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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 291: 122276, 2023 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-36623348

RESUMO

The short-term (0-96 h) response of A. thaliana to the oxidative stress induced by PSII inhibitor metribuzin was examined using Raman spectroscopy. Whole leaves of wildtype (WT, Col-0) and ros1 mutant were scanned and changes in carotenoids were examined. Strong differences in Raman intensity distributions between WT and ros1 were observed. A stronger decrease of carotenoid v1(C=C) band intensity across the leaf was observed in ros1 after 48 h of exposure to metribuzin. It can be assumed that higher sensitivity to oxidative stress in ros1 mutant results in significantly faster degradation of carotenoids.


Assuntos
Arabidopsis , Complexo de Proteína do Fotossistema II , Arabidopsis/metabolismo , Carotenoides/metabolismo , Clorofila/metabolismo , Luz , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Folhas de Planta/metabolismo , Proteínas Tirosina Quinases/metabolismo , Proteínas Proto-Oncogênicas/metabolismo , Análise Espectral Raman
2.
Molecules ; 26(14)2021 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-34299611

RESUMO

A set of twenty-four 3-hydroxynaphthalene-2-carboxanilides, disubstituted on the anilide ring by combinations of methoxy/methyl/fluoro/chloro/bromo and ditrifluoromethyl groups at different positions, was prepared. The compounds were tested for their ability to inhibit photosynthetic electron transport (PET) in spinach (Spinacia oleracea L.) chloroplasts. N-(3,5-Difluorophenyl)-, N-(3,5-dimethylphenyl)-, N-(2,5-difluorophenyl)- and N-(2,5-dimethylphenyl)-3-hydroxynaphthalene-2-carboxamides showed the highest PET-inhibiting activity (IC50 ~ 10 µM) within the series. These compounds were able to inhibit PET in photosystem II. It has been found that PET-inhibiting activity strongly depends on the position of the individual substituents on the anilide ring and on the lipophilicity of the compounds. The electron-withdrawing properties of the substituents contribute towards the PET activity of these compounds.


Assuntos
Cloroplastos/efeitos dos fármacos , Naftalenos/metabolismo , Fotossíntese/efeitos dos fármacos , Spinacia oleracea/efeitos dos fármacos , Cloroplastos/metabolismo , Transporte de Elétrons/efeitos dos fármacos , Herbicidas/química , Herbicidas/metabolismo , Naftalenos/química , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Complexo de Proteína do Fotossistema II/metabolismo , Spinacia oleracea/metabolismo
3.
Chem Biodivers ; 18(7): e2100226, 2021 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-33998137

RESUMO

We report the evaluation of chalcone derivatives as photosystem II (PSII) and plant growth inhibitors. Chalcone derivatives were evaluated as PSII inhibitors through Chl a fluorescence measurement. (E)-Chalcone (6a) and (E)-3-(4-bromophenyl)-1-(4-fluorophenyl)prop-2-en-1-one (6j) showed the best results, reducing the performance index on absorption basis parameter (PIabs ) by 70 %. Additionally, the decrease of TR0 /RC and ET0 /RC parameters indicates that the chalcone derivatives limited the number of active PSII reaction centers and the amount of trapped energy within them. Compounds 6a and 6j both act as post-emergent herbicides at 50 µM, reducing the root biomass of the Ipomoea grandifolia weed by 72 % and 83 %, respectively, corroborating the fluorescence results. The selectivity against weeds as compared to valuable crops by compounds 6a and 6j were evaluated employing Zea mays and Phaseolus vulgaris plants. In these, our newly synthesized compounds showed no effects on biomass accumulation of roots and aerial parts when compared to the control, providing valuable evidence for the role of these compounds as selective inhibitors of the growth of undesired weeds.


Assuntos
Chalconas/farmacologia , Inibidores do Crescimento/farmacologia , Herbicidas/farmacologia , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Biomassa , Chalconas/síntese química , Chalconas/química , Inibidores do Crescimento/síntese química , Inibidores do Crescimento/química , Herbicidas/síntese química , Herbicidas/química , Ipomoea/efeitos dos fármacos , Ipomoea/crescimento & desenvolvimento , Estrutura Molecular , Phaseolus/efeitos dos fármacos , Phaseolus/crescimento & desenvolvimento , Processos Fotoquímicos , Complexo de Proteína do Fotossistema II/metabolismo , Análise de Componente Principal , Zea mays/efeitos dos fármacos , Zea mays/crescimento & desenvolvimento
4.
Biomolecules ; 11(2)2021 02 05.
Artigo em Inglês | MEDLINE | ID: mdl-33562880

