Por décadas a radiação infravermelha tem sido usada de forma estética e terapêutica, e é caracterizada por ter a propriedade de penetrar na pele. O surgimento de novas tecnologias permitiu a criação de têxteis funcionais, entre eles os tecidos contendo biocerâmica, que absorvem o calor do corpo, ativando a biocerâmica presente e emitindo raios infravermelhos longos, que penetram na pele ativando a microcirculação sanguínea. Porém, tecidos desse tipo só tiveram eficiência comprovada por testes clínicos, que são métodos caros e demorados, ou por analogia baseada no tipo de construção. O objetivo deste estudo foi elaborar um método prático para medir a emissividade de tecidos contendo biocerâmica, utilizando um espectrofotômetro de raios infravermelhos, comparar a emissividade desses tecidos, além de realizar uma análise de fluorescência de raios X a fim de descobrir os elementos químicos presentes nos tecidos, para confirmar quaisquer diferenças de emissividade entre os mesmos. Concluiu-se que é possível medir a emissividade de tecidos contendo biocerâmica através do aquecimento das amostras, simulando a ação do tecido junto ao corpo, e posteriormente realizando ensaios em um espectrofotômetro de infravermelhos por transformada de Fourier, onde picos de emissão foram encontrados em cada tecido analisado, o que possibilitou o cálculo da emissividade (expressa em contagens de área) através do ajuste de uma curva gaussiana em cada pico de emissão. Através da fluorescência de raios X foram encontrados diferentes elementos químicos na composição das amostras, podem ser a causa da diferença de emissividade entre os tecidos / The infrared radiation has been used on aesthetic and therapeutic way for decades, and is characterized for being able to penetrate deeply underneath the skin. New technologies appeared, enabling the development of functional textiles, among them textiles containing bioceramics that absorb the body heat, activating the bioceramic on it and emitting far infrared rays, which penetrate into the skin, activating the blood microcirculation. However, the efficiency of this sort of fabrics was proven only by clinical tests, which are very expensive and time consuming, and by construction analogy. The main objective of this study was to develop a practical method for measuring fabrics containing bioceramics emissivity, using an infrared spectrophotometer, comparing the fabrics emissivity, besides doing an X ray fluorescence analysis in order to discover the chemical elements that composes the fabrics, to confirm any emissivity differences between them. It was concluded that it is possible to measure the emissivity of fabrics containing bioceramics by heating the samples, simulating the action of the fabric on the body, and subsequently performing tests on a Fourier transform infrared spectrophotometer, where emission peaks were found on the fabrics, that enabled the emissivity calculation (expressed in area counts) by adjusting a Gaussian curve at each emission peak. By the X ray fluorescence different chemical elements were found on the fabrics composition, which can be the reason for the emissivity difference between them

Metallophilic (metal-metal) interactions are weak interactions between closed-shell (d10, s2) or pseudo-closed-shell (d8) metal cations. This type of interaction is generally believed to be responsible for various intriguing structures, luminescence, catalysis and magnetism. To gain a better understanding of metallophilic interactions, both experimental and computational investigations have been carried out in this thesis. Chapter 1 gave an up-to-date literature review on the definition, significance, and methods of estimating metallophilic interactions. The disputed nature and strength of metallophilic interactions encouraged us to further understand them. Chapter 2 focused on aurophilic interactions between AuI cations. Aurophilic interactions were observed in the solid state, but not well expressed in solution. Further experimental and computational results suggested that the strength of aurophilic interactions were weaker than electrostatic interactions. The nature of aurophilic interactions arose from orbital interactions rather than dispersion. Chapter 3 presented the study of metallophilic interactions between group 10 metal centres, including PtII-PtII, PdII-PdII and NiII-NiII. A series of cyclometalated square-planar metal complexes with different metals or substituents were prepared. PtII-PtII interactions were found to be stronger than PdII-PdII and NiII-NiII interactions. The dimerization constants of the Pt-containing complexes increased in line with increasing electron-withdrawing ability. Chapter 4 investigated the solvent-induced and thermally dependent colour changes of the Pt-containing complexes synthesised in chapter 3. Metallophilic interactions were proposed to be important in influencing the luminescence properties.

