Diploma's thesis describes resolution of cause technological problems in mineral wool manufacturig in company Saint-Gobain Orsil. Main attention is paid to thermal and volatile process in mineral wool from filtration chamber and common commercial sales. Samples of mineral wool were characterizated by thermal analysis (simultaneous TG-DTA), effluent gas analysis (EGA), infrared spectroscopy (FT-IR), electron microscopy (SEM) and X-ray diffraction (XRD). Thermal analysis experiments was used to check thermal volatile processes. Technological problem of burning is linked with rise of isocyanic acid.

The aim of thesis is acquaint with possibilities of fixation biological tissues. Choose a suitable tissue and fix it with formaldehyde and another fixator. Last but not least make measurements which determine effects of formaldehyde on the relaxation time of biological tissues. Mice brains were chosen as a suitable for tissues fixation. Measuring effects of formaldehyde and another fixator to relaxation time carried out at the Institute of Scientific Instuments Academy of Sciences of the Czech Republic.

Derivatives of 3-methyl-1-2-benzothiazolinone hydrazone were formed from the oxidation products of three oxidized unsaturated fatty acids. Aeration with oxygen and heat (65C) was used as a means of accelerating deterioration of lipid samples. Formaldehyde was recovered from oxidized pure standards of oleic, linoleic and linolenic acid methyl esters , and identified using gas chromatography. Formaldehyde was also recovered from oxidized lipid extracts of mechanic ally deboned turkey meat and turkey cluster fat. Gas chromatography was used to measure concentrations of unsaturated fatty acids during the oxidation of extracted lipids. Linoleic and linolenic fatty acids significantly decreased (p < .005) in oxidized lipid extracts from turkey cluster fat stored frozen for six months. Measurement of the amounts of formaldehyde which accumulates as a result of the oxidation of unsaturated fatty acids, may be the most reliable method of assessing the extent of oxidative deterioration in foods.

No description available.

This work focused on decay and dimensional stability of southern pine lumber and environmental issues associated with emissions released during kiln drying of southern pine. In one study decking boards were treated with a 3% resin acid solution to increase the dimensional stability. The boards were placed on a roof and weathered for two years. The increased water repellency reduced moisture gain following summer rainstorms by one-third compared to untreated matched samples, this significantly reduced splitting by half and cupping by one-third. In one study decking boards from matched samples were weathered for two years in the roof setup described above, and in a fungal ground proximity test. The ground proximity samples had slightly more decay than the roof samples. Correlation between decay ratings for the matched samples was 37%, suggesting above-ground decay susceptibility is dependent on the macro- and micro-environment. Decay in roof exposure was modeled based on moisture content factors, whereas decay in ground proximity was modeled by the resin and fatty acids. One study tested pole sections with varying amounts of sapwood, heartwood, and knots dried in a pilot-scale kiln. A sample of the kiln exhaust was measured for volatile organic compounds. Emissions from poles were similar to clear lumber. Emissions from heartwood poles were less than for heartwood lumber, perhaps due to the poles’ sapwood band. The final study was conducted with clear and knotty lumber kiln dried to below 8% moisture content using three kiln schedules. Wood dried to this lower moisture content is used in interior applications or exported. During drying, a sample of the kiln exhaust was analyzed for total VOCs, and a sample of the kiln exhaust was collected and analyzed for hazardous air pollutants via gas chromatography and spectrophotometry. For all three kiln schedules, mills would reach 10 tons of methanol and thus must comply with maximum achievable control technology standards before reaching 25 tons of methanol, formaldehyde, acetaldehyde, acrolein, and propionaldehyde.

