SPME

The aim of this paper was to characterize the complete volatile profile of Conciato Romano cheese, a traditional Italian product aged in a mixture of olive oil, wine, and spices, and its modification during ripening, by using SPME sampling and GC/MS analysis of volatiles and considering the rind and body parts separately. Seventy-six volatile compounds were identified, belonging to chemical classes of acids (8), aldehydes (3), alcohols (14), esters (36), ketones (9), hydrocarbons (1), and terpenes (5). Acids and esters represented the most important chemical classes and are originated from lipolysis and hydrolysis of triglycerides. Aging caused dramatic changes in volatile compounds, particularly on the cheese rind, where the amount of esters, acids, alcohols, and ketones was found particularly abundant at 8 months of aging. Interesting differences were found in volatile headspace composition depending on the external or inner parts. The higher complexity in volatile profile of aged cheese was attributed both to the aging process and tanning mixture. Sensory analysis resulted in higher perception of “sweet” and “stickiness” and significantly lower olfactory persistence in fresh product, while higher values for “salty,” “spicy,” and “persistent” were found in aged ones.

The present review aims to describe the recent and most impactful applications in pollutant analysis using solid-phase microextraction (SPME) technology in environmental, food, and bio-clinical analysis. The covered papers were published in the last 5 years (2014-2019) thus providing the reader with information about the current state-of-the-art and the future potential directions of the research in pollutant monitoring using SPME. To this end, we revised the studies focused on the investigation of persistent organic pollutants (POPs), pesticides, and emerging pollutants (EPs) including personal care products (PPCPs), in different environmental, food, and bio-clinical matrices. We especially emphasized the role that SPME is having in contaminant surveys following the path that goes from the environment to humans passing through the food web. Besides, this review covers the last technological developments encompassing the use of novel extraction coatings (e.g., metal-organic frameworks, covalent organic frameworks, PDMS-overcoated fiber), geometries (e.g., Arrow-SPME, multiple monolithic fiber-SPME), approaches (e.g., vacuum and cold fiber SPME), and on-site devices. The applications of SPME hyphenated with ambient mass spectrometry have also been described.

The volatile compounds in four selected African star apple fruit (Chrysophyllum albidum) varieties were isolated and identified using the headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS). A total of 59 compounds were identified. Application of the aroma extract dilution analysis (AEDA) to the aroma distillates from the fruits revealed 45 odour-active compounds in the flavour dilution (FD) factor range of 4-128. Among them, the highest odour activities (FD factors) were determined for methylhexanoate, acetophenone and ethyl dodecanoate. Moreover, aroma lipophilicity appears to reflect molecular conformation. Further analysis of the similarities and differences between the fruit varieties in terms of the key odourants by the application of PLS-DA and PLS-regression coefficient showed strong positive correlation between the very sweet/sweet varieties and 10 key odourants. The odourants included ethyl acetate, acetyl methyl carbinol, methylhexanoate, sabinene, p-cymene, methylbenzoate, ethylbenzoate, geraniol, cis-α-bergomotene, acetophenone, and ethyl dodecanoate.

The physicochemical (pH, soluble solids, titratable acidity, sugars and organic acids), flavour and sensory properties of five Malaysian durian cultivars (D2, D24, MDUR78, D101 and Chuk) were studied. There were significant differences (P < 0.05) among the five cultivars in terms of all physicochemical characteristics tested with the exception for D2 and MDUR 78, which had similar physicochemical characteristics. Twenty two esters, 14 sulphur compounds, 7 alcohols, 3 aldehydes and 1 ketone were detected in the durian pulp of the five different cultivars using solid-phase microextraction coupled to gas chromatography-time of flight mass spectrometry. Diethyl disulphide, ethyl-n-propyl disulphide, diethyl trisulphide and ethanethiol were the predominant sulphur-containing compounds in all the cultivars. The major esters present in durian were either ethyl propanoate, ethyl-2-methyl butanoate, or propyl-2-methylbutanoate and their levels varied within cultivars. Principal component analysis applied to the data differentiated all cultivars based on 29 volatile flavour compounds exhibiting significant differences (P < 0.05) between cultivars. Principal components 1 and 2 explained 89% of the total variance. A strong correlation was observed between sensory properties with flavour compound and physicochemical characteristics of the fruit.

