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1.
Electrophoresis ; 45(3-4): 234-243, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37847878

RESUMO

In this study, methods for analyzing inorganic ions and carbohydrates in cardioplegia and nephroplegia solutions were developed and validated using ion chromatography with both conductivity and pulsed amperometric detection. The inorganic ions such as sodium, potassium, and calcium were separated by a cation-exchange column with 27 mM methanesulfonic acid as mobile phase at 0.5 mL/min. The anion (chloride) and carbohydrates (mannitol and glucose) were analyzed by an anion-exchange column using a mobile phase of 20 mM sodium hydroxide at 1.0 mL/min. The methods showed a high sensitivity for all analytes, with quantification limits from 0.0002 to 0.06 mg/L. Good linearities between the peak areas and concentrations were found for all analytes within the selected concentration range (R2  > 0.999). Relative standard deviation values for repeatability and interday precision were 0.1%-1.0% and 0.7%-1.6%, respectively. The accuracy was validated by determining the percentage recovery, which was between 98.0% and 101.3% for all analytes, indicating good accuracy of the methods. The robustness was verified by using an experimental design. Finally, real samples were analyzed to determine the content of the analytes. All assay values were between 96.8% and 102.5%.


Assuntos
Carboidratos , Glucose , Cromatografia por Troca Iônica/métodos , Carboidratos/análise , Ânions , Parada Cardíaca Induzida
2.
Environ Sci Technol ; 58(5): 2458-2467, 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38270113

RESUMO

High-resolution mass spectrometry (HRMS)-based suspect and nontarget screening has identified a growing number of novel per- and polyfluoroalkyl substances (PFASs) in the environment. However, without analytical standards, the fraction of overall PFAS exposure accounted for by these suspects remains ambiguous. Fortunately, recent developments in ionization efficiency (IE) prediction using machine learning offer the possibility to quantify suspects lacking analytical standards. In the present work, a gradient boosted tree-based model for predicting log IE in negative mode was trained and then validated using 33 PFAS standards. The root-mean-square errors were 0.79 (for the entire test set) and 0.29 (for the 7 PFASs in the test set) log IE units. Thereafter, the model was applied to samples of liver from pilot whales (n = 5; East Greenland) and white beaked dolphins (n = 5, West Greenland; n = 3, Sweden) which contained a significant fraction (up to 70%) of unidentified organofluorine and 35 unquantified suspect PFASs (confidence level 2-4). IE-based quantification reduced the fraction of unidentified extractable organofluorine to 0-27%, demonstrating the utility of the method for closing the fluorine mass balance in the absence of analytical standards.


Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Animais , Fluorocarbonos/análise , Poluentes Químicos da Água/análise , Espectrometria de Massas , Flúor , Mamíferos
3.
Anal Bioanal Chem ; 416(11): 2871-2882, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38581531

RESUMO

Antarctic seaweeds are vital components of polar marine ecosystems, playing a crucial role in nutrient cycling and supporting diverse life forms. The sulfur content in these organisms is particularly interesting due to its implication in biogeochemical processes and potential impacts on local and global environmental systems. In this study, we present a comprehensive characterization of seaweed collected in the Antarctic in terms of their total sulfur content and its distribution among different classes of species, including thiols, using various methods and high-sensitivity techniques. The data presented in this paper are unprecedented in the scientific literature. These methods allowed for the determination of total sulfur content and the distribution of sulfur compounds in different fractions, such as water-soluble and proteins, as well as the speciation of sulfur compounds in these fractions, providing valuable insights into the chemical composition of these unique marine organisms. Our results revealed that the total sulfur concentration in Antarctic seaweeds varied widely across different species, ranging from 5.5 to 56 g kg-1 dry weight. Furthermore, our investigation into the sulfur speciation revealed the presence of various sulfur compounds, including sulfate, and some thiols, which were quantified in all ten seaweed species evaluated. The concentration of these individual sulfur species also displayed considerable variability among the studied seaweeds. This study provides the first in-depth examination of total sulfur content and sulfur speciation in brown and red Antarctic seaweeds.