RESUMO

The elimination of broadleaf weeds from agricultural fields has become an urgent task in plant and environment protection. Allelopathic control is considered a potential approach because of its exclusive and ecological safety measures. Plant secondary metabolites also called allelochemicals are released from plant leaves, roots, stem, bark, flowers and play significant roles in soil rhizosphere signaling, chemical ecology, and plant defense. The present study was carried out to evaluate the impact of two allelochemicals; ferulic acid (FA) and p-hydroxybenzoic acid (pHBA) on photosynthetic characteristics; Fv/Fm: efficiency of photosystem II photochemistry in the dark-adapted state; ΦPSII: photosynthetic quantum yield; NPQ, non-photochemical quenching; qP, photochemical quenching, and photon energy dissipation (1-qP)/NPQ in Rumex acetosa following 6 days exposure. R. acetosa seedlings were grown in perlite culture, irrigated with Hoagland solution and treated with allelopathic compounds FA and pHBA and were evaluated against the photosynthetic attributes. Both compounds behaved as potent inhibitors of photosynthetic traits such as Fv/Fm, ΦPSII, qP, and NPQ in R. acetosa. Photon energy dissipation (1-qP)/NPQ increased significantly from days 3 to 6. Higher dissipation of absorbed energy indicates the inactivation state of reaction centers and their inability to effectively use the absorbed energy in photosynthesis. These results indicated the potential allelopathic application of FA and pHBA for control of broadleaf weed, Rumex acetosa.


Assuntos
Ácidos Cumáricos/farmacologia , Hidroxibenzoatos/farmacologia , Fotossíntese/efeitos dos fármacos , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Plantas Daninhas/efeitos dos fármacos , Rumex/efeitos dos fármacos , Plântula/efeitos dos fármacos , Agentes de Controle Biológico/farmacologia , Herbicidas/farmacologia , Luz , Feromônios/farmacologia , Fotossíntese/fisiologia , Complexo de Proteína do Fotossistema II/metabolismo , Plantas Daninhas/crescimento & desenvolvimento , Plantas Daninhas/metabolismo , Teoria Quântica , Rumex/crescimento & desenvolvimento , Rumex/metabolismo , Plântula/crescimento & desenvolvimento , Plântula/metabolismo
5.
Sci Rep ; 10(1): 19592, 2020 11 11.
Artigo em Inglês | MEDLINE | ID: mdl-33177549

RESUMO

Conventional photosystem II (PSII) herbicides applied in agriculture can pose significant environmental risks to aquatic environments. In response to the frequent detection of these herbicides in the Great Barrier Reef (GBR) catchment area, transitions towards 'alternative' herbicides are now widely supported. However, water quality guideline values (WQGVs) for alternative herbicides are lacking and their potential ecological impacts on tropical marine species are generally unknown. To improve our understanding of the risks posed by some of these alternative herbicides on marine species under tropical conditions, we tested the effects of four herbicides on the widely distributed diatom Chaetoceros muelleri. The PSII herbicides diuron, propazine, and tebuthiuron induced substantial reductions in both 24 h effective quantum yields (ΔF/Fm') and 3-day specific growth rates (SGR). The effect concentrations, which reduced ΔF/Fm' by 50% (EC50), ranged from 4.25 µg L-1 diuron to 48.6 µg L-1 propazine, while the EC50s for SGR were on average threefold higher, ranging from 12.4 µg L-1 diuron to 187 µg L-1 tebuthiuron. Our results clearly demonstrated that inhibition of ΔF/Fm' in PSII is directly linked to reduced growth (R2 = 0.95) in this species, further supporting application of ΔF/Fm' inhibition as a valid bioindicator of ecological relevance for PSII herbicides that could contribute to deriving future WQGVs. In contrast, SGR and ΔF/Fm' of C. muelleri were nonresponsive to the non-PSII herbicide haloxyfop at the highest concentration tested (4570 µg L-1), suggesting haloxyfop does not pose a risk to C. muelleri. The toxicity thresholds (e.g. no effect concentrations; NECs) identified in this study will contribute to the derivation of high-reliability marine WQGVs for some alternative herbicides detected in GBR waters and support future assessments of the cumulative risks of complex herbicide mixtures commonly detected in coastal waters.


