Esta Tese apresenta duas revisões de literatura: 1. Síntese de aldeídos e cetonas a partir de compostos de enxofre. 2. Síntese de benzaldeídos deuterados. E descrita a reação de sulfenilação de benzil fenil sulfonas, conduzindo a um novo \"synthon\", α-metiltio-benzil fenil sulfona (1). Y-C6H4-CH(SCH3)SO2C6H5 Y = H,CH3,Cl,OCH3,NO2,CN. É relatada a hidrólise ácida de (1), fornecendo benzaldeídos para substituídos. É proposta a decomposição térmica de (1), como um método novo de síntese de benzaldeídos para substituídos. É descrita uma reação de um passo só, envolvendo alquilação e decomposição térmica de (1) e fornecendo cetonas aromáticas. Este método permite sintetizar cetonas contendo grupos sensíveis a ácidos. O método pirolítico é aplicado à síntese de aldeídos aromáticos deuterados, que são obtidos em 98% de pureza isotópica. Os benzaldeídos deuterados e não deuterados são obtidos em bons rendimentos, não se notando diferenças provenientes do caráter eletrônico dos substituintes no anel. É apresentada uma discussão sobre os aspectos mecanísticos da decomposição térmica. / This thesis presents two literature reviews: 1. Synthesis of aldehydes and ketones, starting from the sulphur containing compounds 2. Synthesis of deuterated benzaldehydes. The sulphenylation reaction of benzyl phenyl sulphones, leading to a new \"synthon\", α-methylthio-benzyl phenyl sulphone (1), is described. Y-C6H4-CH(SCH3)SO2C6H5 Y = H,CH3,OCH3,Cl,NO2,CN. Acid hydrolyses of (1) to give p-substituted benzaldehydes are reported. A novel reaction - Thermal Oecomposition of (1) - as an improved method for the synthesis of p-substituted benzaldehydes is proposed. One pot reaction, which consists of alkylation and thermal decomposition of (1), to give aromatic ketones, is reported. Some ketones containing acid-sensitive groups are obtained. The pyrolyt ic method is applied to the synthesis of deuterated aromatic aldehydes, which are obtained in 98% of isotopic purity. The yields of the deuterated and non-deuterated benzaldehydes are good, and do not show any dependence on the eletronic character of the para substituents. A discussion on some mechanistic aspects of the thermal decomposition is presented.

5-nitro-2-(3-phenylpropylamino)-benzoic acid (NPPB) was normally recognised as a Cl- channel inhibitor, but its specificity is in question, since an inhibitory effect against K⁺ channels has been reported. To identify the significance of the molecules structural components, NPPB and related compounds, such as 2-(3-phenylpropylamino) benzoic acid (PPAB), 5- nitro-2-heptylamino benzoic acid (HANB) and 2-nitro-5-heptylamino benzoic acid (HANB-2) were synthesised by reductive amination using various aldehydes and amines. Using internodal cells of the giant green Characean algae, Nitella hookeri, the effects of NPPB and related compounds on cytoplasmic streaming and turgor regulation were determined. Previous experiments stated that cytoplasmic streaming was sensitive to NPPB, PPAB and HANB with IC₅₀ values of 24µmol/L, 455µmol/L, and 6.4mmol/L, respectively. In this report, the IC₅₀ values of purchased NPPB and niflumic acid were found to be 88.65µmol/L and 121.82µmol/L, respectively. Although the IC₅₀ value of purchased NPPB showed a slight difference from that of synthesised NPPB, the results of the cytoplasmic streaming experiment indicated the possibility of this analysis to be a simple assay system for analysing the effects of structural modification to ion channel inhibitors on their biological activity. Moreover, NPPB and PPAB seem to stimulate regulation of turgor pressure under hyperosmotic shock, which can be explained by a blockage of K⁺ efflux during osmotic stress leading to faster recovery of turgor regulation. Additionally, the results of cytosolic free Ca²⁺ analysis using aequorin technology also suggested that the possibility of this analysis to be used as a more direct measure of the inhibitory effect, while the cytoplasmic streaming analysis is a more indirect method. The preliminary results from this research suggest the significance of the simple assay systems for analysing the effects of structural modification ion channel inhibitors, which can be used for future study regarding ion channel structures.

