Thermochimica Acta 657 (2017) 6671

Contents lists available at ScienceDirect

Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Full Length Article

Thermal properties of centrifuged oils measured by alternative MARK

photothermal techniques

R. Carbajal-Valdeza, J.L. Jimnez-Prezb, , A. Cruz-Oreaa, Z.N. Correa-Pachecoc,
M.L. Alvarado-Noguezd, I.C. Romero-Ibarrab, J.G. Mendoza-Alvareza
a
CINVESTAV-IPN, Av. Instituto Politcnico Nacional 2508, Col. San Pedro Zacatenco, Delegacin Gustavo A. Madero, Cdigo Postal 07360, Ciudad de Mxico, Mexico
b
UPIITA, Instituto Politcnico Nacional, Avenida Instituto Politcnico Nacional No. 2580, Col. Barrio la Laguna Ticomn, Gustavo A. Madero, CP 07340, Ciudad de
Mxico, Mexico
c
CONACYT, Centro de Desarrollo de Productos Biticos-Instituto Politcnico Nacional (CEPROBI-IPN), Carretera YautepecJojutla, km 6. San Isidro, C.P. 62731,
Yautepec, Morelos, Mexico
d
ESIME, Instituto Politcnico Nacional, Av. Instituto Politcnico Nacional Edicio 5, Unidad Profesional Adolfo Lpez Mateos, Zacatenco, Delegacin Gustavo A. Madero,
C.P. 07738, Ciudad de Mxico, Mexico

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, thermal characterization of centrifuged aromatic citrus oils was studied using thermal lens (TL) and
Thermal diusivity open photoacoustic cell (OPC). The thermal diusivity (D) was obtained by TL, tting the critical time parameter
Thermal eusivity of the experimental curves to the theoretical values. An experimental arrangement of non-matched mode lasers
Citrus essential oils with a probe and an excitation lasers was used. On the other hand, the thermal eusivity (e) of the samples was
Thermal lens
obtained by using OPC. The thermal conductivity (k) was calculated from the relationship between D and e. The
Open photoacoustic cell
thermal parameters obtained were compared with theoretical values in the literature. UVvis spectroscopy,
Attenuated Total Reectance-Fourier Transform Infrared spectroscopy (ATR-FTIR) and 1H Nuclear Magnetic
Resonance (NMR) were used to determine the absorption coecients and chemical structure of the citrus oils.
The importance of this research work was the determination of the thermal parameters of essential oils as an
alternative technique for quality control application.

1. Introduction esters, whereas the non-volatile fraction contains hydrocarbons, sterols,

Aromatic essential oils have been used since ancient times in cos-
metics, incense or perfumes, as well as for therapeutic, in medicine
(microbial and antispasmodic) and culinary applications [13]. Citrus
essential oils are complex mixtures of chemical compounds that impart
characteristic avor and odor of the fruits. Such chemical compounds
can be classied mainly into three groups: terpenes, sesquiterpenes and
oxygenates. However, the chemical composition depends on cultivation
climate, harvest time, the biotype of plant and nally the process of
extracting oils [46]. Therefore, it is necessary to determine a prole of
the constituents of essential oils, because the variability in chemical
composition determines their quality. Citrus essential oils are char-
acterized by a volatile and non-volatile fraction, resulting in a complex
product of several hundred compounds. Oils are typically composed of
a mixture of a signicant volatile fraction (8599%) that can be further
processed by distillation and the remaining 115% non-volatile residue.
The volatiles are composed of mono- and sesquiterpene hydrocarbons
and their oxygenated derivatives, aliphatic aldehydes, alcohols and
fatty acids, waxes, non-volatile terpenes, carotenoids and avonoids, as
well as coumarins and furocoumarins. The non-volatile residue, which
forms from 1% to 15% of the oil, contains hydrocarbons, sterols, fatty
acids, waxes, carotenoids, coumarins, psoralens, and avonoids [7].
Industrially, physical characteristics commonly used as the rst para-
meter for certication are color, taste, odor, density and refractive
index. The importance of these substances and the variety of methods of
preparation and purication, like the use of analytical techniques make
necessary to determine their composition and characterize them for
authentication purposes. Among alternative techniques used for these
purposes, TL and OPC are important to determine the thermal prop-
erties such as diusivity, eusivity and thermal conductivity. In this
work, four centrifuged essential oils were studied: lemon, orange,
grapefruit and green mandarin. Our results were compared with the
values of the thermal constants of various essential oils from the lit-
erature, obtaining optimal values of new compositions of citrus oils
using two alternative photothermal techniques.

