiesel in blend is necessary. But the probable
hydrolysis processes that affect (in post-production phases) the fatty
acids methyl esters (FAME) in bio-diesel, could strongly increase the
content of organic acids in fuels.
In addition, it must be considered that the use of biomass derived
fuels is today a necessity to achieve major environmental sustainability.
Indeed, considering the drop of total availability of crude oil on earth,
replacing energy sources from fossils to green fuels becomes necessary.
It has been foreseen that jet fuel will be the first fuel that will suffer
of future limitations, being the smallest fraction produced from the
refinery [7]. Several new processes to produce bio-jet fuel from biomass
[8] are under observation. Although, a common problem encountered
is the rigorous monitoring of the TAN, because it could increase also
during the storage due to hydrolytic and/or oxidative degradation
processes [9]. Obviously, the risk of damage of aircraft engine, due to
the presence of acids in the fuel, must be totally nullified considering
the high costs of its maintenance. So, the aviation turbine fuels have to
respect the requirements indicated in well-defined specifications, as
ASTM D1655 [10] and Defence Standard 91-91.
Due to the presence of acid additives (usually added to increase the
lubricant activity), diesel fuels commonly exhibit a TAN higher with
respect to jet fuels, which can be further increased in case of bad post-
production storage conditions.

∗
Corresponding author.
E-mail address: angelo.nicosia@unict.it (A. Nicosia).

