RESUMEN
The effects of the novel [CuL2]Br2 complex (L = bis{4H-1,3,5-triazino [2,1-b]benzothiazole-2-amine,4-(2-imidazole)}copper(II) bromide complex) on the photosystem II (PSII) activity of PSII membranes isolated from spinach were studied. The absence of photosynthetic oxygen evolution by PSII membranes without artificial electron acceptors, but in the presence of [CuL2]Br2, has shown that it is not able to act as a PSII electron acceptor. In the presence of artificial electron acceptors, [CuL2]Br2 inhibits photosynthetic oxygen evolution. [CuL2]Br2 also suppresses the photoinduced changes of the PSII chlorophyll fluorescence yield (FV) related to the photoreduction of the primary quinone electron acceptor, QA. The inhibition of both characteristic PSII reactions depends on [CuL2]Br2 concentration. At all studied concentrations of [CuL2]Br2, the decrease in the FM level occurs exclusively due to a decrease in Fv. [CuL2]Br2 causes neither changes in the F0 level nor the retardation of the photoinduced rise in FM, which characterizes the efficiency of the electron supply from the donor-side components to QA through the PSII reaction center (RC). Artificial electron donors (sodium ascorbate, DPC, Mn2+) do not cancel the inhibitory effect of [CuL2]Br2. The dependences of the inhibitory efficiency of the studied reactions of PSII on [CuL2]Br2 complex concentration practically coincide. The inhibition constant Ki is about 16 µM, and logKi is 4.8. As [CuL2]Br2 does not change the aromatic amino acids' intrinsic fluorescence of the PSII protein components, it can be proposed that [CuL2]Br2 has no significant effect on the native state of PSII proteins. The results obtained in the present study are compared to the literature data concerning the inhibitory effects of PSII Cu(II) aqua ions and Cu(II)-organic complexes.
Asunto(s)
Complejo de Proteína del Fotosistema II , Spinacia oleracea , Clorofila/metabolismo , Transporte de Electrón , Oxígeno/metabolismo , Complejo de Proteína del Fotosistema II/metabolismo , Spinacia oleracea/metabolismoRESUMEN
In this study, the comparative effect of TeA, DCMU, bentazone, DBMIB and MV on prompt fluorescence and the MR820 signal was simultaneously analyzed to provide an insight into how to elucidate their precise influence on Ageratina adenophora photosystems. The herbicides that interrupt electron transport beyond QA, such as TeA, DCMU and bentazone, mainly increased the J-step level of fluorescence rise kinetics as a result of accumulation of QA-, but showed differences in detail. The IP phase disappeared in the presence of DCMU and bentazone with a significant increase in FO value. TeA treatment retained the IP phase with lowering FM. As an inhibitor of plastoquinone re-oxidation, DBMIB increased the I-step (IP phase almost unnoticable) without changing FO and FM values. MV blocking PSI electron transfer through intercepting electrons from the FeS clusters suppressed the IP phase by decreasing the P level. Considering the WIP kinetics, TeA and DBMIB also affected PSI activity. After DCMU and MV treatment, the major change in the MR820 kinetics was the loss of the slow phase due to the complete prevention of electron movement from PSII to re-reduce PC+ and P700+. TeA, bentazone and DBMIB clearly suppressed the MR820 slow phase and decreased the re-reduction rate of PC+ and P700+ (Vred), significantly. However, there were still parts of electrons being donated to PC+ and P700+, showing a smaller slow phase and PC+ and P700+ re-reduction rate. Additionally, TeA and DBMIB also somewhat declined the fast phase and PC and P700 oxidation rate (Vox).
Asunto(s)
Ageratina/efectos de los fármacos , Clorofila A/química , Herbicidas/farmacología , Benzotiadiazinas/farmacología , Dibromotimoquinona/farmacología , Diurona/farmacología , Transporte de Electrón , Fluorescencia , Cinética , Oxidación-Reducción , Paraquat/farmacología , Ácido Tenuazónico/farmacologíaRESUMEN
Increasing inefficiency of production of important agricultural plants raises one of the biggest problems in the modern world. Herbicide application is still the best method of weed management. Traditional herbicides blocking only one of the plant metabolic pathways is ineffective due to the rapid growth of herbicide-resistant weeds. The synthesis of novel compounds effectively suppressing several metabolic processes, and therefore achieving the synergism effect would serve as the alternative approach to weed problem. For this reason, recently, we synthesized a series of nine novel Cu(II) complexes and four ligands, characterized them with different analyses techniques, and carried out their primary evaluation as inhibitors of photosynthetic electron transfer in spinach thylakoids (design, synthesis, and evaluation of a series of Cu(II) based metal-organic complexes as possible inhibitors of photosynthesis, J Photochem Photobiol B, submitted). Here, we evaluated in vitro inhibitory potency of these agents against: photochemistry and carbonic anhydrase activity of photosystem II (PSII); α-carbonic anhydrase from bovine erythrocytes; as well as glutathione reductase from chloroplast and baker's yeast. Our results show that all Cu(II) complexes excellently inhibit glutathione reductase and PSII carbonic anhydrase activity. Some of them also decently inhibit PSII photosynthetic activity.
