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1.
J Photochem Photobiol B ; 253: 112863, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38457992

RESUMO

Phthalocyanines have been described as effective photosensitizers for photodynamic therapy and are therefore, being studied for their biomedical applications. The metalation of photosensitizers can improve their photodynamic therapy potential. Here, we focus on the biological properties of [1,4-Bis(3,6,9,12-Tetraoxatridec-1-yloxy)phthalocyaninato]zinc(II) (ZnPc(αEG4)2) and demonstrate its exceptional anticancer activity upon light stimulation to kill preferentially cancer cells with a start of efficiency at 10 pM. Indeed, in this work we highlighted the high selectivity of ZnPc(αEG4)2 for cancer cells compared with healthy ones and we establish its mechanism of action, enabling us to conclude that ZnPc(αEG4)2 could be a powerful tool for cancer therapy.


Assuntos
Indóis , Compostos Organometálicos , Fotoquimioterapia , Fármacos Fotossensibilizantes/farmacologia , Zinco , Compostos Organometálicos/farmacologia , Compostos de Zinco
2.
Environ Sci Pollut Res Int ; 31(1): 1674-1680, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38147238

RESUMO

Contamination of sunflower seeds with soil Cd is an important issue for food and feed because this species strongly accumulates this metal. The present work reports that seeds from three sunflower varieties (ES Biba, Extrasol, Vellox) cultivated in the field in a calcareous agricultural soil having a moderately high Cd content (1 mg Cd/kg) had Cd contents of 0.84, 0.88 and 0.76 mg Cd/kg, respectively, all exceeding the regulation limit of 0.5 mg Cd/kg seeds for human food. On average, for the three varieties, washing seeds did not affect their total Cd contents but slightly increased the Cd in the kernels at the expense of that in hulls. Despite the Cd content of the whole seeds not differing between the varieties, the Cd fraction in the edible kernel differed significantly between varieties from 78 to 87% of the total seed Cd. The results of this study suggest that (i) the size of the kernel, relative to that of the hull, may affect the dilution of Cd in kernel tissues and (ii) there might be genetic variability for the capacity of transfer of Cd from the hull to the kernel. This opens the perspective to increase food safety by selecting sunflower genotypes that retain more Cd into the hull and transfer less of it to the edible kernel.


Assuntos
Asteraceae , Helianthus , Poluentes do Solo , Humanos , Cádmio/análise , Sementes/química , Solo , Poluentes do Solo/análise
3.
J Hazard Mater ; 465: 133188, 2024 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-38134693

RESUMO

Many experiments showed that exogenous ligands could enhance cadmium (Cd) phytoextraction efficiency in soils. Previous studies suggested that the dissociation and the apoplastic uptake of Cd complex could not fully explain the increase of root Cd uptake. Two hypotheses are evaluated to explain enhanced Cd uptake in the presence of ligand: i) enhanced apoplastic uptake of complex due to reduced apoplastic resistance and ii) complex internalization by membrane transporters. RESULTS: show that the ligand affinity for Cd is a key characteristic determining the potential mechanism for enhanced Cd uptake. When low molecular weight organic acids are applied, the complex dissociation could generally be fast (> 10-3.3 s-1) and result in the increased Cd uptake. When hydrophilic aminopolycarboxylic acids (APCAs) are applied in experiments without water or temperature stresses to the plant, the root water uptake flux could very likely be high (> 10-7.8 dm s-1), and the strong apoplastic complex uptake could enhance the root Cd uptake. When lipophilic APCAs are applied, the strong internalization of the complex by membrane transporters could result in the increased Cd uptake if the maximum internalization rate is high (> 10-12 mol dm-2 s-1). However, the complex internalization by membrane transporters must be experimentally confirmed.


Assuntos
Cádmio , Poluentes do Solo , Cádmio/metabolismo , Solo , Ligantes , Poluentes do Solo/análise , Proteínas de Membrana Transportadoras , Água , Biodegradação Ambiental , Raízes de Plantas/metabolismo
4.
ACS Appl Mater Interfaces ; 15(36): 42942-42953, 2023 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-37647569

RESUMO

Herein, we report for the first time a biocompatible cross-linked trianglamine (Δ) network for the efficient iodine removal from the vapor phase, water, and seawater. In the vapor phase, the cross-linked network could capture 6 g g-1 of iodine, ranking among the most performant materials for iodine vapor capture. In the liquid phase, this cross-linked network is also capable of capturing iodine at high rates from aqueous media (water and seawater). This network displayed fast adsorption kinetics, and they are fully recyclable. This study reveals the high affinity of iodine for the intrinsic cavity of the trianglamine. The synthesized materials are extremely interesting since they are environmentally friendly and inexpensive and the synthesis could easily be scaled up to be used as the material of choice in response to accidents in the nuclear industry.

