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1.
Inorg Chem ; 2024 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-38959250

RESUMO

Anthrax bacillus is a very dangerous zoonotic pathogen that seriously endangers public health. Rapid and accurate qualitative and quantitative detection of its biomarkers, 2,6-dipicolinic acid (DPA), is crucial for the prevention and treatment of this pathogenic bacterium. In this work, a novel Cd-based MOF (TTCA-Cd) has been synthesized from a polycarboxylate ligand, [1,1':2',1″-terphenyl]-4,4',4″,5'-tetracarboxylic acid (H4TTCA), and further doped with Tb(III), forming a dual-emission lanthanide-functionalized MOF hybrid (TTCA-Cd@Tb). TTCA-Cd@Tb can be developed as a high-performance ratiometric fluorescent sensor toward DPA with a very low detection limit of 7.14 nM and high selectivity in a wide detection range of 0-200 µM, demonstrating a big advancement and providing a new option for the detection of DPA.

2.
Inorg Chem ; 62(5): 2236-2243, 2023 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-36689619

RESUMO

Two zero-dimensional inorganic-organic hybrids, namely, [C4mim][Cd(TCDPPA)3] (1) and [C4mpy][Cd(TCDPPA)3] (2), where (TCDPPA)- = 2,2,2-trichloro-N-(di(pyrrolidin-1-yl)phosphoryl)acetamide, (C4mim)+ = 1-butyl-3-methylimidazolium, and (C4mpy)+ = 1-butyl-4-methylpyridinium, have been synthesized via metathesis reactions and characterized systematically. These ionic cadmium-containing inorganic-organic hybrid compounds are assembled from a bulky organic cation and a complex anion constructed from the chelation of three TCDPPA ligands to one cadmium ion. These compounds possess wide band gaps and emit in the deep-blue region intensely with a quantum yield as high as 34.04%. The success of this work provides a new method for the design and fabrication of high-efficiency blue-emitting materials.

3.
Inorg Chem ; 61(43): 17322-17329, 2022 Oct 31.
Artigo em Inglês | MEDLINE | ID: mdl-36260292

RESUMO

The overuse of tetracyclines (TCs) in livestock breeding may cause a series of health and environmental problems. It is necessary to develop more accurate, convenient, and rapid sensing methods toward TCs, but it is still very challenging. In this work, three isostructural zirconium organic frameworks (Zr-MOFs) have been investigated as probes for the fluorescent sensing of TCs in water. By varying the functional group at the central benzene core, their sensing performances toward TCs can be modified. Under optimized conditions, the limit of detection can be as low as 0.08 nM in a wide detection range of 0-147 µM with high sensitivity and selectivity. These Zr-MOFs can also be applied in the detection of TCs in real pork samples with satisfying reliabilities and correctness. This work provides a new method for the design and optimization of fluorescent sensors toward TCs.


Assuntos
Compostos Heterocíclicos , Carne de Porco , Carne Vermelha , Animais , Suínos , Tetraciclinas/química , Corantes Fluorescentes/química , Zircônio/química , Água , Antibacterianos/análise
4.
Chemistry ; 27(52): 13181-13189, 2021 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-34096644

RESUMO

Access to lanthanide acetate coordination compounds is challenged by the tendency of lanthanides to coordinate water and the plethora of acetate coordination modes. A straightforward, reproducible synthetic procedure by treating lanthanide chloride hydrates with defined ratios of the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C2 mim][OAc]) has been developed. This reaction pathway leads to two isostructural crystalline anhydrous coordination complexes, the polymeric [C2 mim]n [{Ln2 (OAc)7 }n ] and the dimeric [C2 mim]2 [Ln2 (OAc)8 ], based on the ion size and the ratio of IL used. A reaction with an IL : Ln-salt ratio of 5 : 1, where Ln=Nd, Sm, and Gd, led exclusively to the polymer, whilst for the heaviest lanthanides (Dy-Lu) the dimer was observed. Reaction with Eu and Tb resulted in a mixture of both polymeric and dimeric forms. When the amount of IL and/or the size of the cation was increased, the reaction led to only the dimeric compound for all the lanthanide series. Crystallographic analyses of the resulting salts revealed three different types of metal-acetate coordination modes where η2 µκ2 is the most represented in both structure types.

