Graduation date: 1956

The volatile flavor fraction of lightly milled wheat grown in eastern Oregon was isolated for study by two methods: steam distillation under vacuum and steam distillation at atmospheric pressure. The sample obtained under vacuum was extracted with ether which was then evaporated to yield the desired wheat essence. Steam distillation at atmospheric pressure provided the headspace vapors that were used for a portion of the gas chromatographic analysis. Identification of the organic substances contained in the volatile flavor fraction was made on the basis of chemical tests, paper chromatography, gas-liquid chromatography, and mass spectrometry. Preliminary testing for amines and carbonyls indicated the presence of both of these functional groups, although in subsequent research amines were not detected. Additional information as to the functional groups present was obtained by subjecting headspace vapor samples to gas chromatography and directing the column effluent into vials containing reagents selected to indicate the presence of alcohols, amines, esters, carbonyls, and mercaptans. A separate set of reagents was used for each eluting peak. Formation of 2, 4-dinitrophenylhydrazone derivatives and determination of their melting points provided one means of tentative identification of carbonyl compounds. Ascending paper chromatography was used to separate the 2, 4-dinitrophenylhydrazone derivatives of the carbonyls into classes and to ultimately assist in the identification of these compounds. A Barber-Colman gas-liquid chromatograph equipped with a flame ionization detector was used as a means of separating the components in the samples. Identification of some of the compounds was possible through comparisons of retention times of the peaks on these columns with retention times of known compounds. Column packings used for gas-liquid chromatography were six percent Apiezon M, six percent Diethylene Glycol Succinate, and three percent Free Fatty Acid Phase, all on a solid support of Anakrom ABS, 90 to 100 mesh. The column was heated isothermally at 75°C with nitrogen as the carrier gas flowing at a pressure of five pounds per square inch. Mass spectra of the wheat essence compounds were obtained by use of an Atlas-MAT Ch-4 mass spectrometer using a two second scan, coupled with a gas-liquid chromatograph. Twelve compounds were identified and six were tentatively identified in the headspace aroma or in the wheat flavor essence. Those identified were acetaldehyde, isobutyraldehyde, butyraldehyde, valeraldehyde, hexanal, heptanal, octanal, crotonaldehyde, 3-methyl-2-butanone, 2, 2-dimethyl-3-pentanone, diacetyl, and ethyl acetate. The compounds tentatively identified included isoamyl alcohol, amyl alcohol, butanone, isovaleraldehyde, cyclopentanone, and phenylacetaldehyde. / Graduation date: 1968

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Thesis (Ph.D.)--University of Nebraska-Lincoln, 2006. / Title from title screen (site viewed May 16, 2007). PDF text: xi, 280 p. : ill. (some col.) ; 2.59Mb. UMI publication number: AAT 3236913. Includes bibliographical references. Also available in microfilm and microfiche formats.

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Typescript, etc. / Digitized by Kansas State University Libraries

