Fotoquímica e fotofísica do ácido 1,4-bis(3-carbóxi-3-oxo-prop-1-enil)benzeno

Este trabalho versa sobre a caracterização espectroscópica do ácido 1,4-bis(3-carbóxi-3-oxo-prop-1-enil)benzeno, substância com potencialidade em complexação de íons metálicos. Para isto foram obtidos espectros de UV/VIS do composto em meio aquoso na presença e ausência de irradiação no ultra-violeta. Foram obtidos um coeficiente de extinção molar de 36.457 L mol-1 cm-1 e uma taxa de degradação de 5,2.10-7 mol L-1 min-1, quando se irradiou uma solução do composto cuja concentração era de 3,2.10-5 mol L-1 em uma cubeta de quartzo de 10mm de caminho ótico a 7,0cm de uma lâmpada de mercúrio de 80W.

Estudo do comportamento térmico dos compostos de Ag+ e Pb2+ com o ligante 1,4-bis(3-carbóxi-3-oxo-prop-1-enil)benzeno

Este trabalho reporta o estudo de compostos binários do dicarboxilato 1,4-bis(3-carbóxi-3-oxo-prop-1-enil)benzeno, C6H4(-CH=CH-CO-COO-)2 , com os cátions metálicos Ag+ e Pb2+, obtidos a partir de soluções aquosas do ligante e dos nitratos dos cátions metálicos, em proporções estequiométricas. Para a caracterização e o estudo do processo de decomposição térmica desses compostos foram empregadas Espectrofotometria de Absorção na Região do Infravermelho com Transformada de Fourier (FT-IR), Análise Elementar (C, H), Complexometria com EDTA, Termogravimetria (TG) e Calorimetria Exploratória Diferencial (DSC).

Crystal structures of 5-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Zn(II)

The crystal and molecular structures of [bis(5-chloro-2-methoxybenzoate)tetraaquamanganese(II)], [pentaaqua(5-chloro-2-methoxybenzoato)cobalt(II)] (5-chloro-2-methoxybenzoate), [pentaaqua(5-chloro-2-methoxybenzoato)nickel(II)] (5-chloro-2-methoxybenzoate) and [aquabis(5-chloro-2-methoxybenzoate)zinc(II)] monohydrate were determined by a single-crystal X-ray analysis. Mn(H2O)4L2 (where L = C8H6ClO3) crystallizes in the monoclinic system, space group P21/c. [Co(H2O)5L]L and [Ni(H2O)5L]L both are isostructural, space group P212121. The crystals of [Zn(H2O)L2] H2O are monoclinic, space group Pc. Mn(II) ion is positioned at the crystallographic symmetry center. Mn(II) and Co(II) ions adopt the distorted octahedral coordination but Zn(II) tetrahedral one.The carboxylate groups in the complexes with M(II) cations function as monodentate, bidentate and/or free COO-groups. The ligands exist in the crystals as aquaanions. The complexes of 5-chloro-2-methoxybenzoates with Mn(II), Co(II) and Zn(II) form bilayer structure.

Cytotoxic and DNA-topoisomerase effects of lapachol amine derivatives and interactions with DNA

The cytotoxic activity of amino (3a-e), aza-1-antraquinone (4a-e) lapachol derivatives against Ehrlich carcinoma and human K562 leukemia cells was investigated. Cell viability was determined using MTT assay, after 48 (Ehrlich) or 96 h (K562) of culture, and vincristine (for K562 leukemia) and quercetin (for Ehrlich carcinoma) were used as positive controls. The results showed dose-dependent growth-inhibiting activities and that the amino derivatives were active against the assayed cells, whereas the 4a-e derivatives were not. The allylamine derivative 3a was the most active against Ehrlich carcinoma, with IC50 = 16.94 ± 1.25 µM, and against K562 leukemia, with IC50 = 14.11 ± 1.39 µM. The analogous lawsone derivative, 5a, was also active against Ehrlich carcinoma (IC50 = 23.89 ± 2.3 µM), although the 5d and 5e derivatives showed lower activity. The interaction between 3a-d and calf thymus DNA was investigated by fluorimetric titration and the results showed a hyperchromic effect indicating binding to DNA as presented of ethidium bromide, used as positive control. The inhibitory action on DNA-topoisomerase II-a was also evaluated by a relaxation assay of supercoiled DNA plasmid, and the etoposide (200 µM) was used as positive control. Significant inhibitory activities were observed for 3a-d at 200 µM and a partial inhibitory action was observed for lapachol and methoxylapachol.

