Abstract
Halloysite (HNT) is a natural inorganic mineral that has many applications in manufacturing. This review (with 192 references) covers (a) the chemical properties of halloysites, (b) the effects of alkali and acid etching on the loading capacity and the release behavior of halloysites, (c) the use of halloysite nanotubes in analytical sciences and drug delivery, and (d) recent trends in the preparation of magnetic HNTs. Synthetic methods such as co-precipitation, thermal decomposition, and solvothermal method are discussed, with emphasis on optimal magnetization. In the analytical field, recent advancements are summarized in terms of applications of HNT-nanocomposites for extraction and detection of heavy metal ions, dyes, organic pollutants, and biomolecules. The review also covers methods for synthesizing molecularly imprinted polymer-modified HNTs and magnetic HNTs. With respect to drug delivery, the toxicity, techniques for drug loading and the various classes of drug-halloysite nanocomposites are discussed. This review gives a general insight on the utilization of HNT in analytical determination and drug delivery systems which may be useful for researchers to generate new ideas.
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References
He H et al (2013) Carbon nanotubes: applications in pharmacy and medicine. Biomed Res Int 2013(578290):1–12
Wu X, Han Y, Zhang X (2017) Spirally structured conductive composites for highly stretchable. Robust Conductors and Sensors 9(27):23007–23016
Baughman RH, Zakhidov AA, de Heer WA (2002) Carbon nanotubes--the route toward applications. Science 297:787–792
Tenne R (2013) Recent advances in the research of inorganic nanotubes and fullerene-like nanoparticles. Front Phys 9:370–377
Rawtani D, Agrawal YK (2012) Halloysite as support matrices: a review. Emerging Materials Research 1:212–220
Lvov Y, Wang W, Zhang L, Fakhrullin R (2016) Halloysite clay nanotubes for loading and sustained release of functional compounds. Adv Mater 28:1227–1250
Mousa MH, Dong Y, Davies IJ (2016) Recent advances in bionanocomposites: preparation, properties, and applications. Int J Polym Mater Polym Biomater 65:225–254
Hanif M et al (2016) Halloysite nanotubes as a new drug-delivery system: a review. Clay Miner 51:469–477
Zhang Y, Tang A, Yang H, Ouyang J (2016) Applications and interfaces of halloysite nanocomposites. Appl Clay Sci 119:8–17
Lvov YM, Shchukin DG, Mohwald H, Price RR (2008) Halloysite clay nanotubes for controlled release of protective agents. ACS Nano 2:814–820
Lvov Y, Aerov A, Fakhrullin R (2014) Clay nanotube encapsulation for functional biocomposites. Adv Colloid Interf Sci 207:189–198
Liu M et al (2016) Polysaccharide-halloysite nanotube composites for biomedical applications: a review. Clay Miner 51:457–467
Liu R, Zhang B, Mei D, Zhang H, Liu J (2011) Adsorption of methyl violet from aqueous solution by halloysite nanotubes. Desalination 268:111–116
Yuan P, Tan D, Annabi-Bergaya F (2015) Properties and applications of halloysite nanotubes: recent research advances and future prospects. Appl Clay Sci 112-113:75–93
Churchman GJ, Davy TJ, Aylmore LAG, Gilkes RJ, Self PG (1995) Characteristics of fine pores in some halloysites. Clay Miner 30:89–98
Tully J, Fakhrullin R, Lvov Y (2015) Halloysite clay nanotube composites with sustained release of chemicals. Nanomaterials and Nanoarchitectures 139:87–118
Lvov YM, DeVilliers MM, Fakhrullin RF (2016) The application of halloysite tubule nanoclay in drug delivery. Expert Opin Drug Deliv 13:977–986
Liu HY, Du L, Zhao YT, Tian WQ (2015) In vitro hemocompatibility and cytotoxicity evaluation of halloysite nanotubes for biomedical application. J Nanomater 16:1–9
Hughes AD, King MR (2010) Use of naturally occurring Halloysite nanotubes for enhanced capture of flowing cells. Langmuir 26:12155–12164
Fakhrullin RF, Lvov YM (2016) Halloysite clay nanotubes for tissue engineering. Nanomedicine 11:2243–2246
Abdullayev E, Lvov Y (2013) Halloysite clay nanotubes as a ceramic “skeleton” for functional biopolymer composites with sustained drug release. J Mater Chem B 1:2894–2903