5.
Adv Healthc Mater ; 12(27): e2301052, 2023 10.
Artigo em Inglês | MEDLINE | ID: mdl-37499629

RESUMO

The concept of using two-photon excitation in the NIR for the spatiotemporal control of biological processes holds great promise. However, its use for the delivery of nucleic acids has been very scarcely described and the reported procedures are not optimal as they often involve potentially toxic materials and irradiation conditions. This work prepares a simple system made of biocompatible porous silicon nanoparticles (pSiNP) for the safe siRNA photocontrolled delivery and gene silencing in cells upon two-photon excitation. PSiNP are linked to an azobenzene moiety, which possesses a lysine group (pSiNP@ICPES-azo@Lys) to efficiently complex siRNA. Non-linear excitation of the two-photon absorber system (pSiNP) followed by intermolecular energy transfer (FRET) to trans azobenzene moiety, result in the photoisomerization of the azobenzene from trans to cis and in the destabilization of the azobenzene-siRNA complex, thus inducing the delivery of the cargo siRNA to the cytoplasm of cells. Efficient silencing in MCF-7 expressing stable firefly luciferase with siRNAluc against luciferase is observed. Furthermore, siRNA against inhibitory apoptotic protein (IAP) leads to over 70% of MCF-7 cancer cell death. The developed technique using two-photon light allows a unique high spatiotemporally controlled and safe siRNA delivery in cells in few seconds of irradiation.


Assuntos
Nanopartículas , Neoplasias , Humanos , RNA Interferente Pequeno/genética , Silício , Porosidade , Transfecção , Linhagem Celular Tumoral
6.
Org Biomol Chem ; 21(32): 6509-6523, 2023 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-37341568

RESUMO

Drug-targeted delivery has become a top priority in the world of medicine in order to develop more efficient therapeutic agents. This is important as a critical underlying problem in cancer therapy stems from the inability to deliver active therapeutic substances directly to tumor cells without causing collateral damage. In this work, zinc(II) phthalocyanine (ZnPc) was selected as a sensitizer and was linked to different targeting agents, which would be recognized by overexpressed proteins in cancer cells. As targeting agents, we first selected the two ligands (DAA1106, PK11195) of the translocator protein (TSPO) and then Erlotinib a binding group of the ATP domain of tyrosine kinase in epidermal growth factor (EGFR). ZnPc was connected via an ethylene glycol chain to either one (n = 1) or four (n = 4) targeting agents. The biological activity of these conjugates ZnPc(ligand)n was investigated on MDA-MB-231 breast human cancer cells and human hepatoma HepG2 cells, first in the dark (cytotoxicity) and then under irradiation (photodynamic therapy). The dark cytotoxicity was extremely low (IC50 ≥ 50 µM) for all of these compounds, which is a required criterion for further photodynamic application. After irradiation at 650 nm, only the conjugates bearing one targeting ligand such as ZnPc-[DAA1106]1, ZnPc-[PK11195]1, and ZnPc-[Erlo]1 showed photodynamic activity, while those linked to 4 targeting agents were inactive. Importantly, fluorescence imaging microscopy showed the colocalization of ZnPc-[DAA1106]1, ZnPc-[PK11195]1 and ZnPc-[erlo]1, at mitochondria, a result that justifies the observed photodynamic activity of these conjugates. This study first shows the impact of the number and the mode of organization of targeting agents on the ability of the sensitizer to cross the cell membrane. When zinc(II) phthalocyanine carries a single targeting agent, a significant photodynamic activity on MDA-MB-231 breast human cancer cells was measured and localization at the mitochondria was demonstrated by fluorescence imaging, thus proving the potential of the sensitizer linked to a targeting agent to improve selectivity. Another important conclusion from this study for the design of future effective PDT drugs using multivalence effects is to control the arrangement of the targeting agents in order to design molecules that will be able to pass the cell membrane barriers.


