Simple column-switching ion chromatography method for determining eight monosaccharides and oligosaccharides in honeydew and nectar
Introduction
Honeydew is excreted by aphids as a sweet waste which consists mainly of various sugars and amino acids (Fischer, Völkl, & Hoffmann, 2005). Sugar compositions of honeydew vary significantly between aphid species but may also vary within a particular aphid species in an age-specific pattern or when feeding on different host plants (Fischer et al., 2005). Besides, there is a relationship between ant tending and honeydew sugar composition (Fischer & Shingleton, 2001). Nectar is another important element in agriculture. Nectar chemistry, including the sugar proportion, may differ among populations, individuals, cultivars or subspecies of the same species (Agostini, Sazima, & Galetto, 2011). In some regions, especially in Central and Eastern Europe, honeydew honey is highly valued in public as it has more benefits on human health than floral (nectar) honey (Simova, Atanassov, Shishiniova, & Bankova, 2012). Moreover, honeydew is appreciably higher in oligosaccharides than the nectar (Simova et al., 2012).
Till now, several methods regarding sugar analysis have been investigated. These include a variety of chromatographic methods such as high performance liquid chromatography (HPLC) (Földházi, 1994, Swallow and Low, 1990), gas chromatography (GC) (Low & Sporns, 1988), and gas chromatography–mass spectrometry (GC–MS) (Molnár-Perl, 1999). All of these methods can be utilized to separate and quantified the major sugars in honey. However, most of them have occasional disadvantages. For example, some chromatography methods require derivatization, such as GC, GC–MS, HPLC-diode array detector (HPLC-DAD) and HPLC-fluorescence detector (HPLC-FLD) (Pico, Martínez, Martín, & Gómez, 2015). HPLC–mass spectrometry (HPLC–MS) is expensive, and HPLC-refractive index detector (HPLC-RI) does not allow the use of a gradient and has low sensitivity (Molnár-Perl, 1999).
Ion chromatography (IC) is a special kind of HPLC which is widely used to analyze cations, anions, and some important biological compounds such as sugars, amino acids, peptides and proteins. For example, IC-pulsed amperometric detection (IC-PAD) is one of the most useful techniques for determination of oligosaccharide (Ouchemoukh et al., 2010, Steppuhn and Wäckers, 2004). PAD proved to be superior to RI detection and evaporative light scattering detection (ELSD) in aspect of selectivity, sensitivity and having possibility of gradient elution (Molnár-Perl, 1999). However, honeydew and nectar contain sugars as well as vitamins, amino acids, proteins. Organics in samples not only lead to damage the IC columns, but also may make erroneous results. Thus, it is important to remove organics from sample before analysis. The conventional sample preparation method is using a reverse-phase pretreatment column, such as Thermo Fisher OnGuard II RP column. Although these pretreatment columns can be reused 5–10 times, the regeneration processes are time-consuming due to manual operations. Therefore, on-line pretreatment method is proposed.
As an effective on-line sample pretreatment method, column-switching technique has been widely used in ion chromatographic system (Huang et al., 2013, Zhu et al., 2013). For example, Yang et al. (2013) proposed a simple IC column-switching method for detection of hexavalent chromium in Colla corii asini. Sample solution with target ions were eluted from a collection loop to analytical columns, with on-line matrix elimination. Zhong, Zhou, Zeng, Ye, and Zhu (2011) used an IC system coupled with on-line column-switching technique to determine anions in organic chemicals of high purity. Zhu et al. (2013) proposed the column-switching IC-PAD method for simultaneous determination of glucose, d-gluconic acid, 2-keto-d-gluconic acid and 5-keto-d-gluconic acid.
In this work, a column-switching IC method was established for the analysis of sugars in honeydew and nectar. The samples could be analyzed after on-line elimination of the matrices. It has potential to provide a fast, convenient, and practical approach for analysis of sugars in biological samples.
Section snippets
Equipment
An ICS 3000 IC system (Thermo-Fisher Scientific Waltham, MA, USA) was employed for all the chromatographic separations, which was equipped with a quaternary pump, a column heater, two six-port valves (P/N 061961, Rheodyne, Cotati, CA, USA). The electrochemical detector (ED50 electrochemical detector, Thermo-Fisher Scientific Waltham, MA, USA) was equipped with a gold working electrode, an pH/Ag/AgCl composite reference electrode. A quaternary pump (Ultimate 3000, Thermo-Fisher Scientific
Separation column
In this study, two IC columns (IonPac PA1 and IonPac PA10) were tested for the sugar separation. It was found that IonPac PA1 column always had a dissolved oxygen peak to interfere separation while IonPac PA10 had better separated performance. Thus, IonPac PA10 guard column and analytical column were selected for this method.