Yu L, Wang H, Zhang Y, Zhang B, Liu J (2016) Recent advances in halloysite nanotube derived composites for water treatment. Environ Sci: Nano 3:28–44
Pasbakhsh P, Churchman GJ, Keeling JL (2013) Characterisation of properties of various halloysites relevant to their use as nanotubes and microfibre fillers. Appl Clay Sci 74:47–57
Fizir M et al (2017) Polymer grafted-magnetic halloysite nanotube for controlled and sustained release of cationic drug. J Colloid Interface Sci 505:476–488
Lvov Y, Abdullayev E (2013) Functional polymer–clay nanotube composites with sustained release of chemical agents. Prog Polym Sci 38:1690–1719
Liu M, Jia Z, Jia D, Zhou C (2014) Recent advance in research on halloysite nanotubes-polymer nanocomposite. Prog Polym Sci 39:1498–1525
Rawtani D, Agrawal YK (2012) Multifarious applications of halloysite nanotubes: a review. Rev Adv Mater Sci 30:282–295
Peixoto AF, Fernandes AC, Pereira C, Pires J, Freire C (2016) Physicochemical characterization of organosilylated halloysite clay nanotubes. Microporous Mesoporous Mater 219:145–154
Yang J et al (2016) Enhanced therapeutic efficacy of doxorubicin for breast Cancer using chitosan oligosaccharide-modified Halloysite nanotubes. ACS Appl Mater Interfaces 8:26578–26590
Zhang H et al (2015) Selective modification of Halloysite nanotubes with 1-Pyrenylboronic acid: a novel fluorescence probe with highly selective and sensitive response to Hyperoxide. ACS Appl Mater Interfaces 7:23805–23811
Bordeepong S, Bhongsuwan D, Pungrassami T, Bhongsuwan T (2011) Characterization of halloysite from Thung Yai District, Nakhon Si Thammarat Province, in Southern Thailand. J Sci Technol 33(5):599–607
Abdullayev E, Joshi A, Wei W, Zhao Y, Lvov Y (2012) Enlargement of Halloysite clay nanotube lumen by selective etching of aluminum oxide. ACS Nano 6:7216–7226
Zhang A-B et al (2012) Effects of acid treatment on the physico-chemical and pore characteristics of halloysite. Colloids Surf A Physicochem Eng Asp 396:182–188
White RD, Bavykin DV, Walsh FC (2012) The stability of halloysite nanotubes in acidic and alkaline aqueous suspensions. Nanotechnology 23:065705
Garcia-Garcia D et al (2017) Characterization of selectively etched halloysite nanotubes by acid treatment. Appl Surf Sci 422:616–625
Wang Q, Zhang J, Zheng Y, Wang A (2014) Adsorption and release of ofloxacin from acid- and heat-treated halloysite. Colloids Surf B: Biointerfaces 113:51–58
Wang Q, Zhang J, Wang A (2013) Alkali activation of halloysite for adsorption and release of ofloxacin. Appl Surf Sci 287:54–61
Kiani G (2014) High removal capacity of silver ions from aqueous solution onto Halloysite nanotubes. Appl Clay Sci 90:159–164
Mellouk S et al (2009) Intercalation of halloysite from Djebel Debagh (Algeria) and adsorption of copper ions. Appl Clay Sci 44:230–236
Luo P et al (2010) Study on the adsorption of neutral red from aqueous solution onto halloysite nanotubes. Water Res 44:1489–1497
Zhao Y, Abdullayev E, Vasiliev A, Lvov Y (2013) Halloysite nanotubule clay for efficient water purification. J Colloid Interface Sci 406:121–129
Li J, Wen F, Pan L, Liu Z, Dong Y (2012) Removal of radiocobalt ions from aqueous solutions by natural halloysite nanotubes. J Radioanal Nucl Chem 295:431–438
Zhang W, Zuo XD, Wu CW (2015) Synthesis and magnetic properties of carbon nanotube-iron oxide nanoparticle composites for hyperthermia: a review. Rev Adv Mater Sci 40:165–176
Xie Y, Qian D, Wu D, Ma X (2011) Magnetic halloysite nanotubes/iron oxide composites for the adsorption of dyes. Chem Eng J 168:959–963
Pan J et al (2011) Selective recognition of 2,4,6-Trichlorophenol by molecularly imprinted polymers based on magnetic Halloysite nanotubes composites. J Phys Chem C 115:5440–5449
Sun S, Zeng H (2002) Size-controlled synthesis of magnetite nanoparticles. J Am Chem Soc 124:8204–8205
Pan J et al (2012) Switched recognition and release ability of temperature responsive molecularly imprinted polymers based on magnetic halloysite nanotubes. J Mater Chem 22:17167–17175
He J et al (2016) Magnetic organic–inorganic nanocomposite with ultrathin imprinted polymers via an in situ surface-initiated approach for specific separation of chloramphenicol. RSC Adv 6:70383–70393