Assuntos
Alga Marinha , Alga Marinha/química , Regiões Antárticas , Peso Molecular , Ecossistema , Enxofre/metabolismo , Compostos de Enxofre/metabolismo , Verduras , Compostos de Sulfidrila/metabolismo
4.
Anal Bioanal Chem ; 416(24): 5325-5333, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39177792

RESUMO

The gravimetric isotope mixture method is the primary method to determine absolute isotope ratios. This method, however, depends on the existence of suitable spike materials and knowledge of their purities. Determining the purity of the spikes can be tedious and labour-intensive. In this publication, an advancement of the gravimetric isotope mixture method, rendering the determination of the purity of the spike materials unnecessary, is presented. The advancement combines mass spectrometry and ion chromatography leading to an approach being independent of the purity of the spike materials. In the manuscript the mathematical background and the basic idea of the novel approach are described using a two-isotope system like copper or lithium.

5.
Anal Bioanal Chem ; 416(20): 4503-4517, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38896239

RESUMO

Residues of various highly polar pesticides and their metabolites are commonly found in numerous food products. Some of these compounds, such as glyphosate, are not only used in large amounts in agriculture, but are also controversially discussed in public. Here, we present a method, employing ion chromatography (IC) coupled to tandem mass spectrometry (IC-MS/MS), for the analyses of glyphosate, aminomethyl phosphonic acid (AMPA), N-acetyl-glyphosate (NAGly), fosetyl, and 10 further highly polar pesticides and metabolites in various plant and animal matrices following a minimal sample preparation by means of the QuPPe method. Thorough investigations showed that an AS19 column enabled the analysis of all 14 compounds within 30 min. The best sensitivity could be obtained with the make-up solvent acetonitrile being admixed to the mobile phase at a 1:2 flow rate ratio. Matrix effects were thoroughly studied in terms of ion suppression and retention time shifts. Conductivity detection was used to monitor elution profiles of matrix co-extractives in comparison with matrix effect profiles obtained by continuous post-column infusion of a mix with 13 highly polar pesticides and metabolites. These tests indicated that a fivefold dilution of QuPPe extracts was suitable for the routine analysis of samples for MRL-conformity, as it considerably reduced matrix effects maintaining sufficient sensitivity and high recovery rates in eight different commodities. The suitability of the final method for its application in routine analysis was verified by the analysis of >130 samples containing incurred residues where the results were compared with two existing LC-MS/MS methods.


Assuntos
Contaminação de Alimentos , Resíduos de Praguicidas , Espectrometria de Massas em Tandem , Espectrometria de Massas em Tandem/métodos , Animais , Contaminação de Alimentos/análise , Resíduos de Praguicidas/análise , Praguicidas/análise , Ânions/análise , Análise de Alimentos/métodos , Cromatografia por Troca Iônica/métodos , Plantas/química
6.
J Sep Sci ; 47(15): e2400235, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-39135212

RESUMO

Poly- and perfluoroalkyl substances (PFAS) are a class of persistent organic pollutants whose high stability and appreciable water solubility have led to near-global contamination. PFAS are bioaccumulative toxins that have been linked to a myriad of disorders and have been detected nearly universally in human blood. Liquid chromatography-tandem mass spectrometry is the most frequent method used for quantitation, though this typically only measures a few dozen of the >14 000 known PFAS and has been shown to account for a small portion of the total organic fluorine present. Sum parameter methods such as total, extractable, and adsorbable organic fluorine have emerged as alternative measurements for PFAS determination. Combustion ion chromatography has become the preferred method for organofluorine measurement where the sorbent or extract containing PFAS is combusted and the emitted hydrofluoric acid (HF) is a measure of the cumulative organofluorine present. Herein we critically review the types of organofluorine measurement, their separation from the sample matrix, and key parameters of the analytical instrument that affect sensitivity, reproducibility, and recovery with regards to PFAS analysis.

