A series of 2-amino-1,4-naphthoquinone derivatives (NQA-NQF) was synthesized by alternative methods (ultrasonication and microwave irradiation), with yields ranging from 40 to 71%, and without the need of further recrystallization. Each compound was evaluated against four Gram-positive (Bacillus subtilis, Enterococcus faecalis, Staphylococcus aureus and Bacillus cereus) and five Gram-negative (Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Acinetobacter baumannii and Klebsiella pneumoniae positive β-lactamase) bacteria strains. The NQF was the most active amino-naphthoquinone derivative with minimum inhibitory concentration (MIC) of 31.2 µg mL-1 against K. pneumoniae positive β-lactamase (a common intestinal bacteria which can cause life-threatening infections). On the other hand, NQA and NQC showed good activity as a potential antibiotic for the bacteria strains assayed, except for K. pneumoniae. In addition, the affinity of these three most active compounds (NQA, NQC, and NQF) for human serum albumin (HSA) was evaluated employing multiple spectroscopic techniques (steady-state, time-resolved, and synchronous fluorescence, as well as circular dichroism), combined with theoretical calculations (molecular docking). The interaction HSA:2-amino-1,4-naphthoquinones occurs spontaneously and moderately inside the subdomain IIA (Sudlow’s site I) via hydrogen bonding and van der Waals forces.

RESUMO: Bovinos e equinos são os animais domésticos com maior incidência de raiva no Brasil. Este estudo avaliou formulários de solicitação de testes para raiva em herbívoros acompanhando amostras enviadas a um laboratório certificado de diagnóstico de raiva no estado do Rio Grande do Sul, Brasil. As informações foram obtidas sistematicamente de todos os formulários enviados ao laboratório em 2013 e 2014 utilizando um instrumento de coleta que selecionou variáveis sobre o tipo de formulário utilizado, município de origem, descrição do animal suspeito, sinais clínicos, coleta de amostra e procedimento de conservação. As 11 variáveis mais relevantes (município de origem, coordenadas geográficas, espécie, gênero, raça, idade, tamanho do rebanho, sinais clínicos, persistência de sinais clínicos, material biológico e conservação da amostra) foram avaliadas quanto à qualidade dos dados inseridos, e os dados percentuais foram calculados por formulário. No total, 603 formulários foram enviados para o laboratório. O formulário mais utilizado foi o FORM SN, (82,0%, 497/603). Dados classificados como “excelentes” e “bons” foram observados apenas para uma variável que descreve a localização de casos suspeitos de raiva ou surtos e animais (espécie, gênero, material biológico). A qualidade da entrada dos dados das variáveis que descrevem coordenadas geográficas, idade, raça, tamanho do rebanho, sinais clínicos, persistência de sinais e método de conservação da amostra variou entre “regular” e “ruim”. A qualidade dos dados dos formulários de solicitação de testes para herbívoros não foi devidamente fornecida em casos suspeitos de síndromes neurológicas, apontando para a necessidade de aumentar a conscientização e melhorar o treinamento do pessoal de campo.

ABSTRACT: Bovines and equines are the domestic animals with the highest incidence of rabies in Brazil. This study evaluated the data input in testing request forms for rabies in herbivores accompanying samples sent to a certified laboratory of rabies diagnosis in the state of Rio Grande do Sul, Brazil. Information was obtained systematically from all forms sent to the laboratory in 2013 and 2014 using a collection instrument that listed variables about the kind of form used, municipality of origin, description of the suspected animal, clinical signs, sample collection, and conservation procedure. The 11 most relevant variables (municipality of origin, geographic coordinates, species, gender, breed, age, herd size, clinical signs, persistence of clinical signs, biological material, and sample conservation) were assessed for the quality of the data entered, and percentage data input was calculated per form. In total, 603 forms were sent to the laboratory. The most used form was the FORM SN, (82.0%, 497/603). “Excellent” and “good” data inputs were observed only for one variable describing the location of suspected rabies cases or outbreaks and animals (species, gender, biological material). Quality of data input of variables describing geographic coordinates, age, breed, herd size, clinical signs, persistence of signs, and sample conservation method varied between “average” and “poor”. The data input in testing request forms for herbivores are not dully supplied in suspected cases neurological syndromes, pointing to the need to increase awareness and improve training of field staff.

The interaction between four antiparasitic drugs (benznidazole (BZL), metronidazole (MTZ), nifurtimox (NFX) and megazol (MZ)) with human serum albumin (HSA), the main vehicle of biodistribution of xenobiotics, hydrophobic, small and endogenous molecules in the bloodstream, was evaluated by multiple spectroscopic techniques and theoretical calculations. In all cases quenching of the fluorescence of HSA by these drugs involve a static mechanism, due to ground state association. There is just one main binding site in HSA for these four ligands (Sudlow’s site I); binding is spontaneous, moderate, does not have any effect on the polarity around the Tyr and Trp residues and does not perturb significantly the secondary structure of the protein. Molecular docking studies suggest hydrogen bonding and hydrophobic interactions as the main binding forces, i.e., BZL associates with the Trp-214 residue via hydrophobic interactions and with Gln-220, Arg-221 and Glu-449 residues via hydrogen bonding; whereas MTZ associates with Leu-197 and Leu-480 residues via hydrophobic interactions and with Trp-214, Glu-449 and Ser-453 via hydrogen bonding. Furthermore, electrostatic interactions were also suggested for HSA:MZ and HSA:NFX.

Binding between bovine serum albumin (BSA) and a plumeran indole alkaloid (PIA) isolated from the stem bark of Aspidosperma cylindrocarpon (Apocynaceae) was studied by spectroscopic techniques (UV-Vis absorption, circular dichroism, steady state and time-resolved fluorescence), combined with molecular docking. Steady state and time resolved fluorescence data revealed that PIA can quench the BSA fluorescence via a static mechanism: energy transfer from BSA to PIA occurs with high probability. The binding is strong (Kb ca. 105-106 L mol-1), spontaneous (ΔG° ca. -35.7 kJ mol-1 at 310 K) and entropy-driven (ΔS° = 0.146 kJ mol-1 K-1). There is just one main binding site (n ca. 1) for the BSA:PIA interaction and the α-helix content of the albumin does not suffer significant perturbation upon PIA binding. Molecular docking results suggest site I as the main binding site to PIA, which is able to interact with the Trp-212, Arg-217, Val-342 and Pro-446 residues.

The interaction between 19-nor-clerodane trans-dehydrocrotonin (from Croton cajucara Benth.) and bovine serum albumin was studied, applying spectroscopic techniques (fluorescence and circular dichroism), combined with molecular modeling. Fluorescence quenching of albumin by the nor-clerodane (kq ca. 1011 mol L-1 s-1 and Stern-Volmer, KSV, increase with temperature) indicates a combination of static and dynamic quenching mechanism. The binding constant (Kb ca. 103 mol L-1) and circular dichroism data suggest that this association is weak and causes only a moderate change in the α-helix content of the protein. Thermodynamic parameters indicate a spontaneous (Gibbs free energy, ΔGº, ca. -21.28 kJ mol-1 at 310 K) and probably entropy-driven (ΔSº = 0.072 kJ mol-1 K-1) association, typical of hydrophobic interactions. The number of binding sites (n ca. 1) indicates one main binding site and molecular modeling suggests subdomain IIIA (Sudlow's site II) as the main binding site to the nor-clerodane, which is able to make hydrophobic interactions with leucine (Leu)-24, phenylalanine (Phe)-36, valine (Val)-40 and tryptophan (Trp)-134 residues.

Ethyl- and n- propylbenzene peroxidation has been studied in the presence of supported gold nanoparticles on TiO2(AuNP@TiO2). The decomposition products obtained from Fenton-induced cumene hydroperoxide decomposition, as well as the oxidation products of ethyl- and n- propylbenzene, implicate the participation of reactive oxygen species adsorbed on the AuNP surface. This surface intermediate is believed to be a fundamental participant in hydrogen abstraction reactions required to facilitate the formation of the observed carbonyl derived product.

The triplet excited state of xanthone was generated and characterized by laser flash photolysis in acetonitrile (λmax=620 nm; t=1.8 ms) and in ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [bmim.PF6] (λmax=620 nm; t=3.0 ms). It reacts with phenols yielding the corresponding xanthone ketyl radical. Stern-Volmer plots for the reaction of triplet xanthone with phenols led to the determination of absolute rate constants for phenolic hydrogen abstraction in the order of ~10(9) Lmol-1s-1 in acetonitrile and ~10(8) Lmol-1s-1 in [bmim.PF6]. The lower diffusioncontrolled rate constant for [bmim.PF6] is responsible for the difference in the phenolic hydrogen abstraction rate constants in this solvent.

Foi estudada a degradação fotooxidativa de QTX (cloreto de 2-hidroxi-3-(3,4-dimetil-9-oxo-9H-tioxanton-2-iloxi)-N,N,N-trimetil-1-propano) em solução aquosa. Os produtos resultantes foram caracterizados por HPLC/ESI-MS e a fotodegradação do corante foi acompanhada por espectroscopia de absorção. O corante apresenta duas bandas em 273 e 402 nm, que decrescem durante a irradiação, enquanto que aparece uma banda na região de 310-350 nm, típica do QTX oxidado. Novos picos devidos aos fotoprodutos da degradação de QTX foram observados por cromatografia e identificados por espectrometria de massa. Os picos em m/z 388, 420 e 270 correspondem a fotoprodutos, e o de m/z 372 é atribuído ao QTX. O pico de m/z 388 corresponde à formação de um grupo sulfóxido e o de m/z 420 sugere a formação de uma sulfona com uma hidroxila no grupo metila. O pico de m/z 270 sugere que o oxigênio reage com QTX abstraindo um hidrogênio do carbono ligado à hidroxila, simultaneamente à eliminação de um grupo amino.

The photooxidative degradation of QTX (2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanium chloride) has been investigated and photoproducts from QTX degradation in aqueous solution were characterized using HPLC/ESI-MS. The photooxidation of the dye was monitored by electronic absorption spectroscopy. The spectrum of the dye shows bands at 273 and 402 nm. During irradiation, the intensity of these bands decreases together with the appearance of a band at 310-340 nm, typical of oxidized QTX. The chromatograms show the presence of new peaks due to photoproducts of QTX degradation that were identified by mass spectroscopy. The peaks at m/z 388, 420 and 270 were attributed to photoproducts, whereas the peak at m/z 372 is due to QTX. The peak at m/z 388 corresponds to the formation of a sulfoxide group and that at m/z 420 suggested the formation of a sulfone with a hydroxyl on the methyl group. The peak at m/z 270 suggests that oxygen reacts with QTX abstracting a hydrogen atom from the carbon bonded the hydroxyl, together with the release of the amino group.

O estado excitado triplete de cetonas pode oxidar substratos biológicos acarretando danos a diversas biomoléculas como aminoácidos, nucleosídeos e mesmo DNA. Como parte de nossos estudos acerca da interação entre carbonilas e fenóis, foi investigada a reatividade do estado excitado triplete de tiocromanona (1) frente a fenóis, em acetonitrila, empregando a técnica de fotólise por pulso de laser de nanossegundo. As constantes de velocidade de supressão obtidas variaram de (1,1 ± 0,1) × 10(8) L mol-1 s-1 (4-cianofenol) a (5,8 ± 1,0) × 10(9) L mol-1 s-1 (hidroquinona). Um gráfico de Hammett para a reação do triplete de 1 com uma série de fenóis contendo substituintes polares resultou em uma constante de reação ρ = -0,90. Este valor negativo para a constante de reação ρ está plenamente de acordo com um mecanismo envolvendo uma transferência acoplada elétron/próton no processo de transferência de hidrogênio do fenol para a carbonila triplete.

Triplet ketones are known to oxidize biological substrates which can lead to damage of several biomolecules such as amino acids, nucleosides and DNA. As part of our systematic study on the interaction between carbonyl compounds and phenols, the triplet reactivity of thiochromanone (1) towards substituted phenols, in acetonitrile, was investigated employing the laser flash photolysis technique. The quenching rate constants ranged from (1.1 ± 0.1) × 10(8) L mol-1 s-1 (4-cyanophenol) to (5.8 ± 1.0) × 10(9) L mol-1 s-1 (hydroquinone). A Hammett plot for the reaction of triplet 1 with phenols containing polar substituents resulted in a reaction constant ρ = -0.90. This negative value observed for the reaction constant ρ is in accord with a mechanism in which the hydrogen transfer from phenols to the triplet carbonyl involves a coupled electron/proton transfer.

A fotorreatividade do estado excitado triplete de tioxantona (TX) foi investigada empregando a técnica de fotólise por pulso de laser. O máximo do comprimento de onda de absorção e o tempo de vida para o seu estado excitado triplete são dependetes do solvente. Quando foram utilizados solventes doadores de hidrogênio, foi observado o surgimento de uma nova banda no espectro de absorção para os transientes, com máximo a 410 nm, a qual foi atribuída ao radical cetila derivado da tioxantona. As constantes de velocidade de supressão para o triplete de tioxantona, k q, variaram de (1,7 ± 0,1) × 10(6) L mol-1 s-1 para tolueno a ca. 10(9) L mol-1 s-1 para fenol e seus derivados contendo substituintes poleres, bem como para indol, trietilamina e DABCO.

The photoreactivity of the triplet excited state of thioxanthone (TX) was investigated employing the laser flash photolysis technique. The wavelength for the absorption maximum and the lifetime of the triplet excited state are solvent dependent. When hydrogen donor solvents were employed, a new band at 410 nm was observed in the triplet absorption spectrum, which was attributed to the ketyl radical derived from thioxantone. Quenching rate constants, k q, ranged from (1.7 ± 0.1) × 10(6) L mol-1 s-1 for toluene to ca. 10(9) L mol-1 s-1 for phenol and its derivatives containing polar substituents, as well as for indole, triethylamine and DABCO.

Objetivou-se, neste trabalho, avaliar o efeito de três temperaturas (5ºC, 8ºC e 11ºC), na qualidade de híbridos de milho verde (Zea maiz L.) com endosperma normal, minimamente processado, durante oito dias de armazenamento, com avaliações a cada dois dias. Foram utilizadas espigas de dois híbridos, sendo um comercial da Sementes Agroceres (Ag 1051) e outro do programa de melhoramento da Embrapa Milho e Sorgo (Embrapa HT1). A temperatura de 5ºC foi a que melhor preservou a qualidade das espigas dos híbridos de milho verde estudados, por proporcionar perda de massa reduzida e manutenção dos teores de sólidos solúveis, frutose e glicose. O híbrido Ag 1051 apresentou menor perda de massa, maiores valores de umidade e maior teor de frutose. O Embrapa HT1 apresentou maiores valores iniciais e finais para os teores de sólidos solúveis e maior valor para a coloração b*. O valor L*, que indica quãoclaro e escuro é produto, também diminuiu ao longo do armazenamento, indicando escurecimento das espigas ao longo do armazenamento.

This work had the aim of evaluating the effect of three temperatures (5ºC, 8ºC and 11ºC) on the quality of fresh-cut corn on the cob (Zea maiz L.) with normal endosperm, for 8 days, with analyses taken every two days. Corn on the cob of two hybrids was used, a commercial common type from Sementes Agroceres (Ag 1051) and the other from the breeding program Embrapa Milho e Sorgo (Embrapa HT1). The temperature of 5ºC was more efficient to preserve the quality of normal corn by promoting reduced mass loss and higher contents of soluble solids, fructose and glucose. The hybrid Ag 1051 presented lower mass loss, higher contents of moisture and higher content of fructose. The hybrid Embrapa HT1 presented higher initial and final values for soluble solids and higher b* value. The L* value also decreased along storage, indicating browning of the corns along the storage.

The spectroscopic behavior of thioxanthone and benzil (diphenylethanedione or dibenzoyl) in the ionic liquid [bmim.PF6] has been investigated employing the laser flash photolysis technique. Triplet-triplet absorption spectra for these carbonyl compounds in [bmim.PF6] are similar to those observed in organic solvents. The triplet lifetime for thioxanthone in desogygenated samples is very long (71 μs), whereas in oxygen-saturated solution is 500 ns, which indicates the low oxygen solubility in this solvent. For benzil, lifetimes of 10 μs in [bmim.PF6] and 3.8 μs in acetonitrile were obtained. The decay for triplet thioxanthone and benzil follows a clear first order kinetics in [bmim.PF6], from which one can conclude that triplet-triplet annihilation is not an important decay process in this solvent.

The effect of the introduction of nitrogen atoms upon the triplet excited state reactivity of 1,4-diaza-9-fluorenone (1) and 1,4-diaza-9-benz[b]fluorenone (2), in acetonitrile, was investigated employing the nanosecond laser flash photolysis technique. The intersystem crossing quantum yield (Φces) for 1 and 2 was determined using 9-fluorenone as a secondary standard (Φces= 0.48, in acetonitrile) and for both diazafluorenones a value of Φces= 0.28 was found. Quenching rate constants ranged from 8.17x10(4) L mol-1 s-1 (2-propanol) to 1.02x10(10) L mol-1 s-1 (DABCO) for 1,4-diaza-9-fluorenone and from 6.95x10(5) L mol-1 s-1 (2-propanol) to 5.94x10(9) L mol-1 s-1 (DABCO) for 1,4-diaza-9-benz[b]fluorenone, depending if the quenching process involves energy, hydrogen or electron transfer. A comparison between quenching rate constants for both diazaflurenones and the parent compound, i.e. 9-fluorenone, a ketone with lowest triple state of ππ* configuration, lead to the conclusion that the reactive triplet excited state for 1,4-diaza-9-fluorenone and 1,4-diaza-9-benz[b]fluorenone has ππ* configuration.

Rate constants for the quenching of 1,3-indandione (1) triplet by olefins and by hydrogen and electron donors were obtained employing the laser flash photolysis technique in benzene solution. These rate constants ranged from 2.5x10(5) Lmol-1s-1 (for 2-propanol) to 5.9x10(9) Lmol-1s-1 (for DABCO). From the quenching rate constants by 1,3-cyclohexadiene, trans- and cis-stilbene a value between 49.3 and 52.4 kcal/mol was estimated for the energy of the triplet state of 1,3-indandione. The npi* character of this triplet state was evidenced by the quenching rate constants obtained when typical hydrogen donors were employed as quenchers. For 2-phenyl-1,3-indandione (2, R=phenyl) a fast Norrish type I reaction is operating which prevents the determination of kinetic and spectroscopic data of its triplet state.