Abstract
A new approach to selectively enhance the ultraviolet (UV) detection sensitivity of titania (TiO2), albeit in the presence of silica (SiO2), alumina (Al2O3), and zinc oxide (ZnO), nanoparticles in capillary electrophoresis (CE) analysis was developed. Interactions of Triton X-100 (TX-100), polyethylene glycol (PEG), and deoxyribonucleic acid (DNA) with TiO2 nanoparticles produced larger CE-UV peaks at various enhancement factors. Single-stranded DNA (ssDNA) was a more effective adsorbate than double-stranded DNA (dsDNA) due to its flexible molecular structure that participated in a stronger interaction with TiO2 nanoparticles via its sugar-phosphate backbone. Disaggregation of TiO2 nanoparticles upon DNA binding due to electrosteric stabilization was validated using dynamic light scattering. PEG coating of TiO2-DNA nanoparticles further enhanced the UV detection sensitivity in CE analysis by providing extra electrosteric stabilization. This analytical technique, which involves binding of TiO2 nanoparticles with DNA followed by coating with PEG, has allowed us to achieve progressively an enhancement factor up to 13.0 ± 3.0 - fold in analytical sensitivity for the accurate determination of disaggregated TiO2 nanoparticles.

Selective enhancement of UV detection sensitivity for TiO2 nanoparticles via electrosteric stabilization using ssDNA and PEG







Similar content being viewed by others
References
United States Environmental Protection Agency. Technical fact sheet—nanomaterials, 2014, EPA,505-F-14-002. https://www.epa.gov/sites/production/files/201403/documents/ffrrofactsheet_emergingcontaminant_nanomaterials_jan2014_final.pdf. Accessed March 2016.
Yolanda P. Challenges in the determination of engineered nanomaterials in foods. Trends Anal Chem. 2016. doi:10.1016/j.trac.2016.06.004.
Brennner SA, Neu-Baker NM, Eastlake AC, Beaucham CC, Geraci CL. NIOSH field studies team assessment: worker exposure to aerosolized metal oxide nanoparticles in a semiconductor fabrication facility. J Occup Environ Hyg. 2016;12:1–31.
Eastlake AC, Beaucham C, Martinez KF, et al. Refinement of the nanoparticle emission assessment technique into the nanomaterial exposure assessment technique (NEAT 2.0). J Occup Environ Hyg. 2016. doi:10.1080/15459624.2016.1167278.
Ding Y, Kuhlbusch TAG, Tongeren MV, et al. Airborne engineered nanomaterials in the workplace—a review of release and worker exposure during nanomaterial production and handling processes. J Hazard Mater. 2016. doi:10.1016/j.jhazmat.2016.04.075.
Filon FL, Bello D, Cherrie JW, Sleeuwenhoek A, Spaan S, Brouwer DH. Occupational dermal exposure to nanoparticles and nano-enabled products: part I—factors affecting skin absorption. Int J Hyg Environ Health. 2016;219:536–44.
Sukwong P, Somkid K, Kongseng S, Pissuwan D, Yoovathaworn K. Respiratory tract toxicity of titanium dioxide nanoparticles and multi-walled carbon nanotubes on mice after intranasal exposure. IET Micro Nano Lett. 2016;11:183–7.
Rehberg M, Nekolla K, Sellner S, et al. Intercellular transport of nanomaterials is mediated by membrane nanotubes in vivo. Small. 2016;12:1882–90.
Hazeem LJ, Bououdina M, Rashdan S, Brunet L, Slomianny C, Boukherroub R. Cumulative effect of zinc oxide and titanium oxide nanoparticles on growth and chlorophyll a content of Picochlorum sp. Environ Sci Pollut Res. 2016;23:2821–30.
Tiede K, Hanssen SF, Westerhoff P, et al. How important is drinking water exposure for the risks of engineered nanoparticles to consumers? Nanotoxicology. 2016;10:102–10.
Wang B, He X, Zhang Z, Zhao Y, Feng W. Metabolism of nanomaterials in vivo: blood circulation and organ clearance. Acc Chem Res. 2013;46:761–9.