This thesis presents applications of near infrared diode lasers to high resolution spectroscopy of transient radical species. Firstly, time resolved near infrared laser gain versus absorption is utilised in Chapter 2 to determine the I∗ quantum yield following ultraviolet photolysis of iodobenzene and its fluorinated analogues. The experimental method is first confirmed by comparison with literature values of the quantum yield for iodomethane photolysis, returning a quantum yield of Φ(I∗) = 0.71 ± 0.04 in good agreement with the literature, before being applied to determine the I∗ quantum yield following 248 nm and 266 nm photolysis of iodobenzene (Φ(I^∗) = 0.28 ± 0.04) and pentafluoroiodobenzene (Φ(I^∗) = 0.32 ± 0.05). The I^∗ quantum yields for 4-fluoroiodobenzene, 2,4-difluoroiodobenzene and 3,5-difluoroiodobenzene are also reported in order to determine the effect of selective fluorination on the dynamics of the photodissociation process. This work complements velocity-map ion imaging studies and spin-orbit resolved ab initio calculations of the ultraviolet photolysis of these compounds. Chapter 3 details the development of a narrow-bandwidth tunable continuous wave ultraviolet radiation source, through sum frequency mixing of tunable near infrared diode lasers with a fixed frequency, high powered, solid state laser. The application of the UV radiation source to spectroscopy of the A¹A₂ − X¹A₁ electronic band of formaldehyde is explored, where absolute absorption cross sections are determined for rotational transitions within the 220410 and 220430 vibronic bands. The sub-Doppler resolution has allowed refinement of the rotational constants for the slowly predissociating excited state of the 2²₀4³₀ vibronic band. The lifetimes of several rotational levels is determined to be in the range 0.74 ns to 1.46 ns. In Chapter 4 the UV radiation source developed in Chapter 3 is applied to the A ²Σ⁺ − X ²Π electronic band of the OH radical. Firstly, this source is utilised to probe a continuous supply of hydroxyl radicals using cavity-enhanced absorption spectroscopy and wavelength modulation spectroscopy. Pressure induced broadening parameters for the Q₁(2) rotational transition for He, Ne, Ar and N₂ buffer gases are also measured. Following the successful application of this source to probe a continuous OH source at atmospheric pressure, the UV spectrometer is used to probe OH radicals from nitric acid photolysis at 193 nm, where the nascent speed distribution and Doppler lineshape is shown to be in excellent agreement with the literature. Time resolved absorption spectroscopy of the nascent OH fragment also returns a translational relaxation constant of k_trans = (3.85±1.06)×10⁻¹⁰cm³molecule⁻¹s⁻¹, which is in good agreement with literature values. These preliminary results indicate the potential of this narrow-bandwidth tunable UV source as an absorption-spectroscopy-based probe of nascent Doppler profiles. Chapter 5 presents the application of frequency-modulated radiation from a near infrared diode laser as a probe of the angular momentum polarisation of the nascent CN fragments, produced by 266 nm photolysis of ICN. These CN fragments are probed in the high rotational states of both the ground and first excited vibrational level on the A ²Π − X ²Σ⁺ electronic transition; in particular these constitute the first measurements of alignment and orientation in the first excited vibrational level at this photolysis wavelength. The alignment parameters reported for both vibrational levels are comparable, indicating that the incoherent dynamics contributing to their formation are the same. In contrast, the orientation of the v = 1 CN fragment is shown to be of opposite sign to that of v = 0 at this photolysis wavelength, although the absolute differences in their orientation parameters are similar to that observed for photolysis at 248 nm. This observation is consistent with coherent orientation arising from phase differences between wavepackets propagating on multiple excited potential energy surfaces.

