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Dopamine, adrenaline and octopamine are small polar molecules that play a vital role in regulatory systems. In this paper, phthalylglycyl chloride was proposed as a derivatization agent for octopamine, adrenaline and dopamine determination in urine for the first time. The derivatization procedure facilitated the use of reversed-phase liquid chromatography with positive electrospray ionization-high-resolution mass spectrometry. An LC-HRMS method was developed that provided quantification limits of 5 ng/mL and detection limits of 1.5 ng/mL for all analytes. The 95-97% yield of derivates was observed after a 10 min derivatization with phthalylglycyl chloride at pH 6.5 and 30 °C. The proposed method was successfully applied to the analysis of human urine samples. The obtained results were compared with those of conventional derivatization procedures with 9-fluorenyl-methoxycarbonyl chloride and dansyl chloride.
Assuntos
Dopamina , Espectrometria de Massas em Tandem , Humanos , Espectrometria de Massas em Tandem/métodos , Epinefrina , Cromatografia Líquida de Alta Pressão/métodos , Cloretos , OctopaminaRESUMO
High-performance liquid chromatography (HPLC) method for direct determination of water impurities in various organic solvents using a column (50 × 4.6 mm, ID) packed with 5 µm faujasite and methanol as an eluent was developed. Detection of the water peaks was performed by using either refractometric or indirect spectrophotometric method at 204 nm. In the first case the limit of detection (LOD) and limit of quantitation (LOQ) were 0.001 wt% and 0.0033 wt%, respectively for a sample volume of 20 µL. A linear calibration plot (R2 = 0.9998) for the water content between 0.01 and 9.55 wt% was obtained. The developed method was applied for the direct analysis of various polar organic solvents including acetonitrile, nitromethane, 1,4-dioxane, 2-ethoxyethanol, methanol, dimethyl sulfoxide (DMSO), ethanol and 2-propanol.
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Água , Zeolitas , Cromatografia Líquida de Alta Pressão/métodos , Metanol/química , Solventes/químicaRESUMO
Adsorption and chromatographic properties of oxidized and hydrogenated 'high pressure and high temperature' synthesised diamond (HPHT) are studied using high-performance liquid chromatography. The retention factors of organic cation (benzyltributylammonium chloride), weak base (aniline), weak acid (benzoic acid), strong acid (benzenesulfonic acid), hydrophobic toluene, and hydrophilic uracil are obtained at varied pH, organic solvent content, and ionic strength of mobile phase. Both adsorbents exhibited moderate polarity with a mixed-mode retention mechanism with a combination of electrostatic, hydrophobic and hydrophilic interactions. Unexpectedly, hydrogenated HPHT revealed significant anion-exchange properties under acidic conditions and cation-exchange properties under alkaline conditions, while only cation-exchange selectivity was noted for oxidized HPHT across the enntire pH range. The retention factors obtained for a set of model compounds including n-alkyl-, polymethyl-, nitro- and halogenated benzenes correlated well with their hydrophobicity (logP) values. The thermal stability of the adsorbent and immutability of retention mechanisms involved was confirmed by linear van't Hoff plots for the investigated compounds.
Assuntos
Temperatura , Cátions , Cromatografia Líquida de Alta Pressão/métodos , Interações Hidrofóbicas e Hidrofílicas , SolventesRESUMO
Macrocyclic glycopeptide antibiotics immobilized on silica are one of the effective classes of stationary phases for chiral recognition and HPLC separation of a wide range of optically active compounds. Enantioselectivity primarily depends on the chemical structure of the chiral ligand, immobilization chemistry, and separation conditions. In the present work, three new chiral stationary phases (CSPs) based on macrocyclic antibiotic eremomycin were prepared and investigated for enantioseparation of amino acids. Two eremomycin derivatives, including simple non-substituted amide and bulky adamantyl amide, provided important information on the role of the carboxylic group in the eremomycin structure in the chiral recognition mechanism concerning amino acid optical isomers. One more CSP having a chlorine atom in the same position elucidates the role of the first aromatic ring in the eremomycin structure as a crucial point for chiral recognition. CSP with immobilized chloreremomycin was the most successful among the phases prepared in this work. It was additionally investigated under various separation conditions, including the type and content of the organic solvent in the eluent, the effects of different additives, and the concentration and pH of the buffer. Importantly, an efficient enantioselective separation of amino acids was achieved with pure water as the eluent.