Miranda RR, Silveira ALRD, de Jesus IP, et al. Effects of realistic concentrations of TiO2 and ZnO nanoparticles in Prochilodus lineatus juvenile fish. Environ Sci Pollut Res. 2016;23:5179–88.
Andersen CP, King G, Plocher M, et al. Germination and early plant development of ten plant species exposed to titanium dioxide and cerium oxide nanoparticles. Environ Toxicol Chem. 2016. doi:10.1002/etc.3374.
Wiechers JW, Musee N. Engineered inorganic nanoparticles and cosmetics: facts, issues, knowledge gaps and challenges. J Biomed Nanotechnol. 2010;6:408–31.
Weir A, Westerhoff P, Fabricius L, Hristovski K, Goetz N. Titanium dioxide nanoparticles in food and personal care products. Environ Sci Technol. 2012;46:2242–50.
Spinazzè A, Cattaneo A, Limonta M, Bollati V, Bertazzi PA, Cavallo DM. Titanium dioxide nanoparticles: occupational exposure assessment in the photocatalytic paving production. J Nanopart Res. 2016;18:151–63.
Khan MJ, Maskat MY. Interaction of titanium dioxide nanoparticles with human serum albumin: a spectroscopic approach. Int J Pharm Pharm Sci. 2014;6:43–6.
Yu R, Wu J, Liu M, et al. Toxicity of binary mixtures of metal oxide nanoparticles to Nitrosomonas europaea. Chemosphere. 2016;153:187–97.
Bondarenko OM, Heinlaan M, Sihtmäe M, et al. Multilaboratory evaluation of 15 bioassays for (eco)toxicity screening and hazard ranking of engineered nanomaterials: FP7 project NANOVALID. Nanotoxicology. 2016;28:1–14.
Patel S, Patel P, Undre SB, Pandy SR, Singh M, Bakshi S. DNA binding and dispersion activities of titanium dioxide nanoparticles with UV/vis spectrophotometry, fluorescence spectroscopy and physicochemical analysis at physiological temperature. J Mol Liq. 2016;213:304–11.
Zhu RR, Wang SL, Zhang R, Sun XY, Yao SD. A novel toxicological evaluation of TiO2 nanoparticles on DNA structure. Chin J Chem. 2007;25:958–61.
Li S, Zhu H, Zhu R, Sun X, Yao S, Wang S. Impact and mechanism of TiO2 nanoparticles on DNA synthesis in vitro. Sci China Ser B Chem. 2008;51:367–72.
Gurra JR, Wang ASS, Chen CH, Jan KY. Ultrafine titanium dioxide particles in the absence of photoactivation can induce oxidative damage to human bronchial epithelial cells. Toxicology. 2005;213:66–73.
Armand L, Tarantini A, Beal D, et al. Long-term exposure of A549 cells to titanium dioxide nanoparticles induces DNA damage and sensitizes cells towards genotoxic agents. Nanotoxicology. 2016;10:913–23.
Rao A, Schoenenberger M, Gnecco E, et al. Characterization of nanoparticles using atomic force microscopy. J Phys Conf Ser. 2007;61:971–6.
Yan N, Zhu Z, He D, Jin L, Zheng H, Hu S. Simultaneous determination of size and quantification of gold nanoparticles by direct coupling thin layer chromatography with catalyzed luminol chemiluminescence. Sci Rep. 2016. doi:10.1038/srep24577.
Corredor C, Borysiak MD, Wolfer J, Westerhoff P, Posner JD. Colorimetric detection of catalytic reactivity of nanoparticles in complex matrices. Environ Sci Technol. 2015;49:3611–8.
Plata DL, Reddy CM, Gschwend PM. Thermogravimetry–mass spectrometry for carbon nanotube detection in complex mixtures. Environ Sci Technol. 2012;46:12254–61.
Fabricius AL, Duester L, Meermann B, Ternes TA. ICP-MS-based characterization of inorganic nanoparticles—sample preparation and off-line fractionation strategies. Anal Bioanal Chem. 2014;406:467–79.
Voracova I, Kleparnik K, Liskova M, Foret F. Determination of ζ-potential, charge, and number of organic ligands on the surface of water soluble quantum dots by capillary electrophoresis. Electrophoresis. 2015;36:867–74.
