Thesis (Ph. D.)--Princeton University, 1994. / Title in Greek (romanized); subtitle in English. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--Princeton University, 1994. / Title in Greek (romanized); subtitle in English. Includes bibliographical references.

Linalool is a key intermediate for the production of important fragrance chemicals such as geraniol, nerol, geranial, and neral. Linalool can be produced via a two-step process from α-pinene which is a major component of crude sulphated turpentine (CST) a foul-smelling, volatile waste product of the pulp and paper industry. The key step in this process is the pyrolysis step which involves the isomerisation of cis-2-pinanol to linalool and requires high temperatures (600-650°C) and is not very selective due to the decomposition of the product itself under these conditions. A client of the CSIR, Teubes Pty. Ltd., is a manufacturer of flavour and fragrance compounds for the local and international fragrance market and expressed an interest in producing linalool since the company would then gain access to other valuable fragrance chemicals via relatively simple processes. Earlier work conducted by AECI, R & D did not meet with much success since the selectivity to linalool was very poor and the process could hardly be deemed as scalable. The main objective of this project was therefore to develop a process for the selective isomerisation of cis-2-pinanol to linalool with minimum by-product formation and using process equipment that could be scaled to full-scale production. Since cis-2- pinanol could not be purchased in sufficient quantities for process development, a process had to be developed for the bench-scale preparation of kilogram quantities of cis-2-pinanol from α-pinene obtained from the client. Although this synthesis formed a minor part of this investigation, several process improvements and innovations were introduced to produce high quality cis-2-pinanol, in very good yields at kilogram scale. A major part of this investigation was the design and set up of a pyrolyis rig capable of operating at elevated temperatures (400 - 750°C) for the evaluation of various process parameters. Various vaporizer, reactor, and condensation systems were evaluated for their ability to cope with the demanding conditions on a consistent basis. The initial part of the investigation was a screening exercise to evaluate various process parameters as well as solvents, materials of construction, catalysts, etc. A comprehensive statistical design was also conducted to determine the critical process parameters and the model obtained was used to predict the optimum conditions required for the preparation of in-specification product on a consistent basis. These conditions were used in the preparation of a 1kg sample which was required by theclient for market evaluation purposes. The use of a novel microreactor system was also evaluated for the pinanol pyrolysis reaction. To our knowledge, this is the first time that a microreactor has been successfully used for this type of reaction in the Fragrance industry and a patent application is being filed by the CSIR. The kinetics of the reaction in both the tubular reactor system and the microreactor system was investigated. Computer modelling studies on both the systems were also conducted. The raw material cost to produce a kilogram of linalool is $1.40. There is a significant margin of 60.8 percent between the raw material cost of linalool and the current selling price ($3.57/kg). This clearly indicates that the project is potentially feasible from an economic point of view and we can now proceed with confidence to the next stage which is the engineering design, building and commissioning of the large scale pyrolysis rig. The rest of the process steps will be conducted on existing equipment currently present at the CSIR’s large scale facility (Imbiza in Isando, Gauteng).

Thesis (Ph. D.)--Columbia University, 1932. / Vita. Bibliography: p. [50].

The liquid phase autoxidation of the readily available sesquiterpene valencene to the commercially important perfuming agent nootkatone utilizing gaseous oxygen at atmospheric pressure has been investigated. Catalyst systems involving transition metal salts and complexes, and phase-transfer catalysts have been evaluated under different conditions of valencene concentration, catalyst concentration, reaction temperature, solvent and oxygen flow rate. Of eighteen candidate catalysts for the oxidation of valencene to nootkatone, chlorocarbonylbis (triphenylphosphine) iridium (Vaska's catalyst) demonstrated good activity and appeared to show the best potential for future work.