https://doi.org/10.1016/j.dyepig.2018.09.045
Received 17 July 2018; Received in revised form 18 September 2018; Accepted 18 September 2018
Available online 21 September 2018
0143-7208/ © 2018 Elsevier Ltd. All rights reserved.
P.G. Mineo et al.
Most of the acidity sensors commercially available have been de-
veloped to perform pH measurements in aqueous phase, so the organic
nature of fuels is an apparently insurmountable issue. In general, these
sensors are electrochemical-based and badly affected by the non-polar
nature of the solvents and/or by the complex matrix of fuels. Several
efforts to develop specific sensors for fuels [11] have been made, but
these systems have to work on diluted fuels and off-line.
Porphyrins are one of the most studied natural molecules because of
their role in a myriad of biologic processes and their unique features.
Indeed, their high molar absorption coefficient, the possibility to
modulate their solubility in many solvents, the capability to act as a
molecular sensor and the ability, in particular cases, to form self-as-
sembled supramolecular systems in aqueous media [12], puts in evi-
dence these systems in many fields of the scientific research.
Authors have found applications of porphyrin derivatives in several
fields such as: amino-acids sensors [13,14], DNA binder [15,16], pH
sensor [17], optically active compound [18], and photosensitizer in
photodynamic therapy (PDT) [19–22]. However, the main issue of their
use is the solubility of the same porphyrin derivative in different classes
of solvents (aqueous, paraffinic, aromatic, etc.).
In this landscape, this study wants to propose a multi-solvent so-
luble PEGylated porphyrin-based derivative, able to act as an optical
sensor to constantly monitor on-line the amount of acids contained in a
fuel.
In particular, good results have been obtained with the 5,10,15,20-
p-(ω-methoxypolyethyleneoxyphenyl) porphyrin (P, see Scheme 1),
having four poly(ethylene glycol) branches with an average poly-
merization degree of about 8. Such functionalization of the tetrakis-(p-
hydroxyphenyl) porphyrin, which is soluble only in a few of organic
solvents, allows the full solubility in a large class of aqueous and or-
ganic solvents.
The peculiar acidic sensing capability of this derivative was tested in
toluene, gasoline, diesel and jet fuel, examining the change of its
UV–vis and fluorescence spectroscopy response. Potentially, using P as
a fuel additive, its spectroscopic signal variation could be easily mon-
itored on-line, and in real time, directly in the engine's fuels piping (by
means of suitable optical devices), thus giving an indication about the
TAN number.
2. Experimental
2.1. Materials
All solvents and basic materials were commercial products (Sigma-
Aldrich). The fuels used in this work are samples of European (Italian)
commercially distributed fuels.
2.2. Instrumentation
UV–visible spectra were recorded on a Shimadzu UV-1601 spec-
trophotometer at 25 ± 0.1 °C, using quartz cuvettes with a 1 cm path
length and toluene or commercial fuels as solvents. The analyses were
Scheme 1. Synthesis of the 5,10,15,20-p-(ω-methoxypolyethyleneoxyphenyl) porphyrin (P).
148
Dyes and Pigments 161 (2019) 147–154
conducted on fuel as it is.
Luminescence measurements were carried out using a Jasco FP-
8200 spectrophotometer, equipped with a 150 W xenon lamp, using
quartz cuvettes with a 1 cm path length.
Thermogravimetric analyses were conducted using a Perkin-Elmer
TGA 7 equipped with a TAC 7/DX with a thermal ramp of 10 °C min−1,
in oxidative atmosphere (air, 60 mL min−1).
Differential scanning calorimetry (DSC) measurements were con-
ducted by means of a TA Q20 instrument, equipped with a Refrigerant
Cooling System, with a heating rate of 10 °C min−1, in the −90 to
+90 °C temperature range and under an anhydrous N2 atmosphere
(60 mL min−1).
MALDI-TOF (Matrix-Assisted Laser Desorption/Ionization Time of
Flight) mass spectra were acquired by a Voyager DE (PerSeptive
Biosystem) using an acquisition protocol reported elsewhere [23–25].
MALDI-TOF mass spectrometer calibration and average molecular mass
determination were performed as reported in previous cases [26,27].
The trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene]-mal-
onitrile (DCTB) was used as matrix. The m/z values reported in text
refer to molecular ions of the most abundant isotope of each element in
the molecule.
1
H NMR spectra were acquired on a UNITY−INOVA Varian instru-
ment operating at 500 MHz, using VNMR for software acquisition and
processing, using CD2Cl2 as solvent. The chemical shifts were expressed
in ppm by comparison with the CH2Cl2 residue signal. The spectra were
acquired at 300 K (spin lock time 0.5 s).
FT-IR spectra were obtained by using a Perkin Elmer Spectrum One
spectrophotometer.
2.3. Synthesis of the 5,10,15,20-p-(ω-methoxypolyethyleneoxyphenyl)
porphyrin
The synthesis of the 5,10,15,20-p-(ω-methoxypolyethyleneox-
yphenyl) porphyrin (P) has been reported elsewhere [28]. Briefly (see
Scheme 1), the chlorinated derivative of a Poly(ethyleneglycol)-methyl
ether (PEGMEC) with a polymerization degree of about 8 (1 g,
2.86 mmol), was dissolved in a H2O/THF 1:1 mixture (12 mL). At the
same time, the tetrakis-(p-hydroxyphenyl) porphyrin (0.24 g,
0.354 mmol) was dissolved in a sodium hydroxide 0.5 M aqueous so-
lution (2.84 mL). The two solutions were then mixed and refluxed for
76 h. The reaction produced a mixture of mono, di, tri and tetra func-
tionalized porphyrin derivatives [28].
This mixture was acidified using acetic acid, dried with rotary
evaporator and kept under vacuum at 80 °C for 24 h. Then it was se-
parated into its components by means of column chromatography,
using silica gel as the stationary phase and a mixture of CHCl3/
C2H5OH/(C2H5)3N (97:2:1) as eluent. P, corresponding to the first
chromatographic eluted band, was obtained as a waxy solid (yield
30%). The structure of P was confirmed by means of MALDI-TOF, NMR,
and FT-IR techniques. FT-IR (KBr, cm−1): 3000-2800 (CeH aliphatic
stretching), 1640 (C]C phenyl stretching), 1460 (CeH deformation),
1353 (CeN axial deformation), 1248 and 1105 (CeOeC asymmetric
P.G. Mineo et al. Dyes and Pigments 161 (2019) 147–154

Fig. 1. MALDI-TOF mass spectrum of P.