Liu L, Feng F, Hu Q, et al. Capillary electrophoretic study of green fluorescent hollow carbon nanoparticles. Electrophoresis. 2015;36:2110–9.
Li YQ, Guan LY, Zhang HL, et al. Distance dependent metal-enhanced quantum dots fluorescence analysis in solution by capillary electrophoresis and its application to DNA detection. Anal Chem. 2011;83:4103–9.
Lin KH, Chu TC, Liu FK. On-line enhancement and separation of nanoparticles using capillary electrophoresis. J Chromatogr A. 2007;1161:314–21.
Li L, Yu H, Liu D, You T. A novel dark-field microscopy technique coupled with capillary electrophoresis for visual analysis of single nanoparticles. Analyst. 2013;138:3705–10.
Bouri M, Salghi R, Algarra M, Zougagh M, Ríos A. A novel approach to size separation of gold nanoparticles by capillary electrophoresis-evaporative light scattering detection. RSC Adv. 2015;5:16672–7.
Franze B, Engelhard C. Fast separation, characterization, and separation of gold and silver nanoparticles and their ionic counterparts with micellar electrokinetic chromatography coupled to ICP-MS. Anal Chem. 2014;86:5713–20.
Spink CH, Chaires JB. Selective stabilization of triplex DNA by poly(ethylene glycols). J Am Chem Soc. 1995;117:12887–8.
Nakano S, Karimata H, Ohmichi T, Kawakami J, Sugimoto N. The effect of molecular crowding with nucleotide length and cosolute structure on DNA duplex stability. J Am Chem Soc. 2004;126:14330–1.
Feng B, Frykholm K, Nordena B, Westerlund F. DNA strand exchange catalyzed by molecular crowding in PEG solutions. Chem Commun. 2010;46:8231–3.
Biplab KC, Paudel SN, Rayamajhi S, et al. Enhanced preferential cytotoxicity through surface modification: synthesis, characterization and comparative in vitro evaluation of Triton X-100 modified and unmodified zinc oxide nanoparticles in human breast cancer cell. Chem Cent J. 2016;10:1–10.
Lee SJ, Cho IH, Kim H, Hong SJ. Microstructure characterization of TiO2 photoelectrodes for dye-sensitized solar cell using statistical design of experiments. Trans Electr Electron Mater. 2009;10:177–81.
Sun P, Zhang K, Fang J, Lin D, Wang M, Han J. Transport of TiO2 nanoparticles in soil in the presence of surfactants. Sci Total Environ. 2015;15:527–8.
Dhawan A, Sharma V. Toxicity assessment of nanomaterials: methods and challenge. Anal Bioanal Chem. 2010;398:589–605.
Murdock RC, Stolle LB, Schrand AM, Schlager JJ, Hussain SM. Characterization of nanomaterial dispersion in solution prior to in VitroExposure using dynamic light scattering technique. Toxicol Sci. 2008;101:239–53.
Teeguarden J, Hinderliter P, Orr G, Thrall B, Pounds J. Particokinetics in vitro: dosimetry considerations for in vitro nanoparticles toxicity assessments. Toxicol Sci. 2007;95:300–12.
Romero-Cano MS, Martın-Rodrıguez A, de las Nieves FJ. Electrosteric stabilization of polymer colloids with different functionality. Langmuir. 2001;17:3505–11.
Kunitsyn VG, Kuznetsov PA, Demchenko EN, Gimautdinova OI. Structural study of methylated and non-methylated duplexes by IR Fourier spectroscopy. Open J Phys Chem. 2015;5:87–92.
Aksoy C, Severcan F. Role of vibrational spectroscopy in stem cell research. Spectrosc Int J. 2012;27:167–84.
Jokerst JV, Lobovkina T, Zare RN, Gambhir SS. Nanoparticle PEGylation for imaging and therapy. Nanomedicine (Lond). 2011;6:715–28.
Du Y, Ren W, Li Y, et al. The enhanced chemotherapeutic effects of doxorubicin loaded PEG coated TiO2 nanocarriers in an orthotopic breast tumor bearing mouse model. J Mater Chem B. 2015;3:1518–28.
Cheng TL, Chuang KH, Chen BM, Roffler SR. Analytical measurement of PEGylated molecules. Bioconjugate Chem. 2012;23:881–99.
