Fabrication of novel bifunctional nanohybrid based on layered rare-earth hydroxide with magnetic and fluorescent properties

Abstract

We demonstrate the fabrication of a novel magnetic nanohybrid involving the drug molecule 5-aminolevulinic acid (5-ALA) intercalated Gd–Eu layered rare-earth hydroxide (LRH) coated on magnesium ferrite particles (MgFe₂O₄). The structure, thermostability, morphology, luminescence properties, cytotoxic effect and magnetism are investigated. The 5-ALA intercalated composite may correspond to a monolayered vertical arrangement, and the thermal stability of organics is enhanced after intercalation. The LRH precursor shows red emission of Eu³⁺ and the maximum emission peak of the composite is at 451 nm, corresponding to the blue emission. The detection of drug molecules can be realized through the change of luminescence. The magnetic nanohybrid shows strong magnetic sensitivity, which provides an easy and efficient way to separate 5-ALA-MgFe₂O₄@LGd_0.95H:Eu_0.05 particles from a sol or a suspension system and to carry drugs to targeted locations under an external magnetic field. The cytotoxic effect of MgFe₂O₄@LRH is observed with a sulforhodamine B (SRB) colorimetric assay, which has low cytotoxic effects on selected cells. The fabrication of novel bifunctional drug carriers based on LRH with magnetic and fluorescent properties has potential applications in drug detection and drug delivery.

Keywords

layered rare-earth hydroxide / magnesium ferrite / nanohybrid / magnetism / luminescence

References

[1] Slowing I I, Vivero-Escoto J L, Wu C W, . Mesoporous silica nanoparticles as controlled release drug delivery and gene transfection carriers. Advanced Drug Delivery Reviews, 2008, 60(11): 1278–1288

[2] Wang Y, Zhao Q, Han N, . Mesoporous silica nanoparticles in drug delivery and biomedical applications. Nanomedicine: Nanotechnology, Biology and Medicine, 2015, 11(2): 313–327

[3] Karimi M, Solati N, Amiri M, . Carbon nanotubes part I: preparation of a novel and versatile drug-delivery vehicle. Expert Opinion on Drug Delivery, 2015, 12(7): 1071–1087

[4] Wang C J, Chen T C, Lin J H, . One-step preparation of hydrophilic carbon nanofiber containing magnetic Ni nanoparticles materials and their application in drug delivery. Journal of Colloid and Interface Science, 2015, 440: 179–188

[5] Geng F, Matsushita Y, Ma R, . General synthesis and structural evolution of a layered family of Ln₈(OH)₂₀Cl₄·nH₂O (Ln= Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y). Journal of the American Chemical Society, 2008, 130(48): 16344–16350

[6] Gu Q Y, Qiu X, Liu J J, . Nanostructured layered terbium hydroxide containing NASIDs: In vitro physicochemical and biological evaluations. Journal of Nanoscience and Nanotechno-logy, 2018, 18(8): 5320–5326

[7] Arruebo M. Drug delivery from structured porous inorganic materials. Wiley Interdisciplinary Reviews: Nanomedicine and Nanobiotechnology, 2012, 4(1): 16–30

[8] Ju R, Gu Q. Biohybrid based on layered terbium hydroxide and applications as drug carrier and biological fluorescence probe. Applied Organometallic Chemistry, 2018, 32(1): e3926

[9] Saifullah B, Hussein M Z B. Inorganic nanolayers: structure, preparation, and biomedical applications. International Journal of Nanomedicine, 2015, 10: 5609–5633

[10] Gu Q, Chen W, Duan F, . Fabrication of a nano-drug delivery system based on layered rare-earth hydroxides integrating drug-loading and fluorescence properties. Dalton Transactions, 2016, 45(30): 12137–12143

[11] Choy J H, Oh J M, Choi S J. Layered double hydroxides as controlled release materials. Comprehensive Biomaterials II, 2017, 4: 705–718

[12] Hesse D, Badar M, Bleich A, . Layered double hydroxides as efficient drug delivery system of ciprofloxacin in the middle ear: an animal study in rabbits. Journal of Materials Science: Materials in Medicine, 2013, 24(1): 129–136

[13] Choy J H, Jung J S, Oh J M, . Layered double hydroxide as an efficient drug reservoir for folate derivatives. Biomaterials, 2004, 25(15): 3059–3064

[14] Frey S T, Guilmet S L, Egan R G III, . Immobilization of the aminopeptidase from Aeromonas proteolytica on Mg²⁺/Al³⁺ layered double hydroxide particles. ACS Applied Materials & Interfaces, 2010, 2(10): 2828–2832

[15] Tyner K M, Schiffman S R, Giannelis E P. Nanobiohybrids as delivery vehicles for camptothecin. Journal of Controlled Release, 2004, 95(3): 501–514

[16] Hussein M Z, Nasir N M, Yahaya A H J. Controlled release compound based on metanilate-layered double hydroxide nanohybrid. Journal of Nanoscience and Nanotechnology, 2008, 8(11): 5921–5928