Assuntos
Compostos Organometálicos , Fotoquimioterapia , Humanos , Fotoquimioterapia/métodos , Ligantes , Isoindóis , Compostos Organometálicos/farmacologia , Compostos Organometálicos/química , Receptores ErbB , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/química , Linhagem Celular Tumoral , Receptores de GABA
7.
Am J Trop Med Hyg ; 108(2): 424-427, 2023 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-36535248

RESUMO

Anopheles darlingi is the main vector of malaria in South America. In French Guiana, malaria transmission occurs inland and along the rivers with a regular reemergence in the lower Oyapock area. Control against malaria vectors includes indoor residual spraying of deltamethrin and the distribution of long-lasting impregnated bednets. In this context, the level of resistance to pyrethroids was monitored for 4 years using CDC bottle tests in An. darlingi populations. A loss of susceptibility to pyrethroids was recorded with 30-minute knock-down measured as low as 81%. However, no pyrethroid molecular resistance was found by sequencing a 170 base pair fragment of the S6 segment of domain II of the voltage-gated sodium channel gene. Fluctuation of resistance phenotypes may be influenced by the reintroduction of susceptible alleles from sylvatic populations or by other mechanisms of metabolic resistance.


Assuntos
Anopheles , Inseticidas , Malária , Piretrinas , Animais , Anopheles/genética , Guiana Francesa , Resistência a Inseticidas/genética , Mosquitos Vetores/genética , Malária/prevenção & controle , Piretrinas/farmacologia , Inseticidas/farmacologia , Controle de Mosquitos
8.
Life (Basel) ; 12(12)2022 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-36556409

RESUMO

BACKGROUND: In addition to their great optical properties, nanodiamonds (NDs) have recently proved useful for two-photon-excited photodynamic therapy (TPE-PDT) applications. Indeed, they are able to produce reactive oxygen species (ROS) directly upon two-photon excitation but not with one-photon excitation; Methods: Fluorescent NDs (FNDs) with a 100 nm diameter and detonation NDs (DNDs) of 30 nm were compared. In order to use the gems for cancer-cell theranostics, they were encapsulated in a bis(triethoxysilyl)ethylene-based (ENE) periodic mesoporous organosilica (PMO) shell, and the surface of the formed nanoparticles (NPs) was modified by the direct grafting of polyethylene glycol (PEG) and amino groups using PEG-hexyltriethoxysilane and aminoundecyltriethoxysilane during the sol-gel process. The NPs' phototoxicity and interaction with MDA-MB-231 breast cancer cells were evaluated afterwards; Results: Transmission electronic microscopy images showed the formation of core-shell NPs. Infrared spectra and zeta-potential measurements confirmed the grafting of PEG and NH2 groups. The encapsulation of the NDs allowed for the imaging of cancer cells with NDs and for the performance of TPE-PDT of MDA-MB-231 cancer cells with significant mortality. CONCLUSIONS: Multifunctional ND@PMO core-shell nanosystems were successfully prepared. The NPs demonstrated high biocompatibility and TPE-PDT efficiency in vitro in the cancer cell model. Such systems hold good potential for two-photon-excited PDT applications.

9.
Front Psychol ; 13: 993458, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36329744

RESUMO

The psychosocial safety climate (PSC) reflects workers' perceptions of senior management's concern for mental health. Because the COVID-19 pandemic has exacerbated organizational issues, PSC could be a target for interventions attempting to preserve both the psychological health of employees and the economic health of companies. This study examines the direct and indirect relationships between PSC and work performance through two indicators of psychological health, psychological distress and post-traumatic growth, during a health crisis, i.e., prior to the second confinement in France. To this end, 2,004 participants from the French workforce completed a survey in October 2020. The results of mediation analyses indicate that PSC has a direct and positive influence on post-traumatic growth (PTG) and performance, as well as a direct negative influence on psychological distress. PSC also has an indirect positive influence on performance via psychological distress. Organizations that wish to jointly address mental health and performance at work would benefit from optimizing PSC.

