Abstract
In this study, Congo red anionic dye was removed from an aqueous solution using powdered Citrus limetta peel. The adsorbent was evaluated with the use of FTIR and SEM. The highest dye removal was achieved when the operating parameters were optimized, including pH = 6.0, adsorbent dose = 0.4 g, contact time = 90 min, initial adsorbate conc. = 10 ppm, and temperature = 60 °C. The pseudo-second-order model was investigated to have the best fit for the kinetics of the process, with R2 = 0.9918 and Qe(cal) = 0.206 mg g-1, which is very close to the experimental Qe(exp) = 0.191 mg g-1. These two models’ plots showed that both physical and chemical adsorption were feasible. ΔG and ΔH being negative suggest that the adsorption was thermodynamically favorable and spontaneous. Testing the suggested technique with groundwater resulted in an 82% CR adsorption efficiency. Due to the incredible removal capacity of CR dyes from industrial effluents, research suggests that CLPP can be used as substitute adsorbents for the treatment of wastewater from the weaving and dyeing industries.
HIGHLIGHTS
Citrus limetta peel powder is cheap, effective and potential adsorbent for Congo red adsorption from wastewater.
The protonated part of hydroxyl and carboxyl group of CLPP combine with negative part of Congo red dye for adsorption of dye molecules.
Adsorbent characterization, optimized parameters, and adsorbent recovery were studied.
Kinetics, isotherm models, and thermodynamics were evaluated.
INTRODUCTION
The availability of fresh, clean drinking water decreases as the population is increasing. It is impossible to overstate the importance of water for human consumption. The solubility of all contaminants or solutes makes water quality gradually decrease (Wang & Chu 2011; Imran et al. 2022). Water pollution causes worldwide harmful diseases and kills about 15,000 people every day. As a result, the first logical step in solving this enormous issue is the recovery of clean water from wastewater. According to the World Bank, the textile business is one of the most polluting industries on the planet (Khan & Malik 2014). The Comprehensive Regulation of Contaminant Services Regulations of South Korea, which is applicable to both water and air pollution, identifies workplaces that produce more than 80 tons of air pollutants annually or more than 2,000 of water pollutants daily (Kim et al. 2022). It is common knowledge that dumping dyes into waterways lowers sunlight penetration, boosts biological (BOD) and chemical (COD) oxygen consumption, slows respiration, and restricts plant growth (Al-Tohamy et al. 2022). Synthetic dyes are resistant, bioaccumulative, poisonous, mutagenic, and carcinogenic substances (Lellis et al. 2019).



CR was formerly used to color fabrics, but lighter, stain-resistant dyes have now replaced it. It is still used in histology to stain tissues for microscopic study and as an acid-base indicator since it turns red in the presence of alkalies and blue in the presence of acids (Swan & Zaini 2019). Along with similar dyes from the textile, printing and dyeing, paper, rubber, and plastic sectors, it is a serious effluent concern. Consequently, CR has been prohibited because of its cancer-causing properties (El-Ahmady et al. 2020).
For the decolorization of effluents, different kinds of processes are available, including ozonation, membrane separation, coagulation/flocculation, co-precipitation, oxidation, electrolysis, microorganism degradation, photochemical, and adsorption employing various types of adsorbents (Sharma & Kaur 2018; Samsami et al. 2020). Because it is a cheap method for extracting pigments or decolorizing textile pollutants, adsorption has been found to be one of the most successful and established wastewater treatment processes in the textile industry (Chai et al. 2021), Agricultural wastes such as rice husk (Chuah et al. 2005), sugarcane (Sarker et al. 2017), orange peel (Alwared et al. 2021), banana peel (Akpomie & Conradie 2020), dried neem leaf (Bhattacharyya & Sharma 2004), and corncobs (Peñafiel et al. 2020), as well as byproducts such as sugarcane husk, bamboo sawdust, moss, mud, kaolin, red soil, alumina, leaf extract, wood pellets, powdered peanut shells powder, and other lingo-cellulosic wastes have been used to study biosorption (Sharma & Kaur 2018), The benefits of adopting these materials include their widespread availability and inexpensive cost, as well as the fact that they do not require regeneration.
EXPERIMENTATION AND METHODS
Chemicals and equipment
Nitric acid and sodium hydroxide (NaOH) were utilized as chemicals in the research studies, while deionized water was used throughout the study. UV–Vis spectrophotometer, scanning electron microscope (SEM), Fourier-transform infrared (FTIR) spectrophotometer, centrifugation machine, microwave, pH meter, weighing machine, conical flasks, beakers, pipettes, and a hot plate are all required during the entire procedure.
Preparation of CR dye solution
CR dye with a molecular formula and molar mass of 696.665 g mol−1 was collected from a chemistry laboratory, and to make 1,000
dye stock solutions, CR was dissolved in 500 ml of deionized water, and the solution was then further diluted as needed.
Collection of adsorbents

