Multisyringe Chromatography Research Articles

Determination of Vitamin E in Spirulina Platensis Extracts and Photoprotective Creams by Multi-Syringe Chromatography (MSC) and High-Performance Liquid Chromatography (HPLC)

The determination of vitamin E as chemical marker in Spirulina platensis hydroalcoholic extracts and creams is reported by the use of high-performance liquid chromatography (HPLC) and multi-syringe chromatography (MSC). The validation of the HPLC method using a methanol as the mobile phase showed linearity (r = 0.9994), a quantification limit of 1.25 µg mL−1, favorable precision with a relative standard deviation less than 1.5%, and a recovery of 98.9%. The samples were pretreated with potassium hydroxide/ethanol and extracted with petroleum ether. The resulting solid residue was dissolved in methanol before analysis. MSC was developed using a monolithic column coupled to a multi-syringe system. Both on-line and pretreated samples were analyzed by this method. The results obtained for the hydroalcoholic extract of S. platensis by HPLC and MSC were in agreement.

Development of an automated system for the analysis of inorganic chloramines in swimming pools via multi-syringe chromatography and photometric detection with ABTS

Inorganic chloramines are disinfection by-products resulting from the unwanted reaction between chlorine used as disinfectant in swimming pools and nitrogenous compounds brought by bathers. This parameter (total chloramines or combined chlorine) is currently measured on site by a colorimetric method that does not allow to measure only inorganic chloramines. In this paper, a multi-syringe chromatography system combined with a post column derivatization is applied for the first time for the specific detection of the three individual inorganic chloramines (monochloramine, dichloramine and trichloramine). These latter ones are separated using a low-pressure monolithic C18 column, and separately detected after a post-column reaction with the chromogenic reagent ABTS (2,2′-azino-bis-(3-ethyl-benzothiazoline)-6-sulfonic acid-diammonium salt). Development of two ABTS reagents provides discrimination of chlorine and monochloramine that are not separated on the column. Optimization of the experimental conditions enables determination of inorganic chloramines with very good detection limits (around 10 μg eq.Cl2 L−1) without interferences from other chlorinated compounds such as organic chloramines or free available chlorine. The validation of the whole procedure has been successfully applied to real swimming pools samples.

Determination of priority phenolic pollutants exploiting an in-syringe dispersive liquid-liquid microextraction-multisyringe chromatography system.

An automatic phenolic compounds analyzer is presented. The system performs online magnetic-stirring-assisted dispersive liquid-liquid microextraction before multisyringe chromatography (MSC) using a monolithic Chromolith Flash RP-18e column. The extraction behavior of the followingphenolic pollutants: phenol, 2-nitrophenol, 4-nitrophenol, 2-chlorophenol, 2,4-diclorophenol, and 2,4,6-trichlorophenol, has been studied. A critical comparison of extractants (tributyl phosphate, acetonitrile, hexane, and 1-chlorobutane) and disperser solvents (acetone, acetonitrile, ethanol, methanol, 1-propanol, and 2-propanol) was made. Tributyl phosphate and acetonitrile were chosen as the extractant and the disperser solvent, respectively, since these showed the best performance. Phenols were online back-extracted into NaOH and neutralized before multi-isocratic chromatographic separation. The proposed analyzer can be applied for wide linear working ranges, i.e., between 40 and 20,000μgL(-1). The precision of the developedsystem has been proved, with maximum values for the intraday and interday precision of 4.4% and 5.2%, respectively, expressed as relative standard deviation, and high preconcentration factors (9.3-10.5) for most of the compounds studied. The method developed was successfully applied to natural water samples.

Potential of multisyringe chromatography for the on-line monitoring of the photocatalytic degradation of antituberculosis drugs in aqueous solution

