, Volume 25, Issue 12, pp 7017–7029 | Cite as

Fluorescent CdTe-QD-encoded nanocellulose microspheres by green spraying method

  • Qingshun Guan
  • Ruyuan Song
  • Weibing WuEmail author
  • Lei Zhang
  • Yi Jing
  • Hongqi Dai
  • Guigan Fang
Original Paper


With water-soluble CdTe quantum Dots (QDs) as fluorescent labels and TEMPO-oxidized cellulose nanofibrils (CNF) as matrix, dual-color QD-encoded microspheres were prepared by mechanical spraying, freeze-molding and subsequent electrostatic cross-linking by calcium ion. The entire preparation process was accomplished in aqueous phase without any chemical treatment. The nanocellulose microspheres possessed porous structure and were able to be dispersed stably in water in the form of hydrogels. CdTe QDs were efficiently fixed in the network of intertwined nanofibrils via hydrogen bonding with CNF, making the microspheres to obtain high photoluminescence (PL) intensity and identifiable encoding signals consisting of seven kinds of microsphere arrays. The crystalline structure and chemical composition of both CdTe QDs and CNF were not affected during the preparation process. The comparision of PL behaviors of CdTe QDs and QD-encoded microspheres in different media indicate that CNF matrix provided good protection of QDs and improved the PL intensity and photostability.

Graphical Abstract

Dual-color CdTe-encoded nanocellulose microspheres were prepared via pure physical process in aqueous phase. The fluorescent microspheres possessed high photoluminescence intensity and identifiable seven kinds of encoding signals. The nanocellulose matrix provided good protection of CdTe QDs and improved the photoluminescence intensity and photostability.


Quantum dots Fluorescent microspheres Nanocellulose Fluorescence coding 



The support of this work by the Natural Science Foundation of Jiangsu Province (BK20171450), National Key Research and Development Program of China (2017YFD0601005), and Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) are gratefully acknowledged.


