Facile, One-pot Synthesis of S-doped Carbon Quantum Dots for Hydrogen Peroxide Detection

doi:10.21203/rs.3.rs-2242696/v1

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Facile, One-pot Synthesis of S-doped Carbon Quantum Dots for Hydrogen Peroxide Detection

https://doi.org/10.21203/rs.3.rs-2242696/v1

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ABSTRACT

We have developed a green, facile and economical route to synthesise luminescent carbon quantum dots from pulp free juice of Citrus limon in ethylene glycol. The obtained graphitic carbon dots with an average size of 3 nm exhibits strong UV absorption. Dependence of excitation wavelength on blue emitting carbon dots is investigated. This spectral behaviour remains unchanged with sulphur doping in carbon dots. They show good biocompatibility while inhibiting the growth of DLA cancerous cells. Moreover optical properties of S-doped carbon quantum dots are utilised to detect hydrogen peroxide with a detection limit of 0.49 mM.

GRAPHICAL ABSTRACT

Since their introduction in 2004, Carbon Quantum Dots (CDs) [1], tremendous scientific endeavors have been devoted to develop CDs based light emitting diodes [2], fluorescent sensors [3], drug delivery [4] and imaging [5]. Low cost, inexpensive precursors, eco-friendly nature, chemical inertness and low cytotoxicity makes these fluorescent carbonaceous materials an ideal alternative to many prominent semiconductor dots [6]. Many researchers achieved synthesis of fluorescent CDs from various chemicals like citric acid [7], urea [8] and phosphorus-rich phytic acid [9]. But the eco-friendly non-toxic starting materials was explored in a more meaningful manner on the synthesis of CDs from leaves of aloe [10], cardamom [11],P.amboinicus [12] etc fruits like papaya [13] lychee [14] etc, vegetables like potato [15], beetroot [16] cabbage [17]etc, and even from breads, biscuits jaggery etc. Easy availability and carbonization-friendly chemical composition of leaves, vegetables and fruits has made them the favourite source of carbon among the scientific community. Among natural sources, citrus fruits are reservoirs of carbon in the form of organic acids like citric acid and malic acid in their fleshy parts as well as oxalic acid and malonic acid in their peels [18]. CDs obtained by Federico Calì et al [19] from lemon waste were applied for a method of communication among biodevices. Lemon based CDs were prepared for Hg(II) [20], Fe³⁺ ion [21] and riboflavin [22] detection and live cell imaging [23]applications. Hui Ding et. al. achieved synthesis of near-infrared emitting [24] and red emitting [25] CDs using lemon for bio-imaging applications. Moreover, CDs of much enhanced fluorescence properties, high quantum yield and tunable chemical properties can be obtained by doping heteroatoms, especially nitrogen (N) and sulphur (S) [26, 27, 28]. Even though these reports have sufficient data to establish the cyto-friendly nature of lemon prepared CDs, none of them proves to be therapeutic or shows anticancer activity.

The significance of anti-cancer properties of CDs is widely discussed recently due to the influence of lifestyle, global warming and climatic conditions on human health. Tao Feng et. al [29] reacted with citric acid and diethylenetriamine in presence of nitrogen at 170°C to obtain carbon quantum dots that can act as pH responsive nano drug carriers with multicolour imaging abilities. Quinoline based carbon quantum dots synthesised by S. Karthik et. al [30] used a photo-response mechanism for designing an anticancer drug delivery system. The quenching of green luminescence in CDs prepared by Walaa E. Omer et. al [31] from ortho phenyl-enediamine(o-PD) was used to monitor changing concentration of cancer antigen-125 (CA-125) which provided an easy and cost-effective method for the early diagnosis of ovarian cancer. Toxic effects of mushroom based CDs on MDA-MB-231 breast cancer cells and HEK-293 cells from the kidney was explored by T. Boobalan et. al [32]. CDs prepared from four spices - black pepper, turmeric, red chilli and cinnamon by NagamalaiVasimalai et. al. showed an increase in death of cancerous human glioblastoma cells (LN-229) that affects the brain or spine [33]. Cancer cell line MCF-7, HepG-2, and A375 showed growth inhibition in presence of CDs obtained by Hua Yao et. al. from ginsenoside which is a natural glycoside extracted from plant genus Panax [34]. Moreover, considering the eco-friendly and biocompatibility, biomass derived CDs are to be explored more for their wide applicability.