and symmetric axial deformation). The fluorescence quantum yield is
ϕ = 0.10, determined by comparison with a standard (tetrakis-[p-
phenyl] porphyrin, ϕ = 0.11 in toluene).
1
H NMR (CD2Cl2, δ, ppm): 8.90 (s, 8 H, CeH pyrrolic), 8.13 (d,
J = 8.6 Hz, 8 H, CeH phenolic in ortho respect to the phenolic oxygen),
7.33 (d, J = 8.6 Hz, 8 H, CeH phenolic in meta respect to the phenolic
oxygen), 4.42 (t, J = 4.5, 8 H, CeH PEG in α to the phenolic oxygen),
4.02 (t, J = 4.5, 8 H, CeH PEG in β to the phenolic oxygen), range
3.85–3.43 (m, 110 H, CeH PEG chains), range 3.38–3.30 (s, 12 H,
terminal methyl groups), −2.80 (s, 2 H, NeH pyrrolic). 13C NMR
(CD2Cl2, δ, ppm): 159.1, 134.9, 120.2 (C quaternary), 135.9, 113.2
(phenyl C in meta and ortho positions respect to the phenolic oxygen),
131.4 (pyrrole tertiary C), 72.2–68.2 (PEG secondary C), 68.2 (terminal
methyl groups). DSC: Tg = −59 °C; Tmelt = 42 °C, ΔHmelt = 17.70 J/g.
Calcd for C86O23N4H114 (1571.59 + n44.03). MALDI-TOF (m/z, see
Fig. 1): 1572.61 + n44.03 (MH+, *), 1682.58 + n44.03 (MNa+, #),
1918.60 + n44.03 (MK+, °). Average molecular weights, determined
by means of MALDI-TOF MS [23–27] (Da): Mw = 2040, Mn = 2020.
3. Results and discussion
3.1. Spectroscopic analysis of fuels
Some European (in particular, Italian) commercial fuels were ana-
lysed by means of UV–vis and fluorescence spectroscopies to highlight
the spectroscopic profile of the pigments dissolved in them (Fig. 2). This
because for fiscal purpose in several Europe States the addition of dyes
and tracking compounds in diesel and gasoline fuels is obligatory to
discriminate the fuels for the purpose of application e.g. commercial,
agrochemical. Differently, because the jet fuels are used in the purest
form possible and other applications are not useful, the addition of
pigments is not necessary.
The UV–vis spectrum of Diesel used in this study is shown in Fig. 2
(black line). It essentially consists of a strong absorption in the UV

2.4. Spectroscopic titrations

The acid titration experiments were conducted in toluene and in

fuels solutions of P (1,6*10−6 M, about 3 ppm), using trifluoroacetic
acid (TFA) as titrator. In each case, after every acid addition, an aliquot
of the P solution was analysed with UV–vis and fluorescence (exciting
at the wavelength of the free-P Soret band and to those of the proto-
nated form) spectroscopies correcting the spectra in consideration of
the further dilutions.

2.5. Diesel neutralization treatment

To neutralize all the acidic species present in commercial diesel

fuels, a treatment with sodium carbonate was performed. The sample
was passed through a chromatographic column filled with Na2CO3. This
Fig. 2. UV–vis absorption spectra of pure fuels: diesel (black line), gasoline (red
neutralization treatment did not alter the amount of dyes contained in
line) and jet fuel (green line). (For interpretation of the references to colour in
the fuels. this figure legend, the reader is referred to the Web version of this article.)