10.
Sci Total Environ ; 850: 157907, 2022 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-35985599

RESUMO

The objective of this study was to assess the effects of different intensities of biomass harvesting, and the possible effects of compensation methods, on forest functioning. To do so, we carried out a split-plot experiment (SW France) crossing four different intensities of biomass harvesting (Stem-Only Harvest [SOH], Aboveground Additional Harvest [AAH], Belowground Additional Harvest [BAH], and Whole-Tree Harvest [WTH]) and three compensation methods (control [C], wood ash application [A] and phosphorus fertilisation [P]). The experimental treatments were followed by the plantation of pines (Pinus pinaster). The environmental consequences of treatments on soil and vegetation were evaluated 11 years after the tree plantation. Despite their low additional biomass exports (+10 % for AAH to +34 % for WTH), the non-conventional harvest practices exported much higher quantities of nutrients than the conventional SOH technique (+145 % of exported N in WTH). Additional biomass harvests impacted the soil organic matter content, with negative effects on P-organic, soil cation exchange capacity, exchangeable Ca, and most extractible nutrients. However, tree nutritional status was improved by P-fertiliser or wood ash. We observed a positive effect of wood ash application on soil pH and nutrient content but, like additional harvests, wood ash application decreased the pool of soil organic carbon (~10 %). Overall, the experiment showed that exporting more forest biomass due to the additional harvesting of biomass had negative consequences on the ecosystem biogeochemistry. Additional harvests have impoverished the soil, and decreased the soil organic carbon content. Importantly, applying nutrients as fertiliser or wood ash did not compensate for all the negative impacts of biomass exports and the method of wood ash recycling in forests could even decrease the soil organic carbon.


Assuntos
Pinus , Solo , Biomassa , Carbono , Ecossistema , Fertilização , Fertilizantes , Florestas , Fósforo , Solo/química , Árvores/química
11.
J Agric Food Chem ; 70(26): 8085-8096, 2022 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-35730681

RESUMO

Durum wheat is one of the cereal crops that accumulates the highest concentrations of cadmium (Cd) and deoxynivalenol (DON) mycotoxin in its grains, thereby affecting the safety of products made of durum wheat grains (pasta and semolina). This study investigates in planta the interaction between Cd and Fusarium graminearum, the main causal agent of DON accumulation in grains. A pot experiment was designed to characterize the response of durum wheat to F. graminearum infection at three levels of Cd exposure: 0.1, 2, and 10 mg Cd kg-1 soil, which showed that the accumulation of Cd and DON resulted from interacting processes. On the one hand, plant exposure to Cd reduced the concentration of DON in grains. The mitigating effect of Cd on DON accumulation was attributed to the restricted growth of F. graminearum, which could result from enhanced plant resistance to the fungal pathogen induced by Cd exposure. On the other hand, F. graminearum infection of durum wheat increased the Cd concentration in the grains. The promoting effect of Fusarium infection on Cd accumulation was attributed to decoupling of the allocation of Cd and photoassimilates to the grains and to the reduced strength of the grain sink for photoassimilates caused by the fungus. Provided that this result is confirmed in field conditions, it suggests that in Cd-contaminated soils, particular attention should be paid to agronomic practices that affect Fusarium head blight disease to avoid further increase in the risk of exceeding the regulatory limit set by the European Union for Cd in durum wheat.


Assuntos
Fusarium , Micotoxinas , Cádmio , Grão Comestível/química , Micotoxinas/análise , Doenças das Plantas/microbiologia , Tricotecenos , Triticum/microbiologia
12.
Cancers (Basel) ; 14(10)2022 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-35625963

RESUMO

Star-shaped hydrophobic porphyrins, acting as powerful fluorescent two-photon photosensitizers for oxygen in organic solvents, can easily be loaded into PMLABe polymeric nanoparticles at various concentrations. In this contribution, the performance of these porphyrin-containing nanoparticles in terms of photodynamic therapy (PDT) is compared to those of the corresponding water-soluble porphyrin analogues when irradiated in MCF-7 cancer cells. While quite promising results are obtained for performing PDT with these nanoparticles, validating this approach as a mean for using more easily accessible and less expensive photosensitizers, from a synthetic perspective, we also show that their luminescence can still be used for bioimaging purposes in spite of their confinement in the nanoparticles, validating also the use of these nano-objects for theranostic purposes.

