Thesis (doctoral)--Universits̈at Leipzig, 1911. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Chicago, 1940. / Lithoprinted. Includes bibliographical references.

No description available.

Faculty of Science; School of Chemistry; PhD Thesis / ortho-Ethoxy-trans-cinnamic acid (OETCA) has been known to form three polymorphs - the α , β and γ polymorphs which crystallize in P1 (Z=2), R3 (Z=18) and C2/c (Z=8), respectively. These polymorphs have long been of interest from polymorphism and solid-state photoreactivity perspectives but have, until now, never been fully characterized. In this thesis the complete structures of these polymorphs and their photodimerization products are presented. In addition, a new polymorph, the α' polymorph [P1 (Z=6)], which is only obtainable from the α polymorph via a reversible solid-state phase transformation at 60 °C, has been discovered and characterised. In all the polymorphs of OETCA, the smallest building component is the hydrogen-bonded carboxylic acid R22(8) dimers. These dimers further aggregate via CH...O interactions to form a ribbon motif in the α , α' and γ polymorph structures. Structural and solid-state reactivity differences in these three polymorphs are therefore due to differences in the arrangement of these ribbons. With few exceptions, solid state [2+2] photodimerization reactions have been found to obey the topochemical principle. Such reactions occur with minimal structural movement in which the contact distance between reacting double bonds is between 3.5 and 4.2 Å. In this respect the solid-state reactivity of both the α and α' polymorphs is especially interesting and unusual, and indicate that significant movement - both molecular and structural - is possible and necessary for reactions to occur in these polymorphs. Both polymorphs yield the centrosymmetric dimer product 2,2' diethoxy-α-truxillic acid. Photodimerization in the layered structure of the α polymorph, where the double bond contact distance is at 4.54 Å beyond reasonable photodimerization distance, is probably initially enabled by crystal defects. While the α' polymorph is structurally very similar to the α polymorph it is instead composed of two reaction sites with double bond contact distances of 3.72 and 4.99 Å, respectively. This polymorph's solid-state reactivity has as a consequence been found to be temperature dependent, with only 66.7% conversion being achieved at 293 K and 100% conversion occurring at 343 K; reaction at 343 K involves both a significant conformation change in a reaction product as well as a heat and reaction driven phase change. In the γ polymorph the closest distance between the double bonds is 5.26 Å, which together with the structural rigidity imposed by its herring bone structure ensures that no photodimerization occurs. The β polymorph is really a solvate containing either benzene or thiophene within channels in the structure. The interactions between the solvent and OETCA molecules play an important role in maintaining the symmetry and integrity of the structure. The thiophene and benzene forms of the β polymorph are isomorphous and yield a mirror product (2,2'-diethoxy-β-truxinic acid) upon photodimerization - the molecules involved being related by a 4.0 Å translation along the unit cell c axis.

