CARBON QUANTUM DOTS OBTAINED FROM NATURAL RESOURCES

FROM SOUTH AMERICA, USED AS TRACERS FOR THE OIL INDUSTRY.

Steven Salgado 1, Jaime Gallego 2, Camilo A. Franco1,* and Farid B. Cortés 1

1
Grupo de Investigación en Fenómenos de Superficie—Michael Polanyi,
Departamento de Procesos y Energía, Facultad de Minas, Universidad Nacional de Colombia,
Sede Medellín, Medellín 050034, Colombia; sjsalgadog@unal.edu.co (S.J.S.)
2
Química de Recursos Energéticos y Medio Ambiente, Instituto de Química,
Universidad de Antioquia UdeA, Calle 70 No. 52-21, Medellín 050010, Colombia;
andres.gallego@udea.edu.co
* Correspondence: fbcortes@unal.edu.co (F.B.C.); caafrancoar@unal.edu.co (C.A.F.)

Abstract: The main objective of this study is to evaluate the viability of South American
fruits as precursors for the synthesis of Carbon Quantum Dots (CQD) and their application
as tracers for the oil industry. The selected fruits the “Araza” (Eugenia Spititata) 1. The
“mortino” (Vaccinium meriodionale) 2. Guava (Psidium) 3. “Passiofruit” (Passiflora edulis)
4
. The selection of each of this fruits was due to their acid content, and the lack of literature
study of this as precursors for CQD development, Each fruit was turned into juice and
applied a microwave synthesis process with Ethylenediamine to dope them with N, to turn
the CQD to the blue light wavelength. To measure their CQD capability and further tracer
capability as well, the materials were characterized with size analysis, FTIR,
Termogravimetric analysis and in a fluorescence spectrometer to measure their fluorescence.
This tests indicated that the mortino CQD were the ones with the best particle size and
fluorescence characteristics. Furthermore dynamic testing with a displacement test for each
of the fruit CQD indicated that they were optimal for mass recovery and tracer capability,
showing again the mortino as the most viable as a commercial option for Carbon Quantum
Dots, taking in account the need to improve the purity of the quantum dots in the process
and possible further functionalization to resist reservoir environments.

1. Introduction

The scarcity of conventional oil reserves, associated with the depletion of wells, lack of
mobility of remaining oil, and economic inefficiency of barrel production, has made the
natural production systems not worth or impossible to use in recent times. This conditions
are associated with the believes of reaching the peak oil production in history 5. In this regard,
unconventional oil resources are becoming increasingly important in the quest for energy
supply, already making an important impact in international oil economy by reducing US
energy import dependency 6. The unconventional oil resources associated to the term are
bitumen, extra-heavy and heavy oil, oil shale, oil from shale sources rocks and other non-
traditional reservoirs 7. This unconventional reservoirs demand working on tight rocks and
difficult environments. On the other hand, the conventional reservoirs that still are not fully
depleted or still can be exploited, can use secondary recovery techniques, that range from
thermal methods to the use of chemicals and hydraulic fracturing to increase the oil recovery
rate 8.
Because of the further complexity of these methods, the study of the reservoir has become
important to a completely new level recently. Reservoir characterization improvement, water
flood optimization, remaining oil saturation (Sor) determination, fluid pathways, and well
connectivity are some of the tests and information needed to perform an appropriate oil (or
gas) production in the modern oil industry 9. This information can be supplied by the use the
tracer technology that can enter the system without disturbing it and being easily identifiable
10
.
Tracers are chemical substances introduces to the system, that can be detected by measuring
a specific characteristic, as can be fluorescence. They can be defined as an infinitesimal and
identifiable part of a mass that can be introduced or can be there naturally, and can be used
to keep track of the trajectory of that mass, being affected by the movement of the mass as a
whole, but should not affect the movement of the mass itself 9. Tracers have been used since
the early 1900´s in hydrology 11. However, they only have been used in the oil industry ever
since the 1950´s to keep track of injection fluids by “marking” them. Some of the
characteristics that tracers need to accomplish to be suitable for the oil industry are being
stable thermally and through time, non-adsorptive in rock surface, easy and fast quantitative
analysis at low concentrations, low toxicity, etc… Being the radioactive type the most used
since tracer introduction in the oil industry 12, and more recently neutral anionic, cationic
species, inorganic elements or fluorescent molecules 13. The historic use of radioactive
tracers are due to the advantages of being able to be identical to some non-radioactive
molecules in the phases they are tracking, which makes them identifiable without changing
the fluid composition, and also because of the low concentrations needed for detection limits
14
. Nowadays do to regulatory actions and new and safer technology being able to replace
radioactive tracers with even more advantages, their used is been reduced.

