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PAPER

Photodegradation of 2-mercaptobenzothiazole
and 1,2,3-benzotriazole corrosion inhibitors in
Cite this: Phys. Chem. Chem. Phys.,
2014, 16, 25152 aqueous solutions and organic solvents
Maria Serdechnova,*a Vladimir L. Ivanov,b M. Rosario M. Domingues,c
Dmitry V. Evtuguin,d Mario G. S. Ferreiraa and Mikhail L. Zheludkevichae

The photochemical degradation of 2-mercaptobenzothiazole (MBT) and 1,2,3-benzotriazole (BTA)

inhibitors was studied in the present work in aqueous and in organic solutions. The extent of photo-
degradation was assessed by UV-Vis spectroscopy and the main reaction products were identified by
tandem electrospray ionization mass spectrometry (ESI-MS/MS). The analysis of degradation products upon
UV irradiation revealed the predominant formation of dimeric compounds from MBT and oligomeric
structures from BTA, which were further converted into aniline. The increase of the quantum yield of MBT
Received 28th August 2014, and BTA photodegradation reactions under aerobic conditions both in aqueous and organic solvents was
Accepted 3rd October 2014 explained by an increase of the spin–orbit conversion of the singlet radical pairs into the triplet radical pairs
DOI: 10.1039/c4cp03867c in the presence of oxygen. These triplet pairs further dissociate into free radicals, or convert to the parent
compounds. At the early stage of UV irradiation, free radical coupling leads essentially to dimer formation in
www.rsc.org/pccp the case of MBT and to the formation of oligomers in the case of BTA irradiation.

Introduction triazole and thiazole derivatives are widely considered as

potential inhibitors to be added to the technological medium13
The utilization of inhibitors for minimizing metal corrosion and recently to the active protective coatings as well.14 The
attracts increasing interest.1,2 The area of self-healing protective mechanism of action of such inhibitors is not fully understood;
coatings, involving the anti-corrosion inhibitors, is developing however, the adsorption properties are expected to explain their
very fast in the last decade due to the strong industrial demand.3–5 anticorrosion effect.15–18
One of the main strategies is based on the incorporation of 1,2,3-Benzotriazole (BTA) and 2-mercaptobenzothiazole (MBT)
inhibitor compounds into polymer, hybrid or inorganic layers.6,7 are the most widely used corrosion inhibitors for copper,19
The concept has been well known for decades when different aluminum20 and other metals.21–24 The attention to them is fast
inhibitor pigments were used to confer active protection to the growing in recent years, thanks to their efficiency as standalone
polymer paints. The most effective inhibitor pigments were inhibitors,17,18 or as a part of synergistic mixtures.13,25,26 They
composed of moderately-soluble chromate-based salts such as have a wide number of applications in aeronautic, automotive
strontium chromate.8,9 However, the strong oxidizing potential and shipbuilding industries.
of chromate, which is responsible for its unique inhibiting The high industrial demand of anti-corrosion inhibitors
potential, is also the reason for the high toxicity and carcino- stimulates their application also under atmospheric conditions,
genicity of this compound. While exploring the new environ- where they undergo degradation induced by solar irradiation.27–29
mentally friendly alternative inhibitors much attention was The photodegradation of anticorrosion additives results in loss of
paid to the organic heterocyclic compounds.10–12 For example their protective properties and environmental hazards.30,31
Up to now only a few studies on the behavior of MBT and
a
CICECO/Department of Material Engineering and Ceramics, University of Aveiro,
BTA under irradiation have been performed. Thus, it was shown
3810-193 Aveiro, Portugal. E-mail: [email protected]; Fax: +351-234-425-300 that in the 2-mercaptobenzothiazole structure, the C–S bond is
b
Department of Chemistry, Lomonosov Moscow State University, Leninskiye gory 1, relatively weak and renders the homolytic cleavage under UV
119991, Moscow, Russia irradiation.32 It was proposed33 that MBT decomposition under
c
Mass Spectrometry Centre, Organic Chemistry and Natural Products Research
irradiation occurs via both singlet and triplet excited states
Unit/Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
d
CICECO/Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
and decomposes very faster in the presence of oxidizing agents
e
Institute of Materials Research, Helmholtz-Zentrum Geesthacht, (like O3, ref. 34). However, the products of the photodegradation
Max-Planck-Strasse 1, 21502 Geesthacht, Germany reaction, proposed in the literature, and mechanisms of their