Among various biosensors, hydrogen peroxide sensors have always been utilised in chemical, pharmaceutical, biological, environmental and clinical processes. Zheng et al. has illustrated that peroxidase-like catalytic activity of CDs can be used for detection of hydrogen peroxide [35]. Fluorescence based H₂O₂ detection method was proposed by J.Wei et al. which used gelatin-based CDs prepared by hydrothermal synthesis in presence of Fe³⁺ ions [36]. Many carbon quantum dot based assays utilised MnO₂ nanosheets as a potential intermediate to accomplish sensing of various analytes. In vivo sensing of ascorbic acid was reached by WanyingZhai et. al. on suppressing fluorescence of 7-Hydroxycoumarin [37]. The same principle of fluorescence quenching by MnO₂ nanosheets was used by some researchers in H₂O₂ sensing systems as well. A combination of first-order scattering, fluorescence, and second-order scattering was used by QianTang et. al. for dual-mode H₂O₂ sensing systems in MnO₂-blue fluorescent CD nanocomposite [38]. A sensing system for determining levels of H₂O₂ in marine food samples was developed using CDs from citric acid and ethanediamine by Keke Ning et. al. [39]. Carbon quantum dots synthesised by Jiapei Gu et. al. from dried peony flowers also used fluorescence quenching mechanism by MnO₂ nanosheets for sensing of glucose in human serum samples by virtue of H₂O₂ generation on enzymatic conversion of glucose by glucose oxidase [40]. Among them, most of them are based on aqueous or ethanolic solutions for their synthesis and easy solubility. Considering the long term stability of solutions free from aggregation induced fluorescence quenching, it is essential to explore H₂O₂ sensors based on other solvents. Here, we report a simple route for synthesis of carbon quantum dots from lemon extract via heat treatment using ethylene glycol. Together with our effort for determining the cell viability and anticancer efficiency of CDs, we developed a turn-on fluorescence sensor for hydrogen peroxide detection.

2.1. Materials

Chemicals used including Ethylene Glycol (Merck, ≥ 99%), Potassium Permanganate (KMnO₄), MES buffer (2-(N-morpholino) ethanesulfonic acid, C₆H₁₃NO₄S) and Thiourea (CH₄N₂S) were of analytical reagent grade. Ripe C. limon for carbon dot synthesis was purchased from the local market. All the solutions were prepared in ultra-pure water. Whatsman filter paper (~ 110 µm thickness) is used throughout for the filtering of solutions obtained.

2.2. Preparation of Carbon Quantum Dots

The synthesis route of carbon dots is similar to the one reported in literature with slightly different experimental conditions [41]. CDs were formed by a simple one step heat treatment procedure of pulp free freshly squeezed lemon extract. 90 ml of filtered lemon juice was mixed with 60 ml of ethylene glycol and heated in a paraffin sealed beaker at 150°C for 24 hrs. Sulphur doped CDs (S-CDs) were synthesised by adding thiourea to the mixture before thermal treatment. Dark brown coloured carbon dot solutions obtained were filtered and used for further characterizations.

2.3. Preparation of MnO₂ nanosheets

Manganese dioxide nanosheets were synthesised by reduction of potassium permanganate (KMnO₄) using 2-(N-morpholino) ethanesulfonic acid (MES) buffer [42]. 0.18 M KMnO₄ solution is added dropwise to equal volume of 0.11 M MES solution while stirring. After a few minutes, the solution starts to turn brown. When kept undisturbed after complete addition of KMnO₄, a black-brown slurry is formed which is then filtered using filter paper. The filtrate is washed thoroughly with alcohol and ultra-pure water. The residue is kept at 80°C for about 16 hours to obtain MnO₂ nanosheets.

2.4. Detection of hydrogen peroxide

In a typical process, MnO₂ nanosheet powder was weighed and sonicated with ethylene glycol for about 15 minutes to get 4, 8, 12, 16 and 20 millimolar concentrations. These were then added to the solution of S-CDs in ethylene glycol and stirred continuously for 30 minutes to obtain MnO₂ - modified CDs. The photoluminescence spectra on excitation at a wavelength of 370 nm was determined for each concentration. To the maximum concentration among them, various concentrations of freshly prepared hydrogen peroxide solution were added and thoroughly shaken. The spectra were recorded at the same excitation wavelength and slit width for emission measurements.

Transmission electron microscope (TEM) image (Fig. 1.(a)) shows the crystalline nature and morphology of S-CDs. It can be seen that particles are uniformly formed and almost spherical in shape. The histogram plotted (inset of Fig. 1.(a)) shows that particles have an average size of 3 nm. The existence of the crystalline graphite-like structure is confirmed in S-CDs from the HR-TEM image (Fig. 1.(b)). The interplanar spacing of 0.253 nm in S-CDs is due to the (100) phase of hexagonal graphite.

The Selected Area Electron Diffraction (SAED) pattern given in Fig. 2 indicates the poly-nanocrystalline nature of the S-CDs [43]. The interplanar distances calculated from the SAED pattern are found to be 0.20 nm and 0.24 nm which are associated with the (100) and (002) planes which illustrates effective formation of graphitic carbon structures.

The XRD pattern of S-CDs shown in Fig. 3. reveals that the sample has a broad diffraction peak around 2θ = 21^o which corresponds to the (002) plane of graphite ((JCPDS file number: 41-1487). This peak can be attributed to the turbostratic phase of carbon present in CDs [44].