Thesis (PhD)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: Aged distilled spirits such as whiskey are complex mixtures of flavour compounds in an ethanol-water matrix. The flavour compounds involved can have widely different volatility and relative amounts. Many of the organoleptic properties that make whiskey suitable for commercial sale have their origin in reactions occurring during the ageing process in oak wood barrels. To investigate the complex changes that take place during spirit ageing a preparative fractional vacuum distillation process was developed. Both high and low volatility compounds could be individually isolated as fractions and free from both the ethanol matrix and the fermentation fusel alcohols. This allowed a range of sensory and analytical procedures to be conducted on these fractions, in particular to investigate changes occurring during ageing. Gas chromatographic (GC) analysis of the low volatility fraction is complicated by the fact that both the compounds and their ethanol matrix have very similar chromatographic behaviour when separated simultaneously on standard chromatographic phases. Compound and matrix co-elution becomes a major problem and conditions for mass spectrometric (MS) investigation are disadvantageous. A two-dimensional GC configuration using dissimilar chromatographic phases was configured to overcome these limitations. Using this approach 27 compounds were separated and identified. Headspace injection was used to increase detection sensitivity. Changes with ageing for seven compounds present at very low levels were quantified. In addition changes in the most abundant compounds were quantified by standard split injection, and changes in trace level sulfur compounds by headspace injection with sulfur chemiluminescent detection (SCD). Increases of the concentrations of pleasant fruity ethyl esters and acetates were established. Volatile sulfides with generally objectionable aroma showed concomitant major decreases. Appropriate techniques could also be applied to the low volatility compounds recovered from the whiskey water fraction. High temperature GC-MS analysis of an extract of the water fraction allowed the identification of 30 compounds. Three phenolic esters were identified in whiskey for the first time. These compounds were synthesised and shown to be contributory to desirable ageing flavour. Increases in concentrations of 16 oak derived compounds during alO year ageing period were established. Several compounds increased significantly over this time period. Ratios of aromatic phenolic aldehydes, and changes in these ratios during ageing, were unique to the type of barrel used in these experiments. This suggests that the final sensory properties of aged whiskey may be more dependent on wood parameters than previously thought. Preparative reverse phase High Pressure Liquid Chromatography (HPLC) with an ethanol water gradient was used to further fractionate an extract of the low volatility compounds. Subsequent analysis and sensory testing allowed a group separation of compounds with each group contributing characteristic attributes to the total flavour. One group contained the three new phenolic esters together with a number of other unidentified compounds. This group was found to be important for desirable ageing flavour that seems to develop slowly with time. Further studies in this area to understand the individual and synergistic contributions of the many facets of ageing chemistry will have important commercial implications. / AFRIKAANSE OPSOMMING: Verouderde spiritus soos Whiskey is 'n komplekse mengsel van geurstowwe in 'n etanolwater oplossing. Die vlugtigheid van die geurstowwe asook die konsentrasies waarin hul aanwesig is, varieer aansienlik. Verskeie van die sintuiglike eienskappe wat kommersiële waarde aan whiskey verleen, het huloorsprong in reaksies wat tydens die verouderingsproses in eikehoutvate plaasvind. Ten einde die ingewikkelde veranderinge wat tydens die veroudering van spiritus plaasvind, te ondersoek, is 'n preparatiewe fraksionele vakuumdistillasieproses ontwikkel. Hoogs vlugtige en minder vlugtige verbindings kon geskei word in afsonderlike fraksies wat vry was van etanol en fuselalkohole. Dit het die sintuiglike en fisies-chemiese analises van die fraksies moontlik gemaak, veralom die veranderings wat tydens veroudering plaasvind, te ondersoek. Gaschromatografiese (GC) analise van die fraksie met 'n lae vlugtigheid word gekompliseer deur die feit dat hierdie komponente en die etanol waarin dit opgelos is soortgelyke chromatografiese eienskappe toon wanneer hul gelyktydig op standaard gaschromatografie fases geskei word. Die gelyktydige eluering van dié komponente en etanol waarin hul opgelos is, skep 'n probleem wat nadelig vir massaspektrometriese (MS) analise is. Die beperkings is oorkom deur die gebruik van tweedimensionele GC en stasionêre fases met uiteenlopende eienskappe. Op dié wyse is 27 verbindings geskei en geïdentifiseer. Die veranderinge in konsentrasies tydens veroudering is vir sewe verbindings gekwantifiseer. Veranderinge in die konsentrasies van die verbindings teenwoordig in die hoogste konsentrasies is gekwantifiseer deur split-inspuitings, terwyl veranderinge in die spoorkonsentrasies van vlugtige swawelverbindings mbv dampfase-inspuitings en met swawel chemolumisensie deteksie (SCD) bepaal is. Toenames in die konsentrasies van die aangename vrugtige esters en asetate is bepaal. Vlugtige sulfiede met meesalonaanvaarbare aromas toon gelyktydige groot afnames. Geskikte tegnieke is ook gebruik vir die herwinning van minder vlugtige verbindings met die waterfase van whiskey. Hoë temperatuur GC-MS analises van 'n ekstrak van die waterfase het die identifikasie van 30 komponente moontlik gemaak. Drie fenoliese esters is vir die eerste keer in whiskey gevind. Hierdie verbindings is gesintetiseer en hul bydrae tot die gewenste verouderingsgeur is sintuiglik bevestig. Toenames in die konsentrasies van 16 eikehoutverwante verbindings gedurende 'n verouderingsperiode van 10 jaar is bepaal. 'n Betekenisvolle toename het voorgekom in die konsentrasies van verskeie van hierdie whiskey verbindings. Die verhoudings van aromatiese fenoliese aldehiede en die verandering in die verhoudings tydens veroudering was kenmerkend van die tipe eikehoutvat wat gebruik is. Dié bevinding dui daarop dat die fenole sintuiglike eienskappe van verouderde whiskey meer afhanklik mag wees van eikehout parameters as wat voorheen algemeen aanvaarbaar is. Preparatiewe omgekeerde fase hoëdrukvloeistofchromatografie met etanol/water as 'n gradient elueermiddel is gebruik om 'n ekstrak van die minder vlugtige verbindings verder te fraksioneer. Verdere GC-, MS- en sintuiglike analise het die skeiding van groepe van verbindings waarvan elk kenmerkende bydraes tot die totale geur lewer, moontlik gemaak. Een groep het drie nuut geïdentifiseerde fenoliese esters, tesame met 'n aantal ongeïdentifiseerde verbindings, bevat. Daar is vasgestel dat hierdie groep 'n belangrike bydrae maak tot die gewenste geur wat klaarblyklik stadig tydens veroudering ontwikkel. Verdere ondersoeke in hierdie verband om die individuele en sinergistiese bydraes van verskeie fasette van die chemie van veroudering te verstaan, kan belangrike kommersiële implikasies hê.