Eine neue Methodenkombination aus Headspace-Festphasenmikroextraktion (Solid-Phase Microextraction, SPME) und Gaschromatographie (GC) zur Schnellbestimmung von Aromastoffen in Spirituosen wird vorgestellt. Nach Zugabe von Phosphatpufferlösung (pH 7) und Dicyclohexylmethanol als internem Standard werden die Proben für 5 min thermisch equilibriert (60 °C) und die Analyten danach 5 min mit Polydimethylsiloxan-SPME-Fasern aus dem Headspace extrahiert. Die Desorption erfolgt im Injektor des GC-Systems bei 220 °C. HS-SPME erlaubt neben der Bestimmung von a-Thujon und b-Thujon bei Anwendung von Flammenionisationsdetektion den simultanen Nachweis der Aromastoffe Pulegon, Safrol, Isosafrol und bei Verwendung von massenspektrometrischer Detektion auch von b-Asaron. Die Methode zeigt für alle Analyten eine sehr gute Linearität mit Korrelationskoeffizienten über 0,98 und eine sehr gute Präzision mit Variationskoeffizienten zwischen 1,5 und 9,9 %. Die Empfindlichkeit der Methode mit Bestimmungsgrenzen von weniger als 0,02 mg/l bei massenspektrometrischer Detektion ist ausreichend zur Kontrolle der Höchstmengen gemäß Aromenverordnung. Beim Vergleich der neuen HS-SPME/GC-Methode mit konventionellen Extraktionsverfahren wie Destillation, Flüssig-Flüssig-Extraktion oder Festphasenextraktion zeigt sich eine signifikante lineare Korrelation der Ergebnisse (R > 0.99). Gegenüber den klassischen Methoden bietet HS-SPME eine wesentlich vereinfachte und verkürzte Probenvorbereitung, ohne Einsatz von Lösungsmitteln und mit minimalen Probenmengen, jedoch mit der gleichen Empfindlichkeit und Reproduzierbarkeit.

A solvent free solid-phase microextraction (SPME) method has been developed to determine methyl mercury and Hg(II) in sediment, seawater and biota samples from TTC area (Mumbai, India) using gas chromatograph-mass spectrometer (GC-MS). The analytical method consists of phenylation with Na[B(C 6 H 5 ) 4 ], simultaneous solid-phase microextraction of the derivatives, followed by a final GC-MS analysis. Experimental design methodology was used for optimization of important process parameter, like SPME fiber coating (nature and thickness), extraction time, extraction temperature, and pH. After extraction, the fiber is directly injected to the injector port of GC for desorption, separation and quantification. The absolute detection limits obtained for methylmercury and inorganic mercury were 0.02 and 0.05 ng as Hg, respectively. Standard reference materials were analyzed for validation of the methodology. The total mercury content in different matrices was determined using hydride generation atomic adsorption spectrometry (HG-AAS). .in (R.M. Tripathi). mulation in superior organism due to its high affinity to SH group of proteins and lipid tissues in living organisms . The target organ for methyl mercury toxicity is the central nervous system, especially the brain, and may occur at doses as low as 3 g kg −1 in humans (WHO, 1976). The high toxicity of mercury species at low concentration levels has stimulated the development of species selective analytical methodologies for accurate and sensitive qualitative and quantitative determination of these species in environmental matrices. Liquid chromatography-piezoelectric detection [8], GC-MS [9], CV-AFS [10,11], CV-AAS [12,13], ICP-MS [14-16], MIP-AES [14,17], FAPES [18], GC-FAPES [19]

Headspace-solid phase microextraction coupled with gas chromatography-mass spectrometry analysis were used to provide the volatile profile of roasted chickpea as a means of unravelling and elucidating roasted chickpea as a prerequisite in developing chickpea snack item for the health and functional food sectors. The results of the HS- SPME and optimization analysis using response surface methodology showed that DVB/CAR/PDMS was the most effective fibre and further results revealed the extraction temperature to be the dominant factor. A total of 61 volatile compounds were identified in the roasted chickpea. The best response within the range studied was established at 60o C extraction temperature, 30 min of equilibrium time and 15 min of extraction time. The volatile compounds iden- tified comprised of aldehydes (25%), hydrocarbons (25%), terpenoids (20%), esters (8%), ketones (8%), alcohols (8%) and heterocyclic (8%). The results further indicated that the final model was significantly (P < 0.05) fitted for the response variable (total flavour peak area) studied with a relatively high R 2 (0.9658).

