Skip to main content
SpringerLink
Log in

One-pot synthesis of SiO2@SiO2 core-shell microspheres with controllable mesopore size as a new stationary phase for fast HPLC separation of alkyl benzenes and β-agonists

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

Monodisperse SiO2@SiO2 core-shell silica microspheres (CSSM) with enlarged mesopores perpendicular to the particles surface were prepared using a dual-templating approach. With cetyltrimethyl ammonium bromide as the template and octyltrimethyl ammonium bromide as an auxiliary chemical, the pore size can be enlarged from 2.6 to 10.6 nm. The average shell thickness can be increased from 31 nm to 97 nm by adjusting the concentrations of the surfactants under continuous addition of tetraethyl orthosilicate. After coating twice, the resulting CSSM has a uniform mesoporous shell of about 198 nm thickness and a narrow pore size distribution. The CSSM were then modified with octadecyltrichlorosilane to give a material referred to as CS-C18. It was evaluated by separating the mixture of methylbenzene (toluene), ethylbenzene, n-propylbenzene, n-butylbenzene, n-amylbenzene and hexylbenzene. The baseline separation of the six alkyl benzenes is achieved within 2 min. Compared to a commercial column of type BEH-C18, CS-C18 shows a faster and better separation even at lower back pressure. It was also applied to the fast separation of benzo[a]pyrene, salbutamol, ractopamine and clenbuterolin residues in pork samples. The high column efficiency and better reproducibility suggest that the CSSM can be used as a matrix for fast separation and analysis of several kinds of small analytes.

A dual-templating approach was utilized to produce the core shell microsphere with controllable mesopore channels by using hexadecyltrimethylammonium bromide (CTAB) as the template and trioctylmethylammonium bromide (TOMAB) as an auxiliary chemical to enlarge the size of CTAB micelles.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Gritti F, Guiochon GJ (2010) Performance of new prototype packed columns for very high pressure liquid chromatography. J Chromatogr A 1217:1485–1495

    Article  CAS  PubMed  Google Scholar 

  2. Salisbury JJ (2008) Fused-core particles: a practical alternative to sub-2 micron particles. J Chromatogr Sci 46:883–886

    Article  CAS  PubMed  Google Scholar 

  3. McCalley DV (2011) Some practical comparisons of the efficiency and overloading behaviour of sub-2 μm porous and sub-3 μm shell particles in reversed-phase liquid chromatography. J Chromatogr A 1218:2887–2897

    Article  CAS  PubMed  Google Scholar 

  4. Fekete F, Oláh E, Fekete J (2012) Fast liquid chromatography: the domination of core-shell and very fine particles. J Chromatogr A 1228:57–71

    Article  CAS  PubMed  Google Scholar 

  5. Horvath C, Lipsky SR (1969) Column design in high pressure liquid chromatography. J Chromatogr Sci 7:109–116

    Article  CAS  Google Scholar 

  6. Kirkland JJ, Schuster SA, Johnson WL, Boyes BE (2013) Fused-core particle technology in high-performance liquid chromatography: an overview. J Pharmaceut Anal 3:303–312

    CAS  Google Scholar 

  7. Wang XL, Barber WE, Long WJ (2012) Applications of superficially porous particles: high speed, high efficiency or both? J Chromatogr A 1228:72–88

    Article  CAS  PubMed  Google Scholar 

  8. Guiochona G, Gritti F (2011) Shell particles, trials, tribulations and triumphs. J Chromatogr A 1218:1915–1938

    Article  Google Scholar 

  9. Min Y, Jiang B, Wu C, Xia SM, Zhang XD, Liang Z, Zhang LH, Zhang YK (2014) 1.9 μm superficially porous packing material with radially oriented pores and tailored pore size for ultra-fast separation of small molecules and biomolecules. J Chromatogr A 1356:148–156

    Article  CAS  PubMed  Google Scholar 

  10. Dong HJ, Brennan JD (2011) 1.9 μm superficially porous packing material with radially oriented pores and tailored pore size for ultra-fast separation of small molecules and biomolecules. Chem Commun 47:1207–1209

    Article  CAS  Google Scholar 

  11. Ahmed A, Ritchie H, Myers P, Zhang HF (2012) One-pot synthesis of spheres-on-sphere silica particles from a single precursor for fast HPLC with low back pressure. Adv Mater 24:6042–6048

    Article  CAS  PubMed  Google Scholar 

  12. Dong HJ, Brennan JD (2012) One-pot synthesis of silica core-shell particles with double shells and different pore orientations from their nonporous counterparts. J Mater Chem 22:13197–13203

    Article  CAS  Google Scholar 

  13. Kirkland JJ, Truszkowski FA, Dilks CH Jr, Engel GS (2000) Superficially porous silica microspheres for fast high-performance liquid chromatography of macromolecules. J Chromatogr A 890(1):3–13