In the multi-step synthesis of Lilestralis, a synthetic muguet fragrance, the kinetics and mechanism of the formation of 3-(3-t-butylphenyl)-2-methylpropan-1-ol (m-LOL) and 4-(3-t-butylphenyl)-2-methylpropan-1-ol (p-LOL) from 2-methyl-3-phenylpropan-1-ol (MPP) and isobutylene using concentrated liquid phosphoric acid as a catalyst was investigated. By-products that include phosphate esters of MPP, m-LOL and p-LOL and oligomers of isobutylene were produced during this reaction and their role within the kinetics and mechanism was also investigated. When crystalline phosphoric acid is dissolved in water, it can form equilibrium polyphosphate mixtures at high acid concentrations. The phosphate species have the general formula Hn+2PnO3n+1 and consist of species such as orthophosphoric acid (H3PO4), pyrophosphoric acid (H4P2O7) and triphosphoric acid (H5P3010). The presence of polyphosphate within liquid phosphoric acid solutions used in this study was investigated using 31P NMR. To investigate the influence of water on the reaction, a number of experiments were performed using 1,4-dioxane as a solvent. This was chosen as the boiling points and density are similar to water, although it is classified as an aprotic solvent. Phosphate esters of MPP, m-LOL and p-LOL are produced as by-products and can potentially undergo hydrolysis when water is present, therefore reactions using aqueous phosphoric acid solutions may not give a true reflection of the concentration of phosphate esters produced. The use of heterogeneous catalysts was also investigated in order to improve yield and selectivity for p-LOL and m-LOL. These include acid catalysts such as solid phosphoric acid supported on Kieselguhr (SPA), sulphated zirconia and ultra stable zeolite-Y (H-USY).

Dissertação (mestrado) - Pontifícia Universidade Católica do Paraná, Curitiba, 2007 / Bibliografia: f. 177-185 / O objetivo principal desse trabalho foi o de analisar a relação associativa entre os valores, benefícios e atributos percebidos pelas consumidoras de perfumes de luxo residentes na cidade de Curitiba (PR). Para essa finalidade, foi aplicado o Modelo de Ca / The main objective of this study is to analyze the associative relation between values, benefits and attributes perceived by the consumers of luxury fragrances living in Curitiba (PR). For this purpose the methodology used was the Means-and-Chain Model pr

Orientador: Marcos Nogueira Eberlin / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-07T11:19:58Z (GMT). No. of bitstreams: 1 Marques_LygiadeAzevedo_M.pdf: 2432568 bytes, checksum: 7bf6003b0fa0df13e1ba0f91d7ebf00b (MD5) Previous issue date: 2006 / Resumo: Neste trabalho aplicamos técnicas avançadas de espectrometria de massas, (MALDI-TOF e ESI-MS) na análise de micotoxinas em alimentos e na tipificação e verificação de fraudes em perfumes. Aplicamos a técnica MALDI-TOF em análises de micotoxinas, e esta mostrou excelente desempenho nas análises de aflatoxinas e ocratoxina e vantagem sobre a técnica de escolha atual, o método ELISA. Esta vantagem é principalmente maior especificidade através de maior exatidão em medidas de massas e, portanto, maior confiabilidade. O Planejamento de experimento foi uma ferramenta valiosa para obtenção das melhores condições e estudo dos parâmetros de interferência. O limite de detecção encontrado para a técnica foi da ordem de 25 pg para aflatoxinas e de 1 ng para ocratoxina, com perspectiva de melhoria através de aumento da massa amostral em estudos futuros para adaptação da metodologia de extração na matriz de interesse à técnica MALDI-TOF. A técnica ESI-MS foi utilizada para a tipificação e detecção de perfumes proporcionando, através da análise de componentes principais (PCA), a diferenciação com segurança entre perfumes originais, falsos e inspirados, utilizando como indicadores componentes polares não majoritários característicos de cada categoria avaliada. Este estudo abre caminho para que esta técnica seja utilizada na avaliação de perfumes que estão sob suspeita de falsificação com auxilio de uma biblioteca de "fingerprint" de perfumes por ESI-MS. O emprego da técnica de MALDI-TOF também é uma opção vantajosa para o monitoramento da qualidade de grãos quanto a presença de toxinas indesejáveis, bem como ameaças de bioterrorismo. / Abstract: In this work we applied advanced mass spectrometry techniques (MALDI-TOF and ESI-MS) to micotoxin analysis in food and for the typification and detection of counterfeit perfumes. MALDI-TOF was applied to micotoxin analysis, which showed excellent performance for the analysis of aflatoxins and ochratoxin with advantage over the current technique of choice, the ELISA method. This advantage is mainly its greater specifity due the exactness of the measurements, therefore with higher reliability. The surface analysis was a valuable tool to attain the best conditions and study the interference of several parameters. The detection limit found for the technique was 25 pg for aflatoxins and 1 ng for ochratoxins, with perspective of improvement through increase of the sample mass in future studies for adaptation of the methodology of extration in the matrix of interest for the MALDI-TOF technique. The ESI-MS technique was used for typification and detection of counterfeit perfumes, providing, through principal component analysis (PCA), the characterization of original, counterfeit and inspired perfumes, using as minoritarian polar compounds as diagnostic ions of each perfume category evaluated. We envisage that the method can be used to establish a ESI-MS fingerprinting library of perfumes for comparison with those from samples under investigation, and that such a library could be updated constantly by the addition of ESI-MS of new perfumes even before they are commercially released. MALDI-TOF technique is also an advantageous option for the monitoring of crop quality relating to the presence of undesirable toxins, as well as bioterrorism threats by micotoxin poisoning. / Mestrado / Quimica Analitica / Mestre em Química

