Dually emissive P,N-co-doped carbon dots for fluorescent and photoacoustic tissue imaging in living mice
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Abstract
Hydrothermal treatment of a mixture of ethylene diamine, phosphoric acid and citric acid under ambient pressure generates fluorescent carbon dots that are co-doped with phosphorus and nitrogen. These have features such as (a) both green fluorescence (peaking at 430 nm; 30% quantum yield) and red fluorescence (peaking at 500 nm, quantum yield 78%), (b) wavelength-dependent emission peaks, and (c) insensitivity to changes of pH values, dot concentration and ionic strength. The C-dots are useful for both fluorescent (FL) and photoacoustic (PA) imaging of living tissue. PA imaging warrants better spatial resolution and allows deeper tissues to be imaged compared to most optical imaging techniques. It is essential to assign a photoacoustic contrast agent as most of the diseases do not show a natural photoacoustic contrast in their early stage. The dually emitting C-dots are shown to be a useful contrast agent for PA and FL imaging of mice tumors. Intravenous administration of the C-dots resulted in strong signals in both PA and FL imaging.
Photographs of the excitation wavelength-dependent fluorescence of P,N-doped C-dots obtained from ethylenediamine, phosphoric acid and citric acid. Intravenous administration of the C-dots resulted in strong signals in both photoacoustic (PA) and fluorescent (FL) imaging.
Keywords
Carbon quantum dots Dual emission Quantum yield Wavelength-dependent emission Toxicity Mouse tumor Cancer diagnosisNotes
Acknowledgements
TKM and NP would like to thank SERB, DST, (Project File no- SR/FT/LS-76/2012) and DBT Government of India for providing financial support respectively. Also thanks to “TWAS Programme” for financial support.
Compliance with ethical standards
All animal experiments reported herein were performed according to a protocol approved by the Peking University Institutional Animal Care and Use Committee.
Supplementary material
References
- 1.Krysmann MJ, Kelarakis A, Dallas P, Giannelis EP (2012) Formation mechanism of carbogenic nanoparticles with dual photoluminescence emission. J Am Chem Soc 134:747–750CrossRefGoogle Scholar
- 2.Zhou J, Tang J, Deng S, Yan F, Li W, Qu M (2017) Carbon dots doped with heteroatoms for fluorescent bioimaging: a review. Microchim Acta 184:343. doi: 10.1007/s00604-016-2043-9
- 3.Parvin N, Mandal TK, Roy P (2013) Polyelectrolyte carbon quantum-dots: new player as a noninvasive imaging probe in drosophila. J Nanosci Nanotechnol 13(10):6499–6505CrossRefGoogle Scholar
- 4.Mandal TK, Parvin N (2011) Rapid detection of bacteria by carbon quantum dots. J Biomed Nanotechnol 7(6):846–848CrossRefGoogle Scholar
- 5.Zhou J, Lin P, Ma J, Shan X, Feng H, Chen C, Chen J, Qian Z (2013) Facile synthesis of halogenated carbon quantum dots as an important intermediate for surface modification. RSC Adv 3:9625–9628CrossRefGoogle Scholar
- 6.Wolfbeis OS (2015) An overview of nanoparticles commonly used in fluorescent bioimaging. Chem Soc Rev 44(14):4743–4768CrossRefGoogle Scholar
- 7.Zuo P, Lu X, Sun Z, Guo Y, He H (2016) A review on syntheses, properties, characterization and bioanalytical applications of fluorescent carbon dots. Microchim Acta 183:519–542. doi: 10.1007/s00604-015-1705-3 CrossRefGoogle Scholar
- 8.Hu S, Trinchi A, Atkin P, Cole I (2015) Tunable photoluminescence across the entire visible Spectrum from carbon dots excited by white light. Angew Chem Int Ed 54:2970–2974CrossRefGoogle Scholar