Assuntos
Aminoácidos , Cromatografia de Fase Reversa , Dióxido de Silício/química , Estereoisomerismo , Antibacterianos/química , Cromatografia Líquida de Alta Pressão/métodos , AminasRESUMO
A simple and highly efficient method for the determination of highly toxic arsenic species using non-covalently aminated silica is proposed. The polyamines including poly(hexamethyleneguanidine), poly(4,9-dioxadodecane-1,12-guanidine), hexadimethrine, and poly(diallyldimethylammonium) were tested as silica modifiers. The prepared adsorbents allow effective preconcentration of anionic species of arsenic from aqueous solutions. It was found that As(V) can be quantitatively extracted from solutions at pH 4.5-7.0 by the anion exchange mechanism in less than 5 min, while neutral at this pH As(III) was not adsorbed at these conditions. A reaction with 2,3-dimercapto-1-propanesulphonic acid, which resulted in the formation of the negatively charged complex of As(III) with adsorbents was used for its quantitative extraction from solutions with a pH of 3.5-6.5. A system of two cartridges filled with poly(diallyldimethylammonium) modified silica and the on-line reaction of As(III) with 2,3-dimercapto-1-propanesulphonic acid proceeding between the cartridges was used for separate preconcentration and determination of As(V) and As(III) at pH 5. The proposed method was used for four-year monitoring of natural water pollution by arsenic in the area of residence of the indigenous peoples of Tyva Republic (Russia).
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Arsênio , Concentração de Íons de Hidrogênio , Poliaminas , Dióxido de Silício , ÁguaRESUMO
The regularities of the retention of alkanoic and alkanesulfonic acids homologues were investigated for the set of 36 anion-exchange columns produced by various manufacturers. The role of hydrophobic and electrostatic interactions in the retention and separation of organic anions was studied. The methylene selectivity increments α(CH2) were measured for the studied columns with 10 mM sodium hydroxide eluent. The influence of matrix, surface area, polar group structure, ion-exchange capacity, the density of charged functional groups on the surface and other characteristics of anion-exchangers on resin hydrophobicity was considered. A unified approach for the measurements of hydrophobic properties of anion-exchange resins is proposed and the ratio of chloride retention factor (k Cl) to α(CH2) was introduced as mixed-mode factor. The synergetic effect of electrostatic and hydrophobic interactions was observed.
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Since the advent of diamond-based adsorbents in the late 1960s, the interest in their use for solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) has steadily increased. This is primarily due to their unique properties, such as extreme chemical and thermal stability, high mechanical strength and biocompatibility, and complex mixed-mode retention mechanisms. Currently, the most commonly used synthetic diamonds in SPE and HPLC are detonation nanodiamonds (DND), high-pressure high-temperature (HPHT) diamonds, and chemical vapour deposition (CVD) diamonds. These diamonds have been either used as individual particles (in both modified and unmodified forms), or for surface modification, or entrapped within composites and core-shell particles to develop new diamond-based adsorbents. These diamond-based adsorbents have been used for a variety of applications, including streamlined proteome analysis; extraction of anions, cations, actinides, uranium, lanthanides, alkaline earth metals, transition metals, and post-transition metals; and development of reversed-phase, normal phase, hydrophilic interaction, ion chromatography, and mixed-mode liquid chromatography columns, to name but a few. These varied applications of different types of diamonds are typically governed by their specific properties. This review discusses the various surface and bulk properties of DND, HPHT diamonds, and CVD diamonds that facilitate or limit their use in different SPE and HPLC based applications.
Assuntos
Diamante/química , Extração em Fase Sólida/métodos , Cromatografia Líquida de Alta Pressão , Interações Hidrofóbicas e Hidrofílicas , Nanodiamantes/ultraestrutura , TemperaturaRESUMO
An ion chromatography (IC) system with switching recycling column was developed for the determination of bromate in drinking water with high chloride content. The system included a pump, two switching valves, guard column and analytical column, suppressor and a conductivity detector. In this method, the single eluent was used for both online collection and matrix elimination, and bromate was eluted from the concentrator column to the analytical column circularly. Under the optimized separation conditions, the method showed good linearity (r = 0.9995) in the range of 1-100 µg/L and repeatability (RSD ≤ 4.80%, n = 6). The limit of detection was 0.2 µg/L (S/N = 3) with 1000 µL sample volume injections. The method was applied to analysis of drinking and tap waters, and satisfactory recoveries of spiked samples between 96.8% and 108.7% were obtained. The result showed that the recycling column-switching system can be useful for the determination of traces of bromate in high-chloride samples, which is required in production of the drinking water and quality control of the final product.