Tian X et al (2016) Cr(VI) reduction and immobilization by novel carbonaceous modified magnetic Fe3O4/halloysite nanohybrid. J Hazard Mater 309:151–160
Liu C et al (2017) In Situ reduced and assembled three-dimensional graphene aerogel for efficient dye removal. J Alloys Compd 714:522–529
Jia Z, Li Z, Ni T, Li S (2017) Adsorption of low-cost absorption materials based on biomass (Cortaderia selloana flower spikes) for dye removal: kinetics, isotherms and thermodynamic studies. J Mol Liq 229:285–292
Peng Q, Liu M, Zheng J, Zhou C (2015) Adsorption of dyes in aqueous solutions by chitosan–halloysite nanotubes composite hydrogel beads. Microporous Mesoporous Mater 201:190–201
Konicki W, Hehniniak A, Arabczyk W, Mijowska E (2017) Removal of anionic dyes using magnetic Fe@graphite core-shell nanocomposite as an adsorbent from aqueous solutions. J Colloid Interface Sci 497:155–164
da Silva LA et al (2017) Methylene blue oxidation over iron oxide supported on activated carbon derived from peanut hulls. Catal Today 289:237–248
Dutta DP, Venugopalan R, Chopade S (2017) Manipulating carbon nanotubes for efficient removal of both cationic and anionic dyes from wastewater. Chemistryselect 2:3878–3888
Gupta K, Khatri OP (2017) Reduced graphene oxide as an effective adsorbent for removal of malachite green dye: plausible adsorption pathways. J Colloid Interface Sci 501:11–21
Kolodynska D, Halas P, Franus M, Hubicki Z (2017) Zeolite properties improvement by chitosan modification-sorption studies. J Ind Eng Chem 52:187–196
Liu W et al (2018) Mixed hemimicelle solid-phase extraction based on magnetic halloysite nanotubes and ionic liquids for the determination and extraction of azo dyes in environmental water samples. J Chromatogr A 1551:10–20
Wan XY, Zhan YQ, Long ZH, Zeng GY, He Y (2017) Core@double-shell structured magnetic halloysite nanotube nano-hybrid as efficient recyclable adsorbent for methylene blue removal. Chem Eng J 330:491–504
Massaro M et al (2017) Synthesis and characterization of Halloysite–Cyclodextrin Nanosponges for enhanced dyes adsorption. ACS Sustain Chem Eng 5:3346–3352
Liu Y et al (2014) Halloysite nanotubes@reduced graphene oxide composite for removal of dyes from water and as supercapacitors. J Mater Chem A 2:4264–4269
Gao C et al (2016) Novel Fe3O4/HNT@rGO composite via a facile co-precipitation method for the removal of contaminants from aqueous system. RSC Adv 6:49228–49235
Zhu J, Wang Y, Liu J, Zhang Y (2014) Facile one-pot synthesis of novel spherical zeolite–reduced graphene oxide composites for cationic dye adsorption. Ind Eng Chem Res 53:13711–13717
Liu L et al (2012) The removal of dye from aqueous solution using alginate-halloysite nanotube beads. Chem Eng J 187:210–216
Jiang L et al (2014) Surface modifications of halloysite nanotubes with superparamagnetic Fe3O4 nanoparticles and carbonaceous layers for efficient adsorption of dyes in water treatment. Chem Res Chin Univ 30:971–977
Luo P et al (2011) Removal of methylene blue from aqueous solutions by adsorption onto chemically activated halloysite nanotubes. Korean J Chem Eng 28:800–807
Du Y, Zheng P (2014) Adsorption and photodegradation of methylene blue on TiO2-halloysite adsorbents. Korean J Chem Eng 31:2051–2056
Shu Z et al (2015) Nanoporous-walled silica and alumina nanotubes derived from halloysite: controllable preparation and their dye adsorption applications. Appl Clay Sci 112-113:17–24
Shu Z et al (2016) Preparation of halloysite-derived mesoporous silica nanotube with enlarged specific surface area for enhanced dye adsorption. Appl Clay Sci 132-133:114–121
Riahi-Madvaar R, Taher MA, Fazelirad H (2017) Synthesis and characterization of magnetic halloysite-iron oxide nanocomposite and its application for naphthol green B removal. Appl Clay Sci 137:101–106
Duan J, Liu R, Chen T, Zhang B, Liu J (2012) Halloysite nanotube-Fe3O4 composite for removal of methyl violet from aqueous solutions. Desalination 293:46–52
Chaari I, Moussi B, Jamoussi F (2015) Interactions of the dye, C.I. direct orange 34 with natural clay. J Alloys Compd 647:720–727
Kiani G, Dostali M, Rostami A, Khataee AR (2011) Adsorption studies on the removal of malachite green from aqueous solutions onto halloysite nanotubes. Appl Clay Sci 54:34–39