7.
J Sep Sci ; 47(18): e202400536, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39302689

RESUMO

Relative to suppressed conductometric anion exchange chromatography, conductometric ion exclusion chromatography (IEC) is much less popular. Poor limit of detection and manual preparation of eluent are primarily responsible for this. We describe an electrodialytic phosphoric eluent generator for the online production of phosphoric acid eluent at a concentration exceeding 35 mM. It is a sandwiched configuration consisting of three channels isolated by stacked anion exchange membranes and a bipolar membrane plus stacked anion exchange membrane. Such a unique configuration ensures the production of gas-free eluent, obviating the need for a gas removal device. The resulting eluent concentration is controlled by varying the current. Coupled with an ultraviolet absorbance detector, a 0.04-16.67 mg/L limit of detection for model organic acids was achieved by IEC equipped with an electrodialytic phosphoric eluent generator.

8.
J Sep Sci ; 47(17): e2400369, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39252170

RESUMO

Epoxy resins, as important thermosetting polymers, exhibit excellent adhesion to various substrates. In view of this, reticulate coating of triglycidyl isocyanate with triethylenetetramine was introduced onto the surface of poly(styrene-divinylbenzene) utilizing amine curing reaction to obtain poly(styrene-divinylbenzene)@triglycidyl isocyanate-triethylenetetramine composite microspheres. The amino groups and epoxy groups of triglycidyl isocyanate-triethylenetetramine endowed poly(styrene-divinylbenzene) with good reactivity, which could be quaternized under mild conditions to obtain an anion exchange chromatographic stationary phase. The quaternized poly(styrene-divinylbenzene)@triglycidyl isocyanate-triethylenetetramine was characterized by scanning electron microscope, Fourier-transform infrared spectroscopy, N2 adsorption-desorption experiment, et al. The chromatographic performance of the customized column was evaluated by separating seven conventional anions, organic weak acids, and carbohydrates. Poly(styrene-divinylbenzene)@triglycidyl isocyanate-triethylenetetramine possesses the uniform size of poly(styrene-divinylbenzene) microspheres and good reactivity of triglycidyl isocyanate-triethylenetetramine, which offers a flexible strategy for the preparation of anion exchange stationary phase. The column exhibits excellent chemical and mechanical stability and chromatographic performance. Finally, the column was successfully applied for the determination of nitrite in pickles.

9.
Molecules ; 29(14)2024 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-39064991

RESUMO

Ion chromatography and related techniques have been the most popular separation methods used in the determination of organic and inorganic anions and cations, predominantly in water and wastewater samples. Making progress in their development and introducing new stationary phases, methods of detection and preparation of samples for analyses have given rise to the broadening of their analytical range. Nowadays, they are also used for substances that are not ionic by nature but can convert to such forms under certain conditions. These encompass, among others, carbohydrates, whose role and significance in humans' lives and environment is invaluable. Their presence in the air is mostly due to the industrial burning of biomass for energy production purposes. In addition, the content of sugars in plants, fruits and vegetables, constituting the base of human diets, affects our health condition. Given that, there is not only a need for their determination by means of routine methods but also for searching for novel analytical solutions. Based on literature data from the past decade, this paper presents the possibilities and examples of applications regarding ion chromatography and related techniques for the determination of carbohydrates in environmental samples, biomass and plants constituting food or raw materials for food production. Attention has been paid to the virtues and limitations of the discussed separation methods in this respect. Moreover, perspectives on their development have been defined.


Assuntos
Carboidratos , Carboidratos/análise , Carboidratos/química , Cromatografia por Troca Iônica/métodos , Humanos , Biomassa , Plantas/química
10.
Molecules ; 29(16)2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39202924

