he thermal behaviour in the solid state of various substituted aminobenzoic acids (3-aminobenzoic acid (3-ABA), 4-aminobenzoic acid (4-ABA), 3-aminosalicylic acid (3-ASA), 4-aminosalicylic acid (4-ASA), and 5-aminosalicylic acid (5-ASA), as well as the "parent" benzoic acid (BA) and salicylic acid (SA) as reference substances, and possible decomposition products: 2-aminophenol (2-AP), 3-aminophenol (3-AP) and 4-aminophenol (4-AP), has been examined. The various sets of isomers studied showed considerable and interesting differences. Most sublimed well before melting, generally with an increasing rate of mass loss beyond their very different melting points. The existence of ranges of isomers allows for the comparison of their behaviour, including such aspects as melting, vaporisation, and the influence of products on the course of decomposition of initially-solid reactants. The differences in behaviour of 4-ASA and 5-ASA were the most remarkable, with 5-ASA being far more stable and apparently not decarboxylating readily, while 4-ASA sublimed at temperatures below the melting point, becoming less stable and decarboxylating in the liquid form. There is also a marked difference in the thermal behaviour of 3-ASA, as compared with 4-ASA and 5-ASA. It decarboxylated at higher temperatures (260°C) than 4-ASA (150°C). The addition of the possible decomposition products to these compounds showed faster decomposition for 4-ASA mixed with 3-AP. The sodium salts of 3-ASA and 4-ASA decarboxylate while that of 5-ASA did not. Binary mixtures of the substances listed above with beta-cyclodextrin (BCD), hydroxypropylbeta-cyclodextrin (HPBCD) and gamma-cyclodextrin (GCD) were prepared (by simple physical mixing or by kneading with a solvent) and were then examined for possible interactions using DSC, TG-FTIR, HSM, XRD and NMR. Generally, kneaded mixtures showed greater changes in thermal behaviour from that of the individual components than the physical mixtures, but changes in the physical mixtures were also significant. Comparison of the effects of the different CDs on the thermal behaviour of individual ASA isomers showed that HPBCD has the greatest interaction with 3-ASA and 5-ASA, followed by GCD, while BCD generally showed the least interactions. For 4-ASA, the effect of GCD is more marked than for 3-ASA and 5-ASA. GCD has the largest molecular cavity.

Thesis submitted for the Degree of Doctor of Medicine in the University of the Witwatersrand, Johannesburg / The interest of the biochemist in para-aminobenzoic acid is very recent and, indeed, only goes back about five years, but in this time quite a voluminous literature has accumulated on the biological aspects and importance of this aniline derivative. Attention was originally focussed on it indirectly as a result of the intensive research devoted to the understanding of the mode of action of the various sulphonamides, which were shown during the last decade to be very powerful chemothera-peutic agents against many bacteria. Fildes (1940, propounded the hypothesis that p-aminobenzoic acid was an essential meta-bolite for bacteria, that it was normally associated with an enzyme system in the bacterial cell, and that sulphanilamide, being structurally similar to p-aminobenzoic acid, was capable in sufficient concentration of displacing p-aminobenzoic acid from its enzyme and stopping this essential line of metabolism. Fildes further suggested that a substance which was found to be an essential metabolite for bacteria would also be essential in the animal kingdom, so that such a substance might be found to act as a vitamin in the higher animals and even in man. In 19U1 interest in p-aminobenzoic acid was intensified with the announcement by Ansbacher (19U1J that p-eminobenzoic acid was actually a vitamin and should be included in the vita¬min B complex. In this thesis, studies on the absorption and excretion of p-aminobenzoic acid are reported, the estimation of p-amino- bensoic acid being based on its property of antagonising the Bulphonamides. Evidence is presented that p-arainobenzoic acid la excreted ae p-acetylaminobenzoic acid, and that its conjuga- tion with the acetyl radical probably takeB place in the liver. Further it is suggested that the experiments performed do not lend support to the view that p-aminobenzolc acid is a vitamin for man. Finally the various physiological effects of p-aminobenzoic acid are discussed and an attempt is made to gauge its function in the living organism. Preliminary experiments indicating a new, hitherto unreported, role of p-aminobenzoic acid are re¬corded, namely its ability in large doses to increase the re¬sistance of animals to disease. / IT2017

Thesis (Habilitationschrift)--Technische Hochschule "Fridericiana" zu Karlsruhe, 1906. / Includes bibliographical references (p. 104).