  1. Benhamou K, Dufresne A, Magnin A, Mortha G, Kaddami H (2014) Control of size and viscoelastic properties of nanofibrillated cellulose from palm tree by varying the TEMPO-mediated oxidation time. Carbohydr Polym 99:74–83CrossRefGoogle Scholar
  2. Cai HL, Sharma S, Liu WY, Mu W, Liu W, Zhang XD, Deng YL (2014) Aerogel microspheres from natural cellulose nanofibrils and their application as cell culture scaffold. Biomacromolecules 15:2540–2547CrossRefGoogle Scholar
  3. Chen H, Lin H, Xu J, Wang B, Lin ZB, Zhou JC, Wang YS (2015) Chromaticity-tunable phosphor-in-glass for long-lifetime high-power warm w-LEDs. J Mater Chem C 3:8080–8089CrossRefGoogle Scholar
  4. Cretich M, Sola L, Gagni P, Chiari M (2013) Novel fluorescent microarray platforms: a case study in neurodegenerative disorders. Expert Rev Mol Diagn 13:863–873CrossRefGoogle Scholar
  5. Dabbousi B, Rodriguez J, Mikulec F, Heine J, Mattoussi H, Ober R, Jensen K, Bawendi M, Rodriguez-Viejo J (1997) (CdSe)ZnS core–shell quantum dots: synthesis and characterization of a size series of highly luminescent nanocrystallites. J Phys Chem B 101:9463–9475CrossRefGoogle Scholar
  6. Dong B, Song H, Qin R, Bai X, Wang F, Fan L, Pan G, Lu S, Ren X, Zhao H (2008) White luminescence by up-conversion from thin film made with Ln3+-doped NaYF4 nanoparticles. J Nanosci Nanotechnol 8:1254–1257PubMedGoogle Scholar
  7. Erogbogbo F, Yong KT, Roy I, Hu R, Law  WC, Zhao W, Ding H, Wu F, Kumar R, Swihart MT (2010) In vivo targeted cancer imaging, sentinel lymph node mapping and multi-channel imaging with biocompatible silicon nanocrystals. ACS Nano 5:413–423CrossRefGoogle Scholar
  8. Fournier-Bidoz S, Jennings TL, Klostranec JM, Fung W, Rhee A, Li D, Chan WC (2008) Facile and rapid one-step mass preparation of quantum-dot barcodes. Angew Chem 120:5659–5663CrossRefGoogle Scholar
  9. Fukuzumi H, Saito T, Isogai A (2013) Influence of TEMPO-oxidized cellulose nanofibril length on film properties. Carbohydr Polym 93:172–177CrossRefGoogle Scholar
  10. Gao XH, Nie SM (2004) Quantum dot-encoded mesoporous beads with high brightness and uniformity: rapid readout using flow cytometry. Anal Chem 76:2406–2410CrossRefGoogle Scholar
  11. Gong YJ, Gao MY, Wang DY, Möhwald H (2005) Incorporating fluorescent CdTe nanocrystals into a hydrogel via hydrogen bonding: toward fluorescent microspheres with temperature-responsive properties. Chem Mater 17:2648–2653CrossRefGoogle Scholar
  12. Han MY, Gao XH, Su JZ, Nie S (2001) Quantum-dot-tagged microbeads for multiplexed optical coding of biomolecules. Nat Biotechnol 19:631CrossRefGoogle Scholar
  13. Hodlur RM, Rabinal MK (2014) A new selenium precursor for the aqueous synthesis of luminescent CdSe quantum dots. Chem Eng J 244:82–88CrossRefGoogle Scholar
  14. Huang C, Hong Y, Yan X, Xiao L, Huang K, Gu W, Liu K, Shi W (2016) Carbon quantum dot decorated hollow In2S3 microspheres with efficient visible-light-driven photocatalytic activities. Rsc Adv 6(46):40137–40146CrossRefGoogle Scholar
  15. Insin N, Tracy JB, Lee H, Zimmer JP, Westervelt RM, Bawendi MG (2008) Incorporation of iron oxide nanoparticles and quantum dots into silica microspheres. ACS Nano 2:197–202CrossRefGoogle Scholar
  16. Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85CrossRefGoogle Scholar
  17. Jiang J, Oberdörster G, Biswas P (2009) Characterization of size, surface charge, and agglomeration state of nanoparticle dispersions for toxicological studies. J Nanopart Res 11:77–89CrossRefGoogle Scholar
  18. Leng YK, Sun K, Chen XY, Li WW (2015) Suspension arrays based on nanoparticle-encoded microspheres for high-throughput multiplexed detection. Chem Soc Rev 44:5552–5595CrossRefGoogle Scholar
  19. Li I, Yeh CS (2010) Synthesis of Gd doped CdSe nanoparticles for potential optical and MR imaging applications. J Mater Chem 20:2079–2081CrossRefGoogle Scholar
  20. Liu JG, Liang JG, Han HY, Sheng ZH (2009a) Facile synthesis and characterization of CdTe quantum dots–polystyrene fluorescent composite nanospheres. Mater Lett 63:2224–2226CrossRefGoogle Scholar
  21. Liu QH, Liu J, Guo J-C, Yan X-L, Wang D-H, Chen L, F-y Yan, Chen L-G (2009b) Preparation of polystyrene fluorescent microspheres based on some fluorescent labels. J Mater Chem 19:2018–2025CrossRefGoogle Scholar
  22. Liu Q, Yin Y, Hao N, Qian J, Li L, You T, Mao H, Wang K (2018a) Nitrogen functionlized graphene quantum dots/3D bismuth oxyiodine hybrid hollow microspheres as remarkable photoelectrode for photoelectrochemical sensing of chlopyrifos. Sens Actuators B Chem 260:1034–1042CrossRefGoogle Scholar
  23. Liu YY, Sui YL, Liu C, Liu CQ, Wu MY, Li B, Li YM (2018b) A physically crosslinked polydopamine/nanocellulose hydrogel as potential versatile vehicles for drug delivery and wound healing. Carbohydr Polym 188:27–36CrossRefGoogle Scholar
  24. Ma Q, Wang X, Li Y, Shi Y, Su X (2007) Multicolor quantum dot-encoded microspheres for the detection of biomolecules. Talanta 72:1446–1452CrossRefGoogle Scholar