CoordenaÃÃo de AperfeiÃoamento de NÃvel Superior / Neste trabalho à relatado o estudo fitoquÃmico de Sclerolobium rugosum, espÃcie da famÃlia Leguminosae, subfamÃlia Caesalpinoideae, uma planta encontrada nas margens de rios da regiÃo Nordeste do Brasil.NÃo existe nenhum estudo cientÃfico sobre a espÃcie, exceto a propriedade adstringente citado na medicina popular. A investigaÃÃo fitoquÃmica a partir dos extratos hexÃnico e etanÃlico da casca e lenho da raiz de S. rugosum atravÃs de cromatografia de gel de sÃlica, levou ao isolamento e identificaÃÃo do: lupeol, -sistosterol e estigmasterol glicosilados e um Ãster derivado do Ãcido cinÃmico (trans-triacontila-4-hidroxicinamato) (Tabela 01, pÃg. X). Os derivados reacionais foram obtidos tendo em vista a confirmaÃÃo das estruturas, treinamento das tÃcnicas usuais em laboratÃrio e, visando efetuar em etapa posterior, testes de atividades biolÃgicas. Os compostos naturais foram isolados e purificados utilizando a tÃcnica de cromatogrÃfica em coluna de gel de sÃlica (CC). A formaÃÃo dos derivados reacionais foi acompanhada atravÃs de cromatografia em camada delgada (CCD). A determinaÃÃo estrutural dos produtos naturais e seus derivados foram feitas por mÃtodos espectromÃtricos incluÃdo: RMN 1H e 13C (ressonÃncia magnÃtica nuclear), IV (infravermelho) e EM (espectro de massa). Com estas tÃcnicas tambÃm foi possÃvel estabelecer a configuraÃÃo relativa produtos naturais e seus derivados. / This work reports the study phytochemical investigation Sclerolobium rugosum, specie of the Leguminosae family, subfamily Caesalpinoideae, a plant found on the margins of rivers in the Northeast of Brazil. There is no any scientific study about this specie, except the astringent property cited in the folk medicine. Phytochemical investigation of hexane and ethanol extracts of bark and wood of the roots of S. rugosum using silica gel allowed to isolation and identification of: Lupeol, -sistosterol and stigmasterol glycosides and one ester derivative of cinnamic acid (trans-triacontyl-4-hydroxicinnamate) (Table 01, p. X). Derivatives reactions were obtained in order to determine structures, training of the usual techniques in the laboratory and to make further studies of biological activities. Natural compounds were isolated and purified using the technique of column chromatography on silica gel (CC). The formation of derivatives reactions were accompanied by Thin-Layer Chromatography (TLC). Structure determination of natural products and derivates were done by spectrometric methods including: NMR 1H and 13C (nuclear magnetic resonance), IR (Infrared) and MS (mass spectrum). With these techniques was also possible of establish the relative configuration of compounds and derivatives.

In response to a need for a natural antimicrobial to replace sodium benzoate, cinnamic acid was chosen. Due to cinnamic acid's solubility issues, α-cyclodextrin was used as a host molecule to form an inclusion complex with the cinnamic acid molecule. The cinnamic acid: α-cyclodextrin inclusion complex was then characterized using phase solubility analysis, proton nuclear magnetic resonance (H-NMR), and solid inclusion. Phase solubility analysis verified the maximum amount of cinnamic acid that α-cyclodextrin was able to host. H-NMR was used to determine the complex association constant, determine the chemical shifts of available protons, and yield a stoichiometry for the complex. The solid inclusion complex allowed for a physical formation of the complex, yielding further information in support of the complex stoichiometry. Microbiological tests were also performed to quantify the antimicrobial abilities of the complex, the guest, and the host against the yeast Saccharomyces cerevisiae and mold Paecilomyces variotii. Results indicated that approximately 990.29 ppm in aqueous solution was the maximum amount of cinnamic acid in the complex. The 2:1 stoichiometry yields an association constant of 21.7 M-1. Results also indicated that the cinnamic acid readily conformed to fit within the α-cyclodextrin host molecule, which remained a rigid structure. An 8.9% weight to weight of cinnamic acid was calculated for the solid inclusion again reinforcing a 2:1 stoichiometry. Microbiological studies showed little to no inhibition power by the complex at varying concentrations against S. cerevisiae and P. variotii. Free cinnamic acid showed greater antimicrobial activity compared with free α-cyclodextrin and the complex. / Master of Science in Life Sciences

Yes / We report formation of polymorphs and new eutectics and cocrystals of curcumin, a sparingly water-soluble active component in turmeric, structurally similar to cinnamic acid. The curcumin polymorphs were formed using liquid antisolvent precipitation, where acetone acted as a solvent and water was used as the antisolvent. The metastable form 2 of curcumin was successfully prepared in varied morphology over a wide range of solvent-to-antisolvent ratio and under acidic pH conditions. We also report formation of new eutectics and cocrystals of curcumin with cinnamic acid acting as a coformer. The binary phase diagrams were studied using differential scanning calorimetry and predicted formation of the eutectics at the curcumin mole fraction of 0.15 and 0.33, whereas a cocrystal was formed at 0.3 mole fraction of curcumin in the curcumin–cinnamic acid mixture. The formation of the cocrystal was supported with X-ray powder diffraction, the enthalpy of fusion values, Fourier-transform infrared spectroscopy, and scanning electron microscopy. The hydrogen bond interaction between curcumin and cinnamic acid was predicted from Fourier-transform infrared spectra, individually optimized curcumin and cinnamic acid structures by quantum mechanical calculations using Gaussian-09 and their respective unit cell packing structures.