[17] Pan D, Zhang H, Zhang T, . A novel organic–inorganic microhybrids containing anticancer agent doxifluridine and layered double hydroxides: Structure and controlled release properties. Chemical Engineering Science, 2010, 65(12): 3762–3771

[18] Choi S J, Oh J M, Choy J H. Safety aspect of inorganic layered nanoparticles: size-dependency in vitro and in vivo. Journal of Nanoscience and Nanotechnology, 2008, 8(10): 5297–5301

[19] bin Hussein M Z, Zainal Z, Yahaya A H, . Controlled release of a plant growth regulator, α-naphthaleneacetate from the lamella of Zn–Al-layered double hydroxide nanocomposite. Journal of Controlled Release, 2002, 82(2–3): 417–427

[20] Khan A I, Lei L, Norquist A J, . Intercalation and controlled release of pharmaceutically active compounds from a layered double hydroxide. Chemical Communications, 2001, (22): 2342–2343

[21] Zhang K, Xu Z P, Lu J, . Potential for layered double hydroxides-based, innovative drug delivery systems. International Journal of Molecular Sciences, 2014, 15(5): 7409–7428

[22] Mei X, Ma J, Bai X, . A bottom-up synthesis of rare-earth-hydrotalcite monolayer nanosheets toward multimode imaging and synergetic therapy. Chemical Science, 2018, 9(25): 5630–5639

[23] Geng F, Ma R, Sasaki T. Anion-exchangeable layered materials based on rare-earth phosphors: unique combination of rare-earth host and exchangeable anions. Accounts of Chemical Research, 2010, 43(9): 1177–1185

[24] Gu Q, Su F, Ma S, . Controllable luminescence of layered rare-earth hydroxide composites with a fluorescent molecule: blue emission by delamination in formamide. Chemical Communications, 2015, 51(13): 2514–2517

[25] Gu Q, Wu Y, Yu S. Organic–inorganic luminescent composites obtained by the intercalation of organic dyes into the layered rare-earth hydroxides. Inorganica Chimica Acta, 2019, 487: 162–168

[26] Gándara F, Perles J, Snejko N, . Layered rare-earth hydroxides: a class of pillared crystalline compounds for intercalation chemistry. Angewandte Chemie, 2006, 45(47): 7998–8001

[27] Gandara F, Puebla E G, Iglesias M, . Controlling the structure of arenedisulfonates toward catalytically active materials. Chemistry of Materials, 2009, 21(4): 655–661

[28] Li W, Gu Q, Su F, . Intercalation of azamacrocyclic crown ether into layered rare-earth hydroxide (LRH): secondary host–guest reaction and efficient heavy metal removal. Inorganic Chemistry, 2013, 52(24): 14010–14017

[29] Wei P R, Cheng S H, Liao W N, . Synthesis of chitosan-coated near-infrared layered double hydroxide nanoparticles for in vivo optical imaging. Journal of Materials Chemistry, 2012, 22(12): 5503–5513

[30] Evans D G, Duan X. Preparation of layered double hydroxides and their applications as additives in polymers, as precursors to magnetic materials and in biology and medicine. Chemical Communications, 2006, (5): 485–496

[31] Zhang H, Pan D, Duan X. Synthesis, characterization, and magnetically controlled release behavior of novel core–shell structural magnetic ibuprofen-intercalated LDH nanohybrids. The Journal of Physical Chemistry C, 2009, 113(28): 12140–12148

[32] Gu Q, Sun Y, Chu N, . Intercalation of amino acids into Eu³⁺-doped layered gadolinium hydroxide and quenching of Eu³⁺ luminescence. European Journal of Inorganic Chemistry, 2012, 2012(28): 4407–4412

[33] Cavani F, Trifirò F, Vaccari A. Hydrotalcite-type anionic clays: Preparation, properties and applications. Catalysis Today, 1991, 11(2): 173–301

[34] Wu X, Li J G, Ping D H, . Structure characterization and photoluminescence properties of (Y_0.95−xGd_xEu_0.05)₂O₃ red phosphors converted from layered rare-earth hydroxide (LRH) nanoflake precursors. Journal of Alloys and Compounds, 2013, 559: 188–195

[35] Pérez-Ramírez J, Mul G, Kapteijn F, . In situ investigation of the thermal decomposition of Co–Al hydrotalcite in different atmospheres. Journal of Materials Chemistry, 2001, 11(3): 821–830

Acknowledgements

This work was supported by the Youth Top-notch Talent Training Program for Universities and Colleges under Beijing Municipality (CIT&TCD201804035), the National Natural Science Foundation of China (Grant No. 21601016), the Project of Construction of Innovative Teams and Teacher Career Development for Universities and Colleges under Beijing Municipality (IDHT20180508), and the Construction of Scientific Research Platform (2018XK002).

RIGHTS & PERMISSIONS

2020 Higher Education Press