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1.
Int J Mol Sci ; 25(9)2024 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-38732028

RESUMO

The development of turn-based inhibitors of protein-protein interactions has attracted considerable attention in medicinal chemistry. Our group has synthesized a series of peptides derived from an amino-functionalized ferrocene to investigate their potential to mimic protein turn structures. Detailed DFT and spectroscopic studies (IR, NMR, CD) have shown that, for peptides, the backbone chirality and bulkiness of the amino acid side chains determine the hydrogen-bond pattern, allowing tuning of the size of the preferred hydrogen-bonded ring in turn-folded structures. However, their biological potential is more dependent on their lipophilicity. In addition, our pioneering work on the chiroptical properties of aminoferrocene-containing peptides enables the correlation of their geometry with the sign of the CD signal in the absorption region of the ferrocene chromophore. These studies have opened up the possibility of using aminoferrocene and its derivatives as chirooptical probes for the determination of various chirality elements, such as the central chirality of amino acids and the helicity of peptide sequences.


Assuntos
Aminoácidos , Compostos Ferrosos , Metalocenos , Peptídeos , Compostos Ferrosos/química , Aminoácidos/química , Metalocenos/química , Peptídeos/química , Ligação de Hidrogênio , Estereoisomerismo
2.
J Hazard Mater ; 471: 134451, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38691935

RESUMO

Anaerobic biotechnology for wastewaters treatment can nowadays be considered as state of the art methods. Nonetheless, this technology exhibits certain inherent limitations when employed for industrial wastewater treatment, encompassing elevated substrate consumption, diminished electron transfer efficiency, and compromised system stability. To address the above issues, increasing interest is being given to the potential of using conductive non-biological materials, e,g., iron sulfide (FeS), as a readily accessible electron donor and electron shuttle in the biological decontamination process. In this study, Mackinawite nanoparticles (FeS NPs) were studied for their ability to serve as electron donors for p-chloronitrobenzene (p-CNB) anaerobic reduction within a coupled system. This coupled system achieved an impressive p-CNB removal efficiency of 78.3 ± 2.9% at a FeS NPs dosage of 1 mg/L, surpassing the efficiencies of 62.1 ± 1.5% of abiotic and 30.6 ± 1.6% of biotic control systems, respectively. Notably, the coupled system exhibited exclusive formation of aniline (AN), indicating the partial dechlorination of p-CNB. The improvements observed in the coupled system were attributed to the increased activity in the electron transport system (ETS), which enhanced the sludge conductivity and nitroaromatic reductases activity. The analysis of equivalent electron donors confirmed that the S2- ions dominated the anaerobic reduction of p-CNB in the coupled system. However, the anaerobic reduction of p-CNB would be adversely inhibited when the FeS NPs dosage exceeded 5 g/L. In a continuous operation, the p-CNB concentration and HRT were optimized as 125 mg/L and 40 h, respectively, resulting in an outstanding p-CNB removal efficiency exceeding 94.0% after 160 days. During the anaerobic reduction process, as contributed by the predominant bacterium of Thiobacillus with a 6.6% relative abundance, a mass of p-chloroaniline (p-CAN) and AN were generated. Additionally, Desulfomonile was emerged with abundances ranging from 0.3 to 0.7%, which was also beneficial for the reduction of p-CNB to AN. The long-term stable performance of the coupled system highlighted that anaerobic technology mediated by FeS NPs has a promising potential for the treatment of wastewater containing chlorinated nitroaromatic compounds, especially without the aid of organic co-substrates.


Assuntos
Compostos Ferrosos , Nitrobenzenos , Anaerobiose , Nitrobenzenos/metabolismo , Nitrobenzenos/química , Compostos Ferrosos/química , Compostos Ferrosos/metabolismo , Poluentes Químicos da Água/metabolismo , Poluentes Químicos da Água/química , Nanopartículas/química , Oxirredução , Eliminação de Resíduos Líquidos/métodos , Compostos de Anilina/química , Compostos de Anilina/metabolismo , Águas Residuárias/química , Reatores Biológicos
3.
Molecules ; 29(9)2024 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-38731638