Zou M, Du M, Zhu H, Xu C, Fu Y (2012) Green synthesis of halloysite nanotubes supported ag nanoparticles for photocatalytic decomposition of methylene blue. J Phys D Appl Phys 45(325302):3722–3727
Cheng ZL, Sun W (2015) Preparation of N-doped ZnO-loaded halloysite nanotubes catalysts with high solar-light photocatalytic activity. Water Sci Technol 72:1817–1823
Yao P, Zhong S, Shen Z (2015) TiO2/Halloysite composites Codoped with carbon and nitrogen from melamine and their enhanced solar-light-driven photocatalytic performance. Int J Photoenergy 2015:1–8
Jiang L, Huang Y, Liu T (2015) Enhanced visible-light photocatalytic performance of electrospun carbon-doped TiO2/halloysite nanotube hybrid nanofibers. J Colloid Interface Sci 439:62–68
Li C, Wang J, Feng S, Yang Z, Ding S (2013) Low-temperature synthesis of heterogeneous crystalline TiO2-halloysite nanotubes and their visible light photocatalytic activity. J Mater Chem A 1:8045–8054
Li C, Wang J, Guo H, Ding S (2015) Low temperature synthesis of polyaniline-crystalline TiO2-halloysite composite nanotubes with enhanced visible light photocatalytic activity. J Colloid Interface Sci 458:1–13
Li C, Zhou T, Zhu T, Li X (2015) Enhanced visible light photocatalytic activity of polyaniline-crystalline TiO2-halloysite composite nanotubes by tuning the acid dopant in the preparation. RSC Adv 5:98482–98491
Chen H et al (2015) Trapping characteristic of halloysite lumen for methyl orange. Appl Surf Sci 347:769–776
Zeng X, Sun Z, Wang H, Wang Q, Yang Y (2016) Supramolecular gel composites reinforced by using halloysite nanotubes loading with in-situ formed Fe3O4 nanoparticles and used for dye adsorption. Compos Sci Technol 122:149–154
Li X et al (2015) Halloysite–CeO2–AgBr nanocomposite for solar light photodegradation of methyl orange. Appl Clay Sci 104:74–80
Maity J, Ray SK (2018) Chitosan based nano composite adsorbent-synthesis, characterization and application for adsorption of binary mixtures of Pb(II) and cd(II) from water. Carbohydr Polym 182:159–171
Zhu K et al (2017) Silane-modified halloysite/Fe3O4 nanocomposites: simultaneous removal of Cr(VI) and Sb(V) and positive effects of Cr(VI) on Sb(V) adsorption. Chem Eng J 311:236–246
Zhou T, Li C, Jin H, Lian Y, Han W (2017) Effective adsorption/reduction of Cr(VI) oxyanion by Halloysite@polyaniline hybrid nanotubes. ACS Appl Mater Interfaces 9:6030–6043
Luo P et al (2011) Preparation and characterization of Silane coupling agent modified Halloysite for Cr(VI) removal. Ind Eng Chem Res 50:10246–10252
Wang X et al (2016) Rapid adsorption of cobalt (II) by 3-aminopropyltriethoxysilane modified halloysite nanotubes. Korean J Chem Eng 33:3504–3510
Xiao J et al (2016) Preparation of halloysite@graphene oxide composite and its application for high-efficient decontamination of U(VI) from aqueous solution. J Mol Liq 220:304–310
Ashrafzadeh Afshar E, Taher MA, Fazelirad H (2017) Ultra-trace determination of thallium(I) using a nanocomposite consisting of magnetite, halloysite nanotubes and dibenzo-18-crown-6 for preconcentration prior to its quantitation by ET-AAS. Microchim Acta:791–797
Chiew CSC et al (2016) Halloysite/alginate nanocomposite beads: kinetics, equilibrium and mechanism for lead adsorption. Appl Clay Sci 119:301–310
Wang Y, Zhang X, Wang Q, Zhang B, Liu J (2014) Continuous fixed bed adsorption of cu(II) by halloysite nanotube-alginate hybrid beads: an experimental and modelling study. Water Sci Technol 70:192–199
Choo CK et al (2016) Chitosan/halloysite beads fabricated by ultrasonic-assisted extrusion-dripping and a case study application for copper ion removal. Carbohydr Polym 138:16–26
Tian X, Wang W, Wang Y, Komarneni S, Yang C (2015) Polyethylenimine functionalized halloysite nanotubes for efficient removal and fixation of Cr (VI). Microporous Mesoporous Mater 207:46–52
Afzali D, Fayazi M (2016) Deposition of MnO2 nanoparticles on the magnetic halloysite nanotubes by hydrothermal method for lead(II) removal from aqueous solutions. J Taiwan Inst Chem Eng 63:421–429
Fayazi M, Taher MA, Afzali D, Mostafavi A (2016) Fe3O4 and MnO2 assembled on halloysite nanotubes: a highly efficient solid-phase extractant for electrochemical detection of mercury(II) ions. Sensors Actuators B Chem 228:1–9
