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1.
Anal Bioanal Chem ; 415(13): 2535-2545, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36539609

RESUMO

A new approach is introduced for rapid and reliable bacteria detection in food. Namely, static headspace-comprehensive two-dimensional gas chromatography (HS-GC × GC) with backflushing. The introduced approach provides fast detection of Escherichia coli (E. coli) in enriched ultra-high-temperature processed (UHT) dairy milk. The presence of E. coli may be indicated by detecting microbial volatile organic compounds emanating from test solutions inoculated with E. coli. In the present investigation, HS-GC × GC analysis is preceded by conventional enrichment in nutrient broth and inoculated samples are clearly discernable from controls following as little as 15 h sample enrichment. Headspace equilibration for 28 min followed by an 8 min GC × GC analysis of enriched test solutions reduces time-to-response by approximately one full day compared to conventional culture-based methods. The presence of ethanol, 1-propanol, and acetaldehyde may be used as a putative marker of E. coli contamination in milk and the introduced approach is able to detect single-cell initial bacterial load. Faster, reliable detection of pathogens and/or spoilage microbes in food products is desirable for the food industry. The described approach has great potential to complement the conventional workflow and be utilised for rapid microbial screening of foodstuff.


Assuntos
Escherichia coli , Compostos Orgânicos Voláteis , Animais , Cromatografia Gasosa-Espectrometria de Massas/métodos , Leite/química , Etanol/análise , Bactérias , Compostos Orgânicos Voláteis/análise
2.
Anal Bioanal Chem ; 415(13): 2483-2492, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36378281

RESUMO

An approach using pyrolysis with comprehensive two-dimensional gas chromatography with flame ionization detection is introduced for identifying common isolated plastic polymers. A quadrupole mass spectrometer is employed as a parallel detector to aid method development and improve polymer identification in complex matrices. Common plastic polymers including polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyamide, poly(methyl methacrylate), styrene-butadiene rubber, and polyethylene terephthalate are accurately identified within a total analysis time of 45 min. A strategy to enhance compatibility of high-resolution capillary gas chromatography using a 150-µm internal diameter column technology and a larger internal volume microfurnace-based pyrolyzer is discussed. This strategy resulted in minimizing the band broadening effect caused by the pyrolyzer's internal volume and overcoming the slow pressure buildup when the sample is inserted into the furnace. Prolonged pressure buildup to reach a final pressure setting can cause a safety shutdown to the pneumatic control system. The developed approach is complementary to spectroscopic techniques by offering mass based, chemical composition analysis of plastics.

3.
J Food Sci ; 87(3): 982-997, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-35175625

RESUMO

Coffee aroma is a complex mixture of volatile compounds. This study characterized the important aroma-active compounds associated with consumer liking in formulated coffee-flavored dairy beverages. Nine coffee-flavored dairy beverages were formulated: low fat-low coffee; medium fat-low coffee; high fat-low coffee; low fat-medium coffee; medium fat-medium coffee; high fat-medium coffee; low fat-high coffee; medium fat-high coffee; and high fat-high coffee. Regular coffee consumers, (n = 231) used a nine-point hedonic scale to rate acceptance of aroma. Volatile compounds were extracted by head space-solid phase micro-extraction (HS-SPME) and analyzed by gas chromatography-mass spectrometry-olfactometry (GC-MS-O) using a modified frequency (MF) approach. Fifty-two aroma-active compounds were detected. Thirty-one aroma-active compounds were considered important compounds with MF-value ≥ 50%. The total number of aroma-active compounds and their intensity were affected because of fat and coffee concentration. Partial least squares regression (PLSR) was performed to determine the relationship between aroma-active compounds and liking. PLSR analysis identified three groups of compounds regarding liking. Twenty-five compounds were associated with positive liking, for example, 2-(methylsulfanylmethyl) furan (coffee like). Sixteen compounds were negatively associated with liking, for example, 2-methoxyphenol (bacon, medicine like). Eleven detected compounds had no association with liking, for example, butane-2,3-dione (butter, fruit like). Practical Application: The result of this study may be applied to formulate coffee-flavored dairy beverages to maximize consumer acceptance and aroma-liking. This study suggested too low coffee concentration is not desirable. Too much fat affects aroma release and/or alters the characteristic coffee flavor which negatively affects consumer acceptance.