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Bromatos/análise , Cromatografia por Troca Iônica/métodos , Água Potável/química , Cloretos/química , Limite de Detecção , Modelos Lineares , Reprodutibilidade dos TestesRESUMO
Stir-bar sorptive extraction (SBSE) is a popular solvent-less sample preparation method, which is widely applied for the sampling and preconcentration of a wide range of non-polar solutes. A typical stir-bar for SBSE is composed of a polydimethylsiloxane (PDMS) film, coated onto a glass jacket with an incorporated magnet core. Sampling is carried out by direct immersion or by exposing the stir-bar to the headspace of the sample. To-date the majority of reported SBSE devices have used PDMS as the sorbent, with a few alternative commercially SBSE coatings available (such as polyethylene glycol and polyacrylate), which limits the applicability of SBSE to more polar and hydrophilic solutes. The interest in more selective extraction has been the driving force behind the recent development of novel SBSE coatings, particularly those exhibiting selectivity towards more polar solutes. During the last decade, a significant number of novel SBSE coatings were introduced utilising different fabrication approaches, including surface adhesion, molecular imprinting, sol-gel technology, immobilised monoliths, and solvent exchange processes. A range of nano- and micro-carbon-based materials, functional polymers, metal organic frameworks (MOFs), and inorganic nanoparticles have been employed for this purpose. Some of these SBSE coatings have exhibited higher thermal and chemical stability and delivered wider selectivity profiles. This review aims to summarise these significant developments, reported over the past six years, with specific attention to novel materials and selectivity for extending the potential applications of SBSE.
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The constitutional repeating unit structures of poly(pyromellitic dianhydride-co-4,4'-oxydianiline) or polyamiÑ acid, butyric acid and complexes between butyric acid and one, two or three units of polyamiÑ acid were calculated using the density functional theory method (DFT B3LYP) on a 6-31G(d,p) basis with the basis set superposition error (BSSE) correction in the program Gaussian 09. The optimised structures of the template and polyamiÑ acid allowed to establish intermolecular non-covalent interactions during imprinting and, based on the results, develop a method of polyimide-based molecularly imprinted polymer preparation using butyric acid as template. It was shown that the optimum molar ratio of reagents used for the synthesis of molecularly imprinted polymer is 1:1 (interaction energy ∆E = 43.2 kJ/mol). In the presence of a large number of polyamic acid units in prepolymerisation complexes, the self-association of polyamic acid and the steric hindrance, which reduce the stability of the complexes, occur. The simulation results are in good agreement with experimental data. When analysing the energy values and parameters of bonds of the complexes, it was shown that butyric acid interacts with carboxyl groups from units of polyamiÑ acid via hydrogen bonding of moderate strength. The IR spectra of a complex between structural unit of polyamic acid and butyric acid were also obtained in order to understand the intermolecular interactions responsible for the molecular recognition. According to the IR spectra, it was shown that the vibrations of the C=O and O-H groups of butyric acid and polyamic acid participating in the interaction are weakened; their vibration frequencies are reduced. The polyimide structure was also constructed in the work. It was shown that two polyimide chains interact with each other due to hydrogen bonds between the hydrogen atoms of the benzene rings and the oxygen of the imide groups.
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The data processing workflow for LC-MS based metabolomics study is suggested with signal drift correction, univariate analysis, supervised learning, feature selection and unsupervised modelling. The proposed approach requires only an annotation-free peak table and produces an extremely reduced set of the most relevant features together with validation via Receiver Operating Characteristic analysis for selected predictors, cross-validation and unsupervised projection. The presented study was initially optimised by its own experimental set and then was successfully tested by using 36 datasets from 21 publicly available metabolomics projects. The suggested workflow can be used for classification purposes in high dimensional metabolomics studies and as a first step in exploratory analysis, data projection, biomarker selection, data integration and fusion.