He W et al (2015) Removal of UO 2 2+ from aqueous solution using halloysite nanotube-Fe3O4 composite. Korean J Chem Eng 33:170–177
Amjadi M, Samadi A, Manzoori JL (2015) A composite prepared from halloysite nanotubes and magnetite (Fe3O4) as a new magnetic sorbent for the preconcentration of cadmium(II) prior to its determination by flame atomic absorption spectrometry. Microchim Acta 182:1627–1633
Amjadi M, Samadi A, Manzoori JL, Arsalani N (2015) 5-(p-Dimethylaminobenzylidene) rhodanine-modified magnetic halloysite nanotubes as a new solid phase sorbent for silver ions. Anal Methods 7:5847–5853
Li R, Hu Z, Zhang S, Li Z, Chang X (2013) Functionalized halloysite nanotubes with 2-hydroxybenzoic acid for selective solid-phase extraction of trace iron(III). Int J Environ Anal Chem 93:767–779
Li R et al (2012) Highly selective solid-phase extraction of trace Pd(II) by murexide functionalized halloysite nanotubes. Anal Chim Acta 713:136–144
Kadi S et al (2012) Preparation, characterisation and application of thermally treated Algerian halloysite. Microporous Mesoporous Mater 158:47–54
Dong Y, Liu Z, Chen L (2011) Removal of Zn(II) from aqueous solution by natural halloysite nanotubes. J Radioanal Nucl Chem 292:435–443
Chiew CSC et al (2016) Stability and reusability of alginate-based adsorbents for repetitive lead (II) removal. Polym Degrad Stab 123:146–154
Sadeghi S, Sheikhzadeh E (2009) Solid phase extraction using silica gel modified with murexide for preconcentration of uranium (VI) ions from water samples. J Hazard Mater 163:861–868
Demir A, Arisoy M (2007) Biological and chemical removal of Cr(VI) from waste water: cost and benefit analysis. J Hazard Mater 147:275–280
Zhang C-L, Cui S-J, Wang Y (2015) Adsorption removal of pefloxacin from water by halloysite nanotubes. J Ind Eng Chem 23:12–15
Vasapollo G et al (2011) Molecularly imprinted polymers: present and future prospective. Int J Mol Sci 12:5908–5945
Schirmer C, Meisel H (2009) Synthesis and evaluation of molecularly imprinted polymers (MIP) with affinity for the polypeptide Nisin. Food Anal Methods 2:257–263
Cheong WJ, Yang SH, Ali F (2013) Molecular imprinted polymers for separation science: a review of reviews. J Sep Sci 36:609–628
Piletsky SA, Piletska EV, Karim K, Freebairn KW, Legge CH, Turner APF (2002) Polymer cookery: influence of polymerization conditions on the performance of molecularly imprinted polymers. Macromolecules 35:7499–7504
Pardo A, Mespouille L, Dubois P, Duez P, Blankert B (2012) Targeted extraction of active compounds from natural products by molecularly imprinted polymers. Open Chemistry 10:751–765
Haupt K (2003 Sep 1) Molecularly imprinted polymers: the next generation. Anal Chem 75(17):376A–383A
Idil N, Mattiason B (2017) Imprinting of microorganisms for biosensor applications. Sensors (Basel) 17(4):29
Selvolini G, Marrazza G (2017) MIP-based sensors: promising new tools for cancer biomarker determination. Sensors (Basel) 17(4):29
Chen L, Xu S, Li J (2011) Recent advances in molecular imprinting technology: current status, challenges and highlighted applications. Chem Soc Rev 40:2922–2942
Yin J, Cui Y, Yang G, Wang H (2010) Molecularly imprinted nanotubes for enantioselective drug delivery and controlled. Chem Commun (Camb) 46(41):7688–7690
Hemmatpour H, Haddadi-Asl V, Roghani-Mamaqani H (2015) Synthesis of pH-sensitive poly (N,N-dimethylaminoethyl methacrylate)-grafted halloysite nanotubes for adsorption and controlled release of DPH and DS drugs. Polymer 65:143–153
Li X, Yang Q, Ouyang J, Yang H, Chang S (2016) Chitosan modified halloysite nanotubes as emerging porous microspheres for drug carrier. Appl Clay Sci 126:306–312
Pan J et al (2012) Selective recognition of 2,4,5-trichlorophenol by temperature responsive and magnetic molecularly imprinted polymers based on halloysite nanotubes. J Mater Chem 22:3360–3369
Qiu X-Z, Liang Y, Guo H-S, Wang X-B, Lin C-X (2015) Determination of phenolic compounds in environmental water by HPLC combination with on-line solid-phase extraction using molecularly imprinted polymers. J Nanosci Nanotechnol 15:9578–9584