- 9.Shi Y, Pramanik A, Tchounwou C, Pedraza F, Crouch RA, Chavva SR, Vangara A, Sinha SS, Jones S, Sardar D, Hawker C, Ray PC (2015) Multifunctional biocompatible graphene oxide quantum dots decorated magnetic Nanoplatform for efficient capture and two-photon imaging of rare tumor cells. ACS Appl Mater Interfaces 7:10935–10943CrossRefGoogle Scholar
- 10.Ge J, Lan M, Zhou B, Liu W, Guo L, Wang H, Jia Q, Niu G, Huang X, Zhou H, Meng X, Wang P, Lee CS, Zhang W, Han X (2014) A graphene quantum dot photodynamic therapy agent with high singlet oxygen generation. Nat Commun 5:4596. doi: 10.1038/ncomms5596 Google Scholar
- 11.Ge J, Jia Q, Liu W, Guo L, Liu Q, Lan M, Zhang H, Meng X, Wang PF (2015) Red-emissive carbon dots for fluorescent, photoacoustic, and thermal Theranostics in living mice. Adv Mater 27:4169–4177CrossRefGoogle Scholar
- 12.Sun X, Brucknerb C, Lei Y (2015) One-pot and ultrafast synthesis of nitrogen and phosphorus co-doped carbon dots possessing bright dual wavelength fluorescence emission. Nanoscale 7:17278–17282CrossRefGoogle Scholar
- 13.Parvin N, Mandal TK (2016) Synthesis of a highly fluorescence nitrogen-doped carbon quantum dots bioimaging probe and its in vivo clearance and printing applications. RSC Adv 6:18134CrossRefGoogle Scholar
- 14.Jin SH, Kim DH, Jun GH, Hong SH, Jeon S (2013) Tuning the photoluminescence of graphene quantum dots through the charge transfer effect of functional groups. ACS Nano 7:1239–1245CrossRefGoogle Scholar
- 15.Zhu A, Qu Q, Shao Z, Kong BT (2012) Carbon-dot-based dual-emission Nanohybrid produces a ratiometric fluorescent sensor for in vivo imaging of cellular copper ions. Angew Chem 124: 7297 Angew Chem Int Ed 51:7185CrossRefGoogle Scholar
- 16.Li C (2014) Imaging macrophages with nanoparticles. Nat Mater 13:110CrossRefGoogle Scholar
- 17.Gaiduk A, Yorulmaz M, Ruijgrok PV, Orrit M (2010) Room-temperature detection of a single molecule’s absorption by photothermal contrast. Science 330:353CrossRefGoogle Scholar
- 18.Wang LV, Hu S (2012) Photoacoustic tomography: in vivo imaging from organelles to organs. Science 335:1458CrossRefGoogle Scholar
- 19.Maeda A, Bu J, Chen J, Zheng G, DaCosta RS (2014) Dual in vivo photoacoustic and fluorescence imaging of HER2 expression in breast tumors for diagnosis, margin assessment, and surgical guidance. Mol Imaging 13:1Google Scholar
- 20.Pu K, Shuhendler AJ, Jokerst JV, Mei J, Gambhir SS, Bao Z, Rao J (2014) Semiconducting polymer nanoparticles as photoacoustic molecular imaging probes in living mice. Nat Nanotechnol 9:233CrossRefGoogle Scholar
- 21.Nalwa HS (1991) Optical and X-ray photoelectron spectro-scopic studies of electrically conducting benzimidazobenzophenanthroline type ladder polymers original research article. Polymer 32:802–807CrossRefGoogle Scholar
- 22.Morgan WE, Stec WJ, Albridge RG, Wazer JRV (1971) π-bond feedback Interpretated from the binding energy of "2p" electrons of phosphorus. Inorg Chem 10:926–930CrossRefGoogle Scholar
- 23.Wu XLR (2006) Inhibition of catalytic oxidation of carbon/carbon composites by phosphorus. Carbon 44:141CrossRefGoogle Scholar
- 24.Rosas JM, Ruiz-Rosas R, Rodríguez-Mirasol J, Cordero T (2012) Kinetic study of the oxidation resistance of phosphorus-containing activated carbons. Carbon 50:1523CrossRefGoogle Scholar
- 25.Zhang J, Zhao Z, Xia Z, Dai L (2015) A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat Nanotechnol 10:444–452CrossRefGoogle Scholar
- 26.Gong X, Hu Q, Paau MC, Zhang Y, Shuang S, Dong C, Choi MMF (2014) Red-green-blue fluorescent hollow carbon nanoparticles isolated from chromatographic fractions for cellular imaging. Nanoscale 6:8162–8170CrossRefGoogle Scholar
