ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

In Situ Synthesis of Fluorescent Carbon Dots/Polyelectrolyte Nanocomposite Microcapsules with Reduced Permeability and Ultrasound Sensitivity

View Author Information
Materials Research Institute, School of Engineering and Materials Science, and Centre for Condensed Matter and Materials Physics, School of Physics and Astronomy, Queen Mary University of London, London E1 4NS, United Kingdom
Cite this: ACS Nano 2016, 10, 10, 9608–9615
Publication Date (Web):September 29, 2016
Copyright © 2016 American Chemical Society

    Article Views





    Read OnlinePDF (7 MB)
    Supporting Info (1)»


    Abstract Image

    Designing and fabricating multifunctional nanocomposite microcapsules are considerable interests in both academic and industrial research aspects. This work first reports an innovative approach to in situ synthesize and assemble fluorescent carbon dots (CDs) into polyelectrolyte microcapsules, obtaining highly biocompatible nanocomposite microcapsules with excellent luminescence that facilitate imaging and identification in vitro, yet with the feasibility to load small molecules and ultrasound responsiveness to trigger their release. CDs are produced in situ in (PAH/PSS)4 microcapsule shells by carbonization of dextran molecules under relatively mild hydrothermal treatment. Compared with the collapsed and film-like (PAH/PSS)4 microcapsules, the novel composite microcapsules show a free-standing structure, smaller size, and thicker shell. CDs are proven to be fabricated and embedded in PAH/PSS multilayers, and the formed PAH/PSS/CD microcapsules are endowed with strong luminescence, as verified by the transmission electron microscopy, fluorescence spectra, and confocal laser scanning microscopy results. The in situ formation of CDs in capsule shells also empowers these capsules with ultrasound responsiveness and reduced permeability. The feasibility of encapsulation of small molecules (rhodamine B) and ultrasound-triggered release is also shown. Most importantly, due to the intrinsic biocompatible property and photostability of CDs, these fluorescent PAH/PSS/CD microcapsules show negligible cell toxicity and low photobleaching, which are impossible for capsules composited with conventional organic dyes and semiconductor quantum dots.

    Supporting Information

    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.6b05088.

    • Color change of microcapsule suspensions and precipitations before and after heating with dextran; FTIR profiles of CDs and microcapsules with and without CDs; TEM, UV–vis, and ζ-potential characterization of pure CDs; morphology and structure characterization (SEM and TEM) of PE capsules heated in H2O; photoluminescence emission data of PAH/PSS/CD microcapsules and that of CDs from dextran and glucose; photostability characterization of PAH/PSS/CD capsules; CLSM images of PAH/PSS/CD films; cell viability data of CDs, pure PAH/PSS capsules, and heated PAH/PSS capsules without CDs; cell uptake images of PAH/PSS/CD capsules and their quantitative uptake data; cell uptake images of CDs; long-time release data of RhB from PAH/PSS/CD microcapsules; CLSM image of PAH/PSS spheres with RhB encapsulated inside; ultrasound-triggered release of RhB from the PAH/PSS spheres; SEM images of PAH/PSS spheres upon different ultrasonication time (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 59 publications.

