Abstract
Light harvesting in photosynthesis is currently an issue on-debate and studied widely in all over the world. Studies on light harvesting mainly focus on enlightening molecular mechanism of the process and enhancing absorption capacity of light harvesting complexes (LHCs). Enhancement of absorption capacity of LHCs can be done either by natural methods or by synthetic methods. Quantum dots (QDs), fluorescent semiconductor nanocrystals, are important constituents of inorganic–organic hybrid structures which are built to enhance absorption capacity of LHCs through synthetic methods. In this study, we synthesized carbon and heteroatom doped carbon QDs through a microwave assisted synthesis method. Each QD had unique photophysical and structural properties. Photosynthetic pigments (PP) (isolated from spinach leaves) were mixed with each QD separately to build a QD–PP hybrid structure. Our results revealed that significant amount of energy is transferred from carbon QDs to PPs and therefore chlorophyll fluorescence capacity of PPs enhanced significantly in 360–420 nm excitation wavelength interval. Our results suggested that non-toxic, inexpensive and easily synthesized carbon QDs can be an important constituent for hybrid structures to enhance absorption capacity of LHCs in highly energetic region of visible spectrum.
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References
Alivisatos AP (1996) Semiconductor clusters, nanocrystals, and quantum dots. Science 80(271):933–937. https://doi.org/10.1126/science.271.5251.933
Amjad M, Iqbal M, Faisal A et al (2019) Hydrothermal synthesis of carbon nanodots from bovine gelatin and PHM3 microalgae strain for anticancer and bioimaging applications. Nanoscale Adv. https://doi.org/10.1039/c9na00164f
Bacon M, Bradley SJ, Nann T (2014) Graphene quantum dots. Part Part Syst Charact 31:415–428
Bawendi MG, Carroll PJ, Wilson WL, Brus LE (1992) Luminescence properties of CdSe quantum crystallites: resonance between interior and surface localized states. J Chem Phys. https://doi.org/10.1063/1.462114
Bhatt S, Bhatt M, Kumar A et al (2018) Green route for synthesis of multifunctional fluorescent carbon dots from Tulsi leaves and its application as Cr(VI) sensors, bio-imaging and patterning agents. Colloids Surf B Biointerfaces. https://doi.org/10.1016/j.colsurfb.2018.04.008
Bourlinos AB, Trivizas G, Karakassides MA et al (2015) Green and simple route toward boron doped carbon dots with significantly enhanced non-linear optical properties. Carbon N Y 83:173–179. https://doi.org/10.1016/j.carbon.2014.11.032
Britton J, Antunes E, Nyokong T (2010) Fluorescence quenching and energy transfer in conjugates of quantum dots with zinc and indium tetraamino phthalocyanines. J Photochem Photobiol A Chem 210:1–7. https://doi.org/10.1016/j.jphotochem.2009.12.013
Budak E, Aykut S, Paşaoğlu ME, Ünlü C (2020) Microwave assisted synthesis of boron and nitrogen rich graphitic quantum dots to enhance fluorescence of photosynthetic pigments. Mater Today Commun 24:100975. https://doi.org/10.1016/j.mtcomm.2020.100975
Carbonaro R, Corpino M, Salis F et al (2019) On the emission properties of carbon dots: reviewing data and discussing models. J Carbon Res. https://doi.org/10.3390/c5040060
Chandra S, Pradhan S, Mitra S et al (2014) High throughput electron transfer from carbon dots to chloroplast: a rationale of enhanced photosynthesis. Nanoscale. https://doi.org/10.1039/c3nr06079a
Cho SJ, Maysinger D, Jain M et al (2007) Long-term exposure to CdTe quantum dots causes functional impairments in live cells. Langmuir 23:1974–1980. https://doi.org/10.1021/la060093j
Clapp AR, Medintz IL, Mauro JM et al (2004) Fluorescence resonance energy transfer between quantum dot donors and dye-labeled protein acceptors. J Am Chem Soc 126:301–310. https://doi.org/10.1021/ja037088b
Clapp AR, Medintz IL, Tetsuo Uyeda H et al (2005) Quantum dot-based multiplexed fluorescence resonance energy transfer. J Am Chem Soc 127:18212–18221. https://doi.org/10.1021/ja054630i