RESUMO

The potential of utilizing inorganic constituents in processed animal proteins (PAPs) for species identification in animal feeds was investigated, with the aim of using these constituents to ensure the quality and authenticity of the products. This study aimed to quantify the inorganic content across various PAP species and assess whether inorganic analysis could effectively differentiate between PAP species, ultimately aiding in the identification of PAP fractions in animal feeds. Four types of PAPs, namely bovine, swine, poultry, and fish-based, were analyzed and compared to others made up of feathers of vegetal-based feed. Also, three insect-based PAPs (Cricket, Silkworm, Flour Moth) were considered in this study to evaluate the differences in terms of the nutrients present in this type of feed. Ionic chromatography (IC) was used to reveal the concentrations of NO3-, NO2, Cl-, and SO42-, and inductively coupled plasma optical emission spectroscopy (ICP-OES) to detect Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, P, Si, Sr, Ti, and Zn. The application of multivariate chemometric techniques to the experimental results allowed us to determine the identification capability of the inorganic composition to identify correlations among the variables and to reveal similarities and differences among the different species. The results show the possibility of using this component for discriminating between different PAPS; in particular, fish PAPs are high in Cd, Sr, Na, and Mg content; swine PAPs have lower metal content due to high fat; feathers and vegetal feed have similar Al, Si, and Ni, but feathers are higher in Fe and Zn; and insect PATs have nutrient levels comparable to PAPs of other origins but are very high in Zn, Cu, and K.


Assuntos
Ração Animal , Animais , Ração Animal/análise , Bovinos , Suínos , Compostos Inorgânicos/análise , Plumas/química , Aves Domésticas
11.
Bull Environ Contam Toxicol ; 112(4): 55, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38565721

RESUMO

In August 2021, the Mar Menor, a saltwater lagoon located in the Region of Murcia (Spain), suffered a tragic environmental episode of dystrophic crisis and anoxia. The appearance of numerous dead fish in different areas of the lagoon over the course of days put all the authorities and the population of the area on alert. This paper shows a case study of what happened in the lagoon in terms of the presence of the most common inorganic pollutants. Measurements of the concentration of nitrogen species, phosphates and main heavy metals were carried out at different sampling sites in the Mar Menor from May 2021 to November 2022. Chemical analyses were carried out for each of the species under study. These analyses provide valuable information about the dystrophic crisis caused by a classic eutrophication process that began with the excessive nutrient input into the Mar Menor. Ion chromatography and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) were used as instrumentation for the quantification of these samples. The species whose values were greatly increased after the tragic episode described above were nitrates. The concentration varied significantly at the different sampling sites throughout the study. On the last sampling date, decreased concentrations of all the species were measured at each of the sampling sites, coinciding with the apparent good state of the lagoon.


Assuntos
Poluentes Químicos da Água , Animais , Poluentes Químicos da Água/análise , Monitoramento Ambiental , Cromatografia Gasosa-Espectrometria de Massas , Nitratos/análise , Espanha
12.
Artigo em Zh | MEDLINE | ID: mdl-38538243

RESUMO

Objective: To establish a method for the determination of n-butylamine in the air of the workplace by ion chromatography. Methods: In February 2022, on-site sampling was carried out using an atmospheric sampler. N-butylamine was adsorbed by a neutral silica gel tube and then performed for qualitative and quantitative determination by ion chromatography after ultrasonic desorption with 10 mmol/L sulfuric acid solution. Results: The linear range of the method was 0.0375-100.0 µg/ml, the linear equation of the standard curve was y=0.0713x-0.0327, the correlation coefficient was 0.9992. The detection limit of the method was 11.25 µg/L, and the lower limit of quantification was 37.50 µg/L, the lowest quantitative concentration was 0.025 mg/m(3) (in term of sampling 7.5 L). The average desorption efficiency of the method was 91.50%-95.38%, the precision was 1.10%-2.30%, the standard recovery was 83.83%-100.02%, sampling efficiency was 100.00%. Conclusion: This method is fast, sensitive and accurate, and can be used for the determination of n-butylamine in the air of workplace.


Assuntos
Poluentes Ocupacionais do Ar , Butilaminas , Poluentes Ocupacionais do Ar/análise , Cromatografia/métodos , Local de Trabalho
13.
Environ Sci Technol ; 57(48): 20159-20168, 2023 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-37934924