Assuntos
Diatomáceas/efeitos dos fármacos , Herbicidas/toxicidade , Diatomáceas/crescimento & desenvolvimento , Diurona/toxicidade , Ecotoxicologia/métodos , Compostos de Metilureia/toxicidade , Microalgas/efeitos dos fármacos , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Piridinas/toxicidade , Triazinas/toxicidade , Poluentes Químicos da Água/toxicidade
6.
Chem Biodivers ; 17(11): e2000484, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32960490

RESUMO

Our search for candidates for photosynthesis inhibitors is allowing us to report the effect of two acetogenins identified in Annona coriacea Mart. leaves, ACG-A and ACG-B, a non-adjacent bis-THF and a mono-THF types, respectively. This is an important class of natural products which presents biological properties such as anticancer, neurotoxic, larvicidal and insecticidal. However, this is only the second report associated to its herbicidal activity. Their mechanisms of action on the light reactions of the photosynthesis were elucidated by polarographic techniques. Compounds inhibited the noncyclic electron transport on basal, phosphorylating, and uncoupled conditions from H2 O to methyl viologen (MV); therefore, they act as Hill reaction inhibitors. Studies on fluorescence of chlorophyll a (ChL a) indicated that they inhibited the acceptor side of PSII between P680 and PQ-pool, exactly as the commercial herbicide DCMU does.


Assuntos
Acetogeninas/química , Annona/química , Acetogeninas/isolamento & purificação , Acetogeninas/metabolismo , Acetogeninas/farmacologia , Annona/metabolismo , Clorofila A/química , Cloroplastos/metabolismo , Transporte de Elétrons/efeitos dos fármacos , Luz , Fotossíntese/efeitos dos fármacos , Fotossíntese/efeitos da radiação , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Complexo de Proteína do Fotossistema II/metabolismo , Folhas de Planta/química , Folhas de Planta/metabolismo , Spinacia oleracea/metabolismo
7.
J Agric Food Chem ; 68(40): 11105-11113, 2020 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-32915575

RESUMO

The use of nano- and microparticles as a release system for agrochemicals has been increasing in agricultural sector. However, the production of eco-friendly and smart carriers that can be easily handled in the environment is still a challenge for this technology. In this context, we have developed a biodegradable release system for the herbicide atrazine with magnetic properties. Herein, we investigated the (a) physicochemical properties of the atrazine-loaded magnetic poly(ε-caprolactone) microparticles (MPs:ATZ), (b) in vitro release kinetic profile of the herbicide, and (c) phytotoxicity toward photosynthesis in the aquatic fern Azolla caroliniana. The encapsulation efficiency of the herbicide in the MPs:ATZ was ca. 69%, yielding spherical microparticles with a diameter of ca. 100 µm, a sustained-release profile, and easily manipulated with an external magnetic field. Also, phytotoxicity issues showed that the MPs:ATZ maintained their herbicidal activity via inhibition of PSII, showing lower toxicity compared with the nonencapsulated ATZ at 0.01 and 0.02 µmol·L-1. Therefore, this technology may conveniently promote a novel magnetic controlled release of the herbicide ATZ (with the potential to be collected from a watercourse) and act as a nutrient boost to the nontarget plant, with good herbicidal activity and reduced risk to the environment.


Assuntos
Sistemas de Liberação de Medicamentos/métodos , Herbicidas/química , Magnetismo/métodos , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Poliésteres/química , Atrazina/química , Sistemas de Liberação de Medicamentos/instrumentação , Liberação Controlada de Fármacos , Gleiquênias/efeitos dos fármacos , Gleiquênias/metabolismo , Herbicidas/farmacologia , Magnetismo/instrumentação , Nanopartículas/química , Fotossíntese/efeitos dos fármacos , Complexo de Proteína do Fotossistema II/metabolismo , Poliésteres/farmacologia
8.
Photochem Photobiol ; 96(6): 1233-1242, 2020 11.
Artigo em Inglês | MEDLINE | ID: mdl-32534470

RESUMO

We report the synthesis of twelve indole derivatives bearing nitro or amide groups via Fischer indole methodology followed by reduction/acetylation and amidation reactions. After thorough characterization, these indoles were subjected to a number of studies in order to evaluate their bioactive potential as photosynthesis and plant growth inhibitors. Firstly, these molecular hybrids were evaluated as photosystem II (PSII) inhibitors through chlorophyll a (Chl a) fluorescence measurement. In this study, 6-chloro-8-nitro-2,3,4,9-tetrahydro-1H-carbazole (15a) and 5-chloro-2,3-dimethyl-7-nitro-1H-indole (15b) showed the best results by reducing the phenomenological parameters of reaction centers ABS/RC, TR0 /RC and ET0 /RC of PSII. Electron chain blockage by these compounds may lead to diminished ATP synthesis and CO2 fixation which interrupt the plant development. The compounds 15a and 15b both act as postemergent herbicides, reducing the dry biomass of Ipomoea grandifolia and Senna alata weeds by an average of 40% and 37%, respectively, corroborating the fluorescence results. Additionally, the molecular docking study revealed that the presence of strong electron-withdrawing groups at the indole phenyl ring is important for the ligand's interaction with the binding pocket of protein D1 on PSII. The optimization of these molecular features is the goal of our research group in further understanding and development of new potent herbicides.


