Proposta metodológica para análise da ocorrência de sinergismo e efeitos potencializadores entre aleloquímicos

Os procedimentos envolvendo a análise de sinergismo entre aleloquímicos têm envolvido, basicamente, a utilização de concentrações fixas. Neste trabalho, propõe-se um modelo teórico envolvendo quatro possibilidades de respostas: uma que demonstra a existência de sinergismo (possibilidade A do modelo); outra que revela a inexistência de sinergismo (possibilidade B do modelo); e duas que revelam que uma substância potencializa o efeito de outra (possibilidades C e D do modelo). Para efeito de teste do modelo, utilizaram-se duas substâncias químicas (ácido 3,4,5-trimetoxibenzóico [S1] e ácido verátrico [S2]) isoladas das folhas de Parkia pendula, com atividade alelopática já comprovada, nas seguintes proporções: S1 pura, S2 pura e combinações de S1 e S2, nas seguintes proporções: 3:1, 1:1 e 1:3. Como plantas indicadoras foram utilizadas as plantas daninhas malícia (Mimosa pudica) e mata-pasto (Senna obtusifolia). Os resultados, analisados em relação às quatro possibilidades estabelecidas no modelo teórico, permitiram inferir a inexistência de efeitos sinérgicos entre as duas substâncias testadas. As variações entre os resultados obtidos e a possibilidade B do modelo podem ser atribuídas ao potencial inibitório da substância e à sensibilidade das espécies receptoras às substâncias testadas.

Avaliação do potencial biológico de plantas pertencentes ao cerrado brasileiro e seus compostos de interesse farmacológico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Substâncias químicas com atividades alelopáticas presentes nas folhas de Parkia pendula (Leguminosae)

Os objetivos deste trabalho foram isolar, identificar e caracterizar a atividade alelopática de substâncias químicas produzidas por Parkia pendula. Os efeitos alelopáticos foram avaliados sobre a germinação de sementes e o desenvolvimento da radícula das plantas daninhas malícia (Mimosa pudica) e mata-pasto (Senna obtusifolia). O processo de isolamento das substâncias envolveu a extração com solvente em ordem crescente de polaridade, e a elucidação estrutural foi realizada via Ressonância Magnética Nuclear, espectro de COSY e de HETCOR. Os bioensaios foram desenvolvidos em condições controladas de 25 ºC de temperatura e fotoperíodo de 12 (germinação) e 24 horas (desenvolvimento da radícula). Foram isolados e identificados nas folhas da P. pendula os seguintes aleloquímicos: ácido 3,4,5-trimetoxibenzóico (S1), ácido 3,4-dimetoxibenzóico (S2) e o Blumenol A (S3). Comparativamente, S1 e S2 apresentaram maior atividade alelopática. Os efeitos promovidos sobre o desenvolvimento da radícula foram de maior magnitude do que aqueles verificados sobre a germinação das sementes. As substâncias isoladas mostraram baixo potencial inibitório da germinação das sementes, especialmente as sementes de mata-pasto. Os efeitos alelopáticos inibitórios estiveram positivamente associados à concentração das substâncias, embora em alguns casos esses efeitos não tenham correspondido às diferenças estatísticas.

Dicroísmo circular vibracional e eletrônico na determinação da configuração absoluta de benzopiranos de Peperomia obtusifolia e Piper gaudichaudianum (Piperaceae): implicações biológicas e biossintéticas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Investigação biossintética, transcriptômica e proteômica em espécies de Piperaceae

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Abordagens biossintéticas em piper tuberculatum auxiliada pela síntese de precursores fenilpropanoídicos

Pós-graduação em Química - IQ

Investigação da origem biossintética de cromenos e cromanos em Piper aduncum e Peperomia obtusifolia (Piperaceae)

Pós-graduação em Química - IQ

Bioprospecção em espécies de Inga (Fabaceae Mimosoideae)