RESUMO

Research on per- and polyfluoroalkyl substances (PFAS) frequently incorporates organofluorine measurements, particularly because they could support a class-based approach to regulation. However, standardized methods for organofluorine analysis in a broad suite of matrices are currently unavailable, including a method for extractable organofluorine (EOF) measured using combustion ion chromatography (CIC). Here, we report the results of an international interlaboratory comparison. Seven laboratories representing academia, government, and the private sector measured paired EOF and PFAS concentrations in groundwater and eel (Anguilla rostrata) from a site contaminated by aqueous film-forming foam. Among all laboratories, targeted PFAS could not explain all EOF in groundwater but accounted for most EOF in eel. EOF results from all laboratories for at least one replicate extract fell within one standard deviation of the interlaboratory mean for groundwater and five out of seven laboratories for eel. PFAS spike mixture recoveries for EOF measurements in groundwater and eel were close to the criterion (±30%) for standardized targeted PFAS methods. Instrumental operation of the CIC such as replicate sample injections was a major source of measurement uncertainty. Blank contamination and incomplete inorganic fluorine removal may introduce additional uncertainties. To elucidate the presence of unknown organofluorine using paired EOF and PFAS measurements, we recommend that analysts carefully consider confounding methodological uncertainties such as differences in precision between measurements, data processing steps such as blank subtraction and replicate analyses, and the relative recoveries of PFAS and other fluorine compounds.


Assuntos
Anguilla , Fluorocarbonos , Água Subterrânea , Poluentes Químicos da Água , Animais , Fluorocarbonos/análise , Água Subterrânea/química , Água , Flúor/análise , Flúor/química , Poluentes Químicos da Água/análise
14.
Anal Bioanal Chem ; 415(25): 6333-6343, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37599331

RESUMO

Furan fatty acids (FuFAs) are valuable minor fatty acids, which are known for their excellent radical scavenging properties. Typically, the furan moiety is embedded in an otherwise saturated carboxyalkyl chain. Occasionally, these classic FuFAs are accompanied by low amounts of unsaturated furan fatty acids (uFuFAs), which additionally feature one double bond in conjugation with the furan moiety. A recent study produced evidence for the occurrence of two pairs of E-/Z-uFuFA isomers structurally related to saturated uFuFAs. Here, we present a strategy that allowed such trace compounds to be enriched to a level suited for structure determination by NMR. Given the low amounts and the varied abundance ratio of the four uFuFA isomers, the isolation of individual compounds was not pursued. Instead, the entire isomer mixture was enriched to an amount and purity suitable for structure investigation with contemporary NMR methods. Specifically, lipid extracted from 150 g latex, the richest known source of FuFAs, was subsequently fractionated by countercurrent chromatography (CCC), silver ion, and silica gel column chromatography. Analysis of the resulting mixture of four uFuFAs isomers (2.4 mg in an abundance ratio of 56:23:11:9) by different NMR techniques including PSYCHE verified that the structures of the two most abundant isomers were E-9-(3-methyl-5-pentylfuran-2-yl)non-8-enoic acid and E-9-(3-methyl-5-pent-1-enylfuran-2-yl)nonanoic acid. Additionally, we introduced a computer-based method to generate an averaged chromatogram from freely selectable GC/MS runs of CCC fractions without the necessity of pooling aliquots. This method was found to be suitable to simplify subsequent enrichment steps.

15.
Anal Bioanal Chem ; 415(22): 5337-5352, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37394521

RESUMO

Analyzing the composition of (human) urine plays a major role in the fields of biology and medicine. Organic molecules (such as urea, creatine) and ions (such as chloride, sulfate) are the major compounds present in urine, the quantification of which allows for the diagnosis of a subject's health condition. Various analytical methods have been reported for studying urine components and validated on the basis of known and referenced compounds. The present work introduces a new method able to simultaneously determine both major organic molecules and ions contained in urine, by combining ion chromatography using a conductimetric detector with mass spectroscopy. The analysis of organic and ionized compounds (anionic and cationic) was achieved in double injections. For quantification, the standard addition method was used. Human urine samples were pre-treated (diluted and filtered) for IC-CD/MS analysis. The analytes were separated in 35 min. Calibration ranges (0-20 mg.L-1) and correlation coefficients (> 99.3%) as well as detection (LODs < 0.75 mg.L-1) and quantification (LOQs < 2.59 mg.L-1) limits were obtained for the main organic molecules (lactic, hippuric, citric, uric, oxalic acids, urea, creatine, and creatinine) and ions (chloride, sulfate, phosphate, sodium, ammonium, potassium, calcium, and magnesium) contained in urine. The intra- and inter-day accuracies of the analytes consistently ranged from 0.1 to 5.0%, and the precision was within 4.0%. For all analytes, no significant matrix effects were observed, and recoveries ranged from 94.9 to 102.6%. Finally, quantitative results of analytes were obtained from 10 different human urine samples.