5.
Inorg Chem ; 60(3): 1869-1876, 2021 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-33471501

RESUMO

A series of ionic uranyl-containing complexes, namely [C2mim]2[UO2(ccnm)4] (1), [C4mim]2[UO2(ccnm)4] (2), [N1111]2[UO2(ccnm)4][H2O]2 (3), and [P2444]2[UO2(dcnm)2(ccnm)2] (4) [(ccnm)- = carbamoylcyanonitrosomethanide; dcnm = dicyanonitrosomethanide; (C2mim)+ = 1-ethyl-3-methylimidazolium; (C4mim)+ = 1-butyl-3-methylimidazolium; (N1111)+ = tetramethylammonium; (P2444)+ = tributyl(ethyl)phosphonium)], were isolated from in situ formed dcnm-based ionic liquids and characterized systematically. It was found that the dcnm anions transformed into ccnm anions during the reactions. These anions coordinate with the uranyl cations in chelate or terminal monodentate coordination mode, affording negative divalent complex anions which can combine with different organic cations and form ionic uranyl-containing complexes. Plenty of C-H···O, N-H···O, C-H···N, N-H···N, and H···H weak interactions are formed in the crystal structures. The transformation of cyano to amide groups contributes to the crystallinity and leads to higher melting points as well as the luminescence quenching of these compounds.

6.
Ecotoxicol Environ Saf ; 213: 112029, 2021 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-33578103

RESUMO

As primary polymer material in industrial products, bisphenol A (BPA) has become one of the most productive chemicals. Excluding its endocrine-disrupting property, BPA can also produce excessive reactive oxygen species (ROS). Nevertheless, the underlying toxic mechanisms of BPA-induced oxidative damages to plants are still unknown. In this work, glutathione S-transferase Phi8 was used as biomarker to evaluate the hazardous oxidative effects of BPA at the molecular level. Firstly, the intrinsic fluorescence of AtGSTF8 was statically quenched along with complex formation and structural and conformational changes, which led to the loosening and unfolding of the framework of AtGSTF8 as well as the increase of hydrophilicity around Trp residues. Then a single binding site was predicted for AtGSTF8 towards BPA and the complex formation was predominantly driven by hydrophobic interactions owing to the positive ΔH and ΔS. Besides, the predicted binding site of BPA was close to the H-site of AtGSTF8 which was surrounded by several hydrophobic amino acids based on the molecular docking results. The activity of glutathione S-transferase was declined and the plant growth was destroyed upon complex formation. The investigation of the binding mechanism of BPA with AtGSTF8 at molecular level would provide experimental assessments on toxicological effects of BPA on plants.


Assuntos
Arabidopsis/fisiologia , Compostos Benzidrílicos/toxicidade , Glutationa Transferase/metabolismo , Fenóis/toxicidade , Arabidopsis/metabolismo , Proteínas de Arabidopsis/metabolismo , Compostos Benzidrílicos/metabolismo , Sítios de Ligação , Simulação de Acoplamento Molecular , Oxirredução , Estresse Oxidativo/efeitos dos fármacos , Fenóis/metabolismo , Espécies Reativas de Oxigênio/metabolismo
7.
Inorg Chem ; 59(21): 15824-15831, 2020 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-33090775

RESUMO

Three uranyl carboxylates, namely, (UO2)(L1)(H2O)0.5 (1), [(UO2)(L2)(H2O)]·2H2O (2), and [(UO2)(L2)(H2O)]·(CH3CN) (3), were synthesized hydrothermally from 2',3',5',6'-tetramethyl-(1,1':4',1″-terphenyl)-4,4″-dicarboxylic acid (H2L1) and 2',5'-dimethyl-(1,1':4',1″-terphenyl)-3,3″-dicarboxylic acid (H2L2), which are all steric carboxylic acid ligands but vary with the carboxylic acid group position and methyl group number. It is found that compound 1 displays a three-dimensional 8-fold-interpenetrated net with channels running along the c direction. Compounds 2 and 3 are isostructural, and all display two-dimensional-layered crystal structures but contain different guest molecules. The photophysical measurements reveal that compounds 1 and 2, which contain disordered water molecules, are luminescence-quenched, whereas compound 3 containing acetonitrile molecules is luminescent.