It is here where nanotechnology takes a stand, and enters in the oil industry with the
introduction of quantum dots, defined as small (less than 100 nanometers) particles, that have
optical and electronic properties that react when UV light enters the media, in this process an
electron gets excited and enters a higher energy state, illuminates the quantum dots (QD). As
the electron returns to its base state, the energy absorbed from the UV light is emitted at a
specific wavelength that can be interpreted as fluorescence, being this the characteristic that
identifies them as tracers. The most commonly used QDs are cadmium selenide (CdSe),
cadmium telluride (CdTe) 15. Recently a new QD technology has arrived, the carbon based
quantum dots, or carbon quantum dots (CQD). This are nanomaterials with certain
heteroatoms and functional groups on their structure, as Carbon, Oxygen, and Nitrogen
amongst others. This specific composition gives them optical properties, as emitting
fluorescence at a certain wavelength that changes according to the size of the CQD that can
also be tuned. This possibility of changing emission wavelength (and thus color), 16 makes
them attractive to use in different environments. The other important property is their low
toxicity and simple synthesis methods, which makes them easy to test in laboratory for
different objectives, as biomaging, or tracers in the oil industry. This materials were first
obtained by accident during the purification of a single-walled carbon nanotubes through
preparative electrophoresis 17. There are various types of synthetic methods to create CQDs,
like chemical ablation18, electrochemical carbonization19, laser ablation20,
hydrothermal/solvothermal treatment21, and microwave irradiation22. The latter of these
methods is the simplest and the one used in this article, using citric acid as a precursor for
the synthesis.

In the constant need to use green resources, and the use of nitric acid in the synthesis of the
CQDs from microwave irradiation, the idea of using natural resources from fruits and fruit
residue brings the light for the creation of this study. The fruits selected are all associated
with the South American natural resource system and accessible in the Colombian market.
The fruits used for the synthesis are the “Araza” (Eugenia Spititata) from the Amazon
Rainforest vegetation from Brazil, Colombia and Ecuador 1. The “mortino” (Vaccinium
meriodionale) from the Colombian mounts 2. Guava (Psidium) native from parts of the
Western Hemisphere (Mexico, Central and South America) 3. “Passiofruit” (Passiflora
edulis) native from the troipical and subtropical areas from South America 4. All these fruits
have considerable acid content in them, and in this article, their capability to be used as
precursors for Carbon Quantum Dots is tested.

2. Materials and Methods

2.1 Materials. Ethylenediamine for synthesis at 99% purity (Pan Reac AppliChem,
Barcelona, Spain ) was used for doping the CQD with Nitrogen (N). The mortino, guava and
passion fruit are all obtained from the same local market (Medellin, Colombia). The Araza
is obtained from the Colombian Amazon. Their acid content was measured and they were
always bought there to keep a consistent raw material to use for the CQD synthesis.

2.2 Methods 2.2.1 Sample preparation. In the case of guava, passionfruit and araza, the
fruit are cut into pieces; the mortino does not need to be cut because of its small size. The
blending process is as follows, 300 g of fruit is put into a blender, and 20 mL of deionized
water added to ensure that the resulting mixture is uniform and does not have many lumps.
This obtained mixture is strained to eliminate the excess of solid retained in the mixture.
Finally, a fixed volume of the mixture is added into a test tube (the empty test tube is weighted
beforehand), and microwaved for 3 minutes at 200 W, to eliminate the excess water.