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The concentration changes of the original MBT and BTA com-

pounds were defined via the change of the optical density of the
solution at a specific wavelength. The intensity of the absorbed light
was defined by the photocell system F-4, calibrated with a ferri-
Fig. 1 The proposed photolysis mechanism of 1,2,3-benzotriazole.35
oxalate actinometer.39 The quantum yield of the reaction was
calculated using the ‘‘Mathcad-15’’ software.
formation are quite different and sometimes contradict each
Analyses
other. For example, it was notified that BTA is surprisingly stable
to the UV irradiation in aqueous solution.35 However, in other The absorption spectra were recorded on a spectrophotometer
studies, the formation of different BTA degradation products Shimadzu UV-2101 PC (Shimadzu, Japan). The electrospray
such as 6-diazo-2,4-cyclohexadien-1-imine,36 iminocarbene37 mass spectra (ESI-MS) and tandem mass spectra (ESI-MS/MS)
and 6-iminofulvene38 has been reported (Fig. 1). were acquired using a LXQ linear ion trap mass spectrometer
The aim of this work is to perform a systematic study of MBT (ThermoFinnigan, San Jose, CA, USA). For the analysis pre-
and BTA photodegradation reactions on a mechanistic level viously prepared samples (original and irradiated) were diluted
identifying the products of their photodegradation and kinetics hundred times with ultra-pure methanol. Positive ion ESI-MS
of the respective processes. The final goal is to understand if and MS/MS spectra were acquired using the following condi-
these inhibitive compounds are able to sustain under intensive tions: nitrogen sheath gas 30 psi, spray voltage 5 kV, heated
UV light exposure without sufficient degradation. capillary temperature 275 1C, capillary voltage 1 V, and tube
lens voltage 40 V. The flow rate was set to 8 mL min 1 and the
voltage applied was 5 kV. Nitrogen was used as nebulizing and
Materials and methods drying gas. Full scan mass spectra ranging from m/z 100 to 1500
Materials were acquired. In the MSn experiments, collision energy varied
between 15 and 25 of normalized collision. Data acquisition
2-Mercaptobenzothiazole, C7H5NS2, (97%) was supplied by
was carried out using an Xcalibur data system.
Sigma-Aldrich Chem. Comp. (USA). 1,2,3-benzotriazole, C6H5N3,
(499%) was purchased from Sigma-Aldrich Chemie GmbH
(Germany). The inhibitors were used as received without any Results
further purification. Borate and acetate standard buffers (pH 9.2
and 4.0 respectively) were prepared using commercially available The MBT irradiation was performed using a mercury lamp using
PA grade chemicals. Milli-Q water was used for the preparation a light filter Hg313 to separate off the intensive line of mercury
of aqueous solutions. The PA grade organic solvents (iso-propanol, emission at 313 nm. In the case of BTA the irradiation of the
methanol and hexane) and 96% ethanol supplied by Sigma- sample was carried out with the full light range of the lamp.
Aldrich Chemie GmbH (Germany) were used.
Photolysis of MBT and BTA in aqueous solution
UV irradiation assays The changes in the absorption spectra of aqueous BTA and
The solutions of MBT and BTA (concentration ca. 3  10 4 mol L 1) MBT solutions during the irradiation are evidenced in Fig. 2.
were irradiated employing a high pressure mercury lamp DRSh-500 Fairly a significant decrease of optical density in solution of MBT
using quartz cells (10  10 mm). Spectrally clean argon was used for at 320 nm and in solution of BTA at 256 nm revealed the decom-
the deaeration of the solutions. The quantum yield of the reaction position of heterocyclic inhibitors under irradiation. The evolution
was defined as a ratio between the amount of decomposed original of spectra is in good agreement with previously published results
compound and the amount of light absorbed by this compound. obtained in the air-saturated medium.33 A significant increase

Fig. 2 UV-Vis absorption spectra of MBT (a) and BTA (b) in aqueous solution upon irradiation: 0 s, 60 s, 360 s, 1260 s, 2160 s, 4160 s and 5940 s
respectively.

