SCIENCE CHINA Materials, Volume 60, Issue 9: 881-891(2017) https://doi.org/10.1007/s40843-017-9101-5

Ethylene glycol-mediated synthetic route for production of luminescent silicon nanorod as photodynamic therapy agent

More info
  • ReceivedMay 31, 2017
  • AcceptedAug 16, 2017
  • PublishedSep 5, 2017


One-dimensional silicon nanorod (SiNR) has attracted considerable interest because of its unique morphology and electronic-optical properties that render SiNRs suitable for a broad spectrum of applications, such as field-effect transistor, drug carrier, solar cell, nanomechanical device, and lithium-ion battery. However, studies aiming to identify a new synthetic method and apply SiNR in the biomedical field remain limited. This study is the first to use an ethylene glycol-mediated synthetic route to prepare SiNR as a multicolor fluorescent probe and a new photodynamic therapy (PDT) agent. The as-prepared SiNR demonstrates bright fluorescence, excellent storage and photostability, favorable biocompatibility, excitation-dependent emission, and measurable quantity of 1O2 (0.24). On the basis of these features, we demonstrate through in vitro studies that the SiNR can be utilized as a new nanophotosensitizer for fluorescence imaging-guided cancer treatment. Our work leads to a new production process for SiNRs that can be used not only as PDT agents for therapy of shallow tissue cancer but also as excellent, environment-friendly, and red light-induced photocatalysts for the degradation of persistent organic pollutants in the future.

Funded by

National Natural Science Foundation of China(51472252,51572269)

Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17030400)


This work was supported by the National Natural Science Foundation of China (51472252 and 51572269) and the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17030400).

Interest statement

The authors declare that they have no conflicts of interest.

Contributions statement

Ge J and Wang P proposed and designed the project. Ge J, Jia Q, Liu Q and Chen M synthesized the SiNRs, designed and carried out the experiments, and wrote the manuscript. Liu W and Zhang H analyzed the data.

Author information

Qingyan Jia is now a PhD candidate at the Technical Institute of Physics and Chemistry, Chinese Academy of Sciences. His current research is focused on the preparation of nanomaterials for phototherapy of cancer.

Jiechao Ge is currently a full professor at the Technical Institute of Physics and Chemistry, Chinese Academy of Sciences. His research interests mainly concentrate on the synthesis of nanomaterials and their applications in phototheranostics and photocatalysts.

Qingyun Liu is currently a full professor at the College of Chemical and Environmental Engineering, Shandong University of Science and Technology. Her research interests mainly focus on the preparation of porphyrin/phthyana-inorganic nanocomposites and their application in photocatalysts.


Supplementary information

Supporting data are available in the online version of the paper.


[1] Lucky SS, Soo KC, Zhang Y. Nanoparticles in photodynamic therapy. Chem Rev, 2015, 115: 1990-2042 CrossRef PubMed Google Scholar

[2] Cheng L, Wang C, Feng L, et al. Functional nanomaterials for phototherapies of cancer. Chem Rev, 2014, 114: 10869-10939 CrossRef PubMed Google Scholar

[3] Chen G, Roy I, Yang C, et al. Nanochemistry and nanomedicine for nanoparticle-based diagnostics and therapy. Chem Rev, 2016, 116: 2826-2885 CrossRef PubMed Google Scholar

[4] Fan W, Huang P, Chen X. Overcoming the Achilles' heel of photodynamic therapy. Chem Soc Rev, 2016, 45: 6488-6519 CrossRef PubMed Google Scholar

[5] Jia Q, Ge J, Liu W, et al. Gold nanorod@silica-carbon dots as multifunctional phototheranostics for fluorescence and photoacoustic imaging-guided synergistic photodynamic/photothermal therapy. Nanoscale, 2016, 8: 13067-13077 CrossRef PubMed ADS Google Scholar

[6] Zhou Z, Song J, Nie L, et al. Reactive oxygen species generating systems meeting challenges of photodynamic cancer therapy. Chem Soc Rev, 2016, 45: 6597-6626 CrossRef PubMed Google Scholar

[7] Liu G, Qin H, Amano T, et al. Direct fabrication of the graphene-based composite for cancer phototherapy through graphite exfoliation with a photosensitizer. ACS Appl Mater Interfaces, 2015, 7: 23402-23406 CrossRef Google Scholar

[8] Idris NM, Gnanasammandhan MK, Zhang J, et al. In vivo photodynamic therapy using upconversion nanoparticles as remote-controlled nanotransducers. Nat Med, 2012, 18: 1580-1585 CrossRef PubMed Google Scholar

