Skip to main content
Log in

Gold nanorods crosslinking PNIPAM hydrogels via dynamic Au-thiolate interaction with stretchable, adhesive, self-healing, and photothermal properties

  • Original Paper
  • Published:
Gold Bulletin Aims and scope Submit manuscript

Abstract

Gold nanorod (AuNR) nanocomposite hydrogels have attracted increasing attention due to the photothermal effect of AuNRs. However, a facile strategy that avoids multi-step surface modification for synthesis of AuNR crosslinkers is still a critical challenge. Here, AuNRs crosslinking PNIPAM hydrogels were prepared by polymerization of NIPAM with N,N′-bis(acryloyl)cystamine (BACA)-modified AuNRs as crosslinkers. BACA contains a disulfide bond in the structure. Dynamic and reversible Au-thiolate bonding was formed by directly mixing AuNRs and BACA to facilely prepare AuNR crosslinkers before hydrogel formation. The addition of AuNRs gives hydrogels their photothermal effect and remarkable mechanical behaviors. Hydrogels could repeatedly adhere to the surface of pigskin, metal, plastic, and glass with a relatively stable adhesion. The damaged hydrogels heal within 2 min with near-infrared (NIR) laser (808 nm, 300 mW∙cm−2) irradiation. This work provides a line of thinking for improvement of PNIPAM hydrogels, making them promising for further applications in biomedicine.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Haraguchi K, Takehisa T (2002) Nanocomposite hydrogels: a unique organic-inorganic network structure with extraordinary mechanical, optical, and swelling/de-swelling properties. Adv Mater 14(16):1120–1124

    Article  CAS  Google Scholar 

  2. Merino S, Martin C, Kostarelos K, Prato M, Vazquez E (2015) Nanocomposite hydrogels: 3D polymer-nanoparticle synergies for on-demand drug delivery. ACS Nano 9(5):4686–4697

    Article  CAS  Google Scholar 

  3. Thoniyot P, Tan MJ, Karim AA, Young DJ, Loh XJ (2015) Nanoparticle-hydrogel composites: concept, design, and applications of these promising, multi-functional materials. Adv Sci 2(1–2):1400010

    Article  Google Scholar 

  4. Lv SW, Liu Y, Xie M, Wang J, Yan XW, Li Z, Dong WG, Huang WH (2016) Near-infrared light-responsive hydrogel for specific recognition and photothermal site-release of circulating tumor cells. ACS Nano 10(6):6201–6210

    Article  CAS  Google Scholar 

  5. Labouret T, Audibert JF, Pansu RB, Palpant B (2015) Plasmon-assisted production of reactive oxygen species by single gold nanorods. Small 11(35):4475–4479

    Article  CAS  Google Scholar 

  6. Jayabal S, Sathiyamurthi R, Ramaraj R (2014) Selective sensing of Hg2+ ions by optical and colorimetric methods using gold nanorods embedded in a functionalized silicate sol-gel matrix. J Mater Chem A 2(23):8918–8925

    Article  CAS  Google Scholar 

  7. Shiotani A, Mori T, Niidome T, Niidome Y, Katayama Y (2007) Stable incorporation of gold nanorods into N-isopropylacrylamide hydrogels and their rapid shrinkage induced by near-infrared laser irradiation. Langmuir 23(7):4012–4018

    Article  CAS  Google Scholar 

  8. Highley CB, Kim M, Lee D, Burdick JA (2016) Near-infrared light triggered release of molecules from supramolecular hydrogel-nanorod composites. Nanomedicine 11(12):1579–1590

    Article  CAS  Google Scholar 

  9. Qu Y, Chu B, Peng JR, Liao JF, Qi TT, Shi K, Zhang XN, Wei YQ, Qian ZY (2015) A biodegradable thermo-responsive hybrid hydrogel: therapeutic applications in preventing the post-operative recurrence of breast cancer. NPG Asia Mater 7:e207

    Article  CAS  Google Scholar 

  10. Chung S, Lee H, Kim HS, Kim MG, Lee LP, Lee JY (2016) Transdermal thiol-acrylate polyethylene glycol hydrogel synthesis using near infrared light. Nanoscale 8(29):14213–14221