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of optical density at around 350–500 nm has been observed in Products of photodegradation reaction in aqueous solution
BTA solution, similarly to that previously reported for BTA Electrospray ionization (ESI-MS) mass spectra of original and
irradiated in basic media35 and at 77 1C36 yielded a so-called irradiated MBT and BTA aqueous solutions were registered in
‘‘yellow intermediate’’.36 In both absorption spectra (MBT and order to evaluate the primary reaction products.
BTA) the isosbestic points have been detected. The presence of Organic inhibitors were dissolved in water, irradiated for
the isosbestic points indicates that the ratio between photo- about 1 hour and further diluted 100 times with ultra-pure
degradation products remains constant up to a very deep level methanol before being injected into the electrospray source.
of the photolysis. Comparison of ESI-MS spectra obtained before and after the
The quantum yields of the photodegradation reaction in the irradiation of MBT and BTA allowed the identification of newly
aqueous solution were determined as (4.5  0.5)  10 3 for formed molecular ions. As an example, Fig. 4 shows the ESI-MS
MBT and (5  1)  10 3 for BTA. It should be noted that a spectrum of the original aqueous BTA and solution after UV
significant decrease of the decomposition rate and the quantum irradiation. The essentially protonated [M + H]+ adducts
yield of the reaction occurs in the case of irradiation of de-aerated derived from BTA were observed in ESI-MS spectra. The mole-
solutions. Hence the presence of oxygen promotes the photo- cular ion [M + H]+ of non-modified BTA at m/z 120 and the new
degradation of MBT and BTA under realistic conditions when ion assigned to the dimerization product of BTA at m/z 213 were
these inhibitors are used in active coatings and oxygen from air detected (Fig. 4a). At the same time, no significant amounts of
can provide an accelerating effect on the photolysis processes. low molecular products below 120 Da have been observed. The
ESI-MS/MS (MS2) spectrum of the molecular ion at m/z 213 and
Photodegradation of MBT and BTA at variable pH the MS3 spectrum of the ion at m/z 185 are presented in Fig. 4c
The photodegradation reaction of MBT and BTA was studied and 4d, respectively, thus confirming the proposed structures.
both in basic and acidic media. The irradiation of both inhibitors It was evident that BTA degradation by photolysis leads to
was performed in borate buffer at pH 9.2 and in sodium acetate the cleavage of the triazole cycle followed by nitrogen release
buffer at pH 4.0. The absorption spectra of MBT and BTA and the dimerization of the formed aniline radical with BTA
(Fig. 3a and 3b, respectively) irradiated under basic conditions cation-radical via coupling.
were significantly different to those acquired in neutral medium, The detailed MS/MS fragmentation patterns of MBT and
because they deal with the anionic forms of aforementioned BTA and their oligomeric irradiation products are listed in
compounds. Table 1. The structural analysis clearly confirmed the formation
A decrease of optical density of MBT solution at 310 nm and of dimers during MBT irradiation and the formation of dimers
of BTA solution at 275 nm evidenced the decomposition of and conjugated oligomeric structures during UV irradiation of
heterocyclic inhibitors in their anionic form. In the case of BTA, BTA. Interestingly, the detected oligomers undergo further
the irradiation in basic solution leads to only a minor increase transformations when the storage solution is exposed to day-
of the optical density between 350 and 500 nm in comparison light with the formation of low molecular weight products.
with the irradiation in neutral medium. These transformations might include autoxidation steps.
The quantum yield of the MBT photodegradation reaction in The analysis of photodegradation products during the irradia-
basic aqueous solution is close to 0.03. The absorption spectra of tion of MBT and BTA in the aqueous solutions with adjusted pH
MBT and BTA in the acidic aqueous solution were similar to the (acidic and basic) was not performed due to the inconvenience of
spectra without pH adjustment. The quantum yield of the MBT mass spectrometry analysis of solutions rich in inorganic ions.
photodegradation in an acidic environment is equal to (2  0.2) 
10 4. BTA photodegradation both under acidic and basic condi- Photolysis of MBT and BTA in organic solvents
tions during the irradiation occurs much slower in comparison In order to better understand the photodegradation pathways for
with neutral solution (quantum yield is less than 10 4). MBT and BTA, the photolysis was carried out also in iso-propanol

Fig. 3 UV-Vis spectra of MBT (a) and BTA (b) irradiated under basic conditions: 0 s, 60 s, 360 s, 960 s, 2160 s, 3960 s and 5760 s respectively.