Assuntos
Odorantes , Compostos Orgânicos Voláteis , Bebidas/análise , Café , Odorantes/análise , Olfatometria , Paladar , Compostos Orgânicos Voláteis/análise
4.
J Food Sci ; 86(11): 5004-5015, 2021 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-34653256

RESUMO

The fat content of a product has the potential to influence consumer liking via mouthfeel, taste, and aroma modification. This study aims to determine the effects of fat and coffee concentration on sensory attributes and consumer liking of iced-coffee beverages. Nine iced-coffee beverages were formulated: low fat-low coffee; medium fat-low coffee; high fat-low coffee; low fat-medium coffee; medium fat-medium coffee; high fat-medium coffee; low fat-high coffee; medium fat-high coffee; and high fat-high coffee. Fat content was adjusted using different concentrations of cream, and coffee using different concentrations of Nescafé Blend 43. Regular coffee consumers (n = 231) rated their overall liking using a 9-point hedonic scale and completed a ranked preference based on degree of liking of all samples. Consumers also rated liking for sensory attributes: appearance, aroma, sweetness, coffee intensity, mouthfeel, and aftertaste. There were significant relationships between 1/ fat and 2/ coffee and liking of iced-coffee beverages (p < 0.001). There were three clusters of consumers based on iced-coffee preferences. Response surface curve indicated that overall liking of iced-coffee beverages increased with the increase of fat and coffee concentration to a certain level, then continuing to increase the fat and coffee concentration decreases overall liking. The finding of this study provides valuable information on how fat and coffee concentrations can be adjusted to modify consumer acceptance of iced-coffee beverages. PRACTICAL APPLICATION: The results of this research could be applied to reformulate iced-coffee beverages, while ensuring consumer acceptance. In addition, this research provides evidence that sweetness, aftertaste, coffee-intensity, and mouthfeel are important sensory attributes associated with consumer liking of iced-coffee beverages.


Assuntos
Café , Comportamento do Consumidor , Bebidas , Preferências Alimentares , Gelo , Paladar
5.
Foods ; 10(8)2021 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-34441728

RESUMO

Rice is consumed as a staple food by more than half of the world's population. Due to a higher fibre and micronutrient content, brown rice is more nutritious than white rice, but the consumption of brown rice is significantly lower than that of white rice, primarily due to sensory attributes. Therefore, the present research aimed to identify the sensory attributes which drive liking of Australian-grown brown and white rice varieties. Participants (n = 139) tasted and scored (9-point hedonic scale) their liking (i.e., overall liking, aroma, colour and texture) of brown and white rice types of Jasmine (Kyeema), Low GI (Doongara), and Medium grain rice (Amaroo). In addition, participants scored aroma, colour, hardness, fluffiness, stickiness, and chewiness, on Just About Right Scales. A within-subjects crossover design with randomised order (William's Latin Square design) was used with six repeated samples for liking and Just About Right scales. Penalty analyses were applied to determine the relative influence of perception of sensory attributes on consumer liking of the rice varieties. Across all varieties, white rice was liked more than brown rice due to the texture and colour, and Jasmine rice was preferred over Low GI and Medium Grain. Rice texture (hardness and chewiness) was the most important sensory attribute among all rice varieties and aroma was important for driving of liking between white rice varieties.