149
P.G. Mineo et al.
Fig. 3. Toluene solution of P: UV–vis spectra of the free-P (continuous black
line) and of the protonated-P (continuous red line); fluorescence emission
spectra of the free-P (λexc 423.5 nm, dashed black line) and of the protonated-P
(λexc 451 nm, dashed red line). (For interpretation of the references to colour in
this figure legend, the reader is referred to the Web version of this article.)
region. There are also three partially overlapped broad bands at 413,
442, and 475 nm, indicative of the presence of fiscal dyes (FD).
A similar absorption spectrum appears for gasoline (Fig. 2, red line)
with two peaks at 405 nm and 431 nm of minor intensity due to the
dissolved FD. Instead, the UV–vis spectrum of the jet fuel does not show
any significant absorption in the range 350–700 nm for the absence of
FD.
3.2. Spectroscopic analysis of 5,10,15,20-p-(ω-
methoxypolyethyleneoxyphenyl) porphyrin
The UV–vis absorption spectrum of the 5,10,15,20-p-(ω-methox-
ypolyethyleneoxyphenyl) porphyrin (P) in toluene solution (continuous
black line in Fig. 3), shows the typical Soret band at 423.5 nm, together
Fig. 4. UV–vis titration of P in toluene. In the inset the UV–vis intensity ratio values as a function of the acid concentration, calculated between absorption bands at
451 nm and 423.5 nm, is reported.
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Dyes and Pigments 161 (2019) 147–154
to the four Q-bands at 518, 555, 595 and 653 nm (with a molar ex-
tinction coefficient of 454000 M−1 cm−1, calculated in correspondence
of the Soret band). The fluorescence emission spectrum (dashed black
line in Fig. 3), obtained exciting at the wavelength of the Soret band,
shows a strong fluorescence emission at 654 nm.
The acidification of the solution of P, including the protonation of
the porphyrin core, results in clear spectral changes observed in Fig. 3
(continuous red line) [17,29,30]. As expected, it can be noticed the
decrease of the Soret band at 423.5 nm and the appearance of a new
band centred at 451 nm, whereas both the intensity and number of the
Q-bands decrease making way to a single Q-band centred at 688 nm.
Regarding the corresponding fluorescence emission spectrum
(Fig. 3, red dashed line), the protonation of the porphyrin determines
the quenching of the emission band at 654 nm (λexc 423.5 nm) and the
appearance of a new emission band at 712 nm (λexc 451 nm), due to the
porphyrin di-cation species formation [31].
A similar behaviour was observed for the solution of P in other
organic solvents (as THF, data here omitted for brevity).
3.3. Acidity measurements
Acidity determination in organic solvents, so it is an issue due to the
need to create the suitable ambient for acid-base catalysed reactions.
Toluene is one of the most used common organic solvent, so it was
chosen to test the acidic sensing ability of P. The acid titration was
conducted using a diluted solution of TFA as titrator (see experimental
part).
The UV–vis absorption spectra (Fig. 4) exhibited critical variations
as a consequence of the porphyrin core protonation. In particular, the
disappearance of both the free-P Soret at 423.5 nm and the four Q-
bands (at 518, 555, 595 and 653 nm) and the formation of a new Soret
band at 451 nm and a Q-band at 688 nm, can be observed.
The values of the ratios between the UV–vis absorption intensity at
451 nm and 423.5 nm showed a strong variation as a function of the
acid amount added in the concentration range from 1*10−6 M to about
1*10−3 M (see inset in Fig. 4), remaining constant at about 7 at higher
acidity.
Such behaviour of the absorption intensity ratio value suggested a
P.G. Mineo et al.
Fig. 5. a) Fluorescence emission spectra of P in toluene, at λexc 423.5 nm and λexc 451 nm (in inset). b) Fluorescence emission intensity ratio values calculated
between emission intensities at: 654 nm (λexc 423.5 nm) and 712 nm (λexc 451 nm) [black line], and 712 nm (λexc 451 nm) and 654 nm (λexc 423.5 nm) [red line], as a
function of the acid concentration. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
useful application of P as an indicator of the acidity variation in aro-
matic organic media.
The fluorescence emission spectra (λexc 423.5 nm), relative to the
titration of P in toluene using a solution of TFA, are shown in Fig. 5a. It
can be observed as the intensity of the fluorescence emission band of
the free-P species, centred at 654 nm, decreases as a consequence of the
protonation, whereas an increasing emission appears at 712 nm ex-
citing the solution at the wavelength of the P-protonated species
(λexc 451 nm, see inset in Fig. 5a).
The plot of the fluorescence emission intensity ratio values, calcu-
lated between the bands at 654 nm (λexc 423.5 nm) and 712 nm
(λexc 451 nm), as a function of the acid concentration, shows a wide
linearity from 0 to about 1*10−5 M acid concentration (Fig. 5b, black