[9] Lucky SS, Muhammad Idris N, Li Z, et al. Titania coated upconversion nanoparticles for near-infrared light triggered photodynamic therapy. ACS Nano, 2015, 9: 191-205 CrossRef PubMed Google Scholar

[10] Yuan L, Lin W, Zheng K, et al. Far-red to near infrared analyte-responsive fluorescent probes based on organic fluorophore platforms for fluorescence imaging. Chem Soc Rev, 2013, 42: 622-661 CrossRef PubMed Google Scholar

[11] Li Y, Bai X, Xu M, et al. Photothermo-responsive Cu7S4@polymer nanocarriers with small sizes and high efficiency for controlled chemo/photothermo therapy. Sci China Mater, 2016, 59: 254-264 CrossRef Google Scholar

[12] Chen Y, Shi J. Mesoporous carbon biomaterials. Sci China Mater, 2015, 58: 241-257 CrossRef Google Scholar

[13] Naito K, Tachikawa T, Cui SC, et al. Single-molecule detection of airborne singlet oxygen. J Am Chem Soc, 2006, 128: 16430-16431 CrossRef PubMed Google Scholar

[14] Seidl C, Ungelenk J, Zittel E, et al. Tin tungstate nanoparticles: a photosensitizer for photodynamic tumor therapy. ACS Nano, 2016, 10: 3149-3157 CrossRef Google Scholar

[15] Hackenberg S, Scherzed A, Harnisch W, et al. Antitumor activity of photo-stimulated zinc oxide nanoparticles combined with paclitaxel or cisplatin in HNSCC cell lines. J Photochem Photobiol B-Biol, 2012, 114: 87-93 CrossRef PubMed Google Scholar

[16] Vankayala R, Kuo CL, Nuthalapati K, et al. Nucleus-targeting gold nanoclusters for simultaneous in vivo fluorescence imaging, gene delivery, and NIR-light activated photodynamic therapy. Adv Funct Mater, 2015, 25: 5934-5945 CrossRef Google Scholar

[17] Samia ACS, Chen X, Burda C. Semiconductor quantum dots for photodynamic therapy. J Am Chem Soc, 2003, 125: 15736-15737 CrossRef PubMed Google Scholar

[18] Ge J, Lan M, Zhou B, et al. A graphene quantum dot photodynamic therapy agent with high singlet oxygen generation. Nat Commun, 2014, 5: 4596 CrossRef PubMed ADS Google Scholar

[19] Ge J, Jia Q, Liu W, et al. Carbon dots with intrinsic theranostic properties for bioimaging, red-light-triggered photodynamic/photothermal simultaneous therapy in vitro and in vivo. Adv Healthcare Mater, 2016, 5: 665-675 CrossRef PubMed Google Scholar

[20] Ge J, Lan M, Liu W, et al. Graphene quantum dots as efficient, metal-free, visible -light-active photocatalysts. Sci China Mater, 2016, 59: 12-19 CrossRef Google Scholar

[21] Wang H, Yang X, Shao W, et al. Ultrathin black phosphorus nanosheets for efficient singlet oxygen generation. J Am Chem Soc, 2015, 137: 11376-11382 CrossRef PubMed Google Scholar

[22] Peng F, Cao Z, Ji X, et al. Silicon nanostructures for cancer diagnosis and therapy. Nanomedicine, 2015, 10: 2109-2123 CrossRef PubMed Google Scholar

[23] Peng F, Su Y, Zhong Y, et al. Silicon nanomaterials platform for bioimaging, biosensing, and cancer therapy. Acc Chem Res, 2014, 47: 612-623 CrossRef PubMed Google Scholar

[24] Teo BK, Sun XH. Silicon-based low-dimensional nanomaterials and nanodevices. Chem Rev, 2007, 107: 1454-1532 CrossRef PubMed Google Scholar

[25] He Y, Fan C, Lee ST. Silicon nanostructures for bioapplications. Nano Today, 2010, 5: 282-295 CrossRef Google Scholar

[26] McVey BFP, Tilley RD. Solution synthesis, optical properties, and bioimaging applications of silicon nanocrystals. Acc Chem Res, 2014, 47: 3045-3051 CrossRef PubMed Google Scholar

[27] Yue Y, Zheng K, Zhang L, et al. Origin of high elastic strain in amorphous silica nanowires. Sci China Mater, 2015, 58: 274-280 CrossRef Google Scholar

