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E. Silva, D. S. Vieira, N. K. Monteiro and C. A. Martinez-Huitle, New J. Chem., 2017, DOI:
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 Page 1 of 20 New Journal of Chemistry
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Understanding the behavior of caffeine on boron-doped diamond surface:
Voltammetric, DFT, QTAIM and ELF studies

mison Rick Lopes da Silva,aDanyelle Medeiros de Arajo,aEvanimek Bernardo Sabino da Silva,aDavi

Serradella Vieira,a Norberto de Kssio Vieira Monteiro*a and Carlos Alberto Martinez Huitlea
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Institute of Chemistry, Federal University of Rio Grande do Norte, Natal, Rio Grande do Norte, Brazil, CEP
59078-970.

*Corresponding author. Email: norbertokv@gmail.com.

Graphical Abstract

Abstract

The work started from a cyclic and differential pulse voltammetry analysis by using boron doped diamond

electrode (BDD) to understand the behavior of caffeine on its surface as well as the correlation of

experimental figures with theoretical calculations. Voltammetric results clearly reveal that a direct electron

transfer is achieved as the main mechanistic behavior suffered by the caffeine on the BDD surface during its

electrochemical oxidation. From the information provided by experimental measurements, it was

computationally characterized a cluster of BDD surface to verify the interactions of caffeine with the
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electrode, obtaining thermodynamic parameters and geometric interactions by DFT, QTAIM and ELF

calculations. According the energetic analyzes obtained by DFT, the more and less stable geometries were

thermodynamically determined, indicating that, the topological data of the geometries of interactions were

made using QTAIM and ELF to verify the influences that occurred during the interaction and relate to
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interaction energy.

Introduction

The interest in the investigation of degradation of several organic compounds occurs because the

contamination is attained by different ways, principally from industries. The caffeine (C8H10N4O2) (see

Figure 1) is an alkaloid belonging to methylxanthine family. In humans, caffeine acts as a central nervous

system stimulant,1 and it is present in cola drinks, coffee, energy drinks. For this reason, it is a very

important compound in the food industry. Caffeine is also employed in the pesticide industry because it

serves as a natural insecticide since it may paralyze and kill some insects feeding on the plant.2 For the

pharmaceutical industry, caffeine maybe used for pain relief in headaches with doses of 65 mg or more, e.g.:

paracetamol/caffeine drug.3

Figure 1: Chemical structure of caffeine

In this frame, as the caffeine is considerably used in different industries, it can be considered as a

potential pollutant when discharged in aquatic systems. This compound can be determined during its

degradation, alone or mixed with the intermediates generated during its elimination and many different

methods have been proposed for simultaneous caffeine assays, including chromatography,46

spectrophotometry,7 spectrofluorimetry,8 and voltammetry.911 Therefore, the interest in developing

treatment methods, for use in environmental monitoring and restoring, has grown during the last years. The
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industries produce during their processes, different solid and liquid wastes containing toxic compounds; and

their detection, quantification and treatment are necessary before discharge these pollutants in the aquatic

eco-systems.12

In this frame, electrochemical technologies have been the subject of several investigations to be used
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in analytical and environmental applications.13 In the first case, electrochemical techniques (cyclic

voltammetry, chronoamperometry, chronocoulometry, differential pulse voltammetry, linear sweep

voltammetry, etc.,) can be fast in detection, less expensive, and with the merits of low detection limit and

high accuracy as well as less complicated than the other techniques (high performance liquid

chromatography, atomic absorption, gas chromatography and so on).14 Meanwhile, for environmental

applications, the use of electrochemical technologies for depolluting effluents is a feasible alternative since

these procedures allow to degrade the organic pollutants dissolved in water to decrease their toxicity.

In the case of detection for environmental applications, the nature of sensor materials is an important

feature that must be considered. In this frame, BDD has special characteristics that enables highly sensitive

detection of various chemical species, response precision and response stability.13,15 The detection of

chemical species using electrochemistry is mainly given by oxidation processes,16,17 classifying the electrode

material as active and non-active, as well as the categories of reactions mechanisms (direct and/or indirect).