8.
Inorg Chem ; 59(10): 7227-7237, 2020 May 18.
Artigo em Inglês | MEDLINE | ID: mdl-32364712

RESUMO

A robust general route to lanthanide dicyanamide (DCA-) complexes has been developed where f-element salts are dissolved in DCA--based ionic liquids (ILs) directly or formed in situ, forcing coordination of these normally weakly coordinating soft N-donor anions, even in an ambient, non-moisture-excluding environment. A series of lanthanide complexes [C2mim][Ln(DCA)4(H2O)4] (C2mim = 1-ethyl-3-methylimidazolium; Ln = La, Nd, Eu, Tb, Dy, and Yb) and [C2mim]3n[La(OH2)4(µ2-DCA)4]n[La(OH2)2(µ3-DCA)3(µ2-DCA)4]2n(Cl)4n were crystallized under a variety of conditions using this methodology and structurally characterized using single crystal X-ray diffraction. Although not all examples were isostructural, the dominant feature across the series was the presence of [Ln(DCA)4(H2O)4]- anionic nodes with all terminal DCA- ligands accepting hydrogen bonds from the coordinated water molecules forming a 3D metal organic framework. To determine if any structural clues might aid in the further development of the synthetic methodology, the metal-free IL [C1mim][DCA] (C1mim = 1,3-dimethylimidazolium), a room-temperature solid, crystalline analogue of the reaction IL, which is liquid at room temperature, was also prepared and structurally characterized. The ready isolation of these compounds allowed us to begin an investigation of the physical properties such as the luminescence at room and low temperatures for the Eu, Tb, and Dy representatives.

9.
Inorg Chem ; 59(1): 818-828, 2020 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-31841315

RESUMO

A series of anhydrous acetate salts with uranium {[C2C1im][UO2(OAc)3] (1), [C2C2im][UO2(OAc)3] (2), and [C4C1im][UO2(OAc)3] (3)}, lanthanides {[C2C2im]2[La(OAc)5] (4) and [C2C1im]2[Nd(OAc)5] (5)}, and strontium {[C2C1im]n[Sr(OAc)3]n (6)} (where C2C1im = 1-ethyl-3-methylimidazolium, C2C2im = 1,3-diethylimidazolium, C4C1im = 1-butyl-3-methylimidazolium, and OAc = acetate) have been prepared and structurally characterized. Both lanthanides and strontium are common components of the nuclear fuel waste, and their separation from uranium is an important but still challenging task. A new synthetic approach with dialkylimidazolium acetate ionic liquids (ILs) as the solvent has been developed for the direct synthesis of homoleptic acetates from the corresponding hydrates and, unexpectedly, hardly soluble f-element oxides. Although the group of characterized compounds shows perfect structural variability, all actinide and lanthanide metal ions form monomeric complex anions where the metal cation coordinates to five ligands including two oxygen atoms in the case of uranium, as is commonly observed for uranyl compounds. Crystallographic analyses revealed that the complex [UO2(OAc)3]- anions possess rather standard D3h symmetry featuring a hexagonal-bipyramidal coordination environment, while the lanthanide anions [Ln(OAc)5]2- are fully asymmetric and the Ln3+ cations are 10-coordinated in the form of a distorted bicapped tetragonal antiprism. This is the first report of lanthanide ions coordinated in this fashion. For Sr2+, 9-fold coordination through oxygen atoms in the form of a strongly distorted tricapped trigonal prism is observed. The crystallization of anhydrous, homoleptic, anionic acetate complexes from such a large variety of different metal salts appears to be due to the properties of dialkylimidazolium acetate ILs themselves, including enhanced basicity from the high concentration of free anions and their greater affinity for hydrogen-bonding solutes relative to metal cations.