The Energy-dispersive X-ray (EDX) spectroscopy images (Fig. 4) of CDs and S-CDs was analysed to determine elements present in carbon dots. Both CDs yielded a carbon-oxygen ratio of 3:2, indicating a fairly high formation of graphitic structures in them. The combined presence of 7 wt% nitrogen and sulphur in S-CDs confirms the S-doping in a larger ratio.

From the Fourier transform infrared (FTIR) spectrum of the CDs (Fig. 5), the observed peak values are in good agreement with the reported data for carbon quantum dots. The characteristic bands observed at 3291 cm^− 1 for both CDs and S-CDs can be attributed to stretching vibration of O-H groups during carbonization [45]. The dominant C = O stretching vibrations at 1737 cm^− 1 is the evidence for the existence of more carboxylate groups on the surfaces of the CDs due to carbonization at high temperature [46]. A small band peaked at 1630 cm^− 1 is due to C = C stretching mode [47]. A broad band peaked at 860 cm^− 1 is due to C-H bending vibrations while bands in range 1000 cm^− 1 to 1240 cm^− 1 shows that the surface of the C-dots contains C-H and C-O-C bonds. The existence of the C-H bond [48] is indicated by the bands at 2940 cm^− 1 and 2876 cm^− 1. The C-O-C stretching vibrations in CDs is due to contributions from compounds such as volatile acids, sugars and amino acids present in the lemon juice [45].

The absorption spectra (Fig. 6) of carbon quantum dots in ethylene glycol consists of a broad and strong absorption in the UV-Visible region of the spectrum. S-CDs shows strong absorption at 240 nm which is due to π – π* transition of sp² hybridised graphitic core. An absorption band between 250 nm and 300 nm wavelength present in both the CDs can be attributed to n – π* transition corresponding to edge states of the carbon dot core. These edge states are part of the interface between sp² hybridised and sp³ hybridised carbon. This emissive centre is the reason for the bright blue luminescence of the carbon dots. The low energy absorption tail from 320–400 nm in CDs is due to the n – π* transition of the C = O bond. This is due to contributions from surface state transitions which are more prominent for CDs [49].

The emission spectra of both the quantum dots were recorded for varying excitation wavelengths. The CDs and S-CDs exhibit strong blue emission in the range of 440–470 nm upon UV excitations with maximum emission peaking at 448 nm wavelength. It can be observed that CDs (Fig. 7) and S-CDs (Fig. 8) showed a mixed nature of excitation dependence. From the normalised fluorescence spectra (inset of Fig. 7 and Fig. 8) the emission spectra of all excitations till 350 nm wavelength coincides for both QDs which suggests the excitation independent nature of fluorescence spectra of CDs. This behaviour changes to excitation dependent emission at higher excitation wavelengths with a red shift in emission wavelengths. Though the heterogeneous core-size distribution could be one of the factors responsible for red shift in PL as in many semiconductor nanodots, low synthesis temperature routes compared to other elemental quantum dots makes surface fluorescence emission a plausible explanation[50].

CDs and S-CDs were synthesised at 150^oC resulting in effective carbonization and pyrolysis which in turn lead to the presence of surface states along with molecular states in CDs. Surface of CDs is often composed of many small organic fluorescence moieties. They are attached with many functional groups like –OH,-COOH, -CO or even thiol groups. These groups are randomly linked to the dots with no well defined structural order and are often responsible for weak electronic transitions. The photoluminescence properties observed are attributed to the result of the synergistic contribution of these optically active centres in the core, molecular and surface states of the dots [51]. Thus CDs with excitation independent emission in aqueous medium changes into wavelength specific PL emitting CD in a less protic solvent like ethylene glycol.

The mixed nature of wavelength dependence in our CDs can be intelligibly understood from the plot of emission peak wavelength for increasing excitation wavelength (Fig. 9). Both the CDs have almost constant PL peak wavelength till 350 nm excitations which are red shifted for higher excitations.

The short termin vitro cytotoxicity studies were done on rat spleen cells (RSC) by comparing the cell toxicity with the addition of varying volumes of CDs using trypan dye. Dead cells take up the blue colour of the dye while live cells don’t acquire the colour. So, live cells are counted to evaluate % Cell viability. A similar trypan blue exclusion method was opted to find anticancer activity of dots towards Dalton’s lymphoma ascites(DLA) cells. In this case, dead cells are counted separately to evaluate the % Cell death.

It can be observed that (Fig. 10) both CDs and S-CDs showed negligible cell killing effects on RSC and there is higher survival of these normal cells even at higher concentration. Though cell viability of normal cells remains almost constant even at all concentrations, it is evident that anticancer activity of both CDs increases with concentration. Compared to S-CDs, the undoped counterpart exhibits higher DLA tumour cell deaths at higher concentration. Absence of dopant chemicals and reduced surface functionalization in CDs also makes them more anti-cancer efficient compared to S-CDs. These dots are hence biocompatible with immense potential for application in the field of therapeutic treatment.