« Mémoires pour l'histoire des comtes de Toulouse et du Languedoc, de M. BESLY ». Ce titre, qui occupe le feuillet 1 du ms. 4920, ne correspond qu'à une partie des matières qui y sont contenues et dont la table (fol. 2) donne une idée plus exacte. Notre ms. est, en somme, un recueil de notes et de mémoires sur divers sujets, de la main de Jean Besly, jurisconsulte et historien, né en 1572, à Coulonges-les-Royaux, et mort en 1644 à Fontenay-le-Comte, en Poitou.

Contient : 1 « Advis sur l'histoire genealogique de la maison de France des Srs de Saincte Marthe, envoiez le 4 mars, l'an 1635 » ; 2 « Memoires des chanceliers de France » ; 3 « Annotations sur les Memoires de M. Jean Du Tillet » ; 4 « Observatio de Conradi Salicis, imperatoris, et Giselae, ejus uxoris cognatione » et « de Henrico IV, imperatore » ; 5 « Chronologie des règnes des rois de France des deux premières lignées » ; 6 « Collection de plusieurs extraicts d'histoires, chroniques et tiltres touchant le mariage du roi Philippe Ier avec Bertrade de Montfort, son divorce, et l'excommunication qu'il encourut pour ce faict » ; 7 « Philippe Auguste. Sur la dissolution du mariage du roy Philippes Auguste avec Ingeburge de Dannemark » ; 8 « Memoires pour le Bearn », savoir : a. « Memoires de la souveraineté de Bearn » (fol. 127 à 138); b. « Bearn, ou traicté du Bearn et des seigneurs qui en ont tenu le tiltre » (fol. 139 à 153); c. Les feuillets 144 et 145, 146 à 148, 152 et 153 contiennent trois brouillons de lettres sur le même sujet, et le second est daté du « 1er novembre 1620 »; d. « Memoire des vicomtes de Bearn » (fol. 154-159); e. « Memoire des vicomtes de Bearn » (fol. 160-5) ; f. « Force braves seigneurs » (fol. 166-9); g. « Memoires du Bearn » (fol. 170-8) ; 9 Foix ; 10 Suite des Mémoires concernant le Bearn, savoir : h. « Fors et costumas de Bearn » (fol. 180); i. « Extraict d'un gros inventaire du tresor des cartes de Bearn » (fol. 181); j. Vicomtes de Bearn (fol. 183-4) ; 11 Comtes de Toulouse, chronique en provençal : « Aiso es comtes que ag d'Azam entro al diluvi... Anno Domini MCC LXXV, iij die introitus mensis junii obiit nobilis vir dominus Sicardus Alamanni, cujus anima requiescat in pace » ; 12 Lettre signée : « Gaudineau » et adressée de « Luçon, le 24 may 1620... à M. l'advocat du roy et mayre, à Fontenay » ; 13 Factum contre « defuncte Jeh. de S. Martin, qui par son testament avait violé la coutume de Poitou » ; 14 Vicomtes de Bearn ; 15 « Project de l'origine de Hugues, roy d'Italie » ; 16 Poitou, Guyenne, Toulouse, ou histoire des comtes de Toulouse ; 17 Au feuillet 254 brouillon de lettre; au feuillet 255 dessins de sceaux : a. « S. Raimundi, Dei gra comitis Tolose, march. Provincie »; b. Autre figure, même légende. Dans a, le comte de Toulouse est représenté assis; dans b., il est représenté à cheval. Au feuillet 257 dessins de sceaux : a. « S. Alfonsus, fili. reg. Franc., comes Pict. et Tolose »; b. « S. R. Dalfini, comitis clr. ». Au feuillet 259 dessins de sceaux : a. Sigillum Ademari »; b. contresceau : « comitis Valemtinensis ». Au feuillet 261 dessins de sceaux : a. « S. comitis Provincie »; b. « Sigillum Raimundi Berengeri ». Au feuillet 262 dessins de sceaux : a. « S. comisse, uxoris Bereng., comitis et march. Provincie et comitis Forcalhari »; b. « Arma comitis a Sabaudie et marchis Italie » ; 18 « Mathildis comitissa » ; 19 Hugues, roi d'Italie, et Mathilde, la comtesse ; 20 Les mariages consanguins ; 21 Anthemius, etc., note adressée à l'év. de Poitiers, mise au net « le 16 fevrier 1640 » ; 22 « Regnante Christo », note sur cette formule ; 23 « Memoires pour Mr Du Chasteler-Barlot, contre les quatre tiltres qu'on luy oppose touchant la capitainerie de l'isle de Bouyn » ; 24 Lettre concernant les comtes d'Auvergne ; 25 Lettre ; 26 Lettre sur Chastelaillon et La Rochelle. Date : « A Fontenay le Comte, le 19 mars 1628 » ; 27 Lettre concernant Hugues Capet. Date : « A Paris, ce 7 mars 1633 ». Signé : « Besly » ; 28 « Galliae distributio » ; 29 Note sur la ville de « Vivonne » ; 30 Note sur Thouars et ses vicomtes ; 31 « De Melusine, dame de Lezignan » ; 32 « De S. Hilario Trevirensi » ; 33 Mémoire sur les comtes de Toulouse