Corresponding author.
E-mail address: jimenezp@s.cinvestav.mx (J.L. Jimnez-Prez).

http://dx.doi.org/10.1016/j.tca.2017.09.014
Received 11 June 2017; Received in revised form 3 September 2017; Accepted 13 September 2017
Available online 15 September 2017
0040-6031/ 2017 Elsevier B.V. All rights reserved.
R. Carbajal-Valdez et al. Thermochimica Acta 657 (2017) 6671

Table 1
Thermal lens experiment parameters.

Pe - Excitation laser power (at 514.5 nm) 30 mW

Pp - Probe laser power (at 632.8 nm) 1 mW
e - Excitation laser spot size 4.9 103 cm
1p - Probe laser spot size at cell 1.81 102 cm
m - Constant parameter 13.691
V - Constant parameter 1.22
Zc - Focal distance 6.56 cm
Z2 - Distance 2 m
L - Length of sample cell 1.0 cm
Fig. 1. Themal lens (TL) experimental setup. Sample Essential Oil

2. Experimental

2.1. Thermal lens (TL)

The TL spectrometry experimental setup is observed in Fig. 1. The

sample is exposed to an excitation laser beam to generate a local tem-
perature increase and to a probe beam that passes through the sample.
There is an increase in temperature because of the heat produced from
the absorbed energy in the sample generating a lens-like optical eect
detected by the probe. The propagation of the probe beam laser through Fig. 2. Open photoacoustic cell (OPC) experimental setup.
the TL results in either a defocusing or a focusing of the beam center.
Subsequently, the intensity of the probe beam is measured using a de-
tector [8,9].
The theory of the TL is expressed in terms of the Fresnell diraction
theory based in the phase shift on the probe beam after passing through
the sample [911]. The analytical expression for the probe beam in-
tensity is as follows:
2
2mV
I (t ) = I (0) 1 tan1
2 [(1 + 2m ) 2 + V 2] tc + 1 + 2m + V 2

2t (1)
where, I(t) is the time dependence of the probe laser beam at the de-
tector. I(0), is the initial value of I(t) for t zero, is the phase shift of the
probe beam after passing through the sample due to the increase in
temperature.
wp 2
V=
Z1
Zc
; m= ( )
we
(2) where Zc is the confocal distance of the probe
beam, Z1 is the distance from the probe beam waist to the sample. wp is
the probe beam spot size and we is the excitation beam spot sizes at the
sample [9].
Pe Ae L dS Fig. 3. Cross section of the open photoacoustic cell (OPC).
=
k dT (3)
where Pe is the excitation beam power, Ae is the optical absorption to exchange heat with the environment. The technique consists of a
coecient of the sample at the excitation beam wavelength, L is the modulated beam, obtained with a mechanical chopper, at an angular
sample thickness, k is the thermal conductivity, is the laser wave- frequency of = 2f. The OPC experimental setup is observed in
length of the probe beam, and (ds/dT) is the temperature coecient of Fig. 2. A detail of the cross section of the photoacoustic cell is shown in
the optical path length change at the probe beam wavelength. Fig. 3. In the photoacoustic cell, the liquid sample is placed on the
The characteristic time constant of the thermal lens tc depends on aluminum foil of known thermal eusivity. An electret microphone
the excitation beam spot size at the sample we, and thermal diusivity D connected to the cell detects the heat generated due to the temperature
it can be expressed as: rise and then it diuses into the photoacoustic (PA) gas chamber
modulating the pressure (acoustic waves) within the PA cell. A lock-in
we 2
D= amplier interfaced with a data acquisition system measures the mi-
4tc (4)
crophone-response signal [13].
and tc can be determined by tting Eq. (1) to the experimental For the calculation of the thermal eusivity the obtained photo-
data. The TL was calibrated with water to compare with the values acoustic signal of each sample is normalized, by using the photo-
reported in the literature. The experimental parameters of TL are acoustic signal when the sample is air, and the following equation is
summarized in Table 1. used [14]:
l 0 0 c0
2.2. Open photoacoustic cell technique (OPC) es =
IR (5)
3
The Open photoacoustic cell technique (OPC) was used for the where 0 is the density of the used aluminum foil (2.7 g cm ), c0 is the
thermal eusivity measurements [12]. The thermal eusivity measures specic heat of the aluminum foil (0.9 Jg1 C1), l0 is the thickness of
essentially the thermal impedance of the sample, or the sampls ability the aluminum foil (0.0016 cm), = 2 f being f the modulation