Assuntos
Cromatografia Líquida , Metabolômica , Modelos Biológicos , Software , Espectrometria de Massas em Tandem , Metabolômica/métodos , Reprodutibilidade dos Testes , Fluxo de TrabalhoRESUMO
The development and application of non-porous and porous sorptive rods, comprised of polydimethylsiloxane-microdiamond (PDMS-MD) composites, is reported. The PDMS-MD composites were made porous using inorganic salt (NaCl and NaHCO3) particles as dissolvable templates. Materials with pore size of ~40⯵m down to ~5⯵m were produced. The advantages of incorporating up to ~60%microdiamond (2-4⯵m) into PDMS included: (1) significant increase in the density, which saw the rods sink within the aqueous sample without addition of secondary metal or glass materials, (2) significant improvement in mechanical stability (the porous composite rods could be thermally treated multiple times before application, unlike porous PDMS), (3) increased thermal stability up to 450-500 °C with only 6% weight loss of volatile components, and (4) higher thermal conductivity, estimated to be 108% higher than for PDMS. The PDMS-MD investigated as a sorbent for extraction, followed by liquid desorption and GC-FID analysis. Recovery of the sorbent for test solutes, isoamyl acetate, ethyl hexanoate, ethyl octanoate, ethyl decanoate, and phenethyl acetate, was found to range from ~87% to >100, with RSD of 2.10-12.50% in synthetic wine samples. Non-porous composite rods provided similar % recoveries to a commercial sorptive device (PDMS Twister), whereas porous rods showed improved % recovery for most of the test solutes (>10-20%) when applied under similar conditions. The limits of detection (LOD) for the above solutes within the developed method ranged from 0.60 to 27.30⯵g L-1). Application of the PDMS-MD-LD-GC-FID method to white wine samples demonstrated how the PDMS-MD composite material can be applied as a robust and an efficient sorptive phase for trace chemical analysis.
Assuntos
Técnicas de Química Analítica/métodos , Diamante/química , Dimetilpolisiloxanos/química , Vinho/análise , Cromatografia Gasosa , Limite de Detecção , Água/químicaRESUMO
A new ion chromatography method has been developed to study graphene oxide (GO) reduction by monitoring hydrazine concentration in the GO suspension. The method is based on ion chromatographic separation of hydrazine (from excess ammonia) and its selective determination by electrochemical detection. The developed analytical protocol overcame the significant practical challenges of atmospheric hydrazine oxidation and minimised the matrix interference in both separation and detection which result from the excess of ammonium with respect to hydrazine (up to 5.8â¯×â¯104 times) in GO reduction experiments. Chromatographic separations were achieved using a high capacity IonPac CS16 cation-exchange column with a 30â¯mM methanesulfonic acid (MSA) eluent, within an analysis time of less than 20â¯min. Detection of hydrazine as hydrazinium ion using electrochemical detector was linear between 10⯵M and 4â¯mM, with LOD and LOQ values of 3⯵M and 10⯵M, respectively. Standard additions confirmed 103⯱â¯0.8% recovery. The developed method was successfully used to determine the point of complete GO reduction with hydrazine. Reaction curves for GO reduction generated using the method were compared to results from Fourier-transform infrared spectroscopy and Raman spectroscopy to verify the utility of the approach.
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A series of complexing adsorbents is prepared by coating silica particles with linear polyhexamethylene guanidinium (PHMG) chloride followed by saturation with a number of sulphonated nitrosonaphthols reagents electrostatically retained by positively charged polymer layer. PHMG coated silica is hydrolytically stable even during treatment with 6 M HCl heated up to 50 °C. The adsorption of 1-nitroso-2-naphthol-3,6-disulfonic acid (nitroso-R-salt), 2-nitroso-1-naphthol-4-sulfonic acid (nitroso-N-salt), and 2-nitroso-1-naphthol-3,6-disulfonic acid (nitroso-K-salt) on PHMG modified silica was studied. The effective immobilisation of sulphonated nitrosonaphthols was achieved in the range of pH of 3 - 8, while the adsorption of the monosulphonated reagent (nitroso-N-salt) is twice as high as the disulphonated analogues (nitroso-R-salt and nitroso-K-salt). The adsorption of Cu(II), Fe(III), Co(II), Ni(II), Al(III), Zn(II), Pb(II), Mn(II), and Cr(III) on prepared complexing adsorbents under static and dynamic conditions was studied as a function of time, pH, sample volume, and presence of interfering ions. Metal ions can be desorbed by using 1 M HCl or 1 M HNO3. The preconcentration factors of metals under optimized conditions are varied from 20 to 80. The developed method was used for the preconcentration of trace metals from natural waters followed by ICP-OES determination. The sub-ppb limits of detection of metals are achieved.