The crystal and molecular structure of bis (pyridoxamine) copper (II) dinitrate monohydrate

The crystal structure of Cu(PM)2(N03hoH20 (where PM is pyridoxamine, CSHI2N202) has been determined from three dimensional x-ray diffraction data. The crystals are triclinic, space group pI, a = 14.248 (2), b = 8.568 (1), c = 9.319 (1) 1, a = 94.08 (1), e = 89.73 (1), y~~ 99.18 (1)°, z = 2, jl(MoK) = 10.90 em-I, Po = 1.61 g/cm3 and Pc = 1.61 g/em3• The structure a was solved by Patterson techniques from data collected on a Picker 4-circle diffractometer to 26max = 45°. All atoms, including hydrogens, have been located. Anisotropic thermal parameters have been refined for all nonhydrogen atoms. For the 2390 independent reflections with F ? 3cr(F) , R = 0.0408. The results presented here provide the first detailed structural information of a metal complex with PM itself. The copper atoms are located on centres of symmetry and each is chela ted by two PM zwitterions through the amino groups and phenolate oxygen atoms. The zwitterionic form found in this structure involves the loss of a proton from the phenolate group and protonation of the pyridine ring nitrogen atoms. The two independent Cu(PM)2 moieties are symmetrically bridged by a single oxygen atom from one of the nitrate groups. The second nitrate group is not coordinated to the copper atoms but is central to an extensive hydrogen bonding network involving the water molecule and uncoordinated functional groups of PM.

Bis-and tris (amidine) fluoroboron cations and related systems studies by Multinuclear NMR and fast atom bombardment mass spectometry

The formation and the isolation of fluoroboron salts, (D2BF2+)(PF6-), (DD'BF2+)(PF6-) and (D3BF2+)(PF6-)2, have been carried out. 1,8-Diazabicyclo [5,4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4,3,O]non-5-ene (DBN), extremely strong organic bases, were introduced into the fluoroboron cation systems and induced a complicated redistribution reaction in the D/BF3/BC13 systems. The result was the formation of all BFnCI4-n-, D.BFnCI3-n and fluoroboron cation species which were detected by 19p and 11B NMR spectrometry. The displacement reaction of CI- from these D.BFnCI3-n (n = 1 and 2) species by the second entering ligand is much faster than in other nitrogen donor containing systems which have been previously studied. Tetramethylguanidine, oxazolines and thiazolines can also produce similar reactions in D/BF3/BCI3 systems, but no significant BFnC4-n- species were observed. As well as influences of their basicity and their steric hindrance, N=C-R(X) (X = N, 0 or S) and N=C( X)2 (X = N or S) structures of ligands have significant effects on the fonnationof fluoroboron cations and the related NMR parameters. D3BF2+ and some D2BF2+ show the expected inertness, but (DBU)2BF2+ shows an interestingly high reactivity. (D2BF2+)(X-) formed from weak organic bases such as pyridine can react with stronger organic bases and form DD'BF2+ and D'2BF2+ in acetone or nitromethane. Fast atom bombardment mass spectrometry is doubly meaningful to this work. Firstly, FABMS can be directly applied to the complicated fluoroboron cation containing solution systems as an excellent complementary technique to multinuclear NMR. Secondly, the gas-phase ion substitution reaction of (D2BF2+)(PF6-) with the strong organic bases is successfully observed in a FABMS ion source when the B-N bond is not too strong in these cations.