  25. Naseri N, Deepa B, Mathew AP, Oksman K, Girandon L (2016) Nanocellulose-based interpenetrating polymer network (IPN) hydrogels for cartilage applications. Biomacromolecules 17:3714–3723CrossRefGoogle Scholar
  26. Rankin JM, Neelakantan NK, Lundberg KE, Grzincic EM, Murphy CJ, Suslick KS (2015) Magnetic, fluorescent, and copolymeric silicone microspheres. Adv Sci 2:1500114CrossRefGoogle Scholar
  27. Rogach AL, Franzl T, Klar TA, Feldmann J (2007) Aqueous synthesis of thiol-capped CdTe nanocrystals: state-of-the-art. J Phys Chem C 111:14628–14637CrossRefGoogle Scholar
  28. Saito T, Nishiyama Y, Putaux JL, Vignon M, Isogai A (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 7:1687–1691CrossRefGoogle Scholar
  29. Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8:2485–2491CrossRefGoogle Scholar
  30. Saito T, Hirota M, Tamura N, Kimura S, Fukuzumi H, Heux L, Isogai A (2009) Individualization of nano-sized plant cellulose fibrils by direct surface carboxylation using TEMPO catalyst under neutral conditions. Biomacromolecules 10:1992–1996CrossRefGoogle Scholar
  31. Salama A, Shukry N, El-Sakhawy M (2015) Carboxymethyl cellulose-g-poly (2-(dimethylamino) ethyl methacrylate) hydrogel as adsorbent for dye removal. Int J Biol Macromol 73:72–75CrossRefGoogle Scholar
  32. Schneider R, Wolpert C, Guilloteau H, Balan L, Lambert J, Merlin C (2009) The exposure of bacteria to CdTe-core quantum dots: the importance of surface chemistry on cytotoxicity. Nanotechnology 20:225101CrossRefGoogle Scholar
  33. Shen Q, You Z, Yu Y, Qin T, Su Y, Wang H, Wu C, Zhang F, Yang H (2018) A carbon quantum dots/porous InVO4 microsphere composite with enhanced photocatalytic activity. Eur J Inorg Chem 9:1080–1086CrossRefGoogle Scholar
  34. Sukhanova A, Nabiev I (2008) Fluorescent nanocrystal-encoded microbeads for multiplexed cancer imaging and diagnosis. Crit Rev Oncol Hematol 68:39–59CrossRefGoogle Scholar
  35. Wilson R, Cossins AR, Spiller DG (2006) Encoded microcarriers for high-throughput multiplexed detection. Angew Chem Int Ed 45:6104–6117CrossRefGoogle Scholar
  36. Wu W-B, Wang M-L, Sun Y-M, Huang W, Cui Y-P, Xu C-X (2008) Color-tuned FRET polystyrene microspheres by single wavelength excitation. Opt Mater 30(12):1803–1809CrossRefGoogle Scholar
  37. Wu W-B, Liu C, Wang M-L, Zhou S-R, Jiang W, Sun Y-M, Cui Y-P, Xu C-X (2009) Uniform silica nanoparticles encapsulating two-photon absorbing fluorescent dye. J Solid State Chem 182(4):862–868CrossRefGoogle Scholar
  38. Wu SL, Dou J, Zhang J, Zhang SF (2012) A simple and economical one-pot method to synthesize high-quality water soluble CdTe QDs. J Mater Chem 22:14573–14578CrossRefGoogle Scholar
  39. Yu H-Y, Kima IS, Niessner R, Knopp D (2012) Multiplex competitive microbead-based flow cytometric immunoassay using quantum dot fluorescent labels. Anal Chim Acta 750:191–198CrossRefGoogle Scholar
  40. Zhang PF, He Y, Ruan Z, Chen FF, Yang J (2012a) Fabrication of quantum dots-encoded microbeads with a simple capillary fluidic device and their application for biomolecule detection. J Colloid Interface Sci 385:8–14CrossRefGoogle Scholar
  41. Zhang K, Fischer S, Geissler A, Brendler E (2012b) Analysis of carboxylate groups in oxidized never-dried cellulose II catalyzed by TEMPO and 4-acetamide-TEMPO. Carbohydr Polym 87:894–900CrossRefGoogle Scholar
  42. Zhang F, Ren H, Dou J, Tong GL, Deng YL (2017) Cellulose nanofibril based-aerogel microreactors: a high efficiency and easy recoverable W/O/W membrane separation system. Sci Rep 7:40096CrossRefGoogle Scholar
  43. Zhou D, Lin M, Chen ZL, Sun HZ, Zhang H, Sun HC, Yang B (2011) Simple synthesis of highly luminescent water-soluble CdTe quantum dots with controllable surface functionality. Chem Mater 23:4857–4862CrossRefGoogle Scholar
  44. Zou L, Gu ZY, Zhang N, Zhang YL, Fang Z, Zhu WH, Zhong XH (2008) Ultrafast synthesis of highly luminescent green-to near infrared-emitting CdTe nanocrystals in aqueous phase. J Mater Chem 18:2807–2815CrossRefGoogle Scholar
  45. Zou C, Foda MF, Tan X, Shao K, Wu L, Lu Z, Bahlol HS, Han H (2016) Carbon-dot and quantum-dot-coated dual-Emission core-satellite silica nanoparticles for ratiometric intracellular Cu2+ imaging. Anal Chem 88:7395–7403CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Jiangsu Co-Innovation Center for Efficient Processing and Utilization of Forest Resources, Jiangsu Provincial Key Lab of Pulp and Paper Science and TechnologyNanjing Forestry UniversityNanjingChina
  2. 2.Key Laboratory for Organic Electronics and Information, National Jiangsu, Synergetic Innovation Center for Advanced Materials (SICAM)Nanjing University of Posts and TelecommunicationsNanjingChina
  3. 3.Institute of Chemical Industry of Forestry ProductsChinese Academy of ForestryNanjingChina

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