Assuntos
Desenho de Fármacos , Indóis/farmacologia , Nitrogênio/química , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Indóis/química
9.
Sci Rep ; 10(1): 7612, 2020 05 06.
Artigo em Inglês | MEDLINE | ID: mdl-32376837

RESUMO

Herbicide contamination of nearshore tropical marine ecosystems is widespread and persistent; however, risks posed by most 'alternative' herbicides to tropical marine microalgae remain poorly understood. Experimental exposures of the important but understudied microalgae Rhodomonas salina to seven individual Photosystem II (PSII) inhibitor herbicides (diuron, metribuzin, hexazinone, tebuthiuron, bromacil, simazine, propazine) led to inhibition of effective quantum yield (ΔF/Fm') and subsequent reductions in specific growth rates (SGR). The concentrations which reduced ΔF/Fm' by 50% (EC50) ranged from 1.71-59.2 µg L-1, while the EC50s for SGR were 4-times higher, ranging from 6.27-188 µg L-1. Inhibition of ΔF/Fm' indicated reduced photosynthetic capacity, and this correlated linearly with reduced SGR (R2 = 0.89), supporting the application of ∆F/Fm' inhibition as a robust and sensitive indicator of sub-lethal toxicity of PSII inhibitors for this microalga. The three non-PSII inhibitor herbicides (imazapic, haloxyfop and 2,4-Dichlorophenoxyacetic acid (2,4-D)) caused low or no toxic responses to the function of the PSII or growth at the highest concentrations tested suggesting these herbicides pose little risk to R. salina. This study highlights the suitability of including R. salina in future species sensitivity distributions (SSDs) to support water quality guideline development for the management of herbicide contamination in tropical marine ecosystems.


Assuntos
Herbicidas/toxicidade , Microalgas/efeitos dos fármacos , Clima Tropical , Poluentes Químicos da Água/toxicidade , Ecotoxicologia , Microalgas/enzimologia , Microalgas/crescimento & desenvolvimento , Complexo de Proteína do Fotossistema II/antagonistas & inibidores
10.
ScientificWorldJournal ; 2019: 1030236, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31346323

RESUMO

The unicellular halotolerant cyanobacterium Aphanothece halophytica is a potential dark fermentative producer of molecular hydrogen (H2) that produces very little H2 under illumination. One factor limiting the H2 photoproduction of this cyanobacterium is an inhibition of bidirectional hydrogenase activity by oxygen (O2) obtained from splitting water molecules via photosystem II activity. The present study aimed to investigate the effects of the photosystem II inhibitors carbonyl cyanide m-chlorophenyl hydrazone (CCCP) and 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) on H2 production of A. halophytica under light and dark conditions and on photosynthetic and respiratory activities. The results showed that A. halophytica treated with CCCP and DCMU produced H2 at three to five times the rate of untreated cells, when exposed to light. The highest H2 photoproduction rates, 2.26 ±â€Š0.24 and 3.63 ±â€Š0.26 µmol H2 g-1 dry weight h-1, were found in cells treated with 0.5 µM CCCP and 50 µM DCMU, respectively. Without inhibitor treatment, A. halophytica incubated in the dark showed a significant increase in H2 production compared with cells that were incubated in the light. Only CCCP treatment increased H2 production of A. halophytica during dark incubation, because CCCP functions as an uncoupling agent of oxidative phosphorylation. The highest dark fermentative H2 production rate of 39.50 ±â€Š2.13 µmol H2 g-1 dry weight h-1 was found in cells treated with 0.5 µM CCCP after 2 h of dark incubation. Under illumination, CCCP and DCMU inhibited chlorophyll fluorescence, resulting in a low level of O2, which promoted bidirectional hydrogenase activity in A. halophytica cells. In addition, only CCCP enhanced the respiration rate, further reducing the O2 level. In contrast, DCMU reduced the respiration rate in A. halophytica.