Zhou C et al (2015) Water-compatible halloysite-imprinted polymer by Pickering emulsion polymerization for the selective recognition of herbicides. J Sep Sci 38:1365–1371
Dai J et al (2014) Highly-controllable imprinted polymer nanoshell at the surface of magnetic halloysite nanotubes for selective recognition and rapid adsorption of tetracycline. RSC Adv 4:7967–7978
Zhu X, Li H, Zhou H, Zhong S (2015) Fabrication and evaluation of protein imprinted polymer based on magnetic halloysite nanotubes. RSC Adv 5:66147–66154
Zhu X et al (2016) Halloysite-based dopamine-imprinted polymer for selective protein capture. J Sep Sci 39:2431–2437
Xie A et al (2016) Hollow imprinted polymer nanorods with a tunable shell using halloysite nanotubes as a sacrificial template for selective recognition and separation of chloramphenicol. RSC Adv 6:51014–51023
Ma P et al (2016) A biomimetic Setaria viridis-inspired imprinted nanoadsorbent: green synthesis and application to the highly selective and fast removal of sulfamethazine. RSC Adv 6:9619–9630
Margot J, Copin P-J, von Gunten U, Barry DA, Holliger C (2015) Sulfamethoxazole and isoproturon degradation and detoxification by a laccase-mediator system: influence of treatment conditions and mechanistic aspects. Biochem Eng J 103:47–59
Husain M, Husain Q (2007) Applications of redox mediators in the treatment of organic pollutants by using Oxidoreductive enzymes: a review. Crit Rev Environ Sci Technol 38:1–42
Kadam AA, Jang J, Lee DS (2017) Supermagnetically tuned Halloysite nanotubes functionalized with Aminosilane for covalent laccase immobilization. ACS Appl Mater Interfaces 9:15492–15501
Zhai R et al (2013) Chitosan–halloysite hybrid-nanotubes: horseradish peroxidase immobilization and applications in phenol removal. Chem Eng J 214:304–309
Yao J et al (2014) Immobilization of laccase on chitosan–halloysite hybrid porous microspheres for phenols removal. Desalin Water Treat:1–9
Ma W, Dai J, Dai X, Da Z, Yan Y (2016) Preparation and characterization of chitosan/halloysite magnetic microspheres and their application for removal of tetracycline from an aqueous solution. Desalin Water Treat 57:4162–4173
Tsoufis T et al (2017) Halloysite nanotube-magnetic iron oxide nanoparticle hybrids for the rapid catalytic decomposition of pentachlorophenol. Chem Eng J 313:466–474
Huo P et al (2013) Photocatalytic degradation of antibiotics in water using metal ion@TiO2/HNTs under visible light. Desalin Water Treat 52:6985–6995
Li J et al (2015) Enhanced photocatalytic activity of g-C3N4-ZnO/HNT composite heterostructure photocatalysts for degradation of tetracycline under visible light irradiation. RSC Adv 5:91177–91189
Abolghasemi MM, Arsalani N, Yousefi V, Arsalani M, Piryaei M (2016) Fabrication of polyaniline-coated halloysite nanotubes by in situ chemical polymerization as a solid-phase microextraction coating for the analysis of volatile organic compounds in aqueous solutions. J Sep Sci 39:956–963
Fizir M et al (2018) QbD approach by computer aided design and response surface methodology for molecularly imprinted polymer based on magnetic halloysite nanotubes for extraction of norfloxacin from real samples. Talanta 184:266–276
Saraji M, Jafari MT, Mossaddegh M (2016) Halloysite nanotubes-titanium dioxide as a solid-phase microextraction coating combined with negative corona discharge-ion mobility spectrometry for the determination of parathion. Anal Chim Acta 926:55–62
Darvishnejad M, Ebrahimzadeh H (2017) Halloysite nanotubes functionalized with a nanocomposite prepared from reduced graphene oxide and polythiophene as a viable sorbent for the preconcentration of six organochlorine pesticides prior to their quantitation by GC/MS. Microchim Acta 184:3603–3612
Wu K, Feng R, Jiao Y, Zhou C (2017) Effect of halloysite nanotubes on the structure and function of important multiple blood components. Mater Sci Eng C Mater Biol Appl 75:72–78
Krejcova K, Deasy PB, Rabiskova M (2013) Diclofenac sodium entrapment and release from halloysite nanotubules. Ceska Slov Farm 62:28–34
Hillier S, Ryan PC (2002) Identification of halloysite (7 Å) by ethylene glycol solvation: the 'MacEwan effect'. Clay Miner 37:487–496
