Supramolecular synthesis has gained much attention in recent years. Such an approach to synthesis represents an attractive alternative to traditional, multi-step synthesis, especially for making complex, nanoscopic structures. Of particular interest, in the context of this work, is the use of metal-organic interactions to direct the self-assembly of nanoscopic architectures. These interactions are highly directional, relatively "strong" (compared to other supramolecular interactions) and kinetically labile, which allows for "self-correction" and in turn the production, often in high yield, of defect-free products. This also means that a number of related, yet structurally diverse products (supramolecular isomers) could be isolated. The work presented herein demonstrates the supramolecular synthesis of related, yet structurally diverse family of metal-organic nanoscale supramolecular architectures that are based on the ubiquitous paddle-wheel dimetal tetracarboxylate secondary building unit (SBU) and angular dicarboxylate ligands. It also demonstrates that the SBU self-assembles into clusters of four (tetragonal) and three (trigonal) nanoscale secondary building units (nSBU), which further self-assemble into nanoscale structures that include discrete (0D) faceted polyhedra, tetragonal 2D sheets and another 2D sheet that conforms to the so-called Kagom lattice. In addition, the work herein demonstrates that synthesis under thermodynamic equilibrium conditions facilitates "self-correction" so that the most stable thermodynamic product is obtained. Synthesis, characterization and crystal structure analysis of these structures is presented herein.

Submitted by Raniere Barreto (raniere.barros@ufvjm.edu.br) on 2018-05-09T19:53:59Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) gledsa_alves_vieira.pdf: 4026237 bytes, checksum: ab95ab6fc9e23f45607c9d0ed51e9f54 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2018-05-14T14:36:10Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) gledsa_alves_vieira.pdf: 4026237 bytes, checksum: ab95ab6fc9e23f45607c9d0ed51e9f54 (MD5) / Made available in DSpace on 2018-05-14T14:36:10Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) gledsa_alves_vieira.pdf: 4026237 bytes, checksum: ab95ab6fc9e23f45607c9d0ed51e9f54 (MD5) Previous issue date: 2016 / Novos poli?steres a partir do ?cido isoft?lico e glicerol foram sintetizados por policondensa??o. As amostras foram sintetizadas em diferentes condi??es obtidas pela combina??o das vari?veis: propor??o molar ?cido isoft?lico:glicerol, temperatura, press?o e tempo de rea??o, denominadas AM1 (1,0:2,3; 195 ?C; 1,0 atm; 100 min), AM10 (1,0:1,5, 210 ?C; 0,29 atm; 30 min), AM11 (1:1,5, 203 ?C, 1,0 atm; 60 min), AM12 (1:1,5, 197 ?C; 1,0 atm; 110 min) e AM13 (1,0:2,3, aquecimento por micro-ondas; 1,0 atm; 3 mim). As amostras obtidas foram caracterizadas por espectroscopia na regi?o de infravermelho (FTIR), an?lise termogravim?trica (TGA) e calorimetria diferencial explorat?ria (DSC) e difratometria de raios-x (DRX). Filmes dos poli?steres foram analisados por microscopia eletr?nica de varredura (MEV) e ?ngulo de contato. A partir dos espectros de FTIR foi poss?vel confirmar a esterifica??o para todos os materiais sintetizados pelo aparecimento da banda em ~1710 cm-1 , caracter?stica da liga??o C=O de ?ster. A an?lise das curvas de TGA e suas derivadas (DTG) demonstrou para o poli?ster AM1 duas etapas de degrada??o t?rmica predominantes: em 214 ?C e 393 ?C. O poli?ster AM10 apresentou dois principais picos de degrada??o t?rmica localizadas em 247 ?C e 373 ?C. Os poli?steres AM11, AM12 e AM13 apresentaram picos de degrada??o bem pr?ximas entre si, em 415 ?C, 423 ?C e 413 ?C, respectivamente. A partir dos termogramas de DSC constatou-se a temperatura de transi??o v?trea de cada poli?ster em 47,31 ?C, 48,06 ?C, 39,62 ?C, 17,44 ?C, 56,44 ?C, para AM1, AM10, AM11, AM12 e AM13, respectivamente. Os picos das temperaturas de fus?o foram identificadas para a AM1 em 131,9 ?C, AM10 em 131,2 ?C, 148.0 ?C e 164,5 ?C, para a AM11 em 144,5 ?C e 160,7 ?C, para AM12 em 149,6 ?C, 163,5 ?C, 169,7 ?C e para a AM13 em 131,9 ?C e 149,2 ?C. Os difratogramas demonstraram que os materiais sintetizados s?o semicristalinos. A micrografias de MEV revelaram uma morfologia homog?nia para as amostras AM12 e AM13, e heterog?nea com dom?nios escuros AM10 e AM11. Os valores da energia livre superficial foram 66, 59, 61 e 67 mN.m-1 para as amostras AM10, AM11, AM12 e AM13, respectivamente. Testes de for?a necess?ria para romper a ader?ncia foram realizados nos diferentes tipos de amostras que se comportaram de forma vari?vel nos cinco diferentes substratos utilizados. No substrato de vidro, a?o e cobre o poli?ster AM10 apresentou maior resist?ncia para a separa??o das placas com o valor de 4,18, 5,88 e 8,19 Kgf/mm?, respectivamente. No alum?nio a AM11 apresentou valor de 2,02 Kgf mm?. E, na madeira o poli?ster AM12 demonstrou press?o necess?ria para o rompimento de 4,40 Kgf/mm?. Esses resultados demonstram a possibilidade de aplica??o dos poliesteres sintetizados neste trabalho como adesivos hot melt. / Disserta??o (Mestrado Profissional) ? Programa de P?s-Gradua??o em Tecnologia, Sa?de e Sociedade, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016. / New polyester from isophthalic acid and glycerol were synthesized by polycondensation. The samples were synthesized at different conditions obtained by the combination of variable, namely isophthalic acid: glycerol molar ratio, temperature, pressure and reaction time. These different experimental conditions yielded samples called AM1 (1.0:2.3, 195 ?C; 1.0 atm; 100 min), AM10 (1.0:1.5, 210 ?C; 0.29 atm, 30 min), AM11 (1:1.5, 203 ?C, 1.0 atm, 60 min), AM12 (1:1.5; 197 ?C; 1.0 atm; 110 min) and AM13 (1.0:2.3, microwave heating; 1.0 atm, 3 min). Samples were characterized by infrared spectroscopy (FTIR) spectroscopy, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), X-ray diffractometry (XRD). Films of polyesters were analyzed by scanning electron microscopy (SEM) and contact angle. FTIR spectra confirmed that the esterification occurred for all materials synthesized by the appearance of the band at ~ 1710 cm-1, characteristic of the C=O stretching. TGA curve and its derivatives (DTG) demonstrated two main thermal degradation peaks at 214 ?C and 393 ?C for AM1 sample. The AM10 polyester presented two main thermal degradations peaks located at 247 ?C and 373 ?C. The thermal degradation peaks of AM11, AM12 and AM13 were very close and occurred at 415 ?C, 423 ?C, and 413 ?C, respectively. From the DSC thermograms, it was found glass transition temperature of each polyester at 47.31 ?C, 48.06 ?C, 39.62 ?C, 17.44 ?C, 56.44 ?C, for AM1, AM10, AM11, AM12 and AM13, respectively. Melting temperature was founded for AM1 at 131.9 ?C, for AM10 at 131.2 ?C, 148.0 ?C and 164.5 ?C, for AM11 at 144.5 and 160.7 ?C, for AM12 at 149.6 ?C, 163.5 ?C and 169.7 ? C, and for AM13 at 131.9 ? C and 149.2 ?C. The XRD difratograms reveled that syntethized materials are semi-crystalline. MEV analisys revealed the existence of dark domains for AM10 and AM11 samples, and a homogeneous smooth surface for AM12 and AM13 samples. Surface free energy values were of 66, 59, 61 and 67 mN.m-1 for AM10, AM11, AM12 and AM13, respectively. Single lap shear tests were carried out in five different types of substrates. For glass, steel and copper AM10 showed greater resistance, with shear strengh value of 4.18 Kgf mm? 5.88 Kgf mm? and 8.19 kgf mm?, respectively. For aluminum, AM11 showed a shear strengh value of 2.02 kgf mm?. And, for wood, AM12 showed shear strengh value of 4.40 kgf mm?. These results revealed technological applicability for polyesteres synthetized here, such as their use as hot melt adhesives.