6.
J Chromatogr A ; 1651: 462330, 2021 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-34161833

RESUMO

A new automated micro liquid-liquid extraction technique was successfully developed. This novel syringe-based technique capitalizes on the advantages of vigorous fluid agitation and the shearing effect of two fluids with different properties to achieve high extraction efficiency. The technique is at least 20 times faster than mechanical shaking or sonication in achieving a similar recovery even with a hydrophilic probe molecule such as 1,4-dioxane in an aqueous medium. Excellent repeatability with a relative standard deviation as low as 0.56% over a five-day test, n = 2 per day, was demonstrated with 1,4-dioxane. Other model compounds in aqueous matrices evaluated, including phenolics and extraction solvents like chloroform and hexane, showed similar performance in repeatability. An added advantage of this technique involves performing multiple extractions. Its capabilities in conducting complicated extraction steps and minimizing the use of organic solvents as low as 200 µL to achieve a preconcentration effect were demonstrated. The technique is suitable for use with emulsion-forming samples without further sample manipulation by incorporating a demulsifier such as acetone during the extraction process. The technique was found to be efficient and environmentally friendly with low solvent waste. This technique is ideal for implementation in automated high throughput and cost-effective quality assurance laboratory environments.


Assuntos
Microextração em Fase Líquida/métodos , Automação , Emulsões , Microextração em Fase Líquida/tendências , Solventes/química , Água/química
7.
J Chromatogr A ; 1642: 462032, 2021 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-33714769

RESUMO

Liquid-liquid extraction is one of the most widely used and simplest sample preparation techniques. However, consumption of large volumes of organic solvent and manual handling are two major drawbacks of this technique. A multifunction autosampler syringe is introduced which permits automated liquid-liquid extraction in an enclosed operating environment, with low consumption of organic solvents. The device described herein features a micromixer function in addition to common autosampler syringe features like accurate and precise aspirating and dispensing. To test the functionality of the micromixer syringe, manual extraction of caffeine from a tea infusion and semi-automated extraction of dichloroethane from water were carried out. Excellent recoveries of caffeine from a tea infusion (89% recovery with 1.3% RSD) and dichloroethane from water (107% recovery with 10% RSD) were obtained. Two automated workflows were tested using the micromixer syringe mounted in a laboratory autosampler. Standalone automated micro liquid-liquid extraction was performed for sample preparation of selected polychlorinated biphenyl (PCB) congeners prior to comprehensive two-dimensional gas chromatography - electron capture detection analysis. Extraction of PCBs using the described approach used substantially less solvent than a validated solid-phase extraction approach whilst delivering equivalent results for samples with high-level PCBs. Finally, fully automated extraction and GC-MS analysis of polynuclear aromatic hydrocarbons (PAHs) from water samples was performed. Mean recoveries of extraction for PCB and PAH analysis were > 70% using 4 min automated liquid-liquid extractions.


Assuntos
Extração Líquido-Líquido/instrumentação , Extração Líquido-Líquido/métodos , Compostos Orgânicos/isolamento & purificação , Água/química , Cromatografia Gasosa-Espectrometria de Massas , Compostos Orgânicos/análise , Bifenilos Policlorados/análise , Bifenilos Policlorados/isolamento & purificação , Hidrocarbonetos Policíclicos Aromáticos/análise , Hidrocarbonetos Policíclicos Aromáticos/isolamento & purificação , Solventes , Seringas , Poluentes Químicos da Água/análise
8.
Compr Rev Food Sci Food Saf ; 19(5): 2380-2420, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-33336982

RESUMO

Sensory analysis is a key method to assess flavor quality and to characterize consumer preference and acceptance, whereas instrumental analysis helps to identify flavor compounds. The combination of sensory analysis and instrumental analysis provides a platform for revealing key flavor compounds associated with consumer liking. This review discusses sensory evaluation, aroma analysis, and separation techniques using coffee as a central theme where possible to explore the aforementioned techniques. Emerging statistical methodologies are discussed along with their role in tying together discrete studies to reveal important flavor compounds that are either positively or negatively associated with consumer liking. Coffee is very widely studied, a fact that may be partially ascribed to its immense popularity in modern society. To this end, more than 100 sensory lexicons have been developed and implemented to describe specific coffee characteristics and around 1,000 volatile compounds have been identified in coffee. As a remarkably complex sample coffee has provided substantial impetus for adoption of new analytical approaches such as multidimensional separation technologies. This review describes common and emerging analytical techniques that have been employed for coffee analysis, with a particular emphasis placed on those associated with determination of volatile compounds. A comprehensive list of volatile compounds reported in coffee from 1959-2014 is included herein.