RESUMO

Copper-catalyzed azide-alkyne cycloaddition click (CuAAC) reaction is widely used to synthesize drug candidates and other biomolecule classes. Homogeneous catalysts, which consist of copper coordinated to a ligand framework, have been optimized for high yield and specificity of the CuAAC reaction, but CuAAC reaction with these catalysts requires the addition of a reducing agent and basic conditions, which can complicate some of the desired syntheses. Additionally, removing copper from the synthesized CuAAC-containing biomolecule is necessary for biological applications but inconvenient and requires additional purification steps. We describe here the design and synthesis of a PNN-type pincer ligand complex with copper (I) that stabilizes the copper (I) and, therefore, can act as a CuAAC catalyst without a reducing agent and base under physiologically relevant conditions. This complex was immobilized on two types of resin, and one of the immobilized catalyst forms worked well under aqueous physiological conditions. Minimal copper leaching was observed from the immobilized catalyst, which allowed its use in multiple reaction cycles without the addition of any reducing agent or base and without recharging with copper ion. The mechanism of the catalytic cycle was rationalized by density functional theory (DFT). This catalyst's utility was demonstrated by synthesizing coumarin derivatives of small molecules such as ferrocene and sugar.


Assuntos
Alcinos , Azidas , Química Click , Cobre , Reação de Cicloadição , Cobre/química , Química Click/métodos , Ligantes , Catálise , Azidas/química , Alcinos/química , Cumarínicos/química , Compostos Ferrosos/química , Metalocenos/química , Estrutura Molecular
4.
Bioresour Technol ; 401: 130713, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38641305

RESUMO

The mainstream anaerobic ammonium oxidation (anammox) faces considerable challenges with low-strength municipal wastewater. A Fe(Ⅱ)-amended partial denitrification coupled anammox (PD/A) process was conducted and achieved a long-term and efficient nitrogen and phosphorus removal, yielding effluent total nitrogen and phosphorus concentrations of 1.97 ± 1.03 mg/L and 0.23 ± 0.13 mg/L, respectively, which could well meet more stringent effluent discharge standard of some wastewater treatment plants in specific geographical locations, e.g., estuaries. Fe(Ⅱ)-driven vivianite formation provided key nucleuses for the optimization of the spatial distribution of heterotrophic and anammox bacteria with enhanced extracellular polymeric substances as key driving forces. Metagenomics analysis further revealed the increase of key genes, enhancing anammox bacteria homeostasis, which also bolstered the resistance to environmental perturbations. This study provided a comprehensive sight into the function of Fe(Ⅱ) in mainstream PD/A process, and explored a promising alternative for synergetic nitrogen and phosphorus removal for low-strength municipal wastewater treatment.


Assuntos
Nitrogênio , Fósforo , Águas Residuárias , Fósforo/metabolismo , Nitrogênio/metabolismo , Águas Residuárias/química , Águas Residuárias/microbiologia , Bactérias/metabolismo , Bactérias/genética , Purificação da Água/métodos , Oxirredução , Desnitrificação , Reatores Biológicos/microbiologia , Processos Heterotróficos , Compostos Ferrosos/metabolismo , Eliminação de Resíduos Líquidos/métodos , Anaerobiose
5.
Int J Mol Sci ; 25(8)2024 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-38673758

RESUMO

Animal tumors serve as reasonable models for human cancers. Both human and animal tumors often reveal triplet EPR signals of nitrosylhemoglobin (HbNO) as an effect of nitric oxide formation in tumor tissue, where NO is complexed by Hb. In search of factors determining the appearance of nitrosylhemoglobin (HbNO) in solid tumors, we compared the intensities of electron paramagnetic resonance (EPR) signals of various iron-nitrosyl complexes detectable in tumor tissues, in the presence and absence of excess exogenous iron(II) and diethyldithiocarbamate (DETC). Three types of murine tumors, namely, L5178Y lymphoma, amelanotic Cloudman S91 melanoma, and Ehrlich carcinoma (EC) growing in DBA/2 or Swiss mice, were used. The results were analyzed in the context of vascularization determined histochemically using antibodies to CD31. Strong HbNO EPR signals were found in melanoma, i.e., in the tumor with a vast amount of a hemorrhagic necrosis core. Strong Fe(DETC)2NO signals could be induced in poorly vascularized EC. In L5178Y, there was a correlation between both types of signals, and in addition, Fe(RS)2(NO)2 signals of non-heme iron-nitrosyl complexes could be detected. We postulate that HbNO EPR signals appear during active destruction of well-vascularized tumor tissue due to hemorrhagic necrosis. The presence of iron-nitrosyl complexes in tumor tissue is biologically meaningful and defines the evolution of complicated tumor-host interactions.