Staling in beer is inevitable. Oxidation and increased temperatures are the main causes of stale flavors in bottled beers. Since 1934, research has been done to identify compounds and pathways involved in creating stale flavors. Although many research papers report stale flavors, there is not a lexicon per se of stale aromas for North American lagers. This study has been divided into two parts, 1) the process of developing a lexicon for stale aromas for North American lagers and its application, and 2) the use of a consumer panel to determine whether the North American lager consumer has a preference for aged versus fresh beer and whether the consumer could perceive a difference between the two. In the first study, three brands of North American lagers were aged in 27°C storage for three months and 38°C storage for two weeks. A lexicon for staling aroma for North American lagers was created, using a trained descriptive panel. The lexicon had two tiers; the first tier had five descriptors that were category headings for the second tier of descriptors. Panelists were instructed to rate the first tier descriptors, but using the descriptors in the second tier was optional. To validate the lexicon, descriptive analysis was performed on the stored samples. The data were analyzed using principal components analysis (PCA) for the first tier descriptors and generalized procrustes analysis (GPA) for the second tier descriptors. The lexicon was used successfully, characterizing the control beers as sulfury and fruity and the aged beers as sweet brown. Within the sulfury category, panelists described control beers with the attributes perm solution and skunky. Within the sweet brown category, panelists described the aged beers with the descriptors baked pineapple and honey. The beers stored at different storage temperatures behaved differently across time. The maps constructed with PCA and GPA show a tendency for control samples to start out sulfury and, through time, age with sweet brown characteristics. In the second study, a consumer panel was implemented to 1) determine if the average North American lager consumer had a preference for fresh versus stored beer, and 2) to determine if perceivable differences existed between the fresh versus stored samples. A consumer test was designed using the three North American lagers that were tested in the trained panel. The target number of consumers for each brand was 100. The aged beer was stored at 38°C for 1 and 2 weeks, and the control was stored at 1°C for that time period. A preference test, followed by a triangle test, was performed on control versus 1 week at 38°C and control versus 2 week at 38°C for each brand (2 preference and 2 triangle tests for each brand; control versus 1 week and control versus 2 weeks). The results showed no significant preference for any brand/time point. Brand A had the only significant difference (p <0.05) between samples stored at 38°C for 2 weeks and the control (The results showed no preference). Additional research must be done for more conclusive information, but this research shows that a small group of North American lager consumers do not have a preference between aged beer and fresh beer and, for the most part, cannot tell a difference between aged beer and fresh beer. / Graduation date: 2002