Croce R, Van Amerongen H (2014) Natural strategies for photosynthetic light harvesting. Nat Chem Biol 10:492–501
Croce R, van Amerongen H (2020) Light harvesting in oxygenic photosynthesis: structural biology meets spectroscopy. Science 80:369. https://doi.org/10.1126/science.aay2058
DallOsto L, Ünlü C, Cazzaniga S, Van Amerongen H (2014) Disturbed excitation energy transfer in Arabidopsis thaliana mutants lacking minor antenna complexes of photosystem II. Biochim Biophys Acta - Bioenergy 1837:1981–1988. https://doi.org/10.1016/j.bbabio.2014.09.011
Dayal S, Lou Y, Samia ACS et al (2006) Observation of non-förster-type energy-transfer behavior in quantum dot-phthalocyanine conjugates. J Am Chem Soc 128:13974–13975. https://doi.org/10.1021/ja063415e
Dubertret B, Skourides P, Norris DJ et al (2002) In vivo imaging of quantum dots encapsulated in phospholipid micelles. Science 80(298):1759–1762. https://doi.org/10.1126/science.1077194
Gong Y, Zhao J (2018) Small carbon quantum dots, large photosynthesis enhancement. J Agric Food Chem. https://doi.org/10.1021/acs.jafc.8b01788
Govorov AO (2008) Enhanced optical properties of a photosynthetic system conjugated with semiconductor nanoparticles: The role of Förster transfer. Adv Mater. https://doi.org/10.1002/adma.200702999
Hewageegana P, Apalkov V (2010) Graphene quantum dots. In: Sattler KD (ed) Handbook of nanophysics: functional nanomaterials. CRC Press, Bica Raton
Hildebrandt N, Spillmann CM, Russ Algar W et al (2017) Energy transfer with semiconductor quantum dot bioconjugates: A versatile platform for biosensing, energy harvesting, and other developing applications. Chem Rev 117:536
Jiang K, Sun S, Zhang L et al (2015) Red, green, and blue luminescence by carbon dots: full-color emission tuning and multicolor cellular imaging. Angew Chem - Int Ed. https://doi.org/10.1002/anie.201501193
Jung JH, Kotal M, Jang MH et al (2016) Defect engineering route to boron nitride quantum dots and edge-hydroxylated functionalization for bio-imaging. RSC Adv 6:73939–73946. https://doi.org/10.1039/c6ra12455k
Kundu S, Patra A (2017) Nanoscale strategies for light harvesting. Chem Rev 117:712
Larson DR, Zipfel WR, Williams RM et al (2003) Water-soluble quantum dots for multiphoton fluorescence imaging in vivo. Science 80(300):1434–1436. https://doi.org/10.1126/science.1083780
Leblanc G, Winter KM, Crosby WB et al (2014) Integration of photosystem i with graphene oxide for photocurrent enhancement. Adv Energy Mater. https://doi.org/10.1002/aenm.201301953
Li LS, Yan X (2010) Colloidal graphene quantum dots. J Phys Chem Lett. https://doi.org/10.1021/jz100862f
Li H, Shao FQ, Huang H et al (2016) Eco-friendly and rapid microwave synthesis of green fluorescent graphitic carbon nitride quantum dots for vitro bioimaging. Sensors Actuators B Chem 226:506–511. https://doi.org/10.1016/j.snb.2015.12.018
Liang Q, Ma W, Shi Y et al (2013) Easy synthesis of highly fluorescent carbon quantum dots from gelatin and their luminescent properties and applications. Carbon N Y 60:421–428. https://doi.org/10.1016/j.carbon.2013.04.055
Lu K, Shen D, Dong S et al (2020) Uptake of graphene enhanced the photophosphorylation performed by chloroplasts in rice plants. Nano Res. https://doi.org/10.1007/s12274-020-2862-1
Mackowski S, Kamińska I (2016) Energy transfer in graphene-based hybrid photosynthetic nanostructures. In: Nayak PK (ed) Recent advances in graphene research. IntechOpen, Rijeka
Medintz IL, Pons T, Susumu K et al (2009) Resonance energy transfer between luminescent quantum dots and diverse fluorescent protein acceptors. J Phys Chem C 113:18552–18561. https://doi.org/10.1021/jp9060329
Michalet X, Pinaud FF, Bentolila LA et al (2005) Quantum dots for live cells, in vivo imaging, and diagnostics. Science 80(307):538–544
Nabiev I, Rakovich A, Sukhanova A et al (2010) Fluorescent quantum dots as artificial antennas for enhanced light harvesting and energy transfer to photosynthetic reaction centers. Angew Chem - Int Ed 49:7217–7221. https://doi.org/10.1002/anie.201003067