Made available in DSpace on 2014-06-11T19:30:19Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-05-05Bitstream added on 2014-06-13T18:40:20Z : No. of bitstreams: 1 arruda_lb_me_bauru.pdf: 4132261 bytes, checksum: ec76a96792be6b1907a354c279109181 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Há cerca de 20 anos foi descoberto o efeito magnetoresitivo em multicamadas magnéticas. Desde então, a spintrônica evoluiu de um fenômeno científico complexo para tornar-se uma tecnologia multibilionária. Dentre os parâmetros necessários para o desenvolvimento da spintrônica - a nova eletrônica que se baseia na manipulação não somente da carga, mas também do spin dos portadores -, está o controle eficiente da injeção e a detecção de portadores polarizados em spin, através de uma interface ferromagneto/semicondutor (isolante) - FM/SC(I). A utilização de semicondutores magnéticos diluídos (SMD), como ferromagnetos polarizadores de corrente, é uma solução possível para melhorar a eficiência na injeção de correntes de spins. A despeito do bom desempenho obtido com os SMDs funcionais desenvolvidos até hoje, sua baixa temperatura crítica impossibilita a utilização em temperatura ambiente. Atualmente, o progresso no campio da spintrônica depende fortemente do desenvolvimento de novos SMDs, nos quais as informações de carga e spin passam se manipuladas externamente em altas temperaturas. Em especial, é possível o desenvolvimento de semicondutores magnéticos diluídos que sejam transparentes, aumentando em muito seu potencial de aplicação em dispositivos magneto-ópticos, o que os torna naturalmente muito mais interessantes do que eletrodos ferromagneticos metálicos. A presente proposta se enquadra no plano de ampliação das linhas de atuação do grupo que inclui a implementação de técnicas sonoquímicas de síntese de materiais nanoestruturados, com potenciais aplicações em spintrônica. A mesma está baseada na preparação de amostras nanoscópicas de ZnO e TiO2 dopadas com Co²+, preparadas por irradiação ultrassônica e que terão sua estrutura investigada pelas técnicas de difração de Raios X (DRX) e microscopias eletrônicas (MEV e MET)... / The phenomenon of magnetoresistive effect was discovered about twenty years ago in magnetic multilayers and opened a new field in physics, the so called spintronics, which is based on the manipulation of not only charge but also the spin of the carriers. Also, the efficient control of injection and detection of spin polarized carriers through an interface ferromagnetic/semiconductor insulator plays a role. Since then, the field of spintronics-based devices changed from an only complex scientific problem to become a multibillionaire technological issue. The use of diluted magnetic semiconductors (DMS) as current polarizers ferromagnets is one possible solution to the improvement of efficiency in the injection of spin currents. Despiste the good performance obtained with the functional DMS, their low critical temperature makes impossible the use of such devices at room temperature. Currently, progress in the field of spintronics depends heavily on the development of new DMSs, in which the charge and spin information can be manipulated at higher temperatures. In particular, it is possible the development of diluted magnetic semiconductors that are transparent; highly increasing potential application of these materials in magneto-optical devices, making them more interesting than ferromagnetic metalic electrodes. This work fits into the expansion plan of action lines of our group that includes the implementation of sonochemical technics of nanostructured materials with potential applications in spintronics, based on the preparation of nanometric size samples of Co²+ - doped ZnO and TiO2. prepared by ultrasonic irradiation. Structural characterization was performed by X-ray diffraction analyses (XRD) associated to Rietveld Refinement and electronic microscopy techniques (SEM and TEM). The optical characterization was done by UV-Vis mesurements between 200 and 800 nm and evaluating... (Complete abstract click electronic access below)