Assuntos
Ditiocarb , Hemoglobinas , Óxido Nítrico , Animais , Óxido Nítrico/metabolismo , Ditiocarb/farmacologia , Ditiocarb/química , Camundongos , Hemoglobinas/metabolismo , Hemoglobinas/química , Espectroscopia de Ressonância de Spin Eletrônica/métodos , Detecção de Spin/métodos , Neovascularização Patológica/metabolismo , Linhagem Celular Tumoral , Modelos Animais de Doenças , Camundongos Endogâmicos DBA , Compostos Ferrosos/química
6.
Bioorg Med Chem ; 105: 117716, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38608329

RESUMO

In this study, a series of new formylpiperazine-derived ferroptosis inhibitors were designed and synthesized based on the structure of a known ferroptosis inhibitor, ferrostatin-1 (Fer-1). The anti-ferroptosis activity of these synthetic compounds in human umbilical vein endothelial cells (HUVECs) induced by Erastin was evaluated. It was found that some of the new compounds, especially compound 26, showed potent anti-ferroptosis activity, as evidenced by its ability to restore cell viability, reduce iron accumulation, scavenge reactive oxygen species, maintain mitochondrial membrane potential, increase GSH levels, decrease LPO and MDA content, and upregulate GPX4 expression. Moreover, compound 26 exhibited superior microsomal stability than Fer-1. The present results suggest that compound 26 is a promising lead compound for the development of new ferroptosis inhibitors for the treatment of vascular diseases.


Assuntos
Sobrevivência Celular , Cicloexilaminas , Desenho de Fármacos , Ferroptose , Células Endoteliais da Veia Umbilical Humana , Piperazinas , Humanos , Ferroptose/efeitos dos fármacos , Piperazinas/farmacologia , Piperazinas/síntese química , Piperazinas/química , Células Endoteliais da Veia Umbilical Humana/efeitos dos fármacos , Relação Estrutura-Atividade , Cicloexilaminas/farmacologia , Cicloexilaminas/química , Cicloexilaminas/síntese química , Sobrevivência Celular/efeitos dos fármacos , Estrutura Molecular , Fenilenodiaminas/farmacologia , Fenilenodiaminas/química , Fenilenodiaminas/síntese química , Relação Dose-Resposta a Droga , Espécies Reativas de Oxigênio/metabolismo , Compostos Ferrosos/farmacologia , Compostos Ferrosos/química , Compostos Ferrosos/síntese química , Potencial da Membrana Mitocondrial/efeitos dos fármacos
7.
Biosens Bioelectron ; 256: 116276, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38599073

RESUMO

Fat mass and obesity-associated protein (FTO) has gained attention as the first RNA N6-methyladenosine (m6A) modification eraser due to its overexpression being associated with various cancers. In this study, an electrochemiluminescence (ECL) biosensor for the detection of demethylase FTO was developed based on DNAzyme-mediated CRISPR/Cas12a signal cascade amplification system and carboxylated carbon nitride nanosheets/phosphorus-doped nitrogen-vacancy modified carbon nitride nanosheets (C-CN/PCNV) heterojunction as the emitter. The biosensor was constructed by modifying the C-CN/PCNV heterojunction and a ferrocene-tagged probe (ssDNA-Fc) on a glassy carbon electrode. The presence of FTO removes the m6A modification on the catalytic core of DNAzyme, restoring its cleavage activity and generating activator DNA. This activator DNA further activates the trans-cleavage ability of Cas12a, leading to the cleavage of the ssDNA-Fc and the recovery of the ECL signal. The C-CN/PCNV heterojunction prevents electrode passivation and improves the electron-hole recombination, resulting in significantly enhanced ECL signal. The biosensor demonstrates high sensitivity with a low detection limit of 0.63 pM in the range from 1.0 pM to 100 nM. Furthermore, the biosensor was successfully applied to detect FTO in cancer cell lysate and screen FTO inhibitors, showing great potential in early clinical diagnosis and drug discovery.