Sensory evaluation and instrumental methods were applied to the evaluation of strawberry juice concentrate (68°Brix) stored at 20°C which had been produced both commercially (C-SJC) and in a pilot plant (SJC). Sensory evaluation included taste and aroma ratings by intensity scaling and time-intensity of taste, and visual colorimetry by matching Munsell color chips. Instrumental analyses included tristimulus colorimetry (i.e. Hunter colorimeter), spectrophotometric colorimetry for pigment analyses, titrametric analyses for acidity (pH and titratable acidity) and free α-amino acids (formol number), and headspace gas analyses for CO₂ and O₂. During six days storage of C-SJC, a decrease in concentration of anthocyanins and increase in polyphenolics (tannin) was associated with an increase in astringency. Free α-amino acids were observed to decrease, while CO₂ was released. These changes were associated with an increase in musty/moldy and pungent aromas. Free sugars and titratable acidity did not change. The pilot plant SJC was processed from blanched and unblanched fruit to evaluate the relative importance of oxidase activity (i.e. polyphenoloxidase) prior to pasteurization. The blanching treatment increased the astringency and sourness in unstored SJC. These affects were associated with an increase in concentration of polyphenolics (tannin). During storage, the blanch treatment decreased the rate of anthocyanin loss and decreased the release rate of CO₂, yet degradation rates were still high. The 0₂ concentration in headspace did not change significantly during storage indicating that polyphenoloxidase (PPO) activity during storage was low. The musty/moldy and pungent aromas increased similarly to C-SJC. A chemical mechanism accounting for these changes is proposed where products from the oxidative degradation of ascorbic acid contribute directly or indirectly to the degradation of anthocyanins to yield browning. Further, high initial concentrations and subsequent decreases during C-SJC storage of free α-amino acids indicate that Strecker degradation is a participating mechanism. Associations of browning with the development of off-flavors suggest this chemical mechanism forms odor-active volatile compounds. / Graduation date: 1989

Malt, wort and beer samples representing a single pilot brew were extracted from Celite columns with Freon 114. Total extracts were analyzed by gas chromatography/mass spectrometry. Compounds were identified that were unique or common to beer, wort or malt and quantities present were determined for those common to the three sample types. Concentrated extracts were separated by liquid chromatography on partially deactivated silica gel packed in Teflon tubes, using Freon 11 as the solvent. Fractions from liquid chromatography were analyzed by descriptive sensory evaluation. Those fractions selected as bearing cereal-like, grassy, nutty or malty aroma characteristics were analyzed by gas chromatography. Freon extracts and fractions were found suitable for descriptive sensory evaluation and this was used to advantage in locating fractions with the desired aroma characteristics. Cereal-like, grassy, nutty or malty aroma characters were associated with liquid chromatographic fractions containing primarily alcohols, aldehydes and ketones. The Ascending Method of Limits for determination of the threshold of added substances in beer was critically reviewed and a new threshold test was developed. The new test design reduces the sample requirement from eighteen to twelve for each session. In contrast to the Ascending Method of Limits, the new test design was amenable to statistical evaluation and statement of a level of confidence for the threshold intervals determined. Both a nine-point intensity scale of difference from the labeled reference and a category scale were applied to the new test design. Intensity scale data were normalized and subjected to analysis of variance and a series of one-sided t-tests to determine individual and combined panel threshold intervals. Category scale data were analyzed by a rank sums test to determine individual thresholds and the R-index values thus obtained were subjected to analysis of variance and orthogonal contrasts of means to establish the combined panel threshold. The intensity scale method applied to the new test design provided the lowest and narrowest estimates of the threshold interval in comparative testing with the category scale method and the Ascending Method of Limits and, in addition, required fewer replications than the category scale method to establish the threshold interval. / Graduation date: 1989