A presente tese trata da análise conformacional e estudo das interações eletrônicas de algumas 2-(fenilselanil)-2-(metoxi)-4\'-substituídas-acetofenonas (série I) e das 2-(4-substituídasfenilsulfanil)-2-(metoxi)-4\'-substituídas-acetofenonas (série II) contendo grupos doadores, hidrogênio e atraentes de elétrons na posição para dos anéis fenacílico [4\'-Y-PhC(O)] e fenilsulfanílico (S-Ph-4-X). Através da resolução das bandas de νCO, foi constatada a ocorrência de isomerismo conformacional nos solventes de constante dielétrica crescente (n-C6H14, CCl4, CHCl3, CH2Cl2, CH3CN) em ambas as séries. Cinco compostos da série II apresentaram ressonância de Fermi (RF) no infravermelho e precisaram ser deuterados. Os dados espectroscópicos são concordantes tanto com os resultados dos cálculos de otimização e frequência em fase gasosa quanto com a simulação do efeito do solvente (PCM), no nível de teoria B3LYP/6-31+G(d,p). Em ambas as séries, foram encontradas três conformações estáveis c1, c2 e c3, sendo que c2 é significativamente mais estável que c1 e c3. O confôrmero c1 possui o oxigênio metoxílico e o carbonílico em sinperiplanar enquanto os grupos -SePh/- SPh estão em anticlinal. Os confôrmeros c2 e c3 possuem o hidrogênio metínico em sinperiplanar com a carbonila enquanto os grupos -OMe e -SePh/-SPh estão na anticlinal. O confôrmero c1 pode ser atribuído ao componente de banda (IR) de maior frequência νCO. Da mesma forma, c2 e c3 são o componente de frequência intermediária e de menor frequência, respectivamente, na série I enquanto que na série II eles coalescem em apenas um componente de menor frequência. Os cálculos de PCM mimetizam os dados espectroscópicos, i.e. é possível constatar a inversão populacional entre c1 e c2, conforme a polaridade do solvente aumenta. Através do cálculo de frequências anarmônicas e construção da PED, foram encontrados dois modos vibracionais que combinados interagem com νCO originando a RF (série II). Um modo é de alta frequência e envolve uma porcentagem considerável de &#948C-H(metínico), o outro modo é esqueletal. A análise das interações orbitalares (NBO) mostrou que os confôrmeros c1 e c2 são estabilizados pela transferência de cargas entre LpO5→σ*CS/Se (ca. 18 kcal mol-1) enquanto c3 é estabilizado pela interação menos intensa LpO5→σ*C-C (ca. 9,5 kcal mol-1). As interações eletrônicas foram investigadas a partir dos contatos interatômicoscurtos com apoio das cargas atômicas parciais. Apesar de c1 e c2 apresentarem praticamente a mesma estabilidade em termos de interações orbitalares, o primeiro é fortemente desestabilizado pela repulsão eletrostática entre os átomos O&#948-CO...O&#948-OMe negativamente carregados separados por uma distância menor que a soma dos raios de van der Waals. Este contato curto entre os dipolos C&#948+=O&#948- e C&#948+−O&#948- é responsável pela maior frequência de νCO de c1 frente c2 e c3. A maior estabilidade de c1 nos solventes mais polares, porém, deve-se à melhor solvatação local destes dipolos. As análises dos monocristais (raios-X) indicou que os compostos assumem, no estado sólido, a conformação menos estável c1, obtida em fase gasosa. Não foram encontradas diferenças significativas no que se refere aos substituintes Y e X. Conclui-se que a estabilidade global das conformações é determinada pelo balanço energético entre as interações orbitalares e eletrostáticas, nas duas séries estudadas. / This thesis reports the conformational analysis and the electronic interactions study of some 2-(phenylselanyl)-2-(methoxy)-4\'-substituted-acetophenones (series I) and 2-(4-substitutedphenylsulphanyl)-2-(methoxy)-4\'-substituted-acetophenones (series II) bearing electron donating, hydrogen and electron attracting substituents in the para position of the phenacyl [4\'-Y-PhC(O)] and phenylsulphanyl (S-Ph-4-X). The occurrence of conformational isomerism in crescent dielectric constant solvents (n-C6H14, CCl4, CHCl3, CH2Cl2, CH3CN) in the two series was studied through the νCO infrared band decomposition. From the series II compounds, five presented Fermi resonance (FR) and had to be deuterated. The spectroscopic data are in line with theoretical calculations results for optimization and frequency in gas phase as well as for solvent effect simulation (PCM), both in B3LYP/6-31+G(d,p) level. Three stable conformers (c1, c2 and c3) were found for both series being the c2 significantly more stable than c1 and c3. Particularly in the c1 conformer, the methoxyl and the carbonyl oxygens are in sinperiplanar orientation while the -SePh/-SPh groups are in anticlinal. In the c2 and c3 conformers the methyne hydrogen assume a sinperiplanar geometry with respect to the carbonyl whereas both -OMe and -SePh/-SPh are in anticlinal. The c1 conformer can be ascribed to the highest frequency νCO band component (IR). So, c2 and c3 ones can be ascribed to the medium and the lowest frequency νCO component, respectively, in the series I whereas in the series II they come together (coalescence) in one single band component. The PCM calculations are in good agreement with spectroscopic data i.e. it