To further investigate the H₂O₂ sensing ability, emission spectra of S-CDs with various concentrations of MnO₂ are examined (Fig. 11.a). It can be observed that emission intensity is quenched upon addition of MnO₂. This can be well explained from the spectral overlap observed between UV-visible absorption spectrum of MnO₂ and emission spectrum of S-CDs (Fig. 11.b). The broad absorption band ranging from 350 nm to 550 nm that overlaps with blue emissions of S-CDs makes MnO₂ nanosheets the perfect candidate for H₂O₂ assay [52]. Ultrasound sonication of the MnO₂ nanosheet powder with S-CDs alters the surface features of dots. Nanosheets will mask the CDs and turn OFF its ability to emit radiation. These nanosheets act as an efficient quenching agent for luminescence by covering the surface of nanoparticles [42].

From Fig. 12.a it can be inferred that fluorescence intensity of S-CDs are regained after addition of different concentrations of H₂O₂. The fluorescence regaining efficiency of MnO₂ modified S-CDs is linearly correlated with H₂O₂ concentration from 0.06 mM to 1 mM (Fig. 12.b). Thus the sensor exhibits a linear response to hydrogen peroxide concentration with a detection limit of 0.49 mM.On the addition of hydrogen peroxide solutions of various concentrations, the MnO₂ nanosheet modified dots will start deteriorating. Luminescence by CDs is gradually recovered on adding higher concentrations of H₂O₂ solution. At a particularly higher concentration of H₂O₂ the nanosheet will be completely decomposed and all CDs will show fluorescence. This recovery of luminescence can be attributed to reduction of MnO₂ to Mn²⁺ mediated by H₂O₂. This reduction reaction can be represented as [52, 53, 54].

MnO ₂ + H₂O₂ + 2H⁺ → Mn²⁺ + 2H₂O + O₂

Thus, by measuring the intensity of radiation emitted by MnO₂ modified carbon dots, we can even quantify the amount of H₂O₂ added. The real images of fluorescence under 370 nm excitation wavelength, observed from MnO₂ modified carbon dots after addition of different concentrations of H₂O₂ is shown in Fig. 13. The biofriendly S-CDs can be effectively utilised for designing a fluorescent probe for sensitive determination of H₂O₂.

In summary, carbon quantum dots were prepared via a facile heat treatment method using a natural green source in ethylene glycol. UV-visible absorption spectrum of CDs and sulphur doped CDs sheds light on core structure and surface states of CDs. Better understanding of photophysics and luminescence mechanisms of CDs are achieved from excitation dependent emission spectra of both CDs. Low cytotoxicity values and good optical properties made them a potential candidate for biosensing and bioimaging applications. A green eco-friendly method was proposed for detection of hydrogen peroxide using MnO₂ nanosheet - modified sulphur doped lemon CDs in ethylene glycol. The fluorescence regaining of S-CDs by H₂O₂opens up an economic and simple method to set up a biological assay. This methodology can be reciprocated in sensing biological enzymes which on catalysis produces hydrogen peroxide.

Declarations

Ethical Approval

Not Applicable

Competing interests

All authors have no conflicts to disclose.

Funding

Not Applicable

Authors' contributions

All authors contributed to the study, conception and design. Material preparation, data collection and analysis were performed by Joyal Jain Palakulam and Jibin P O. Tessy Paul and Anupama K involved in interpretation and analysis of observations. The draft manuscript was prepared by Joyal Jain Palakulam. Experimental observations are analyzed in detail and final manuscript was prepared by Ann Mary K A. All authors read and approved the final manuscript.

ACKNOWLEDGEMENT

Authors are grateful to Centre for Nano and Soft Matter Sciences (CeNS), Bengaluru, Karnataka; Sophisticated Analytical Instrument Facilities (SAIF), Kottayam, Kerala and DST-FIST supported Central Instrumentation Facilities, St. Thomas College, Kerala for providing the characterization facilities. We also thank Amala Cancer Research Centre, Thrissur, Kerala for their assistance in cytotoxicity measurements.