line). Differently, the plot of the inverse ratios (712 nm/654 nm) shows
linearity in the range from 2*10−4 M to about 0,1 M (Fig. 5b, red line).
Then, these data suggest that the fluorescence emission of P could be a
good indicator of the acidity of organic media.
There are organic media as fuels for which is very important to
monitor the acidity. In fact, the level of acidity in these cases is very
critical for the possibility to provoke a corrosive wear of the metal and/
or polymer parts (as seals, pipes, etc.) of the vehicle's engines.
The acidity of the fuels is usually monitored only during their pro-
duction, neglecting very often that an unexpected increase could occur
as a consequence of bad storage conditions or fortuitous contamination.
A solution to this problem could be the application of a suitable on-
line sensor in a point along the engine's fuel pipes which would allow,
in real time, the monitoring of the quality of the fuel used, preventing
any decline of motor performances and guaranteeing its health.
To study the ability of P as acid sensor when added (in very low
concentration, about 3 ppm) in gasoline, diesel and jet fuels, several
UV–vis and fluorescence titration experiments were conducted.
The UV–vis spectrum of the P-gasoline solution shows the porphyrin
absorption bands partially overlapped to the fuel's FD signals (see also
Figs. 2 and 3). However, the Soret band at 421 nm, and the Q-bands at
517, 553, 595 and 652 nm are still clearly evident. The addition of
increasing amounts of TFA (Fig. 6) provoked the disappearing of these
signals and the evolution of two new bands centred at 449 nm and
680 nm.
The plot of the ratios between the absorption intensity values at
421 nm and 449 nm as a function of the TFA concentration is shown in
the inset of Fig. 6. It can be noticed a variation between 4*10−6 M and
4*10−4 M acid concentration, with the lowest ratio value of 0.63
reached with a 5*10−4 M acid concentration. These data suggest that,
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Dyes and Pigments 161 (2019) 147–154
fixed a critical acidity, corresponding to a threshold value of the 421/
449 absorbance intensity ratio, it is possible to set up a sensor that gives
advices when the acid concentration in the fuel is near or exceed this
limit. (LOD = 1.09*10−5 M, LOQ = 1.45*10−5 M).
Due to their chemical nature, diesel fuels have a much higher
acidity with respect to gasoline. They contain a major percentage of
organic acids (as naphthenic and cresylic acids, for example) and sev-
eral acid additives often added for various technological purposes as
anti-icing, anti-oxidant, metal deactivator, pipes cleaner or perfor-
mance improver.
The acid amount of a commercial diesel sample was clearly evi-
denced adding P (3 ppm) to the fuel and examining the corresponding
UV–vis spectrum (Fig. 7, dashed black line). So, to test the sensing re-
sponse of P to the changing acidity in this fuel, before carrying out the
titration experiment, the commercial diesel was neutralized through a
treatment with Na2CO3 (see experimental part). As expected, the
UV–vis spectra collected during the acid titration of this neutralized
sample showed the decreasing of the free-P Soret signal at 421 nm and a
concomitant increase of the bands at 440 and at 696 nm (Fig. 7).
Nevertheless, as a consequence of the low concentration of P
(3 ppm), the spectra were affected by an interference due to the overlap
between the bands of FD dissolved in the diesel and the protonated P
optical absorption Soret band at 440 nm, making this band not suitable
for evaluating of the acidic concentration in this fuel.
Instead, the protonated-P Q-band at 696 nm is free of interferences,
so that it was chosen, together with the free-P Soret-band at 421 nm, to
calculate the absorption intensity ratio values for the monitoring of the
titration.
Then the calculated UV–vis 421/696 nm absorption intensity ratio
values were plotted as a function of the acid concentration (see inset in
Fig. 7). In the range from about 5*10−6 M to 10−4 M acid concentra-
tion, a strong variation of this ratio from 900 to about 16 with the
lowest value at an acid concentration of 8*10−5 M, was observed.
Based on these results, also the not-neutralized diesel fuel, added of
P, was analysed by means of the UV–vis spectroscopy. The obtained
value 20 of the ratio between the absorption intensities at 421 nm and
696 nm corresponded to a 5*10−5 M acid concentration in this com-
mercial fuel.
Also in this case, examining the fluorescence emission spectra of the
diesel it was observed that the signals due to the contained FD overlap
those of the protonated-P species. In these conditions only the high
intensity of the free-P fluorescence emission at 654 nm (with both λexc
421 and 449 nm) was clearly observed. The acid titration of the P-diesel
P.G. Mineo et al. Dyes and Pigments 161 (2019) 147–154