10.
Inorg Chem ; 58(2): 1382-1390, 2019 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-30588807

RESUMO

By the introduction of terephthalic acid, tetramethylammonium chloride, and Zn2+ ions, three new uranyl triphosphonates with varying crystal structures, namely, [H3O][(UO2)2(HL)]·H2O (1), [NMe4][(UO2)2(HL)(H2O)]·H2O (2), and [(UO2)3Zn(H2L)2(H2O)2]·3H2O (3), where H6L = benzene-1,3,5-triyltris(methylene) triphosphonic acid, have been successfully synthesized and characterized by means of powder and single crystal XRD, IR, EA, TGA, UV-vis, and luminescence. These three compounds all possess three-dimensional framework structures with hydrium, tetramethylammonium, and Zn2+ as the respective countercations. The uranium(VI) center luminescence of compounds 1 and 2 is completely quenched. However, the incorporation of Zn2+ into the matrix of uranyl phosphonate in the case of compound 3 results in the emerging of the typical intense vibronic emissions of U(VI), demonstrating that zinc phosphonate can behave as sensitizer of uranyl phosphonates. The quenching and sensitization mechanism were also discussed.

11.
Inorg Chem ; 58(17): 11569-11578, 2019 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-31436092

RESUMO

Four strongly luminescent ionic liquids with complex lanthanide saccharinate anions, [C4mim]3[Eu(Sac)6(H2O)2] (1), {C4mpy}5{[Ln(Sac)6(H2O)2][Ln(Sac)5(H2O)3]}{(H2O)2(CH3CN)2} (Ln = Sm for 2a; Ln = Eu for 2b), and [C4mpy]3[Eu(Sac)6][CH3CN] (3) (C4mim = 1-butyl-3-methylimidazolium; C4mpy = N-butyl-4-methylpyridinium; Sac = saccharinate), have been obtained by reacting the ionic liquids 1-butyl-3-methylimidazolium saccharinate, [C4mim][Sac], and N-butyl-4-methylpyridinium saccharinate, [C4mpy][Sac], with the respective lanthanide saccharinates. Single-crystal X-ray diffraction analyses reveal the respective lanthanide center to be six- or eight-coordinated by five or six saccharinate anions and two or three aqua ligands in the cases of 1 and 2 when lanthanide saccharinated hydrate was employed as the starting material. Coordination of water to the lanthanide can be avoided when using the anhydrous lanthanide saccharinate as shown by the structure of 3. Using a co-solvent, acetonitrile, to facilitate the reaction led to incorporation of solvent molecules into the crystal structure of the final materials (2 and 3). Differential scanning calorimetry analyses reveal that 1 is an ionic liquid whereas 2 and 3 are low-temperature molten salts. The three europium(III)-containing compounds (1, 2b, and 3) all show characteristic intense red emissions of Eu(III) upon excitation into levels of the saccharinate ligands (321 nm) or Eu(III) (393 nm). At room temperature, the decay times of 1 and 2b are all ∼0.5 ms, whereas the decay time of 3 amounts to 3.85 ms due to removal of aqua ligands in the first coordination sphere; accordingly, the quantum efficiencies of 1, 2b, and 3 were determined to be 15.9%, 22.95%, and 57.75%, respectively. The CIE chromaticity coordinates for all Eu compounds are in the red region and approach the NTSC standard CIE values when the temperature is increased. Sm(III)-containing compound 2a shows characteristic Sm(III) emission peaks. As expected, the CIE coordinates of samarium compound 2a fall in the orange-red region.

12.
Inorg Chem ; 56(23): 14524-14532, 2017 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-29160695

RESUMO

Four new uranyl triphosphonates, namely, [N(CH4)4][UO2(H3L)][H2O] (1), [(UO2)1.5(H3L)(H2O)1.5][H2O] (2), [NBu4][(UO2)3.5(H2L)2][(H2O)4.5] (3), and [(UO2)1.5(H3L)(H2O)2.5][(H2O)2.5] (4), where H6L = benzene-1,3,5-triyltris(methylene)triphosphonic acid, were obtained from a triphosphonate ligand in the presence of different quaternary ammonium cations. The structural characterization revealed that the introduction of quaternary ammonium cation had a major impact on the structure formation of uranyl phosphonates. Compound 1 possesses a three-dimensional anionic framework structure. Tetramethylammonium cations are accommodated in the channels, serving as counterions and structure directing agents. Compound 2 also displays a three-dimensional framework structure but is neutral, because the tetrapropylammonium cations are not involved in the crystal structure. Compound 3 has an intercalation structure; between the layers are the tetrabutylammonium cations, balancing the charge and strengthening the supramolecular structure with C-H···O interactions. No obvious uptake of N2 and CO2 could be observed for compound 2 due to the shrinkage of the framework and structural transformation. Compound 2 undergoes single-crystal to single-crystal transformation under vacuum, leading to the formation of compound 4, which possesses a two-dimensional layer structure. The photophysical properties of these compounds were also investigated.