Assuntos
Dioxigenase FTO Dependente de alfa-Cetoglutarato , Técnicas Biossensoriais , Sistemas CRISPR-Cas , DNA Catalítico , Técnicas Eletroquímicas , Limite de Detecção , Medições Luminescentes , Metalocenos , Dioxigenase FTO Dependente de alfa-Cetoglutarato/química , Dioxigenase FTO Dependente de alfa-Cetoglutarato/metabolismo , Humanos , DNA Catalítico/química , Técnicas Eletroquímicas/métodos , Nitrilas/química , Endodesoxirribonucleases/química , Endodesoxirribonucleases/metabolismo , Proteínas Associadas a CRISPR/química , Adenosina/análogos & derivados , Adenosina/análise , Adenosina/química , Nanoestruturas/química , Compostos Ferrosos/química , Proteínas de Bactérias/química , Proteínas de Bactérias/genética
8.
Water Sci Technol ; 89(7): 1682-1700, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38619897

RESUMO

In this research, ascorbic acid (AA) was used to enhance Fe(II)/Fe(III)-activated permonosulfate (PMS) systems for the degradation of fluoranthene (FLT). AA enhanced the production of ROS in both PMS/Fe(II) and PMS/Fe(III) systems through chelation and reduction and thus improved the degradation performance of FLT. The optimal molar ratio in PMS/Fe(II)/AA/FLT and PMS/Fe(III)/AA/FLT processes were 2/2/4/1 and 5/10/5/1, respectively. In addition, the experimental results on the effect of FLT degradation under different groundwater matrixes indicated that PMS/Fe(III)/AA system was more adaptable to different water quality conditions than the PMS/Fe(II)/AA system. SO4·- was the major reactive oxygen species (ROS) responsible for FLT removal through the probe and scavenging tests in both systems. Furthermore, the degradation intermediates of FLT were analyzed using gas chromatograph-mass spectrometry (GC-MS), and the probable degradation pathways of FLT degradation were proposed. In addition, the removal of FLT was also tested in actual groundwater and the results showed that by increasing the dose and pre-adjusting the solution pH, 88.8 and 100% of the FLT was removed for PMS/Fe(II)/AA and PMS/Fe(III)/AA systems. The above experimental results demonstrated that PMS/Fe(II)/AA and PMS/Fe(III)/AA processes have a great perspective in practice for the rehabilitation of FLT-polluted groundwater.


Assuntos
Compostos Férricos , Fluorenos , Poluentes Químicos da Água , Espécies Reativas de Oxigênio , Poluentes Químicos da Água/química , Peróxidos/química , Compostos Ferrosos
9.
Biosensors (Basel) ; 14(4)2024 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-38667154

RESUMO

We designed and optimized a glucose biosensor system based on a screen-printed electrode modified with the NAD-GDH enzyme. To enhance the electroactive surface area and improve the electron transfer efficiency, we introduced graphene oxide (GO) and ferrocene-modified linear poly(ethylenimine) (LPEI-Fc) onto the biosensor surface. This strategic modification exploits the electrostatic interaction between graphene oxide, which possesses a negative charge, and LPEI-Fc, which is positively charged. This interaction results in increased catalytic current during glucose oxidation and helps improve the overall glucose detection sensitivity by amperometry. We integrated the developed glucose sensor into a flow injection (FI) system. This integration facilitates a swift and reproducible detection of glucose, and it also mitigates the risk of contamination during the analyses. The incorporation of an FI system improves the efficiency of the biosensor, ensuring precise and reliable results in a short time. The proposed sensor was operated at a constant applied potential of 0.35 V. After optimizing the system, a linear calibration curve was obtained for the concentration range of 1.0-40 mM (R2 = 0.986). The FI system was successfully applied to determine the glucose content of a commercial sports drink.


Assuntos
Técnicas Biossensoriais , Compostos Ferrosos , Glucose , Grafite , Metalocenos , Polietilenoimina , Grafite/química , Metalocenos/química , Compostos Ferrosos/química , Polietilenoimina/química , Glucose/análise , Eletrodos , Oxirredução
11.
Eur J Med Chem ; 271: 116429, 2024 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-38663284

