Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2012 Oct 16;84(20):8457-60.
doi: 10.1021/ac302438m. Epub 2012 Sep 25.

Hypercrosslinked large surface area porous polymer monoliths for hydrophilic interaction liquid chromatography of small molecules featuring zwitterionic functionalities attached to gold nanoparticles held in layered structure

Yongqin Lv  1 , Zhixing Lin, Frantisek Svec
Affiliations

Hypercrosslinked large surface area porous polymer monoliths for hydrophilic interaction liquid chromatography of small molecules featuring zwitterionic functionalities attached to gold nanoparticles held in layered structure

Yongqin Lv et al. Anal Chem. .

Abstract

A novel approach to porous polymer monoliths hypercrosslinked to obtain large surface areas and modified with zwitterionic functionalities through the attachment of gold nanoparticles in a layered architecture has been developed. The capillary columns were used for the separation of small molecules in hydrophilic interaction liquid chromatography mode. First, a monolith with a very large surface area of 430 m(2)/g was prepared by hypercrosslinking from a generic poly(4-methylstyrene-co-vinylbenzyl chloride-co-divinylbenzene) monolith via a Friedel-Crafts reaction catalyzed with iron chloride. Free radical bromination then provided this hypercrosslinked monolith with 5.7 at % Br that further reacted with cystamine under microwave irradiation, resulting in a product containing 3.8 at % sulfur. Clipping the disulfide bonds with tris(2-carboxylethyl) phosphine liberated the desired thiol groups that bind the first layer of gold nanoparticles. These immobilized nanoparticles were an intermediate ligand enabling the attachment of polyethyleneimine as a spacer followed by immobilization of the second layer of gold nanoparticles which were eventually functionalized with zwitterionic cysteine. This layered architecture, prepared using 10 nm nanoparticles, contains 17.2 wt % Au, more than twice than that found in the first layer alone. Chromatographic performance of these hydrophilic monolithic columns was demonstrated with the separation of mixtures of nucleosides and peptides in hydrophilic interaction chromatography (HILIC) mode. A column efficiency of 51,000 plates/m was achieved for retained analyte cytosine.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Scanning electron micrographs of the internal structures of the hypercrosslinked poly(4-methylstyrene-co-vinylbenzene chloride-co-divinylbenzene) monoliths attached with 5 (a), 10 (b), 15 (c) nm gold nanoparticles monolayer, and 10 nm gold nanoparticle dual-layer (d).
Figure 2
Figure 2
HILIC isocratic separation of nucleosides using cysteine functionalized monoliths with a monolayer of 10 (a), and 15 nm gold nanoparticles (b). Conditions: Columns: 159 mm × 100 μm i.d. (a), 168 mm × 100 μm i.d. (b). mobile phase, 25 mmol/L ammonium formate (pH 3.2) in 90:10 vol% acetonitrile-water; flow rate, 0.5 μL/min; UV detection 254 nm; temperature 25°C. Peaks: thymine (1), adenosine (2), cytidine (3), cytosine (4), guanosine (5).
Figure 2
Figure 2
HILIC isocratic separation of nucleosides using cysteine functionalized monoliths with a monolayer of 10 (a), and 15 nm gold nanoparticles (b). Conditions: Columns: 159 mm × 100 μm i.d. (a), 168 mm × 100 μm i.d. (b). mobile phase, 25 mmol/L ammonium formate (pH 3.2) in 90:10 vol% acetonitrile-water; flow rate, 0.5 μL/min; UV detection 254 nm; temperature 25°C. Peaks: thymine (1), adenosine (2), cytidine (3), cytosine (4), guanosine (5).
Figure 3
Figure 3
HILIC isocratic separation of nucleosides using PEI functionalized 10 nm GNP monolayer monolith (a), and PEI-cysteine functionalized 10 nm GNP dual-layer monolith (b). Columns: 100 μm i.d. × 171 (a) and 165 mm (b). For other conditions see Fig. 2.
Figure 4
Figure 4
HILIC separation of peptides using cysteine functionalized 10 nm GNP monolayer monolith (a), and PEI-cysteine functionalized 10 nm GNP dual-layer monolith (b). Conditions: Columns: 159 mm 100 μm i.d. (a), 165 mm × 100 μm i.d. (b). mobile phase: A - 10 mmol/L triethylammonium phosphate buffer (pH 2.8), B - 5 vol.% of 10 mmol/L triethylammonium phosphate buffer (pH 2.8) in acetonitrile, gradient from 100 to 60% B in A in 10 min, flow rate 1.0 μL/min, UV detection 210 nm, temperature 25°C. Peaks: Impurity (1), Phe-Gly-Phe-Gly (2), Val-Try-Val (3), Gly-Phe (4), Gly-Leu (5), Gly-Try (6), Lys-Val (7), Gly-Gly-Gly (8).
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

See all "Cited by" articles

References

    1. Hjertén S, Liao JL, Zhang R. J Chromatogr A. 1989;473:273–275.
    2. Tennikova TB, Svec F, Belenkii BG. J Liquid Chromatogr. 1990;13:63–70.
    3. Svec F, Fréchet JMJ. Anal Chem. 1992;54:820–822.
    1. Svec F. J Chromatogr A. 2012;1228:250–262. - PMC - PubMed
    1. Urban J, Svec F, Fréchet JMJ. J Chromatogr A. 2010;1217:8212–8221. - PMC - PubMed
    2. Urban J, Svec F, Fréchet JMJ. Anal Chem. 2010;82:1621–1623. - PMC - PubMed
    1. Xu Y, Cao Q, Svec F, Fréchet JMJ. Anal Chem. 2010;82:3352–3358. - PMC - PubMed
    2. Cao Q, Xu Y, Liu F, Svec F, Fréchet JMJ. Anal Chem. 2010;82:7416–7421. - PubMed
    3. Lv YQ, Alejandro Maya F, Fréchet JMJ, Svec F. J Chromatogr A. 2012 doi: 10.1016/j.chroma.2012.04.007. - DOI - PubMed
    1. Guihen E, Glennon JD. Anal Lett. 2003;36:3309–3336.
    2. Zhong ZY, Male KB, Luong JHT. Anal Lett. 2003;36:3097–3118.

Publication types

MeSH terms