In this work, the electrochemical behavior of caffeine towards BDD surface was studied by means of

electroanalytical techniques such as cyclic and differential pulse voltammetries in order to understand the

oxidation mechanism follows when caffeine and electrode surface suffer interactions. From this information

it is possible to know if the reaction occurs by direct oxidation, at catalytic sites of the electrode, or occurs

by indirect oxidation, mediated by hydroxyl radicals generated by electrolysis of water. Based on these

experimental results, density functional theory (DFT)1820, quantum theory of atoms in molecules

(QTAIM)2123 and electron localization function (ELF)24,25 were used to study the behavior of oxidation of

caffeine, and consequently, the electrochemical measurements were correlated with the computational

methods of theoretical chemistry. It is important to indicate that, a limited number of reports have been

published in the last years related to the electrochemical behavior and theoretical chemistry at BDD

electrode. For this reason, the proposal of this work is to contribute to the molecular understanding of
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oxidation processes on BDD surface by using voltammetry analyzes as well as DFT, QTAIM and ELF

calculations.

Experimental details
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All reagents were of analytical grade, and all solutions were prepared with Milli-Q water.

New Journal of Chemistry Accepted Manuscript

Voltammetric analysis (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)) were

performed with a potentiostat/galvanostat AUTOLAB model PGSTAT302N by using a three-electrode cell

consisted of an Ag/AgCl (3.0 M) as reference electrode, a platinum wire as counter electrode and a BDD as

working electrode, with an area of 1.45 cm2. Experiments were carried out at room temperature (25C). In

the case of CV, repetitive cycles were registered in the potential range from 1.0 V to 2.0 V varying scan rate

of 50-200 mV s-1 in 0.5 M H2SO4 as supporting electrolyte in presence or absence of caffeine. In the case of

DPV, the parameters used were potential window between 1.2-1.8 V; scan rate of 10 mV s1, amplitude

pulse of 100 mV and 0.5 M of H2SO4 as supporting electrolyte. The analyte concentration was evaluated in

the range from 6.610-5 M to 8.010-4 M. The above optimized parameters were used for all measurements.

Calibrations were analyzed by ordinary linear least-square regression and the relevant results (slopes and

intercepts) are reported with their confidence interval, P = 95%.

Computational Details

The calculations were carried out using the Gaussian 09 program package26 by access to National

Center for High Performance Processing (CENAPAD-UNICAMP/SP). Geometries were optimized at the

B3LYP/6-31G27 level for caffeine molecule, diamond supercell and complex of adsorption diamond-

caffeine. The diamond supercell was built in Avogadro Software28 (version 1.1.1), the cluster of the

diamond was constructed from the Crystallographic Information File (CIF) obtained from the database

(Crystallography Open Database).29 It was created a supercell (1x3x3) and a boron atom was randomly

inserted into the surface (1 0 0)30 and optimized with B3LYP/6-31G level and then single point calculation

using B3LYP/6-31*G(d,p) and the empirical dispersion correction GD3BJ31,32 using Gaussian 09 package.

From Gaussian calculations, optimized interactions geometry and electron density were generated for later
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use in QTAIM calculations. All topological information of electronic density (), laplacian of electronic

density (
2), ellipsity () and ELF were performed by Multiwfn14,33 version 3.3.9.