In this study, a multisyringe chromatography system (MSC) using a C18 monolithic column was proposed for the on-line monitoring of the photocatalytic degradation of isoniazid (INH, 10mgL−1) and pyrazinamide (PYRA, 5mgL−1) mixtures in aqueous solution using a small sample volume (200μL) with an on-line filtration device in a fully automated approach. During the photocatalytic oxidation using TiO2 or ZnO semiconductor materials, total organic carbon (TOC) and the formed intermediates were analyzed off-line using ion chromatography, ion exclusion HPLC, and ESI-MS/MS. The results showed that TiO2 exhibits a better photocatalytic activity than ZnO under UV irradiation (365nm) for the degradation of INH and PYRA mixtures, generating 97% and 92% degradation, respectively. The optimal oxidation conditions were identified as pH 7 and 1.0gL−1 of TiO2 as catalyst. The mineralization of the initial organic compounds was confirmed by the regular decrease in TOC, which indicated 63% mineralization, and the quantitative release of nitrate and nitrite ions, which represent 33% of the nitrogen in these compounds. The major intermediates of INH degradation included isonicotinamide, isonicotinic acid, and pyridine, while the ESI-MS/MS analysis of PYRA aqueous solution after photocatalytic treatment showed the formation of pyrazin-2-ylmethanol, pyrazin-2-ol, and pyrazine. Three low-molecular weight compounds, acetamide, acetic acid and formic acid, were detected during INH and PYRA decomposition. PYRA was more resistant to photocatalytic degradation due to the presence of the pyrazine ring, which provides greater stability against OH attack.

Individual volatile fatty acids determination by chromogenic derivatization coupled to multi-syringe chromatography

In this paper, a new multisyringe chromatography (MSC) system is proposed for a simple and accurate measurement of individual volatile fatty acids (VFA) in anaerobic treatment processes. The determination method is based on the derivatization of VFA with N-(1-naphthyl) ethylenediamine (EDAN) followed by the separation of VFA derivatives on an Onyx C18 monolithic column (25mm×4.6mm i.d.). Chromatographic separation conditions have been investigated and were found to be optimal with a mixture of acetonitrile and formic acid 0.1% (ratio 35/65), providing good separation of C2–C5 VFA in 8min. Optimization of the derivatization reaction was also carried out with special attention paid to the buffering capacity of the reaction medium, so as to be able to deal with samples of various characteristics in terms of alkalinity or of VFA concentration range. Individual VFA could be quantified between 0.05–2.5gL−1 with LOD of 0.01–0.02gL−1. Overall procedure time was about 18min for one analytical cycle, which fulfils the requirement of real-time monitoring of an anaerobic digester. Validation of the system developed has been assessed by application of the procedure to sludge samples from various origins, and comparative results with gas chromatography analyses showed satisfactory correlation (R²>0.98).

Multisyringe Chromatography (MSC): An Effective and Low Cost Tool for Water-Soluble Vitamin Separation

The advent of monolithic columns has facilitated the combination of chromatographic techniques with nonseparation flow techniques by virtue of the low overpressure introduced by them. Thus far, these combinations have provided excellent results derived from the high selectivity of liquid chromatography and ease of sample handling in nonseparation flow techniques. The joint use of multisyringe flow injection analysis and monolithic columns has provided multisyringe chromatography (MSC). Simultaneous spectrophotometric determination of ascorbic acid, nicotinic acid, nicotinamide, pyridoxine hydrochloride, thiamine hydrochloride, and riboflavin in commercial drinks using a MSC method, is described in this contribution as an inexpensive alternative to classical HPLC. The MSC method provides baseline separation of all these compounds with resolutions values greater than 2, except for B1 and B6 with resolution of 1,2. A ChromolithTM Flash RP-18e (50 mm × 4.6 mm) column, a multisyringe burette provided with two 10 mL high-precision bidirectional syringes and an 8-port multiposition valve were used for a dual isocratic chromatographic separation in our study.

Applicability of multisyringe chromatography coupled to on-line solid-phase extraction to the simultaneous determination of dicamba, 2,4-D, and atrazine

Simultaneous determination of three herbicides (dicamba, 2,4-D, and atrazine) has been achieved by on-line solid-phase extraction (SPE) coupled to multisyringe chromatography (MSC) with UV detection. The preconcentration conditions were optimized; a preconcentration flow rate of 0.5 mL min(-1) and elution at 0.8 mL min(-1) were the optimum conditions. A C(18) (8 mm i.d.) membrane extraction disk conditioned with 0.3 mol L(-1) HCl in 0.5% MeOH was used. A 3-mL sample was preconcentrated, then eluted with 0.43 mL 40:60 water-MeOH. A C(18) monolithic column (25 mm × 4.6 mm) was used for chromatographic separation. Separation of the three compounds was achieved in 10 min by use of 0.01% aqueous acetic acid-MeOH (60:40) as mobile phase at a flow rate of 0.8 mL min(-1). The limits of detection (LOD) were 13, 57, and 22 μg L(-1) for dicamba, 2,4-D, and atrazine, respectively. The sampling frequency was three analyses per hour, and each analysis consumed only 7.3 mL solvent. The method was applied to spiked water samples, and recovery between 85 and 112% was obtained. Recovery was significantly better than in the conventional HPLC-UV method. These results indicated the reliability and accuracy of this flow-based method. This is the first time this family of herbicides has been simultaneously analyzed by on-line SPE-MSC using a monolithic column.