    1. Jin Zhang, Ru Zhang, Yangyang Liu, Ya-Ru Kong, Hong-Bin Luo, Yang Zou, Lu Zhai, Xiao-Ming Ren. Acidic Groups Functionalized Carbon Dots Capping Channels of a Proton Conductive Metal–Organic Framework by Coordination Bonds to Improve the Water-Retention Capacity and Boost Proton Conduction. ACS Applied Materials & Interfaces 2021, 13 (50) , 60084-60091.
    2. Polina A. Demina, Olga A. Sindeeva, Anna M. Abramova, Ekaterina S. Prikhozhdenko, Roman A. Verkhovskii, Ekaterina V. Lengert, Andrei V. Sapelkin, Irina Yu. Goryacheva, Gleb B. Sukhorukov. Fluorescent Convertible Capsule Coding Systems for Individual Cell Labeling and Tracking. ACS Applied Materials & Interfaces 2021, 13 (17) , 19701-19709.
    3. Kartik Ravishankar, K. M. Shelly, Abathodharanan Narayanan, Raghavachari Dhamodharan. Rapid, Solvent-Free Synthesis of Amorphous, Photoluminescent, Carbon Nanodots from Imidazole and Maleic Anhydride Solids. ACS Sustainable Chemistry & Engineering 2019, 7 (15) , 13206-13216.
    4. Mikhail V. Zyuzin, Alexander S. Timin, Gleb B. Sukhorukov. Multilayer Capsules Inside Biological Systems: State-of-the-Art and Open Challenges. Langmuir 2019, 35 (13) , 4747-4762.
    5. Sisi Cao, Rui Tang, Gail Sudlow, Zheyu Wang, Keng-Ku Liu, Jingyi Luan, Sirimuvva Tadepalli, Anushree Seth, Samuel Achilefu, Srikanth Singamaneni. Shape-Dependent Biodistribution of Biocompatible Silk Microcapsules. ACS Applied Materials & Interfaces 2019, 11 (5) , 5499-5508.
    6. Anton L. Popov, Nelli Popova, David J. Gould, Alexander B. Shcherbakov, Gleb B. Sukhorukov, Vladimir K. Ivanov. Ceria Nanoparticles-Decorated Microcapsules as a Smart Drug Delivery/Protective System: Protection of Encapsulated P. pyralis Luciferase. ACS Applied Materials & Interfaces 2018, 10 (17) , 14367-14377.
    7. Qizhang Huang, Yueyun Fang, Jifu Shi, Yanliang Liang, Yanqing Zhu, and Gang Xu . Flower-Like Molybdenum Disulfide for Polarity-Triggered Accumulation/Release of Small Molecules. ACS Applied Materials & Interfaces 2017, 9 (41) , 36431-36437.
    8. Meiyu Gai, Johannes Frueh, Valeriya L. Kudryavtseva, Alexey M. Yashchenok, and Gleb B. Sukhorukov . Polylactic Acid Sealed Polyelectrolyte Multilayer Microchambers for Entrapment of Salts and Small Hydrophilic Molecules Precipitates. ACS Applied Materials & Interfaces 2017, 9 (19) , 16536-16545.
    9. Jun Chen, Sithira Ratnayaka, Aaron Alford, Veronika Kozlovskaya, Fei Liu, Bing Xue, Kenneth Hoyt, and Eugenia Kharlampieva . Theranostic Multilayer Capsules for Ultrasound Imaging and Guided Drug Delivery. ACS Nano 2017, 11 (3) , 3135-3146.
    10. Olga A. Sindeeva, Polina A. Demina, Zhanna V. Kozyreva, Albert R. Muslimov, Olga I. Gusliakova, Valeriia O. Laushkina, Ekaterina A. Mordovina, Daria Tsyupka, Olga S. Epifanovskaya, Anastasiia Yu. Sapach, Irina Yu. Goryacheva, Gleb B. Sukhorukov. Labeling and Tracking of Individual Human Mesenchymal Stromal Cells Using Photoconvertible Fluorescent Microcapsules. International Journal of Molecular Sciences 2023, 24 (17) , 13665.
    11. Gulia Bikbaeva, Anna Pilip, Anastasia Egorova, Ilya Kolesnikov, Dmitrii Pankin, Kirill Laptinskiy, Alexey Vervald, Tatiana Dolenko, Gerd Leuchs, Alina Manshina. All-in-One Photoactivated Inhibition of Butyrylcholinesterase Combined with Luminescence as an Activation and Localization Indicator: Carbon Quantum Dots@Phosphonate Hybrids. Nanomaterials 2023, 13 (17) , 2409.
    12. Chunyu Zhou, Jialing Du, Hanqing Zhao, Zhili Xiong, Longshan Zhao. Green synthetic carbon quantum dots based on waste tobacco leaves and its application to detecting borax content in flour and its products. Journal of Molecular Structure 2023, 1278 , 134959.
    13. Zixin Yang, Yan Han, Wenwen Peng, Lin Wang, Xiaoxing Yan. Effect of Fluorane Microcapsule Content on Properties of Thermochroic Waterborne Topcoat on Tilia europaea. Polymers 2022, 14 (17) , 3638.