13.
Environ Sci Pollut Res Int ; 29(20): 29268-29284, 2022 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-34508312

RESUMO

Accumulation of copper (Cu) in soils due to the application of fungicides may be toxic for organisms and hence affect winegrowing sustainability. Soil parameters such as pH and dissolved organic matter (DOM) are known to affect the availability of Cu. In this study, we investigated the contribution of chromophoric and fluorescent DOM properties to the prediction of Cu availability in 18 organic vineyard soils in the Bordeaux winegrowing area (France). The DOM parameters, assessed through absorbance and fluorescence analyses, and proxies for Cu availability (total soluble Cu and free ionic Cu2+) were measured in 0.01 M KCl extracts. Total soluble Cu (CuKCl) varied 23-fold while free ionic Cu2+ varied by a factor of 4600 among the soils. DOC concentrations were similar among the soils, but the samples differed in the quality of DOM as assessed by optical spectroscopy. Multilinear regression models with and without DOM quality parameters were investigated to predict Cu availability. The best model for CuKCl successfully explained 83% of variance and included pH, CuT, and two DOM fluorescence quality indices, the FI fluorescence index, which distinguishes between microbial and higher plant origins, and the HIX humification index. For the prediction of Cu2+, pH alone explained 88% of variance and adding DOM parameters did not improve modelling. The two Cu availability proxies were related to pH. This study confirms the prominent role of pH in Cu availability and underlines the importance of DOM quality to better predict Cu solubility.


Assuntos
Cobre , Matéria Orgânica Dissolvida , Solo , Cobre/química , Fazendas , Compostos Orgânicos/análise , Solo/química
14.
ACS Appl Mater Interfaces ; 13(26): 30337-30349, 2021 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-34159778

RESUMO

The efficient, versatile, and straightforward synthesis of the first N-alkyl analogues of induline 3B (8a and 8b) is reported. Thanks to the introduction of lipophilic substituents and their attractive photophysical properties (far-red emission and production of singlet oxygen), phenazinium 8b can be used as a theranostic agent and shows, at very low concentrations (100 nM), a remarkable ability to (i) image cells and zebrafish embryos with high quality under both mono- (514 nm) and biphotonic (790 and 810 nm) excitations, (ii) efficiently and quickly penetrate cancer cells rather than healthy fibroblasts, and (iii) induce a total or almost total cancer cell death in vitro and in vivo after illumination (λexc = 540-560 nm). The molecular structure of 8b is based on a triamino-phenazinium core only, with no need for additional components, highlighting the emergence of a minimalistic and versatile class of fluorescent probes for targeted photodynamic cancer therapy.


Assuntos
Antineoplásicos/uso terapêutico , Corantes Fluorescentes/uso terapêutico , Fenazinas/uso terapêutico , Fármacos Fotossensibilizantes/uso terapêutico , Animais , Antineoplásicos/síntese química , Antineoplásicos/metabolismo , Antineoplásicos/efeitos da radiação , Linhagem Celular Tumoral , Fibroblastos/metabolismo , Corantes Fluorescentes/síntese química , Corantes Fluorescentes/metabolismo , Corantes Fluorescentes/efeitos da radiação , Humanos , Luz , Neoplasias/diagnóstico por imagem , Neoplasias/tratamento farmacológico , Fenazinas/síntese química , Fenazinas/metabolismo , Fenazinas/efeitos da radiação , Fotoquimioterapia , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/metabolismo , Fármacos Fotossensibilizantes/efeitos da radiação , Medicina de Precisão/métodos , Oxigênio Singlete/metabolismo , Ensaios Antitumorais Modelo de Xenoenxerto , Peixe-Zebra
15.
Sci Total Environ ; 778: 146428, 2021 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-34030371

RESUMO

Speciation of Cd in soil solutions strongly determines the fate of this toxic metal in the environment. Generally, in soil solutions, Cd predominantly binds to the dissolved organic matter (DOM). The determination of the quantity and reactivity of DOM that actually complexes Cd in soil solutions is challenging for operational purposes. Therefore, this study tested whether Cd2+ concentration in soil solutions could effectively be predicted by considering complexation with a single mean organic ligand assumed to be a fraction of DOM of unspecified nature or assumed to be purely fulvic acids (FA) with reactivity as described in WHAM VII. The reactivity of the unspecified ligand and the concentration of FA were modelled and fitted to experimental data from 76 agricultural soils with low Cd contents. The optimal reactivity and FA concentration that minimized the relative error (RE) of predictions of the concentration of Cd2+ in soil solutions were either considered constant across soils or modelled from soil properties by multiple linear regressions (MLR) or random forests (RF), giving 6 models, the predictive value of which was assessed by 10-folds cross-validation. When the reactivity of the mean ligand and the optimal FA concentration were considered constant across soils, the models were biased and 66.9% of predictions had relative errors below a factor of 2. By contrast, if the reactivity of the mean ligand or the optimal FA concentration were allowed to vary with soil characteristics, these performances increased to 95.5%, soil pH being the main predictor and RF being slightly more efficient than MLR. With more than 95% of the relative errors of prediction below a factor of 2, the models developed in this work could be valuable for assessing Cd speciation in the solution of soils having a low Cd content.