abstract: Transient molecules are of great importance having proposed applications in quantum science and technology and tests of fundamental physics. In the present dissertation, the transient molecules studied are SrOH, ThF, ThCl, YbF and YbOH; each having been selected because of their proposed application. Specifically, SrOH is a candidate of constructing a molecular magneto-optical trap (MOT). The simple actinide molecules, ThF and ThCl, were selected as ligand bonding model systems to gain insight into chemical processing of Spent Nuclear Fuel. The lanthanides YbF and YbOH are venues for the determination of electron electric dipole moment (eEDM) and the studies in this dissertation provide the requisite properties for those experiments. Intense supersonic molecular beams of these transient molecules were generated via laser ablation and spectroscopically characterized using a novel medium-resolution two-dimensional (2D) spectroscopic approach, as well as high-resolution laser induced fluorescence (LIF). The 2D medium resolution approach, which was used in the studies SrOH, ThF, ThCl and YbOH, uses a multiplexing method that simultaneously records dispersed fluorescence and excitation spectra. A significant advantage of 2D-LIF imaging is that all the electronics states can be targeted to determine the electronics states and associated vibrational spacing individually. Consequently, in the 2D spectra of ThF, ThCl and YbOH, several previously unobserved band systems have been detected in one single scan. For the DF spectra of SrOH and YbOH, the determined branching ratios show that the transitions of these molecules are diagonal (i.e. Δv=0), which is essential for the proposed potential for laser cooling. In the high-resolution of YbF, ThF, ThCl and SrOH optical spectra were recorded to an accuracy of ±30 MHz, which represents an unprecedented precision of 1:10+8. In addition to field free spectra, optical Stark and Zeeman studies were performed to determine the most fundamental magneto-and electro-static properties. Effective Hamiltonian operators were employed to analyze the recorded spectra and determine the spectroscopic parameters. This data set also establishes a contribution toward developing new computational methodologies for treating relativistic effects and electron correlation. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2019

Two independent studies were conducted to assess the effects of feeding condensed tannin (CT)-containing forages to continuous cultures to evaluate their impacts on ruminal fermentation and digestibility, with an emphasis on methane (CH4) and ammonia-N (NH3-N) production. In Chapter 3, treatments consisted of: 1) 100% alfalfa hay (AH), 2) 50% AH and 50% birdsfoot trefoil hay (dry matter (DM) basis; AHBFTH), and 3) 100% birdsfoot trefoil hay (BFTH). Three replicated runs lasted 8 d each, with the first 5 d allowed for microbial adaptation to the diets, and 3 d for data collection and sampling. Methane, neutral detergent fiber (NDF) degradability, and total volatile fatty acid (VFA) production and profiles were not affected by the dietary treatments. However, NH3-N concentration and flow were reduced when replacing the AH with the BFTH. It was concluded that feeding a CT-containing diet (BFTH) increased the in vitro N utilization. In Chapter 4, five total mixed ration (TMR) diets were evaluated, each containing a different forage source as hay: 1) alfalfa (AHT), 2) cicer milkvetch (CMVHT), 3) Norcen birdsfoot trefoil (NBFTHT), 4) Oberhaunstadter birdsfoot trefoil (OBFTHT), and 5) sainfoin (SFHT). Total VFA production and acetate molar proportion were not influenced by treatments. However, molar proportion of propionate increased by the CMVHT, and decreased by the SFHT. Acetate to propionate ratio decreased with the CMVHT and the OBFTHT, but increased with the SFHT when compared to the AHT. Digestibilities of DM and NDF were not influenced by dietary treatments. Total CH4 production decreased by all treatments when compared to the AHT, whereas CH4 production expressed as mM per g of NDF digested was reduced only by the CMVHT and the OBFTHT. Ammonia-N concentration decreased when feeding the CMVHT and the SFHT. Feeding the CMVHT decreased ruminal concentration of C18:0, while ruminal C18:1 cis and trans isomers were greatest with the CMVHT. Because these effective tannin-free and tanniniferous legumes did not have negative impacts on ruminal fermentation, they can maintain potential productive performance of lactating dairy cows when fed as main forage sources in TMR diets.

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No description available.

A key part of the development of new polymeric materials focuses on the use of flame-retardant additives, which help to reduce the inherent flammability of polymers and the production of smoke and toxic gases. The aim of this thesis was the preparation, characterization and application of new polymeric flame-retardant additives, which can lead to intumescent systems when mixed with ¨commodity¨ polymers. The synthesis of this kind of additives was carried out by chemical modification of different polymeric structures (alcohols, polyketones, polyaziridines) with phosphorous moieties, previously described as promoting flame retardance structures, and/or nitrogen containing moieties. The efficacy of some of these additives was tested by blending with polypropylene, one of the most commonly used thermoplastic. Flame retardancy behaviour of the blends, as well their compatibility and mechanical properties were studied, in order to observe how the flame retardant additives may affect the substrate properties. / Una parte fundamental del desarrollo de nuevos materiales poliméricos se centra en la utilización de agentes retardantes a la llama, los cuales contribuyen a reducir la inherente combustibilidad de los polímeros y la producción de humos y de gases tóxicos. El objetivo del presente trabajo ha sido la preparación, characterización y aplicación de nuevos aditivos retardantes a la llama de tipo polimérico que pueden dar lugar al mezclarse con polímeros termoplásticos de gran consumo a sistemas de tipo intumescente. La síntesis de estos additivos se ha llevado a cabo por modificación química de diferentes estructuras polimericas (alcoholes, policetonas, poliaziridinas) con compuestos fosforados, descritos previamente como promotores de retardancia a la llama y/o compuestos con nitrogeno. La eficacidad de algunos de estos additivos ha sido estudiada por mezclarse con polipropileno, uno de los más utilizados termoplasticos.