No / Investigations of structural reactivity, molecular interactions and vibrational characterization of pharmaceutical drugs are helpful in understanding their behaviour. The aim of this study is to determine the molecular, electronic and chemical properties of the antibiotic drug nitrofurantoin (NF), after cocrystallisation with 3-aminobenzoic acid (3ABA) and to understand how those changes lead to variation of properties in the cocrystal NF–3ABA. NF–3ABA formation is explained by stabilization via the hydrogen-bond network between NF and 3ABA molecules. It is thoroughly characterized by IR, Raman and CP-MAS solid-state 13C NMR techniques, along with quantum chemical calculations. The results of IR, Raman, and 13C NMR analyses showed that imide N–H23 and C12[double bond, length as m-dash]O of NF interact with the acid C[double bond, length as m-dash]O and –OH groups in 3-ABA, respectively. Therefore the IR, Raman, and 13C NMR spectra verified the formation of N–H⋯O and O–H⋯O hydrogen bonds. To study hydrogen bonding interactions theoretically in NF–3ABA, two functionals B3LYP and wB97X-D have been used. A comparison is made between the results obtained by B3LYP and those predicted at the wB97X-D level. It is found that wB97X-D is best applied density functional theory (DFT) functional to describe the hydrogen bonding interactions. The strength and nature of hydrogen bonding in NF–3ABA have been analysed by quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis. To validate the results obtained by QTAIM theory and to study the long-range forces, such as van der Waals interactions, the steric effects in NF–3ABA, the reduced density gradient (RDG) and the isosurface have been plotted using Multiwfn software. QTAIM and isosurface analysis suggested that the hydrogen bonding interactions present in NF–3ABA are moderate in nature. The calculated HOMO–LUMO energy gap shows that NF–3ABA is more active than NF and 3ABA. Chemical reactivity descriptors are calculated to understand the various aspects of pharmacological sciences. Chemical reactivity parameters show that NF–3ABA is softer and chemically more reactive than NF. The results suggest that cocrystals can be a feasible alternative for positively changing the targeted physicochemical properties of an active pharmaceutical ingredient (API). / Royal Society of Chemistry for the mobility grant (2015/17); DST (New Delhi) under the DST purse programme; UGC under the BSR meritorious fellowship scheme; DST, India under the Indo-Brazil project

Controlling crystal polymorphism, the ability of a molecule to crystallise in different solid forms, is one of the grand, ongoing challenges in materials science. In the pharmaceutical industry particularly, where up to half of the active pharmaceutical active ingredients exhibit polymorphic behaviour, it is of paramount importance to rationalise the impact of experimental conditions, such as the nature of the solvent, on the obtainment of a specific c crystal form. As strategies for the selection of polymorphs is still, by and large, based on a trial-and-error approach, it is necessary to acquire a fundamental understanding of the factors controlling the formation of a speci fic solid-state structure during crystallisation from solution. During this doctoral research project, we have conducted a computer simulation study of the early stages of crystallisation of meta-aminobenzoic acid, an important model system in the investigation of polymorphic phenomena. This molecule can in fact form five different polymorphic forms whose selective crystallisation from solution chiefly depends on the nature of the solvent. Molecular models and computational chemistry methods, based on density functional theory and molecular dynamics, have been developed and applied to quantify the processes surrounding the crystallisation of meta-aminobenzoic acid: solvent-solute separation, solute aggregation and surface reactivity. The aim was to identify what controls, at the molecular level, the polymorphic selection process during crystallisation from solution of this important active pharmaceutical ingredient. The results show that the solvent play a signi cant role during the key stages of meta-aminobenzoic acid crystallisation by controlling both the kinetics and thermodynamics of solute desolvation, formation of prenucleation clusters and surface reactivity. This work represents a paradigm of the role of molecular processes during the early stages of nucleation in affecting polymorph selection during crystallisation from solution.

No description available.