2.2.2 Nitrogen doping. Doping is a widely used approach to tune the photoluminic properties
of these types of materials. The N doping is the most studied enhance of the CQDs emission,
it works by making a shift on the Fermi level (thermodynamic work required to add an
electron to a body23). As Nitrogen has an extra electron compared to Carbon, the areas with
the doped Nitrogen tend to have an excess of donors in the CQD24, and depending of the N
content after the doping process, the CQDs have specific PL intensities25. The amine
molecules besides functioning as N doping precursors also work as surface passivating agents
for the CQDs, which enhance the PL performance. The process is to let the liquid mixture of
the fruit go to room temperature after eliminating water excess, and then in a vacuum
environment add between 0.2 to 0.5 mL of Ethylenediamine. The resulting reaction is
exothermic and will heat the test tube, shake the test tube to ensure that the reaction takes
place in all the liquid mixture and then let the mixture reach room temperature again.

2.2.3 Microwave irradiation synthesis. Microwave irradiation is a rapid and low cost
method of CQD synthesis. After the N-doping process with ethylenediamine, the mixture is
heated at 500W for various time periods that ranged from 4 to 7 minutes26. The obtained red-
brown foamy solid is weighted (weight difference between empty test tube and test tube with
solid), and after that dissolved in deionized water, this solution is dissolved into a desire
concentration (ppm [mg/L]) and left at room temperature for further analysis. The process
from 2.2.1 to 2.2.3 is showcased in Figure 1.

Figure 1. Representation of the steps described in 2.2.1, 2.2.2 and 2.2.3 to obtain Carbon Quantum Dots from
fruit in aqueous media

2.2.4 Material Characterization. Fourier transform infrared (FTIR) spectra of the 4 CQDs
were recorded with a IRAffinity-1S from (Shimadzu Corp., Japan) Fourier transform
spectrometer, in order to identify the functional groups presented in the synthesized CQD
samples. Thermo gravimetric Analysis (TGA) was performed in a thermogravimetric
analyzer Q50 (TA Instruments, Inc., New Castel, DE, USA) to study the behavior of the
CQDs at well temperatures (over 70 °C or 158° F). DLS was performed to obtain the mean
particle size at different CQD solution concentration, to verify the nanometric size of the
particles, and the isometric point was found with a Nanoplus Zeta/Nanoparticle analyzer from
Particulate Systems, (Georgia, United States). Transmission electron microscopy (TEM)
images of the CQDs were obtained to see morphology, microstructures and size distribution
in the CQDs.
2.2.5 Fluorescence Spectroscopy. Fluorescence emission spectra of the CQD at different
concentrations were obtained at room temperature in an LS 55 Spectrophotometer
(PerkinElmer Inc., Massachusetts, USA) with xenon lamp as the light source for the
excitation. Fluorescence spectra corresponds to an energy emission or absorption intensity
distribution, at different wavelengths for a sample 27. Fluorescence is a property associated
to some materials, which absorb radiation from an ultraviolet light source or light from the
visible spectra, and emit it to a different wavelength (normally higher)28. The excitation and
emission wavelengths are characteristics to each material; the intensity of the wavelength
depends on the concentration of the material in the solution.

For each material a fluorescence calibration curve, which can be used for the displacement
test, because it can detect the concentration of an unknown sample according to the
fluorescence of said sample. To make it, emission of samples at different concentrations of
each CQD are measured (0, 100, 250, 500 and 1000 ppm), each sample gives an emission
intensity, and the relationship between this data can give a linear regression, that can be used
to associate fluorescence for an unknown sample to a specific concentration.