RESUMO

Amodiaquine (AQ) is a potent antimalarial drug used in combination with artesunate as part of artemisinin-based combination therapies (ACTs) for malarial treatment. Due to the rising emergence of resistant malaria parasites, some of which have been reported for ACT, the usefulness of AQ as an efficacious therapeutic drug is threatened. Employing the organometallic hybridisation approach, which has been shown to restore the antimalarial activity of chloroquine in the form of an organometallic hybrid clinical candidate ferroquine (FQ), the present study utilises this strategy to modulate the biological performance of AQ by incorporating ferrocene. Presently, we have conceptualised ferrocenyl AQ derivatives and have developed facile, practical routes for their synthesis. A tailored library of AQ derivatives was assembled and their antimalarial activity evaluated against chemosensitive (NF54) and multidrug-resistant (K1) strains of the malaria parasite, Plasmodium falciparum. The compounds generally showed enhanced or comparable activities to those of the reference clinical drugs chloroquine and AQ, against both strains, with higher selectivity for the sensitive phenotype, mostly in the double-digit nanomolar IC50 range. Moreover, representative compounds from this series show the potential to block malaria transmission by inhibiting the growth of stage II/III and V gametocytes in vitro. Preliminary mechanistic insights also revealed hemozoin inhibition as a potential mode of action.


Assuntos
Amodiaquina , Antimaláricos , Compostos Ferrosos , Metalocenos , Plasmodium falciparum , Antimaláricos/farmacologia , Antimaláricos/química , Antimaláricos/síntese química , Compostos Ferrosos/química , Compostos Ferrosos/farmacologia , Plasmodium falciparum/efeitos dos fármacos , Metalocenos/química , Metalocenos/farmacologia , Amodiaquina/farmacologia , Amodiaquina/química , Relação Estrutura-Atividade , Estrutura Molecular , Humanos , Testes de Sensibilidade Parasitária , Relação Dose-Resposta a Droga
12.
Trials ; 25(1): 270, 2024 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-38641845

RESUMO

BACKGROUND: The World Health Organization recommends universal iron supplementation for children aged 6-23 months in countries where anaemia is seen in over 40% of the population. Conventional ferrous salts have low efficacy due to low oral absorption in children with inflammation. Haem iron is more bioavailable, and its absorption may not be decreased by inflammation. This study aims to compare daily supplementation with haem iron versus ferrous sulphate on haemoglobin concentration and serum ferritin concentration after 12 weeks of supplementation. METHODS: This will be a two-arm, randomised controlled trial. Gambian children aged 6-12 months with anaemia will be recruited within a predefined geographical area and recruited by trained field workers. Eligible participants will be individually randomised using a 1:1 ratio within permuted blocks to daily supplementation for 12 weeks with either 10.0 mg of elemental iron as haem or ferrous sulphate. Safety outcomes such as diarrhoea and infection-related adverse events will be assessed daily by the clinical team (see Bah et al. Additional file 4_Adverse event eCRF). Linear regression will be used to analyse continuous outcomes, with log transformation to normalise residuals as needed. Binary outcomes will be analysed by binomial regression or logistic regression, Primary analysis will be by modified intention-to-treat (i.e., those randomised and who ingested at least one supplement dose of iron), with multiple imputations to replace missing data. Effect estimates will be adjusted for baseline covariates (C-reactive protein, alpha-1-acid glycoprotein, haemoglobin, ferritin, soluble transferrin receptor). DISCUSSION: This study will determine if therapeutic supplementation with haem iron is more efficacious than with conventional ferrous sulphate in enhancing haemoglobin and ferritin concentrations in anaemic children aged 6-12 months. TRIAL REGISTRATION: Pan African Clinical Trial Registry PACTR202210523178727.


Assuntos
Anemia Ferropriva , Anemia , Criança , Humanos , Ferro , Anemia Ferropriva/diagnóstico , Anemia Ferropriva/tratamento farmacológico , Sais/metabolismo , Sais/uso terapêutico , Gâmbia , Compostos Ferrosos/efeitos adversos , Ferritinas , Anemia/tratamento farmacológico , Hemoglobinas/metabolismo , Suplementos Nutricionais , Inflamação/tratamento farmacológico , Heme/metabolismo , Heme/uso terapêutico , Ensaios Clínicos Controlados Aleatórios como Assunto
13.
Proc Natl Acad Sci U S A ; 121(17): e2316452121, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38621125