Charles University Faculty of Pharmacy in Hradec Králové Department of Pharmaceutical chemistry and Pharmaceutical analysis Author: Jana Žecová Supervisor: PharmDr. Jan Zitko, Ph.D. Title of diploma thesis: Compounds combining pyrazinamide and 4-aminobenzoic acid fragments as potential antituberculars Tuberculosis is a severe infectious disease, which has been afflicting the human world population for centuries. It's figuring in the scale of the deadliest diseases as well as the occurring of strains resistant to therapy requires a serious approach to this problem and the research of new therapeutic means. Among the actual antituberculars figure two compounds, PZA and PAS. Pyrazinamide is a first line drug, and its derivatives are subject of the research in the Department of Pharmaceutical chemistry and Pharmaceutical analysis. Structurally similar to 4-aminobenzoic acid, PAS is a second line antitubercular, which is again actual in the therapy of resistant form of TBC. This diploma thesis treats about possibilities of the use of compounds combining fragments of PZA and 4-aminobenzoic acid as potential antituberculars. Furthermore, this thesis evaluates the influence of PAS fragment in the derivatives prepared with this antimycobacterial purpose. The theoretical part describes the actual state of...

In organic-inorganic hybrid compounds an organic and an inorganic component are combined to form either a coordination or an ionic material. Relevant to the current study are hybrid materials composed of an organic part that contains one or more functional groups, for example amine, amide or carboxylic acid functional groups, and a metal halide inorganic portion. These functional materials display a range of interesting and desired properties, as evidenced from numerous literature reports on their properties. In order to utilise these properties in applications, a detailed understanding of the way that the crystal structure influences the properties of a material is required. However, before this step can be achieved, it is necessary to obtain information on the structural trends of the materials, and to use the approach of crystal engineering to identify robust supramolecular synthons that may afford structural control and prediction. The aim of the current study was to investigate the synthesis and crystal structures of hybrid materials, both ionic and coordination, composed of divalent transition metal halides and the organic components 4-aminobenzoic acid, 4-aminobenzamide and isonicotinic acid, and to identify the structural trends and crystal engineering synthons displayed by these materials. A secondary objective was the preliminary identification of properties exhibited by selected materials, in order to decide on the suitability of the materials for detailed future property investigations. Part of the work describes the investigation of the structural characteristics of coordination materials prepared by the combination of the organic and inorganic components. Five novel crystal structures of coordination materials were determined, and these are compared with six related coordination structures reported in the literature. Two of the novel structures display interesting one-dimensional coordination polymers, one of which has never been reported previously in the literature. The molecular and structural characteristics of both the novel and the literature coordination structures are presented in detail, and this discussion includes a description of the coordination geometry, the molecular geometry, packing trends, hydrogen bonding interactions and aromatic interactions. A comparison study across the three families of organic components in which the structural trends, hydrogen bonding interactions, aromatic interactions, ligand geometry and coordination modes are compared, is included. The results of the synthesis of the coordination materials by means of a mechanochemical method are presented, and the products afforded by this method are compared with those prepared via solution crystallisation. Finally, the results of preliminary studies of the thermal and electronic propertries of the materials are presented and interpreted. The combination of the hybrid components as cations and anions to form ionic materials yielded nine novel structures, and these were compared with five related ionic structures reported in the literature. The novel structures include three polar structures that contain the 4-ammoniumbenzamide cation, and to our knowledge no structures containing this cation have ever been reported in the literature, hence a significant contribution to the structural knowledge of perhalometallate salts of 4-ammoniumbenzamide is made by this study. In addition two novel structures display interesting one-dimensional and two-dimensional polymeric anions, respectively, are reported. The discussion of the novel and literature ionic structures includes a description of the molecular geometry of each of the components, the identification of packing trends, and an analysis of the hydrogen bonding and aromatic interactions occurring in the structures. The structures of all three families of organic components are compared, and trends in structural type, anion geometry, water inclusion, hydrogen bonding and functional group recognition are presented. In addition, a detailed analysis of robust crystal engineering synthons occurring in these structures is presented. Lastly the results of preliminary property investigations of the thermal and electronic properties of the materials are presented and discussed / Dissertation (MSc)--University of Pretoria, 2011. / Chemistry / unrestricted