1. Xu, X.; Ray, R.; Gu, Y.; Ploehn, H. J.; Gearheart, L.; Raker, K.; Scrivens, W. A. Electrophoretic Analysis and Purification of Fluorescent Single-Walled Carbon Nanotube Fragments. J. Am. Chem. Soc. 2004, 126 (40), 12736–12737. https://doi.org/10.1021/ja040082h.
2. Zhang, X.; Zhang, Y.; Wang, Y.; Kalytchuk, S.; Kershaw, S. V.; Wang, Y.; Wang, P.; Zhang, T.; Zhao, Y.; Zhang, H.; Cui, T.; Wang, Y.; Zhao, J.; Yu, W. W.; Rogach, A. L. Color-Switchable Electroluminescence of Carbon Dot Light-Emitting Diodes. ACS Nano 2013, 7 (12), 11234–11241. https://doi.org/10.1021/nn405017q.
3. Li, M.; Chen, T.; Gooding, J. J.; Liu, J. Review of Carbon and Graphene Quantum Dots for Sensing. ACS Sens. 2019, 4 (7), 1732–1748. https://doi.org/10.1021/acssensors.9b00514.
4. Nair, A.; Haponiuk, J. T.; Thomas, S.; Gopi, S. Natural Carbon-Based Quantum Dots and Their Applications in Drug Delivery: A Review. Biomed.Pharmacother.2020,132,110834. https://doi.org/10.1016/j.biopha.2020.110834.
5. Zhou, J.; Zhou, H.; Tang, J.; Deng, S.; Yan, F.; Li, W.; Qu, M. Carbon Dots Doped with Heteroatoms for Fluorescent Bioimaging: A Review. Microchim. Acta 2017, 184 (2), 343–368. https://doi.org/10.1007/s00604-016-2043-9.
6. Kumari, R.; Sahu, S. K. Effect of Solvent-Derived Highly Luminescent Multicolor Carbon Dots for White-Light-Emitting Diodes and Water Detection. Langmuir 2020, 36 (19), 5287–5295. https://doi.org/10.1021/acs.langmuir.0c00631.
7. J.Ren, L.Malfatti and P.Innocenzi; Citric Acid Derived Carbon Dots, the Challenge of Understanding the Synthesis-Structure Relationship. C 2021, 7, 2. https://doi.org/10.3390/c7010002
8. WiktorKasprzyk, Tomasz Świergosz, SzczepanBednarz, Karolina Walas, Natalia V. Bashmakova and Dariusz Bogdał; Luminescence phenomena of carbon dots derived from citric acid and urea – a molecular insight; Nanoscale, 2018, 10, 13889. https://doi.org/10.1039/C8NR03602K
9. Wei Wang, Yongmao Li, Lu Cheng, Zhiqiang Cao and Wenguang Liu; Water-soluble and phosphorus-containing carbon dots with strong green fluorescence for cell labelling; J. Mater. Chem. B, 2014,2, 46–48. https://doi.org/10.1039/C3TB21370F
10. Hua Xu, Xiupei Yang, Gu Li, Chuan Zhao and Xiangjun Liao; Green Synthesis of Fluorescent Carbon Dots for Selective Detection of Tartrazine in Food Samples; J. Agric. Food Chem. 2015, 63, 6707 − 6714. https://doi.org/10.1021/acs.jafc.5b02319
11. Maria Zaib, Ammama Akhtar, Faseeha Maqsood, Tayyaba Shahzadi; Green Synthesis of Carbon Dots and Their Application as Photocatalyst in Dye Degradation Studies; Arabian Journal for Science and Engineering, volume 46, 437–446 (2021). https://doi.org/10.1007/s13369-020-04904-w
12. Raja Dineshkumar, Nagaraj Murugan, J M Abisha Rani1, M Arthanareeswari, P Kamaraj, S Devikala, Navaneethan Duraisamy and Ashok K Sundramoorthy; Synthesis of highly fluorescent carbon dots from Plectranthusamboinicus as a fluorescent sensor for Ag + ion; 2019 Mater. Res. Express 6 104006. https://doi.org/10.1088/2053-1591/ab3a7b
13. Kasibabu, B.S.B., D’souza, S.L., Jha, S. et al. Imaging of Bacterial and Fungal Cells Using Fluorescent Carbon Dots Prepared from Carica papaya Juice. J Fluoresc 25, 803–810 (2015). https://doi.org/10.1007/s10895-015-1595-0
14. MingyueXue, Mengbing Zou, Jingjin Zhao, Zhihua Zhan and Shulin Zhao; Green preparation of fluorescent carbon dots from lychee seeds and their application for the selective detection of methylene blue and imaging in living cells; J. Mater. Chem. B, 2015,3, 6783–6789. https://doi.org/10.1039/C5TB01073J
15. Vaibhavkumar N. Mehta, Sanjay Jha, Rakesh Kumar Singhal and Suresh Kumar Kailasa; Preparation of multicolor emitting carbon dots for HeLa cell imaging; New J. Chem., 2014,38, 6152–6160. https://doi.org/10.1039/C4NJ00840E
16. Vikram Singh, Kundan S. Rawat, Shachi Mishra, Tanvi Baghel, Soobiya Fatima, Aijaz A. John, NavodayamKalleti, Divya Singh, Aamir Nazir, Srikanta K. Rath and Atul Goel; Biocompatible fluorescent carbon quantum dots prepared from beetroot extract for in vivo live imaging in C. elegans and BALB/c mice; J. Mater. Chem. B, 2018, 6, 3366–3371. https://doi.org/10.1039/C8TB00503F
17. Al-MahmnurAlam, Byung-Yong Park, Zafar Khan Ghouri, Mira Park and Hak-Yong Kim; Synthesis of carbon quantum dots from cabbage with down- and up-conversion photoluminescence properties: excellent imaging agent for biomedical applications; Green Chem., 2015,17, 3791–3797. https://doi.org/10.1039/C5GC00686D
18. Robert L. Clements; Organic Acids in Citrus Fruits. I. Varietal Differences; Journal of Food Science; May 1964, Volume 29, Issue 3, 276–280. https://doi.org/10.1111/j.1365-2621.1964.tb01731.x
19. Federico Calì, Valentina Cantaro, Luca Fichera, Roberta Ruffino, Giuseppe TrussoSfrazzetto, Giovanni Li-Destri and Nunzio Tuccitto; Carbon Quantum Dots from Lemon Waste Enable Communication among Biodevices. Chemosensors 2021,9, 202. https://doi.org/10.3390/