[28] Bryce BA, Reuter MC, Wacaser BA, et al. Contactless measurement of surface dominated recombination in gold- and aluminum-catalyzed silicon vapor–liquid–solid wires. Nano Lett, 2011, 11: 4282-4287 CrossRef PubMed ADS Google Scholar

[29] Sun Q, You Q, Pang X, et al. A photoresponsive and rod-shape nanocarrier: single wavelength of light triggered photothermal and photodynamic therapy based on AuNRs-capped and Ce6-doped mesoporous silica nanorods. Biomaterials, 2017, 122: 188-200 CrossRef PubMed Google Scholar

[30] Tang B, Niu J, Yu C, et al. Highly luminescent water-soluble CdTe nanowires as fluorescent probe to detect copper(II). Chem Commun, 2005, 281: 4184-4186 CrossRef PubMed Google Scholar

[31] Liu J, Fu TM, Cheng Z, et al. Syringe-injectable electronics. Nat Nanotech, 2015, 10: 629-636 CrossRef PubMed ADS Google Scholar

[32] Liu C, Gallagher JJ, Sakimoto KK, et al. Nanowire–bacteria hybrids for unassisted solar carbon dioxide fixation to value-added chemicals. Nano Lett, 2015, 15: 3634-3639 CrossRef PubMed ADS Google Scholar

[33] Peng F, Su Y, Wei X, et al. Silicon-nanowire-based nanocarriers with ultrahigh drug-loading capacity for in vitro and in vivo cancer therapy. Angew Chem Int Ed, 2013, 52: 1457-1461 CrossRef PubMed Google Scholar

[34] Heitsch AT, Fanfair DD, Tuan HY, et al. Solution−liquid−solid (SLS) growth of silicon nanowires. J Am Chem Soc, 2008, 130: 5436-5437 CrossRef PubMed Google Scholar

[35] Lu X, Hessel CM, Yu Y, et al. Colloidal luminescent silicon nanorods. Nano Lett, 2013, 13: 3101-3105 CrossRef PubMed ADS Google Scholar

[36] Lu X, Korgel BA. A single-step reaction for silicon and germanium nanorods. Chem Eur J, 2014, 20: 5874-5879 CrossRef PubMed Google Scholar

[37] Lu X, Anderson KJ, Boudjouk P, et al. Low temperature colloidal synthesis of silicon nanorods from isotetrasilane, neopentasilane, and cyclohexasilane. Chem Mater, 2015, 27: 6053-6058 CrossRef Google Scholar

[38] Song B, Zhong Y, Wu S, et al. One-dimensional fluorescent silicon nanorods featuring ultrahigh photostability, favorable biocompatibility, and excitation wavelength-dependent emission spectra. J Am Chem Soc, 2016, 138: 4824-4831 CrossRef PubMed Google Scholar

[39] Skrabalak SE, Wiley BJ, Kim M, et al. On the polyol synthesis of silver nanostructures: glycolaldehyde as a reducing agent. Nano Lett, 2008, 8: 2077-2081 CrossRef PubMed ADS Google Scholar

[40] Sun Y, Xia Y. Shape-controlled synthesis of gold and silver nanoparticles. Science, 2002, 298: 2176-2179 CrossRef PubMed ADS Google Scholar

[41] Chen J, Herricks T, Xia Y. Polyol synthesis of platinum nanostructures: control of morphology through the manipulation of reduction kinetics. Angew Chem Int Ed, 2005, 44: 2589-2592 CrossRef PubMed Google Scholar

[42] Yue H, Zhao Y, Ma X, et al. Ethylene glycol: properties, synthesis, and applications. Chem Soc Rev, 2012, 41: 4218-4244 CrossRef PubMed Google Scholar

[43] Baruwati B, Varma RS. Synthesis of monodispersed tantalum(V) oxide nanospheres by an ethylene glycol mediated route. Cryst Growth Des, 2010, 10: 3424-3428 CrossRef Google Scholar

[44] Zhou H, Liu Q, Liu W, et al. Template-free preparation of volvox-like CdxZn1−x S nanospheres with cubic phase for efficient photocatalytic hydrogen production. Chem Asian J, 2014, 9: 811-818 CrossRef PubMed Google Scholar

[45] Zhang Q, Cobley C, Au L, et al. Production of Ag nanocubes on a scale of 0.1 g per batch by protecting the NaHS-mediated polyol synthesis with argon. ACS Appl Mater Interfaces, 2009, 1: 2044-2048 CrossRef PubMed Google Scholar