Asunto(s)
Inhibidores de Anhidrasa Carbónica/farmacología , Anhidrasas Carbónicas/metabolismo , Complejos de Coordinación/farmacología , Cobre/farmacología , Glutatión Reductasa/antagonistas & inhibidores , Fotosíntesis/efectos de los fármacos , Complejo de Proteína del Fotosistema II/metabolismo , Animales , Biocatálisis/efectos de los fármacos , Dióxido de Carbono/metabolismo , Bovinos , Cloroplastos/efectos de los fármacos , Cloroplastos/metabolismo , Eritrocitos/efectos de los fármacos , Eritrocitos/metabolismo , Glutatión Reductasa/metabolismo , Concentración de Iones de Hidrógeno , Concentración 50 Inhibidora , Cinética , Ligandos , Oxidación-Reducción , Relación Estructura-Actividad Cuantitativa , Saccharomyces cerevisiae/metabolismo , Spinacia oleracea/metabolismo , Factores de TiempoRESUMEN
Although quinones present a large array of biological activities, a few studies on the herbicidal potential of 2,5-bis(alkyl/arylamino)-1,4-benzoquinones have been reported to date. In this work, starting from benzoquinone, 13 2,5-bis(alkyl/arylamino)-1,4-benzoquinones were prepared in 46 - 93% yield. The products were fully characterized by spectroscopic analyses and their phytotoxicity against Cucumis sativus and Sorghum bicolor seedlings was investigated. At 100 ppm, compounds caused 10 - 88% growth inhibition of the dicotyledonous species, whereas the monocotyledon was less affected. Most compounds exerted little inhibitory effect on a cyanobacterial model strain. However, at 100 µm, compounds 8 - 10 caused about 50% inhibition of algal growth, and compounds 1 and 2 reduced cell viability in the 1 - 10 µm range. The ability of benzoquinone derivatives to interfere with the light-driven ferricyanide reduction by isolated spinach chloroplasts was evaluated. Some substances showed a moderate effect as uncouplers, but no relationship was found between this property and their biological activity, indicating that the herbicidal effect is not associated with the inhibition of the photosynthetic electron transport chain. Phytotoxic compounds were not toxic to insects, strengthening the possibility that they may serve as lead for the development of eco-friendly herbicides.
Asunto(s)
Aminas/química , Benzoquinonas/farmacología , Cucumis sativus/efectos de los fármacos , Herbicidas/farmacología , Sorghum/efectos de los fármacos , Animales , Benzoquinonas/síntesis química , Benzoquinonas/química , Cucumis sativus/crecimiento & desarrollo , Relación Dosis-Respuesta a Droga , Herbicidas/síntesis química , Herbicidas/química , Insectos/efectos de los fármacos , Estructura Molecular , Sorghum/crecimiento & desarrolloRESUMEN
Natural phytotoxins and their synthetic analogs are a potential source of new bioactive compounds for agriculture. Analogs of rubrolides, a class of γ-alkylidene-γ-lactones isolated from different ascidians, have been shown to interfere with the photosynthetic electron-transport chain, yet their activity needs to be improved. With this aim, ten 5-aryl-6-benzyl-4-bromopyridazin-3(2H)-ones were prepared in yields ranging from 44 to 88% by reaction of their correspondent γ-alkylidene-γ-lactones with NH2 NH2 . The structures of these rubrolide analogs were determined by (1) H- and (13) C-NMR, 2D-NMR (COSY and HETCOR), NOE difference, and MS techniques. These compounds were evaluated for their abilities of interfering with the light-driven reduction of ferricyanide by isolated spinach chloroplasts. Lactones with electron-withdrawing substituents in the para-position of the benzylidene ring were the most effective inhibitors. Characterization of the activity of 11b/11b' suggested a mechanism based on the interaction with the plastoquinone binding site of photosystem II. Addition of several compounds to the culture medium of a cyanobacterial model strain was found to inhibit algal growth. However, the relative effectiveness was not consistent with their activity in vitro, suggesting the occurrence of multiple targets and/or detoxyfication mechanisms. Indeed, the compounds showed differential effects on the heterotrophic growth of some crop species, Cucumis sativus and Sorghum bicolor. Pyridazin-3(2H)-ones 12e, 12i, and 12j, which have been found poorly active against the photosynthetic electron transport, were the most effective in inhibiting the growth of some weeds, Ipomoea grandifolia and Brachiaria decumbens, under greenhouse conditions.