La régulation transcriptionnelle des gènes est un processus indispensable sans lequel la diversité phénotypique des cellules ainsi que l’adaptation à leur environnement serait inexistant. L’identification des éléments de régulation dans le génome est d’une importance capitale afin de comprendre les mécanismes gouvernant l’expression des gènes spécifiques à un type cellulaire donné. Ainsi, suite au pic de LH, le follicule ovarien entre dans un programme intensif de différentiation cellulaire, orchestré par des modifications majeures du profile transcriptionnel des cellules de granulosa, déclenchant ultimement l’ovulation et la lutéinisation, processus indispensables à la fertilité femelle. L’hypothèse supportée par cette étude stipule qu’une réorganisation de la structure chromatinienne survient aux régions régulatrices d’une panoplie de gènes dans les heures suivant le pic de LH et qu’en isolant et identifiant ces régions, il serait possible de retrouver des éléments essentiels aux processus d’ovulation et de lutéinisation. Ainsi, en utilisant un protocole standard de superovulation chez la souris, les éléments de régulation se modifiant 4h suivant l’administration de hCG ont été isolés et identifiés dans les cellules de granulosa en utilisant la méthode FAIRE (Formaldehyde-Assisted Isolation of Regulatory Elements) combinée à un séquençage haut débit. Cette étude a démontré que suite au stimulus ovulatoire, les cellules de granulosa subissent une reprogrammation majeure des éléments de régulation, qui est corrélée avec une modification drastique de leurs fonctions biologiques. De plus, cette étude a mis en évidence une association majoritaire des éléments de régulation à des régions intergéniques distales et à des introns, indiquant que ces régions ont une importance capitale dans la régulation transcriptionnelle dans les cellules de granulosa. Cette étude a également permis d’identifier une panoplie de régulateurs transcriptionnels reconnus pour être essentiels à la fonction ovarienne, ainsi que leur sites de liaison dans le génome, démontrant que la méthode FAIRE est une méthode assez puissante pour permettre la prédiction d’événements moléculaires précis ayant un sens physiologique réel. / Identification of regulatory elements in the genome is of paramount importance to understanding the mechanisms governing the expression of specific genes in a given cell type. Following the LH surge, the ovarian peri-ovulatory follicle enters an intensive program of cellular differentiation, orchestrated by major changes in the transcriptional profile of granulosa cells, ultimately triggering ovulation and luteinization, processes essentials for fertility in females. In the mouse, several genes essential to the success of this program are induced 2 to 6 hours after the ovulatory stimulus. Using a standard protocol for superovulation in mice, the regulatory elements were isolated and identified in granulosa cells 4h after administration of hCG using the method FAIRE (Formaldehyde-Assisted Isolation of Regulatory Elements) combined with next generation sequencing. The results of this analysis demonstrate that after the ovulatory stimulus, granulosa cells undergo a major reprogramming of regulatory elements, which is correlated with the extensive changes in their biological functions. In addition, this study showed that most regulatory elements were associated with distal intergenic regions and introns, indicating that these regions are important in transcriptional regulation in granulosa cells. A variety of transcriptional regulators known to be essential for ovarian function, and their binding sites were also identified in this analysis, demonstrating that the FAIRE method has the power to predict molecular events that have correlates in the known physiology of ovarian processes.

Lors de cette étude, j'ai effectué des recherches sur trois sortes d'assemblages du bois : les colles naturelles, les colles synthétiques et le soudage sans colles, ceci dans le but d'améliorer les performances de fabrication des panneaux de particules, des panneaux contreplaqués, des lamellés-collés et des composites. Dans ce travail, le contenu d'étude inclut les éléments suivants : 1) L'assemblage des panneaux semi-extérieurs ou extérieurs par les colles naturelles : Trois types différents de tannins (les tannins hydrolysables de châtaigniers, les tannins condensations de pin radiata et les tannins condensations de mimosa) sont étudiés. 2) L'assemblage des panneaux extérieurs par les colles synthétiques : Différents types d'additifs (le nanoargile, des précurseurs oligomériques de poly (amine-ester) et glutaraldéhyde) pour améliorer leurs performances. La résine MUF (Mélamine-Urée-Formaldéhyde) est obtenue sous forme de poudre par séchage d'atomisation ainsi sa durée de vie est potentiellement infinie.3) L'assemblage des panneaux extérieurs par soudage sans colles : Deux matériaux (l'huile et la lignine acétylée) pour améliorer les résistances à l'eau. Toutes les propriétés physico-chimiques et mécaniques ont été étudiées en mettant en oeuvre des techniques d'analyse et d'évaluation telles que la thermomécanique TMA, la cristallographie aux rayons X (XRD), la résonance magnétique nucléaire 13C RMN, la spectrométrie de masse MALDI-TOF, et la fabrication des panneaux en laboratoire. Finalement, nous avons amélioré les caractéristiques des panneaux avec les colles ou sans colles et spécifiquement la résistance à l'eau pour une utilisation extérieure / In this studied, wood based composites were assembled with the natural adhesive (tannin adhesive), the synthesis adhesive (MUF) and the welding wood without adhesive. These wood composites include particleboard, plywood and glulam. We focus on these works as follows: 1) Three different types of tannins (chestnut hydrolysable tannins, pine condensation tannins and mimosa condensation tannins) as thermosetting or cold-setting adhesive were studied to assemble particleboard, plywood and glulam for application to semi-exterior or exterior. 2) The characteristics of MUF resins for particleboard applications have been improved through a number of additives (nanoclay, hyperbranched polymer and glutaraldehyde), the powder adhesive of MUF was obtained by spray-drying technologies, and it could be prolonger the shelf-life of MUF adhesive. It also can be application to exterior after enhancing. 3) The blockboard for application exterior was assembling by welded dowels, two differents materials (sun flower oil and acetylated lignin) were used to improve the water resistance. These physical, chemical and mechanical properties of these assemblages was investigated by implementing some techniques such as thermomechanical analysis (TMA), X-ray diffraction (XRD), nuclear magnetic resonance (13C NMR), matrix-assisted laser desorption/ionization mass spectroscometry (MALDI-TOF), and by manufacturing wood composites. Finally, the performances of these wood composites were apparent improved whether with the tannin adhesive, the MUF adhesive or the welding wood without adhesive, especially improved the water resistance of wood composites for exterior applications