Fritz G, Schadler V, Willenbacher N, Wagner NJ. Electrosteric stabilization of colloidal dispersions. Langmuir. 2002;18:6381–90.
Pettersson A, Marino G, Pursiheimo A, Rosenholm JB. Electrosteric stabilization of Al2O3, ZrO2 and 3Y-ZrO2 suspensions: effect of dissociation and type of polyelectrolyte. J Colloid Interface Sci. 2000;228:73–81.
Hang J, Shi L, Feng X, Xiao L. Electrostatic and electrosteric stabilization of aqueous suspensions of barite nanoparticles. Powder Technol. 2009;192:166–70.
Pacia M, Warszyński P, Macyk W. UV and visible light active aqueous titanium dioxide colloids stabilized by surfactants. Dalton Trans. 2014;43:12480–5.
Zhang X, Wang F, Liu B, Kelly EY, Servos MR, Liu J. Adsorption of DNA oligonucleotides by titanium dioxide nanoparticles. Langmuir. 2014;30:839–45.
Cleaves HJ, Crapster-Pregont E, Jonsson CM, Jonsson CL, Sverjensky DA, Hazen RA. The adsorption of short single-stranded DNA oligomers to mineral surfaces. Chemosphere. 2011;83:1560–7.
Shi B, Shin YK, Hassanali AA, Singer SJ. DNA binding to the silica surface. J Phys Chem B. 2015;119:11030–40.
Dharanivasan G, Jesse DMI, Chandirasekar S, Rajendiran N, Kathiravan K. Label free fluorometric characterization of DNA interaction with cholate capped gold nanoparticles using ethidium bromide as a fluorescent probe. J Fluoresc. 2014;24:1397–406.
Laborda F, Bolea E, Lamana JJ. Single particle inductively coupled plasma mass spectrometry for the analysis of inorganic engineered nanoparticles in environmental samples. TrEAC. 2016;9:15–23.
Hofer R, Textor M, Spencer ND. Alkyl phosphate monolayers, self-assembled from aqueous solution onto metal oxide surfaces. Langmuir. 2001;17:4014–20.
Zwahlen M, Tosatti S, Textor M, Hahner G. Orientation in methyl- and hydroxyl-terminated self-assembled alkanephosphate monolayers on titanium oxide surfaces investigated with soft x-ray absorption. Langmuir. 2002;18:3957–62.
Rapuano R, Carmona-Ribeiro AM. Physical adsorption of bilayer membranes on silica. J Colloid Interface Sci. 1997;193:104–11.
Faure B, Salazar-Alvarez G, Ahniyaz A, et al. Dispersion and surface functionalization of oxide nanoparticles for transparent photocatalytic and UV-protecting coatings and sunscreens. Sci Technol Adv Mater. 2013;14:1–23.
Barrère F, Lebugle A, Blitterswijk CA, Groot K, Layrolle P. Calcium phosphate interactions with titanium oxide and alumina substrates: an XPS study. J Mater Sci Mater Med. 2003;14:419–25.
Chung YA, Chen YH, Chang PL. Strategies of fluorescence staining for trace total ribonucleic acid analysis by capillary electrophoresis with argon ion laser-induced fluorescence. Electrophoresis. 2015;36:1781–4.
Mori Y. Size-selective separation techniques for nanoparticles in liquid. KONA Powder Part J. 2015;32:102–14.
Leopold K, Philippe A, Wörle K, Schaumann GE. Analytical strategies to the determination of metal-containing nanoparticles in environmental waters. Trends Anal Chem. 2016. doi:10.1016/j.trac.2016.03.026.
Acknowledgments
Financial support from NSERC Canada is gratefully acknowledged. S. Alsudir thanks the Saudi Ministry of Higher Education for her scholarship.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
(PDF 379 kb)
Rights and permissions
About this article
Cite this article
Alsudir, S., Lai, E.P.C. Electrosteric stabilization of colloidal TiO2 nanoparticles with DNA and polyethylene glycol for selective enhancement of UV detection sensitivity in capillary electrophoresis analysis. Anal Bioanal Chem 409, 1857–1868 (2017). https://doi.org/10.1007/s00216-016-0130-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-016-0130-8