This research was carried out to determine the effects of pre-rigor injection of beef semimembranosus muscle with nine proteases from plant and microbial sources, on the volatile profile of cooked beef after 1 day and 21 days post-mortem (PM) storage using Solid-phase microextraction gas chromatography mass spectrometry analysis. A total of 23 aldehydes, 5 ketones, 3 furans, 8 nitrogen and sulphur compounds, 4 alkanes, 7 alcohols and 6 terpenes were detected. Eleven volatile compounds characteristic of ginger flavour were detected in zingibain-treated meat. Benzaldehyde significantly increased (p&lt;0.05) only in kiwifruit juice (KJ), fungal 31 protease and Asparagus protease (ASP) treated samples from 1 day to 21 days PM storage. A significant increase (p&lt;0.05) in 3-methylbutanal was observed in KJ, bacterial and fungal protease treated samples at 21 days PM storage. Treatments with bromelain, papain, ASP, actinidin, and KJ (except KJ 21 days) proteases resulted in flavour profi...

Multiple, highly sensitive chemical techniques were used to analyze ancient pottery vessels from an excavated cemetery in Colima, west-central Mexico, dated to the Capacha phase (ca. 1500-1000 B.C). A double-chambered jar type, together with bowl and miniature cup types, are hypothesized to have been used as a pre-Hispanic distillation still. The results from the ancient vessels were compared to those from modern replica jars of the same types in which agave had been successfully distilled to a high-alcoholic beverage. Chemical biomarkers of agave in the modern replicas were absent from the ancient vessels, as were compounds of other native natural products of the region (e.g., maize, hog plum, prickly pear, etc.). Archaeological and archaeobotanical considerations, while suggestive, also provided no definitive evidence for a pre-Hispanic distillation hypothesis. Our study is placed within a broader ancient context of how this important technology for medicines, aromatics, metal purification, and alcoholic beverages, developed in east Asia and the Middle East, later to be adopted in Europe and brought to the New World. While an independent invention of a distillation apparatus in Mexico is yet to be proved, our goal is to stimulate further research and discussion, possibly leading to more compelling evidence.

Volatiles are important flavor compounds of fruit juices and beverages. In this study, a headspace Solid-phase microextraction (SPME) gas chromatography-mass spectrometry (GC-MS) was used to analyze the volatile components in starfruit juices. Several experimental parameters (e.g. adsorption temperature, adsorption time, and sample volume) were optimized to improve sampling efficiency in two aspects; maximum adsorption and selective adsorption of volatile components onto SPME fiber. The following conditions were found to be optimal for selectivity and sensitivity: adsorption temperature of 50°C for 30 min, with a 65 μm divinylbenzene/polydimethylsiloxane (DVB/PDMS)-coated fiber with a sample volume of 15 g in a 30-ml vial. The proposed technique could be applied for the analysis of volatile compounds that contribute to starfruit juices flavor in different cultivars, and also their ripening stages.

http://www.degruyter.com/view/j/ijfe.2013.9.issue-2/ijfe-2012-0004/ijfe-2012-0004.xml 
http://umexpert.um.edu.my/file/publication/00003103_103388.pdf

Understanding the aroma profile of wines made from cold climate grapes is needed to help winemakers produce quality aromatic wines. The current study aimed to add to the very limited knowledge of aroma-imparting compounds in wines made from the lesser-known Frontenac and Marquette cultivars. Headspace solid-phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS) with simultaneous olfactometry was used to identify and quantify selected, aroma-imparting volatile organic compounds (VOC) in wines made from grapes harvested at two sugar levels (22 • Brix and 24 • Brix). Aroma-imparting compounds were determined by aroma dilution analysis (ADA). Odor activity values (OAV) were also used to aid the selection of aroma-imparting compounds. Principal component analysis and hierarchical clustering analysis indicated that VOCs in wines produced from both sugar levels of Marquette grapes are similar to each other, and more similar to wines produced from Frontenac grapes har...