16.
Anal Chem ; 93(17): 6865-6872, 2021 05 04.
Artigo em Inglês | MEDLINE | ID: mdl-33881841

RESUMO

Antibodies not only play a major role in clinical diagnostics and biopharmaceutical analysis but also are a class of drugs that are regularly used to treat numerous diseases. The identification of antibody-epitope binding sites is then of great interest to many emerging medical and bioanalytical applications, particularly to design monoclonal antibodies (mAb) mimics taking advantage of amino acid residues involved in the binding. Among relevant antibodies, the monoclonal antibody rituximab has received significant attention as it is exploited to treat several cancers including non-Hodgkin's lymphoma and chronic lymphocytic leukemia, as well as some autoimmune disorders such as rheumatoid arthritis. The binding of rituximab to the targeted cells occurs via the recognition of the CD20 epitope. A crystallographic study has shown that the binding area, named paratope, is located at the surface of rituximab. Combining the SPOT method and the complementary surface plasmon resonance technique allowed us to detect an extended recognition domain buried in the pocket of the rituximab Fab formed by four ß-sheets. More generally, the present study offers a comprehensive approach to identify antibody-epitope binding sites.


Assuntos
Antígenos CD20 , Ressonância de Plasmônio de Superfície , Anticorpos Monoclonais Murinos , Sítios de Ligação , Epitopos , Rituximab
17.
Pharmaceuticals (Basel) ; 14(5)2021 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-33924752

RESUMO

The combination of photodynamic therapy and chemotherapy is a promising strategy to enhance cancer therapeutic efficacy and reduce drug resistance. In this study two zinc(II) phthalocyanine-tin(IV) conjugates linked by a triethylene glycol chain were synthesized and characterized. In these complexes, the zinc(II) phthalocyanine was used as a potential photosensitizer for PDT and the tin complex was selected as cytostatic moiety. The two dyads composed of zinc(II) phthalocyanine and tin complexes exhibited high cytotoxicity, in absence of light stimulation, against MCF-7 human breast cancer cells with low LC50 values in the range of 0.016-0.453 µM. In addition, these complexes showed superior cytotoxicity than their mixture of equimolar component, accompanied with a higher activity towards cancer cells compared to human healthy fibroblasts. However, under irradiation of the zinc phthalocyanine unit (at 650 nm) no photodynamic activity could be detected, due to the most likely quenching of zinc(II) phthalocyanine singlet excited state by the nearby tin complex according to a photoinduced electron transfer process. This study demonstrates the potential of heterometallic anticancer chemotherapeutics composed of a zinc phthalocyanine and tin complex, and it highlights that the development of such conjugates requires that the sensitizer preserves its photophysical properties and in particular its singlet oxygen sensitization ability in the conjugate in order to combine the PDT activity with the cytotoxicity of the anticancer drug.