Asunto(s)
Compuestos Aza/farmacología , Lactonas/farmacología , Fotosíntesis/efectos de los fármacos , Compuestos Aza/química , Brachiaria/efectos de los fármacos , Brachiaria/crecimiento & desarrollo , Cucumis sativus/efectos de los fármacos , Cucumis sativus/crecimiento & desarrollo , Relación Dosis-Respuesta a Droga , Ipomoea/efectos de los fármacos , Ipomoea/crecimiento & desarrollo , Lactonas/química , Modelos Moleculares , Estructura Molecular , Sorghum/efectos de los fármacos , Sorghum/crecimiento & desarrolloRESUMEN
Thirty novel chemical compounds were designed and synthesized expecting that they would be possible inhibitors. From this number eleven were organic bases, twenty-four were their organic derivatives and fourteen were metal complexes. Screening of these chemicals by their action on photosynthetic electron transfer (PET) and carbonic anhydrase (CA) activity (CAA) of photosystem II (PSII), α-CA, as well as ß-CA was done. Several groups were revealed among them. Some of them are capable to suppress either one, two, three, or even all of the measured activities. As example, one of the Cu(II)-phenyl sulfonylhydrazone complexes (compound 25) suppresses CAA of α-CA by 88%, CAA of ß-CA by 100% inhibition; CAA of PSII by 100% and the PSII photosynthetic activity by 66.2%. The Schiff base compounds (12, 15) and Cu(II)-phenyl sulfonylhydrazone complexes (25, 26) inhibited the CAA and PET of PSII significantly. The obtained data indicate that the PSII donor side is a target of the inhibitory action of these agents. Some physico- or electrochemical properties such as diffusion coefficient, number of transferred electrons, peak potential and heterogeneous standard rate constants of the compounds were determined in nonaqueous media. pKa values were also determined in nonaqueous and aqueous media. Availability in the studied group of novel chemical agents possessing different inhibitory activity allow in future to isolate the "active part" in the structure of the inhibitors responsible for different inhibitory mechanisms, as well as to determine the influence of side substituters on its inhibitory efficiency.
Asunto(s)
Inhibidores de Anhidrasa Carbónica/farmacología , Anhidrasas Carbónicas/metabolismo , Fotosíntesis/efectos de los fármacos , Complejo de Proteína del Fotosistema II/antagonistas & inhibidores , Complejo de Proteína del Fotosistema II/metabolismo , Evaluación Preclínica de Medicamentos , Electroquímica , Compuestos Organometálicos/farmacología , Pisum sativum/enzimología , Procesos Fotoquímicos , Complejo de Proteína del Fotosistema II/químicaRESUMEN
In a search of new efficient herbicides of natural origin, four derivatives were prepared from labdane-8α,15-diol (1) and 15-O-acetyl-8α-hydroxy labdane (2) isolated from Croton ciliatoglanduliferus. Their inhibitory activity on photosynthetic electron transport on fresh, broken spinach chloroplasts and on the growth of plants were determined. Derivative 15-O-benzoyl-8α-hydroxy labdane (5) was seven times more active than 2 as reaction Hill inhibitor. Complex of 5 with the adjuvant 2-hydroxypropyl-ß-cyclodextrin (5:HPB) (200 µM) was sprayed on Physalys ixocarpa (green tomato) plants; 48 h later the complex inhibited PS II by transforming the active reaction centers to silent reaction centers or "heat sinks". After 72 h this effect disappeared, probably 5:HPB was metabolized by the plant. Chlorophyll a fluorescence of Trifolium alexandrinum (clover) leaves was affected with 5:HPB at the level of PQ pool reduction. 5:HPB decreases the tomato and clover dry-biomass, without affecting Lolium perenne (grass) plants, suggesting that complex 5 acts as selective herbicide for dicotyledonous plants.