A rapid headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS) method has been developed for the determination of eugenol in serum samples after enzymatic cleavage. Eugenol is a characteristic marker for the consumption of certain alcoholic beverages including some digestif bitters and herbal liqueurs as well as wood-cask-aged spirits. This method enables the detection of eugenol with a limit of detection (LOD) of 3.2 ng/ml and a limit of quantification (LOQ) of 4.8 ng/ml in serum samples with excellent precision (5.3% intraday, 6.9% interday) and linearity (correlation coefficient R 2 = 0.992). Our findings confirm that eugenol undergoes a rapid phase II metabolism as it occurs completely conjugated as eugenol glucuronide in serum. Free eugenol was not detectable in any of our samples, which necessitated enzymatic cleavage with ␤-glucuronidase prior to HS-SPME sampling. In vivo experiments were conducted with a volunteer, who consumed a digestif bitter beverage on three different days under controlled conditions. At defined intervals, blood samples were taken from the subject. Using these blood samples, concentration/time profiles for serum eugenol glucuronide were determined. A rapid resorption leads to a peak eugenol glucuronide concentration directly after drinking (up to 1742 ng/ml if 78 mg of eugenol are ingested) followed by a decrease during the next 3 h. Blood samples were also taken from 20 drivers claiming to have consumed drinks containing eugenol. In five of the samples, eugenol glucuronide was detected at serum concentrations ranging from 12.1 to 172.3 ng/ml. These test results, in particular, confirm that the analysis of volatile compounds can be useful in forensic toxicology for the verification of post-offence alcohol consumption claims.

A number of adsorbents are available commercially as coatings for SPME fibers but some analytical methodologies might demand specific properties for the extraction of selected compounds, special coatings that have particular volume and a selectivity towards particular analytes. This paper presents a simple, fast, effective and environmental friendly methodology for the determination of accelerants in arson samples using headspace solid-phase microextraction coupled to gas chromatography. A new fiber prepared by sol-gel method, containing 1:1 molar ratio of octyltriethoxysilane (C 8-TEOS): methyltrimethoxysilane (MTMOS) was employed in this technique. The efficiency of the new fiber coating prepared by solgel technology for the determination of accelerants was compared to that of commercial PDMS/DVB fibers. Polydimethylsiloxane divinylbenzene (PDMS/DVB) is the most common fiber coating for the extraction of hydrocarbon compounds. Compared with commercial PDMS/DVB fiber, the new homemade fiber exhibited higher extraction capability and good selectivity for accelerants. The homemade fiber was also applied for the simulated arson samples. The home-made SPME adsorbent was shown to be a good alternative to commercially available fiber for the determination of accelerants in arson cases. Abstrak Pelbagai jenis gentian penjerap bagi teknik SPME wujud di pasaran. Namun demikian, ciri-ciri khas bagi pengekstrakan sebatian yang terpilih, salutan khas dengan isipadu tertentu dan keterpilihan terhadap analit tertentu diperlukan dalam beberapa kaedah analisis. Kertas kerja ini membentangkan suatu kaedah yang mudah, pantas, efektif dan mesra alam sekitar untuk menentukan bahan penggalak kebakaran dalam sampel kebakaran yang disengajakan dengan menggunakan teknik pengekstrakan fasa pepejal mikro yang dihubungkan dengan kromatografi gas. Gentian baru yang digunakan dalam teknik ini disediakan melalui kaedah "sol-gel", di mana ia terdiri daripada C 8-TEOS dan MTMOS dalam nisbah 1:1. Keberkesanan gentian penjerap baru yang disediakan melalui teknologi "sol-gel" untuk penentuan bahan penggalak kebakaran dibandingkan dengan gentian penjerap yang diperolehi secara komersil (PDMS/DVB). Gentian PDMS/DVB adalah gentian yang biasa digunakan dalam pengekstrakan sebatian hidrokarbon. Berbanding dengan gentian PDMS/DVB, gentian buatan sendiri yang baru menunjukkan kapasiti pengekstrakan yang lebih tinggi dan keterpilihan yang baik bagi bahan penggalak kebakaran. Gentian buatan sendiri ini juga diaplikasikan pada sampel simulasi kebakaran yang disengajakan. Gentian buatan sendiri untuk teknik SPME menunjukkan suatu alternatif yang baik kepada gentian komersial bagi penentuan bahan penggalak kebakaran dalam kes kebakaran yang disengajakan

Speciation analysis by solid phase microextraction (SPME) is explored for the pesticide atrazine in an aqueous dispersion of model latex nanoparticles. It is found that the rate of extraction is governed by coupled diffusion of free and particle-bound analyte towards the solid/solution interface. The nanoparticles do not enter the solid phase: the eventual equilibrium analyte concentration in the solid phase is dictated by the parti tion coefficient k wf and the concentration of the free analyte in the sample solution. The rate of release of atrazine from the latex particles is fast on the effective time scale of the microextraction process. All together, the results indicate that SPME has the potential of developing into a powerful technique for dynamic speciation analysis of organic compounds in aqueous media.