Assuntos
Carbonil Cianeto m-Clorofenil Hidrazona/farmacologia , Cianobactérias/efeitos dos fármacos , Cianobactérias/metabolismo , Diurona/farmacologia , Hidrogênio/metabolismo , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Respiração Celular/efeitos dos fármacos , Respiração Celular/efeitos da radiação , Clorofila A/metabolismo , Escuridão , Hidrogenase/metabolismo , Fotossíntese/efeitos dos fármacos
11.
Pest Manag Sci ; 75(6): 1564-1570, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-30632275

RESUMO

BACKGROUND: Weed competition is a major limitation to worldwide lentil (Lens culinaris Medik.) production in part due to limited effective safe herbicide options. Metribuzin is a photosystem II inhibiting herbicide that provides broad spectrum weed control, however it causes excessive injury in lentil. Dose response analysis of photosystem II inhibiting herbicides and DNA sequencing of the psbA chloroplast gene occurred to quantify the spectrum and mechanism of herbicide resistance in two ethyl-methanesulfonate (EMS) induced mutant lentils. RESULTS: Compared to susceptible parent PBA Flash, the level of metribuzin resistance was 33-fold for mutant M043 and 10-fold for M009. No improvement in resistance occurred in either mutant to bromoxynil, diuron, bromacil and atrazine herbicides. Nucleotide sequencing of the psbA gene of both mutants identified a substitution at position 751 compared to PBA Flash. The resulting deduced amino acid sequence indicated an Ala251 Thr substitution as being most likely responsible for the high level of metribuzin resistance. CONCLUSIONS: The Ala251 Thr substitution discovered in this study is unique in mutagenized higher plants and the first report of an induced psbA target site mutation in higher plants. This target site metribuzin resistance is likely to have a significant impact on lentil production in Australia and worldwide. © 2019 Society of Chemical Industry.


Assuntos
Resistência a Herbicidas/genética , Lens (Planta)/efeitos dos fármacos , Lens (Planta)/genética , Mutação , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Proteínas de Plantas/genética , Triazinas/farmacologia , Relação Dose-Resposta a Droga , Inibidores Enzimáticos/farmacologia
12.
J Photochem Photobiol B ; 185: 1-9, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-29852327

RESUMO

Photosynthetic oxygen evolution occurs through the oxidation of water at a catalytic Mn4CaO5 cluster in photosystem II and is promoted by chloride, which binds at two sites near the Mn4CaO5 cluster. Fluoride is a competitive inhibitor of chloride activation, but study of its effects is complicated by the possibility that it may form an insoluble CaF2 complex. In this study, the effects of fluoride were studied using PSII lacking the PsbP and PsbQ subunits, which help to regulate the requirements for the inorganic cofactors Ca2+ and Cl-. In this preparation, which allows easy exchange of ions, it was found that F- does not directly remove Ca2+ even when catalytic turnovers take place, suggesting that fluoride is not able to access the inner coordination sphere of Ca2+. By monitoring the loss in O2 evolution activity, the dissociation constant of F- was estimated to be about 1 mM in intact PSII, consistent with previous studies, and about 77 mM in PSII lacking the extrinsic subunits. The significantly higher value for PSII lacking PsbP and PsbQ is consistent with results for other ions. The effects of F- on electron transfer to Tyr Z was also studied and found to show similar trends in PSII with and without the two extrinsic subunits, but with a more pronounced effect in PSII lacking the extrinsic subunits. These results indicate that in PSII lacking PsbP and PsbQ, fluoride does not directly interact with or remove Ca2+ and inhibits O2 evolution in a manner comparable to PSII with the extrinsic subunits intact.


Assuntos
Fluoretos/metabolismo , Complexo de Proteína do Fotossistema II/metabolismo , Proteínas de Plantas/metabolismo , Cálcio/química , Espectroscopia de Ressonância de Spin Eletrônica , Fluoretos/química , Oxigênio/metabolismo , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Proteínas de Plantas/antagonistas & inibidores , Ligação Proteica , Subunidades Proteicas/genética , Subunidades Proteicas/metabolismo , Cloreto de Sódio/química , Cloreto de Sódio/metabolismo , Fluoreto de Sódio/química , Fluoreto de Sódio/metabolismo , Spinacia oleracea/metabolismo , Tirosina/química , Tirosina/metabolismo
13.
Sci Rep ; 8(1): 2755, 2018 02 09.
Artigo em Inglês | MEDLINE | ID: mdl-29426901

RESUMO

Photosystem II (PSII) catalyses the photoinduced oxygen evolution and, by producing reducing equivalents drives, in concert with PSI, the conversion of carbon dioxide to sugars. Our knowledge about the architecture of the reaction centre (RC) complex and the mechanisms of charge separation and stabilisation is well advanced. However, our understanding of the processes associated with the functioning of RC is incomplete: the photochemical activity of PSII is routinely monitored by chlorophyll-a fluorescence induction but the presently available data are not free of controversy. In this work, we examined the nature of gradual fluorescence rise of PSII elicited by trains of single-turnover saturating flashes (STSFs) in the presence of a PSII inhibitor, permitting only one stable charge separation. We show that a substantial part of the fluorescence rise originates from light-induced processes that occur after the stabilisation of charge separation, induced by the first STSF; the temperature-dependent relaxation characteristics suggest the involvement of conformational changes in the additional rise. In experiments using double flashes with variable waiting times (∆τ) between them, we found that no rise could be induced with zero or short ∆τ, the value of which depended on the temperature - revealing a previously unknown rate-limiting step in PSII.