RESUMO

The main sources of redox gradients supporting high-productivity life in the Europan and other icy ocean world oceans were proposed to be photolytically derived oxidants, such as reactive oxygen species (ROS) from the icy shell, and reductants (Fe(II), S(-II), CH4, H2) from bottom waters reacting with a (ultra)mafic seafloor. Important roadblocks to maintaining life, however, are that the degree of ocean mixing to combine redox species is unknown, and ROS damage biomolecules. Here, we envisage a unique solution using an acid mine drainage (AMD)-filled pit lakes analog system for the Europan ocean, which previous models predicted to be acidic. We hypothesize that surface-generated ROS oxidize dissolved Fe(II) resulting in Fe(III) (hydr)oxide precipitates, that settle to the seafloor as "iron snow." The iron snow provides a respiratory substrate for anaerobic microorganisms ("breathing iron"), and limits harmful ROS exposure since they are now neutralized at the ice-water interface. Based on this scenario, we calculated Gibbs energies and maximal biomass productivities of various anaerobic metabolisms for a range of pH, temperatures, and H2 fluxes. Productivity by iron reducers was greater for most environmental conditions considered, whereas sulfate reducers and methanogens were more favored at high pH. Participation of Fe in the metabolic redox processes is largely neglected in most models of Europan biogeochemistry. Our model overcomes important conceptual roadblocks to life in icy ocean worlds and broadens the potential metabolic diversity, thus increasing total primary productivity, the diversity and volume of habitable environmental niches and, ultimately, the probability of biosignature detection.


Assuntos
Gelo , Ferro , Espécies Reativas de Oxigênio , Neve , Oxirredução , Compostos Ferrosos
14.
Luminescence ; 39(4): e4745, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38644416

RESUMO

This study introduces a novel chemiluminescence (CL) approach utilizing FeS2 nanosheets (NSs) catalyzed luminol-O2 CL reaction for the measurement of three pharmaceuticals, namely venlafaxine hydrochloride (VFX), imipramine hydrochloride (IPM), and cefazolin sodium (CEF). The CL method involved the phenomenon of quenching induced by the pharmaceuticals in the CL reaction. To achieve the most quenching efficacy of the pharmaceuticals in the CL reaction, the concentrations of reactants comprising luminol, NaOH, and FeS2 NSs were optimized accordingly. The calibration curves demonstrated exceptional linearity within the concentration range spanning from 4.00 × 10-7 to 1.00 × 10-3 mol L-1, 1.00 × 10-7 to 1.00 × 10-4 mol L-1, and 4.00 × 10-6 to 2.00 × 10-4 mol L-1 with detection limits (3σ) of 3.54 × 10-7, 1.08 × 10-8, and 2.63 × 10-6 mol L-1 for VFX, IPM, and CEF, respectively. This study synthesized FeS2 NSs using a facile hydrothermal approach, and then the synthesized FeS2 NSs were subjected to a comprehensive characterization using a range of spectroscopic methods. The proposed CL method was effective in measuring the aforementioned pharmaceuticals in pharmaceutical formulations as well as different water samples. The mechanism of the CL system has been elucidated.


Assuntos
Cefazolina , Compostos Ferrosos , Imipramina , Medições Luminescentes , Luminol , Cloridrato de Venlafaxina , Cefazolina/análise , Cefazolina/química , Cloridrato de Venlafaxina/análise , Cloridrato de Venlafaxina/química , Imipramina/análise , Imipramina/química , Medições Luminescentes/métodos , Luminol/química , Nanoestruturas/química , Luminescência
15.
Environ Sci Technol ; 58(16): 7186-7195, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38598770

RESUMO

Remediation of large and dilute plumes of groundwater contaminated by oxidized pollutants such as chromate is a common and difficult challenge. Herein, we show that in situ formation of FeS nanoparticles (using dissolved Fe(II), S(-II), and natural organic matter as a nucleating template) results in uniform coating of aquifer material to create a regenerable reactive zone that mitigates Cr(VI) migration. Flow-through columns packed with quartz sand are amended first with an Fe2+ solution and then with a HS- solution to form a nano-FeS coating on the sand, which does not hinder permeability. This nano-FeS coating effectively reduces and immobilizes Cr(VI), forming Fe(III)-Cr(III) coprecipitates with negligible detachment from the sand grains. Preconditioning the sand with humic or fulvic acid (used as model natural organic matter (NOM)) further enhances Cr(VI) sequestration, as NOM provides additional binding sites of Fe2+ and mediates both nucleation and growth of FeS nanoparticles, as verified with spectroscopic and microscopic evidence. Reactivity can be easily replenished by repeating the procedures used to form the reactive coating. These findings demonstrate that such enhancement of attenuation capacity can be an effective option to mitigate Cr(VI) plume migration and exposure, particularly when tackling contaminant rebound post source remediation.