Adsorption batch studies
Batch adsorption analyses were utilized to optimize a number of adsorption characteristics, including temperature (0, 10, 20, 30, 40, 50, and 60 °C), initial concentration of adsorbate CR dye (5, 10–100 ppm), amount of adsorbent (C. limetta peel powder; CLPP) dose (0.1–1.0 g), and pH (1–12). Throughout the experiments, just one adsorption parameter was adjusted at a time, keeping the others unchanged. After shaking, centrifugation was performed, and the quantity of CR dye contained in the sample solution was quantified by measuring absorbance at 496 nm using a UV–Vis spectrophotometer.





Identification of ![]()
45 mL of 0.1 M solutions were taken in several 100 mL conical flasks to identify the point of zero charge
of the adsorbent, and 1 g of the adsorbent was added to each flask in a range of 1–12. Now, 0.1 M HCl/NaOH solutions were used to adjust the
values of these solutions in the range of 1–12. Each flask's total amount of solution was exactly 50 mL. After 2 days, the final pH of the liquids in these flasks was tested. The difference between initial pH and final pH values
was plotted against initial pH. The junction point of the curve of ΔpH versus
was noted as
of the CLPP.
CHARACTERIZATION OF ADSORBENT
FTIR spectroscopy analysis
Using a Perkin Elmer FTIR spectrophotometer, the position of different functional groups (located at the surface of CLPP) was identified. The FTIR analysis of the adsorbent was carried out using a 100 mg pallet of potassium bromide (KBr) with a spectrum range of 4,000–600 (Tiernan et al. 2020).
Scanning electron microscopy (SEM) analysis
The adsorbent was investigated using an SEM both before and after adsorption (JEOL, JSM-6510LV, Japan). In order to eliminate the hazardous CR dye, the morphological characteristics and texture of C. limetta were determined by using an SEM.
RESULTS AND DISCUSSION
FTIR analysis of CLPP












FTIR spectrum analysis of CLPP
FTIR peak of CLPP (![]() | Assignment . |
---|---|
3,337 | O–H |
2,917 | CH3/C–H asymmetric stretching vibration |
1,690, 1,647 | C–O stretching of carboxylic bond |
1,453 and 1,421 | Aromatic compound |
1,377 | C–H groups |
1,183 | C–O–C asymmetric stretching |
1,037 | C–O stretching of alcohol |
FTIR peak of CLPP (![]() | Assignment . |
---|---|
3,337 | O–H |
2,917 | CH3/C–H asymmetric stretching vibration |
1,690, 1,647 | C–O stretching of carboxylic bond |
1,453 and 1,421 | Aromatic compound |
1,377 | C–H groups |
1,183 | C–O–C asymmetric stretching |
1,037 | C–O stretching of alcohol |
FTIR spectrum of Congo red dye before adsorption (a) and after adsorption (b) (Oyekanmi et al. 2021).
FTIR spectrum of Congo red dye before adsorption (a) and after adsorption (b) (Oyekanmi et al. 2021).
SEM analysis of CLPP
SEM image of CLPP biomass (a) biomass loaded with CR (b) (Reproduced with permission from Shakoor & Nasar (2016)).
SEM image of CLPP biomass (a) biomass loaded with CR (b) (Reproduced with permission from Shakoor & Nasar (2016)).
Effect of pH
(a) Effect of pH on adsorption of CR using CLPP. (b) Graph for determination of point of zero charge .
(a) Effect of pH on adsorption of CR using CLPP. (b) Graph for determination of point of zero charge .
The point of zero charge () provides the best explanation for how pH solution affects dye absorption. As a consequence of pH, it is an advantageous and useful surface characteristic for identifying whether the surface is positively or negatively charged. The point of zero charge (
) value for CLPP was 6.6 (Figure 6(b)). This indicates that the adsorbent (CLPP) surface is positively charged at pH values below 8, net zero at pH 8, and negatively charged at pH values above 8. So, any anionic dye, like CR, is better able to adhere to the surface of the CLPP in a solution with a pH lower than 8. Due to the electrostatic force of attraction, the surface of the CLPP adsorbent becomes positively charged, which enhances the absorption of anionic dye. The removal of anionic dyes tartrazine and methyl blue yielded similar results (Ali et al. 2022; Rani & Chaudhary 2022).
Effect of adsorbent dose