67
R. Carbajal-Valdez et al. Thermochimica Acta 657 (2017) 6671

frequency of the excitation beam in the sample, and IR is the slope of the
normalized photoacoustic signal, as a function of the square root of f.
The cell (Fig. 3) was calibrated with water to compare with the values
reported in the literature. The obtained value for distilled water was
(eH2O = 1487.05 47Ws1/2 /m2C) and the reported values are
eH2O = 1640Ws1/2 /m2C and eH2O = 1595Ws1/2 /m2C[14]). It can be
seen, that the obtained value was similar to the reported values. In the
case of the studied essential oils they contains, among others compo-
nents, ethanol and the reported thermal eusivity of ethanol is 0.0585
(Ws1/2/(cm2 C)) [15].
Measurements of absorption coecients and chemical structure
were determined by complementary techniques such as UVvis spec-
troscopy, ATR-FTIR and 1H NMR.

3. Results and discussion

Dierent oil batches for the essential oils (lemon, orange, grapefruit
and green mandarin) were used (Chemical aromatic SA Mexico).
Essential oils were obtained from the pericarp of citrus peel by scrap-
ping or breaking the oil cells near the fruits surface and using water to
drag the oil in the form of an emulsion, which was centrifuged to obtain
the cold pressed oil [16]. Samples measurements were done at room
temperature. A total of 10 measurements were made for each essential
oil under the same conditions.
In Fig. 4, the UVvis spectra of centrifuged citrus oils of lemon,
orange, grapefruit, and green mandarin oils can be seen. An absorbance
peak is observed in the region of 300350 nm for the centrifuged citrus
oils due to monoterpene alcohols (terpenes with OH). The bands at
400450 nm and 660 nm are related to the presence of carotenoids and
chlorophylls that give the characteristic color to oil and fruit. The
spectra were recorded for essential oils extracted by centrifugation.
Changes were observed due to dierences in chemical composition of
the dierent oils [17,18].
In Fig. 5 the ATR-FTIR spectra for the dierent oils can be seen. Due
to the similar chemical composition of the oils, these spectra showed
the typical characteristic absorption bands. The characteristic absorp-
tion bands for essential oils are present: the broad band between 3036
and 2784 cm1 that corresponds to the asymmetrical and symmetrical
stretching vibration of the aliphatic eCH in CH2 and CH3 groups and
eOH stretching for alcohol and phenols. At 1743 cm1 the ester car-
bonyl functional groups of the triglycerides are assigned. The trigly-
cerides are the principal components in oils. The most relevant mono-
terpene components occurring in these oils are limonene and -
terpinene, but and pinene, myrcene, sabinene, octanal, de-
canal, citral, sinensal, and nootkatone can also be present [19]. In
lemon, orange and grapefruit essential oils, limonene occurs at levels of
Fig. 5. FTIR spectra of lemon, green mandarin, orange and grapefruit essential oil sam-
ples. (For interpretation of the references to colour in this gure legend, the reader is
referred to the web version of this article.)
approximately 95% and in other citrus oils at 5078%. Thus, the ATR-
FTIR spectra of these oils are mainly characterized by limonene vi-
brational modes to be seen at 877 cm1 (out-of-plane bending of the
terminal methylene group), at 1442 cm1 ( CH2) and at 1644 cm1
[20]. The individual (C]C) stretching vibrations of both mono-
terpenes are found at 1658 cm1 ( pinene) and 1640 cm1 (-
pinene), respectively. Also, pinene presents the characteristic signal
of the CH at 787 cm1, -pinene shows the absorption band of the
terminal methylene group at 873 cm1 and of the cyclohexane ring at
853 cm1. Finally, the bands at 800 and 950 cm1 are associated to the
wagging vibrations of CH and CH2 groups.
Among monoterpenes, numerous aldehyde derivatives can be well
recognized by ATR-FTIR spectroscopy where the intense IR band due to
the C]O stretching mode is seen between 1782 and 1569 cm1 (blue
circle), and the increased of the peak at 1158 cm1 (red circle) for
(C]C) in aromatics. These were observed only for lemon oil compared
to the other essential oils.
Fig. 6 shows the 1H NMR spectrum of lemon essential oil. The
spectrum shows the resonances of limonene (Table 2). The signal at
0.66 ppm is attributed to a compound with a pinenic structure. Then,
methylenic protons of all insaturated fatty chains were observed in the
1.2 region. In 1.62 and 1.66 ppm there are the squalene and the li-
monene signals, respectively. In the inset, the signals at 1.66 and 1.72