Assuntos
Café/química , Comportamento do Consumidor , Odorantes , Aromatizantes , Humanos , Paladar , Compostos Orgânicos Voláteis
9.
J Chromatogr A ; 1613: 460669, 2020 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-31732157

RESUMO

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 µm down to ~5 µm were produced. The advantages of incorporating up to ~60%microdiamond (2-4 µm) 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 µg 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/química
10.
Anal Chem ; 91(17): 11223-11230, 2019 09 03.
Artigo em Inglês | MEDLINE | ID: mdl-31393704

RESUMO

A 3D-printed microreactor for post-column reactions was successfully integrated with comprehensive two -dimensional  gas chromatography. A two-stage post-column reaction provided a carbon-independent response, enhanced the flame ionization detection uniformity, and improved the detector sensitivity. These enhancements are critical to overcome challenges in analyses using comprehensive two-dimensional gas chromatography and flame ionization detection, which aim to separate and quantify multiple components. Post-column reaction flame ionization detection eliminated the requirement of multilevel and multicompound calibration, it enabled the determination of target analytes with a single-carbon-containing calibration compound with an accuracy of ±10%, and it improved the sensitivity for compounds that were not efficiently ionized by flame ionization detection. Extra column band-broadening caused by the incorporation of the 3D-printed microreactor was minimized using optimized reactor operating parameters and intercolumn connectivity. Chromatographic fidelity was in the practical domain of comprehensive 2D gas chromatography. Typical peak widths at half-height using the described approach ranged from 165 to 235 ms for probe compounds with retention factors spanning 5 < k < 40.

11.
Food Chem ; 275: 15-23, 2019 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-30724181

RESUMO

This study investigated the volatile phytochemical diversity of 30 samples obtained from experimental hybrid and commercial H. lupulus L. plants. Essential oils distilled from these samples were analysed by high resolution gas chromatography coupled with accurate mass time-of-flight mass spectrometry (GC-accTOFMS). A total of 58 secondary metabolites, mainly comprising 18 esters, 6 monoterpene hydrocarbons, 2 oxygenated monoterpenes, 20 sesquiterpene hydrocarbons, 7 oxygenated sesquiterpenes, and 4 ketones, were positively or tentatively identified. A total of 24 metabolites were detected in all samples, but commercial cultivars (selected for brewing performance) had fewer compounds identified compared to experimental genotypes. Chemometrics analyses enabled distinct differentiation of experimental hybrids from commercial cultivars, discussed in terms of the different classes of compounds present in different genotypes. Differences among the mono- and sesquiterpenoids, appear to be related to either: i) the genetic origin of the plants; or ii) the processes of bioaccumulation of the identified secondary metabolites.


Assuntos
Humulus/química , Óleos Voláteis/análise , Austrália , Cerveja , Cromatografia Gasosa-Espectrometria de Massas/métodos , Genótipo , Humulus/genética , Humulus/metabolismo , Monoterpenos/análise , Óleos Voláteis/química , Compostos Fitoquímicos/análise , Metabolismo Secundário , Sesquiterpenos/análise
12.
Anal Chim Acta ; 1047: 231-237, 2019 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-30567655

RESUMO

Removal of organic solvent from sample extracts is required before analysis by reversed phase HPLC to preserve chromatographic performance and allow for bigger injection volumes, boosting sensitivity. Herein, an automated on-line extraction evaporation procedure is integrated with HPLC analysis. The evaporation occurs inside a 200 µm microfluidic channel confined by a vapor permeable membrane. A feedback control algorithm regulates evaporation rate keeping the output flow rate constant. The evaporation process across this membrane was firstly characterized with water/solvent mixtures showing organic solvent removal capabilities. This system allowed continuous methanol, ethanol and acetonitrile removal from samples containing up to 80% organic solvent. An evaporative injection procedure was developed demonstrating the use of the device for fully integrated extract reconstitution coupled to HPLC analysis, applied to analysis of the antibiotic chloramphenicol in milk samples. Sample reconstitution and collection was performed in less than 10 min and can be executed simultaneously to HPLC analysis of the previous sample in a routine workflow, thus having minimal impact on the total sample analysis time when run in a sequence.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Solventes/química , Acetonitrilas/química , Animais , Cloranfenicol/isolamento & purificação , Etanol/química , Metanol/química , Microfluídica/métodos , Leite/química , Sistemas On-Line
13.
J Chromatogr A ; 1573: 151-155, 2018 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-30217384