Effect of contact time
At 10 ppm initial CR concentrations, the effect of contact time of CLPP adsorption capacity was investigated. The adsorption capacity rises with contact time and attains equilibrium after 90 min, as shown in Figure 8. It mostly originates from the presence of these binding sites on the powdered C. limetta peel that hinders any additional adsorption. This may be due to the fact that there are initially quite enough sites on the surface, which makes adsorption relatively simple. However, as time passes, the adsorbent surface gets saturated, slowing down the rate of adsorption (Suryavanshi & Shukla 2010). However, within the first 50 min, the rise is relatively higher. Experimental results are given in Supplementary Table S3.
Effect of initial dye concentration
Effect of temperature
Adsorption kinetic models
The adsorption kinetic model is crucial in regulating the effectiveness of the adsorption process and the rate at which adsorbate is taken up, which regulates the residence duration at the solid surface interface. The adsorption of CR was investigated using kinetic models: pseudo-first-order and pseudo-second-order, intraparticle diffusion model, and liquid film diffusion model (Wekoye et al. 2020).
Pseudo-first-order kinetic model












Pseudo-second-order kinetic model





Intraparticle diffusion model








Liquid film diffusion model
The movement of adsorbate molecules through a liquid film that supports the solid adsorbent is considered to be the rate-determining step in the adsorption process.



Results from the intraparticle diffusion model, the pseudo-second-order kinetic model, the pseudo-first-order kinetic model, and the liquid film model are summarized in Table 2 in the appropriate order. Because it has the highest slope coefficient (0.9912) and closest to unity among the other models, the pseudo-second-order (PSO) kinetic model is used to explain the present adsorption process, as shown in Table 2. Furthermore, in the situation of the pseudo-second-order kinetics, there is a clear consensus between calculated and experimental demonstrating that the data fits well with the pseudo-second-order model.
Results of all discussed kinetic models
Kinetic models . | Parameters . | Values . |
---|---|---|
Pseudo-first-order | ![]() | 0.312 ![]() |
![]() | 0.191 ![]() | |
![]() | 5.808 ![]() | |
![]() | 0.9585 | |
Pseudo-second-order | ![]() | 4.316 × 10−5![]() |
![]() | 0.191 ![]() | |
![]() | 0.206 ![]() | |
![]() | 0.9912 | |
Intraparticle diffusion model | ![]() | 0.0114 ![]() |
![]() | 0.9795 | |
Liquid film model | ![]() | 0.0319 ![]() |
![]() | 0.967 |
Kinetic models . | Parameters . | Values . |
---|---|---|
Pseudo-first-order | ![]() | 0.312 ![]() |
![]() | 0.191 ![]() | |
![]() | 5.808 ![]() | |
![]() | 0.9585 | |
Pseudo-second-order | ![]() | 4.316 × 10−5![]() |
![]() | 0.191 ![]() | |
![]() | 0.206 ![]() | |
![]() | 0.9912 | |
Intraparticle diffusion model | ![]() | 0.0114 ![]() |
![]() | 0.9795 | |
Liquid film model | ![]() | 0.0319 ![]() |
![]() | 0.967 |
Adsorption isotherms
The adsorption process must be completely quantified before it can be used commercially. These mathematical models explain the interactions between the adsorbent and the adsorbate, as well as the adsorption capacity. The most suitable isotherm model in the adsorption process is done by analyzing concentration data from tests utilizing several isotherm models. Langmuir, Freundlich, D-R, and Temkin isotherms for CR adsorption onto CLPP adsorbent were used in this study.
Langmuir isotherm model
The solid adsorbent's capacity for adsorption is restricted. Only one molecule of a solute may interact with each active site, which is all identical (monolayer adsorption). The adsorbate molecules do not interact with one another (Chen 2015).