2.2.6 Displacement Test. Figure 2 shows a representation of the experimental setup used
for this procedure. In one (1) there is a beaker with 1000 mL of the CQD solution at 100 ppm
of CQDs of each fruit. In two (2) is the displacement pump that will pump the solution and
the water into the porous media on three (3), which is made out of clean silica sand (Ottawa
sand, US Sieves 30-40 mesh). After that the effluents go to a collecting tube, and finally are
tested for fluorescence and retention

Figure 2. Schematic representation of the experimental setup for the displacement tests in the CQDs

3. Results and Discussion.

3.1 Chemical and physical composition of precursors.

3.1.1 Araza. Araza is a spherical berry with a diameter from 7 to 12 cm, there are two
specific species, stipitata and sororia, the used species in this study is the sororia,
 due to its bigger fruit size, better efficiency of juice production and acid content.
According to29, the moisture content of araza in a base of 100 g of pulp is of around
90%.

Table 1. Composition of Araza

Component Sororia araza
Longitudinal Diameter [cm] 6.99
Fresh weight [g] 227.33
Crust [weight %] 5.98
Pulp [weight %] 71.97
Seed [weight %] 22.04
Pulp Acid content [anhydrous citric acid %] 2.199
Crust Acid content [anhydrous citric acid %] 2.217

3.1.2 Mortino. Mortino is a native wild plant from Colombia and Ecuador, from its
main characteristics there are the high content of polyphenols due to the presence
of sugars, fibers, lipids, minerals and vitamins. Also compounds as poly-
polyphonic acids are recognized in its structure. The moisture content is of around
85% in dry base30.

Table 2. Composition of Mortino

Component Mortino
Longitudinal Diameter [cm] 0.5-1
TA (g of citric acid per 100g of fruit) 1.35
pH 2.85

3.1.3 Guava. Guava is a tropical fruit belonging to the Myrtaceae family, consumed as
fresh fruit and also processed to juice, and other sub products. According to31, the
moisture content in dry base is 84.9 %

Table 3. Composition of Guava

Component Guava
Longitudinal Diameter [cm] 3-10
TA (g of citric acid per 100g of fruit) 4.43
pH 4.1

3.1.4 Passion Fruit. This is a tropical fruit, with an acid flavor, the different types vary
in size, color and flavor. It comes from the Brazil Amazonian forest, and it’s
cultivated in the cost and jungle areas of Peru. The plant belongs to the
Pasifloracea family. The moisture content of the Passion Fruit in dry base is
around 85%

Table 4. Composition of Passion Fruit

 Component Passion Fruit
Longitudinal Diameter [cm] 4-10
TA (g of citric acid per 100g of fruit) 0.87
pH 3.1

3.2 Characterization of the fruit CQDs

3.2.1 Fourier-Transform Infrared Spectroscopy

Figure 3. FTIR of the fruit CQDs

Figure 3 shows the 4 FTIR for each of the fruit CQDs. The araza FTIR has very defined
strong peaks at 3600 that can be associated with an N-H stretching, another one at 2350 that
attributes to the presence of O=C=O carbon dioxide in the process. And it also displays a
series of bandas from 1700 to 1500, that can be associated with C=O and C-N absorption.
The mortino FTIR has bands in the region from 2800-3500 cm-1, that can be potentially
assigned to O-H, and N-H bending vibrations, the band around 2120 can be associated with
a CΞC stretching, and the band around 1552 can be attributed to the stretching vibration of
C= C. For the Guava, the peak around 3600 can be associated with an N-H stretching, around
3100 and 2840 the bandas can be assigned to O-H and N-H bending vibrations, around 1670
the peak can be assigned to the presence of a C=O stretching associated to the formation of
an amide compound. For the Passion fruit FTIR the band around 3300 that can be assigned
to O-H and N-H vibrations, around 2080 a C=C=N ketenimine stretching can be seen, around
1630 the vibration of C=O bonds is identified.