Fig. 4. UVvis spectrum of centrifuged citrus oils: lemon, orange, grapefruit and green
mandarin. (For interpretation of the references to colour in this gure legend, the reader
is referred to the web version of this article.) Fig. 6. 1H NMR spectrum of the lemon essential oil (CDCl3, 750 MHz NMR).

68
R. Carbajal-Valdez et al. Thermochimica Acta 657 (2017) 6671

Table 2 experimental data is represented by the red line.

Signals present in 1HNMR lemon oil spectrum. The thermal diusivity of the citrus oils was measured at room
temperature. From the best t of Eq. (1) to the experimental data the
Signal ppm Lemon oil
obtained values were: D = (7.18 0.05) 108 m2 s1, D =
Geranial/neral 9.710 9.8810 (7.22 0.03) 108 m2 s1, D = (7.33 0.03) 108 m2 s1,
p-cymene 7.1 7.1 and D = (7.39 0.04) 108 m2 s1 citrus oils: lemon, orange,
linalool 5.88
grapefruit, and green mandarin, respectively. These results are shown
limonene 5.30.62 4.63, 4.7, 1.73, 1.66,
1.47. in Table 3. These values are in agreement with the diusivity values
terpene 4.534.60 4.60 obtained by other analytical techniques [18,22].
squalene 1.62 1.62 Thermal eusivity values for the samples can be seen in Fig. 9, as an
Methylenic protons of all insaturated fatty 1.25 0.231.25 example of the best tting of Eq. (5). The obtained values of e were for
chains
citrus oils of lemon, orange, grapefruit, and green mandarin are:
Methylenic protons of palmitic and stearic 1.20 1.181.23
fatty chains (0.0532 0.0026) W s1/2 m2 C1, (0.0508 0.0016) W s1/
wax 0.98 0.97
2
m2 C1, (0.0489 0.0011) W s1/2 m2 C1, and
Methyl of linolenic fatty chains 0.92 0.92 (0.0646 0.0034) W s1/2 m2 C1, respectively. The reported
Methyl of linoleic fatty chains 0.84
thermal eusivity of ethanol = 0.0585 (W s1/2 m2 C1). These va-
lues agree with the eusivity values obtained with other techniques
shows the limonene contributions signals. Additionally, other sig- [22].
nicant correlations were also observed at 5.0 ppm and 2.0 ppm region. As can be seen, the thermal conductivity (k) is the result of the
It is noticeable that the intensity of 4.7 ppm corresponds to limonene thermal diusivity (D) and the thermal eusivity (es) of the sample. The
signal. The sample contains p-cymene with its characteristic resonance obtained results from Fig. 9 are summarized in Table 3, where the
at 7.1 ppm. It is well known that limonene and p-cymene are com- values for thermal diusivity (D) and thermal eusivity (e) were used to
calculate the thermal conductivity (k) using the relationshipk = es D
ponents of lemon oil. On area from 9.8 to 10.0 ppm and from 5 to
for the dierent citrus oils [23].
6 ppm signals were assigned to geranial and neral, two unsaturated
The obtained values of thermal diusivity, eusivity and con-
aldehydes characteristic of lemon oil. As shown in Fig. 6, neral and
ductivity for the evaluated citrus oils are similar to the values reported
geranial displayed many overlapped signals, but they could be readily
in the literature with k ranging from 0.130 0.006 to
distinguished by chemical shifts of the aldehyde proton (9.9 and
0.142 0.007 W/m C [19]. This slight dierence can be related to a
10.0 ppm, respectively), the methyl in cis or trans position (1.98 and
variation in chemical composition of these essential oils related with
2.17 ppm, respectively) and the overlapping signals observed for CH2 at
the extraction process [5,6]. The measured values lie in the range of
2.23 ppm in geranial [21].
centrifuged essential oils samples, as observed in Table 3.
Fig. 7. shows the 1H spectrum for the dierent citric essential oils:
It can be seen from the properties in Table 3, that there is a tendency
orange, grapefruit and green mandarin. All citric essential oils shown
for the thermal properties, having lemon oil the lowest value of diu-