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / The aim of the present research was to evaluate the physical and mechanical properties of LVL reinforced with fiberglass with two types of resins. Pinus elliottii veneers with 1,5 mm thickness were used to manufacture of the LVL panels. The panels were manufactured in two steps. The first one was the assembling of the LVL panels with nine layers of wood veneer glued with phenol-formaldehyde resin. The second step consisted into reinforcing the LVL with fiberglass impregnated with epoxy resin (E) or isophthalic resin (I). The treatments were: panels without reinforcement (T), panels reinforced with one fiberglass layer (E T1 e I T1), panels reinforced with two fiberglass layers (E T2 e I T2) and panels reinforced with four fiberglass layers (E T3 e I T3). The size of panel was 45 cm x 34 cm x 1,08 cm. The physical properties tested were density and moisture content. The mechanical properties tested were: static bending in flatwise and edgewise position, modulus of elasticity (MOE) and modulus of rupture (MOR); glueline shear strength by compression loading; hardness test; and non-destructive test by ultrasound method. The epoxy and the isophthalic resin showed similar mechanical performance among the different treatments.The resistence and stiffness of the panels were influenced by the reinforcement. The MOE in flatwise position was influenced by one reinforcement layer and the MOR was influenced by two reinforcement layers. In the edgewise position the MOE and the MOR values remained constant among the treatments with two fiberglass reinforcement layers. The MOE in nondestructive test had higher values when compared with the destructive method, however these values remained stable with two layers of reinforcement. Two layers of reinforcement on the tensile and compression side had higher values in hardness test. The epoxy resin presented higher glueline resistence and higher percentage of wood failure. Isophthalic and phenolic resin presented similar values of glueline strenght, however the isophthalic resin had lower percentage of wood failure. Thus, the reinforcement with one layer of fiberglass imprenated with epoxy resin on the tensile side would be enough to promote the mechanical qualities of LVL. / O objetivo desta pesquisa foi avaliar as propriedades físico-mecânicas de painéis de lâminas paralelas (LVL) reforçadas com camadas de fibra de vidro inpregnadas com dois tipos de matrizes. Lâminas de madeira de Pinus ellliottii com espessura de 1,5 mm foram utilizadas na fabricação dos painéis. A montagem dos painéis foi realizada em duas etapas. A primeira consistiu na fabricação dos painéis LVL com nove camadas de lâminas de madeira unidas com resina à base de fenol-formaldeído na gramatura de 190 g/m2 em linha simples. E a segunda etapa consistiu na aplicação do reforço de fibra de vidro impregnado com resinas epóxi (E) ou poliéster isoftálica com NPG (I). Os tratamentos utilizados foram: painéis sem reforços (T), painéis com uma camada de fibra de vidro (E T1 e I T1), painéis com duas camadas de fibra de vidro, sendo uma camada no lado de compressão e uma camada no lado de tração (E T2 e I T2) e painéis com quatro camadas de fibra de vidro, duas camadas do lado de compressão e duas camadas no lado de tração separados por uma lâmina de madeira (E T3 e I T3). Foram realizadas três repetições por tratamento, totalizando 21 painéis. As dimensões finais dos painéis foram 45 cm x 34 cm x 1,08 cm. Para determinar a qualidade dos painéis LVL foram avaliadas as propriedades físicas (massa específica e teor de umidade) e a resistência mecânica (flexão estática na posição flatwise e egdewise, resistência ao cisalhamento, dureza Janka e teste não destrutivo utilizando ultrassom). A