According to literature knowledge, the FTIR that represents closer the compounds of the
previous studies of Quantum Dot particles made out of carbon material are the mortino
CQDs, with the respective Carbon-Oxygen bonds, and the Nitrogen doping presence more
clear in this.24

3.2.2 Particle size distribution and isoelectric point.

The particle size and distribution was made in a DLS, to measure the approximate size of the
CQD in different water ppm concentrations, the results were taken from around 50 ppm to
10 ppm, because at higher concentrations, the size got increasingly larger, which can be
attributed to particle agglomeration.

Table 5. Particle Size and Isoelectric Point of fruit CQDs

CQD Size Dp50 [nm] Isoelectric Point (pH)
Araza 90 3,3
Mortino 64 3,0
Guava 75 2,5
Passion Fruit 80 2,8

As Table 5 shows, the mortino CQD have the smallest particle size, and this gives them a
shift to the blue wavelength bigger than the rest of the fruit CQDs, as for the Isoelectric Point,
it can be seen that all of the fruit CQDs have a similar pH isoelectric point in which the
properties of the nanomaterial can lose any potential adsorptive capabilities, further studies
can try to acknowledge this properties, and their applications as possible treatments for
precipitation prevention.
3.2.3 Thermogravimetric analysis

3.2.3.1 Air atmosphere TGA

Figure 4. TGA of Araza in air Atmosphere Figure 5. TGA of Mortino in air Atmosphere

Figure 6. TGA of Guava in air Atmosphere Figure 7. TGA of Passion Fruit in air Atmosphere

The air atmosphere TGA show the behavior of the CQD in an oxidation atmosphere at high
temperatures. From the figures it can be said that all the CQD loss all of their mass in a range
from 450 to 535 C°. The mortino and guava CQD present a high first derivative value in
before the 200 C° point, which indicates that a significant mass loss takes place, but for the
mortino CQD, the loss before 100 C° is 10% which is the least in this range for all of the
CQD. The passion fruit and the araza have a more significant mass loss at higher
temperatures.
 3.2.3.2 Nitrogen atmosphere TGA

Figure 8.TGA of Mortino in Nitrogen Atmosphere Figure 9.TGA of Araza in Nitrogen Atmosphere

Figure 10. TGA of Passion Fruit in Nitrogen Atmosphere Figure 11. TGA of Guava in Nitrogen Atmosphere

The Nitrogen atmosphere TGA give an inert atmosphere that can relate better to reservoir
conditions. In this conditions, the mass loss when 800 C° are reached in all samples varies
between 70 and 90%. It can be seen in Figure 11 that the Passion Fruit has the better thermal
stability at low temperatures, followed by the mortino and being the araza the fastest to loss
mass at 125 C°.
 3.2.4 Fluorescence spectroscopy

Fluorescence is a type of luminescence phenomena, it corresponds to the nature of the excited

state of the particles when a light source is used to excite them. In this case the electron in
the excited orbital is paired to the electron in the ground-state orbital. Consequently, the
return to the ground state is spin-allowed and occurs rapidly by emission of a photon27. After
the synthesis process of each fruit CQD, a visual test was performed with a commercial
flashlight that creates light source of 365 nm of wavelength. The doped CQD are expected
to emit a blue light wavelength back, as it can be seen in Figure 12 for a mortino CQD in
water dilution, at daylight there is no visual emission, but in dark room conditions, and under
the UV flashlight, a clear color blue emission can be seen. This emission can only be obtained
at low concentrations of the CQD (between 50 and 500 ppm), because at higher concentration
the dilution becomes a dark color that prevents the possible fluorescence emission.