[46] Hu JS, Ren LL, Guo YG, et al. Mass production and high photocatalytic activity of ZnS nanoporous nanoparticles. Angew Chem Int Ed, 2005, 44: 1269-1273 CrossRef PubMed Google Scholar

[47] Wang Y, Jiang X, Xia Y. A solution-phase, precursor route to polycrystalline SnO2 nanowires that can be used for gas sensing under ambient conditions. J Am Chem Soc, 2003, 125: 16176-16177 CrossRef PubMed Google Scholar

[48] Sun Y, Yin Y, Mayers BT, et al. Uniform silver nanowires synthesis by reducing AgNO3 with ethylene glycol in the presence of seeds and poly(vinyl pyrrolidone). Chem Mater, 2002, 14: 4736-4745 CrossRef Google Scholar

[49] Yin YX, Jiang LY, Wan LJ, et al. Polyethylene glycol-directed SnO2 nanowires for enhanced gas-sensing properties. Nanoscale, 2011, 3: 1802-1806 CrossRef PubMed ADS Google Scholar

[50] Jiang X, Wang Y, Herricks T, et al. Ethylene glycol-mediated synthesis of metal oxide nanowires. J Mater Chem, 2004, 14: 695 CrossRef Google Scholar

[51] Li CC, Cai WP, Cao BQ, et al. Mass synthesis of large, single-crystal Au nanosheets based on a polyol process. Adv Funct Mater, 2006, 16: 83-90 CrossRef Google Scholar

[52] Shao S, Qiu X, He D, et al. Low temperature crystallization of transparent, highly ordered nanoporous SnO2 thin films: application to room-temperature hydrogen sensing. Nanoscale, 2011, 3: 4283-4289 CrossRef PubMed ADS Google Scholar

[53] Cao AM, Hu JS, Liang HP, et al. Self-assembled vanadium pentoxide (V2O5) hollow microspheres from nanorods and their application in lithium-ion batteries. Angew Chem Int Ed, 2005, 44: 4391-4395 CrossRef PubMed Google Scholar

[54] Zhong LS, Hu JS, Liang HP, et al. Self-assembled 3D flowerlike iron oxide nanostructures and their application in water treatment. Adv Mater, 2006, 18: 2426-2431 CrossRef Google Scholar

[55] Ge J, Chen P, Jia Q, et al. A facile high-speed vibration milling method to mass production of water-dispersible silicon quantum dots for long-term cell imaging. RSC Adv, 2015, 5: 35291-35296 CrossRef Google Scholar

[56] Fernando KAS, Sahu S, Liu Y, et al. Carbon quantum dots and applications in photocatalytic energy conversion. ACS Appl Mater Interfaces, 2015, 7: 8363-8376 CrossRef Google Scholar

[57] Liu JH, Cao L, LeCroy GE, et al. Carbon “quantum” dots for fluorescence labeling of cells. ACS Appl Mater Interfaces, 2015, 7: 19439-19445 CrossRef Google Scholar

[58] Lin L. Synthesis and optical property of large-scale centimetres-long silicon carbide nanowires by catalyst-free CVD route under superatmospheric pressure conditions. Nanoscale, 2011, 3: 1582-1591 CrossRef PubMed ADS Google Scholar

[59] Xiao L, Gu L, Howell SB, et al. Porous silicon nanoparticle photosensitizers for singlet oxygen and their phototoxicity against cancer cells. ACS Nano, 2011, 5: 3651-3659 CrossRef PubMed Google Scholar

[60] Park JH, Gu L, von Maltzahn G, et al. Biodegradable luminescent porous silicon nanoparticles for in vivo applications. Nat Mater, 2009, 8: 331-336 CrossRef PubMed ADS Google Scholar

[61] Shiohara A, Prabakar S, Faramus A, et al. Sized controlled synthesis, purification, and cell studies with silicon quantum dots. Nanoscale, 2011, 3: 3364-3370 CrossRef PubMed ADS Google Scholar

[62] Kovalev D, Fujii M. Silicon nanocrystals: photosensitizers for oxygen molecules. Adv Mater, 2005, 17: 2531-2544 CrossRef Google Scholar

[63] Low SP, Voelcker NH, Canham LT, et al. The biocompatibility of porous silicon in tissues of the eye. Biomaterials, 2009, 30: 2873-2880 CrossRef PubMed Google Scholar

[64] Xing C, Liu L, Tang H, et al. Design guidelines for conjugated polymers with light-activated anticancer activity. Adv Funct Mater, 2011, 21: 4058-4067 CrossRef Google Scholar