resina epóxi e a resina isoftálica apresentaram as mesmas qualidades mecânicas nos diferentes tratamentos. A aplicação do reforço influenciou na resistência e na rigidez do painel. Na flexão estática na posição flatwise o módulo de elasticidade (MOE) foi influenciado por uma camada de reforço e o módulo de ruptura (MOR) por duas camadas de reforço. Na posição edgewise os valores de MOE e do MOR se mantiveram estáveis com a aplicação de duas camadas de reforços de fibra de vidro. O MOE pelo método ultrassônico apresentou valores maiores quando comparado com o método estático; em ambos os métodos os valores mantiveram-se estáveis com a aplicação de duas camadas de reforço. A dureza Janka foi maior para as painéis com mais camadas de fibra de vidro na posição de tração e compressão. A resina epóxi apresentou maior resistência ao cisalhamento e maior percentual de falhas na madeira, enquanto que a resina isoftálica, apesar de apresentar valores de resistência similares à fenólica, não apresentou boa adesão à madeira, representada pelo baixo percentual de falhas na madeira. A aplicação de uma camada de reforço de fibra de vidro com resina epóxi na posição de tração seria o suficiente para melhorar as qualidades mecânicas dos painéis LVL fabricados com lâminas de madeira de pinus unidas com fenol-formaldeído.

Metal organic framework compounds have emerged as an important part of inorganic coordination chemistry during the last two decades. In this thesis, the metal-organic frameworks (MOFs) compounds of 5-substituted isophthalic acids have been investigated. As part of the investigations, preparation of MOF compounds of different 5-substituted isophthalic acids such as 5-aminoisophthalaic acid, 5-nitroisophthalaic acid and 5-sulphoisophthalaic acid have been accomplished. Structures of the newly synthesized compounds were established by single crystal X-ray diffraction technique. Magnetic properties of the transition metal based compounds have been studied by SQUID/PPMS magnetometer. The ligand-sensitized metal-center emission has been studied on the Eu3+ and Tb3+ doped MOF compounds of Y and La. Up-conversion luminescence properties of Nd based compound have also been studied. The labile nature of the coordinated and lattice water molecules was established by employing dynamic in-situ single crystal to single crystal structural transformation studies. In addition, the site selective substitution in homometallic MOF compounds and their subsequent thermal decomposition to mixed-metal spinel oxides have also been investigated. In Chapter 1 of the thesis an overview of the metal-organic framework compounds is presented. In Chapter 2, the synthesis, structure and properties of 5-aminoisophthalate compounds of 3d metals and the rare earth metals are presented. In some of these compounds the coordinate and the lattice water molecules can be removed and reinserted with the retention of single crystallinity. Also some of the isostructural compounds exhibits interesting magnetic behaviors. Partial substitution of the Y3+/La3+ compounds of 5-aminoisophthalate with Eu3+/Tb3+ exhibits characteristics metal centered emission (red = Eu3+ and green = Tb3+). In Chapter 3, the three dimensional compounds of 5-nitroisophthalate and 4, 4’-oxybisbenzoate with cobalt and the high – throughput screening in the synthesis of metal-organic frameworks (MOFs) for the Cu(CH3COO)2.H2O – NIPA – heterocyclic ligand systems are presented. In chapter 4, the single crystal to single crystal transformation with temperature dependent dimensionality cross-over and structural reorganizations in two copper based compounds of 5-sulfoisopphthalate and 5-nitroisophthalate are presented. In chapter 5, the site selective substitution in a homometallic MOF compound and its subsequent decomposition to mixed-metal spinel oxides are presented.