20. Aschalew Tadesse, Mebrahtu Hagos, DharmasothRamaDevi, KalothBasavaiah, and NewayBelachew; Fluorescent-Nitrogen-Doped Carbon Quantum Dots Derived from Citrus Lemon Juice: Green Synthesis, Mercury(II) Ion Sensing, and Live Cell Imaging; ACS Omega 2020 5 (8), 3889–3898. https://doi.org/10.1021/acsomega.9b03175
21. Elia M. Schneider, Amadeus Bärtsch, Wendelin J. Stark, and Robert N. Grass; Safe One-Pot Synthesis of Fluorescent Carbon Quantum Dots from Lemon Juice for a Hands-On Experience of Nanotechnology; Journal of Chemical Education 2019 96 (3), 540–545. https://doi.org/10.1021/acs.jchemed.8b00114
22. Severino S. Monte-Filho, Stefani I.E. Andrade, Marcelo B. Lima, Mario C.U. Araujo; Synthesis of highly fluorescent carbon dots from lemon and onion juices for determination of riboflavin in multivitamin/mineral supplements; Journal of Pharmaceutical Analysis, Volume 9, Issue 3, 2019, 209–216, https://doi.org/10.1016/j.jpha.2019.02.003
23. Aschalew Tadesse, Dharmasoth Rama Devi, Mebrahtu Hagos, Gangarao Battu, KelothBasavaiah; Facile green synthesis of fluorescent carbon quantum dots from citrus lemon juice for live cell imaging; Asian Journal of Nanoscience and Materials, 2018, 1(1), 36–46. https://dx.doi.org/10.26655/ajnanomat.2018.1.5
24. Hui Ding, Xuanxuan Zhou, Botao Qin, Ziyuan Zhou, Yunpeng Zhao; Highly fluorescent near-infrared emitting carbon dots derived from lemon juice and its bioimaging application; Journal of Luminescence 211 (2019) 298–304. https://doi.org/10.1016/j.jlumin.2019.03.064
25. Hui Ding, Yuan Ji, Ji-Shi Wei, Qing-Yu Gao, Zi-Yuan Zhou and Huan-Ming Xiong; Facile synthesis of red-emitting carbon dots from pulp-free lemon juice for bioimaging; J. Mater. Chem. B, 2017,5, 5272–5277. https://doi.org/10.1039/C7TB01130J
26. Tapas Kumar Mondal, AbhisekGupta,Bikash Kumar Shaw, Supriya Mondal, Uttam Kumar Ghoraic and Shyamal K. Saha; Highly luminescent N-doped carbon quantum dots from lemon juice with porphyrin-like structures surrounded by graphitic network for sensing applications; RSC Adv., 2016,6, 59927–59934. https://doi.org/10.1039/C6RA12148A
27. Dong Sun, Rui Ban, Peng-Hui Zhang, Ge-Hui Wu, Jian-Rong Zhang, Jun-Jie Zhu; Hair fiber as a precursor for synthesising of sulphur- and nitrogen-co-doped carbon dots with tunable luminescence properties; Carbon, Volume 64, 2013, 424–434. https://doi.org/10.1016/j.carbon.2013.07.095
28. Tapas Kumar Mondal, AbhisekGupta,Bikash Kumar Shaw, Supriya Mondal, Uttam Kumar Ghoraic and Shyamal K. Saha; Highly luminescent N-doped carbon quantum dots from lemon juice with porphyrin-like structures surrounded by graphitic network for sensing applications; RSC Adv., 2016,6, 59927–59934. https://doi.org/10.1039/C6RA12148A
29. Tao Feng, Xiangzhao Ai, Huimin Ong and Yanli Zhao; Dual-Responsive Carbon Dots for Tumor Extracellular Microenvironment Triggered Targeting and Enhanced Anticancer Drug Delivery; ACS Appl. Mater. Interfaces 2016, 8, 29, 18732–18740. https://doi.org/10.1021/acsami.6b06695
30. S. Karthik, Biswajit Saha, Sudip Kumar Ghosh and N. D. Pradeep Singh; Photoresponsive quinoline tethered fluorescent carbon dots for regulated anticancer drug delivery; Chem. Commun., 2013,49, 10471–10473. https://doi.org/10.1039/C3CC46078A
31. Walaa E. Omer, Mostafa F. Abdelbar, Nesma M. El-Kemary, Naoki Fukata and Maged A. El-Kemary; Cancer antigen 125 assessment using carbon quantum dots for optical biosensing for the early diagnosis of ovarian cancer; RSC Adv., 2021,11, 31047–31057. https://doi.org/10.1039/D1RA05121K
32. T. Boobalan, M. Sethupathi, N. Sengottuvelan, Ponnuchamy Kumar, P. Balaji, BalázsGulyás, Parasuraman Padmanabhan, Subramanian Tamil Selvan, and A. Arun;Mushroom-Derived Carbon Dots for Toxic Metal Ion Detection and as Antibacterial and Anticancer Agents; ACS Appl. Nano Mater. 2020, 3, 6, 5910–5919. https://doi.org/10.1021/acsanm.0c01058
33. Vasimalai, N.; Vilas-Boas, V.; Gallo, J.; Cerqueira, M. d. F.; Menéndez-Miranda, M.; Costa-Fernández, J. M.; Diéguez, L.; Espiña, B.; Fernández-Argüelles, M. T. Beilstein J. Nanotechnol. 2018, 9, 530–544. https://doi.org/10.3762/bjnano.9.51
34. Yao H, Li J, Song Y, Zhao H, Wei Z, Li X, Jin Y, Yang B, Jiang J. Synthesis of ginsenoside Re-based carbon dots applied for bioimaging and effective inhibition of cancer cells. Int J Nanomedicine. 2018;13:6249–6264. https://doi.org/10.2147/IJN.S176176
35. Zheng AX, Cong ZX, Wang JR, Li J, Yang HH, Chen GN. Highly-efficient peroxidase-like catalytic activity of graphene dots for biosensing. BiosensBioelectron. 2013 Nov 15; 49:519 − 24. https://doi.org/10.1016/j.bios.2013.05.038
36. Jianfei Wei, Li Qiang, Jun Ren, Xiangling Ren, Fangqiong Tanga and Xianwei Meng; Fluorescence turn-off detection of hydrogen peroxide and glucose directly using carbon nanodots as probes; Anal. Methods, 2014,6, 1922–1927. https://doi.org/10.1039/C3AY41837E