Rao L, Tang Y, Lu H et al (2018) Highly photoluminescent and stable n-doped carbon dots as nanoprobes for Hg2+ detection. Nanomaterials. https://doi.org/10.3390/nano8110900
Schmitt FJ, Maksimov EG, Hätti P et al (2012) Coupling of different isolated photosynthetic light harvesting complexes and CdSe/ZnS nanocrystals via Förster resonance energy transfer. Biochim Biophys Acta 1817:1461
Shen P, Xia Y (2014) Synthesis-modification integration: one-step fabrication of boronic acid functionalized carbon dots for fluorescent blood sugar sensing. Anal Chem 86:5323–5329. https://doi.org/10.1021/ac5001338
Shen J, Zhu Y, Yang X, Li C (2012) Graphene quantum dots: emergent nanolights for bioimaging, sensors, catalysis and photovoltaic devices. Chem Commun 48:3686–3699. https://doi.org/10.1039/c2cc00110a
Shiohara A, Hoshino A, Hanaki K-I et al (2004) On the cyto-toxicity caused by quantum dots. Microbiol Immunol 48:669–675. https://doi.org/10.1111/j.1348-0421.2004.tb03478.x
Sulowska K, Wiwatowski K, Szustakiewicz P et al (2018) Energy transfer from photosystem I to thermally reduced graphene oxide. Mater (Basel, Switzerland) 11:1567. https://doi.org/10.3390/ma11091567
Tchounwou PB, Yedjou CG, Patlolla AK, Sutton DJ (2012) Heavy metal toxicity and the environment. EXS 101:133–164
Ünlü C, Drop B, Croce R, van Amerongen H (2014) State transitions in Chlamydomonas reinhardtii strongly modulate the functional size of photosystem II but not of photosystem I. Proc Natl Acad Sci 111:3460–3465. https://doi.org/10.1073/pnas.1319164111
Ünlü C, Polukhina I, van Amerongen H (2016) Origin of pronounced differences in 77 K fluorescence of the green alga Chlamydomonas reinhardtii in state 1 and 2. Eur Biophys J 45:209–217. https://doi.org/10.1007/s00249-015-1087-9
Xu G, Zeng S, Zhang B et al (2016) New generation cadmium-free quantum dots for biophotonics and nanomedicine. Chem Rev 116:12234–12327
Yang MQ, Zhang N, Pagliaro M, Xu YJ (2014) Artificial photosynthesis over graphene-semiconductor composites. Are we getting better? Chem. Soc. Rev. 43:8240–8254
Zhao L, Wang Y, Zhao X et al (2019) Facile synthesis of nitrogen-doped carbon quantum dots with chitosan for fluorescent detection of Fe3+. Polymers 11:1731
Zheng C, Huang L, Guo Q et al (2018) Nonlinear optical responses of carbon quantum dots anchored on graphene oxide hybrid in solid-state transparent monolithic silica gel glasses. Opt Laser Technol. https://doi.org/10.1016/j.optlastec.2018.06.013
Acknowledgements
We thank Dr. Ahmet Gül for support and letting use of UV–Vıs spectrometer. We also thank Dr. Bünyamin Karagöz and his laboratory crew for support and letting use of Fluorescence Spectrometer. We would like to thank Dr. İsmail Koyuncu for the FTIR measurements and data analysis. The FTIR measurements and data analysis were performed in MEM-TEK (National Membrane Technologies Research and Development Center). The TEM measurements and data analysis were performed in Eskişehir Osmangazi University—Central Research Laboratory and Application Center.
Funding
This work was supported by TUBITAK (The Scientific and Technological Research Council of Turkey) under Career Development Programme for Young Researchers (Career Programme) (Programme No: 3501) [Grant number: 118Z259].
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EB and CÜ designed research; EB, DE performed research; CÜ, EB and DE analyzed data; CÜ and EB wrote the paper.
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CÜ has received research grants from TUBITAK (The Scientific and Technological Research Council of Turkey). The authors declare that they have no conflict of interest.
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Budak, E., Erdoğan, D. & Ünlü, C. Enhanced fluorescence of photosynthetic pigments through conjugation with carbon quantum dots. Photosynth Res 147, 1–10 (2021). https://doi.org/10.1007/s11120-020-00786-z
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DOI: https://doi.org/10.1007/s11120-020-00786-z