Fig. 6. UV–vis titration of P (3 ppm) in gasoline; in inset the UV–vis absorption intensity ratio values as a function of the TFA concentration, calculated considering
the absorption intensities at 421 and 449 nm.

showed a decrease of the fluorescence emission intensity band of P as a
function of the amount of acid added, with a total quenching of the
emission at about 1*10−3 M acid concentration (data not reported for
brevity).
These data suggested that UV–vis optical properties of P are better
than fluorescence ones to be used as an acidity indicator when it is
mixed to a diesel fuel (LOD = 6.59*10−6 M, LOQ = 8.79*10−6 M).
In the case of jet fuels, because of the high technology and sensi-
tivity of the aviation engines and the consequent high costs of their
reparations, it is much more important to monitor their acidity, also
taking into account that the acidity values may increase over time due
to bad storage conditions and/or unexpected contamination of fuel
tanks. Also in this case it could be advantageous the use of P as an
optical sensor; in fact, recording the emission spectrum of P-fuel, it is
possible to detect when the dangerous concentration of acid, estab-
lished in some fuels specifications as in Defence Standard 91-91 or
ASTM D1655, is reached. Typically, the TAN limit for jet fuel is about
0.015, corresponding to a concentration of acid about 2*10−4 M.
Since in the jet fuel there is usually much less acid than in diesel fuel
(as evidenced by the absence of the characteristic protonated-P bands at
455 and 649 nm in the UV–vis spectrum of a sample of jet fuel added of
P) the acid titration experiments were conducted adding P (3 ppm) to

Fig. 7. UV–vis titration of P-diesel; the dashed black line is the spectrum of the not-neutralized P-diesel. In the inset, the intensity absorption ratio values, calculated
between the bands at 421 and 696 nm, as a function of the acid concentration, are reported.

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P.G. Mineo et al. Dyes and Pigments 161 (2019) 147–154

Fig. 8. a) UV–vis titration of P (3 ppm) in jet fuel. In the inset, fluorescence emission spectra collected with λexc 423 nm and the spectrum of the two-months stored
sample (black dashed line) are reported; b) Fluorescence emission intensity exciting at 423 nm as a function of the acid amount is shown. The red rectangle represents
the law TAN limit and the red arrows the emission intensity and acid concentration of the two-months stored jet fuel sample. (For interpretation of the references to
colour in this figure legend, the reader is referred to the Web version of this article.)