18.
Dalton Trans ; 50(13): 4583-4592, 2021 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-33705511

RESUMO

The discovery of novel anticancer chemotherapeutics is fundamental to treat cancer more efficiently. Towards this goal, two dyads consisting of a gold porphyrin appended to organotin(iv) entities were synthesized and their physicochemical and biological properties were characterized. One dyad contains a gold porphyrin connected to a tin(iv) cation via a malonate and two phenyl ligands (AuP-SnPh2), while the other contains two tin(iv) cations each chelated to one carboxylic acid group of the malonate and three phenyl ligands (AuP-Sn2Ph6). The mode of chelation of Sn(iv) to the malonate was elucidated by IR spectroscopy and 119Sn NMR. In the solid state, the complexes exist as coordination polymers in which the tin is penta-coordinated and bridged to two different malonate units. In solution the chemical shifts of 119Sn signals indicate that the tin complexes are in the form of monomeric species associated with a tetra-coordinated tin cation. The therapeutic potential of these new compounds was assessed by determining their cytotoxic activities on human breast cancer cells (MCF-7) and on healthy human fibroblasts (FS 20-68). The study reveals that the dyads are more potent anticancer drugs than the mixture of their individual components (gold porphyrin and reference tin complexes). Therefore, the covalent link of organotin complexes to a gold porphyrin induces a synergistic cytotoxic effect. The dyad AuP-SnPh2 shows high cytotoxicity (0.13 µM) against MCF-7 along with good selectivity for cancer cells versus healthy cells. Finally, it was also shown that the dyad AuP-Sn2Ph6 exhibits a very high anticancer activity (LC50 = 0.024 µM), but the presence of two tin units induces strong cytotoxicity on healthy cells too (LC50 = 0.032 µM). This study underscores, thus, the potential of the association of gold porphyrin and organotin complexes to develop anticancer metallo-drugs.


Assuntos
Antineoplásicos/farmacologia , Complexos de Coordenação/farmacologia , Ouro/farmacologia , Malonatos/farmacologia , Porfirinas/farmacologia , Estanho/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/química , Proliferação de Células/efeitos dos fármacos , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Relação Dose-Resposta a Droga , Ensaios de Seleção de Medicamentos Antitumorais , Ouro/química , Humanos , Malonatos/química , Estrutura Molecular , Porfirinas/química , Relação Estrutura-Atividade , Estanho/química , Células Tumorais Cultivadas
19.
J Hazard Mater ; 401: 123131, 2021 01 05.
Artigo em Inglês | MEDLINE | ID: mdl-32763672

RESUMO

Contamination of durum wheat grain by cadmium (Cd) threatens food safety and is of increasing concern because regulations concerning Cd are becoming stricter due to its toxicity. This work aimed at using soil variables and cultivar types to build models to predict whether durum wheat grain Cd will conform with current and possibly lower regulatory thresholds. We combined multiple Gaussian and logistic regressions and the random forest algorithm to take advantage of their strength. Models tested using cross-validation produced excellent performances including for the lowest regulatory threshold of 0.1 mg Cd/kg, half of the current one: 79-85% of the non-conformity cases were detected and the reliability of predictions was 69-82%. The models enabled identification of a x1.4 variability in grain Cd content between cultivars that do not have the low Cd accumulation allele of the Cdu1 gene. The models confirmed that for the grain Cd content, the between-cultivar variability had much less influence than the phytoavailability of Cd in soil, the critical contexts of which were characterized by the models. For farmers, these models are valuable tools to predict whether durum wheat production will conform with existing and future Cd regulation in foodstuffs.


Assuntos
Cádmio , Poluentes do Solo , Cádmio/análise , Grão Comestível/química , Reprodutibilidade dos Testes , Solo , Poluentes do Solo/análise , Triticum/genética
20.
PLoS One ; 15(8): e0234098, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32817616

RESUMO

In French Guiana, the malaria, a parasitic infection transmitted by Anopheline mosquitoes, remains a disease of public health importance. To prevent malaria transmission, the main effective way remains Anopheles control. For an effective control, accurate Anopheles species identification is indispensable to distinguish malaria vectors from non-vectors. Although, morphological and molecular methods are largely used, an innovative tool, based on protein pattern comparisons, the Matrix Assisted Laser Desorption / Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) profiling, emerged this last decade for arthropod identification. However, the limited mosquito fauna diversity of reference MS spectra remains one of the main drawback for its large usage. The aim of the present study was then to create and to share reference MS spectra for the identification of French Guiana Anopheline species. A total of eight distinct Anopheles species, among which four are malaria vectors, were collected in 6 areas. To improve Anopheles identification, two body parts, legs and thoraxes, were independently submitted to MS for the creation of respective reference MS spectra database (DB). This study underlined that double checking by MS enhanced the Anopheles identification confidence and rate of reliable classification. The sharing of this reference MS spectra DB should make easier Anopheles species monitoring in endemic malaria area to help malaria vector control or elimination programs.


Assuntos
Anopheles/classificação , Mosquitos Vetores/classificação , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos , Animais , Anopheles/química , Guiana Francesa , Malária/classificação , Malária/transmissão , Especificidade da Espécie , Tórax
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