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Fig. 4 Proposed fragmentation of BTA and the dimer formed during irradiation in the aqueous solution: (a) full ESI-MS spectrum of BTA after irradiation,
(b) MS2 of the [M + H]+ at m/z 120 corresponding to the non-modified BTA, (c) MS2 of the [M + H]+ ion at m/z 213 corresponding to the newly formed
dimer, (d) MS3 of the ion at m/z 185.

solution. iso-Propanol was chosen for several reasons: (1) it does region as original BTA and undergoes further photodegradation
not contain any aqueous impurities, (2) it is polar and (3) it has a under irradiation. The contribution of autoxidation reactions
low energy C–H bond. This facilitates the radical reaction between with reactive oxygen species to the degradation of these inter-
the organic inhibitory compound and the solvent molecule mediate compounds may be proposed by analogy to aerobic
(in comparison with aqueous media) and can help in the photolysis of pesticides structurally similar to BTA.40 The for-
elucidation of reaction pathways. The changes in absorption mation of this intermediate was not observed in the case of
spectra of MBT in iso-propanol solution are quite similar to de-aerated solution. The final reaction product had the maximum
those registered in aqueous solution for the non-dissociated absorbance at around 275 nm.
molecular form of the substrate. The quantum yield of reaction The proposed structures for the intermediate and final pro-
was (3.6  0.5)  10 3. The quantum yield of the MBT photo- ducts of BTA and final MBT photodegradation products in iso-
degradation was significantly decreased when carried out in the propanol solution were identified by ESI-MS/MS using an ion
de-aerated iso-propanol solution (less than 10 4). trap mass spectrometer (Table 1). The examples of ESI-MS and
The significant difference occurs in the case of BTA irradia- MS/MS spectra of the original MBT ([M + H]+ at m/z 168) and the
tion in iso-propanol and aqueous solutions. Firstly, the absence dimer formed during the photolysis in the iso-propanol solution
of the optical density increase between 350 and 550 nm was are presented in Fig. 6. The obtained results indicate that
observed in organic medium (the optical density slightly similarly to BTA the dimerization of MBT occurs via coupling
increases at around 300–400 nm). The photolysis of BTA was of phenyl radicals.
monitored using the characteristic band at about 250 nm Following the experiment with iso-propanol solution as a
(Fig. 5). The optical density of solution decreases due to the solvent, n-hexane, which is less polar in comparison with iso-
photodegradation of BTA during the first 30–40 min, being propanol and contains C–H bonds with higher energy than
further increased up to ca. 100 min of photoirradiation and fall energy of the C–H bond of the tertiary carbon atom in iso-
down in the period of 100–250 min (Fig. 5). propanol, was chosen. Fig. 7 shows the changes in MBT
This behavior can be explained by the formation of the (Fig. 7a) and BTA (Fig. 7b) absorption spectra in hexane under
intermediate product, which absorbs the UV light in the similar UV irradiation.

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Table 1 The detailed MS/MS fragmentation patterns of MBT and BTA and their oligomeric irradiation products

2-Mercaptobenzothiazole 1,2,3-Benzotriazole
Proposed structure m/z values of the proposed m/z values of the proposed m/z values of the proposed
compound [M + H]+ and compound [M + H]+ and compound [M + H]+ and
product ions observed in product ions observed in product ions observed in
the ESI-MS/MS spectra Proposed structure the ESI-MS/MS spectra Proposed structure the ESI-MS/MS spectra

Original compound Original compound

m/z of [M + H]+ is 168 m/z of [M + H] + is 120 — —
136 (–S), 135 (–SH), 124 92 (–N2), 65 (–N3CH)
(–SC), 109 (–SCNH), 92
(–S2CH)

Irradiated aqueous solution Irradiated aqueous solution Stored aqueous solution

+ +

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m/z of [M + H] is 185 m/z of [M + H] is 213 m/z of [M + H]+ is 213
167 (–H2O), 153 (–S), 185 (–N2), 158 (–N3CH), 185 (–N2), 158 (–N3CH),
139 (–SCH2), 144 (–N3C2H3), 144 (–N3C2H3),
121 (–SCOH4) 142 (–N3C2H5), 142 (–N3C2H5),
118 (–N3C4H5) 118 (–N3C4H5)
m/z of [M + H]+ is 301 Derivatives with m/z of Derivatives with m/z of
268 (–SH), 166 (–C7H4SN) [M + H]+ from about 550 to 600 [M + H]+ from about 350 to 450

m/z of [M + H]+ is 348 Fragmentation due to: Fragmentation due to:

330 (–H2O), 304 (–SC), –H2O –H2O
272 (–S2C), –C (benzene ring –C (benzene ring
229 (–C6H6SN), transformation) transformation)
181 (C7H5S2N), –N2 (BTA to aniline –N2 (BTA to aniline
167 (–C7H3S2NO) transformation) transformation)
–C6N (formation of shorter –C6N or C5H5 (formation of
oligomer structures) shorter oligomer structures)