37. WanyingZhai, Chunxia Wang, Ping Yu, Yuexiang Wang, Lanqun Mao; Single-Layer MnO2 Nanosheets Suppressed Fluorescence of 7-Hydroxycoumarin: Mechanistic Study and Application for Sensitive Sensing of Ascorbic Acid In Vivo; Anal. Chem. 2014, 86, 24, 12206–12213. https://doi.org/10.1021/ac503215z.
38. Qian Tang, Zhe Sun, Min Qing, Lei Wang, Yu Ling, Nian Bing Li, Hong Qun Luo; An optical sensing system with ratiometric and turn-off dual-mode of CDs@MnO2 nanosheets for the determination of H2O2 and glucose based on a combination of first-order scattering, fluorescence, and second-order scattering; Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 264, 2022, 120299. https://doi.org/10.1016/j.saa.2021.120299.
39. Keke Ning,GuoqiangXiang,CuicuiWang,FeihongHuang,JinzhiLiu,LanlanZhang,MinminYan,BingqianHu,Wen Lei; ‘Turn-on’ fluorescence sensing of hydrogen peroxide in marine food samples using a carbon dots–MnO2 probe; Luminescence. 2020;1–6. https://doi.org/10.1002/bio.3799
40. Jiapei Gu, Xiangqian Li, Zhan Zhou, Wanqiang Liu, Kai Li, Jinwei Gao, Ying Zhaob and Qianming Wang; 2D MnO2 nanosheets generated signal transduction with 0D carbon quantum dots: synthesis strategy, dual-mode behaviour and glucose detection; Nanoscale, 2019, 11, 13058. https://doi.org/10.1039/C9NR03583D
41. Dutta Choudhury, S.; Chethodil, J. M.; Gharat, P. M.; P. K., P.; Pal, H. PH-Elicited Luminescence Functionalities of Carbon Dots: Mechanistic Insights. J. Phys. Chem. Lett. 2017, 8 (7), 1389–1395. https://doi.org/10.1021/acs.jpclett.7b00153.
42. Renren Deng, XiaojiXie, Marc Vendrell, Young-Tae Chang and Xiaogang Liu; Intracellular Glutathione Detection Using MnO2-Nanosheet-Modified Upconversion Nanoparticles; J. Am. Chem.Soc. 2011, 133, 20168 − 20171. https://doi.org/10.1021/ja2100774.
43. Savita Chaudhary, Sandeep Kumar, Bhawandeep Kaur and S. K. Mehta; Potential prospects for carbon dots as a fluorescence sensing probe for metal ions; RSC Adv., 2016,6, 90526–90536. https://doi.org/10.1039/C6RA15691F
44. S. K. Bajpai, A. D’Souza, Basharat Suhail; Blue light-emitting carbon dots (CDs) from a milk protein and their interaction with Spinacia oleracea leaf cells; International Nano Letters (2019) 9:203–212 https://doi.org/10.1007/s40089-019-0271-9
45. Ajayeoba, Titilayo &Atanda, Olusegun & Adewale, Obadina& Bankole, Mobolaji &Brumbley, Steven; The potential of lemon juice-ogi steep liquor mixtures in the reduction of Listeria monocytogenes contamination of ready-to-eat vegetables; 2016, LWT - Food Science and Technology. http://dx.doi.org/10.1016/j.lwt.2016.08.022.
46. Pin-Che Hsu, Zih-Yu Shih, Chia-Hsin Lee and Huan-Tsung Chang; Synthesis and analytical applications of photoluminescent carbon nanodots; Green Chem., 2012,14, 917–920. https://doi.org/10.1039/C2GC16451E.
47. Poly(ethylene glycol)/carbon quantum dot composite solid films exhibiting intense and tunable blue–red emission; Y. Hao, et al.; Appl. Surf. Sci., 2014, http://dx.doi.org/10.1016/j.apsusc.2014.05.095.
48. Bui ThiHoan, Phuong Dinh Tam, Vuong-Hung Pham; Green Emission Carbon Quantum Dots from Lemon Juice for Selective Detection of Fe3 + Ions; VNU Journal of Science: Mathematics – Physics, Vol. 35, No. 1, 2019, 62–69. http://dx.doi.org/10.25073/2588-1124/vnumap.4317.
49. Reckmeier, C. J.; Wang, Y.; Zboril, R.; Rogach, A. L. Influence of Doping and Temperature on Solvatochromic Shifts in Optical Spectra of Carbon Dots. J. Phys. Chem. C 2016, 120 (19), 10591–10604. https://doi.org/10.1021/acs.jpcc.5b12294.
50. Sharma, A.; Gadly, T.; Gupta, A.; Ballal, A.; Ghosh, S. K.; Kumbhakar, M. Origin of Excitation Dependent Fluorescence in Carbon Nanodots. J. Phys. Chem. Lett. 2016, 7 (18), 3695–3702. https://doi.org/10.1021/acs.jpclett.6b01791.
51. Cao, L.; Meziani, M. J.; Sahu, S.; Sun, Y.-P. Photoluminescence Properties of Graphene versus Other Carbon Nanomaterials. Acc. Chem. Res. 2013, 46 (1), 171–180. https://doi.org/10.1021/ar300128j.
52. Hai-Bo Wang, Ying Chen, Na Li1 & Yan-Ming Liu; A fluorescent glucose bioassay based on the hydrogen peroxide-induced decomposition of a quencher system composed of MnO2 nanosheets and copper nanoclusters; Mikrochimica Acta; Heidelberg Vol. 184, Iss. 2, Feb 2017: 515–523. https://doi.org/10.1007/s00604-016-2045-7.
53. Juan Chen, Hongmin Meng, Yuan Tian, Ran Yang, Dan Du, Zhaohui Li, Lingbo Qu and Yuehe Lin; Recent advances in functionalized MnO2 nanosheets for biosensing and biomedicine applications; Nanoscale Horiz., 2019, 4, 321–338. https://doi.org/10.1039/C8NH00274F
54. Jing Yuan, Yao Cen, Xiang-Juan Kong, Shuang Wu, Chen-Liwei Liu, Ruqin Yu, and Xia Chu ; MnO2-Nanosheet-Modified UpconversionNanosystem for Sensitive Turn-On Fluorescence Detection of H2O2 and Glucose in Blood; ACS Appl. Mater. Interfaces 2015, 7, 19, 10548–10555. https://doi.org/10.1021/acsami.5b02188