13.
Inorg Chem ; 54(5): 2088-90, 2015 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-25689139

RESUMO

A Cu(+)-CP based on the tetranuclear unit {[(HSQPA)2Cu4(bipy)4]·2H2O}n·2nH2O has been constructed through Cu(2+) salt, 2-(sulfonylquinlium-8-yloxy)phthalic acid (H3SQPA), and 4,4'-bipyridine (bipy). This Cu(+)-CP combined with 2,2,6,6-tetramethylpiperidine-1-oxyl as the cocatalyst is an effective catalyst for aerobic oxidation of alcohols and the synthesis of benzoxazoles and can be recycled at least four times without losing its catalytic activity.


Assuntos
Álcoois/química , Benzoxazóis/síntese química , Cobre/química , Óxidos N-Cíclicos/química , Compostos Organometálicos/química , Polímeros/química , Benzoxazóis/química , Catálise , Modelos Moleculares , Estrutura Molecular , Compostos Organometálicos/síntese química , Oxirredução
14.
Inorg Chem ; 53(17): 9027-35, 2014 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-25121823

RESUMO

Four salts containing imidazolium cations and europium(III)- or terbium(III)-centered complex anions have been successfully synthesized from an ethanol/H2O solution. The single-crystal X-ray diffraction analyses reveal that these compounds have a common formula of [R][Ln(DETCAP)4] [R = 1-ethyl-3-methylimidazolium (C2mim), Ln = Eu (1) and Tb (2); R = 1-butyl-3-methylimidazolium (C4mim), Ln = Eu (3) and Tb (4); DETCAP = diethyl-2,2,2-trichloroacetylphosphoramidate], in which the lanthanide centers are chelated by four chelating pseudo-ß-diketonate ligands (DETCAP)(-), forming the respective complex anions. Their thermal behaviors and stabilities were also investigated to study the role of the length of the side chain in the cations. Fluorescence measurements at both room temperature and liquid-nitrogen temperature show that these materials show intense characteristic europium(III) or terbium(III) emissions and have long decay times. Their overall quantum yields were determined to be in the range of 30-49%.


Assuntos
Imidazóis/química , Elementos da Série dos Lantanídeos/química , Ânions , Varredura Diferencial de Calorimetria , Cátions , Luminescência
15.
Dalton Trans ; 51(3): 1041-1047, 2022 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-34935817

RESUMO

Lanthanide-uranyl phosphonates possess intriguing crystal structures and huge application prospects, but the construction of these materials remains challenging. In this work, we demonstrate that new uranyl and lanthanide-uranyl sulfonylphosphonates with elegant crystal structures and photophysical properties can be assembled hydrothermally by employing the heterofunctional diethyl phosphonate (diethyl ((phenylsulfonyl)methyl)phosphonate, Et2L) as a precursor ligand, which provides an effective strategy for the construction of lanthanide-uranyl phosphonates.

16.
Spectrochim Acta A Mol Biomol Spectrosc ; 229: 117955, 2020 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-31887676