Irradiated iso-propanol solution Irradiated iso-propanol solution Prolonged irradiation of iso-propanol solution
+
m/z of [M + H] is 228 Derivatives with m/z of Derivatives with m/z of
211 (–OH), 210 (–H2O), [M + H]+ from about 590 to 730 [M + H]+ from about 300 to 350
193 (–SH3), 175 (–SOH5)

m/z of [M + H]+ is 333 Fragmentation due to: Fragmentation due to:

257 (–CS2), 224 (–CS3H), –C (benzene ring –3C, 5H (iso-propanol radical)
197 (–C2S3NH2), transformation) –2N (BTA to aniline
167 (–C7S2NH6) –N2 (BTA to aniline transformation)
transformation) –C, –4H (parts of iso-propanol)
–C6N (formation of shorter
oligomer structures)

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Discussion
The formation of intermediate short-living products during the
MBT and BTA photolysis, which were previously described in
the literature,35 and a great number of radical recombination
products, which we have found during this work, indicates that
the initial stage of the photochemical reaction is the photo-
dissociation of the N–N bond in the case of the BTA compound
and C–S in the case of the MBT compound. The dissociation
energy of the C–S bond is equal to 84.9 kcal mol 1 and the S–H
bond is equal to 76.2 kcal mol 1.41 The energy of the light at
313 nm is equal to 91.35 kcal mol 1.
Since the energy of UV light at 313 nm is higher than the
energy of both chemical bonds, their dissociation is energeti-
Fig. 5 The optical density of the BTA solution at 250 nm during the cally feasible. The photodissociation of bonds in organic mole-
irradiation experiment.
cules occurs after the formation of radical pairs in a singlet
state. Radical pairs in the singlet state have very short lifetime
The changes of the absorption spectra of MBT in the hexane due to the high rate of recombination of the parent molecules.
solution are very similar to the irradiation of the molecular form The dissociation of the chemical bonds and the formation
of MBT in aqueous solution (Fig. 7a). The quantum yield of the of free radicals occur from the triplet radical pairs, which are
reaction was (4.5  0.5)  10 3. The irradiation of the BTA in the formed as a result of the spin–orbit conversion of singlet radical
hexane solution leads to the formation of the product with pairs.42 This fact explains very low quantum yields of the photo-
maximum absorbance at ca. 240 nm. No increase of optical chemical reactions. It is well-known that paramagnetic oxygen
density between 350 and 550 nm was observed (Fig. 7b). quenches both singlet and triplet excited states of molecules.42

Fig. 6 Proposed fragmentation of MBT and the dimer formed during its irradiation in the iso-propanol solution: (a) full ESI-MS spectrum of MBT after
irradiation, (b) MS2 of the [M + H]+ ion at m/z 168 corresponding to the non-modified MBT, (c) MS2 of the [M + H]+ ion at m/z 333 corresponding to the
formed dimer, and (d) MS3 of the [M + H]+ ion at m/z 257.

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Fig. 7 The irradiation of MBT (a) and BTA (b) in hexane: 0 s, 60 s, 360 s, 960 s, 1260 s, 2460 s and 4260 s respectively.

In this work, we assume that oxygen increases the spin–orbit of a set of colored oligomers and even six-membered cyclic
conversion of singlet radical pairs into triplet pairs. However, the intermediate products that were registered by mass spectro-
dynamic interaction of dissolved oxygen with singlet radical scopy analysis of degradation products (Table 1). It should be
pairs of the irradiated compound is hardly possible due to the mentioned that since the quantum yields of the photodegradation
low concentration of oxygen in the solution and a short lifetime reactions and main products of the photolysis are practically
of singlet radical pairs. More likely, oxygen forms a complex with independent of the solvent (water, isopropanol, n-hexane), we
the original BTA or MBT molecules, leading to a static spin–orbit assume that the mechanism of the BTA and MBT photodestruction
interaction between oxygen and the radical pair, because these is determined by photophysical and photochemical properties of
compounds are good electron donors while oxygen is a powerful the substrates.
electron acceptor. Triplet radical pairs further either convert The initial step of BTA photodecomposition can be repre-
back to the singlet radical pairs, which recombine under aerobic sented similarly to MBT and includes the photodissociation
conditions by oxygen attack, or dissociate into a free radical form. of the N–N bond (N–N bond energy in PhNH–NH2 is about
The free radicals further participate in subsequent chemical 41.2 kcal mol 1, ref. 41) followed by the formation of a radical
reactions, mainly in coupling of mesomeric radical structures pair in the singlet state. This pair either further recombines to
forming dimers (Table 1). The proposed mechanism of free the original BTA compound or converts in the presence of
radical formation by photolysis of the C–S bond in MBT is oxygen to the triplet pair, which has longer lifetime and trans-
shown in Fig. 8. A similar mechanism can be proposed for the forms into a diazo-compound (Fig. 9).36
photodissociation of the S–H bond. The formed diazo-compound undergoes further photo-
Despite the similar values of quantum yields of MBT and degradation under UV irradiation (Fig. 10).
BTA photodegradations, the degradation of BTA occurs much As it was previously shown,35 the intermediate cation (i) adsorbs
slower than MBT under irradiation by a standard reference light around 350–450 nm, and transforms into biradical (ii).
light source or under sunlight. This can be explained by the
shift of BTA absorption spectra to the shorter wavelength UV
region, where the radiation of lamps and energy of the sunlight
near the Earth surface decreases. Taken into consideration that
sunlight reaching the Earth’s surface (mainly UV-A, with varying
amounts of UV-B) contains only a very small amount of short
wave-length UV radiation.43 BTA looks more resistant to sunlight
in comparison to MBT. However, the prolonged irradiation leads
to the interesting reaction behavior of BTA related to the formation