MONOLITHIC COLUMNS IN FLOW ANALYSIS: A REVIEW OF SIC AND MSC TECHNIQUES

Coupling of monolithic column with flow systems opens a new area in chromatographic separation of multicompound sample in low pressure systems, with the advantage of flow programming and possibility of sample manipulation. These columns combined with sequential injection analysis and multisyringe flow injection have been obtained by sequential injection chromatography (SIC) and multisyringe chromatography (MSC), respectively. These methods have been applied mainly to separated components of pharmaceutical formulations with results similar to those obtained using high performance liquid chromatography (HPLC). In the present mini-review, SIC and MSC systems are compared, and we present the advantages and drawbacks with regard to conventional separation techniques.

Applicability of multisyringe chromatography coupled to cold-vapor atomic fluorescence spectrometry for mercury speciation analysis

In this paper, a novel automatic approach for the speciation of inorganic mercury (Hg 2+), methylmercury (MeHg +) and ethylmercury (EtHg +) using multisyringe chromatography (MSC) coupled to cold-vapor atomic fluorescence spectrometry (CV/AFS) was developed. For the first time, the separation of mercury species was accomplished on a RP C18 monolithic column using a multi-isocratic elution program. The elution protocol involved the use of 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)–acetonitrile (99:1, v/v), followed by 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)–acetonitrile (90:10, v/v). The eluted mercury species were then oxidized under post-column UV radiation and reduced using tin(II) chloride in an acidic medium. Subsequently, the generated mercury metal were separated from the reaction mixture and further atomized in the flame atomizer and detected by AFS. Under the optimized experimental conditions, the limits of detection (3 σ) were found to be 0.03, 0.11 and 0.09 μg L −1 for MeHg +, Hg 2+ and EtHg +, respectively. The relative standard deviation (RSD, n = 6) of the peak height for 3, 6 and 3 μg L −1 of MeHg +, Hg 2+ and EtHg + (as Hg) ranged from 2.4 to 4.0%. Compared with the conventional HPLC–CV/AFS hyphenated systems, the proposed MSC–CV/AFS system permitted a higher sampling frequency and low instrumental and operational costs. The developed method was validated by the determination of a certified reference material DORM-2 (dogfish muscle), and was further applied for the determination of mercury species environmental and biological samples.

Multisyringe chromatography (MSC) using a monolithic column for the determination of sulphonated azo dyes

A methodology based on multisyringe chromatography with a monolithic column was developed to determine three sulphonated azo textile dyes: Acid Yellow 23, Acid Yellow 9 and Acid Red 97. An ion pair reagent was needed because of the low affinity between the monolithic column and the anionic dyes. The proposed analytical system is simple, versatile and low-cost and has great flexibility in manifold configuration. The method was optimized through experimentation based on experimental design methodology. For this purpose two blocks of full factorial 2 3 were done sequentially. In the first experimental plan, the factors studied were: the % of acetonitrile in organic phase, the % of H 2O in the mobile phase and the kind of ion pair reagent. In this stage, a simple configuration was used which has only one syringe for the mobile phase. After the first experimentation, we added a second syringe with a second mobile phase to the multisyringe module and performed a second full factorial 2 3. The factors studied in this case were: the % of acetonitrile in the second mobile phase, the pH and the concentration of ion pair reagent in both mobile phases. After this design, the optimal conditions were selected for obtaining a good resolution between the peaks of yellow dyes (1.47) and the elution of red dye in less than 8 min. The methodology was validated by spiking different amounts of each dye in real water samples, specifically, tap water, well water and water from a biological wastewater lagoon.