RESUMO

As a most abundant plasticizer, Di-(2-ethylhexyl) phthalate (DEHP) has been widely used in agriculture with an associated potential toxicity to many species including plants via the production of the excessive reactive oxygen species (ROS). However, the potential toxic mechanisms of the plasticizer DEHP-induced oxidative damage to plants remain unknown. The antioxidant enzyme glutathione peroxidase has been suggested as biomarkers to reflect over excessive oxidative stress. In this study, the effect of DEHP on AtGPX6 was evaluated by multi-spectroscopic techniques and molecular docking method. The fluorescence intensity of AtGPX6 was reduced by the static quenching mechanism upon the addition of DEHP. The predominant forces in complex formation was mainly impelled by hydrogen bonding and Van der Waals forces based on the negative ΔH and ΔS, which was in accordance with the molecular docking results. In addition, the secondary structural changes resulted from the complex formation were investigated in presence of different amounts of DEHP by the combination of fluorescence, UV-vis absorption and Circular dichroism spectra, which revealed the loosening and unfolding of the framework of AtGPX6 accompanied with the enhancement of the hydrophilicity around the tryptophan residues. The exploration of the interaction mechanism of DEHP with AtGPX6 at molecular level would help to evaluate the toxicity of the plasticizers and forecast the related adverse effects on plants.


Assuntos
Proteínas de Arabidopsis/metabolismo , Arabidopsis/metabolismo , Biomarcadores/metabolismo , Dietilexilftalato/toxicidade , Estresse Oxidativo/efeitos dos fármacos , Fosfolipídeo Hidroperóxido Glutationa Peroxidase/metabolismo , Plastificantes/toxicidade , Medição de Risco/métodos , Antioxidantes/metabolismo , Arabidopsis/efeitos dos fármacos , Espécies Reativas de Oxigênio/metabolismo
17.
Int J Biol Macromol ; 145: 165-172, 2020 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-31863837

RESUMO

As the most widely used plasticizer, di-(2-ethylhexyl) phthalate (DEHP) has been extensively applied to agriculture. However, its excessive accumulation may cause the active oxygen damage in plants and further lead to the destruction of antioxidant enzymes. As a core component of the glutathione antioxidant enzyme system, glutathione S-transferases (GSTs) have been reported as biomarkers for assessing oxidative damage induced by environmental pollutants, but the underlying toxic molecular mechanism has rarely been exploited. In this article, the interaction mechanism of Arabidopsis thaliana glutathione S-transferase AtGSTF8 and plasticizer DEHP was investigated at the molecular level by multispectral methods. The enzyme activity changes of AtGSTF8 upon binding with DEHP were also evaluated. A single binding site of AtGSTF8 towards DEHP was predicted and the binding force was presumed mainly by Van der Waals' force and hydrogen bonding based on static quenching mechanism. Besides, the deconstructions of the protein skeleton were also deduced based on the multispectral results and the hazardous effects of DEHP on plants growth were further demonstrated. This work will help to clarify the functional mechanism between the plasticizer DEHP and the antioxidant enzyme AtGSTF8 at the molecular level, and providing useful information for further study of the toxic effects of DEHP on plant antioxidant systems.


Assuntos
Arabidopsis/efeitos dos fármacos , Dietilexilftalato/toxicidade , Glutationa Transferase/metabolismo , Ácidos Ftálicos/toxicidade , Antioxidantes/metabolismo , Arabidopsis/metabolismo , Poluentes Ambientais/toxicidade , Glutationa/metabolismo , Peroxidação de Lipídeos/efeitos dos fármacos , Oxirredução/efeitos dos fármacos , Estresse Oxidativo/efeitos dos fármacos , Plastificantes/toxicidade , Poluentes Químicos da Água/toxicidade
18.
Spectrochim Acta A Mol Biomol Spectrosc ; 226: 117597, 2020 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-31629975

RESUMO

Along with non-biodegradability and accumulation in agricultural soil, lead (II) ions exert considerable harmful effects on plants even at trace amount, especially for the oxidative damages elicited by the lead ions-induced excessive reactive oxygen species (ROS). The glutathione peroxidases were reported to be correspondent with the oxidative stress induced by heavy metals. However, limited data are available about the potential hazardous mechanisms of the lead ions-induced oxidative damage to plants at molecular level. In this study, the harmful impacts of lead ions on Arabidopsis thaliana glutathione peroxidase 6 (AtGPX6) were assessed based on multi-spectroscopic measurements and molecular docking study. The characteristic fluorescence of AtGPX6 was quenched by lead ions with static mechanism at different temperatures. AtGPX6 exhibits a single binding site with lead ions, and then the complex formation was mainly driven by hydrogen bonding interaction and van der Waals forces on account of the negative ΔH and ΔS. The secondary structural changes were observed from the synchronous fluorescence, UV-visible absorption and Circular dichroism spectra, which led to loosen and unfold of the protein framework accompanied by the incremental hydrophobicity around the vicinity of the tryptophan residues. Therefore, this work illustrates the detailed binding mode between lead (II) ions and glutathione peroxidase 6 from Arabidopsis thaliana and the toxic effects on antioxidative defense system induced by lead ions at molecular level.