Naphthalene is a volatile solid that often has been used as a pesticide to treat artifacts, particularly ethnographic material, and natural history col-lections. Naphthalene residues pose an ongoing health risk in museums and to communities that receive contaminated artifacts through cultural repatriation. The Museum of the American Indian disposed of its supply of &quot;moth flakes&quot; in 1985, but noxious residues remain on collections. It has been demonstrated that naphthalene vapors become stronger in humid air, which increases the potential health risk. A method for quantifying naphthalene vapor concentrations using SPME-GC/FID is pre-sented, and the relationship between naphthalene, water vapor, and textile fibers is explored as a step in the development of a treatment to remediate the pesticide residues.

... Over the past few years, method based on headspace solid phase microextraction (HS-SPME) has been used extensively in the analysis of volatile compounds in fruits (Chen et al., 2005, Kourkoutas et al., 2006 and Riu-Aumatell et al., 2004). ... Joseph, MI, USA) was used. ...

Isolation and characterization of leaf volatiles in Anemopsis californica (Nutt.) Hook. and Arn. (A. californica) was performed using steam distillation, solid-phase microextraction, and supercritical fluid extraction. Thirty-eight compounds were detected and identified by gas chromatography; elemicin was the major component of the leaf volatiles. While the composition of the leaf volatiles varied with method of extraction, R-pinene, sabinene, -phellandrene, 1,8-cineole, piperitone, methyl eugenol, (E)-caryophyllene, and elemicin were usually present in readily detectable amounts. Greenhousereared clones of a wild population of A. californica had an identical leaf volatile composition with the parent plants. Steam-distilled oil had antimicrobial properties against 3 (Staphylococcus aureus, Streptococcus pneumoniae, and Geotrichim candidum) of 11 microbial species tested. Some of this bioactivity could be accounted for by the R-pinene in the oil.

The composition of the essential oil of the endemic Viola etrusca Erben from Monte Labbro (Italy) has been studied for the first time. It was made up almost exclusively of methyl salicylate (96%), together with many other mono- and sesquiterpenes and non-terpenic alcohols and aldehydes. In addition, the SPME technique has been used to evaluate the volatiles emitted in vivo by different-coloured flowers. Copyright © 2002 John Wiley & Sons, Ltd.

Colony integrity and survival in honeybees is regulated by chemical signals that are actively produced by glands and syner-gically transmitted between the members. A number of these signals regulate the typical age-related division of labor among the worker bees performing different tasks at different ages. In this study, the analysis of the cuticular profiles in Apis mellifera ligus-tica Spinola, 1806 workers at various tasks (newly emerged, nurse and forager bees) was performed using in vivo solid-phase microextraction gas chromatography-mass spectrometry (SPME-GC-MS). The use of in vivo SPME shed new light on the complexity of the molecular pattern on the epicuticle of honeybees. The identified molecules are mainly hydrocarbons, saturated and unsaturated carboxylic acids, and to a less extent, esters, sterols, aldehydes, and alcohols. Their relative abundance between the three task groups was evaluated using descriptive statistics and multivariate pattern recognition analysis (i.e., principal component analysis, PCA, and linear discriminant analysis, LDA). Eleven molecules namely nonacosane, pentacosane, (Z)-12-penta-cosene, 11-tricosene, 11-methylnonacosane, squalene, 13-methyl-heptacosane, heptacosane, heneicosane, docosane and tricosane, occur with high frequency in newly emerged, nurse, and forager bees. The compounds that contributed the most for the separation of the three task groups in the PCA were pentacosane, (Z)-12-pen-tacosene, 13-methylheptacosane and squalene; while for LDA, nonacosane, 11-methylnonacosane and pentacosane were the molecules that contributed most to the discrimination.

A solvent free solid-phase microextraction (SPME) method has been developed to determine methyl mercury and Hg(II) in sediment, seawater and biota samples from TTC area (Mumbai, India) using gas chromatograph-mass spectrometer (GC-MS). The analytical method consists of phenylation with Na[B(C 6 H 5) 4 ], simultaneous solid-phase microextraction of the derivatives, followed by a final GC-MS analysis. Experimental design methodology was used for optimization of important process parameter, like SPME fiber coating (nature and thickness), extraction time, extraction temperature, and pH. After extraction, the fiber is directly injected to the injector port of GC for desorption, separation and quantification. The absolute detection limits obtained for methylmercury and inorganic mercury were 0.02 and 0.05 ng as Hg, respectively. Standard reference materials were analyzed for validation of the methodology. The total mercury content in different matrices was determined using hydride generation atomic adsorption spectrometry (HG-AAS).