similar spectra. Limonene has been also determined in the orange,
sivity, the highest eusivity and conductivity. On the other hand, the oil
grapefruit and mandarin oils. The 1H spectrum of these oils is char-
with the highest diusivity was green mandarin, having the lowest
acterized by the presence of the resonance at 4.64 ppm due to ]CH2
values of thermal eusivity and conductivity, these two trends are ac-
protons of limonene. In the 1H NMR spectrum of mandarin oils, (see the
cording to the relationk = es D , respectively. From spectroscopic
signals in Table 2), the resonances of limonene (terpene) at 4.64 and
techniques: UVvis spectroscopy, ATR-FTIR and 1H NMR results, some
5.37 ppm region and the signal at 0.7 ppm due to a pinenic structure
changes or dierences were observed in characteristic peaks due to the
are present.
chemical composition of lemon oil, where the most relevant mono-
From Fig. 8, the transient thermal lens (TL) signal evolutions for
terpene components with respect to the other aromatic oils are present
citrus oils: lemon, orange, grapefruit and green mandarin are observed.
in its structure. It has been found in the literature that also the per-
A decrease of the signal as time passes is observed. The open circles
centage of heterocyclic and other compounds varies greatly among ci-
correspond to the experimental data and the best t of Eq. (1) to the
trus species [26]. Then, the precursor oil used for photothermal mea-
surements must be taken into account. From ATR-IR and 1H NMR the
complex chemical structure of citrus oils and factors like pretreatment
of peels and dierent extraction process such as distillation must be
taken into account as studied by other authors [27].
It is important to highlight, that essential oils are the mixture of
dierent organic molecules. In the case of our studied citrus oils, che-
mical composition is similar being limonene the major component
followed by -pinene, -pinene and -terpinene, among others.
Dierence between oils, arises from minority components, which, give
dierent properties according to their concentration in the essential oil.
For example, the group of aldehydes such as neral, geranial and de-
canal, among others. Fig. 4 shows the UVvis spectra. As mentioned
before, the bands at 400450 nm and 660 nm are related to the pre-
sence of carotenoids, which have many C]C groups in their structure,
and chlorophylls, which includes C]C and C]O functional groups in
dierent concentrations for the essential oils [18]. From ATR-FTIR
spectroscopy in Fig. 5, an intense band due to the C]O between 1782
and 1569 cm1 (blue circle) was observed. Moreover, an increase of the
peak at 1158 cm1 (red circle) for (C]C) is observed due to aromatic
Fig. 7. 1H NMR spectra of the dierent citric essential oils: orange mandarin, grapefruit, groups like limonene and -terpinene [28]. Some representative che-
and green mandarin. (For interpretation of the references to colour in this gure legend, mical structures of essential oils are observed in Fig. 10. The presence of
the reader is referred to the web version of this article.) this chemical compounds were also conrmed by 1H NMR spectra from

69
R. Carbajal-Valdez et al. Thermochimica Acta 657 (2017) 6671

Fig. 8. Transient thermal lens signal for citrus oils: a)

lemon, b) orange, c) grapefruit, and d) green man-
darin. Experimental data correspond to open circles.
The red line represents the best t of Eq. (1) to the
experimental data. (For interpretation of the refer-
ences to colour in this gure legend, the reader is
referred to the web version of this article.)

Table 3
Dependence of thermal diusivity (D), thermal eusivity (e), thermal conductivity (k) and tting parameters (tc and ) for the dierent citrus oils.