Assuntos
Proteínas de Arabidopsis/química , Proteínas de Arabidopsis/metabolismo , Chumbo/química , Chumbo/farmacocinética , Simulação de Acoplamento Molecular , Fosfolipídeo Hidroperóxido Glutationa Peroxidase/química , Fosfolipídeo Hidroperóxido Glutationa Peroxidase/metabolismo , Arabidopsis/efeitos dos fármacos , Arabidopsis/enzimologia , Arabidopsis/metabolismo , Sítios de Ligação , Fenômenos Biofísicos , Dicroísmo Circular , Fluorescência , Íons/química , Íons/farmacocinética , Modelos Moleculares , Estresse Oxidativo/efeitos dos fármacos , Ligação Proteica , Domínios Proteicos/efeitos dos fármacos , Espectrometria de Fluorescência , Espectrofotometria Ultravioleta
19.
Dalton Trans ; 49(12): 3809-3815, 2020 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-31820767

RESUMO

A series of lanthanide diphosphonates, namely Ln(HL)(H2O)2 (Ln = Nd 1, Eu 2, Tb 3 and Er 4), have been synthesized from a semirigid diphosphonate ligand, (5-methyl-1,3-phenylene)bis(methylene)bisphosphonic acid (H4L). These lanthanide diphosphonates have been systematically characterized by using powder and single-crystal X-ray diffraction, elemental analysis, TGA, IR, UV-vis absorption and luminescence techniques. The single-crystal XRD measurements revealed that these compounds all have two-dimensional layered crystal structures. Among these four compounds, 1, 2 and 4 are isostructural and crystallize in the P21/c space group, whereas compound 3 crystallizes in the P21 space group. These compounds display the characteristic emissions of the respective lanthanide ions. The sensing properties of compound 3 were investigated which revealed that it could be used as a luminescent probe for Fe3+ and Cr2O72- with good selectivity and sensitivity.

20.
Spectrochim Acta A Mol Biomol Spectrosc ; 216: 411-417, 2019 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-30925335

RESUMO

Accumulation of cadmium ions may result in adverse effects on plant due to the oxidative stress via destructions of antioxidants and antioxidant enzymes. As the core component of the glutathione antioxidant system, glutathione S-transferases (GSTs) have been reported as biomarkers for evaluating the metal-induced oxidative damage to plants, but the potential toxicity and underlying toxic molecular mechanisms remain unknown. This article investigated the molecular interactions of cadmium ions with Arabidopsis thaliana glutathione S-transferase phi8 (AtGSTF8) by multi-spectroscopic techniques and enzyme activity measurements. The intrinsic fluorescence of AtGSTF8 was quenched statically upon the addition of cadmium ions accompanied with the complex formation and structural and conformational alterations from multiple spectroscopic measurements, resulting in deconstructed protein skeleton and microenvironmental alterations around the Tyr and Trp residues. A single binding site was predicted for AtGSTF8 towards cadmium ions and the van der Walls interactions and hydrogen bonds are the major driving forces of the interaction. In addition, the transferase activity changes of AtGSTF8 upon the addition of cadmium ions have been observed. The implementation of this work helps to clarify the mechanism of oxidative damage and antioxidant enzymes response induced by heavy metal accumulation in plant at molecular level.


Assuntos
Proteínas de Arabidopsis/metabolismo , Arabidopsis/metabolismo , Cádmio/metabolismo , Glutationa Transferase/metabolismo , Arabidopsis/química , Proteínas de Arabidopsis/química , Sítios de Ligação , Cátions Bivalentes/metabolismo , Glutationa Transferase/química , Estresse Oxidativo , Ligação Proteica , Estrutura Secundária de Proteína , Termodinâmica
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