This review highlights developments of Solid Phase MicroExtraction in toxins analysis after 2005. It covers the major mycotoxins such as aflatoxins and ochratoxins where applications have been reported in the literature and some cyanobacteria toxins. Solid Phase MicroExtraction can act as an important sampling and sample preparation tool for the analysis of toxins in various matrices expanding its existing broad spectrum of analytes.

Volatile organic compounds (VOCs) emitted from materials during degradation can be a valuable source of information. In this work, the emissions of furfural and acetic acid from cellulose were studied using solid-phase micro-extraction (SPME) in combination with gas chromatography-mass spectrometry. Two sampling techniques were employed: static headspace sampling using SPME for 1 h at 40 o C after 18-h sample preparation at 80 o C in a closed glass vial, and contact SPME in a stack of paper (or a book). While a number of VOCs are emitted from paper under conditions of natural or accelerated degradation, two compounds were confirmed to be of particular diagnostic value: acetic acid and furfural. The emissions of furfural are shown to correlate with pH of the cellulosic environment. Since pH is one of the most important parameters regarding durability of this material, the developed method could be used for non-destructive evaluation of historical paper.

A passive sampling method, using retracted solid-phase microextraction (SPME)-gas chromatography-mass spectrometry and time-weighted averaging, was developed and validated for tracking marker volatile organic compounds (VOCs) emitted during aerobic digestion of biohazardous animal tissue. The retracted SPME configuration protects the fragile fiber from buffeting by the process gas stream, and it requires less equipment and is potentially more biosecure than conventional active sampling methods. VOC concentrations predicted via a model based on Fick's first law of diffusion were within 6.6-12.3% of experimentally controlled values after accounting for VOC adsorption to the SPME fiber housing. Method detection limits for five marker VOCs ranged from 0.70 to 8.44 ppbv and were statistically equivalent (p > 0.05) to those for active sorbenttube-based sampling. The sampling time of 30 min and fiber retraction of 5 mm were found to be optimal for the tissue digestion process.

Naphthalene is a volatile solid that often has been used as a pesticide to treat artifacts, particularly ethnographic material, and natural history collections. Naphthalene residues pose an ongoing health risk in museums and to communities that receive contaminated artifacts through cultural repatriation. The Museum of the American Indian disposed of its supply of "moth flakes" in 1985, but noxious residues remain on collections. It has been demonstrated that naphthalene vapors become stronger in humid air, which increases the potential health risk. A method for quantifying naphthalene vapor concentrations using SPME-GC/FID is presented, and the relationship between naphthalene, water vapor, and textile fibers is explored as a step in the development of a treatment to remediate the pesticide residues.

In der in VO (EG) 2091/2002 mitgeteilten offiziellen Referenzmethode zur Bestimmung von Anethol in Spirituosen durch Gaschromatographie (GC) wird für zuckerhaltige Spirituosen (z. B. Sambuca) ein arbeitsintensives und zeitaufwendiges Extraktionsverfahren vorgeschrieben, da bei direkter Injektion der Proben eine Kontamination des GC-Injektors erfolgen würde. Ziel der vorliegenden Arbeit war daher, die Extraktion von Anethol aus Spirituosenproben zu verbessern. Dazu wurde eine gegenüber der Referenzmethode wesentlich beschleunigte Flüssig-Flüssig-Extraktion (FFE) mit n-Hexan entwickelt. Daneben wurde als moderne Alternative die Headspace-Festphasenmikroextraktion (Solid-phase microextraction, HS-SPME) evaluiert. Sowohl FFE als auch HS-SPME zeigten sehr gute Linearitäten mit Korrelationskoeffizienten über 0,99 und sehr gute Präzisionen zwischen 0,8 und 4,7 %. Beim Vergleich beider Verfahren, sowie der Referenzmethode zeigte sich eine signifikante lineare Korrelation der Ergebnisse (R > 0,95). Erstmals konnte gezeigt werden, dass HS-SPME/ GC/MS eine schnelle, empfindliche und robuste Alternative für die Analyse von Anethol in alkoholischen Getränken darstellt. Gegenüber der Referenzmethode wurde mit beiden Verfahren bei vergleichbarer Präzision eine wesentlich verkürzte und vereinfachte Probenvorbereitung erreicht, wobei HS-SPME durch die nur 6-minütige vollautomatische Extraktion die größten Vorzüge bietet.