Assuntos
Clorofila A/metabolismo , Fluorescência , Complexo de Proteína do Fotossistema II/metabolismo , Spinacia oleracea/metabolismo , Synechococcus/metabolismo , Synechocystis/metabolismo , Tilacoides/metabolismo , Fotossíntese , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Temperatura
14.
Biochim Biophys Acta Bioenerg ; 1859(4): 292-299, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-29410217

RESUMO

It is known, that the multi-subunit complex of photosystem II (PSII) and some of its single proteins exhibit carbonic anhydrase activity. Previously, we have shown that PSII depletion of HCO3-/CO2 as well as the suppression of carbonic anhydrase activity of PSII by a known inhibitor of α­carbonic anhydrases, acetazolamide (AZM), was accompanied by a decrease of electron transport rate on the PSII donor side. It was concluded that carbonic anhydrase activity was required for maximum photosynthetic activity of PSII but it was not excluded that AZM may have two independent mechanisms of action on PSII: specific and nonspecific. To investigate directly the specific influence of carbonic anhydrase inhibition on the photosynthetic activity in PSII we used another known inhibitor of α­carbonic anhydrase, trifluoromethanesulfonamide (TFMSA), which molecular structure and physicochemical properties are quite different from those of AZM. In this work, we show for the first time that TFMSA inhibits PSII carbonic anhydrase activity and decreases rates of both the photo-induced changes of chlorophyll fluorescence yield and the photosynthetic oxygen evolution. The inhibitory effect of TFMSA on PSII photosynthetic activity was revealed only in the medium depleted of HCO3-/CO2. Addition of exogenous HCO3- or PSII electron donors led to disappearance of the TFMSA inhibitory effect on the electron transport in PSII, indicating that TFMSA inhibition site was located on the PSII donor side. These results show the specificity of TFMSA action on carbonic anhydrase and photosynthetic activities of PSII. In this work, we discuss the necessity of carbonic anhydrase activity for the maximum effectiveness of electron transport on the donor side of PSII.


Assuntos
Anidrases Carbônicas/metabolismo , Elétrons , Mesilatos/farmacologia , Fotossíntese/fisiologia , Complexo de Proteína do Fotossistema II/metabolismo , Pisum sativum/enzimologia , Acetazolamida/farmacologia , Bicarbonatos/metabolismo , Dióxido de Carbono/metabolismo , Inibidores da Anidrase Carbônica/farmacologia , Clorofila/metabolismo , Clorofila A , Transporte de Elétrons/efeitos dos fármacos , Transporte de Elétrons/efeitos da radiação , Concentração de Íons de Hidrogênio , Cinética , Luz , Oxigênio/metabolismo , Pisum sativum/efeitos dos fármacos , Pisum sativum/efeitos da radiação , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Tilacoides/efeitos dos fármacos , Tilacoides/enzimologia , Tilacoides/efeitos da radiação
15.
Bioorg Med Chem Lett ; 27(9): 1881-1885, 2017 05 01.
Artigo em Inglês | MEDLINE | ID: mdl-28363749

RESUMO

N-(Alkoxyphenyl)-2-hydroxynaphthalene-1-carboxamides (series A) and N-(alkoxyphenyl)-1-hydroxynaphthalene-2-carboxamides (series B) affecting photosystem (PS) II inhibited photosynthetic electron transport (PET) in spinach chloroplasts. Their inhibitory activity depended on the compound lipophilicity as well as on the position of the alkoxy substituent. The most potent PET inhibitors were 2-hydroxy-N-phenylnaphthalene-1-carboxamide and N-[3-(but-2-yloxy)phenyl]-2-hydroxynaphthalene-1-carboxamide within series A (IC50=28.9 and 42.5µM, respectively) and 1-hydroxy-N-(3-propoxyphenyl)naphthalene-2-carboxamide and 1-hydroxy-N-(3-ethoxyphenyl)-naphthalene-2-carboxamide (IC50=2.0 and 3.1µM, respectively) within series B. The inhibitory activity of C'(3) or C'(4) alkoxy substituted compounds of series B was considerably higher than that of C'(2) ones within series A. The PET-inhibiting activities of both series were compared with the PET inhibition of isomeric N-alkoxyphenyl-3-hydroxynaphthalene-2-carboxamides (series C) reported recently. Interactions of the studied compounds with chlorophyll a and aromatic amino acids present in pigment-protein complexes mainly in PS II were documented by fluorescence spectroscopy. The section between P680 and plastoquinone QB in the PET chain occurring on the acceptor side of PSII can be suggested as the site of action of the compounds.