Interfacing on-line solid phase extraction with monolithic column multisyringe chromatography and chemiluminescence detection: An effective tool for fast, sensitive and selective determination of thiazide diuretics

A new, multisyringe flow injection set-up has been developed for the completely automated determination of trace thiazide compounds with diuretic action in different types of samples. The proposed instrumental set-up exploits for the first time, a low pressure on-line solid phase extraction–liquid chromatography–chemiluminescence detection method. This novel combination of sample treatments in flow systems expands the current applicability of low pressure liquid chromatography due to the isolation/preconcentration of the target compounds, besides high selectivity and sensitivity. For the determination of three thiazide compounds named hydroflumethiazide, furosemide and bendroflumethiazide, the proposed set-up provided with the preconcentration of only 1 mL of sample, limits of detection of 3, 60 and 40 μg L −1, respectively. Furthermore wide linear dynamic ranges of 6–4000, 140–20,000 and 90–40,000 μg L −1, respectively, were obtained. Besides of this, a high injection throughput of 12 h −1 was also achieved. As in sports, thiazide diuretics are prohibited substances, the proposed method has been applied to their determination in urine samples. Furthermore the potential of the proposed method as a fast-screening approach for emerging contaminants in waters has been also tested by applying it to well water and leachates from a solid waste landfill.

Contribution of multi-commuted flow analysis combined with monolithic columns to low-pressure, high-performance chromatography

The advent of monolithic columns has facilitated the combination of chromatographic techniques with non-separation flow techniques [particularly sequential injection analysis (SIA) and multi-syringe flow-injection analysis (MSFIA)] by virtue of the low overpressure introduced by monolithic columns. So far, these combinations have provided excellent results derived from the high selectivity of liquid chromatography and ease of sample handling in non-separation flow techniques. The joint use of SIA and monolithic columns has provided SI chromatography (SIC), which could enormously facilitate sample treatments (e.g., derivatization, photooxidation or preconcentration). However, the combination of MSFIA and monolithic columns has led to multi-syringe chromatography (MSC), which extends the advantages of SIC (e.g., by implementing post-column reactions in order to derivatize eluates). We discuss the advantages and the disadvantages of SIC and MSC, and the problems to be solved in order to optimize their performances.

Multi-syringe chromatography (MSC) system for the on-line solid-phase extraction and determination of hydrochlorothiazide and losartan potassium in superficial water, groundwater and wastewater outlet samples

In this paper, a combination of multi-syringe chromatography analysis technique with extraction disks sorbents for the pre-concentration and determination of hydrochlorothiazide and losartan potassium in superficial water, groundwater and wastewater outlet samples has been developed. The system developed was proved for the determination of hydrochlorothiazide and losartan potassium in spiked water samples with recoveries ranging from 95 to 118%. The method involves the on-line enrichment of the targeted analytes from spiked water samples onto a Cation-SR sorbent material. The analytes are subsequently eluted and transported to the monolithic column, Chromolith Flash RP-18e column (25 mm × 4.6 mm i.d.). The mobile phase used was 10 mM potassium dihydrogen phosphate (pH 3.0):acetonitrile:methanol (60:30:10 v/v/v), flow-rate 0.8 mL min −1. UV detection is carried out at 226 nm. Under the optimized chemical and physical variables, the detection limit for hydrochlorothiazide and losartan potassium calculated as 3 Syx/b was 0.07 and 0.09 mg L −1, respectively, for a sample loading volume of 1.0 mL.

Simultaneous determination of β-lactamic antibiotics by a new high-performance low-pressure chromatographic system using a multisyringe burette coupled to a monolithic column (MSC)

A technique based on multisyringe chromatography (MSC) was developed to determine three beta-lactamic antibiotics. Amoxicillin (AMOXI), ampicillin (AMPI) and cephalexin (CEPHA) were analyzed using a system with a very simple design and very low-cost equipment consisting of a multisyringe module, three low-pressure solenoid valves, a monolithic Chromolith Flash RP-18e column and a diode array spectrophotometric detector monitoring at 250 nm. Mobile phases containing methanol:acetic acid (0.1 M)-sodium acetate (0.1 M), pH 6.2, were tested for various ratios of methanol:acetic acid-sodium acetate, but a ratio of 10:90 gave optimum results with a flow rate of 2 ml min(-1). Validation parameters were evaluated for amoxicillin. The response to amoxicillin was linear over the range 0.04-0.4 mg/mL, with a correlation coefficient of 0.9996; precisions, evaluated as the repeatability for 0.04, 0.16 and 0.4 mg/mL amoxicillin, were 0.6%, 0.1% and 0.6%, respectively. Recovery from a generic formulation of amoxicillin was evaluated. The method showed selectivity in the presence of excipients commonly used in capsules, and satisfactory specificity was observed for amoxicillin and hydrolytic degradation products. The linearity was also evaluated for cephalexin and ampicillin. The conditions selected for MSC separation were compared with those for a HPLC system, and similar results were obtained in terms of chromatographic parameters but a difference in retention times was observed.