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Facile, One-pot Synthesis of S-doped Carbon Quantum Dots for Hydrogen Peroxide Detection

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Abstract

ABSTRACT

GRAPHICAL ABSTRACT

1. INTRODUCTION

2. EXPERIMENTAL SECTION

2.1. Materials

2.2. Preparation of Carbon Quantum Dots

2.3. Preparation of MnO₂ nanosheets

2.4. Detection of hydrogen peroxide

3. RESULTS AND DISCUSSIONS

4. CONCLUSION

Declarations

Declarations

Funding

Authors' contributions

ACKNOWLEDGEMENT

References

Additional Declarations

Supplementary Files

Status:

Version 1

Facile, One-pot Synthesis of S-doped Carbon Quantum Dots for Hydrogen Peroxide Detection

Status:

Version 1

Abstract

ABSTRACT

GRAPHICAL ABSTRACT

1. INTRODUCTION

2. EXPERIMENTAL SECTION

2.1. Materials

2.2. Preparation of Carbon Quantum Dots

2.3. Preparation of MnO2 nanosheets

2.4. Detection of hydrogen peroxide

3. RESULTS AND DISCUSSIONS

4. CONCLUSION

Declarations

Declarations

Funding

Authors' contributions

ACKNOWLEDGEMENT

References

Additional Declarations

Supplementary Files

Status:

Version 1

2.3. Preparation of MnO₂ nanosheets