Results and Discussions

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Cyclic Voltammetry (CV) characterization

The behavior of caffeine-electrolyte system was characterized with BDD electrode in 0.5 mol L-1

H2SO4 at 25C in absence and presence of caffeine in solution (Fig. 2). Fig. 2A shows that, no significant

signals were observed when voltammetric curve was registered in supporting electrolyte (blue curve); only

an important increase on the current is observed after 1.8 V vs Ag/AgCl. Meanwhile, when caffeine was

added in supporting electrolyte, CV profiles show an oxidation system characterize by an anodic peak in the

positive-going step (1.47 V) and by the absence of any cathodic peak on the reverse scan, indicating that

the oxidation is irreversible. In this study, voltammetric profiles were achieved with a short potential

window ranging from 1.0 to 2.0 V, even when BDD electrode can operate in larger potential window. 2,11 It

is because in the literature the caffeine oxidative potential is well-known at different electrode surfaces, but

our interest was to understand the electrochemical behavior towards BDD.2,7,11,34 Additional information

from figure 2A concerns the caffeine oxidation potential, which remains the same at the different caffeine

concentrations (ranging from 6.610-5 M to 8.010-4 M), indicating that analogous oxidation mechanisms

were attained.

Figure 2: Cyclic voltammograms of caffeine: A) Profiles in absence (blue line corresponds to H2SO4 0.5 M)

and in presence of caffeine (different concentrations of caffeine in solution: 6.610-5, 1.310-4, 2.010-4,

2.610-4, 3.210-4, 3.810-4, 4.510-4, 5.110-4, 5.710-4, 6.310-4, 6.810-4, 7.410-4 and 8.010-4 M)
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registered at scan rate of 100 mV s-1. B) Effect of scan rate (range from 50 to 200 mV s-1) on the

electrochemical response at constant concentration of caffeine (6.310-4 M). Inset: Linear behavior of

current response as a function of scan rate root.

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As previously indicated by Martinez-Huitle et al.,11 the probable oxidation mechanism reaction at

BDD surface seems to take place by an overall 4e-, 4H+ process. The first step, a 2e-, 2H+ oxidation of the C-

8 to N-9 bond to give the substituted uric acid, is followed by an immediate 2e-, 2H+ oxidation to the 4,5-

diol analogue of uric acid, that rapidly fragments (See Scheme).

Scheme of anodic oxidation of caffeine.11

Based on the experimental results and the oxidation pathway reported in the literature about the

caffeine, it is clear that the oxidation process is attained before oxygen evolution reaction via a direct

interaction between caffeine and BDD surface. For this reason, it is important to understand the transport

phenomena from solution to electrode surface. Figure 2B allows comparing a series of cyclic voltammetric

i-E curves at different scan rates for acidic solution in presence of caffeine at BDD electrode; in all cases,

the solution concentration was 6.310-4 M. Electrochemical measurements were performed to study the

transport characteristics of caffeine from solution towards BDD surface to evaluate if the diffusion or the

adsorption was the rate-determining step on the electrooxidation mechanism; then, the scan rate effect on the
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peak current was investigated. As can be seen from Figure 2B, the current increased as a function of the

increase on the scan rate from 50 to 200 mVs-1. This current response was found to be directly proportional

to the square root of the scan rate (in the range: 50-200 mVs-1), as indicated in inset of the Fig 2B, which

demonstrates that the electrode reaction was a diffusion-controlled process. This outcome is in agreement
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with data previously reported by Martnez-Huitle and co-workers.11

Based on these electrochemical measurements, the caffeine oxidation is mainly oxidized by direct

transfer of electrons, before the production of hydroxyl radicals at BDD surface.2,35 For this reason,

mechanistic studies must be performed to increase the understanding of the degradation pathways and the

viability of detection of this organic compound. Then, several experiments were performed by using

differential pulse voltammetry (DPV) in order to evaluate the effects of caffeine oxidizability on the BDD

electrode as well as to confirm the influence of surface interactions with caffeine for its detection.

Differential Pulse Voltammetric (DPV) Study

In agreement with the CV results, DPV signal was registered at the BDD as an anodic peak at about 1.44V

(Fig. 3A). As can be seen, the current response increases as a function of the caffeine concentration in

solution. Data obtained analyzing caffeine standard solutions, in acidic media, allowed to point out a linear

relationship existing between peak current and caffeine concentration (Figure 3B). Calibration curves for

caffeine were obtained at BDD electrode, each curve being obtained by evaluating the peak intensity as a

function of the analyte concentration, and considering at least thirteen analyte concentrations. The analysis

of residuals from the linear regression proved that a linear response exists from 6.610-5 M to 8.010-4 M,

with regression coefficients always larger than 0.9954; however, the results also evidenced a little variability

of slopes and intercepts, which can be due to interactions of caffeine with the electrode surface.