is possible to observe a populational inversion between c1 and c2 conformers as the solvent polarity increases. The anharmonic frequencies and PED theoretical treatment revealed that the combination of two vibrational modes interact with the νCO giving rise to the FR (series II): the high frequency one involves a considerable δC-H(methyne) percentage; whilst the other is skeletal. The orbital interactions analysis (NBO) showed that the c1 and c2 conformers are mainly stabilized by charge transfer LpO5→σ*CS/Se (ca. 18 kcal mol-1) while c3 is stabilized by the less intense interaction LpO5→σ*C-C (ca. 9,5 kcal mol-1). The electronic interactions were investigated by means of interatomic short contacts supported by partial atomic charges calculations. In contrast with the almost similar orbital interactions stability of c1 and c2, the former is strongly destabilized by the electrostatic repulsion between Oδ-CO...Oδ-OMe atoms which are negatively charged separated by a distance shorter than the van der Waals radius sum. This short contact between Cδ+=Oδ- and Cδ+−Oδ- dipoles is responsible for the highest νCO frequency of c1 compared to c2 and c3. In the other hand, the greater stabilization of c1 in the more polar solvents is due to the better solvation of those local dipoles. Last, but not least, the X-ray analysis showed that the compounds in the solid state assume the less stable conformation c1, obtained in gas phase. No significative differences were found in terms of the Y and X substituents. It is suggestive that an energetic balance between orbital and electrostatic interactions determines the global stability of conformations in both studied series.

<p>Det råder en unik problematik runt hanteringen av nedlagda militära områden och den information som idag finns rörande sådana områden är ytterst sparsam vilket skapar en kunskapslucka. Det finns inga tydliga riktlinjer för hur arbetsprocessen vid en förändrad markanvändning ska bedrivas vilket skapar ett stort behov för en tydlig arbetsmodell. Den här uppsatsens huvudsyfte har varit att tillgodose detta behov genom att skapa en ny översiktlig och tydlig arbetsmodell. Uppsatsen är utförd i samverkan med Gävle kommun som hade ett önskemål om att få hjälp med att sammanställa information om militära lämningar i Västra Kungsbäck, för att kunna planera för områdets framtid. För att uppfylla denna önskan har en fallstudie av Västra Kungsbäck påbörjats, som visar på var det finns militära lämningar samt en samlad riskbedömning av området. För att skapa den nya arbetsmodellen på bästa sätt utfördes en jämförelsestudie, med hjälp av en analysmatris, av två befintliga arbetsmodeller: Att lära sig leva med OXA och Metodik för Inventering av Förorenade Områden. Vi har upprättat en ny arbetsmodell med fem steg som kan tillämpas på nedlagda militära övnings- och skjutfält som ska genomgå en förändring av markanvändningen. Den nya arbetsmodellen bör dock vidareutvecklas och ses som ett levande dokument som ständigt ska förbättras. Efter ytterligare bearbetning av den nya arbetsmodellen kommer den att fungera som ett vägledande hjälpverktyg vid den fysiska planeringen för ett hållbart samhälle.</p>

Cyclitols are cyclic compounds having hydroxyl groups which attached to different carbons on the ring. Cyclitols have attracted a great deal of attention for having diverse biological activities. Cyclic alcohols play an important role in biological processes such as inhibition of glycosidase, cellular recognition, and signal transduction. In addition to this, these compounds are very important molecules due to being capable of using while synthesizing natural products or pharmaceuticals. In this study, development of new methodology for the synthesis of bis-aminoinositol derivatives was aimed. The starting material, cis-diester, was synthesized from the Diels-Alder reaction of furan and maleic anhydride followed by reaction with MeOH. As a second key compound, trans-diester was obtained from the Diels-Alder reaction of furan and fumaryl chloride followed by esterification. The diester functionality in these two compounds was planned to be converted into the hydrazide upon treatment with hydrazine monohydrate. Before this reaction, double bond was protected via stereo selective oxidation reaction with m-CPBA due to preventing retro Diels-Alder reaction. Then, hydrazide functionality was converted into acyl azide through &beta / -nitroso hydrazide intermediate. Subsequent Curtius rearrangement reaction resulted in the formation of the isocyanate which was converted to the corresponding bis-urethane by treatment with MeOH. Attempt to cleave the oxa-bridge in urethane with sulfamic acid provided the unexpected tricyclic product 148. Furthermore, hydrolysis of isocyanate with aqueous HCl formed the diamine 156. However, O-bridge could not be opened with any reagents used for that of urethane derivative as described above. Then,the cis-diol 157 was synthesized to prevent the neighboring group participitation during the epoxide-opening reaction. Further ring-opening reactions are under investigation.