RESUMO

An effective analytical strategy for targeted analysis of volatile organic compounds which combines two orthogonal separation mechanisms and multiple tunable detection in a compact transportable analytical system is introduced. This strategy uses a commercially available micromachined gas chromatograph comprising a micromachined on-board thermal conductivity detector. The chromatograph capability is enhanced by incorporating a modified diode array detector and a radio frequency modulated ion mobility spectrometry microfabricated electromechanical system. The analytical platform offers powerful detection capabilities of individual compounds and various classes of volatile organic compounds with improved provisional confirmatory capability. The transportable micromachined gas chromatograph employs field replaceable conventional capillary columns for the separation of analytes. The use of a silicon micromachined sample introduction device affords fast injection to minimize band broadening with fast chromatographic separation rendered in the order of minutes. Advantaged synergy also includes leveraging the resolving power of gas chromatography to minimize charge exchange in the ionization chamber of the differential mobility spectrometer for improved detector performance. Performance of this scalable and transportable analytical system is demonstrated with relevant volatile compounds such as acetaldehyde, acetone, carbon disulfide, benzene, and ethyl butyrate having a day-to-day variability less than 5% and with a high degree of reliability.


Assuntos
Técnicas de Química Analítica/instrumentação , Técnicas de Química Analítica/métodos , Cromatografia Gasosa/instrumentação , Compostos Orgânicos Voláteis/análise , Microtecnologia , Reprodutibilidade dos Testes , Silício/química , Compostos Orgânicos Voláteis/química
14.
J Chromatogr A ; 1563: 171-179, 2018 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-29891401

RESUMO

An effective analytical strategy was developed and implemented to exploit the synergy derived from three different detector classes for gas chromatography, namely ultraviolet spectroscopy, flame ionization, and mass spectrometry for volatile compound analysis. This strategy was achieved by successfully hyphenating a user-selectable multi-wavelength diode array detector featuring a positive temperature coefficient thermistor as an isothermal heater to a gas chromatograph. By exploiting the non-destructive nature of the diode array detector, the effluent from the detector was split to two parallel detectors; namely a quadrupole mass spectrometer and a flame ionization detector. This multi-hyphenated configuration with the use of three detectors is a powerful approach not only for selective detection enhancement but also for improvement in structural elucidation of volatile compounds where fewer fragments can be obtained or for isomeric compound analysis. With the diode array detector capable of generating high resolution gas phase spectra, the information collected provides useful confirmatory information without a total dependence on the chromatographic separation process which is based on retention time. This information-rich approach to chromatography is achieved without incurring extra analytical time, resulting in improvements in compound identification accuracy, analytical productivity, and cost. Chromatographic performance obtained from model compounds was found to be acceptable with a relative standard deviation of the retention times of less than 0.01% RSD, and a repeatability at two levels of concentration of 100 and 1000ppm (v/v) of less than 5% (n=10). With this configuration, correlation of data between the three detectors was simplified by having near identical retention times for the analytes studied.


Assuntos
Cromatografia Gasosa-Espectrometria de Massas/métodos , Alcenos/análise , Benzeno/análise , Ionização de Chama , Nitrogênio/análise , Espectrofotometria Ultravioleta , Compostos Orgânicos Voláteis/análise
15.
Anal Chem ; 90(11): 6426-6430, 2018 06 05.
Artigo em Inglês | MEDLINE | ID: mdl-29750505