Yes / Investigations of structural reactivity, molecular interactions and vibrational characterization of pharmaceutical drugs are helpful in understanding their behaviour. The aim of this study is to determine the molecular, electronic and chemical properties of the antibiotic drug nitrofurantoin (NF), after cocrystallisation with 3-aminobenzoic acid (3ABA) and to understand how those changes lead to variation of properties in the cocrystal NF–3ABA. NF–3ABA formation is explained by stabilization via the hydrogen-bond network between NF and 3ABA molecules. It is thoroughly characterized by IR, Raman and CP-MAS solid-state 13C NMR techniques, along with quantum chemical calculations. The results of IR, Raman, and 13C NMR analyses showed that imide N–H23 and C12[double bond, length as m-dash]O of NF interact with the acid C[double bond, length as m-dash]O and –OH groups in 3-ABA, respectively. Therefore the IR, Raman, and 13C NMR spectra verified the formation of N–H⋯O and O–H⋯O hydrogen bonds. To study hydrogen bonding interactions theoretically in NF–3ABA, two functionals B3LYP and wB97X-D have been used. A comparison is made between the results obtained by B3LYP and those predicted at the wB97X-D level. It is found that wB97X-D is best applied density functional theory (DFT) functional to describe the hydrogen bonding interactions. The strength and nature of hydrogen bonding in NF–3ABA have been analysed by quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis. To validate the results obtained by QTAIM theory and to study the long-range forces, such as van der Waals interactions, the steric effects in NF–3ABA, the reduced density gradient (RDG) and the isosurface have been plotted using Multiwfn software. QTAIM and isosurface analysis suggested that the hydrogen bonding interactions present in NF–3ABA are moderate in nature. The calculated HOMO–LUMO energy gap shows that NF–3ABA is more active than NF and 3ABA. Chemical reactivity descriptors are calculated to understand the various aspects of pharmacological sciences. Chemical reactivity parameters show that NF–3ABA is softer and chemically more reactive than NF. The results suggest that cocrystals can be a feasible alternative for positively changing the targeted physicochemical properties of an active pharmaceutical ingredient (API). / V. R. Vangala acknowledges the financial support of the Royal Society of Chemistry for mobility grant (2015/17).

Tendo em conta os constantes problemas que apresentasse com os processos de corrosão, o presente trabalho de pesquisa tem como foco principal a alteração nas propriedades de superfície das ligas de alumínio empregadas nas aeronaves, AA2024 e AA7075, utilizando mono e bicamadas baseadas de octadecil-trimetóxi-silano (ODTMS) + poli(anilina-co-3-aminobenzoico/PAni3ABA) a fim de encontrar melhores condições para a redução da corrosão puntiformes. Posteriormente, avalia-se as características protetoras dos filmes através de testes de corrosão, como potencial de circuito aberto, curvas de polarização anódica e espectroscopia de impedância eletroquímica visando a caracterização do comportamento eletroquímico das amostras. Também foram realizadas análises de microscopia óptica para verificar a eficiência de proteção contra a corrosão dos revestimentos propostos antes e após os ensaios de corrosão. Os resultados obtidos demonstram que as camadas utilizadas melhoram a resistência contra a corrosão na seguinte ordem: PAni3ABA > ODTMS + PAni3ABA > ODTMS, sendo a primeira a que apresentou os melhores resultados como maiores deslocamentos do Ecorr para valores mais positivos, diminuição da icorr e menor número de pontos de corrosão após a realização das curvas de polarização. Além de testes de aderência para os filmes também foram efetuadas caracterizações das ligas por MEV. / Taking into account the constant problems that presents with corrosion processes, this research work has focused primarily on the change in surface properties of aluminum alloys used in aircraft, AA2024 and AA7075, with mono and bilayers using as a base octadecyl trimethoxy silane (ODTMS) + poly (aniline-co-3-aminobenzoic / PAni3ABA) to find optimum conditions for reducing corrosion punctiform. Later, it evaluates the protective features of the films through corrosion tests such as open circuit potential, anodic polarization curves and electrochemical impedance spectroscopy in order to characterize the electrochemical behavior of the samples. They were also carried out optical microscopy analysis to verify the efficiency of protection against corrosion of the coatings proposed before and after corrosion testing. The results obtained show that the layers used improve corrosion resistance in the following order: PAni3ABA> ODTMS + PAni3ABA> ODTMS, the first being the one that presented the best results as larger shifts towards more positive values, reduced and fewer corrosion points after performing the polarization curves. In addition to compliance tests for the films were also made characterizations of alloys by SEM.