    Article  CAS  PubMed  Google Scholar 

  14. Chen W, Jiang K, Mack A, Sachok B, Zhu X, Barber WE, Wang X (2015) Synthesis and optimization of wide pore superficially porous particles by a one-step coating process for separation of proteins and monoclonal antibodies. J Chromatogr A 1414:147–157

    Article  CAS  PubMed  Google Scholar 

  15. Wan G, Xia H, Wang J, Liu J, Song B, Yang Y, Bai Q (2018) Synthesis of SiO2@SiO2 core-shell microspheres using urea-formaldehyde polymers as the templates for fast separation of small solutes and proteins. Chinese Chem Lett 29(1):213–216

    Article  CAS  Google Scholar 

  16. Yoon SB, Kim JY, Kim JH, Park YJ, Yoon KR, Park SK, Yu JS (2007) Synthesis of monodisperse spherical silica particles with solid core and mesoporous shell: mesopore channels perpendicular to the surface. J Mater Chem 17:1758–1761

    Article  CAS  Google Scholar 

  17. Buchel G, Unger KK, Matsumoto A, Tsutsumi K (1998) A novel pathway for synthesis of submicrometer-size solid core/mesoporous shell silica spheres. Adv Mater 10:1036–1038

    Article  Google Scholar 

  18. Caruso RA, Antonietti M (2001) Sol-gel Nanocoating: an approach to the preparation of structured materials. Chem Mater 13:3272–3282

    Article  CAS  Google Scholar 

  19. Schuster SA, Wagner BM, Boyes BE, Kirkland JJ (2010) Wider pore superficially porous particles for peptide separations by HPLC. J Chromatogr Sci 48:566–571

    Article  CAS  PubMed  Google Scholar 

  20. Li W, Zhao DY (2013) Extension of the Stöber method to construct mesoporous SiO2 and TiO2 shells for uniform multifunctional core-shell structures. Adv Mater 25:142–149

    Article  CAS  PubMed  Google Scholar 

  21. Eltohamy E, Shin US, Kim HW (2011) Silica nanoparticles with enlarged nanopore size for the loading and release of biological proteins. Mater Lett 65:3570–3573

    Article  CAS  Google Scholar 

  22. Xia HJ, Wan GP, Chen G, Bai Q (2017) Preparation of superficially porous core-shell silica particle with controllable mesopore by a dual-templating approach for fast HPLC of small molecules. Mater Lett 192:5–8

    Article  CAS  Google Scholar 

  23. Nakabayashi H, Yamada A, Noba M, Kobayashi Y, Konno M, Nagao D (2010) Electrolyte-added one-pot synthesis for producing monodisperse, micrometer-sized silica particles up to 7 μm. Langmuir 26:7512–7515

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgments

This work is supported by the National Nature Science Foundation of China (21874106, 21545007, 21605122), Shaanxi Provincial Science and Technology Coordinating Innovation Projects (2013SZS18-K01), Natural Science Foundation of Shaanxi Province (2018JZ2001, 2018JQ2011) the Foundation of Key Laboratory in Shaanxi Province (2010JS103, 11JS097, 15JS115, 16JS116) and Scientific Research Foundation of the Higher Education Institutions of Henan Province (18B150030).

Author information

Authors and Affiliations

  1. Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Institute of Modern Separation Science, Key Lab of Modern Separation Science in Shaanxi Province, Northwest University, Xi’an, 710069, China

    Hongjun Xia, Jun Wang, Jiawei Liu, Guangpin Wan & Quan Bai

  2. Henan Key Laboratory of Rare Earth Functional Materials, Zhoukou Normal University, Zhoukou, 466001, China

    Hongjun Xia

  3. Shaanxi Research Design Institute of Petroleum and Chemical Industry, Shaanxi Dangerous Chemical Supervision and Inspection Center, Xi’an, 710054, China

    Jun Wang

  4. Hydrocarbon High-efficiency Utilization Technology Research Center, Shaanxi Yanchang Petroleum Group Co. Ltd, Xi’an, 710075, China

    Gang Chen

Authors
  1. Hongjun Xia
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jun Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Gang Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jiawei Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Guangpin Wan
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Quan Bai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Jiawei Liu or Quan Bai.

Ethics declarations

The author(s) declare that they have no competing interests.

Additional information

Publisher’s note

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

Electronic supplementary material

ESM 1

(DOC 13.2 mb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Xia, H., Wang, J., Chen, G. et al. One-pot synthesis of SiO2@SiO2 core-shell microspheres with controllable mesopore size as a new stationary phase for fast HPLC separation of alkyl benzenes and β-agonists. Microchim Acta 186, 125 (2019). https://doi.org/10.1007/s00604-019-3229-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-019-3229-8

Keywords

Search

Navigation