RESUMO

Positive temperature coefficient thermistors acting as heating devices are quickly growing in popularity and are being adapted into critical applications in many sectors from medical to space discovery. Positive temperature coefficient heating offers substantial benefits for miniaturized and portable analytical devices in key aspects such as energy efficiency, safety in overheating, size, scalability, and in discovering new thermal management strategies. These heaters can reach 230 °C without additional requirements for regulating electronics. By incorporating positive temperature coefficient technology into a commercial diode array photometric detector, the detector is made suitable for coupling with gas chromatography. The detector cartridge flow cell is heated to a specific target temperature within the range of 70 to 150 °C without impacting the detector's construction material or imparting any negative effect to the surrounding detector system electronics. Applying a temperature of 150 °C to the cell permits analysis of volatile and semivolatile compounds with a boiling point equivalent to that of n-hexadecene (285 °C). Model compounds of alkene homologues from C8 to C16 showed a maximum peak asymmetry of 1.10 with the heated cell design. A high degree of repeatability was observed with RSD of less than 0.01% in retention time and 3% in peak area ( n = 10).

16.
Anal Chem ; 90(8): 5264-5271, 2018 04 17.
Artigo em Inglês | MEDLINE | ID: mdl-29575899

RESUMO

A novel sequential three-dimensional gas chromatography-high-resolution time-of-flight mass spectrometry (3D GC-accTOFMS) approach for profiling secondary metabolites in complex plant extracts is described. This integrated system incorporates a nonpolar first-dimension (1Dnp) separation step, prior to a microfluidic heart-cut (H/C) of a targeted region(s) to a cryogenic trapping device, directly followed by the rapid reinjection of a trapped solute into a polar second-dimension (2DPEG) column for multidimensional separation (GCnp-GCPEG). For additional separation, the effluent from 2DPEG can then be modulated according to a comprehensive 2D GC process (GC×GC), using an ionic liquid phase as a third-dimension (3DIL) column, to produce a sequential GCnp-GCPEG×GCIL separation. Thus, the unresolved or poorly resolved components, or regions that require further separation, can be precisely selected and rapidly transferred for additional separation on 2D or 3D columns, based on the greater separation realized by these steps. The described integrated system can be used in a number of modes, but one useful approach is to target specific classes of compounds for improved resolution. This is demonstrated through the separation and detection of the oxygenated sesquiterpenes in hop ( Humulus lupulus L.) essential oil and agarwood ( Aquilaria malaccensis) oleoresin. Improved resolution and peak capacity were illustrated through the progressive comparison of the tentatively identified components for GCnp-GCPEG and GCnp-GCPEG×GCIL methods. Relative standard deviations of intraday retentions (1 tR, 2 tR,, and 3 tR) and peak areas of ≤0.01, 0.07, 0.71, and 7.5% were achieved. This analytical approach comprising three GC column selectivities, hyphenated with high-resolution TOFMS detection, should be a valuable adjunct for the improved characterization of complex plant samples, particularly in the area of plant metabolomics.

17.
Anal Chim Acta ; 1000: 303-309, 2018 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-29289323

RESUMO

An evaporative membrane modulator was developed, built and evaluated to avoid loss of performance in the second dimension when coupling two-dimensional liquid chromatography systems. The automated interface reduces the volume after 1D elution on-line by a pre-determined factor, regardless of the separation gradient. This volume reduction ensures that the injection volume in the 2D is appropriate for the second column, avoiding the detrimental effects of overloading. In addition, the fraction solvent composition is constant over the length of the separation increasing reproducibility of 2D separations. The evaporative membrane modulator was demonstrated with a 10-fold reduction, reducing the injection volume from 50 to 5 µL. A consequence of the EMM device is a reduction in the capacity of the first dimension, which is decreased by a factor of 2.4, but the peak width at half maximum was reduced by up to 22% in the second dimension. When band broadening is considered, the corrected peak capacity with the modulator was only 10% lower than that without the modulator, but with a gain in peak height of 2-3, and a decrease in retention time between subsequent peak-slices reduced from 4s to be negligible. This improves peak shape and shows potential to facilitate peak identification and quantification in more complex applications.