Les marcs de raisin issus de la viniculture constituent un gisement de ressource naturelle abondant, sous valorisé et riche en polyphénols. Une méthode d?extraction de ces tannins condensés a été développée et optimisée en vue d'une application en adhésif pour les produits dérivés du bois. Les tannins ont été caractérisés par Résonance Magnétique Nucléaire, spectroscopie Infra Rouge (FTIR), spectrométrie de masse (MALDI TOF) et Analyse Thermomécanique (TMA). Des panneaux de particules ont été fabriqués à l'aide des colles élaborées en laboratoire et testés suivant les normes françaises en vigueur, plusieurs dépassent largement les valeurs seuils / The extraction of condensed tannins from grape pomace was examined using water medium in the presence of different bases as catalyst (NaOH, Na2CO3, NaHCO3 and Na2SO3). Two different extraction processes and the influence of 4 parameters (i.e., temperature, reaction time, chemical reagents and concentration of the chemical reagents) on the tannin extracts yields and properties were studied. The tannin fractions were characterized by Fourier transform-infrared spectroscopy, thermogravimetric analysis, carbon nuclear magnetic resonance spectroscopy and matrix assisted laser desorption ionization time of flight mass spectrometry ( MALDI-TOF ). It was demonstrated that it is possible to extract reactive tannins from grape pomace in basic medium. The tannin extracts obtained by precipitation in acidic conditions display a high phenolic content (Stiasny number higher 95%) but low water solubility and low reactivity toward formaldehyde because of the formation of catechinic acid phlobatannins during the acidification step. The tannins extracts obtained by lyophilization of the liquid, despite of their lower phenolic contents, displayed promising properties for adhesive applications. The optimum temperature of the extraction process was 100 °C, reaction time was 120 min; the best concentration of reagent was 10% (w/w). It was also shown that addition of sulphite ions during the extraction step improved the process :y the introduction of a sulfonic group through sulfitation increased both tannin solubility and reactivity as a result from the opening of the heterocyclic ring during extraction The structure of grape pomace sulfited tannin extracts did not present noticeable discrepancy exception of the ratio of the opening pyran ring which was different as a function of the catalyst used. The opening of pyran ring during the tannins extraction seem to be more important by using Na2CO3 and NaHCO3 than when using NaOH. The FT-IR bands assigned to aromatic ring vibration and carbonyl groups were stronger and no bands attributed to sulfited groups were tested detected in acidified tannins compared to lyophilized tannins. The TG2 results showed that the weight lost of these tannin extracts mainly composed of two steps. The first step starts from room temperature to 200 °C. It is attributed to the mass lost of water and some easy-degraded small low molecules. The secondly steps which is the mainly degradation step of tannin extract samples from 200 to 400 °C. The results from 13C-NMR showed that condensed tannin extracts from grape pomace were consistent with dominant procyanidin units with a minor amount of prodelphinidin units that are linked together by a C4-C8 bond. Relatively low carbonhydrate and high catechinc acid content was observed in acidified tannins compared to lyophilized tannins. It was shown by MADI-TOF experiments that grape pomace tannin extracts are mainly composed of flavoinoid oligomers up to 6 repeating units in lyophilized tannins and 10 repeating units in acidified tannins respectively, with dominant procyanidin units. A small proportion of substitution with glucose and gallic acid was detected in procyanidin units of polyflavonoid oligomers. The degree of polymerization of acidified tannins is higher than lyophilized tannins. Two different formulations (nonfortified tannin adhesive and fortified with addition of 20% of polymeric 4, 4'-diphenyl methane diisocyanate (p-MDI)) were used to press one layer wood particle board. It was shown that the nature of the extraction reagent (NaOH, Na2CO3 or NaHCO3) greatly impacts the properties of the resins and the mechanical properties of the panel internal bonding strengths. The particleboards bonded by the tannins extracted using Na2CO3 as catalyst give the best performance and were good enough to pass relevant international standard specifications for interior grade panels. Formaldehyde emission of these panels was below the European Norm requirements (<= 6.5 mg/ 100g panel)