Parameters of adsorption isotherm models
Isotherm models . | Parameters . | Values . |
---|---|---|
Langmuir isotherm | ![]() | ![]() |
![]() | ![]() | |
![]() | 0.9891 | |
Freundlich isotherm | N | 1.9 ![]() |
![]() | 5.2742 ![]() | |
![]() | 0.9902 | |
Temkin isotherm | B | ![]() |
![]() | ![]() | |
![]() | 12.5 | |
![]() | 0.885 | |
D-R isotherm | Β | ![]() |
![]() | ![]() | |
![]() | 0.99 |
Isotherm models . | Parameters . | Values . |
---|---|---|
Langmuir isotherm | ![]() | ![]() |
![]() | ![]() | |
![]() | 0.9891 | |
Freundlich isotherm | N | 1.9 ![]() |
![]() | 5.2742 ![]() | |
![]() | 0.9902 | |
Temkin isotherm | B | ![]() |
![]() | ![]() | |
![]() | 12.5 | |
![]() | 0.885 | |
D-R isotherm | Β | ![]() |
![]() | ![]() | |
![]() | 0.99 |
(a) Langmuir isotherm's linear plot for removal of CR onto CLPP. (b) Langmuir isotherm's non-linear plot for removal of CR onto CLPP.
(a) Langmuir isotherm's linear plot for removal of CR onto CLPP. (b) Langmuir isotherm's non-linear plot for removal of CR onto CLPP.
Freundlich isotherm model













(a) Freundlich isotherm's linear plot for removal of CR onto CLPP. (b) Freundlich isotherm's non-linear plot for removal of CR onto CLPP.
(a) Freundlich isotherm's linear plot for removal of CR onto CLPP. (b) Freundlich isotherm's non-linear plot for removal of CR onto CLPP.
Temkin isotherm model










(a) Temkin isotherm's linear plot for removal of CR onto CLPP. (b) Temkin isotherm's non-linear plot for removal of CR onto CLPP.
(a) Temkin isotherm's linear plot for removal of CR onto CLPP. (b) Temkin isotherm's non-linear plot for removal of CR onto CLPP.
Dubinin–Radushkevich isotherm model










(a) Dubinin–Radushkevich isotherm's linear plot for removal of CR onto CLPP. (b) Dubinin–Radushkevich isotherm's non-linear plot for removal of CR onto CLPP.
(a) Dubinin–Radushkevich isotherm's linear plot for removal of CR onto CLPP. (b) Dubinin–Radushkevich isotherm's non-linear plot for removal of CR onto CLPP.
The experimental results are best explained by the Freundlich and D-R isotherms, as demonstrated by the determination coefficient in accordance with the graphical depiction and Table 3 listing of the parameters of different isotherms. The slope coefficient for the Langmuir adsorption isotherm model is 0.9891, which is less than the slope coefficient for the Freundlich isotherm model. This difference confirms that the data fits best the Freundlich isotherm model, according to which CR adsorption takes place on the heterogeneous surface of the CLPP. Additionally, a value of n larger than one implies that the procedure of CR adsorption onto CLPP is beneficial, and the calculated value of indicates the physical adsorption. The operating conditions used in the adsorption mechanism (pH, initial concentration, amount of adsorbent, etc.) and the characteristics of the adsorbent determined the adsorption capacity. A comparison of adsorption capacity of different adsorbents for the removal of CR is given in Table 4. The parameter employed for comparison is the adsorption capacity. The value of adsorption capacity, which is in good alignment with the results of the majority of previously published research, suggests that CR might be easily adsorbed on the CLPP developed in this study.
Comparison of adsorption capacity of various adsorbents for Congo red dye removal
Adsorbent . | Maximum adsorption capacity![]() | Reference . |
---|---|---|
Banana peel powder | 1.721 | Mondal & Kar (2018) |
Durian peel powder | 107.52 | Kamsonlian et al. (2013) |
Solanum tuberosum peel | 6.9 | Rehman et al. (2018) |
Peanut shell | 15.09 | Abbas et al. (2012) |
Sugarcane bagasse | 38.2 | Zhang et al. (2011) |
Orange peel powder | 11.919 | Harnal et al. (2020) |
Tea waste | 3 | Foroughi-dahr et al. (2016) |
Powdered eggshell | 95.25 | Zulfikar & Setiyanto (2013) |
Cedrus deodara sawdust | 182.5 | Muneer et al. (2021) |
Aloe vera leaves shell | 1,850 | Khaniabadi et al. (2017) |
Citrus limetta peel powder | ![]() | Present study |
Adsorbent . | Maximum adsorption capacity![]() | Reference . |
---|---|---|
Banana peel powder | 1.721 | Mondal & Kar (2018) |
Durian peel powder | 107.52 | Kamsonlian et al. (2013) |
Solanum tuberosum peel | 6.9 | Rehman et al. (2018) |
Peanut shell | 15.09 | Abbas et al. (2012) |
Sugarcane bagasse | 38.2 | Zhang et al. (2011) |
Orange peel powder | 11.919 | Harnal et al. (2020) |
Tea waste | 3 | Foroughi-dahr et al. (2016) |
Powdered eggshell | 95.25 | Zulfikar & Setiyanto (2013) |
Cedrus deodara sawdust | 182.5 | Muneer et al. (2021) |
Aloe vera leaves shell | 1,850 | Khaniabadi et al. (2017) |
Citrus limetta peel powder | ![]() | Present study |
ARE error analysis