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An improved "heart-cut" column-switching method combining ion-exclusion column, monolithic anion exchange concentrator and capillary anion-exchange column is developed and successfully applied for the determination of inorganic anions (Cl-, Br-, NO3- and HPO42-) at trace level in weak acids. The quantitative determination of selected inorganic anions in the samples of fifteen weak acids and hydrogen peroxide are accomplished with analysis time of 45 min per sample. The obtained limits of detection (LODs) are in the range of 2.1-32.6 ng/L based on the s/n = 3 and injection volume of 50 µL. RSDs for retention time and peak area were all ≤1.89%. A spike-recovery study was performed under these conditions and satisfactory recoveries between 85.3 and 103.9% for all studied anions were obtained.
Assuntos
Ácidos/química , Ânions/análise , Técnicas de Química Analítica/métodos , Cromatografia em Gel , Cromatografia por Troca Iônica , Limite de DetecçãoRESUMO
Electrochemical (EC) detection techniques in flow-based analytical systems such as flow injection analysis (FIA), capillary electrophoresis (CE), and liquid chromatography (LC) have attracted continuous interest over the last three decades, leading to significant advances in EC detection of a wide range of analytes in the liquid phase. In this context, the unique advantages of pulsed amperometric detection (PAD) in terms of high sensitivity and selectivity, and electrode cleaning through the application of pulsed potential for noble metal electrodes (e.g. Au, Pt), have established PAD as an important detection technique for a variety of electrochemically active compounds. PAD is especially valuable for analytes not detectable by ultraviolet (UV) photometric detection, such as organic aliphatic compounds and carbohydrates, especially when used with miniaturised capillary and chip-based separation methods. These applications have been accomplished through advances in PAD potential waveform design, as well as through the incorporation of nanomaterials (NMs) employed as microelectrodes in PAD. PAD allows on-line pulsed potential cleaning and coupling with capillary or standard separation techniques. The NMs are largely employed in microelectrodes to speed up mass and electron transfer between electrode surfaces and to perform as reactants in EC analysis. These advances in PAD have improved the sensitive and selective EC detection of analytes, especially in biological samples with complex sample matrices, and detection of electro-inactive compounds such as aliphatic organic compounds (i.e., formic acid, acetic acid, maleic acids, and ß-cyclodextrin complexes). This review addresses the fundamentals of PAD, the role of pulsed sequences in AD, the utilisation of different EC detectors for PAD, technological advancements in PAD waveforms, utilisation of microelectrodes in PAD techniques, advances in the use of NMs in PAD, the applications of PAD, and prospects for EC detection, with emphasis on PAD in flow-based systems.
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The deposition of chemical reagent inks on paper is a crucial step in the development and fabrication of microfluidic paper-based analytical devices (µPADs). A pen-plotting approach, delivering chemical ink deposition using technical pens filled with reagents and inserted into a desktop electronic plotter, is shown herein to be a versatile, low-cost, simple, rapid, reproducible, and high-throughput solution. The volume of the deposited ink was quantified gravimetrically, confirming that nanoliter volumes of reagents can be deposited reproducibly (e.g. 7.55⯱â¯0.37â¯nL/mm for a plotting speed of 10â¯cm/s) in detection zones of µPADs, typically spatially defined using wax printing. This approach was further investigated with regard to deposition of reagents in different geometrical forms (circular and linear), so demonstrating its applicability for preparation of µPADs with flexible design and application. By adjusting the plotting speed for linear deposition, lines with a relatively large range of widths (≈628-1192⯵m) were created. Circular deposition was also demonstrated via delivery of reagents within wax printed circular fluidic barriers of a range of diameters (inner diameterâ¯=â¯1.5-7â¯mm). These capabilities were practically demonstrated via the fabrication of µPADs, based upon differing detection principles for determination of aluminum in natural waters using Morin as the fluorescent reagent. Traditional µPADs based on digital image colorimetry (DIC) were produced using circular deposition, whilst distance-based µPADs exploited linear deposition. Both types of µPADs developed using this method showed excellent precision for determination of trace concentrations of aluminium (average RSDsâ¯=â¯3.38% and 6.45%, and LODsâ¯=â¯0.5â¯ng (0.25â¯ppm) and 2â¯ng (0.5â¯ppm), for traditional and distance-based detection, respectively).