Tese de doutoramento. Engenharia Química. Faculdade de Engenharia. Universidade do Porto. 2010

GOMES, Clêrton Linhares. Classificação multivariada de perfumes e análise de fragrâncias alérgenas. 2015. 108 f. Tese (Doutorado em Química)-Universidade Federal do Ceará, Fortaleza, 2015. / Submitted by Aline Mendes (alinemendes.ufc@gmail.com) on 2017-01-13T18:18:21Z No. of bitstreams: 1 2015_tese_clgomes.pdf: 5446161 bytes, checksum: ee6e19b40ad30bb7107aec1b836f884f (MD5) / Approved for entry into archive by Jairo Viana (jairo@ufc.br) on 2017-01-19T13:09:38Z (GMT) No. of bitstreams: 1 2015_tese_clgomes.pdf: 5446161 bytes, checksum: ee6e19b40ad30bb7107aec1b836f884f (MD5) / Made available in DSpace on 2017-01-19T13:09:38Z (GMT). No. of bitstreams: 1 2015_tese_clgomes.pdf: 5446161 bytes, checksum: ee6e19b40ad30bb7107aec1b836f884f (MD5) Previous issue date: 2015 / Perfumes are mainly made of ethilic alcohol, water and fragrances. These fragrances are responsible for caracterizarrem nice and unique odor of each perfume. The trade of this product perfumes is very lucrative for being product used by all. Parallel to the legal trade in perfumes, forgery see these products increasing in recent years. Among the fragrances, the highlight was a group of fragrances (limonene, benzyl alcohol, linalool, methyl octanoate, citral, citroneol, hidroxicitroleol, geraniol, eugenol, isoeugenol, anise alcohol, amyl cinnamic alcohol, amyl cinamal, cinnamic alcohol, coumarin, cinnamaldehyde, alpha-isometil ionene liral, lilial, farnesol hexilcinamaldeido benzyl benzoate, benzyl cinnamate, benzyl salicylate) that may cause allergy by contact, leading to dermatitis. Brazilian law (DRC 3/2012 ANVISA) and European (EC 1223/2009) state that when these concentrations exceed the limit of 0.01% (100 ppm) for products rinse and 0.001% (10 ppm) for products with rinse, the manufacturer is obliged to discriminate underin its label their presence. The first part of this work is the multivariate analysis of perfumes, based on the comparative study of 25 original perfumes ecom 25 false through oxidase analysis dose organic compounds by IR, GC-FID and espectroóscopia in the UV region (UV) : and inorganic by ion chromatography and flame photometry. The data generated were processed by a estatistic software, the R Project, giving the PCA, SIMCA and LDA, aiming to differentiate the original edo fake perfume. UV spectroscopy study showed that the original product had major quantity and intensity of bands compared to the fake product, which may be indicative of higher fragrance content. The chemometric treatment allowed the efficient separation into two groups. The analysis of ions and ethanol allowed to observe the fake product has high chloride content (38 ppm) and low ethanol (45%); since the original product had a low content of ions (15 ppm) and high ethanol content (83%). The multivariate study allowed the distinction of counterfeit and original products. The second part comes Dae analysis validation of allergenic fragrances in perfumes, extraídaso by solid phase microextraction and analyse by gas chromatography coupled to mass espectrometric the quadrupole type operating in SIM mode, with small sample size (10 μg.L -1). This method has shown good results of linearity, limit of detection (0,05 to 271 μg.L-1), limit of quantitation (0,017 to 0,900 μg.L-1), intermediate precision (3,0 to 19.3%) , repeatability (8,9 to 19,7%) and recovery (59-115%) for the studied matrix. The authentic perfumes analysis showed that these products have a high allergenic fragrance concentration (LD-190 mg.L-1) and need to be discriminated on their labels. The fake perfume analysis showed that these products have low allergenic fragrances have (LD-56 mg L-1) and who have no fragrances with higher molecular weight, as cinnamaldehyde and benzyl salicylate; this may be one of the reasons It makes the counterfeit product having a low fixing odor. / Perfumes são produtos constituídos essencialmente por álcool etílico, água e fragrâncias. Estas fragrâncias são responsáveis por caracterizar o odor agradável e ímpar de cada perfume. O comércio deste produto é muito lucrativo por ser algo utilizado por todos. Paralelo ao comércio legal de perfumes, sua falsificação vem aumentando nos últimos anos. Dentre as fragrâncias, destacou-se um grupo (limoneno, álcool benzílico, linalol, octanoato de metila, citral, citronelol, hidroxicitronelol, geraniol, eugenol, isoeugenol, álcool anis, álcool amil cinâmico, amil cinamal, álcool cinâmico, cumarina, cinamaldeido, alfa-isometil-ioneno, liral, lilial, farnesol, hexilcinamaldeido benzoato de benzila, cinamato de benzila, salicilato de benzila) que pode ocasionar alergia por contato, levando a uma dermatite. A legislação brasileira (RDC 3/2012 da ANVISA) e a européia (CE 1223/2009) determinam que quando estas concentrações excederem o limite de 0,01% (100 ppm) para produtos com enxágue e 0,001% (10 ppm) para produtos sem enxágue, o fabricante fica obrigado a discriminar no rótulo sua presença. A primeira parte deste trabalho é a análise multivariada de perfumes, partindo do estudo comparativo entre 25 perfumes originais e 25 falsos, através das análises dos compostos orgânicos por infravermelho (IV), CG-DIC e espectroscopia na região do ultravioleta (UV); e inorgânicos por cromatografia de íons e fotometria de chama. Os dados gerados foram processados por um software estatístico, R Project, originando o PCA, SIMCA e LDA, com intuito de diferenciar o perfume original do falso. O estudo de espectroscopia UV mostrou que os produtos originais apresentam maior quantidade e intensidade de bandas quando comparado ao produto falso, o que pode ser um indicativo de maior teor de fragrância. O tratamento por quimiometria permitiu a separação eficiente em dois grupos. A análise de íons e etanol permitiu observar que os produtos falsos apresentam elevados teores de cloreto (38 mg L-1) e baixos de etanol (45 % m/v). Por outro lado, os produtos originais apresentaram em média baixo teor de cloreto (15 mg L-1) e elevado teor de etanol (83%). O estudo multivariado permitiu a distinção de produtos falsos e originais. A segunda parte do trabalho trata da validação de análise de fragrâncias alérgenas em perfumes, extraídas por microextração em fase sólida (MEFS) combinada com cromatógrafia gasosa - espectrometria de massas (CG-EM) do tipo quadripolo operando no modo SIM. Este método demonstrou bons resultados de linearidade, limite de detecção (0,05-271 µg.L-1), limite de quantificação (0,017-0,900 µg.L-1), precisão intermédiária (3,0-19,3%), repetibilidade (8,9-19,7%) e recuperação (59-115%) para a matriz estudada. A análise de perfumes autênticos mostrou que esses produtos apresentam concentração de fragrâncias alérgenas elevadas (LD-190 mg.L-1) e que necessitam ser descriminadas em seus rótulos. A análise de perfumes falsos demonstrou que estes produtos apresentam baixo teor de fragrâncias alérgenas (LD-56 mg.L-1) e que não possuem fragrâncias com massa molar mais elevada, como cinamaldeido e salicilato de benzila; isto pode ser um dos motivos que faz o produto contrafeito possuir baixa fixação de odor.