A rapid HS-SPME-GC-MS (headspace solid-phase microextraction-gas chromatography-mass spectrometry) method has been developed for determination of menthone, isomenthone, neomenthol and menthol in serum samples with and without enzymatic cleavage. These flavour compounds are characteristic markers for consumption of peppermint liqueurs as well as certain digestif bitters, herbal and bitter liqueurs.

The ‘smell’ of illness, disease or age has been known for many centuries, mainly created by volatile organic compounds (VOCs). Dogs were first reported to detect cancer in 2004. Increasingly, the profiles of VOCs are being utilised as non-invasive diagnostic methods.

The aim of the thesis was to develop and evaluate the performance of analytical methods to characterise the disease states of patients utilising selective discrimination, gas chromatography-mass spectrometry (GC-MS) and chemometrics. The primary analytical technique investigated was GC-Time-of-Flight-MS coupled with headspace solid-phase microextraction (HS-SPME-GC-ToFMS). A robust and sensitive method was developed by optimisation of all sample analysis parameters and was applied to clinical samples from bladder and prostate cancer patients and those with hepatic disorders. This evidence was obtained by quantifying an internal standard, present in every sample and blank throughout the studies. Based on these findings, large numbers of clinical samples were analysed with confidence.

Statistically significant mathematical models were developed in partnership with Cranfield University to classify the diseased state of samples and clinically relevant controls. PLS-DA was determined as the best classifier. The results from the HS-SPME-GC-ToFMS studies were highly promising. Bladder cancer gave a mean accuracy of >80 % and even low-grade tumours gave a sensitivity of 73 %, superior to urine cytology. Higher clinical performance was obtained in the prostate cancer study, with BPH distinguishable from cancer. Hepatic disorders were better again (>86 %). Preliminary studies on sepsis detection also showed promise.

Several recommendations were made to enable significant clinical results in the future based on analytical rigour.

We investigated the new solid-phase microextraction method by high-performance liquid chromatography with electrochemical detection for the analysis of biogenic amines. The Carbowax–Templated Resin 50 mm (purple) fibre coating 21 offers good performances for dopamine and serotonin separation, i.e., good selectivity and high sensibility (0.1 mg l). We also tested this fibre for biogenic amines quantification of rat striatum. The coating seems to be selective towards the amines and has low affinity for the metabolites, allowing a good separation and preventing drawbacks from the biological matrix. These first results obtained using this original separation method offer large perspectives of application to many biological samples. 

Isolation and characterization of leaf volatiles in Anemopsis californica (Nutt.) Hook. and Arn. (A. californica) was performed using steam distillation, solid-phase microextraction, and supercritical fluid extraction. Thirty-eight compounds were detected and identified by gas chromatography; elemicin was the major component of the leaf volatiles. While the composition of the leaf volatiles varied with method of extraction, R-pinene, sabinene, -phellandrene, 1,8-cineole, piperitone, methyl eugenol, (E)-caryophyllene, and elemicin were usually present in readily detectable amounts. Greenhousereared clones of a wild population of A. californica had an identical leaf volatile composition with the parent plants. Steam-distilled oil had antimicrobial properties against 3 (Staphylococcus aureus, Streptococcus pneumoniae, and Geotrichim candidum) of 11 microbial species tested. Some of this bioactivity could be accounted for by the R-pinene in the oil.

Naphthalene is a volatile solid that often has been
used as a pesticide to treat artifacts, particularly
ethnographic material, and natural history collections.
Naphthalene residues pose an ongoing
health risk in museums and to communities that
receive contaminated artifacts through cultural
repatriation. The Museum of the American Indian
disposed of its supply of “moth flakes” in 1985, but
noxious residues remain on collections. It has been
demonstrated that naphthalene vapors become
stronger in humid air, which increases the potential
health risk. A method for quantifying naphthalene
vapor concentrations using SPME-GC/FID is presented,
and the relationship between naphthalene,
water vapor, and textile fibers is explored as a step
in the development of a treatment to remediate the
pesticide residues.