Pós-graduação em Química - IQ

Estudo químico dos escapos de Paepalanthus geniculatus Kunth

Eriocaulaceae species are popularly known as sempre-vivas. This family comprising approximately 1.200 species divided into 10 genera, with high endemic levels. Paepalanthus genus has high incidence in the Espinhaço Range region and the report of biological activities. Despite the large number of previous studies with Eriocaulaceae species, Paepalanthus geniculatus has no studies about their scapes, which demonstrates the need for new research to identify their chemical and biological composition. The aim of this work was to study the chemical composition of P. geniculatus ethanolic extract seeking the isolation and identification of metabolites and evaluate the radical scavenging activity of the extract and isolated substances. P. geniculatus were collected in Serra do Cipó-MG in 2013 (Voucher: SANO 3193) and the scapes were dried, crushed and the powder was percolated with ethanol. With the etanolic extract it is carried out a fractionation by gel permeation chromatography, yielding fractions analyzed by TLC assay. The fraction J89 (45,6 mg) was purified by semipreparative HPLC-PDA, resulting in the isolation of substance S1. The fractionation was also performed by medium pressure liquid chromatography, yielding fractions analyzed by TLC assay. The fraction number 4 (92,6 mg) were purified by semipreparative HPLC-PDA resulting in the isolation of substances S2 and S3. The substances S1 and S3 were analyzed by mono and twodimensional NMR, resulting in the identification of 3,4-dihydroxybenzoic acid (protocatechuic acid) and the flavonoid 6-hydroxyquercetin-7-O-β-Dglucopyranoside. The substance S2 were identified by comparison with standards, were it was possible to determine the presence of the flavonoid 6-hydroxy-7- methoxyquercetin-3-O-β-D-glucopyranoside. The evaluation of radical scavenging activity for the extract and the isolated substances using DPPH, showed consistent activity to S1...

Estudo químico dos escapos de Paepalanthus geniculatus Kunth

Eriocaulaceae species are popularly known as sempre-vivas. This family comprising approximately 1.200 species divided into 10 genera, with high endemic levels. Paepalanthus genus has high incidence in the Espinhaço Range region and the report of biological activities. Despite the large number of previous studies with Eriocaulaceae species, Paepalanthus geniculatus has no studies about their scapes, which demonstrates the need for new research to identify their chemical and biological composition. The aim of this work was to study the chemical composition of P. geniculatus ethanolic extract seeking the isolation and identification of metabolites and evaluate the radical scavenging activity of the extract and isolated substances. P. geniculatus were collected in Serra do Cipó-MG in 2013 (Voucher: SANO 3193) and the scapes were dried, crushed and the powder was percolated with ethanol. With the etanolic extract it is carried out a fractionation by gel permeation chromatography, yielding fractions analyzed by TLC assay. The fraction J89 (45,6 mg) was purified by semipreparative HPLC-PDA, resulting in the isolation of substance S1. The fractionation was also performed by medium pressure liquid chromatography, yielding fractions analyzed by TLC assay. The fraction number 4 (92,6 mg) were purified by semipreparative HPLC-PDA resulting in the isolation of substances S2 and S3. The substances S1 and S3 were analyzed by mono and twodimensional NMR, resulting in the identification of 3,4-dihydroxybenzoic acid (protocatechuic acid) and the flavonoid 6-hydroxyquercetin-7-O-β-Dglucopyranoside. The substance S2 were identified by comparison with standards, were it was possible to determine the presence of the flavonoid 6-hydroxy-7- methoxyquercetin-3-O-β-D-glucopyranoside. The evaluation of radical scavenging activity for the extract and the isolated substances using DPPH, showed consistent activity to S1...

Substâncias químicas com atividades alelopáticas presentes nas folhas de Parkia pendula (Leguminosae).

Os objetivos deste trabalho foram isolar, identificar e caracterizar a atividade alelopática de substâncias químicas produzidas por Parkia pendula. Os efeitos alelopáticos foram avaliados sobre a germinação de sementes e o desenvolvimento da radícula das plantas daninhas malícia (Mimosa pudica) e mata-pasto (Senna obtusifolia). O processo de isolamento das substâncias envolveu a extração com solvente em ordem crescente de polaridade, e a elucidação estrutural foi realizada via Ressonância Magnética Nuclear, espectro de COSY e de HETCOR. Os bioensaios foram desenvolvidos em condições controladas de 25 ºC de temperatura e fotoperíodo de 12 (germinação) e 24 horas (desenvolvimento da radícula). Foram isolados e identificados nas folhas da P. pendula os seguintes aleloquímicos: ácido 3,4,5-trimetoxibenzóico (S1), ácido 3,4-dimetoxibenzóico (S2) e o Blumenol A (S3). Comparativamente, S1 e S2 apresentaram maior atividade alelopática. Os efeitos promovidos sobre o desenvolvimento da radícula foram de maior magnitude do que aqueles verificados sobre a germinação das sementes. As substâncias isoladas mostraram baixo potencial inibitório da germinação das sementes, especialmente as sementes de mata-pasto. Os efeitos alelopáticos inibitórios estiveram positivamente associados à concentração das substâncias, embora em alguns casos esses efeitos não tenham correspondido às diferenças estatísticas.

Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl(2)(kappa(3)N(4),N(8),N(11)(1-carboxypropyl)cyclam)]Cl center dot H(2)O

Chemical reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam, fac-[Ru(NO)Cl(2)(kappa(3)N(4),N(8),N(11)(1-carboxypropyl)cyclam)]Cl center dot H(2)O ((1-carboxypropyl) cyclam = 3-(1,4,8,11-tetraazacyclotetradecan-1-yl) propionic acid)), (I) are described. Chloride ligands do not undergo aquation reactions (at 25 degrees C, pH 3). The rate of nitric oxide (NO) dissociation (k(obs-NO)) upon reduction of I is 2.8 s(-1) at 25 +/- 1 degrees C (in 0.5 mol L(-1) HCl), which is close to the highest value found for related complexes. The uncoordinated carboxyl of I has a pK(a) of similar to 3.3, which is close to that of the carboxyl of the non coordinated (1-carboxypropyl) cyclam (pK(a) = 3.4). Two additional pK(a) values were found for I at similar to 8.0 and similar to 11.5. Upon electrochemical reduction or under irradiation with light (lambda(irr) = 350 or 520 nm; pH 7.4), I releases NO in aqueous solution. The cyclam ring N bound to the carboxypropyl group is not coordinated, resulting in a fac configuration that affects the properties and chemical reactivities of I, especially as NO donor, compared with analogous trans complexes. Among the computational models tested, the B3LYP/ECP28MDF, cc-pVDZ resulted in smaller errors for the geometry of I. The computational data helped clarify the experimental acid-base equilibria and indicated the most favourable site for the second deprotonation, which follows that of the carboxyl group. Furthermore, it showed that by changing the pH it is possible to modulate the electron density of I with deprotonation. The calculated NO bond length and the Ru/NO charge ratio indicated that the predominant canonical structure is [Ru(III)NO], but the Ru-NO bond angles and bond index (b.i.) values were less clear; the angles suggested that [Ru(II)NO(+)] could contribute to the electronic structure of I and b.i. values indicated a contribution from [Ru(IV)NO(-)]. Considering that some experimental data are consistent with a [Ru(II)NO(+)] description, while others are in agreement with [Ru(III)NO], the best description for I would be a linear combination of the three canonical forms, with a higher weight for [Ru(II)NO(+)] and [Ru(III)NO].

Validity of (-)-[H-3]-CGP 12177A as a radioligand for the 'putative beta(4)-adrenoceptor' in rat atrium

1 We have recently suggested the existence in the heart of a 'putative beta(4)-adrenoceptor' based on the cardiostimulant effects of non-conventional partial agonists, compounds that cause cardiostimulant effects at greater concentrations than those required to block beta(1)- and Bz-adrenoceptors. We sought to obtain further evidence by establishing and validating a radioligand binding assay for this receptor with (-)-[H-3]-CGP 12177A ((-)-4-(3-tertiarybutylamino-2-hydroxypropoxy) benzimidazol-2-one) in rat atrium. We investigated (-)-[H-3]-CGP 12177A for this purpose for two reasons, because it is a nonconventional partial agonist and also because it is a hydrophilic radioligand. 2 Increasing concentrations of(-)-[H-3]-CGP 12177A, in the absence or presence of 20 mu M (-)-CGP 12177A to define non-specific binding, resulted in a biphasic saturation isotherm. Low concentrations bound to beta(1)- and beta(2)-adrenoceptors (pK(D) 9.4+/-0.1, B-max 26.9+/-3.1 fmol mg(-1) protein) and higher concentrations bound to the 'putative beta(4)-adrenoceptor' (pK(D) 7.5+/-0.1, B-max 47.7+/-4.9 fmol mg(-1) protein). In other experiments designed to exclude beta(1)- and beta(2)-adrenoceptors, (-)-[H-3]-CGP 12177A (1-200 nM) binding in the presence of 500 nM (-)-propranolol was also saturable (pK(D) 7.6+/-0.1, B-max 50.8+/-7.4 fmol mg(-1) protein). 3 The non-conventional partial agonists (-)-CGP 12177A (pK(i) 7.3+/-0.2), (+/-)-cyanopindolol (pK(i) 7.6+/-0.2), (-)-pindolol (pK(i) 6.6+/-0.1) and (+)-carazolol (pk(i), 7.2+/-0.2) and the antagonist (-)-bupranolol (pK(i) 6.6+/-0.2), all competed for (-)-[H-3]-CGP 12177A binding in the presence of 500 nM (-)-propranolol at the 'putative beta(4)-adrenoceptor', with affinities closely similar to potencies and affinities determined in organ bath studies. 4 The catecholamines competed with (-)-[H-3]-CGP 12177A at the 'putative beta(4)-adrenoceptor' in a stereoselective manner, (-)-noradrenaline (pK(iH) 6.3 +/- 0.3, pK(i), 3.5 +/- 0.1), (-)-adrenaline (pK(iH) 6.5 +/- 0.2, pK(iL) 2.9 +/- 0.1), (-)-isoprenaline (pK(iH) 6.2 +/- 0.5, pK(iL) 3.3 +/- 0.1), (+)-isoprenaline (pK(i) < 1.7), (-)-R0363 ((-)-(1-(3,4-dimethoxyphenethylamino)-3-(3,4-dihydroxyphenoxy)-2-propranol)oxalate, pK(i) 5.5 +/- 0.1). 5 The inclusion of guanosine 5-triphosphate (GTP 0.1 mM) had no effect on binding of (-)-CGP 12177A or (-)-isoprenaline to the 'putative beta(4)-adrenoceptor'. In competition binding studies, (-)-CGP 12177A competed with (-)-[H-3]-CGP 12177A for one receptor state in the absence (pK(i) 7.3 +/- 0.2) or presence of GTP (pK(i) 7.3 +/- 0.2). (-)-Isoprenaline competed with (-)-[H-3]-CGP 12177A for two states in the absence (pK(iH) 6.6 +/- 0.3, pK(iL) 3.5 +/- 0.1; % H 25 +/- 7) or presence of GTP (pK(iH) 6.2 +/- 0.5, pK(iL) 3.4 +/- 0.1; % H 37 +/- 6). In contrast, at beta(1)-adrenoceptors, GTP stabilized the low affinity state of the receptor for (-)-isoprenaline. 6 The specificity of binding to the 'putative beta(4)-adrenoceptor' was tested with compounds active at other receptors. High concentrations of the beta(4)-adrenoceptor agonists, BRL 37344 ((RR + SS)[4-[2-[[2-(3-chlorophenyl)-2-hydroxy -ethyl]amino]propyl]phenoxy]acetic acid, 6 mu M), SR 58611A (ethyl((7S)-7-[(2R)-2-(3-chlorophenyl)-2-hydroxyethylamino]-5,6,7,8-tetrahydronaphtyl-2-yloxy) acetate hydrochloride, 6 mu M), ZD 2079 ((+/-)-1-phenyl-2-(2-4-carboxymethylphenoxy)-ethylamino)ethan-1-ol, 60 mu M), CL 316243 (disodium (R,R)-5-[2-[2-(3-chlorophenyl)-2-hydroxyethyl-amino]propyl]- 1,3-benzodioxole-2,2-dicarboxylate, 60 mu M) and antagonist SR 59230A (3-(2-ethylphenoxy)-1-[(1S)-1,2,3,4-tetrahydronaphth-1-ylamino]-2S-2-propanol oxalate, 6 mu M) caused less than 22% inhibition of (-)-[H-3]-CGP 12177A binding in the presence of 500 nM (-)-propranolol. Histamine (1 mM), atropine (1 mu M), phentolamine (10 mu M), 5-HT(100 mu M) and the 5-HT4 receptor antagonist SE 207710 ((1-butyl-4-piperidinyl)-methyl 8-amino-7-iodo-1 ,4-benzodioxan-5-carboxylate, 10 nM) caused less than 26% inhibition of binding. 7 Non-conventional partial agonists, the antagonist (-)-bupranolol and catecholamines all competed for (-)-[H-3]-CGP 12177A binding in the absence of (-)-propranolol at beta(1)-adrenoceptors, with affinities (pK(i)) ranging from 1.6-3.6 log orders greater than at the 'putative beta(4)-adrenoceptor'. 8 We have established and validated a radioligand binding assay in rat atrium for the 'putative beta(4)-adrenoceptor' which is distinct from beta(1)-, beta(2)- and beta(3)-adrenoceptors. The stereoselective interaction with the catecholamines provides further support for the classification of the receptor as 'putative beta(4)-adrenoceptor'.

Nickel complexes with tris(2-aminoethyl)amine (tren): [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2)center dot 6H(2)O (ox = oxalate), {[Ni-2(tren)(3)][ClO4](4)center dot H2O}(n), and [Ni-2(tren)(2)(aepd)][ClO4](4)center dot 2H(2)O (aepd = N-(2-aminoethyl)pyrrolidi

Reaction of K-3[Cr(ox)(3)] (ox = oxalate) with nickel(II) and tris(2-aminoethyl)amine (tren) in aqueous solution resulted in isolation of the bimetallic assembly [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2). 6H(2)O. The polymeric complex {[Ni-2(tren)(3)][ClO4](4). H2O}(n) has been prepared by reaction of nickel(II) perchlorate and tren in aqueous solution. From the same reaction mixture the complex [Ni-2(tren)(2)(aepd)][ClO4](4). 2H(2)O (aepd = N-(2-aminoethyl)pyrrolidine-3,4-diamine), in which a bridging tren ligand contains a carbon-carbon bond between two arms forming a substituted pyrrolidine, has been isolated. The complexes have been characterized by X-ray crystallography. The magnetic susceptibility (300-4.2 K) and magnetization data (2, 4 K, H = 0-5 T) for {[Ni-2(tren)(3)][ClO4](4). H2O}(n) (300 K , 4.23 mu(B)) exhibit evidence of weak antiferromagnetic coupling and zero field splitting (2J = -1.8 cm(-1); \ D\ = 2 cm(-1)) at low temperature. For [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2). 6H(2)O the susceptibility data at 300 K are indicative of uncoupled nickel(II) and chromium(III) sites with zero-field splitting and intramolecular antiferromagnetic coupling predicted at low temperature.

Trends in properties of para-substituted 3-(phenylhydrazo)pentane-2,4-diones

Trends between the Hammett's sigma(p) and related normal sigma(n)(p), inductive sigma(I), resonance sigma(R), negative sigma(-)(p) and positive sigma(+)(p) polar conjugation and Taft's sigma(o)(p) substituent constants and the N-H center dot center dot center dot O distance, delta(N-H) NMR chemical shift, oxidation potential (E-p/2(ox), measured in this study by cyclic voltammetry (CV)) and thermodynamic parameters (pK, Delta G(0), Delta H-0 and Delta S-0) of the dissociation process of unsubstituted 3-(phenylhydrazo)pentane-2,4-dione (HL1) and its para-substituted chloro (HL2), carboxy (HL3), fluoro (HL4) and nitro (HL5) derivatives were recognized. The best fits were found for sigma(p) and/or sigma(-)(p) in the cases of d(N center dot center dot center dot O), delta(N-H) and E-p/2(ox), showing the importance of resonance and conjugation effects in such properties, whereas for the above thermodynamic properties the inductive effects (sigma(I)) are dominant. HL2 exists in the hydrazo form in DMSO solution and in the solid state and contains an intramolecular H-bond with the N center dot center dot center dot O distance of 2.588(3)angstrom. It was also established that the dissociation process of HL1-5 is non-spontaneous, endothermic and entropically unfavourable, and that the increase in the inductive effect (sigma(I)) of para-substitutents (-H < -Cl < -COOH < -F < -NO2) leads to the corresponding growth of the N center dot center dot center dot O distance and decrease of the pK and of the changes of Gibbs free energy, of enthalpy and of entropy for the HL1-5 acid dissociation process. The electrochemical behaviour of HL1-5 was interpreted using theoretical calculations at the DFT/HF hybrid level, namely in terms of HOMO and LUMO compositions, and of reactivities induced by anodic and cathodic electron-transfers. Copyright (C) 2010 John Wiley & Sons, Ltd.