No description available.

The olfactory sensitivity of five male CD-1 mice (Mus musculus) for six amino acids was determined using an operant conditioning paradigm. All animals significantly distinguished dilutions as low as 0.01 mM L-cysteine, 3.3 mM L-methionine, 10 mM L-proline, 0.03 mM D-cysteine, 0.3 mM D-methionine and 10 mM D-proline from the odorless solvent, with individual animals displaying even lower detection thresholds. Among the three different L-forms of the amino acids the mice were most sensitive for cysteine and least sensitive for proline, and among the three D-forms the animals displayed a lower sensitivity for D-proline compared to D-cysteine and D-methionine. A comparison between the present data and results obtained with other species showed that the CD-1 mice displayed a higher sensitivity than human subjects and spider monkeys with three (L-Cysteine, D-cysteine and L-proline) of the six amino acids. Results from this report support the idea that the number of functional olfactory receptor genes is not suitable to predict a species’ olfactory sensitivity.

This thesis focuses on development of novel nanomaterials, including semiconductor quantum dots (QDs) and gold nanoparticles (AuNPs), for fabricating white-light emitting devices and assaying thiols in biological and environmental samples. The thesis mainly contains two divisions. One demonstrates synthesis, optical properties and white-light emissions of alloyed quantum dots and their application to light-emitting devices. The other describes to combine functionalized gold nanoparticles with capillary electrophoresis and accomplish high selectivity and ultrasensitive detection for thiols. First, through one-step aqueous synthesis, alloyed ZnxCd1¡VxSe QDs have been successfully prepared at low temperatures by reacting a mixture of Cd(ClO4)2 and Zn(ClO4)2 with NaHSe using 3-mercaptopropionic acid as a surface-stabilizing agent. The optical properties and composition of the alloyed QDs were highly dependent on the molar ratio of Zn2+ to Cd2+. With the increase in Zn content, a systematic blue shift occurred in the first exciton absorption and band edge emission. Moreover, X-ray diffraction peaks of the alloyed QDs systematically shifted to larger angles simultaneously. These systematic shifts indicated the formation of the alloyed QDs. Interestingly, among these alloyed QDs, Zn0.93Cd0.07Se QDs exhibited white-light emission with quantum yields of 12%. In addition, we discovered that we could adjust the relative strength of the band edge and trap state emissions by controlling the reaction time, thereby attain white-light-emitting QDs. Finally, we blended alloyed QDs with ultraviolet-transparent polydimethylsiloxane (PDMS) to develop a white-light, solid-state lighting device by using a 365-nm UV lamp as the pump source. In the other part of this thesis, we proposed a method for selective enrichment of thiols using Tween 20-capped gold nanoparticles (AuNPs) prior to capillary electrophoresis coupled with laser-induced fluorescence (CE-LIF). By forming Au-S bonds, Tween 20-AuNPs can selectively extract thiols from a complicated matrix. A Tween 20 capping layer not only suppresses nonspecific adsorption, but also enables NPs to disperse in a highly-salinity solution. For analyses of aminothiols, after extraction and centrifugation, thioglycollic acid was utilized to remove aminothiols that attached to the NP surfaces. The extracted aminothiols was derivatized with o-phthalaldehyde (OPA) followed by CE-LIF. The use of this nanoprobe provided approximately 11-, 282-, and 21-fold sensitivity improvements for homocysteine (HCys), glutathione (GSH), and £^-glutamylcysteine (GluCys), respectively. Furthermore, the limits of detection (LODs) at a signal-to-noise ratio of 3 for HCys, GSH, and GluCys are 4013, 80, and 383 pM, respectively. A practical analysis of aminothiols in human urine sample has been accomplished by our proposed method. For another application to determining thiol-containing peptides, we use dithiothreitol to remove thiol-containing peptides from the NP surface through ligand exchange. The released peptides are selectively derivatized with OPA to form tricyclic isoindole derivatives. After injecting a large sample volume, the sensitivity of these peptides was improved by stacking them via using polyethylene oxide (PEO) as additive for on-line concentration and separation. As a result, LODs for GSH, GluCys, and phytochelatins (PC2 ~ PC4) were down to 0.1-6 pM. The proposed method has the lowest LODs for five peptides compared to other reported methods, and it also detect dissolve thiols in seawater in practice. Our proposed method is capable of ultrasensitive detection for thiols in biological and environmental samples.