Essential Oils D(108m2/s) Literature [18,22,24] D(108m2/s) e(104Ws1/2/m2 C) Literature [25] e(104Ws1/2/m2 C) k(W/m C) Literature [25] k(W/m C)

Lemon 7.18 0.05 7.17 0.05 0.0532 0.0026 0.049 0.003 0.142 0.007 0.134 0.001
Orange 7.22 0.03 7.31 0.03 0.0508 0.0016 0.048 0.002 0.136 0.004 0.132 0.001
Grapefruit 7.33 0.03 7.37 0.02 0.0489 0.0011 0.049 0.003 0.133 0.003 0.137 0.002
Green mandarin 7.39 0.04 7.43 0.08 0.0478 0.0022 0.130 0.006

Fig. 9. Open cell photoacoustic spectrum of aromatic

essential oils thermal eusivities of a) lemon, b) or-
ange c) grapefruit and d) green mandarin. (For in-
terpretation of the references to colour in this gure
legend, the reader is referred to the web version of
this article.)

70
R. Carbajal-Valdez et al.
Fig. 10. Main chemical structures of citrus essential oils.
Figs. 6 and 7. Therefore, behavior of photothermal properties are at-
tribute to the dierent functional groups present in the chemical
composition of the oils, being the photothermal techniques an useful
alternative to analyze essential oils and the composition of good quality
centrifuged oils.
4. Conclusions
The applications of thermal lens and open photoacoustic cell for
study of thermal properties in citrus oils centrifuged, have been pre-
sented. Thermal parameters were evaluated for four essential oils.
Thermal eusivity and conductivity of green mandarin sample are re-
ported for the rst time in the literature. Our results were reproducible
compared with the values of the thermal constants of various essential
oils reported in the literature for other photothermal techniques. Also,
results suggest that UVvis, FTIR and NMR spectroscopy can be good
methods to study the chemical ngerprint of essential oils and to
monitor the quality of the same.
Acknowledgments
Thanks to CONACYT, COFAA, and CGPI-IPN, Mxico, for their
partial nancial support. One of the authors (A. Cruz-Orea) is grateful
for the economic support of CONACYT through Project 241330. Also,
we thank Ing. Esther Ayala at the Physics Department of CINVESTAV-
IPN for her technical support.
References
[1] T. Tin Do, F. Hadji-Minaglou, S. Antoniotti, X. Fernandez, Authenticity of essential
oils, Trend Anal. Chem. 66 (2015) 146157.
[2] J. Shankar Raut, S. Mohan Karuppayil, A status review on the medicinal properties
of essential oils, Ind. Crop. Prod. 62 (2014) 250264.
[3] I. Martins, M. Barreiro, M. Coelho, Microencapsulation of essential oils with bio-
degradable polymeric carriers for cosmetic applications, Chem. Eng. J. 245 (2014)
191200.
[4] I. Shakir, S. Salih, Extraction of essential oils from citrus by-products using mi-
crowave steam distillation, Iraq. J. Chem. Petrol. Eng. 16 (2015) 1122.
[5] M. Boukroufa, C. Boutekedjiret, L. Petigny, et al., Bio-renery of orange peels waste:
a new concept based on integrated green and solvent free extraction processes using
71
Thermochimica Acta 657 (2017) 6671
ultrasound and microwave techniques to obtain essential oil, polyphenols and
pectin, Ultrason. Sonochem. 24 (2015) 7279.
[6] F. Chemat, A. Fabiano-Tixier, M. Abert Vian, et al., Solvent-free extraction of food
and natural products, Trend Anal. Chem. 71 (2015) 157168.
[7] P. Quinto, I. Bonaccorsi, P. Dugo, L. Mondello, G. Dugo, Analysis of Citrus essential
oils: state of the art and future perspectives. A review, Flavour Fragr. J. 27 (2012)
98123.
[8] J. Gordon, R. Leite, R. Moore, S. Porto, J. Whinnery, Long-transient eects in lasers
with inserted liquid samples, J. Appl. Phys. 36 (1965) 38.
[9] R. Carbajal Valdez, J.L. Jimnez Prez, A. Cruz-Orea, E. San Martn-Martnez,