Det råder en unik problematik runt hanteringen av nedlagda militära områden och den information som idag finns rörande sådana områden är ytterst sparsam vilket skapar en kunskapslucka. Det finns inga tydliga riktlinjer för hur arbetsprocessen vid en förändrad markanvändning ska bedrivas vilket skapar ett stort behov för en tydlig arbetsmodell. Den här uppsatsens huvudsyfte har varit att tillgodose detta behov genom att skapa en ny översiktlig och tydlig arbetsmodell. Uppsatsen är utförd i samverkan med Gävle kommun som hade ett önskemål om att få hjälp med att sammanställa information om militära lämningar i Västra Kungsbäck, för att kunna planera för områdets framtid. För att uppfylla denna önskan har en fallstudie av Västra Kungsbäck påbörjats, som visar på var det finns militära lämningar samt en samlad riskbedömning av området. För att skapa den nya arbetsmodellen på bästa sätt utfördes en jämförelsestudie, med hjälp av en analysmatris, av två befintliga arbetsmodeller: Att lära sig leva med OXA och Metodik för Inventering av Förorenade Områden. Vi har upprättat en ny arbetsmodell med fem steg som kan tillämpas på nedlagda militära övnings- och skjutfält som ska genomgå en förändring av markanvändningen. Den nya arbetsmodellen bör dock vidareutvecklas och ses som ett levande dokument som ständigt ska förbättras. Efter ytterligare bearbetning av den nya arbetsmodellen kommer den att fungera som ett vägledande hjälpverktyg vid den fysiska planeringen för ett hållbart samhälle.

Cyclitols are of great importance due to their biological activities playing a crucial role in living organisms as well as their synthetic usefulness in the synthesis of other natural compounds or pharmaceuticals. In this study, new synthetic strategies leading to the aminocyclitols were investigated. The synthesis of aminoconduritol and aminoinositol derivatives (173 and 174) were achieved starting from easily available compound, 7-oxa-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride (166) obtained from the Diels-Alder reaction of furan and maleic anhydride. The anhydride functionality in 166 was converted into the half-ester 169 by desymmetrization in methanol. The carboxylic acid moiety in the molecule was used to obtain urethane functionality by making use of Curtius rearrangement. After the cleavage of oxa-bridge with the help of a Lewis acid the aminoconduritol derivative 173 was synthesized. The cis-dihydroxylation of 173 with osmium tetroxide resulted in the formation of inositol derivative 174. Consequently, we developed a new methodology for the synthesis of aminocyclitol derivatives.

Submitted by Erika Demachki (erikademachki@gmail.com) on 2016-08-22T17:02:49Z No. of bitstreams: 2 Dissertação - Suellen Rocha Araújo Castilho - 2016.pdf: 2584243 bytes, checksum: b73318ec0bcbfffa7eb7b840a656cda0 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Erika Demachki (erikademachki@gmail.com) on 2016-08-22T17:05:00Z (GMT) No. of bitstreams: 2 Dissertação - Suellen Rocha Araújo Castilho - 2016.pdf: 2584243 bytes, checksum: b73318ec0bcbfffa7eb7b840a656cda0 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-08-22T17:05:00Z (GMT). No. of bitstreams: 2 Dissertação - Suellen Rocha Araújo Castilho - 2016.pdf: 2584243 bytes, checksum: b73318ec0bcbfffa7eb7b840a656cda0 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2013-02-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The species Acinetobacter baumannii is the most important representative of the genus, being globally considered the pathogen of larger relevance, within the complex A. baumannii – A. calcoaceticus, to healthcare institutions worldwide. Its clinical significance has increased in recent years partly due to its notable capacity of adherence to surfaces due to presence of structures such as pili, production of EPS (exopolysaccharides) and presence of genes that favor biofilm formation, providing larger adhesion between the cells and consequent resistance to the antimicrobials. Another important characteristic is its capacity to regulate or to acquire antibiotic resistance, specifically through oxacilinases, encoded by the gene OXA, that presents potent hydrolytic activity against penicilinase-resistant penicillins. Until the moment, 250 types of OXA were already described. The expression of OXA genes can be increased in the presence of the insertion element ISAba1, which when located upstream of the gene, confer a selective advantage for the isolate when this depends on the efficient expression of a variety of resistance genes. In its absence, the resistance is usually expressed in the presence of two or more OXA genes. The capacity of biofilm formation and the presence of the genes blaPER-1, OXA-23, OXA-40, OXA- 51, OXA-58 and ISAba1 were investigated among 84 isolates from 64 patients of the Intensive Care Units of Goiânia. It was observed that 78.5% of the isolates formed biofilm, of which 23% presented the gene blaPER-1. The presence of OXA-51 gene was detected in all isolates, whereas 64.3% of the isolates had the OXA-23 gene and 24.0% of the isolates had the OXA-58 gene. The ISAba1 gene was detected upstream of the OXA-51, OXA-23 and OXA-58 genes in 33.3% (28/84), 92.6% (50/54) and 10.0% (2/20) of the isolates, respectively. None of the isolates studied presented the gene OXA-40. Of the 62 isolates resistant to imipenem and meropenem, 76.0% possessed the OXA-23 gene while 24.2% of the isolates possessed the OXA-58 gene. Of these isolates, 79.0% (49/62) presented the gene ISAba1. In the present study, the blaPER-1 gene presence was not associated with the biofilm formation, while the presence of OXA genes was related to resistance in Acinetobacter baumannii. / A espécie Acinetobacter baumannii é a representante mais importante do gênero, sendo considerado o patógeno de maior relevância, dentro do complexo A. baumannii – A. calcoaceticus, para as instituições de saúde mundialmente. Sua importância clínica tem aumentado nos últimos anos em parte devido a sua notável capacidade de aderência a superfícies devido a presença de estruturas como pili, produção de EPS (exopolissacarídeo) e presença de genes que favorecem a formação de biofilme, proporcionando maior adesão entre as células e consequente resistência aos antimicrobianos. Outro destaque é sua capacidade de regular ou adquirir resistência, em particular por meio das oxacilinases, codificadas pelo gene OXA, que apresentam atividade hidrolítica potente contra penicilinas resistentes às penicilinases. Até o momento, 250 tipos de OXA já foram descritas. A expressão de genes OXA pode ser aumentada na presença do elemento de inserção ISAba1, localizado à montante do gene, conferindo uma vantagem seletiva para o isolado quando este depende da expressão eficiente de uma variedade de genes de resistência a antibióticos. Na sua ausência, a resistência geralmente é expressa na presença de dois ou mais genes OXA. A capacidade de formar biofilme e a presença dos genes blaPER-1, OXA-23, OXA-40, OXA-51, OXA-58 e ISAba1 foram investigados em 84 isolados provenientes de 64 pacientes de UTIs de Goiânia. Observou-se que 78,5% dos isolados formaram biofilme, dos quais 23% apresentaram o gene blaPER-1. A presença do gene OXA-51 foi detectada em todos os isolados, enquanto que 64,3% dos isolados apresentavam o gene OXA-23, e em 24% dos isolados foi encontrado o gene OXA-58. O gene ISAba1 foi detectado à montante dos genes OXA-51, OXA-23 e OXA-58, em 33,3% (28/84), 92,6% (50/54) e 10% (2/20) dos isolados, respectivamente. Nenhum isolado estudado apresentou o gene OXA-40. Dos 62 isolados resistentes ao imipenem e meropenem, 76% dos isolados possuíam o gene OXA-23 enquanto que 24,2% possuíam o gene OXA-58. Dentre estes isolados, 79% (49/62) apresentaram a sequência de inserção ISAba1. No presente estudo, a presença do gene blaPER-1 não foi associada com a formação de biofilmes, enquanto que a presença de genes OXA estava relacionada à resistência em Acinetobacter baumannii.

Polyketide secondary metabolites constitute a structurally-diverse and clinically-important family of natural products. The wide range of biological activities represented by these substrates have contributed to therapeutic agents with annual sales exceeding $20B USD. Large multi-domain proteins called polyketide synthases (PKSs) use simple building blocks to generate highly-oxygenated and stereochemically-rich frameworks with astonishing selectivity. These substrates often feature rigidifying biases imposed by macrocyclic lactones and substituted heterocycles, which can impact their bioactive conformation. The work of this dissertation combines synthetic chemistry and biochemistry to investigate chemoenzymatic production of macrocyclic polyketide natural products. Research focused on validating a transannular oxa-conjugate addition strategy to assembly 2,6-cis-tetrahydropyran (THP) ring systems, as demonstrated by synthesis of the macrocyclic core to neopeltolide. Ultimately, we wish to apply this chemistry to de novo PKS pathways for rapid, reliable, and sustainable production of THP-bearing products like neopeltolide, and toward building SAR libraries. Additionally, a second study probed the specificity of the macrolactonizing thioesterase (TE) domain from the 6-deoxyerythronolide B (DEBS) biosynthetic pathway. This pathway is the paradigm for type-I PKS systems, and is responsible for producing the macrolide core of erythromycin. Our on-going research evaluates the limits of promiscuity within this specific catalytic domain, to characterize the structural elements required to accurately predict macrolactonization. The long-term goal of this study is to assess the potential applicability of DEBS TE as a generalized cyclization biocatalyst for combinatorial biochemistry and chemoenzymatic research.

Le sujet de cette thèse concerne l'élaboration de macromonomères, de copolymères greffés et de polymères étoiles de type 'mikto-arm'. De telles architectures macromoléculaires ont été synthétisées par la combinaison de techniques de polymérisation contrôlées/vivantes telles que la polymérisation par ouverture de cycle (par métathèse) (RO(M)P) etde chimie 'click' orthogonales : cycloaddition 1,3-dipolaireazoturealcyne catalysée au cuivre (CuAAC) et thiol-ène.Dans un premier temps, des macromonomères originaux à fonctionnalité polymérisable (oxa)norbornène portant deux chaînes macromoléculaires poly(e-caprolactone) (PCL) et/ou poly(oxyde d'éthylène) (POE) ont été synthétisés par combinaison ROP/CuAAC. Les macromonomères à fonctionnalité (oxa)norbornène avec deux chaînes PCL de masse molaire moyenne en nombre (Mn) compris entre 1400 et 5000 g/mol ont été obtenus par ROP organocatalysée. La synthèse des macromonomères POE44-b-PCLn à fonctionnalité norbornène avec un bloc PCL de longueur variable (1100 g/mol <Mn< 4100 g/mol) a été réalisée par combinaison CuAAC/ROP à partir d'un POE 2000 g/mol commercial. Ces macromonomères présentent des propriétés d'auto-assemblage dans l'eau avec une concentration micellaire critique et un rayon hydrodynamique dont les valeurs augmentent avec la longueur du bloc hydrophobe PCL. Dans un second temps, la réactivité de la fonctionnalité (oxa)norbornène des macromonomères a été étudiée par spectroscopie RMN 1H, chromatographie SEC et spectrométrie MALDI-ToF. Des copolymères greffés à squelettepoly(oxa)norbornène à haute densité de greffons PCL et POE ont été obtenus par ROMP en présence d'amorceurs de Grubbs selon la stratégie "grafting through". La thiol-ène a également été utilisée avec succès pour accéder à des copolymères étoiles de type 'mikto-arm' à base de PCL, POE poly(N-isopropylacrylamide). / The objective of the present thesis was the preparation of complex macromolecules by the combination of controlled/livingpolymerization methods such as ring-opening (metathesis) polymerization (RO(M)P) and highly efficient orthogonal chemistries: copper-catalyzed azide-alkyne coupling (CuAAC) and thiol-ene reactions.In the first part of this work, a series of well-defined structural (co)polymers containing a cycloolefin (norbornene (NB) oroxanorbornene (ONB)) functionality bearing two polymer chains including poly(ε-caprolactone) (PCL) and/or poly(ethylene oxide) (PEO) have been successfully prepared using the combination of ring-opening polymerization (ROP) and CuAAC ‘click’ chemistry. Well-defined (oxa)norbornenyl-functionalized bis-PCL polymers with PCL chain ranging from 1400 to 5000 g/mol were obtained by organocatalyst-mediated ROP. Norbornenyl-functionalized PEO-b-PCL block copolymers with PCL block in the range 1100 to 4100 g/mol were synthesized from commercially available PEO 2000 g/mol by CuAAC followed by ROP of CL. The presence of a hydrophilic PEO chain and a hydrophobic PCL chain in norbornenylfunctionalizedPEO-b-PCL copolymers gives rise to self-assembling properties in water solution. Critical micellar concentrations (CMC)are in the range of 0.08 – 0.006 g/L for copolymers with PCL chain length ranging from 10 to 36 CL units, respectively. Thecorresponding micelles show hydrodynamic diameters in range of 10 – 23 nm with low polydispersities.In the second part of this work, well-defined copolymers were used to prepare bottle-brush and (mikto-arm) star copolymersthrough reactions involving the cycloolefin functionality. On the one hand, high density grafting bottle-brush copolymerspoly(oxa)norbornene-g-bisPCL, polynorbornene-g-PEO/PCL (PNB-g-(PEO/PCL)) and PNB-b-(PNB-g-(PEO/PCL)) were achieved by ROMP according to the ‘grafting through’ strategy using Grubbs’ catalysts. On the other hand, PCL, PEO, PNIPAM-based 3-arms star, 4-arms star copolymers were obtained via radical thiol-ene reactions as demonstrated by 1H NMR, SEC and MALDI-ToF MS analysis.The high reactivity of these copolymers toward ROMP and thiol-ene reactions makes them interesting candidates in order toprepare new well-defined copolymers with controlled structures and properties through highly efficient synthetic strategies.

Pyranonaphthoquinone lactones have been recently found to be selective inhibitors of the serine-threonine kinase AKT/PKB. AKT/PKB plays a major role in tumorigenesis, hence these compounds have a great potential to act as anti-cancer agents. They act by a novel bioreductive alkylation mechanism of inhibition of AKT/PKB. In this work, 7-deoxykalafungin, a pyranonaphthoquinone lactone and its deconstruction analogs were synthesized. The structural features of the compounds necessary to inhibit AKT1 potently and selectively were determined. It was observed that compounds with a pyran ring were more potent in inhibiting AKT1. Conversely, flexible compounds were found to be weak inhibitors of AKT1. Also, presence of a lactone ring was found to be favorable in inhibiting AKT1. Of the compounds tested, 7-deoxykalafungin was the most potent inhibitor of AKT1 (IC50 = 0.28 µM against AKT1) and compound 4-61 was the most potent inhibitor of PKA (IC50 = 0.43 µM against PKA).

The underlying theory of “Spin” of an electron and its associated inter-actions causing internal fields and spectral shift to bulk-magnetism iswell established now. Our understanding of spin properties is significant andmore useful than ever before. In recent years there seems to be an enormousinterest towards application oriented materials that harness those spin prop-erties. Theoretical simulations remain in a position to “assist or pilot” theexperimental discovery of new materials.In this work, we have outlined available methodologies for spin coupling inmulti-reference and DFT techniques. We have benchmarked multi-referencespin-Hamiltonian computation in isoelectronic diradicals - Trimethylenemethane(TMM) and Oxyallyl. Also with DFT, parameters are predicted with anewly discovered TMM-like stable diradicals, reported to have large positiveexchange interactions. Excellent agreement were obtained and our findingsemphasize that the dipole-dipole interactions alone can predict the splittingof triplet states and that DFT spin procedures hold well in organic species.We have extended our spin-studies to a highly application oriented ma-terial - nanographene. Using our novel spin-parameter arguments we haveexplained the magnetism of graphene. Our studies highlight a few signifi-cant aspects - first there seems to be a size dependency with respect to thespin-Hamiltonian; second, there is a negligible contribution of spin-orbit cou-pling in these systems; third, we give a theoretical account of spin restrictedand unrestricted schemes for the DFT method and their consequences forthe spin and spatial symmetry of the molecules; and, finally, we highlightthe importance of impurities and defects for magnetism in graphene. Wepredict triplet-singlet transitions through linear response TDDFT for thetris(8-hydroxyquinoline) aluminium complex, an organic molecule shown tohave spintronics applications in recent experiments. Our spin studies werein line with those observations and could help to understand the role of thespin-coupling phenomena. / QC 20120531