Joussein E, Petit S, Delvaux B (2007) Behavior of halloysite clay under formamide treatment. Appl Clay Sci 35:17–24
Li Y, Zhang Y, Zhang Y, Sun J, Wang Z (2017) Thermal behavior analysis of halloysite–dimethylsulfoxide intercalation complex. J Therm Anal Calorim 129:985–990
Tang Y et al (2011) Effects of unfolded and intercalated halloysites on mechanical properties of halloysite–epoxy nanocomposites. Compos A: Appl Sci Manuf 42:345–354
Price RR, Gaber BP, Lvov Y (2001) In-vitro release characteristics of tetracycline HCl, khellin and nicotinamide adenine dineculeotide from halloysite; a cylindrical mineral. J Microencapsul 18:713–722
Yendluri R et al (2017) Paclitaxel encapsulated in Halloysite clay nanotubes for intestinal and intracellular delivery. J Pharm Sci 106:3131–3139
Levis SR, Deasy PB (2003) Use of coated microtubular halloysite for the sustained release of diltiazem hydrochloride and propranolol hydrochloride. Int J Pharm 253:145–157
Yang J-H et al (2016) Drug–clay nanohybrids as sustained delivery systems. Appl Clay Sci 130:20–32
Botella P, Rivero-Buceta E (2017) Safe approaches for camptothecin delivery: structural analogues and nanomedicines. J Control Release 247:28–54
Rizzo C et al (2017) Hybrid supramolecular gels of Fmoc-F/halloysite nanotubes: systems for sustained release of camptothecin. J Mater Chem B 5:3217–3229
Linlin L, Fan H, Wang L, Jin Z (2016) Does halloysite behave like an inert carrier for doxorubicin? 6:54193–54201
Liu M et al (2016) Functionalized halloysite nanotube by chitosan grafting for drug delivery of curcumin to achieve enhanced anticancer efficacy. J Mater Chem B 4:2253–2263
Lee Y, Jung GE, Cho SJ, Geckeler KE, Fuchs H (2013) Cellular interactions of doxorubicin-loaded DNA-modified halloysite nanotubes. Nanoscale 5:8577–8585
Guo M et al (2012) Halloysite nanotubes, a multifunctional Nanovehicle for anticancer drug delivery. Chin J Chem 30:2115–2120
Hu Y et al (2017) Multifunctional halloysite nanotubes for targeted delivery and controlled release of doxorubicin in-vitro and in-vivo studies. Nanotechnology 375101:28
Mock CD, Jordan BC, Selvam C (2015) Recent advances of curcumin and its analogues in breast cancer prevention and treatment. RSC Adv 5:75575–75588
Kerdsakundee N et al (2017) Multifunctional nanotube-Mucoadhesive poly(methyl vinyl ether-co-maleic acid)@Hydroxypropyl methylcellulose acetate succinate composite for site-specific oral drug delivery. Adv Healthc Mater 6:1–20.
Li W et al (2017) Microfluidic assembly of a nano-in-micro dual drug delivery platform composed of halloysite nanotubes and a pH-responsive polymer for colon cancer therapy. Acta Biomater 48:238–246
Massaro M et al (2014) Functionalized halloysite multivalent glycocluster as a new drug delivery system. J Mater Chem B 2:7732–7738
Riela S et al (2016) Dual drug-loaded halloysite hybrid-based glycocluster for sustained release of hydrophobic molecules. RSC Adv 6:87935–87944
Massaro M et al (2016) Direct chemical grafted curcumin on halloysite nanotubes as dual-responsive prodrug for pharmacological applications. Colloids Surf B: Biointerfaces 140:505–513
Shutava TG, Fakhrullin RF, Lvov YM (2014) Spherical and tubule nanocarriers for sustained drug release. Curr Opin Pharmacol 18:141–148
Vergaro V, Lvov YM, Leporatti S (2012) Halloysite clay nanotubes for resveratrol delivery to cancer cells. Macromol Biosci 12:1265–1271
Sun L, Boyer C, Grimes R, Mills DK (2016) Drug coated clay nanoparticles for delivery of chemotherapeutics. Curr Nanosci 12:207–214
Yan S et al (2011) Layer-by-layer assembly of poly(L-glutamic acid)/chitosan microcapsules for high loading and sustained release of 5-fluorouracil. Eur J Pharm Biopharm 78:336–345
Rao KM, Nagappan S, Seo DJ, Ha C-S (2014) pH sensitive halloysite-sodium hyaluronate/poly(hydroxyethyl methacrylate) nanocomposites for colon cancer drug delivery. Appl Clay Sci 97-98:33–42
Jiang W-T, Chang P-H, Tsai Y, Li Z (2016) Halloysite nanotubes as a carrier for the uptake of selected pharmaceuticals. Microporous Mesoporous Mater 220:298–307
Qi R et al (2013) Controlled release and antibacterial activity of antibiotic-loaded electrospun halloysite/poly(lactic-co-glycolic acid) composite nanofibers. Colloids Surf B: Biointerfaces 110:148–155