- 27.Cruz-Silva E, Cullen DA, Gu L, Romo-Herrera JM, Muñoz-Sandoval E, López-Urías F, Sumpter BG, Meunier V, Charlier JC, Smith DJ, Terrones H, Terrones M (2008) Heterodoped nanotubes: theory, synthesis, and characterization of phosphorus-nitrogen doped multiwalled carbon nanotubes. ACS Nano 2:441–448CrossRefGoogle Scholar
- 28.Gong X, Lu W, Liu Y, Li Z, Shuang S, Dong C, Choi MMF (2015) Low temperature synthesis of phosphorous and nitrogen co-doped yellow fluorescent carbon dots for sensing and bioimaging. J Mater Chem B 3:6813–6819CrossRefGoogle Scholar
- 29.Ananthanarayanan A, Wang Y, Routh P, Sk MA, Than A, Lin M, Zhang J, Chen J, Sun H, Chen P (2015) Nitrogen and phosphorus co-doped graphene quantum dots: synthesis from adenosine triphosphate, optical properties, and cellular imaging. Nanoscale 7:8159–8165CrossRefGoogle Scholar
- 30.Amali AJ, Hoshino H, Wu C, Ando M, Xu Q (2014) From metal–organic framework to intrinsically fluorescent carbon nanodots. Chem Eur J 20:8279–8282CrossRefGoogle Scholar
- 31.Wang X, Cao L, Yang ST, Lu F, Meziani MJ, Tian L, Sun KW, Bloodgood MA, Sun YP (2010) Bandgap-Like Strong Fluorescence in Functionalized Carbon Nanoparticles. Angew. Chem. 122: 5438–5442 Angew Chem Int Ed 49:5310–5314CrossRefGoogle Scholar
- 32.Anilkumar P, Wang X, Cao L, Sahu S, Liu JH, Wang P, Korch K, Tackett KN II, Parenzan A, Sun YP (2011) Toward quantitatively fluorescent carbon-based “quantum” dots. Nanoscale 3:2023–2027CrossRefGoogle Scholar
- 33.Wang L, Zhu SZ, Wang HY, Qu SN, Zhang YL, Zhang JH, Chen QD, Xu HL, Han W, Yang B, Sun HB (2014) Common origin of green luminescence in carbon nanodots and graphene quantum dots. ACS Nano 8:2541–2547CrossRefGoogle Scholar
- 34.Bhaisare ML, Talib A, Khan MS, Pandey S, Wu HF (2015) Synthesis of fluorescent carbon dots via microwave carbonization of citric acid in presence of tetraoctylammonium ion, and their application to cellular bioimaging. Microchim Acta 182(13–14):2173–2181CrossRefGoogle Scholar
- 35.Li H, Shao FQ, Zou SY, Yang QJ, Huang H, Feng JJ, Wang AJ (2016) Microwave-assisted synthesis of N, P-doped carbon dots for fluorescent cell imaging. Microchim Acta 183(2):821–826CrossRefGoogle Scholar
- 36.Wang F, Hao Q, Zhang Y, Xu Y, Lei W (2016) Fluorescence quenchometric method for determination of ferric ion using boron-doped carbon dots. Microchim Acta 183(1):273–279CrossRefGoogle Scholar
- 37.Guo Y, Yang L, Li W, Wang X, Shang Y, Li B (2016) Carbon dots doped with nitrogen and sulfur and loaded with copper (II) as a “turn-on” fluorescent probe for cystein, glutathione and homocysteine. Microchim Acta 183(4):1409–1416CrossRefGoogle Scholar
- 38.Yan F, Kong D, Luo Y, Ye Q, He J, Guo X, Chen L (2016) Carbon dots serve as an effective probe for the quantitative determination and for intracellular imaging of mercury (II). Microchim Acta 183(5):1611–1618CrossRefGoogle Scholar
- 39.Simões EF, Leitão JM, da Silva JCE (2016) Carbon dots prepared from citric acid and urea as fluorescent probes for hypochlorite and peroxynitrite. Microchim Acta 183(5):1769–1777CrossRefGoogle Scholar
- 40.Kobayashi H, Watanabe R, Choyke PL (2013) Improving conventional enhanced permeability and retention (EPR) effects; what is the appropriate target? Theranostics 4:81CrossRefGoogle Scholar
- 41.Chong Y, Ma Y, Shen H, Tu X, Zhou X, Xu J, Dai J, Fan S, Zhang Z (2014) The in vitro and in vivo toxicity of graphene quantum dots. Biomaterials 35:5041CrossRefGoogle Scholar