Cadaver-detection dogs are a preferred search tool utilised by law enforcement agencies for the purposes of locating victim remains due to their efficiency and minimal disturbance to the crime scene. In Australia, a specific group of these canines are blood-detection dogs, which are trained to detect and locate blood evidence and search potential crime scenes in cases where a cadaver may not be present. Their role sometimes requires searches to be carried out after considerable time has passed since the crime occurred, and this is important for developing effective training protocols. This study aimed to investigate the volatile organic compounds (VOCs) produced from fresh and aged human blood on various surfaces. Solid phase microextraction (SPME) was used to extract VOCs from the headspace of dried blood samples aged and sampled periodically over 12 months from a non-porous (i.e. aluminium) and porous (i.e. cotton) surface. Samples were analysed using comprehensive two-dimensional...

Non-invasive diagnostics and finding biomarkers of disease in humans have been a very active research area. Some of the analytical technologies used for finding biomarkers of human disease are finding their use in livestock. Non-invasive sample collection from diseased cattle using breath and headspace of fecal samples have been reported. In this work, we explore the use of volatile organic compounds (VOCs) emitted from bovine nasal secretions and serum for finding biomarkers for bovine respiratory disease (BRD). One hundred nasal swabs and 100 serum samples (n = 50 for both 'sick' and 'healthy') were collected at the time of treatment for suspected BRD. Solid-phase microextraction (SPME) was used to collect headspace samples that were analyzed using gas chromatography-mass spectrometry (GC-MS). It was possible to separate sick cattle using non-invasive analyses of nasal swabs and also serum samples by analyzing and comparing volatiles emitted from each group of samples. Four volatile compounds were found to be statistically significantly different between 'sick' and 'normal' cattle nasal swabs samples. Five volatile compounds were found to be significantly different between 'sick' and 'normal' cattle serum samples, with phenol being the common marker. Future studies are warranted to improve the extraction efficiency targeting VOCs preliminarily identified in this study. These findings bring us closer to the long-term goal of real-time, animal-side detection and separation of sick cattle.

Isolation and characterization of leaf volatiles in Anemopsis californica (Nutt.) Hook. and Arn. (A. californica) was performed using steam distillation, solid-phase microextraction, and supercritical fluid extraction. Thirty-eight compounds were detected and identified by gas chromatography; elemicin was the major component of the leaf volatiles. While the composition of the leaf volatiles varied with method of extraction, R-pinene, sabinene, -phellandrene, 1,8-cineole, piperitone, methyl eugenol, (E)-caryophyllene, and elemicin were usually present in readily detectable amounts. Greenhousereared clones of a wild population of A. californica had an identical leaf volatile composition with the parent plants. Steam-distilled oil had antimicrobial properties against 3 (Staphylococcus aureus, Streptococcus pneumoniae, and Geotrichim candidum) of 11 microbial species tested. Some of this bioactivity could be accounted for by the R-pinene in the oil.

Isolation and characterization of leaf volatiles in Anemopsis californica (Nutt.) Hook. and Arn. (A. californica) was performed using steam distillation, solid-phase microextraction, and supercritical fluid extraction. Thirty-eight compounds were detected and identified by gas chromatography; elemicin was the major component of the leaf volatiles. While the composition of the leaf volatiles varied with method of extraction, R-pinene, sabinene, -phellandrene, 1,8-cineole, piperitone, methyl eugenol, (E)-caryophyllene, and elemicin were usually present in readily detectable amounts. Greenhousereared clones of a wild population of A. californica had an identical leaf volatile composition with the parent plants. Steam-distilled oil had antimicrobial properties against 3 (Staphylococcus aureus, Streptococcus pneumoniae, and Geotrichim candidum) of 11 microbial species tested. Some of this bioactivity could be accounted for by the R-pinene in the oil.

A novel extraction technique was reported. The solid phase material, nanofiber, was prepared by electrospinning using polystyrene. Twenty different drugs (10 lg/L in water) were extracted using 1 mg of nanofibers within 5 min. The analytes can be desorpted from the fibers with 50 lL of the methanol and then monitored by LC coupled to a UV detector. Packed-fiber SPE (PFSPE) provide high recoveries (A50%) for some relatively non-polar drugs (log P A1.5) (n-octanol-to-water partition ratio), and relatively low recoveries (9.9–39.8%) for the drugs within the log P window below 1. Experimental optimization of the technique has been carried out using seven representative drugs, edaravone, cinchonine, quinine, voriconazole, chlordiazepoxide, verapamil, and rutonding. Except for edaravone, the maximum yields of seven drugs (0.2 lg/L) from water samples were approximately 100%, and were 33.7–88.2% from human plasma. The advantageous aspect of the technique encompasses high throughput, high sensitivity, simplicity, low cost, and green chemistry.