Para minimizar os impactos ambientais causados pelo lançamento de formaldeído na natureza, é importante o desenvolvimento de tecnologias adequadas para o seu tratamento. Sistemas aeróbios têm sido utilizados, porém, as opções por tratamento anaeróbio estão tendo cada vez mais aceitação, principalmente pelo baixo consumo de energia e baixa produção de lodo. Por outro lado, substâncias tóxicas podem provocar distúrbios em reatores anaeróbios. Algumas pesquisas já foram desenvolvidas quanto ao tratamento biológico anaeróbio de formaldeído, no entanto, ainda não se chegou a um consenso sobre o seu comportamento ou qual o sistema mais eficaz. Nesse trabalho, avaliou-se a degradação e a toxicidade dessa substância em reator anaeróbio horizontal de leito fixo, a fim de trazer subsídios para essa questão. As concentrações de estudo variaram de, aproximadamente, 30 a 1500 mg/L de formaldeído, atingindo-se as eficiências de remoção de até 99,7 % de formaldeído e 92 % de DQO. A presença de ácidos graxos com até cinco carbonos durante a degradação do formaldeído pode indicar uma rota de degradação diferente da sugerida na literatura, onde os produtos intermediários seriam o metanol e o ácido fórmico. O modelo cinético de Monod foi o que melhor representou os dados experimentais, com \'R IND.max\' POT.app\' = 2,79 x \'10 POT.-3\' HCHO/mg SSV.h e \'K IND.S\' POT. app\' = 242,8 mg HCHO/L. / In order to minimize the environmental impacts caused by formaldehyde discharge in the nature, the development of appropriate technologies for its treatment is important. Aerobic systems have been used, however, anaerobic treatment options have been widely studied, mainly due to low energy consumption and sludge production. On the other hand, toxic substances can lead to disturbances in anaerobic reactors. Some formaldehyde anaerobic biological treatment researches have already been developed, although, there is no consensus about its behavior or which is the most efficient system. Degradation and toxicity of this substance were evaluated in horizontal-flow anaerobic immobilized sludge reactor, with the purpose of producing subsidies for this issue. Formaldehyde concentrations ranging from, approximately, 30 to 1500 mg/L were applied in the reactor and formaldehyde and COD removal efficiencies of 99,7% e 92% were achieved, respectively. Volatile fatty acids with up to 5 carbons, found during the formaldehyde degradation, can indicate that degradation followed different routes than those suggested in the literature, that reports the formation of intermediates such as methanol and formic acid. Monod kinetic model fitted well the experimental data, with apparent kinetic parameters estimated as \'R IND.max\' POT. app\' = 2,79 x \'10 POT.-3\' mg HCHO/mg SSV.h and \'K IND.S\' POT. app\' = 242,8 mg HCHO/L.