A preliminary estimation of the Limits of Detection, LOD, was also possible by using the approach based on

the standard deviation of regression: LOD = 3 Sy/x / b, where Sy/x is the residual standard deviation and b is

the slope of the calibration plot. On the basis of the preliminary results obtained, a LOD of about 1.010-7 M

could be estimated.
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Figure 3: A) Differential pulse voltammograms of caffeine at BDD surface by using H2SO4 0.5M as

supporting electrolyte with successive additions of different caffeine concentrations in solution (6.610-5,

1.610-4, 2.010-4, 2.610-4, 3.210-4, 3.810-4, 4.510-4, 5.110-4, 5.710-4, 6.310-4, 6.810-4, 7.410-4

and 8.010-4 M) at scan rate of 10 mV s-1. B) Linear relationship of current peak as a function of caffeine

concentration.

The results obtained by DPV technique clearly indicate that, the electroanalytic approach by using BDD

electrode to quantify caffeine is strongly influenced by the interaction of organic compound with the

diamond surface. In fact, this behavior influences on the calibration linear range because no significant LOD

was achieved and the linearity is affected. These assertions are clearer when the weighted residuals for the

analytic curve are evaluated. Fig 3.B shows that the residuals of the regression are not randomly distributed

around the zero, and a statistical error is present in the measurement, and these are related to the mechanistic

study and the voltammetric behavior previously observed and discussed, where the oxidation of caffeine to

other compounds is feasible and the existence of interactions with the electrode surface is possible.

Mechanistic Studies

Regarding the factors responsible for the oxidation of caffeine, it is possible to cite the very

electronegative atoms as oxygen and nitrogen in its chemical structure; these atoms concentrate the

electronic charge as well as the non-binding electrons. Additionally, there are double bonds that contribute

to the increase of the electronic charge in specific sites on the caffeine structure (Figure 1). With regard to

stability factors, intramolecular hydrogen bonds can protect the existing electrons in the molecule; it is via
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the methyl groups close to oxygen atoms that perform intramolecular hydrogen bonds, and consequently,

assisting to protect the electrons on the oxygen atoms.

Oxidation mechanisms for the elimination of organic pollutants by anodic oxidation are well-known

in the literature.1,16,17,36 Direct oxidation occurs at electrocatalytic sites on electrode surface, when a direct
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electron transfer is attained from the molecule to the anode surface. Meanwhile, the indirect oxidation

occurs when oxidants are produced (such as hydroxyl radicals) and these oxidant species attack the organic

matter and cause its oxidation.

In this frame, restricting our results to analyze the relationship between the electrochemical

measurements (Figures 2, 3 and 4) with the mechanism follows during its oxidation,2,34 it is possible to

assume that before the potential of the water discharge, no hydroxyl radicals are generated, then the

oxidative signal registered in the voltammograms is related to a direct oxidation. Consequently, a specific

interaction of this organic compound with the catalytic site of the anodic material is achieved. For this

reason, the simulation of BDD surface is an ambitious target to understand the degradation pathways.1,2,9,34
9,30,37
In this case, a hydrogen-terminated diamond cluster was constructed because the potential window

used did not allow to reach the electrolysis of water, avoiding that the oxygen coordinates the BDD surface

to remain as the majority form (Figure 4).

A B

Figure 4: Optimized geometry of hydrogen-terminated cluster of boron-doped diamond (BDD), obtained by

the B3LYP/6-31G method. (A) Side view and (B) view from the top (1 0 0).
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The caffeine molecule was disposed at the surface of the diamond cluster (1 0 0), Figure 4, to obtain

the correct interacting geometries for this system. Eight positions were found for the interactions of the

caffeine molecule with surface (1 0 0) of the anodic material. The Figure 5 presents the eight complexes (C1

to C8) obtained.
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C1 C2

C3 C4
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C5 C6

C7 C8
Figure 5: Caffeine-BDD complexes with distances (in Angstron-) and optimized geometrics with

B3LYP/6-31G level of theory.