    14. Fengyan Song, Hao Sun, Hailong Ma, Hui Gao. Porous TiO2/Carbon Dot Nanoflowers with Enhanced Surface Areas for Improving Photocatalytic Activity. Nanomaterials 2022, 12 (15) , 2536.
    15. Mariia Stepanova, Aliaksei Dubavik, Arina Efimova, Mariya Konovalova, Elena Svirshchevskaya, Viktor Zakharov, Anna Orlova. Magneto-Luminescent Nanocomposites Based on Carbon Dots and Ferrite with Potential for Bioapplication. Nanomaterials 2022, 12 (9) , 1396.
    16. Jiajia Wu, Gonglin Chen, Yinnong Jia, Chunyu Ji, Yuting Wang, Yiqun Zhou, Roger M. Leblanc, Zhili Peng. Carbon dot composites for bioapplications: a review. Journal of Materials Chemistry B 2022, 10 (6) , 843-869.
    17. Haiyan Qi, Xiaona Sun, Tao Jing, Jinlong Li, Jun Li. Integration detection of mercury( ii ) and GSH with a fluorescent “on-off-on” switch sensor based on nitrogen, sulfur co-doped carbon dots. RSC Advances 2022, 12 (4) , 1989-1997.
    18. Jishu Mandal, Mriganka Mandal, Tamanna Mallick, Samiran Mondal. The Underlying Mechanism of Quantum Dot-Induced Apoptosis: Potential Application in Cancer Therapy. 2022, 125-142.
    19. Marianna Mamusa, Claudio Resta, Constantina Sofroniou, Piero Baglioni. Encapsulation of volatile compounds in liquid media: Fragrances, flavors, and essential oils in commercial formulations. Advances in Colloid and Interface Science 2021, 298 , 102544.
    20. Shi-da Hou, Shi-lu Zhou, Shu-ming Zhang, Hong-guang Li. Carbon-dot-based solid-state luminescent materials: Synthesis and applications in white light emitting diodes and optical sensors. New Carbon Materials 2021, 36 (3) , 527-545.
    21. Fengyan Song, Hui Gao, Danyang Li, Arseniy V. Petrov, Vladimir V. Petrov, Dongsheng Wen, Gleb B. Sukhorukov. Low intensity focused ultrasound responsive microcapsules for non-ablative ultrafast intracellular release of small molecules. Journal of Materials Chemistry B 2021, 9 (10) , 2384-2393.
    22. Angana Borbora, Uttam Manna. Impact of chemistry on the preparation and post-modification of multilayered hollow microcapsules. Chemical Communications 2021, 57 (17) , 2110-2123.
    23. Behrad Ghiasi, Golnaz Mehdipour, Nooshin Safari, Hamidreza Behboudi, Mohadeseh Hashemi, Meisam Omidi, Yahya Sefidbakht, Amir Yadegari, Michael R. Hamblin. Theranostic applications of stimulus-responsive systems based on carbon dots. International Journal of Polymeric Materials and Polymeric Biomaterials 2021, 70 (2) , 117-130.
    24. Xin Du, Zhenhua Zhang, Xiaodi Zheng, Hongyan Zhang, Dan Dong, Zhenguo Zhang, Min Liu, Jun Zhou. An electrochemical biosensor for the detection of epithelial-mesenchymal transition. Nature Communications 2020, 11 (1)
    25. Sinem Şimşek, Ayça Aktaş Şüküroğlu, Derya Yetkin, Belma Özbek, Dilek Battal, Rükan Genç. DNA-damage and cell cycle arrest initiated anti-cancer potency of super tiny carbon dots on MCF7 cell line. Scientific Reports 2020, 10 (1)
    26. Alina A. Kokorina, Alexey V. Ermakov, Anna M. Abramova, Irina Yu. Goryacheva, Gleb B. Sukhorukov. Carbon Nanoparticles and Materials on Their Basis. Colloids and Interfaces 2020, 4 (4) , 42.
    27. Ekaterina V. Lengert, Semyon I. Koltsov, Jie Li, Alexey V. Ermakov, Bogdan V. Parakhonskiy, Ekaterina V. Skorb, Andre G. Skirtach. Nanoparticles in Polyelectrolyte Multilayer Layer-by-Layer (LbL) Films and Capsules—Key Enabling Components of Hybrid Coatings. Coatings 2020, 10 (11) , 1131.
    28. Hongyue Zhang, Bolun Wang, Xiaowei Yu, Jiyang Li, Jin Shang, Jihong Yu. Carbon Dots in Porous Materials: Host–Guest Synergy for Enhanced Performance. Angewandte Chemie 2020, 132 (44) , 19558-19570.
    29. Hongyue Zhang, Bolun Wang, Xiaowei Yu, Jiyang Li, Jin Shang, Jihong Yu. Carbon Dots in Porous Materials: Host–Guest Synergy for Enhanced Performance. Angewandte Chemie International Edition 2020, 59 (44) , 19390-19402.