Assuntos
Antibacterianos/metabolismo , Naftalenos/metabolismo , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Proteínas de Plantas/antagonistas & inibidores , Spinacia oleracea/efeitos dos fármacos , Antibacterianos/química , Transporte de Elétrons/efeitos dos fármacos , Naftalenos/química , Complexo de Proteína do Fotossistema II/metabolismo , Proteínas de Plantas/metabolismo , Spinacia oleracea/metabolismo
16.
Mol Divers ; 21(2): 437-454, 2017 May.
Artigo em Inglês | MEDLINE | ID: mdl-28299584

RESUMO

Cinnoline, pyridine, pyrimidine, and triazine herbicides were found be inhibitors of the D1 protein in photosystem II (D1 PSII) electron transport of plants. The photosystem II inhibitory activity of these herbicides, expressed by experimental [Formula: see text] values, was modeled by a docking and quantitative structure-activity relationships study. A conformer ensemble for each of the herbicide structure was generated using the MMFF94s force field. These conformers were further employed in a docking approach, which provided new information about the rational "active conformations" and various interaction patterns of the herbicide derivatives with D1 PSII. The most "active conformers" from the docking study were used to calculate structural descriptors, which were further related to the inhibitory experimental [Formula: see text] values by multiple linear regression (MLR). The dataset was divided into training and test sets according to the partition around medoids approach, taking 27% of the compounds from the entire series for the test set. Variable selection was performed using the genetic algorithm, and several criteria were checked for model performance. WHIM and GETAWAY geometrical descriptors (position of substituents and moieties in the molecular space) were found to contribute to the herbicidal activity. The derived MLR model is statistically significant, shows very good stability and was used to predict the herbicidal activity of new derivatives having cinnoline, indeno[1.2-c]cinnoline-ll-one, triazolo[1,5-a] pyridine, imidazo[1,2-a]pyridine, triazine and triazolo[1,5-a] pyrimidine scaffolds whose experimental inhibitory activity against D1 PSII had not been determined up to now.


Assuntos
Compostos Heterocíclicos/química , Compostos Heterocíclicos/farmacologia , Simulação de Acoplamento Molecular , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Complexo de Proteína do Fotossistema II/metabolismo , Relação Quantitativa Estrutura-Atividade , Biologia Computacional , Inibidores Enzimáticos/química , Inibidores Enzimáticos/metabolismo , Inibidores Enzimáticos/farmacologia , Herbicidas/química , Herbicidas/metabolismo , Herbicidas/farmacologia , Compostos Heterocíclicos/metabolismo , Concentração Inibidora 50 , Modelos Lineares , Complexo de Proteína do Fotossistema II/química , Conformação Proteica
17.
J Org Chem ; 82(1): 211-233, 2017 01 06.
Artigo em Inglês | MEDLINE | ID: mdl-28026176

RESUMO

A series of 28 analogues of the phytotoxic geranylcyclohexentriol (-)-phomentrioloxin A (1) has been synthesized through cross-couplings of various enantiomerically pure haloconduritols or certain deoxygenated derivatives with either terminal alkynes or borylated alkenes. Some of these analogues display modest herbicidal activities, and physiological profiling studies suggest that analogue 4 inhibits photosystem II in isolated thylakoids in vitro.


Assuntos
Araceae/efeitos dos fármacos , Diterpenos/farmacologia , Herbicidas/farmacologia , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Diterpenos/síntese química , Diterpenos/química , Herbicidas/síntese química , Herbicidas/química , Complexo de Proteína do Fotossistema II/metabolismo
18.
Bioorg Med Chem Lett ; 26(16): 3862-5, 2016 08 15.
Artigo em Inglês | MEDLINE | ID: mdl-27432762

RESUMO

Ring-substituted 8-hydroxyquinoline-2-carboxanilides inhibited photosynthetic electron transport (PET) through photosystem (PS) II. Their inhibitory efficiency depended on the compound lipophilicity, the electronic properties of the substituent R and the position of the substituent R on the benzene ring. The most effective inhibitors showing IC50 values in the range 2.3-3.6µM were substituted in C'(3) by F, CH3, Cl and Br. The dependence of the PET-inhibiting activity on the lipophilicity of the compounds was quasi-parabolic for 3-substituted derivatives, while for C'(2) ones a slight increase and for C'(4) derivatives a sharp decrease of the activity were observed with increasing lipophilicity. In addition, the dependence of PET-inhibiting activity on electronic Hammett's σ parameter of the substituent R was observed with optimum σ value 0.06 for C'(4) and 0.34 for C'(3) substituted derivatives, while the value of σ parameter did not significantly influence the PET-inhibiting activity of C'(2) substituted compounds. Interactions of the studied compounds with chlorophyll a and aromatic amino acids present in the pigment-protein complexes mainly in PS II were documented by fluorescence spectroscopy. The section between P680 and plastoquinone QB occurring on the acceptor side of PS II can be suggested as the site of action of the compounds.