The outcomes of ARE error analysis for various adsorption isotherms and adsorption kinetic models are presented in Table 5. The results showed that, compared to other adsorption isotherms and kinetic models, the values of the ARE error analysis for the Freundlich isotherm and the pseudo-second-order kinetic model are smaller (although the values of the regression coefficients, i.e., are greater). It was revealed that the Freundlich and pseudo-second-order kinetic models were appropriate for this adsorption process.
ARE error analysis values of adsorption isotherm and adsorption kinetic models
Isotherm models | (i) Langmuir isotherm model | ![]() |
(ii) Freundlich isotherm model | ![]() | |
(iii) Temkin isotherm model | ![]() | |
(iv) Dubinin–Radushkevich isotherm | ![]() | |
Kinetic models | (i) Pseudo-first-order | −60.74977625 |
(ii) Pseudo-second-order | −98.60786052 | |
(iii) Intraparticle diffusion model | −97.20220512 | |
(iv) Liquid film model | −97.8442112 |
Isotherm models | (i) Langmuir isotherm model | ![]() |
(ii) Freundlich isotherm model | ![]() | |
(iii) Temkin isotherm model | ![]() | |
(iv) Dubinin–Radushkevich isotherm | ![]() | |
Kinetic models | (i) Pseudo-first-order | −60.74977625 |
(ii) Pseudo-second-order | −98.60786052 | |
(iii) Intraparticle diffusion model | −97.20220512 | |
(iv) Liquid film model | −97.8442112 |
Thermodynamic of adsorption
The thermodynamic characteristics, such as Gibbs free energy, might be used to study the viability and kind of adsorption. By plotting in contrast to 1/T, a straight-line graph is obtained. The graph's slope is ΔH, while its intercept is ΔS. Where R denotes the general gas constant, and its value is 8.31
, and T denotes the temperature in Kelvin.













Calculated thermodynamic adsorption parameters
![]() ![]() | ![]() ![]() | ![]() ![]() |
---|---|---|
1.6375 | ||
−0.0779 | ||
−2.0062 | ||
−3.0973 | −37.378 | 0.133 |
−3.5164 | ||
−5.1942 | ||
−5.6659 |
![]() ![]() | ![]() ![]() | ![]() ![]() |
---|---|---|
1.6375 | ||
−0.0779 | ||
−2.0062 | ||
−3.0973 | −37.378 | 0.133 |
−3.5164 | ||
−5.1942 | ||
−5.6659 |
Adaptation of the procedure with tap water
Tap water was used to test the suggested procedure's applicability (Javed et al. 2017b; Batool et al. 2021). The experiment was performed under optimized conditions (pH = 6.0, adsorbent dosage = 0.4 g, contact period = 90 min, starting dye concentration = 10 ppm, temperature = 60 °C) to investigate the potential of CLPP for the removal of Congo red dye. According to the results, 82% of the color was removed. The results proved that the employed process is applicable to normal water samples (Naushad et al. 2016).
BIOSORPTION MECHANISM