Thermal diusivity measurements in edible oils using transient thermal lens, Int. J.
Thermophys. 27 (2006) 18901897.
[10] A. Sigman, An Introduction to Laser and Masers, McGraw-Hill, New York, 1971.
[11] J. Gaskill, Linear Systems, Fourier Transform, and Optics, Wiley, New York, 1976.
[12] M. Marquezini, N. Cella, A. Mansanares, H. Vargas, L. Miranda, Open photoacoustic
cell spectroscopy, Meas. Sci. Technol. 2 (1991) 396401.
[13] M. Castro, A. Andrade, R. Franco, P. Miranda, M. Sthel, H. Vargas, R. Constantino,
M. Baesso, Conformations and laser-induced uorescence spectroscopy of jet-cooled
2-(p-uorophenyl) etanol, Chem. Phys. Lett. 411 (2005) 1822.
[14] J.L. Jimnez-Prez, P. Vieyra Pincel, A. Cruz-Orea, Z.N. Correa-Pacheco, Thermal
characterization of a liquid resin for 3D printing using photothermal techniques,
Appl. Phys. A 122 (2016) 556.
[15] J.A. Balderas-Lopz, D. Acosta-Avalos, J.J. Alvarado, O. Zelaya Angel, F. Sanchez-
Sinencio, C. Falcony, A. Cruz-Orea, H. Vargas, Photoacoustic measurements of
transparent liquid samples: thermal eusivity, Meas. Sci. Technol. 6 (1995)
11631168.
[16] A. Di Giacomo, G. Di Giacomo, Essential oil production, in: G. Dugo, A. DiGiacomo
(Eds.), Citrus: The Genus Citrus, Taylor & Francis, London, 2002.
[17] A. Agcs, V. Nagy, Z. Szab, L. Mrk, R. Ohmacht, J. Deli, Comparative study on the
carotenoid composition of the peel and the pulp of dierent citrus oils, Innov. Food
Sci. Emerg. Technol. 8 (2007) 390394.
[18] G. Lpez Muoz, Masters Degree Thesis Titled Implementacin de un sistema de
Espectroscopia Fotoacstica para la caracterizacin termo-ptica de aceites esen-
ciales ctricos, (2011).
[19] H. Schulz, M. Baranska, Chapter 12: fruits and vegetables, in: D. Sun (Ed.), Infrared
Spectroscopy for Food Quality Analysis and Control, Academic Press (Elsevier),
London, 2009.
[20] P. Tongnuanchan, S. Benjakul, T. Prodpran, Properties and antioxidant activity of
sh skin gelatin lm incorporated with citrus essential oils, Food Chem. 134 (2012)
15711579.
[21] L. Mannina, M. D'Imperio, M. Gobbino, I. D'Amico, A. Casini, M. Emanuele,
A. Sobolev, Nuclear magnetic resonance study of avoured olive oils, Flavour Fragr.
J. 27 (2012) 250259.
[22] G.A. Lpez Muoz, R.F. Lpez Gonzlez, J.A. Balderas Lpez, L. Martnez-Prez,
Thermal-diusivity measurements of mexican citrus essential oils using photo-
acoustic methodology in the transmission conguration, Int. J. Thermophys. 32
(2011) 10061012.
[23] J.L. Jimnez-Prez, G. Lpez-Gamboa, A. Cruz-Orea, Z.N. Correa-Pacheco, Estudio
de parmetros trmicos de biodiesel conteniendo nanopartculas de Au usando
tcnicas fototrmicas, Rev. Mex. Ing. Quim. 14 (2015) 481487.
[24] G.A. Lpez Muoz, J.A. Balderas Lpez, R.F. Lpez Gonzlez, Authentication of
concentrated orange essential oils using photoacoustic spectroscopy, Int. J.
Thermophys. 33 (2012) 18341841.
[25] G. Lpez Muoz, J. Balderas Lpez, Photothermal characterization of citrus es-
sential oils and their derivatives, Thermochim. Acta 579 (2014) 4044.
[26] H. Fan, Q. Hu, J. Simon, S. Lou, C. Ho, Authenticity analysis of citrus essential oils
by HPLC-UV-MS on oxygenated heterocyclic components, J. Food Drug Anal. 23
(2015) 3039.
[27] G. Kamal, F. Anwar, A. Hussain, N. Sarri, M. Ashraf, Yield and chemical composi-
tion of Citrus essential oils as aected by drying pretreatment of peels, Int. Food Res.
J. 18 (2011) 12751282.
[28] H. Fan, Q. Wu, J. Simon, S. Lou, C. Ho, Authenticity analysis of citrus essential oils
by HPLC-UV-MS on oxygenated heterocyclic components, J. Food Drug Anal. 23
(2015) 3039.