Mobile phase
Among the 8 sugars, rhamnose, glucose, fructose and sucrose have shorter retention time than the other four sugars (lactose, raffinose, maltose and erlose). In this work,
Conclusion
In this work, a column-switching IC method for simultaneous determination of sugars and matrix elimination was proposed. The on-line pretreatment IC system is effective for the organics elimination in honeydew and nectar samples. The results showed good accuracy, satisfactory precision, wide linearity and low LOD. This method was suitable and reliable for the analysis sugars in various complex samples. It can be extended to trace level detection of other sugars or ions which have redox in
Acknowledgments
This research was financially supported by the Major National Scientific Instrument and Equipment Development Special of China (No. 2012YQ09022903), Key Laboratory of Health Risk Appraisal for Trace Toxic Chemicals of Zhejiang Province, Science and Technique Plan of Zhejiang (No. 2014F50030), and Zhejiang Provincial Natural Science Foundation of China (Nos. Y4110532, LY12B05003, LY13B020001, LQ13B050001).
References (16)
- et al.
A single pump cycling-column-switching technique coupled with homemade high exchange capacity columns for the determination of iodate in iodized edible salt by ion chromatography with UV detection
Food Chemistry
(2013) Simultaneous quantitation of acids and sugars by chromatography: Gas or high-performance liquid chromatography?
Journal of Chromatography A
(1999)- et al.
HPLC sugar profiles of Algerian honeys
Food Chemistry
(2010) - et al.
Quantification of sugars in wheat flours with an HPAEC-PAD method
Food Chemistry
(2015) - et al.
A rapid differentiation between oak honeydew honey and nectar and other honeydew honeys by NMR spectroscopy
Food Chemistry
(2012) - et al.
Analysis of hexavalent chromium in Colla corii asini with on-line sample pretreatment valve-switching ion chromatography
Journal of Chromatography A
(2013) - et al.
Trace analysis of anions in organic matrices by ion chromatography coupled with a novel reversed-phase column for on-line sample
Chinese Chemical Letters
(2011) - et al.
Simultaneous determination of glucose, d-gluconic, 2-keto-d-gluconic and 5-keto-d-gluconic acids by ion chromatography-pulsed amperometric detection with column-switching technique
Talanta
(2013)
Cited by (23)
Separation of saccharides by ion-exchange chromatography
2023, Ion-Exchange Chromatography and Related TechniquesDegradation of hormones in tap water by heterogeneous solar TiO<inf>2</inf>-photocatalysis: Optimization, degradation products identification, and estrogenic activity removal
2021, Journal of Environmental Chemical EngineeringCitation Excerpt :Another useful approach for complex analyses is column switching: it is based on the use of valves, changing the path of the analytes through the chromatograph. It makes it possible to use an extractor column or multidimensional separation processes [18]. Therefore, one of the objectives of this work was to develop a fully automated analytical method and use it in the optimized degradation of estrone, 17β-estradiol, 17α-ethinylestradiol, and estriol, in tap water.
Progress in the pretreatment and analysis of carbohydrates in food: An update since 2013
2021, Journal of Chromatography ACitation Excerpt :HPAEC is a powerful analytical tool for carbohydrate separation due to its ability to separate mono- and oligosaccharides. It has great advantages in terms of its high resolution [14,16,35,42,48,85,86]. Monti et al. [35] employed HPAEC to determine three similar monosaccharides (lactose, galactose and glucose) in hard cheeses.
Application of a simple column-switching ion chromatography technique for removal of matrix interferences and sensitive fluorescence determination of acidic compounds (pharmaceutical drugs) in complex samples
2017, Journal of Chromatography ACitation Excerpt :It is also inferred, that use of IC-FLD was advantageous over HPLC techniques for separation of acidic drugs as it required only 15% of ACN for the isocratic separation of five acidic pharmaceutical drugs in basic media. The presence of inorganic and organic interferences and impurities like fat, cellulose, pigment and wax in complex samples can not only cause problem in quantitation of analyte of interest, but also destroy the analytical columns within hours [12,60,66]. Therefore, their complete elimination is extremely important prior to analysis.
Simple on-line pretreatment of column-switching coupled with ion chromatography for the determination of lactic acid in lobaplatin
2017, Journal of Pharmaceutical and Biomedical AnalysisDifferences between honeydew and blossom honeys: A review
2017, Trends in Food Science and TechnologyCitation Excerpt :Lower values of fructose and glucose in honeydew honey were found by other researchers (Diez et al., 2004; Golob & Plestenjak, 1999; Mateo & Bosch-Reig, 1997; Prodolliet & Hischenhuber, 1998; Weston & Brocklebank, 1999). Honeydew honeys presented much more amounts of maltose and erlose while blossom honey contained higher amounts of glucose and sucrose (Ni et al., 2016). No significant differences in sucrose for both types of honeys were found (Golob & Plestenjak, 1999).