    Article  CAS  Google Scholar 

  11. Jiang SR, Wang K, Dai Y, Zhang XJ, Xia F (2019) Near-infrared light-triggered dual drug release using gold nanorod-embedded thermosensitive nanogel-crosslinked hydrogels. Macromol Mater Eng 304(7):1900087

    Article  Google Scholar 

  12. Kurdtabar M, Baghestani G, Bardajee GR (2019) Development of a novel thermo-responsive hydrogel-coated gold nanorods as a drug delivery system. Gold Bull 52(1):9–17

    Article  CAS  Google Scholar 

  13. Kozlovskaya V, Kharlampieva E, Khanal BP, Manna P, Zubarev ER, Tsukruk VV (2008) Ultrathin layer-by-layer hydrogels with incorporated gold nanorods as pH-sensitive optical materials. Chem Mat 20(24):7474–7485

    Article  CAS  Google Scholar 

  14. Jiang CY, Qian Y, Gao QA, Dong JA, Qian WP (2010) In situ controllable preparation of gold nanorods in thermo-responsive hydrogels and their application in surface enhanced Raman scattering. J Mater Chem 20(39):8711–8716

    Article  CAS  Google Scholar 

  15. Jin X, Jiang J, Liu MH (2016) Reversible plasmonic circular dichroism via hybrid supramolecular gelation of achiral gold nanorods. ACS Nano 10(12):11179–11186

    Article  CAS  Google Scholar 

  16. Nguyen CT, Kasi RM (2015) Nanocomposite hydrogels based on liquid crystalline brush-like block copolymer-Au nanorods and their application in H2O2 detection. Chem Commun 51(61):12174–12177

    Article  CAS  Google Scholar 

  17. Lee H, Chung S, Kim MG, Lee LP, Lee JY (2016) Near-infrared-light-assisted photothermal polymerization for transdermal hydrogelation and cell delivery. Adv Healthc Mater 5(13):1638–1645

    Article  CAS  Google Scholar 

  18. Zeng JF, Shi DJ, Gu YL, Kaneko T, Zhang L, Zhang HJ, Kaneko D, Chen MQ (2019) Injectable and near-infrared-responsive hydrogels encapsulating dopamine-stabilized gold nanorods with long photothermal activity controlled for tumor therapy. Biomacromolecules 20(9):3375–3384

    Article  CAS  Google Scholar 

  19. Qin HL, Zhang T, Li HN, Cong HP, Antonietti M, Yu SH (2017) Dynamic Au-thiolate interaction induced rapid self-healing nanocomposite hydrogels with remarkable mechanical behaviors. Chem 3(4):691–705

    Article  CAS  Google Scholar 

  20. Gonzalez-Rubio G, Diaz-Nunez P, Rivera A, Prada A, Tardajos G, Gonzalez-Izquierdo J, Banares L, Llombart P, Macdowell LG, Palafox MA, Liz-Marzan LM, Pena-Rodriguez O, Guerrero-Martinez A (2017) Femtosecond laser reshaping yields gold nanorods with ultranarrow surface plasmon resonances. Science 358(6363):640–644

    Article  CAS  Google Scholar 

  21. Sun ZF, Yamauchi Y, Araoka F, Kim YS, Bergueiro J, Ishida Y, Ebina Y, Sasaki T, Hikima T, Aida T (2018) An anisotropic hydrogel actuator enabling earthworm-like directed peristaltic crawling. Angew Chem Int Edit 57(48):15772–15776

    Article  CAS  Google Scholar 

  22. Qin HL, Zhang T, Li N, Cong HP, Yu SH (2019) Anisotropic and self-healing hydrogels with multi-responsive actuating capability. Nat Commun 10:2202

    Article  Google Scholar 

  23. Chen CR, Qin HL, Cong HP, Yu SH (2019) A highly stretchable and real-time healable supercapacitor. Adv Mater 31(19):1900573

    Article  Google Scholar 

  24. Wu BS, Ye YC, Li Z, Liu ZY, Pei YY, Chen CR, Qin HL, Liu HH (2019) Fabrication and property of electric-induced self-healing nanocomposite hydrogels. Acta Polym Sin 50(9):932–938