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Multimaterial 3D printing facilitates the rapid production of complex devices with integrated materials of varying properties and functionality. Herein, multimaterial fused deposition modeling (MM-FDM) 3D printing was applied to the fabrication of low-cost passive sampler devices with integrated porous membranes. Using MM-FDM 3D printing, the device body was produced using black polylactic acid, with Poro-Lay Lay-Felt filament used for the printing of the integrated porous membranes (rubber-elastomeric polymer, porous after removal of a water-soluble poly(vinyl alcohol) component). The resulting device consisted of two interlocking circular frames, each containing the integrated membrane, which could be efficiently sealed together without the need for additional O-rings, and prevented loss of enclosed microparticulate sorbent. Scanning electron microscopy (SEM) analysis of the purified composite filament confirmed the porous properties of the material, an average pore size of â¼30 nm. The printed passive samplers with various membrane thicknesses, including 0.5, 1.0, and 1.5 mm, were evaluated for their ability to facilitate the extraction of atrazine as the model solute onto the internal sorbent, under standard conditions. Gas chromatography-mass spectrometry was used to determine the uptake of atrazine by the device from standard water samples and also to evaluate any chemical leaching from the printed materials. The sampler with 0.5 mm thick membrane showed the best performance with 87% depletion and a sampling rate of 0.19 Ld-1 ( n = 3, % RSD = 0.59). The results obtained using these printed sampling devices with integrated membranes were in close agreement to devices fitted with a standard poly(ether sulfone) membrane.
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A new high sensitivity deep-UV LED photometric detector with a z-type flow cell (45â¯nL or 180â¯nL) for miniaturised and portable capillary liquid chromatography (LC) was designed and fabricated to overcome sensitivity limitations due to short pathlength in on-capillary detectors. The new detector has a 10â¯mm geometric pathlength and uses high intensity light-emitting diodes (LED) as light sources in the deep-UV range (254â¯nm and 280â¯nm). No optical reference was necessary due to the low drift in the signal. Stray light was minimized by the use of an adjustable slit with a 0.5â¯mm pinhole. The direct relationship between absorbance and concentration was obtained using dichromate to evaluate the sensitivity and the linearity range of the detector. Performance of the miniaturised version was compared with that obtained from a commercial benchtop detector for capillary LC under the same conditions using the same optical z-cell. The miniaturised version exhibited a superior performance across all parameters, including 3 times higher effective pathlength, 4 times higher upper limit of detector linearity, and 2-5 times lower stray light levels. An application of the new detector was shown with the detection of l-dopa, l-tyrosine, norfenefrine, phenylephrine and tyramine, separated using capillary LC. The baseline noise level recorded was as low as 3.9 µAU. Further, the detector was applied in a miniaturised capillary LC for the indirect detection of common inorganic anions. In comparison to an on-capillary LED detector applied under similar chromatographic conditions, there was a 50 times higher signal to noise (S/N) ratio.
Assuntos
Levodopa/análise , Octopamina/análogos & derivados , Fenilefrina/análise , Fotometria , Tiramina/análise , Tirosina/análise , Cromatografia Líquida/instrumentação , Octopamina/análise , Fotometria/instrumentação , Raios UltravioletaRESUMO
The selectivity for 15 biogenic amines and amino acids shown by three capillary cation-exchange columns, IonPac CS19, CS12A and CS17 (250 × 0.4 mm ID, all from Thermo Fisher Scientific), exhibiting medium, medium low and ultra-low hydrophobicity, and either carboxylic or mixed carboxylic/phosphonic acid functional groups, was investigated. A mixed mode retention mechanism was revealed with ion-exchange, hydrophobic and hydrogen bonding interactions contributing to retention of polar organic molecules on these phases. The relative impact of these interactions was evaluated via the effect of concentration and pH of the eluent (methanesulfonic acid) on the retention of fifteen structurally similar biogenic amines and amino acids. Strong hydrogen bonding interactions were observed between the solute amino acid carboxylic groups and cation-exchange groups from the ion-exchangers. This is the first time retention data correlated with logP data has revealed clustering of the solutes in two groups, according to the presence or absence of a carboxylic acid functional group. In addition, stronger retention behaviour was found for the IonPac CS12A cation-exchanger, containing both carboxylic and phosphonic functional groups. Further assessment of the orthogonality plots of retention factors for the three stationary phases revealed that the columns exhibited different complimentary selectivity that can be utilised to achieve specific separations.