    30. Huy Quang Tran, Mrinal Bhave, Aimin Yu. Current Advances of Hollow Capsules as Controlled Drug Delivery Systems. ChemistrySelect 2020, 5 (19) , 5537-5551.
    31. Shumaila Razzaque, Ying Cheng, Irshad Hussain, Bien Tan. Synthesis of surface functionalized hollow microporous organic capsules for doxorubicin delivery to cancer cells. Polymer Chemistry 2020, 11 (12) , 2110-2118.
    32. Maje Alhaji Haruna, Zhongliang Hu, Hui Gao, Jabbar Gardy, Saminu Musa Magami, Dongsheng Wen. Influence of carbon quantum dots on the viscosity reduction of polyacrylamide solution. Fuel 2019, 248 , 205-214.
    33. Zhongliang Hu, Hui Gao, Srinivasa B. Ramisetti, Jin Zhao, Ehsan Nourafkan, Paul W.J. Glover, Dongsheng Wen. Carbon quantum dots with tracer-like breakthrough ability for reservoir characterization. Science of The Total Environment 2019, 669 , 579-589.
    34. Tarciane da S. Pinto, Priscilla N.S. Rodrigues, Luiz E.S. Marinho, Rodrigo M. Verly, Juan Pedro Bretas Roa, Luiz C.A. de Oliveira, Fabiano V. Pereira, Mariana T.Q. de Magalhães, João P. de Mesquita. Self-assembled hybrid nanocomposite films of carbon dots and hydrolyzed collagen. Materials Chemistry and Physics 2019, 230 , 44-53.
    35. Sven Rutkowski, Tieyan Si, Meiyu Gai, Mengmeng Sun, Johannes Frueh, Qiang He. Magnetically-guided hydrogel capsule motors produced via ultrasound assisted hydrodynamic electrospray ionization jetting. Journal of Colloid and Interface Science 2019, 541 , 407-417.
    36. Huan Yang, Li He, Shuang Pan, Hui Liu, Xiaoli Hu. Nitrogen-doped fluorescent carbon dots for highly sensitive and selective detection of tannic acid. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2019, 210 , 111-119.
    37. Galina Nifontova, Fernanda Ramos-Gomes, Maria Baryshnikova, Frauke Alves, Igor Nabiev, Alyona Sukhanova. Cancer Cell Targeting With Functionalized Quantum Dot-Encoded Polyelectrolyte Microcapsules. Frontiers in Chemistry 2019, 7
    38. Qin Dai, He Zhao, Hongbin Cao, Jun Yang, Wentao Zhao, Tianyu Wang, Linying Liu, Zhuangjun Fan, Guangwei Wang. Photo-triggered conversion of hydrophilic fluorescent biomimetic nanostructures for cell imaging. Chemical Communications 2019, 55 (5) , 596-599.
    39. Bibekananda De. Carbon Dots and Their Polymeric Nanocomposites. 2019, 217-260.
    40. Meiyu Gai, Wenhao Li, Johannes Frueh, Gleb B. Sukhorukov. Polylactic acid sealed polyelectrolyte complex microcontainers for controlled encapsulation and NIR-Laser based release of cargo. Colloids and Surfaces B: Biointerfaces 2019, 173 , 521-528.
    41. Anna V. Vostrikova, Ekaterina S. Prikhozhdenko, Oksana A. Mayorova, Irina Yu. Goryacheva, Nadezda V. Tarakina, Gleb B. Sukhorukov, Andrei V. Sapelkin. Thermal carbonization in nanoscale reactors: controlled formation of carbon nanodots inside porous CaCO3 microparticles. Scientific Reports 2018, 8 (1)
    42. Galina Nifontova, Maria Zvaigzne, Maria Baryshnikova, Evgeny Korostylev, Fernanda Ramos-Gomes, Frauke Alves, Igor Nabiev, Alyona Sukhanova. Next-Generation Theranostic Agents Based on Polyelectrolyte Microcapsules Encoded with Semiconductor Nanocrystals: Development and Functional Characterization. Nanoscale Research Letters 2018, 13 (1)
    43. Yuechen Zhai, Yi Wang, Di Li, Ding Zhou, Pengtao Jing, Dezhen Shen, Songnan Qu. Red carbon dots-based phosphors for white light-emitting diodes with color rendering index of 92. Journal of Colloid and Interface Science 2018, 528 , 281-288.
    44. Ekaterina S. Prikhozhdenko, Daniil N. Bratashov, Anastasiya N. Mitrofanova, Andrei V. Sapelkin, Alexey M. Yashchenok, Gleb B. Sukhorukov, Irina Yu Goryacheva. Solvothermal synthesis of hydrophobic carbon dots in reversed micelles. Journal of Nanoparticle Research 2018, 20 (9)