Assuntos
Anilidas/química , Oxiquinolina/química , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Anilidas/síntese química , Anilidas/metabolismo , Clorofila/química , Clorofila A , Cloroplastos/metabolismo , Transporte de Elétrons , Fotossíntese , Complexo de Proteína do Fotossistema II/metabolismo , Ligação Proteica , Espectrometria de Fluorescência , Spinacia oleracea/metabolismo , Relação Estrutura-Atividade
19.
Photosynth Res ; 129(1): 85-92, 2016 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-27236700

RESUMO

Although it has been believed that wild-type plants are capable of protecting photosystem I (PSI) under high light, our previous study indicates that PSI is sensitive to high light in the shade-established tree species Psychotria rubra. However, the underlying physiological mechanisms are unclear. In this study, we examined the roles of electron transfer from PSII to PSI and PSI redox state in PSI photoinhibition in P. rubra by treatments with lincomycin (Lin), diuron (DCMU), and methyl viologen (MV). After exposure to 2000 µmol photons m(-2) s(-1) for 2 h, PSI activity decreased by 35, 29, 3, and 49 % in samples treated with H2O, Lin, DCMU, and MV, respectively. Meanwhile, the MV-treated samples showed higher P700 oxidation ratio than the H2O-treated samples, suggesting the PSI photoinhibition under high light was accompanied by high levels of P700 oxidation ratio. PSI photoinhibition was alleviated in the DCMU-treated samples but was accelerated in the MV-treated samples, suggesting that PSI photoinhibition in P. rubra was mainly controlled by electron transfer from PSII to PSI. Taking together, PSI photoinhibition is more related to electron transfer from PSII to PSI rather than PSI redox state in P. rubra, which is different from the mechanisms of PSI photoinhibition in Arabidopsis thaliana and cucumber.


Assuntos
Complexo de Proteína do Fotossistema I/antagonistas & inibidores , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Psychotria/fisiologia , Diurona/farmacologia , Transporte de Elétrons , Lincomicina/farmacologia , Oxirredução , Paraquat/farmacologia , Fotossíntese/fisiologia , Psychotria/efeitos da radiação , Árvores
20.
Pest Manag Sci ; 72(9): 1673-80, 2016 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-26929096

RESUMO

BACKGROUND: Propanil-resistant (R) Cyperus difformis populations were recently confirmed in California rice fields. To date, propanil resistance in other weed species has been associated with enhanced aryl acylamidase (AAA)-mediated propanil conversion into 3,4-dichloroaniline. Our objectives were to determine the level of propanil resistance and cross-resistance to other PSII inhibitors in C. difformis lines, and to elucidate the mechanism of propanil resistance. RESULTS: The propanil-R line had a 14-fold propanil resistance and increased resistance to bromoxynil, diuron and metribuzin, but not to atrazine. The R line, however, displayed a fourfold increased susceptibility to bentazon. Interestingly, susceptible (S) plants accumulated more 3,4-dichloroaniline and were more injured by propanil and carbaryl (AAA-inhibitor) applications than R plants, suggesting that propanil metabolism is not the resistance mechanism. psbA gene sequence analysis indicated a valine-219-isoleucine (Val219 Ile) amino acid exchange in the propanil-R chloroplast D1 protein. CONCLUSION: The D1 Val219 Ile modification in C. difformis causes resistance to propanil, diuron, metribuzin and bromoxynil but increased susceptibility to bentazon, suggesting that the Val219 residue participates in binding of these herbicides. This is the first report of a higher plant exhibiting target-site propanil resistance. Tank mixing of bentazon and propanil, where permitted, can control both propanil-R and propanil-S C. difformis and prevent the spread of the resistant phenotype. © 2016 Society of Chemical Industry.


Assuntos
Cyperus/efeitos dos fármacos , Resistência a Múltiplos Medicamentos , Resistência a Herbicidas/genética , Herbicidas/farmacologia , Complexo de Proteína do Fotossistema II/genética , Mutação Puntual/efeitos dos fármacos , Propanil/farmacologia , Benzotiadiazinas/farmacologia , Cyperus/genética , Cyperus/metabolismo , Complexo de Proteína do Fotossistema II/antagonistas & inibidores , Complexo de Proteína do Fotossistema II/metabolismo
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