18.
J Chromatogr A ; 1536: 110-121, 2018 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-28830588

RESUMO

Comprehensive two-dimensional gas chromatography with quadrupole accurate mass time-of-flight mass spectrometry (GC×GC-Q-TOFMS) is employed to profile Humulus lupulus L. (hop) essential oils. Comparison of characterised essential oils allows discrimination among chemotypes. Experimental and commercial hop genotypes displayed distinguishable chemotypic patterns among the volatile secondary metabolites making up their essential oils. In total, 210-306 unique compounds were detected (depending on specific genotype), with 99 of these compounds either positively or tentatively identified. Identified volatile secondary metabolites were grouped into esters, monoterpene hydrocarbons, oxygenated monoterpenes, sesquiterpene hydrocarbons, oxygenated sesquiterpenes and ketones. Terpenoids were the dominant chemical families across all hop genotypes analysed, representing between 67% and 90% of the total ion count. The multidimensional chromatographic profiles of hop essential oils are extremely information-rich, making GC×GC-Q-TOFMS useful for fast screening of new hybrid hop genotypes, and therefore informing breeding strategies to derive new commercial hop cultivars for the development of distinctive and desirable beers.


Assuntos
Cromatografia Gasosa-Espectrometria de Massas , Humulus/química , Óleos Voláteis/química , Cerveja/análise , Genótipo , Humulus/genética , Monoterpenos/análise , Sesquiterpenos/análise , Terpenos/análise
19.
J Chromatogr A ; 1524: 202-209, 2017 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-28987530

RESUMO

We introduce an information rich analytical approach called parallel comprehensive two-dimensional gas chromatography (2GC×2GC). This parallel chromatography approach splits injected samples into two independent two-dimensional column ensembles and provides two GC×GC separations by using contra-directional thermal modulation. The first-dimension (1D) and second-dimension (2D) columns are connected using planar three-port microchannel devices, which are supplied with supplementary flow via two pressure controller modules. Precise carrier gas flow control at the junction of the 1D and 2D columns permits independent control of flow conditions in each separation column. The 2GC×2GC approach provides two entirely independent GC×GC separations for each injection. Analysis of hop (Humulus lupulus L.) essential oils is used to demonstrate the capability of the approach. The analytical performance of each GC×GC separation in the 2GC×2GC experiment is comparable to individual GC×GC separation with matching column configurations. The peak capacity of 2GC×2GC is about 2 times than that of single GC×GC system. The dual 2D chromatograms produced by this single detector system provide complementary separations and additional identification information by harnessing different selectivity provided by the four separation columns.


Assuntos
Técnicas de Química Analítica/métodos , Cromatografia Gasosa , Técnicas de Química Analítica/instrumentação , Óleos Voláteis/isolamento & purificação , Pressão
20.
J Chromatogr A ; 1500: 153-159, 2017 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-28442132

RESUMO

We introduce a gas chromatography detection approach that uses diode array detection operated in series with flame ionisation detection and demonstrate the utility of the detection approach for determination of volatile organic compounds. Diode array detection brings ultraviolet - visible spectroscopy (over a range of 190-640nm) onto the capillary gas chromatography time-scale, where average peak widths of analytes are on the order of 3-5s. The non-destructive nature of the diode array detector affords serially-coupled flame ionisation detection. This arrangement delivers near-simultaneous selective and universal detection without incurring additional analytical time, and without recourse to column flow splitting. The hyphenated technique is shown to be effective for chromatographic applications spanning an equivalent volatility range from C1 to C7n-paraffin hydrocarbons. The approach introduced herein provides increased sensitivity and selectivity for classes of compounds amenable to electronic spectroscopy such as alkenes, dienes, sulfurs, and aromatic compounds. The approach is demonstrated for direct measurement of carbon disulfide in work place atmospheres with a detection limit of 93pg on column and for the direct measurement of 1,3-butadiene in hydrocarbon matrices and ambient air with a detection of 73pg on column, each in less than 5min.


Assuntos
Cromatografia Gasosa/métodos , Ionização de Chama/métodos , Butadienos/análise , Cromatografia Gasosa/instrumentação , Ionização de Chama/instrumentação , Hidrocarbonetos/análise , Limite de Detecção , Parafina/análise , Compostos Orgânicos Voláteis/análise
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