Synthesis and utilization of guanidine catalysts for applications directed towards the preparation of butenolide and modified amino acid derivatives

Development of guanidine catalysts is explored through direct iminium chloride and amine coupling, alongside a 2-chloro-l,3-dimethyl-IH-imidazol-:-3-ium chloride (DMC) induced thiourea cyclization. Synthesized achiral catalyst N-(5Hdibenzo[ d,t][1,3]diazepin-6(7H)-ylidene)-3,5-bis(trifluoromethyl) aniline proved unsuccessful towards O-acyl migrations, however successfully catalyzed the vinylogous aldol reaction between dicbloro furanone and benzaldehyde. Incorporating chirality into the guanidine catalyst utilizing a (R)-phenylalaninol auxiliary, generating (R)-2-((5Hdibenzo[ d,t] [1,3 ]diazepin-6(7H)-ylidene ) amino )-3 -phenylpropan-l-ol, demonstrated enantioselectivity for a variety of adducts. Highest enantiomeric excess (ee) was afforded between dibromofuranone and p-chlorobenzaldehyde, affording the syn conformation in 96% ee and the anti in 54% ee, with an overall yield of30%. Attempts to increase asymmetric induction were focused on incorporation of axial chirality to the (R)phenylalaninol catalyst using binaphthyl diamine. Incorporation of (S)-binaphthyl exhibited destructive selectivity, whereas incorporation of (R)-binaphthyl demonstrated no effects on enantioselectivity. Current studies are being directed towards identifying the catalytic properties of asymmetric induction with further studies are being aimed towards increasing enantioselectivity by increasing backbone steric bulk.

Tetrathiafulvalene and 2,2'-Bipyridine: Bridging both Worlds in the Pursuit of Novel Molecular Materials

The preparation and characterization of two families of building blocks for molecule-based magnetic and conducting materials are described in three projects. In the first project the synthesis and characterization of three bis-imine ligands LI - L3 is reported. Coordination of LI to a series of metal salts afforded the five novel coordination complexes Sn(L4)C4 (I), [Mn(L4)(u-CI)(CI)(EtOH)h (II), [CU(L4)(u-sal) h(CI04)2 (sal = salicylaldehyde anion) (III), [Fe(Ls)2]CI (IV) and [Fe(LI)h(u-O) (V). All complexes have been structurally and magnetically characterized. X-ray diffraction studies revealed that, upon coordination to Lewis acidic metal salts, the imine bonds of LI are susceptible to nucleophilic attack. As a consequence, the coordination complexes (I) - (IV) contain either the cyclised ligand L4 or hydrolysed ligand Ls. In contrast, the dimeric Fe3+ complex (V) comprises two intact ligand LI molecules. In. this complex, the ligand chelates two Fe(III) centres in a bis-bidentate manner through the lone pairs of a phenoxy oxygen and an imine nitrogen atom. Magnetic studies of complexes (II-V) indicate that the dominant interactions between neighbouring metal centres in all of the complexes are antiferromagnetic. In the second project the synthesis and characterization two families of TTF donors, namely the cyano aryl compounds (VI) - (XI) and the his-aryl TTF derivatives (XII) - (XIV) are reported. The crystal structures of compounds (VI), (VII), (IX) and (XII) exhibit regular stacks comprising of neutral donors. The UV -Vis spectra of compounds (VI) - (XIV) present an leT band, indicative of the transfer of electron density from the TTF donors to the aryl acceptor molecules. Chemical oxidation of donors (VI), (VII), (IX) and (XII) with iodine afforded a series of CT salts that where possible have been characterized by single crystal X -ray diffraction. Structural studies showed that the radical cations in these salts are organized in stacks comprising of dimers of oxidized TTF donors. All four salts behave as semiconductors, displaying room temperature conductivities ranging from 1.852 x 10-7 to 9.620 X 10-3 Scm-I. A second series of CT salts were successfully prepared via the technique of electrocrystallization. Following this methodology, single crystals of two CT salts were obtained. The single crystal X-ray structures of both salts are isostructural, displaying stacks formed by trimers of oxidized donors. Variable temperature conductivity measurements carried out on this series of CT salts reveal they also are semiconductors with conductivities ranging from 2.94 x 10-7 to 1.960 X 10-3 S em-I at room temperature. In the third project the synthesis and characterization of a series of MII(hfac)2 coordination complexes of donor ligand (XII) where M2+ = Co2+, Cu2+, Ni2+ and Zn2+ are reported. These complexes crystallize in a head-to-tail arrangement of TTF donor and bipyridine moieties, placing the metal centres and hfac ligands are located outside the stacks. Magnetic studies of the complexes (XV) - (XVIII) indicate that the bulky hfac ligands prevent neighbouring metal centres from assembling in close proximity, and thus they are magnetically isolated.

La asistencia legal al testigo y su situación procesal en la averiguación previa (Análisis del artículo 127 Bis del Código Federal de Procedimientos Penales)

Tesis ( Maestría en Ciencias Penales) U.A.N.L.

La inconstitucionalidad del artículo 21 Bis-8 de la Ley de Hacienda para los Municipios del Estado de Nuevo León

Tesis (Maestría en Derecho Fiscal ) U.A.N.L.