PEREIRA, José Enedilton Medeiros. Espectroscopia vibracional em cristais do ácido trans-cinâmico complexado com európio sob condições extremas. 2014. 90 f. Dissertação (Mestrado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2014. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2014-09-12T19:42:18Z No. of bitstreams: 1 2014_dis_jempereira.pdf: 4086204 bytes, checksum: f746c208810c91b5b87b4ef1b2f4de4a (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2014-09-12T19:50:42Z (GMT) No. of bitstreams: 1 2014_dis_jempereira.pdf: 4086204 bytes, checksum: f746c208810c91b5b87b4ef1b2f4de4a (MD5) / Made available in DSpace on 2014-09-12T19:50:42Z (GMT). No. of bitstreams: 1 2014_dis_jempereira.pdf: 4086204 bytes, checksum: f746c208810c91b5b87b4ef1b2f4de4a (MD5) Previous issue date: 2014 / This work is focused on characterization of a polycrystalline sample of the coordination compound with ions Eu3+ using as a binder the trans-cinnamic acid , [Eu(cin)3]. The interest in coordination with lanthanide compounds is due to their large technological applications. The process of luminescence of coordination compounds containing lanthanide, also called antenna effect, has a main objective the use of new ligands with various applications, both in increasing the efficiency of energy receptors in the ultraviolet region and the development of biomarkers. In this work, to characterize the polycrystalline material, Raman spectroscopy was used to determine the vibrational behavior of the material at ambient temperature and pressure. It was also shown the behavior of the compound at low temperatures, in which variations in various vibrational modes were observed, indicating thus the occurrence of phase transition. Using a diamond anvil cell the material was studied by high hydrostatic pressure Raman spectroscopy. The purpose of this methodology was to map possible phase transitions and discover the occurrence of possible polymorphism. However, until the pressure reached in the experiments - about 5.2 GPa - it was found that the original phase remained stable. A discussion of the luminescence of the sample is also provided in this work. / O presente trabalho está focado na caracterização de uma amostra policristalina do composto de coordenação com íons Eu3+ utilizando como ligante o ácido trans-cinâmico, [Eu(cin)3]. O interesse em compostos de coordenação com lantanídeos deve-se às suas amplas aplicações tecnológicas. O processo de luminescência dos compostos de coordena- ção contendo lantanídeo, também chamado de efeito antena, tem como principal objetivo o uso de novos ligantes com aplicações diversas, tanto no aumento da eficiência de re- ceptores de energia na região do ultravioleta quanto no desenvolvimento de marcadores biológicos. Neste trabalho, para realizar a caracterização do material policristalino, foi utilizada a espectroscopia Raman, a fim de determinar o comportamento vibracional do material à temperatura e pressão ambiente. Também foi verificado o comportamento do composto sob baixas temperaturas, no qual foram observadas variações em vários modos vibracionais, indicando, por conseguinte, a ocorrência de transição de fase. Utilizando uma célula de pressão a extremos de diamante o material foi estudado a altas pressões hidrostáticas através de espectroscopia Raman. O intuito desta metodologia era mapear possíveis transições de fase e descobrir a ocorrência de eventual polimorfismo. Entretanto, até a pressão atingida nos experimentos – cerca de 5,2 GPa – verificou-se que a fase ori- ginal permaneceu estável. Uma discussão sobre a luminescência da amostra também é fornecida neste trabalho.