Figure 12. . Diluted Mortino CQD in a) Daylight and b) UV-light

The fluorescence spectra works with a light excitation source that goes through a filter or
monochromator, and then strikes at the sample. A proportion of the light is absorbed by the
sample, and some of the molecules in the sample fluoresce. The emitted light goes in all
direction, and some of it passes through a second filter or monochromatic and reaches a
detector, that is usually placed at 90° to the incident light beam to minimize the risk of
transmitted or reflected incident light reaching the detector32. The graph of the spectra
delivers the excitation and emission behavior of the CQD diluted sample, at higher
concentrations the intensity increases, but despite said concentration, the maximum
excitation and emission wavelength don’t change, because this is an intensive property of the
material. As a basic rule for a fluorescent material, the maximum emission wavelength at
which the light returns after the process is always higher than the maximum excitation
wavelength.
The fluorescence spectra of each fruit CQD was measured using a pre scan function of the
equipment, which takes a whole range of wavelength of excitation, and a response at the
same range of wavelength for emission, it is used to characterize the maximum excitation
and emission .
 Table 6. Excitation and Emission Wavelength of fruit CQD

Fruit Excitation Wavelength [nm] Emission Wavelength [nm]

Araza 355 460
Mortino 350 458
Guava 348 473
Passion Fruit 336 410

Figure 13. Mortino Fluorescence Spectra at 100 ppm Figure 14.Araza Fluorescence Spectra at 100 ppm

Figure 15. Guava Fluorescence Spectra at 100 ppm Figure 16. Passion Fruit Fluorescence Spectra at 100 ppm

In Table 6 the excitation and emission wavelength of each fruit CQD is reported. The araza
and mortino CQDs have similar wavelengths, which indicates similarity in the structure of
the CQD, although the size difference is the highest between the 4 fruit CQDs, this can be
due to the doping process, that made them have a change in structure similar near to the blue
light spectra. The guava and Passion fruit CQDs have a higher and lower emission
wavelength respectively, that can be associated to the larger particle size detected. From
Figure 13 to Figure 16 the spectra of each fruit is presented, the measured sample is at
100ppm in water for each fruit. The excitation spectra shows a the difference in intensity for
each sample at the maximum emission wavelength, the mortino spectra shows the most
intensity for the same concentration of 100 ppm of around 90 a.u. which indicates that the
mortino has the highest capacity to keep fluorescence and be detectable in lower
concentrations. The spectra for guava, araza and passion fruit, show an emission peak at the
same wavelength as the maximum wavelength of excitation, this can be due to a false reading
that emits the excitation light to the emission light detector, and puts it as a reading of the
emission spectra. It can be seen that the lowest intensity reading is for the passion fruit
spectra, this and the fact that this CQD was the one that produced least with a base of same
juice volume for all the fruits, puts it as the least favorable for viability as a CQD.

3.2.5 Transmission Electron Microscopy (TEM)

Figure 17. TEM Image of the Arazá CQDs

Figure 17 shows the TEM of an araza CQD sample, as it can be seen, a certain number of
dots are present, that range in size from 60 to 80nm for the sample. This ensure the formation
of the nanodots, and also with an EDX made in the same process,

Table 7. EDX for the Araza CQD

Element Weight % Atomic %

C(K) 85.78 87.81
N(K) 11.46 10.06
O(K) 2.75 2.11

The EDX shows that the main elements are carbon, oxygen and nitrogen. The Nitrogen
presence is an indicative of the correct doping process made in the synthesis of the CQDs.

4. Conclusions.

In this work, fruits from South America and Colombia were used as precursors for the
synthesis of Carbon Quantum Dots. The synthesized CQDs were characterized with
physical, chemical and fluorescent properties, to asset the properties that could give away
an optimal performance as tracers for the oil industry. The mortino CQD showed the best
properties between the 4 fruits, giving the smallest particle size, and the highest intensity
at the same concentration for the fluorescence spectra. The TGA analysis gives the
necessity of improvement in purity of the particles, and further studies could use a type
of coating with a metallic material, to improve the thermal stability at reservoir
conditions. The use of this nanoparticles at other types of applications could be viable
due to the simplicity of the synthesis (10-minute process) and the use of raw material that
can also be found as residue in the South American regions.

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