The pH of the adsorbate has an impact on the active site of the biosorption system. The pH of the solution has a substantial impact on the physical interaction of dye molecules on the binding sites of the absorbent. The highest adsorption capacity of Congo red dyes on C. limetta peels was noticed in this research when the solution was acidic (pH 6). C. limetta peels had a positively charged surface characteristics at an acidic pH and many protonated sites () on the surfaces, which increased the electrostatic interaction between the negatively charged CR dye molecules and the positively charged surface of the CLPP. Additionally, at a basic pH, CLPP's surface had many hydroxyl ions (OH), which led to the deprotonation, of the –COOH and –OH groups. This may decrease the electrostatic force between the positively surface charge of the C. limetta peel and the negatively charged CR dye molecules. CR dye adsorption onto the CLPP favored H-bonding and
interaction in addition to electrostatic attraction (Oyekanmi et al. 2021).
Isotherm studies revealed that the D-R and Freundlich models best illustrated experimental data regarding the adsorption of CR dye molecules on the surface of CLPP, suggesting that multilayer adsorption takes place on a miscellaneous surface enriched with negative ions for the adsorption process.
DESORPTION
Recovery of adsorbent (CLPP) and adsorbate (Alrobei et al. 2021) are salient features of wastewater treatment because it demonstrate that this technique is inexpensive. Using sodium hydroxide (NaOH) as a desorbing agent, desorption test was performed to determine whether the CLPP adsorbent can be reused (Javed et al. 2017a; Dai et al. 2019; Lafi et al. 2019). In the experiment, a specific quantity (0.4 g) of CLPP adsorbent containing dye was agitated with 0.01 M NaOH for 25 min. According to the experiment's results (Supplementary Table S16), 80% of the adsorbent was regenerated, making it suitable for use in further adsorption procedures.
CONCLUSION
CLPP has an efficient and appropriate adsorption process for removing harmful, toxic synthetic dyes. The adsorption process of CR was significant within the range investigated. The optimum conditions for 88.2% adsorption of CR were pH 6, 0.4 g of adsorbent dose, 90 min contact time, and initial concentration of 10 ppm within 60 °C.
Different kinetic models, such as pseudo-first-order, pseudo-second-order, and intraparticle diffusion models, as well as the liquid film model, have been used and debated. Kinetic data was better fitted to the pseud-second-order kinetic model as the value of slope coefficient (
) is 0.9918 and
, which is very close to the experimental
.
The appropriate isotherm model for the adsorption process was selected after examining concentration data from the experiment using a number of isotherm models. In this investigation, the Langmuir, Freundlich, Temkin, and D-R isotherm models were adopted. The Freundlich and D-R isotherm models best described the biosorption process since their slope coefficient (
) value is 0.99, which is close to unity, and their ARE error analysis has a lower value.
Overall, the thermodynamic characteristics demonstrated that CR dye adsorption on CLPP was spontaneous, exothermic, and dependent on physical forces.
The FTIR analysis identified a transition in the –OH and –COOH groups, predicting that these groups were mainly in charge of CR dye adsorption C. limetta peel surfaces.
The established technique was 82% applicable with tap water, and the desorption experiment resulted in an 80% regeneration of the adsorbent, indicating that it may be reused for adsorption. C. limetta peels may be employed as a competitive adsorbent for the removal of pollutants from the textiles and coloring industries due to the remarkable removal capacity of CR dyes.
ACKNOWLEDGEMENTS
First and foremost, all praise to Allah, the Almighty, the Most Merciful, for His blessings given to me during my study and in completing this work. I would like to offer my heartfelt appreciation and sincere thanks to my beloved parents, family, and friends for their prayers, support, and encouragement. In addition, my greatest gratitude and appreciation are addressed to my supervisor, Dr Tariq Javed, Lecturer, Department of Chemistry, University of Sahiwal, Sahiwal, Punjab, Pakistan, who has given me his valuable guidance, advice, and encouragement so I could complete this work in time.
FUNDING
No funding was allocated for the study's accomplishment.
DATA TRANSPARENCY STATEMENT
The authors will assure data transparency.
AUTHORS’ CONTRIBUTIONS
All authors contributed equally to this research study. The final manuscript was evaluated and approved by all authors.
DATA AVAILABILITY STATEMENT
All relevant data are included in the paper or its Supplementary Information.
CONFLICT OF INTEREST
The authors declare there is no conflict.