The Figure 5 shows some distances between the caffeine atoms that interact with the BDD when the

oxygen atom interacts, the average is 2.6 referring some distances of the CPs shown in Figure 6. This

shows that the values of CPs indicate weak interactions, confirmed for Laplacian values in Table 1. On the

other hand, the measurement of the intramolecular interactions are around 2.2 and have high values of

eletronic density (Table 1) when compared with the CP values of caffeine-BDD, showing that these

interactions have significant effect of relation between interaction energy (IE) and electronic density shared.

Other example is complex C3 has the caffeine oxygen atom with an intramolecular interaction (2.261 ) and

two intermolecular interactions with the BDD (2.666 and 2.549 ) simultaneously, and the difference
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between the two is clear. Because and ELF exhibit the highest value in the CP intramolecular interaction

when compared to CP interaction with BDD. These results indicate that the interactions and distances are in

agreement with the topological data of Table 1.

The interaction energy (IE) calculations between caffeine and BDD-surface for the eight positions
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found (Figure 5), were performed through the single point energy of complex, caffeine and BDD-surface

and applicated in the Equation (1):

IE = E(complex) - E(caffeine) - E(diamond) (1)

IE values are available in Table 1.

C1 C2

C3 C4
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C5 C6

C7 C8
Figure 6: Optimized geometries of the interactions in the caffeine-diamond complex using B3LYP/6-31G

method and single point with GD3BJ-B3LYP/6-31*G(d,p). The interactions are represented by yellow dots

the critical points between caffeine and diamond.

All properties of matter are somewhat related to density of electronic charge , where one can

associate its topology with delineating atoms and the bonding between them.38 In the Fig. 6, the optimized

geometries of the interactions have bond paths and critical points (CPs) calculated using QTAIM. The

analyzed CPs were those found between the caffeine molecule and the diamond surface (1 0 0) which would

be the electron density present between the two during the calculated interaction. So the idea of using

quantum model is considered innovative in the study of chemical bonding and characterization of intra or
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intermolecular interactions.3941 for each of the CPs it was analyzed: electronic density () laplacian of

electronic density (
2), ellipsity () and electron localization function (ELF).

The IE value indicates that the C4 and C6 complex has the lowest interaction energy IE = -0.525 and

-0.324 eV, respectively, in other words, it is the most thermodynamically stable and should occur more
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easily. On the other hand the C1, C3 and C2 complex has the highest interaction energy IE = -0.223; -0.283

and -0.298 eV, respectively, indicating to be the less thermodynamically stable among the optimized

geometry complexes, and consequently the complex more difficult to occur (Table 1).

Table 1: IE = interaction energy (in eV); corresponding to the geometries exhibit in Fig. 6 and the values of
electronic density (), laplacian of electronic density (
2),ellipsity () andelectron localization function
(ELF) for each critical point obtained in the QTAIM calculations of the convergent interaction geometries
using GD3BJ - B3LYP/6-31*G(d,p).

C1
CP
2 ELF
1 0.007 0.024 0.017 0.059
2 0.005 0.018 0.011 1.182
3 0.007 0.027 0.019 0.089
4 0.001 0.003 0.002 0.492
5 0.001 0.004 0.003 0.121
Total 0.021 0.052
IE -0.223 eV
Intramolecular interactions

6 0.018 0.075 0.049 1.165

C2
CP
2 ELF
1 0.003 0.009 0.008 0.346
2 0.005 0.015 0.016 0.094
3 0.007 0.021 0.026 0.014
Total 0.015 0.050
IE -0.298 eV
Intramolecular interactions
4 0.018 0.075 0.048 1.223