    Google Scholar 

  25. Ji XH, Song XN, Li J, Bai YB, Yang WS, Peng XG (2007) Size control of gold nanocrystals in citrate reduction: the third role of citrate. J Am Chem Soc 129(45):13939–13948

    Article  CAS  Google Scholar 

  26. Zhao X, Yang CX, Chen LG, Yan XP (2017) Dual-stimuli responsive and reversibly activatable theranostic nanoprobe for precision tumor-targeting and fluorescence-guided photothermal therapy. Nat Commun 8:14998

    Article  CAS  Google Scholar 

  27. Li DJ, Gao HC, Li MS, Chen GX, Guan LY, He MH, Tian JF, Cao R (2020) Nanochitin/metal ion dual reinforcement in synthetic polyacrylamide network-based nanocomposite hydrogels. Carbohydr Polym 236:116061

    Article  CAS  Google Scholar 

  28. Xing RT, Liu K, Jiao TF, Zhang N, Ma K, Zhang RY, Zou QL, Ma GH, Yan XH (2016) An injectable self-assembling collagen-gold hybrid hydrogel for combinatorial antitumor photothermal/photodynamic therapy. Adv Mater 28(19):3669–3676

    Article  CAS  Google Scholar 

  29. Rajabi N, Kharaziha M, Emadi R, Zarrabi A, Mokhtari H, Salehi S (2020) An adhesive and injectable nanocomposite hydrogel of thiolated gelatin/gelatin methacrylate/Laponite (R) as a potential surgical sealant. J Colloid Interface Sci 564:155–169

    Article  CAS  Google Scholar 

  30. Rose S, Prevoteau A, Elziere P, Hourdet D, Marcellan A, Leibler L (2014) Nanoparticle solutions as adhesives for gels and biological tissues. Nature 505(7483):382–385

    Article  CAS  Google Scholar 

  31. Zhang CL, Cao FH, Wang JL, Yu ZL, Ge J, Lu Y, Wang ZH, Yu SH (2017) Highly stimuli-responsive Au nanorods/poly(N-isopropylacrylamide) (PNIPAM) composite hydrogel for smart switch. ACS Appl Mater Interfaces 9(29):24857–24863

    Article  CAS  Google Scholar 

  32. Goncalves DPN, Rodriguez RD, Kurth T, Bray LJ, Binner M, Jungnickel C, Gur FN, Poser SW, Schmidt TL, Zahn DRT, Androutsellis-Theotokis A, Schlierf M, Werner C (2017) Enhanced targeting of invasive glioblastoma cells by peptide-functionalized gold nanorods in hydrogel-based 3D cultures. Acta Biomater 58:12–25

    Article  CAS  Google Scholar 

  33. Zhang JY, Du P, Xu DY, Li Y, Peng WC, Zhang GL, Zhang FB, Fan XB (2016) Near-infrared responsive MoS2/poly(N-isopropylacrylamide) hydrogels for remote light-controlled microvalves. Ind Eng Chem Res 55(16):4526–4531

    Article  CAS  Google Scholar 

  34. Zhao X, Liang YP, Huang Y, He JH, Han Y, Guo BL (2020) Physical double-network hydrogel adhesives with rapid shape adaptability, fast self-healing, antioxidant and NIR/pH stimulus-responsiveness for multidrug-resistant bacterial infection and removable wound dressing. Adv Funct Mater 30:1910748

    Article  CAS  Google Scholar 

Download references

Funding

This work was financially supported by the National Natural Science Foundation of China (No. 51703209).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Xiaojin Zhang.

Ethics declarations

Conflict of interest

The authors declare that they have no competing interest.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

ESM 1

(DOCX 2660 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lin, S., Jiang, S., Zhang, Y. et al. Gold nanorods crosslinking PNIPAM hydrogels via dynamic Au-thiolate interaction with stretchable, adhesive, self-healing, and photothermal properties. Gold Bull 54, 59–67 (2021). https://doi.org/10.1007/s13404-021-00293-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13404-021-00293-6

Keywords

Navigation