[65] Yan L, Zhang Y, Xu B, et al. Fluorescent nanoparticles based on AIE fluorogens for bioimaging. Nanoscale, 2016, 8: 2471-2487 CrossRef PubMed ADS Google Scholar

[66] Zhang X, Zhang X, Wang S, et al. Surfactant modification of aggregation-induced emission material as biocompatible nanoparticles: facile preparation and cell imaging. Nanoscale, 2013, 5: 147-150 CrossRef PubMed ADS Google Scholar

[67] Ge J, Jia Q, Liu W, et al. Red-emissive carbon dots for fluorescent, photoacoustic, and thermal theranostics in living mice. Adv Mater, 2015, 27: 4169-4177 CrossRef PubMed Google Scholar

[68] Mathiyazhakan M, Upputuri PK, Sivasubramanian K, et al. In situ synthesis of gold nanostars within liposomes for controlled drug release and photoacoustic imaging. Sci China Mater, 2016, 59: 892-900 CrossRef Google Scholar

[69] Mou J, Chen Y, Ma M, et al. Facile synthesis of liposome/Cu2−xS-based nanocomposite for multimodal imaging and photothermal therapy. Sci China Mater, 2015, 58: 294-301 CrossRef Google Scholar

[70] Zhang LJ, Bian J, Bao LL, et al. Photosensitizing effectiveness of a novel chlorin-based photosensitizer for photodynamic therapy in vitro and in vivo. J Cancer Res Clin Oncol, 2014, 140: 1527-1536 CrossRef PubMed Google Scholar

[71] Hao Y, Zhang B, Zheng C, et al. Multifunctional nanoplatform for enhanced photodynamic cancer therapy and magnetic resonance imaging. Colloids Surfs B-Biointerfaces, 2017, 151: 384-393 CrossRef PubMed Google Scholar

  • Figure 1

    Preparation of SiNRs. (a) Schematic illustration of EG-mediated synthesis of SiNRs. TEM images of the as-prepared SiNRs with different SiCl4 to EG molar ratios: (b) 1:600, (c) 1:400, and (d) 1:200. High-resolution TEM (HRTEM) images of the as-prepared SiNRs with different SiCl4 to EG molar ratios: (e) 1:600, (f) 1:400, and (g) 1:200.

  • Figure 2

    Structural characterization of SiNRs. (a) XRD pattern of the as-prepared SiNRs. (b) FTIR spectra of the as-prepared SiNRs. (c) XPS of the as-prepared SiNRs and Si 2p. (d) Nitrogen adsorption/desorption isotherm and pore-size distribution curve of the SiNRs.

  • Figure 3

    Photochemical property of SiNRs. (a) Absorption spectra of SiNRs. (b) Normalized photoluminescent (PL) emission spectra of SiNRs. (c) pH-dependent PL emission of the as-prepared SiNRs (pH 4‒11). (d) Temporal evolution of the PL spectra of the as-prepared SiNRs in air under cryopreservation. (e) Time-dependent stability comparison of fluorescence signals of HeLa cells labeled by FITC (left) and SiNRs (right) under irradiation of 488-nm laser.

  • Figure 4

    Photophysical property of the SiNRs. (a) The electron spin resonance (ESR) signals of spin traps reacting with 1O2 obtained upon 635-nm laser irradiation of SiNR solution for 10 min in the presence of 2,2,6,6-tetramethylpiperidine (TEMP). (b) Photodegradation of Na2-ADPA with MB under 635-nm laser irradiation. (c) Photodegradation of Na2-ADPA with SiNRs under 635-nm laser irradiation. (d) Decay curves of Na2-ADPA absorption at 378 nm as a function of time in the presence of SiNRs and MB upon 635-nm laser irradiation.

  • Figure 5

    In vitro fluorescence imaging and PDT. (a) Confocal microscopic images of HeLa cells incubated with SiNRs (400 µg mL−1) for 4 h at bright field and exicitation at 488 nm. Scale bars: 20 µm. (b) Relative viability of HeLa cells incubated with various concentrations of SiNRs under dark or irradiation using a 635-nm laser (50 mW cm−2) for 20 min. (c) Time-dependent confocal images of calcein AM (green)/ PI (red)-stained HeLa cells incubated with 400 µg mL−1 SiNRs under 635-nm laser irradiation (50 mW cm−2) for different times (0‒20min). Scale bars: 100 µm.

Copyright 2019 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有