Fig. 9 The proposed mechanism of BTA photodegradation.

Fig. 8 The proposed mechanism of MBT photodegradation. Fig. 10 The proposed mechanism of diazo-compound photodegradation.

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This short lifetime biradical (ii) has several ways for its further Some general features concerning the MBT and BTA application
transformation: in anti-corrosion formulations with relation to their photo-
(a) undergoes the recombination reaction in the organic degradation ability may be considered. Since the absorption
solvent medium to form aniline or its derivatives36 (these were maximum of MBT is around 320 nm and BTA is around
detected among degradation products, Table 1), 260 nm, the lower tolerance towards photodegradation of the
(b) undergoes the regrouping of the benzene ring thus former nearly the Earth’s surface by sunlight (mainly UV-A) may
forming a cyano-cyclopentadiene or its derivatives, be suggested. This fact poses more restrictions to MBT than to
(c) emits a hydrogen atom and leads to oligomerization by BTA. However, for example, for the external aeronautic applica-
reaction with extra BTA molecules (was detected among photo- tions the advantages of BTA over MBT in anti-corrosion formula-
degradation products, Table 1). tions look not so evident, because at an altitude of 10 000–13 000 m
Following the highly conjugated electron system of the above the ground the spectral range of sunlight (significant
formed oligomers that are responsible for the yellowish color contribution of UV-B) imposes the same restrictions to BTA
of the BTA solution after the UV irradiation. as to MBT. The obtained results suggest that the inhibition
The formation of conjugated oligomeric systems was also efficiency of ‘‘self-healing’’ coatings containing these inhibitors
observed for the BTA irradiation in iso-propanol. Unlike the can be strongly affected under certain exploitation conditions,
aqueous solution these compounds are less stable and undergo e.g. when subjected to UV irradiation.
further degradation under irradiation. The final products of the The inhibitory effect of the products from MBT and BTA
BTA photolysis carried out in iso-propanol indicate further photolysis has to be assessed in the frame of future studies in
transformation of oligomers into lower molecular weight com- order to understand if the photodegradation processes will
pounds and their reaction with the solvent (Table 1). have a detrimental impact on the long term performance of
The difference between oligomeric products released in active self-healing coatings for external applications.
the aqueous and iso-propanol solutions can be explained by
the different degrees of conjugation in formed products and the
possibility of the excited molecule to react with the solvent. Acknowledgements
In the iso-propanol solution, the reaction occurs easier than in
The authors would like to thank Fundação para a Ciência e a
water. This leads to the formation of less conjugated com-
Tecnologia em Portugal (FCT grants PEst-C/QUI/UI0062/2013,
pounds, which absorb UV light at the shorter wavelength and
PEst-C/CTM/LA0011/2013 and FCOMP-01-0124-FEDER-037296);
easily undergo further excitation and photodegradation thus
European FP7 projects ‘‘PROAIR’’ (PIAPP-GA-2013-612415), SAR-
forming the reaction products as proposed in Fig. 10.
ISTU ‘‘FP7-AAT-2011-RTD-1’’, the Portuguese National Mass
Spectrometry Network, project ‘‘RNEM’’ (REDE/1504/REM/2005).

Conclusions
References
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