Empresa Brasileira de Pesquisa AgropecuÃria / CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Na indÃstria de processamento de frutas, a polpa de caju à utilizada durante a entressafra do caju para a obtenÃÃo de diversos produtos, tais como o suco de caju. O consumo cada vez mais frequente de alimentos industrializados desperta o interesse na qualidade desses produtos que estÃo sendo consumidos e a influÃncia do processamento ainda à pouco estudada. Por isso a importÃncia em verificar a influÃncia desse processamento nos compostos benÃficos que estÃo presentes no suco de caju. Este trabalho visou quantificar o teor de fenÃlicos e avaliar a atividade antioxidante in vitro pelo mÃtodo ABTS no suco de caju processado. O suco foi obtido a partir dos pedÃnculos do clone de cajueiro CCP 76 em prensa tipo expeller. O tratamento tÃrmico foi realizado em escala de bancada com cinco faixas de temperaturas (55, 65, 75, 85 e 95ÂC) e quatro tempos (5, 15, 30 e 60 minutos). Imediatamente apÃs o tratamento tÃrmico, as amostras foram resfriadas em banho de gelo, e armazenadas em frascos plÃsticos para posterior anÃlise. Os Ãcidos fenÃlicos identificados foram 1-O-trans-cinamoil--D-glucopiranose, Ãcido cinÃmico e seus isÃmeros. Com relaÃÃo à atividade antioxidante, os resultados encontrados utilizando o radical ABTS, apresentaram valores TEAC de 7,11  0,08 para o extrato aquoso e 6,59  0,02 para o extrato metÃnÃlico (ÂM TROLOX/mL de suco). A partir desses resultados pode-se concluir que apesar da mudanÃa na concentraÃÃo dos compostos fenÃlicos durante o processamento, nÃo houve alteraÃÃo na atividade antioxidante do suco de caju em funÃÃo do tratamento tÃrmico. / In the fruit processing industry, the cashew pulp is used during the offseason to obtain various products such as cashew juice. The increasingly frequent consumption of processed foods arouses interest in the products that are being consumed and the influence of processing is still poorly studied. Hence the importance of verifying the influence of processing on the beneficial compounds present in cashew apple juice. This study aimed to quantify the amount of phenolics and evaluate the in vitro antioxidant activity by ABTS method in processed cashew juice. The juice was obtained from the peduncle of the cashew clone CCP 76 in an expeller type press. The thermal treatment was carried out in a bench scale at five temperature (55, 65, 75, 85 and 95  C) and four times (5, 15, 30 and 60 minutes). Immediately after the heat treatment, the samples were cooled in an ice bath and stored in plastic bottles for further analysis. The phenolics were identified as 1-O-trans-cinnamoyl--D-glucopyranose, cinnamic acid and isomers. With regard to antioxidant activity, the results using the ABTS radical, had TEAC values of 7.11  0.08 for the aqueous extract and 6.59  0.02 for the methanol extract (mM Trolox / mL of juice). From these results we can conclude that still of phenolic concentration changes during processing, there was no change on cashew juice antioxidant activity related to thermal treatment.

Cinnamic acids and their derivatives are building blocks for cyclobutanes in many natural products. In nature, dimerization of these derivatives is thought to occur through a [2+2] photocycloaddition. Experimentally, efficient dimerization of these substrates using UV irradiation has predominantly been achieved in the solid state and is thought to be a result of stringent requirements for distance and orientation of the participating olefins. In the following pages a new strategy is presented which achieves [2+2] dimerization of these substrates in solution through the use of a bis-thiourea catalyst that induces proximity via hydrogen bonding while exploiting novel flow technology. Using these platforms, we demonstrate the ability to perform the [2+2] photocycloaddition on a variety of electron rich and poor cinnamates to yield two major truxinic ester products in good yields and regioselectivity. The methodology is also readily scalable to a decagram scale and has enabled access to large quantities of a variety of truxinic ester products. Using a liquid-liquid slug flow strategy greatly accelerated reactivity by nearly four-fold in most cases and has allowed for an expansion of the substrate scope to include historically unreactive substrates such as cinnamamide dimers. This rate increase is attributed to improved mixing and an organic thin film known to occur within these systems. More recently, this flow methodology has been further developed to enable access to various heterodimers similar to those found in various bioactive natural products in a simple and efficient manner by using a cinnamic acid monomer in combination with an excess of cinnamic ester or amide monomer. The heterodimer can be easily separated from the homodimers and unreacted ester or amide monomers through an acid-base workup. Finally, to demonstrate the utility of these methodologies for biological exploration, a small library of truxinic amides was synthesized and underwent biological testing in breast cancer cell lines. Single dose inhibition data showed promising anti-cancer activity. Lastly, this methodology has also been applied to the synthesis of two interesting bioactive natural products, eucommicin A and piperarborenine D in an efficient modular fashion in both cases. These syntheses open the doors to future SAR studies which have yet to be performed on these and most truxinic and truxillic acid derived natural products. / 2020-02-15T00:00:00Z