the fuel without any neutralization pre-treatment. As expected, the

UV–vis absorption spectra, collected during the addition of TFA
(Fig. 8a) showed the intensity reduction of both the free-P Soret band at
423 nm and the four Q-bands with the contemporary increase of the
protonated-P bands at 455 nm and 694 nm; as a particular, it can be
noticed that in this case the detection of the absorbance values was
more facile due to the absence of FD dissolved in the fuel.
Following the titration by means of the fluorescence emission
spectra (inset in Fig. 8a), and in particular monitoring the intensity
reduction of the band at 654 nm as a function of the acid added, a
strong intensity variation (Fig. 8b) was observed in the acid con-
centration range 4*10−6 M to 2*10−4 M, with the total fluorescence
quench at about 6*10−4 M (LOD = 1.15*10−5 M,
LOQ = 1.86*10−5 M).
In order to verify if the presence of P in a jet fuel, in any time, can be
able to detect sudden increases of the acidity, a jet fuel sample was
stored in a vial and put in contact with air and sun light (although not
directly) for two months. At the end, it was observed a decrease of the
fluorescence emission intensity at 654 nm of about 34%, corresponding Fig. 9. TGA trace of P in air atmosphere.
to an acid concentration of about 1.5*10−5 M (Fig. 8b, red arrows);
acid certainly formed during the exposition. happen inside the engine.
Therefore, it can be deduced that the fluorescence emission in-
tensity at 654 nm can be used as an acidity indicator also for jet fuel
added with P. Then, monitoring the disappearance of the fluorescence 4. Conclusions
signal, opportune actions can be taken when the TAN value approaches
the law limit. A porphyrin derivative P, added to toluene and some common
Actually, it can be noticed that similar results were obtained with all commercial fuels, was tried as an acidity sensor to evaluate its ability to
the investigated fuels without FD additives, and, by means of titration measure the acid amount in these fluids. The undesired presence of
experiments conducted on fuels without P, any FD UV–vis absorption acids in a fuel is a big issue because it can put the engine's safety at risk.
profile's change was revealed (data not showed for brevity). Our data have shown that P used in very low concentration (about
Furthermore, the absence of P-aggregates was verified through DLS 3 ppm) is highly sensitive to the presence of acids and to their con-
experiments. centration.
Finally, the potential application of this porphyrin derivative as Both the ratios between the UV–vis absorption ratio signals at
sensor for fuels is not only interesting for its solubility in the common 451 nm and 423.5 nm and that between the fluorescence emission in-
fuels and solvents, but also for the absence of carbonaceous residue tensity signal at 712 nm and 654 nm, were used as probes in the case of
after its combustion. In fact, the P macromolecules dissolved in the toluene. For gasoline, the corresponding ratios were taken considering
fuels follow the pathway through the engine fuel system till the com- the UV–vis absorptions at 421 nm and 449 nm and, in case of diesel at
bustion, so that it is important that it does not leave carbonaceous re- 421 nm and 696 nm. Regarding to the jet fuel, best results were ob-
sidues into the combustion chamber. This occurrence was verified by tained monitoring the quenching of the fluorescence emission signal at
thermogravimetric experiments conducted in oxidative atmosphere 654 nm (λexc 423 nm), that disappeared almost completely at about
(air) in the temperature range 50–800 °C. The obtained TGA trace of P 6*10−4 M acid concentration.
(reported in Fig. 9) shows a continuous weight loss, leaving any residue As have already been demonstrated, both the quenching of the
already at 600 °C. Therefore, it can be assumed that the same result can fluorescence and the UV–vis spectrum changing are associated to the

153
P.G. Mineo et al.
presence of acids in fuels. So, an optical sensor system could be suc-
cessively arranged with just a cheap source (light emitting diodes) to
excite P at 423 nm and/or 451 nm and a suitable photo-detector to
monitor the fluorescence or absorbance variations. In principle, this
spectroscopic signal variation could be easily monitored on-line (in the
engine's fuels piping, also while the engine is running), so that when
limit values of acidity are reached it could be activate an alarm to avoid
the risk of engine damage.
It is important to notice that using P as an indicator, the monitoring
of the acidity content can be adapted to any type of fuels; it will be
sufficient to set a threshold limit value of the absorption intensity or
fluorescence intensity emission ratio as a function of the fuel under
examinations, tuning it from time to time according to the needs.
Furthermore, it was also ascertained that P molecules does not leave
carbonaceous residues after combustion, so that P can remain in the
fuel and carry out its sensing job without any unforeseen risk for the
engine.
Then the use of P as indicator could be a solution to the issue of the
deteriorated fuels. Adding P to the fuel since its storage, it is possible to
detect on-line the presence of acids in fuels at any moment of their
commercial life.
In our knowledge, it is the first case of a dyes-based optical acidity
sensor used in the field of fuels.
Acknowledgements
This work was financially supported by University of Catania “Piano
della Ricerca di Ateneo 2016–2018”, project number
UPB51722152132.
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