A fim de estudar as propriedades dos complexos de ferro com ligantes diirnínicos, tais corno: espectro eletrônico, reatividade dos complexos com cianeto e comportamento fotoquímico, novos complexos (I)ferrosos com diiminas foram preparados e caracterizados. A oxidação, em solução de H2SO4 11 M, dos complexos ferrosos com diiminas produziu os seus análogos férricos. A reação de um dos complexos ferrosos (R e R\' = CH3) com o íon cianeto produziu dois ciano-complexos mistos, onde um destes apresenta um dos ligantes modificado. Obtiveram-se também complexos com 1igantes tridentados(II). (Ver no arquivo em PDF). A investigação dos espectros eletrônicos dos complexos diirnínicos de ferro(II) apresentou três tipos de bandas, resu1tantes de transições de transferência de elétrons interna dos 1igantes (TEIL), metal-1igante (TEML)e transições d-d. As bandas de TEIL ocorrem na região de energia acima de 34 kK As de TEML ocorrem na região de 17 a 24 kK, com evidências indicando que o formato da banda não se deve ao acoplamento vibracional. Observa-se somente uma banda atribuída à transição d-d em 28 kK, usando dados da literatura obtidos para os complexos análogos com dipy e phen foram calculados os valores de B e Dq. Os espectros dos complexos férricos análogos apresentam bandas atribuídas a transições de transferência de elétrons ligante-metal (TELM), na região de 23 a 32 kK, e TEIL, na região de 47 a 50 kK. Verifica-se uma correlação entre a soma das energias das bandas de TEML, dos complexos ferrosos, com as de TELM, dos complexos férricos, e as energias das bandas de TEIL. Para os complexos com ligantes tridentados a atribuição das bandas tornou-se mais difícil devido à complexidade dos espectros. Ocorrem bandas na região de 16 a 21 kK, atribuídas a transições de TEML, e na região de 25 a 51 kK, atribuídas a TEIL. O desdobramento das bandas de TEML sugere uma baixa simetria para estes complexos com ligantes tridentados. Os ciano-complexos mistos obtidos foram caracterizados por espectros de infravermelho e de ressonância magnética nuclear, além das análises de ferro e cianeto. Também foram estudados os seus espectros eletrônicos. As bandas de TEML, que ocorrem na região de 18 a 21 kK em solução aquosa, apresentam uma forte dependência da sua energia com o solvente. Observam-se ainda bandas, na região em tôrno de 50 kK, atribuídas a TEIL. Experiências fotoquímicas indicaram que os complexos diimínicos de ferro(II), preparados neste trabalho, são fotoreativos, quando irradiados com uma lâmpada de mercúrio a média pressão. Há evidências indicando que o mecanismo da decomposição fotoquimica ocorre via ligante. / In order to investigate the properties of iron diimine complexes, six new complexes (I) were synthesized and characterized. The spectral properties, reactivity towards cynanide ions and photochemical behavior of these complexes were studied. In the reaction of the complex with R and R\' = CH3 with the cyanide ion two mixed-cyano complexes were obtained. One of these presents a modified diimine ligand. By chemical oxidation of the ferrous complexes, at high acid concentration, it was possible to study some of the properties of the ferric complexes. Some complexes with tridentade diimine ligands(II) were also studied. (See in the PDF file). The electronic spectra of the ferrous diimine complexes presented three kinds of absorption bands. These bands resulted from transitions due to: internal ligand electron transfer (ILET), metal to ligand electron transfer (MLET) and ligand field (d-d transitions). The ILET bands occur above 34 kK. The MLET bands occur from 17 to 24 kK. Evidence is presented that the structure of the MLET band cannot be accounted for by a vibrational coupling. It was possible to observe a d-d transition at 28 kK. By using literature data for complexes with 2,2\'-bipyridine and phenantroline it was possible to calculate the values and Dq. The corresponding ferric complexes presented bands from 23 to 32 kK and ILET bands from 47 to 50 kK. A correlation is observed between the surn of the frequencies of the MLET bands, of the ferrous complexes, LMET bands, of the ferric complexes, and the frequencies of the ILET bands. In the case of the complexes with tridentade ligands the assignment of the bands is not simple, due to the complexity of the absorption electronic spectra. Possibly, the MLET bands occurs from 16 to 21 kK and the ILET bands from 25 to 51 kK. The splitting of the MLET bands suggests a lower simmetry than D3 for these complexes. The mixed-cyano complexes obtained were characterized by their infrared and nuclear magnetic ressonance spectra and analytical data on Fe and CN contents. The study of the electronic absorption spectra showed a MLET band, in the region from 18 to 21 kK in aqueous solution. ILET bands were observed around 50 kK. The position of the MLET bands showed a strong solvent-dependence. Prelirninary photochernical experirnents indicated that the ferrous diirnine cornplexes are photoreactive, when irradiated with a rnediurn pressure rnercury lamp. Evidence is presented that the rnechanisrn of the photodecornposition occurs via the ligands.

Óxidos e hidróxidos de alumínio vêm sendo alvo de estudos no Laboratório de Matérias-Primas Particuladas Prof. Pérsio de Souza Santos (LPSS) nas últimas seis décadas. Várias rotas de síntese de mono- e tri-hidróxidos foram pesquisadas, bem como as transformações térmicas desses materiais em aluminas de transição e alumina-alfa. Mais recentemente, a síntese de boemita a partir do tratamento hidrotérmico de gibsita vem sendo o principal objeto dos estudos realizados no LPSS. Nesta Tese, a síntese hidrotérmica de boemita a partir de uma gibsita Bayer comercial foi estudada. Os cristais produzidos foram caracterizados por difração de raios X (DRX), por análises térmicas (TGA e DTA) e por microscopia eletrônica de varredura (MEV). Diferentes morfologias de cristais de boemita foram obtidas - cristais com dimensionalidade \"3D\" (cubos e paralelepípedos), \"2D\" (placas espessas, placas finas e placas alongadas) e \"1D\" (placas alongadas e ripas) por meio da variação da composição do meio reacional inicial. Reações conduzidas em meios com pH característico de suspensões de gibsita em água (pH alcalino) resultaram em cristais com morfologia \"3D\" ou \"2D espessa\", enquanto reações conduzidas em meio acidificado (pH = 2,0) resultaram em cristais com morfologia \"2D\". Reações conduzidas em meios acidificados contendo íon acetato levaram a cristais com morfologia \"2D fina e alongada\" ou morfologia \"1D\", dependendo da relação molar [Al : acetato] inicial de íon acetato (morfologia \"1D\" necessita de uma relação molar de no mínimo 1mol Al : 1mol acetato). Os cristais com morfologia \"1D\" e \"2D fina\" apresentaram espessuras nanométricas. A evolução térmica dos cristais de boemita produzidos foi estudada após aquecimentos entre 200ºC e 1200ºC. Todas as boemitas seguiram as transformações térmicas da chamada \"série ?\" , independentemente da sua morfologia, ou seja: boemita -> alumina-? -> alumina-? / alumina-? -> alumina-?. A temperatura de transformação da boemita em alumina-? é afetada pela morfologia dos cristais, ocorrendo em temperaturas mais baixas nos materiais com cristais de espessura nanométrica (morfologias \"1D\" e \"2D fina\"). Alumina-? com diferentes morfologias e diferentes áreas específicas (determinadas pelo método BET aplicado a isotermas de adsorção de nitrogênio gasoso a 77K) foram obtidas: 136 m2/g para alumina-? \"1D\"; 73,4 m2/g para alumina-? \"2D fina e alongada\"; 40,3 m2/g para alumina-? \"3D\". Foi possível, portanto, obter aluminas de transição potencialmente interessantes para aplicações industriais dadas as elevadas áreas específicas observadas. / Aluminum oxides and hydroxides have been the subject of studies in Laboratório de Matérias-Primas Particuladas Prof. Pérsio de Souza Santos (LPSS) in the last six decades. Several synthesis routes for mono- and tri-hydroxides were investigated as well as the thermal processing of these materials into transition aluminas and alpha-alumina. More recently, the synthesis of boehmite from the hydrothermal treatment of gibbsite has been the main object of studies in LPSS. In this Thesis, the hydrothermal synthesis of boehmite from a commercial Bayer gibbsite was studied. The crystals produced were characterized by X-ray diffraction (XRD), thermal analysis (TGA and DTA) and scanning electron microscopy (SEM). Different boehmite crystal morphologies were obtained - crystals \"3D\" (cubes and parallelepipeds), \"2D\" (thick plates, thin and elongated plates) and \"1D\" (elongated plates and strips) by varying the composition the initial reaction medium. Reactions conducted in media with characteristic pH of gibbsite suspension in water (alkaline pH) resulted in crystals with morphologies \"3D\" or \"thick 2D\" while reactions carried out in acidic medium (pH = 2.0) resulted in crystals with morphology \"2D\". Reactions carried out in acidic media containing acetate ion led to crystals with a \"thin and elongated 2D\" morphology or \"1D\" morphology, depending on the pristine [Al: acetate]. molar ratio (\"1D\" morphology requires a pristine molar ratio of at least 1mol Al: 1mol acetate). Crystals with \"1D\" or \"2D thin\" morphologies presented nanometric thickness. The thermal evolution of boehmite crystals produced was studied after heating between 200oC and 1200oC. All boehmites following thermal \"?-series\" transformation, regardless of their morphology, that is: boehmite -> ?-alumina -> ?-alumina /?-alumina -> ?-alumina. The transformation temperature of boehmite into ?-alumina is affected by crystal morphology, occurring at lower temperatures in the materials with nanometer thick crystals (\"1D\" and \"2D thin\" morphologies). ?-alumina with different morphologies and different specific surface areas (determined by BET method applied to adsorption isotherms of gaseous nitrogen at 77K) were obtained: 136 m2/g for ?-alumina \"1D\"; 73.4 m2/g for ?-alumina \"thin and elongated 2D\"; 40.3 m2/g for ?-alumina \"3D\". It was therefore possible to obtain transition aluminas potentially interesting for industrial applications given the high specific surface areas observed.

In this dissertation, I present the results of a systematic study on novel multifunctional nanostructure systems for magnetic hyperthermia applications. All the samples have been synthesized, structurally/magnetically characterized, and tested for magnetic hyperthermia treatment at the Functional Materials Laboratory of the University South Florida. This work includes studies on four different systems: (i) Core/shell Fe/γ-Fe2O3 nanoparticles; (ii) Spherical and cubic exchange coupled FeO/Fe3O4 nanoparticles; (iii) Fe3O4 nano-octopods with different sizes; (iv) High aspect ratio FeCo nanowires and Fe3O4 nanorods. In particular, we demonstrated the enhancement of the heating efficiency of these nanostructures by creating monodisperse and highly crystalline nanoparticles, and tuning their magnetic properties, mainly their saturation magnetization (MS) and effective anisotropy, in controlled ways. In addition, we studied the influence of other parameters, such as the size and concentration of the nanoparticles, the magnitude of the applied AC magnetic field, or different media (agar vs. water), on the final heating efficiency of these nanoparticles. For the core/shell Fe/γ-Fe2O3 nanoparticles, a modest heating efficiency has been obtained, resulting mainly from the strong reduction in MS caused by the shrinkage of the core with time. However, for sizes above 14 nm, the shrinkage process is much slower and the obtained heating efficiency is better than the one exhibited by conventional solid nanoparticles of the same size. In the case of the exchange-coupled FeO/Fe3O4 nanoparticles, we successfully created two sets of comparable particles: spheres with 1.5 times larger MS than the cubes, and cubes with 1.5 times larger effective anisotropy than the spheres, while keeping the other parameters the same. Our results show that increasing the effective anisotropy of the nanoparticles gives rise to a greater heating efficiency than increasing their MS. The Fe3O4 nano-octopods, with enhanced surface anisotropy, present better heating efficiency than their spherical and cubic nanoparticles, especially in the high field region, and we have shown that by tuning their size and the effective anisotropy, we can optimize their heating response to the applied AC magnetic field. For magnetic fields, smaller than 300−400 Oe we found that the smallest nano-octopods give the best heating efficiency. Yet if we increase the AC field value, the bigger octopods show an increased heating efficiency and become more effective. Finally, the FeCo nanowires and Fe3O4 nanorods exhibit enhanced heating efficiency with increasing aspect ratio when aligned in the direction of the applied AC magnetic field, due to the combined effect of shape anisotropy and dipolar interactions. Of all the studied systems, these 1D high aspect ratio nanostructures have displayed the highest heating rates. All of these findings point toward an important fact that tuning the structural and magnetic parameters in general, and the effective anisotropy in particular, of the nanoparticles is a very promising approach for improving the heating efficiency of magnetic nanostructures for enhanced hyperthermia.

Pulsed lasers are studied as new tools to realize competitive nanomanufacturing. The capabilities of pulsed lasers as promising tools for research, design, manufacturing, and control rely on the flexibility due to the great variety of operation parameters, and the inherent precision in aspects of time, spatial resolution, and energy input. As new tools, the fundamental understanding and technological capabilities of pulsed laser-induced chemical synthesis were explored in this dissertation research. In order to study the capabilities of pulsed laser in controlled synthesis, a thermal model was developed to predict the local temperature change due to the very short period of irradiation by a pulsed laser. And combining with the classical Gibbs free energy theories, a set of guidelines were developed for precision control for pulsed laser-induced chemical synthesis. Zinc oxide crystals were studied as an example case, showing the relationship between the wide range variables of pulsed laser including repetition rate, energy area density, power density, irradiation duration, etc. and the material structures of deposited crystals in aspects of crystal density, size, shape, crystalline properties, surface morphologies, growth rate, etc. Mechanisms from thermodynamic and kinetic aspects were explored. Pulsed laser-induced different heating conditions were found to separate two crystallization processes with different energy barriers, one dominated by a burst of nucleation and the other dominated by crystal growth through particle aggregation. For the study of the fundamental mechanisms in crystallization, pulsed laser initiated and controlled the crystallization in its early stage, and the crystal evolution were observed and analyzed by transmission electron microscopy (TEM). Crystal growth from intermediate monomers was first studied by an electron beam under the condition without precursor solution environment, providing crucial process information of crystal evolution, indicating multistage processes by continuous mass and phase transfer among intermediate monomers. This dissertation shows the capabilities of pulsed laser in realizing precision control for the targeted synthesis in nanomanufacturing, providing unique insight to crystallization mechanisms, and extending prospects to scientific research of other energy beam induced processes.

β-lactam antibiotics have been the most widely used drug of choice to combat infectious disease caused by bacteria. Unfortunately, the effectiveness of these antibiotics is drastically threatened by bacterial β-lactamases. β-lactamases are currently responsible for the resistance to most β-lactam antibiotic drugs. For decades, β-lactam β-lactamases inhibitors have been used to reduce bacterial resistance, however, in this study, we will employ the use of 1,2,4-oxadiazolidinone derivatives as a non-β-lactam β-lactamases inhibitor against TEM-1 and P99 β-lactamases. The significance of oxadiazolidinone is the prominent five-membered ring in its structure, which is configurationally stable and present in other biologically active compounds such as linezolid and avibactam. Oxadiazolidinones were synthesized in two steps procedure using nitroalkanes and benzaldehyde as starting materials to produce nitrones, which in turn undergo 1,3- dipolar cycloaddition with substituted isocyanates to give the desired 1,2,4-oxadiazolidin analogs (2a, 2b, 2c and 3). Each product was purified and characterized using 1H NMR and 13C NMR, GC-MS, IR, and UV/Vis analysis. Following their successful synthesis and structural elucidation, they were tested with TEM-1 and P99 serine β-lactamase using Nitrocefin as the substrate to ascertain their effectiveness against β-lactamase. 2a, 2b, 2c and 3 showed inhibition ranging from 12-38 %.

Some compounds, analogous to those found in naturally occurring systems, are found to possess chemotherapeutic activity. Some, in the form of their nucleoside or nucleotide derivatives, are valuable antimetabolites in that they may block normal RNA or DNA polymerisation, or may be incorporated into nucleic acids to form fraudulent, but not necessarily defective, polymers. Modification of natural ring systems, with a view to promoting chemotherapeutic activity is therefore of considerable interest; variation in the position and nature of the modification or ring substituent having a marked effect on chemotherapeutic activity. It is the purpose of this thesis to suggest methods for the facile synthesis of various uracils, pyrazoles and pyrazolo [3,4-d] - pyrimidines with alkyl, aryl and glycosyl substituents such that the nature of the ring substituents is easily varied. To this end a number of ethoxymethylene reagents were prepared which, by reaction with primary amines and hydrazines, would give acyclic intermediates capable of easy cyclisation into the uracil, pyrazole and pyrazolo [3,4-d] pyrimidine ring systems. Variation in the nature of specific substituents being determined by the choice of amine or hydrazine, other substituents being varied by modification of the original reagent. / S.R.G.

<p dir="ltr">Both natural and synthetic macromolecules have gained significant attention over the last two decades as more and more applications have been developed for these types of compounds. In particular, drug delivery and sensing have seen great improvements with the use of biomimetic- and biomacromolecules. A key function for these macromolecules is selective recognition, which has evolved in nature over millions of years, but is difficult to replicate in the laboratory. An essential component of selective recognition is sequence definition of the host, which is a key characteristic found in biomolecules and is essential for the function of proteins and nucleic acids. In this work, I present new methods for creating biomimetic sequence-defined macromolecules through the synthesis of a new sequence-definable macrocycle, an amino acid-functionalized Fréchet-type sequence-defined dendrimer, and a range of new molecular cages. The molecular cages I present in this work are of varying sizes and with different endo- and exohedral functionalities intended for future use as selective recognizers.</p><p dir="ltr">The macrocycle presented in this work is the largest sequence-definable macrocycle reported to date with 20 functionalizable positions, synthesized via iterative exponential growth using a series of copper-catalyzed azide-alkyne cycloadditions (CuAACs). Synthesis of an amino acid functionalized fully sequence-defined Fréchet-type dendrimer was also attempted through a convergent synthesis via a series of CuAACs. However, in this project, I could only reach a second-generation dendron due to solubility issues. This issue should be resolvable in the future by adding solubilizing chains to the dendrons. Finally, a series of new large molecular tetrahedrons were synthesized, enabled by the development of a more facile synthesis of a previously developed vertex. This new methodology made it possible to quickly access large quantities of this key tetrahedron vertex. With the vertex, I was able to synthesize nine new molecular tetrahedrons of various sizes with pore openings of up to 33 Å and with volumes up to 17 nm³.</p>