    45. Yingbo Liu, Daiyong Chao, Liang Zhou, Yanan Li, Ruiping Deng, Hongjie Zhang. Yellow emissive carbon dots with quantum yield up to 68.6% from manganese ions. Carbon 2018, 135 , 253-259.
    46. Meiyu Gai, Maxim A. Kurochkin, Danyang Li, Boris N. Khlebtsov, Luo Dong, Nadja Tarakina, Robin Poston, David J. Gould, Johannes Frueh, Gleb B. Sukhorukov. In-situ NIR-laser mediated bioactive substance delivery to single cell for EGFP expression based on biocompatible microchamber-arrays. Journal of Controlled Release 2018, 276 , 84-92.
    47. Hui Gao, Thaaqib Nazar, Zhongliang Hu, Dongsheng Wen, Gleb B. Sukhorukov. Protective composite silica/polyelectrolyte shell with enhanced tolerance to harsh acid and alkali conditions. Journal of Colloid and Interface Science 2018, 512 , 198-207.
    48. Hui Gao, Xin Zhao, Sijie Chen. AIEgen-Based Fluorescent Nanomaterials: Fabrication and Biological Applications. Molecules 2018, 23 (2) , 419.
    49. B. Sinduja, N. S. K. Gowthaman, S. Abraham John. Selective and sensitive determination of the antidote of heparin using Ag-GQDs by optical methods. Analytical Methods 2018, 10 (17) , 1999-2006.
    50. Yuxiu Chen, Gleb B. Sukhorukov, Pavel Novak. Visualising nanoscale restructuring of a cellular membrane triggered by polyelectrolyte microcapsules. Nanoscale 2018, 10 (35) , 16902-16910.
    51. A. S. Chumakov, Ammar J. Al-Alwani, I. A. Gorbachev, A. V. Ermakov, A. A. Kletsov, E. G. Glukhovskoy, A. V. Kazak, N. V. Usol’tseva, S. N. Shtykov. Temperature and Mixing Ratio Effects in the Formation of CdSe/CdS/ZnS Quantum Dots with 4′-n-octyl-4-p-Cyanobiphenyl Thin Films. BioNanoScience 2017, 7 (4) , 666-671.
    52. Yongzhi Wu, Qiwen Li, Dawei Yang, Jinfeng Liao. Carbon Dots: Highlight on Their Synthesis, Properties and Applications in Tumor Imaging and Therapy. Nanoscience and Nanotechnology Letters 2017, 9 (12) , 1827-1848.
    53. Na Gao, Wen Yang, Hailiang Nie, Yunqian Gong, Jing Jing, Loujun Gao, Xiaoling Zhang. Turn-on theranostic fluorescent nanoprobe by electrostatic self-assembly of carbon dots with doxorubicin for targeted cancer cell imaging, in vivo hyaluronidase analysis, and targeted drug delivery. Biosensors and Bioelectronics 2017, 96 , 300-307.
    54. Rama Krishna Chava, Younghwan Im, Misook Kang. Nitrogen doped carbon quantum dots as a green luminescent sensitizer to functionalize ZnO nanoparticles for enhanced photovoltaic conversion devices. Materials Research Bulletin 2017, 94 , 399-407.
    55. Mariia S. Saveleva, Ekaterina V. Lengert, Dmitry A. Gorin, Bogdan V. Parakhonskiy, Andre G. Skirtach. Polymeric and Lipid Membranes—From Spheres to Flat Membranes and vice versa. Membranes 2017, 7 (3) , 44.
    56. Zhongliang Hu, Jin Zhao, Hui Gao, Ehsan Nourafkan, Dongsheng Wen. Transport and Deposition of Carbon Nanoparticles in Saturated Porous Media. Energies 2017, 10 (8) , 1151.
    57. Yao Li, Jingran Bi, Shan Liu, Haitao Wang, Chenxu Yu, Dongmei Li, Bei-Wei Zhu, Mingqian Tan. Presence and formation of fluorescence carbon dots in a grilled hamburger. Food & Function 2017, 8 (7) , 2558-2565.
    58. Meiyu Gai, Johannes Frueh, Tianyi Tao, Arseniy V. Petrov, Vladimir V. Petrov, Evgeniy V. Shesterikov, Sergei I. Tverdokhlebov, Gleb B. Sukhorukov. Polylactic acid nano- and microchamber arrays for encapsulation of small hydrophilic molecules featuring drug release via high intensity focused ultrasound. Nanoscale 2017, 9 (21) , 7063-7070.
    59. So Young Park, Che Yoon Lee, Ha-Rim An, Hyeran Kim, Young-Chul Lee, Edmond Changkyun Park, Hang-Suk Chun, Hee Young Yang, Sae-Hae Choi, Hee Sik Kim, Kyoung Suk Kang, Hyun Gyu Park, Jong-Pil Kim, Yunju Choi, Jouhahn Lee, Hyun Uk Lee. Advanced carbon dots via plasma-induced surface functionalization for fluorescent and bio-medical applications. Nanoscale 2017, 9 (26) , 9210-9217.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect