Sibylla Trig-Andriana, seu De virginitate, virginum statu et jure tractatus jucundus : ex jure naturali, divino, canonico & civil,; scriptoribus ecclesiasticis & profanis, in gratiam physicorum, medicorum, theologorum & juridicorum paratus /

"De Linea amoris, sive Commentarius in versiculum glossae ... / authore Henrico Kornmanno ..." ; "De annulo triplici, usitato, sponsalitio, signatorio : tractatus absolutissimus, in tres partes divisus / authore Henrico Kornmanno ..."

Particle-species dependent modification of jet-induced correlations in Au plus Au collisions at root s(NN)=200 GeV

Measurements in Au + Au collisions at root s(NN) = 200 GeV of jet correlations for a trigger hadron at intermediate transverse momentum (p(T,trig)) with associated mesons or baryons at lower p(T,assoc) indicate strong modification of the away-side jet. The ratio of jet-associated baryons to mesons increases with centrality and p(T,assoc). For the most central collisions, the ratio is similar to that for inclusive measurements. This trend is incompatible with in-vacuum fragmentation but could be due to jetlike contributions from correlated soft partons, which recombine upon hadronization.

Parton energy loss in heavy-ion collisions via direct-photon and charged-particle azimuthal correlations

Charged-particle spectra associated with direct photon (gamma(dir)) and pi(0) are measured in p + p and Au + Au collisions at center-of-mass energy root(S)(NN) = 200 GeV with the STAR detector at the Relativistic Heavy Ion Collider. A shower-shape analysis is used to partially discriminate between gamma(dir) and pi(0). Assuming no associated charged particles in the gamma(dir) direction ( near side) and small contribution from fragmentation photons (gamma(frag)), the associated charged-particle yields opposite to gamma(dir) (away side) are extracted. In central Au + Au collisions, the charged-particle yields at midrapidity (vertical bar eta vertical bar < 1) and high transverse momentum (3 < (assoc)(PT) < 16 GeV/c) associated with gamma(dir) and pi(0) (vertical bar eta vertical bar < 0.9, 8 < (trig)(PT) < 16 GeV/c) are suppressed by a factor of 3-5 compared with p + p collisions. The observed suppression of the associated charged particles is similar for gamma(dir) and pi(0) and independent of the gamma(dir) energy within uncertainties. These measurements indicate that, in the kinematic range covered and within our current experimental uncertainties, the parton energy loss shows no sensitivity to the parton initial energy, path length, or color charge.

Avaliação da dosagem direta do colesterol-LDL em amostras de sangue de 10.664 pacientes em comparação com o uso da fórmula de Friedewald

OBJETIVO: Avaliar a dosagem direta do colesterol LDL (LDL-C) por um método homogêneo, em comparação com a estimativa pela fórmula de Friedewald, em uma grande população heterogênea. MÉTODOS: As dosagens do colesterol total (ColT) e dos triglicerídeos (Trig) foram realizadas por métodos enzimáticos tradicionais. As dosagens do HDL-C e do LDL-C foram realizadas por métodos diretos, sem precipitação, e a estimativa da fração LDL-C calculada pela fórmula de Friedewald. RESULTADOS: Por análise de regressão linear, os dois métodos apresentaram coeficientes de correlação extremamente significativos (p<0,001). Entretanto, a fórmula de Friedewald apresentou um bias positivo em relação ao método direto, mais pronunciado com níveis de ColT > 201 mg/dL. Este bias positivo também ocorreu com relação a níveis de Trig < 150 mg/dL. Com níveis de Trig entre 151-200 mg/dL e entre 201-300 mg/dL, não foi observado bias entre os dois métodos. Por outro lado, com níveis de Trig entre 301-400 mg/dL, este bias da fórmula de Friedewald tornou-se negativo. CONCLUSÃO: Foi possível demonstrar que a fórmula de Friedewald não apresenta um desempenho homogêneo para a estimativa do LDL-C em amostras com diferentes níveis de Trig, em comparação com o método direto, podendo causar dúvidas na classificação quanto ao risco de desenvolver doença arterial coronariana.

Towards the enantioselective synthesis of lycoricidine alkaloids /

Two efficient, regio- and stereo controlled synthetic approaches to the synthesis of racemic analogs of pancratistatin have been accomplished and they serve as the model systems for the total synthesis of optically active 7-deoxy-pancratistatin. In the Diels-Alder approach, an efficient [4+2] cycloaddition of 3,4-methylenedioxyco- nitrostyrene with Danishefsky's diene to selectively form an exo-nitro adduct has been developed as the key step in the construction of the C-ring of the target molecule. In the Michael addition approach, the key step was a conjugate addition of an organic zinc-cuprate to the 3,4-methylenedioxy-(B-nitrostyrene, followed by a diastereocontroUed closure to form the cyclohexane C-ring of the target molecule via an intramolecular nitro-aldol cyclization on a neutral alumina surface. A chair-like transition state for such a cyclization has been established and such a chelation controlled transition state can be useful in the prediction of diastereoselectivity in other related 6-exo-trig nitroaldol reactions. Cyclization of the above products fi^om both approaches by using a Bischler-Napieralski type reaction afforded two lycoricidine derivatives 38 and 50 in good yields. The initial results from the above modeling studies as well as the analysis of the synthetic strategy were directed to a chiral pool approach to the total synthesis of optically active 7-deoxy-pancratistatin. Selective monsilylation and iodination of Ltartaric acid provided a chiral precursor for the proposed key Michael transformation. The outlook for the total synthesis of 7-deoxy-pancratistatin by this approach is very promising.A concise synthesis of novel designed, optically pure, Cz-symmetrical disulfonylamide chiral ligands starting from L-tartaric acid has also been achieved. This sequence employs the metallation of indole followed by Sfj2 replacement of a dimesylate as the key step. The activity for this Cz-symmetric chiral disulfonamide ligand in the catalytic enantioselective reaction has been confirmed by nucleophilic addition to benzaldehyde in the disulfonamide-Ti (0-i-Pr)4-diethylzinc system with a 48% yield and a 33% e.e. value. Such a ligand tethered with a suitable metal complex should be also applicable towards the total synthesis of 7-deoxy-pancratistatin.

MA160exam00

Exam questions and solutions in LaTex. Diagrams for the questions are all together in the support.zip file, as .eps files

MA160exam01

Exam questions and solutions in LaTex. Diagrams for the questions are all together in the support.zip file, as .eps files

MA160exam01pdf

Exam questions and solutions in PDF

MA160exam00pdf

Exam questions and solutions in PDF

The first preparation of beta-lactones by radical cyclization

beta-Lactones have, for the first time, been prepared by 4-exo-trig radical cyclization. Thus, alpha-ethenoyloxy radicals react in the presence of tributylstannane in a photothermal process to give beta-lactones. Highest yields were obtained when groups capable of stabilizing a carboncentered radical were present at the 3-position of the alkenoate acceptor.

Formation of novel photoadducts from irradiation of 5(S)-5-O-tert-butyldimethylsiloxymethylfuran-2(5H)-one

Irradiation of 5S-5-O-tert-butyldimethylsiloxymethylfuran-2(5H)-one 1 in acetonitrile yields the C2-symmetric bis(lactone), 1S,2S,6S,7S-[3S,10S]-bis-tert-butyldimethylsiloxymethyl-4,9-dioxatricyclo[5.3.0.02,6]deca-5,8-dione 6, and a 3-substituted intramolecular product resulting from an apparent 8-endo-trig cyclisation.

Synthesis of Tetrahydrofurans by Cyclization of Homoallylic Alcohols with Iodine/Iodine(III)

Tetrahydrofuran derivatives can be obtained by cyclo-functionalization of homoallylic alcohols bearing a terminal double bound by using [hydroxy(tosyloxy)iodo]benzene (HTIB, Koser`s reagent) in the presence of a catalytic amount of 12 (20 mol %) in MeOH under mild conditions. This transformation is an overall 5-endo-trig cyclization, which occurs by two different pathways. The first is a 4-exo-trig cyclization followed by ring expansion, whereas the second is an electrophilic addition followed by a 5-endo-tet cyclization.