Assuntos
Cloretos , Creatina , Humanos , Espectrometria de Massas , Cromatografia , Compostos Orgânicos , Sulfatos , Ureia , Cromatografia Líquida de Alta Pressão/métodos
16.
J Sep Sci ; 46(12): e2300038, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-37061853

RESUMO

Among all known compounds with herbicide activity glyphosate, has been the most commercially successful one. Currently, it is under evaluation because of its possible cancerogenic properties. However, the question is-if it is possible to completely withdraw it from use. Before it can happen, it is important to be sure of all its benefits and limitations, and this requires further detailed research. Due to the extent and prevalence of its use, glyphosate ends up in the environment and then in food and our bodies. There are several methods used for their determination. One of them is ion chromatography. Taking into account its advantages and disadvantages, as well as its rapid development, their importance in this field can be expected to increase in the near future. This paper summarizes the literature data from the past 22 years. The applications of ion chromatography in the determination of glyphosate in various types of environmental, food, and other samples are described. Moreover, the methods used so far are compared with the possibilities offered by ion chromatography, which main advantages and benefits are easy availability, low operating costs, green chemistry aspects, and suitable validation parameters.


Assuntos
Herbicidas , Herbicidas/análise , Cromatografia , Glicina/análise , Produtos Agrícolas , Glifosato
17.
Biologicals ; 81: 101664, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36791627

RESUMO

Polysaccharide vaccines essentially used in the prevention of bacterial infections are known to be good immunogens when conjugated to an immunogenic protein using various cyanylating agents. Analysis of residual cyanide in polysaccharide conjugate vaccines is an ardent task due to the complexity of the sample matrices and the lack of suitable methods. We report a selective ion chromatography method with electrochemical detection using IonPac AS7 column for estimation of residual cyanide in meningococcal serogroups A, C, W, Y and X bulk conjugates in presence of other interfering ions. Gold electrode and Ag/AgCl reference electrode ensures sensitivity and reproducibility of cyanide quantitation. The calibration curve of the method is linear having r2 ≥0.990 over the concentration range 1.45 ng/mL to 93.10 ng/mL. The recovery of cyanide in bulk conjugates ranged between 96.0% and 108.9%. The limits of detection and quantitation were 0.50 ng/mL and 1.45 ng/mL which corresponds to 0.31 ng/µg and 0.91 ng/µg of polysaccharide respectively. The method validation and feasibility study were performed using Men W and Men X bulk conjugates respectively with in house residual cyanide specification due to unavailability of pharmacopeia guidelines. The method is reproducible and can accurately quantify residual cyanide in purified meningococcal bulk conjugates.


Assuntos
Infecções Meningocócicas , Vacinas Meningocócicas , Neisseria meningitidis , Humanos , Cianetos , Reprodutibilidade dos Testes , Sorogrupo , Vacinas Meningocócicas/química , Infecções Meningocócicas/prevenção & controle , Polissacarídeos , Cromatografia por Troca Iônica
18.
Molecules ; 28(13)2023 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-37446882