C3
CP
2 ELF
1 0.006 0.022 0.015 0.070
2 0.007 0.027 0.017 0.082
3 0.003 0.010 0.009 0.713
4 0.003 0.010 0.009 0.657
Total 0.019 0.050
IE -0.283 eV
Intramolecular interactions
5 0.018 0.074 0.048 1.254

C4
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CP
2 ELF
1 0.003 0.011 0.007 0.084
2 0.003 0.009 0.009 0.122
3 0.003 0.009 0.009 0.412
4 0.003 0.011 0.011 0.075
5 0.002 0.006 0.007 1.368
6 0.001 0.004 0.002 0.882
7 0.003 0.010 0.010 0.144
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9 0.003 0.010 0.011 0.152
Total 0.024 0.073
IE -0.525 eV
C5
CP
2 ELF
1 0.002 0.006 0.005 5.254
2 0.004 0.015 0.008 1.282
3 0.006 0.021 0.014 0.076
4 0.006 0.022 0.015 0.055
5 0.002 0.007 0.007 0.071
6 0.003 0.010 0.013 0.097
Total 0.023 0.062
IE -0.316 eV
Intramolecular interactions
7 0.019 0.075 0.049 1.144

C6
CP
2 ELF
1 0.002 0.006 0.007 0.503
2 0.002 0.006 0.005 66.591
3 0.007 0.024 0.017 0.123
4 0.005 0.019 0.011 0.317
5 0.005 0.017 0.010 0.778
6 0.006 0.021 0.013 0.231
Total 0.027 0.063
IE -0.324 eV
Intramolecular interactions
7 0.019 0.075 0.049 1.073
8 0.014 0.045 0.047 0.049

C7
CP
2 ELF
1 0.002 0.007 0.007 0.031
2 0.004 0.016 0.008 1.203
3 0.006 0.022 0.015 0.093
4 0.007 0.024 0.017 0.067
5 0.003 0.009 0.011 0.024
Total 0.022 0.058
IE -0.310 eV
Intramolecular interactions
6 0.019 0.075 0.050 1.075
7 0.014 0.045 0.047 0.049

C8
CP
2 ELF
1 0.002 0.007 0.007 0.031
2 0.004 0.016 0.008 1.203
3 0.006 0.022 0.015 0.093
4 0.007 0.024 0.017 0.067
5 0.003 0.009 0.011 0.024
Total 0.022 0.058
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IE -0.310 eV
Intramolecular interactions
6 0.019 0.075 0.049 1.075
7 0.014 0.045 0.047 0.049

QTAIM
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For all the geometries of interactions found, QTAIM calculations were performed to evaluate

topological data between the caffeine molecule and the cluster. The Figure 6 shows the CPs identified by

numbers and in Table 1 the values of (), (
2), (ELF) and () for each CP identified in Figure 6.

Since the values of are (10-2 au) and the Laplacian of the electronic density (
2) > 0 it is clear

that they are weak interactions.17,40,41 Analysis of the sum of the relative to caffeine-diamond interaction of

each complex indicates C4 and C6 as the complexes of higher value (0.024 ua and 0.027 ua, respectively)

between the caffeine molecule and the surface (1 0 0), while C1, C2 and C3 indicates the lowest value

(0.021 ua, 0.015 ua and 0.019 ua, respectively).

The ellipticity measures the extent to which density is preferentially accumulated in a given plane

containing the bond path, in other words, ellipsity is the measure of the electron density distribution in the

CP, so a symmetrically cylindrical distribution presents = 0.23,38 The values presented for show that there

is no uniformity in the distribution of the electronic density in the CPs analyzed. Among all complexes, most

of it CPs have distant from zero. Therefore the electronic density is dispersed between the molecule and

the surface, not being cylindrically distributed in the bond paths

The higher number of CPs and the values are parameters which denote favorable conditions for the

interaction to occur on carbonyl oxygen (N-CO-N) in the C1 and C5-C8 complexes. While in the other

carbonyl (N-CO-C) in the caffeine molecule, the values in the CPs of the C2 and C3 complexes did not

present significant difference to the electronic density sharing. In the case of C2 the CPs bind two hydrogen

atoms and one nitrogen atom with the BDD, while in C3 the oxygen atom that interacts with the BDD (C3:

CP 1 and 2) is also with the atom making intramolecular interaction in caffeine (C3: CP 5), in other words

your electronic density is shared in two different ways, because it the caffeine-diamond interaction CP has a

smaller . Its interesting the case of C4 complex, it has the highest numbers of CPs, and it has one of the

largest amounts of electronic density considering the values between caffeine and BDD. This results
 Page 17 of 20 New Journal of Chemistry
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DOI: 10.1039/C7NJ00386B
clearly shows the protective effect of charge that has the intramolecular interactions in the atomic sites of

high electronic density.

ELF
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New Journal of Chemistry Accepted Manuscript

The ELF of Becke and Edgecombe25 is presented as another procedure for analysis of the direct

connection between the distribution of electronic density and the chemical structure.4244

ELF analysis showed a difference when compared to QTAIM results. The C4 complex presented the

highest total ELF value (0.073 ua) followed by C6 complex (0.063 ua), an opposite result to that obtained

with QTAIM (Table 1). However, both complexes with higher electronic density and IE can be understood

in Figure 7, that shows the coefficient of determination between IE and QTAIM and ELF values of the

complexes. The plot of IE versus Total ELF (Figure 7C) shows a good coefficient of determination (R2 =

0.7433). On the other hand, the plot of IE versus (Figure 7D) showed a poor coefficient of determination

(R2 = 0.1364). In addition, Figure 7A shows a very good linear relation between ELF and numbers of CPs,

however, there is no relation between and numbers of CPs (Figure 7B). Then, we may assume that the ELF

and numbers of CPs are important stability factors in the abovementioned complexes. Thereby, it is clear the

importance of the ELF topological data for the study of caffeine interactions with BDD electrode.

Conclusions

Boron-doped diamond proved to be a reliable material for caffeine analysis, showing useful

responses at different concentrations (Fig.2 and 3). In according to studies the results of the voltammograms

indicated that the electro-oxidation process happens by transfer of electrons on the surface of the

electrode.2,9,11 The sensitivity of the electrode as sensor defines the possibility of using the electrochemical

methodology for analysis. The methodologies of theoretical chemistry herein employed were driven by

experimental results of the voltammetries, resulting in the elucidation of the chemical behavior of electron

transfer for topological analyse,of which among QTAIM and ELF the best results were with ELF for

electronic density related to IE and CPs. The oxygen atom by carbonyl (N-CO-N) is the major responsible

for electron transfer and revealed thermodynamic aspects to the interactions in majority of complexes, the

order of IE indicate the most favorable geometries, the best being the C4 and C6 of the caffeine-diamond
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DOI: 10.1039/C7NJ00386B
complexes. The use of QTAIM and ELF related to DFT revealed ELF as a more accurate tool in the

comparison of IE with electron density in the geometries, besides showing the main sites responsible for the

exchange of electronic density and the intramolecular interactions present in caffeine, acting as Shield of

electron density transfer between the caffeine molecule and the diamond cluster.
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New Journal of Chemistry Accepted Manuscript

Cps Cps

Figure 7: (A) Plot of Total ELF versus Total number of CPs; (B) Plot of Total versus Total number of

CPs; (C) Plot of Total ELF versus IE/eV; and (D) Plot of Total versus IE/eV for all studied complexes.

Acknowledgements

Financial supports from National Council for Scientific and Technological Development (CNPq

465571/2014-0; CNPq - 446846/2014-7 and CNPq - 401519/2014-7), UFRN and FAPESP (2014/50945-4)
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are gratefully acknowledged. A. R. L. da Silva and C. A. Martnez-Huitle gratefully acknowledge the

support and permission supplied by CENAPAD/UNICAMP-SP to develop computational calculations.

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