Tohidi S, Ghaee A, Barzin J (2016) Preparation and characterization of poly(lactic-co-glycolic acid)/chitosan electrospun membrane containing amoxicillin-loaded halloysite nanoclay. Polym Adv Technol 27:1020–1028
Wang Q, Zhang J, Mu B, Fan L, Wang A (2014) Facile preparation of magnetic 2-hydroxypropyltrimethyl ammonium chloride chitosan/Fe3O4/halloysite nanotubes microspheres for the controlled release of ofloxacin. Carbohydr Polym 102:877–883
Tan D et al (2013) Natural halloysite nanotubes as mesoporous carriers for the loading of ibuprofen. Microporous Mesoporous Mater 179:89–98
Tan D et al (2014) Loading and in vitro release of ibuprofen in tubular halloysite. Appl Clay Sci 96:50–55
Li H, Zhu X, Zhou H, Zhong S (2015) Functionalization of halloysite nanotubes by enlargement and hydrophobicity for sustained release of analgesic. Colloids Surf A Physicochem Eng Asp 487:154–161
Li H et al (2016) The combination of adsorption by functionalized halloysite nanotubes and encapsulation by polyelectrolyte coatings for sustained drug delivery. RSC Adv 6:54463–54470
Fan L, Zhang J, Wang A (2013) In situ generation of sodium alginate/hydroxyapatite/halloysite nanotubes nanocomposite hydrogel beads as drug-controlled release matrices. J Mater Chem B 1:6261–6270
Fan L, Li B, Wang Q, Wang A, Zhang J (2014) Superhydrophobic gated Polyorganosilanes/Halloysite Nanocontainers for sustained drug release. Adv Mater Interfaces 1:1300136
Lun H, Ouyang J, Yang H (2014) Natural halloysite nanotubes modified as an aspirin carrier. RSC Adv 4:44197–44202
Ganguly S, Das TK, Mondal S, Das NC (2016) Synthesis of polydopamine-coated halloysite nanotube-based hydrogel for controlled release of a calcium channel blocker. RSC Adv 6:105350–105362
Shi YF, Tian Z, Zhang Y, Shen HB, Jia NQ (2011) Functionalized halloysite nanotube-based carrier for intracellular delivery of antisense oligonucleotides. Nanoscale Res Lett 6:600–608
Wu H et al (2014) Multifunctional nanocarrier based on clay nanotubes for efficient intracellular siRNA delivery and gene silencing. J Biomater Appl 28:1180–1189
Li F et al (1998) Control of apoptosis and mitotic spindle checkpoint by survivin. Nature 396:580–584
Long Z, Zhang J, Shen Y, Zhou C, Liu M (2017) Polyethyleneimine grafted short halloysite nanotubes for gene delivery. Materials Science & Engineering C-Materials for Biological Applications 81:224–235
Ghebaur A, Garea SA, Iovu H (2012) New polymer-halloysite hybrid materials--potential controlled drug release system. Int J Pharm 436:568–573
Zargarian SS, Haddadi-Asl V, Hematpour H (2015) Carboxylic acid functionalization of halloysite nanotubes for sustained release of diphenhydramine hydrochloride. J Nanopart Res 17:1–13
Kurczewska J, Cegłowski M, Messyasz B, Schroeder G (2018) Dendrimer-functionalized halloysite nanotubes for effective drug delivery. Appl Clay Sci 153:134–143
Sabbagh N, Akbari A, Arsalani N, Eftekhari-Sis B, Hamishekar H (2017) Halloysite-based hybrid bionanocomposite hydrogels as potential drug delivery systems. Appl Clay Sci 148:48–55
Rawtani D et al (2017) Development of a novel ‘nanocarrier’ system based on Halloysite nanotubes to overcome the complexation of ciprofloxacin with iron: an in vitro approach. Appl Clay Sci 150:293–302
Acknowledgements
This work was financially supported by the China Scholarship Consul (CSC) grant (No. 2013012007), Independent innovation fund project of agricultural science and technology of Jiangsu Province in 2017(No CX(17)1003), Guizhou Provincial Science and Technology Department Joint Fund Project (Qian Kehe LH word [2016] No. 7076), the Project Funded by Research Project of Environment Protection Department of Jiangsu Province (Grant No.2015026) and Chinese College Students Innovation Project for the R&D of Novel Drugs.
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Fizir, M., Dramou, P., Dahiru, N.S. et al. Halloysite nanotubes in analytical sciences and in drug delivery: A review. Microchim Acta 185, 389 (2018). https://doi.org/10.1007/s00604-018-2908-1
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DOI: https://doi.org/10.1007/s00604-018-2908-1