RESUMO

Alkylresorcinols (∑ARs) are bioactive lipid compounds predominantly found in cereals. These amphiphilic compounds exist in a high structural diversity and can be divided into two main groups, i.e., 5-alkylresorcinols (ARs) and 2-methyl-5-alkylresorcinols (mARs). The pseudocereal quinoa has a very unique AR profile, consisting not only of straight-chain alkyl chains but also iso- and anteiso-branched isomers. Here, we describe a method for the isolation of such methyl-branched ARs and mARs from quinoa. The enrichment of the ∑AR fraction from the lipid extracts by centrifugal partition chromatography (CPC) was followed by ∑AR profiling using countercurrent chromatography (CCC) and GC/MS analysis of CCC fractions. A total of 112 ∑ARs could be detected, 63 of which had not been previously described in quinoa. Due to this high number of ∑ARs, the direct isolation of individual ARs was not possible using conventional CCC. Instead, the more powerful heart-cut mode was applied to enrich the target compounds. A final purification step-the separation of CCC-co-eluting mARs from ARs -was performed via silver ion chromatography. Altogether, ten rare branched-chain ∑ARs (five iso-branched mARs and five anteiso-branched ARs, including mAR19:0-i and AR20:0-a) were isolated with purities up to 98% in the double-digit mg range.


Assuntos
Chenopodium quinoa , Cromatografia Gasosa-Espectrometria de Massas , Isomerismo , Distribuição Contracorrente/métodos , Lipídeos
19.
Molecules ; 28(22)2023 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-38005289

RESUMO

Analytical methods based on the mass balance approach were developed for the purity evaluation of tetracycline hydrochloride, a representative salt compound used in pure veterinary drug analysis. The purity assignment method was used to quantify individual classes of impurities via independent analytical techniques. The mass fraction of the free base or salt form contained in a high-purity organic compound with a hydrochloride salt can be determined. The chloride content by ion chromatography-conductivity detector (IC-CD) and general classes of impurities, including structurally related impurities by liquid chromatography-ultraviolet (LC-UV) detector, water by Karl Fischer (KF) coulometric titration, residual solvents by headspace sampler gas chromatography/mass spectrometry (HS-GC/MS), and non-volatiles by thermogravimetric analyzer (TGA), were considered to calculate the purity of the mass fraction. The chloride content of the salt compound can be considered the main impurity in the mass fraction of the free base in the salt compound. A purity assay using quantitative nuclear magnetic resonance (q-NMR) as a direct determination method was performed to confirm the results of the mass balance method. The assigned purities of the tetracycline free form and its salt form in mass fraction were (898.80 ± 1.60) mg/g and (972.65 ± 1.58) mg/g, respectively, which are traceable to the international system of units (SI). Thus, the procedure for evaluating the purity of the free base and salt forms in the salt compound is newly demonstrated in this study.


Assuntos
Cloretos , Tetraciclina , Cromatografia Líquida/métodos , Cromatografia Gasosa-Espectrometria de Massas
20.
Environ Sci Technol ; 56(12): 7657-7667, 2022 06 21.
Artigo em Inglês | MEDLINE | ID: mdl-35544773

RESUMO

Fairbanks, Alaska, is a subarctic city with fine particle (PM2.5) concentrations that exceed air quality regulations in winter due to weak dispersion caused by strong atmospheric inversions, local emissions, and the unique chemistry occurring under the cold and dark conditions. Here, we report on observations from the winters of 2020 and 2021, motivated by our pilot study that showed exceptionally high concentrations of fine particle hydroxymethanesulfonate (HMS) or related sulfur(IV) species (e.g., sulfite and bisulfite). We deployed online particle-into-liquid sampler-ion chromatography (PILS-IC) in conjunction with a suite of instruments to determine HMS precursors (HCHO, SO2) and aerosol composition in general, with the goal to characterize the sources and sinks of HMS in wintertime Fairbanks. PM2.5 HMS comprised a significant fraction of PM2.5 sulfur (26-41%) and overall PM2.5 mass concentration of 2.8-6.8% during pollution episodes, substantially higher than what has been observed in other regions, likely due to the exceptionally low temperatures. HMS peaked in January, with lower concentrations in December and February, resulting from changes in precursors and meteorological conditions. Strong correlations with inorganic sulfate and organic mass during pollution events suggest that HMS is linked to processes responsible for poor air quality episodes. These findings demonstrate unique aspects of air pollution formation in cold and humid atmospheres.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Aerossóis/química , Poluentes Atmosféricos/análise , Poluição do Ar/análise , Alaska , Monitoramento Ambiental/métodos , Material Particulado/análise , Projetos Piloto , Estações do Ano , Enxofre
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