Assuntos
Cromo , Água Subterrânea , Oxirredução , Poluentes Químicos da Água , Água Subterrânea/química , Cromo/química , Poluentes Químicos da Água/química , Nanopartículas/química , Recuperação e Remediação Ambiental/métodos , Substâncias Húmicas , Compostos Ferrosos/química , Benzopiranos/química
16.
Biochemistry ; 63(8): 1038-1050, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38577885

RESUMO

The ethylene-forming enzyme (EFE) is an Fe(II), 2-oxoglutarate (2OG), and l-arginine (l-Arg)-dependent oxygenase that either forms ethylene and three CO2/bicarbonate from 2OG or couples the decarboxylation of 2OG to C5 hydroxylation of l-Arg. l-Arg binds with C5 toward the metal center, causing 2OG to change from monodentate to chelate metal interaction and OD1 to OD2 switch of D191 metal coordination. We applied anaerobic UV-visible spectroscopy, X-ray crystallography, and computational approaches to three EFE systems with high-resolution structures. The ineffective l-Arg analogue l-canavanine binds to the EFE with O5 pointing away from the metal center while promoting chelate formation by 2OG but fails to switch the D191 metal coordination from OD1 to OD2. Substituting alanine for R171 that interacts with 2OG and l-Arg inactivates the protein, prevents metal chelation by 2OG, and weakens l-Arg binding. The R171A EFE had electron density at the 2OG binding site that was identified by mass spectrometry as benzoic acid. The substitution by alanine of Y306 in the EFE, a residue 12 Å away from the catalytic metal center, generates an interior cavity that leads to multiple local and distal structural changes that reduce l-Arg binding and significantly reduce the enzyme activity. Flexibility analyses revealed correlated and anticorrelated motions in each system, with important distinctions from the wild-type enzyme. In combination, the results are congruent with the currently proposed enzyme mechanism, reinforce the importance of metal coordination by OD2 of D191, and highlight the importance of the second coordination sphere and longer range interactions in promoting EFE activity.


Assuntos
Canavanina , Compostos Ferrosos , Liases , Compostos Ferrosos/metabolismo , Sítios de Ligação , Alanina , Ácidos Cetoglutáricos/metabolismo
17.
J Am Chem Soc ; 146(15): 10263-10267, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38578094

RESUMO

Entomopathogenic fungus Metarhizium majus contains the nine-gene PPZ cluster, with ppzA, encoding a peramine-producing nonribosomal peptide synthetase, as the central component. In this work, the roles of two α-ketoglutarate, iron-dependent oxygenases encoded by the PPZ genes ppzC and ppzD were elucidated. PpzD was found to produce both trans-4-hydroxy-l-proline and trans-3-hydroxy-l-proline in a 13.1:1 ratio, yielding a key precursor for peramine biosynthesis. PpzC was found to act directly on peramine, yielding the novel analogue 8-hydroxyperamine.


Assuntos
Compostos Heterocíclicos com 2 Anéis , Ferro , Ácidos Cetoglutáricos , Metarhizium , Poliaminas , Família Multigênica , Compostos Ferrosos
18.
J Environ Manage ; 357: 120823, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38583380

RESUMO

Fe(II) regeneration plays a crucial role in the electro-Fenton process, significantly influencing the rate of ·OH formation. In this study, a method is proposed to improve Fe(II) regeneration through N-doping aimed at enhancing the adsorption capacity of the activated carbon cathode for Fe(III). N-doping not only enriched the pore structure on the surface of activated carbon, providing numerous adsorption sites, but also significantly increased the adsorption energy for Fe(III). Among the types of nitrogen introduced, pyridine-N exhibited the most substantial enhancement effect, followed by pyrrole-N, while graphite-N showed a certain degree of inhibition. Furthermore, N-doping facilitated the adsorption of all forms of Fe(III) by activated carbon. The adsorption and electrosorption rates of the NAC-900 electrode for Fe(III) were 30.33% and 42.36%, respectively. Such modification markedly enhanced the Fe3+/Fe2+ cycle within the electro-Fenton system. The NAC-900 system demonstrated an impressive phenol degradation efficiency of 93.67%, alongside the lowest electricity consumption attributed to the effective "adsorption-reduction" synergy for Fe(III) on the NAC-900 electrode. Compared to the AC cathode electro-Fenton system, the degradation efficiency of the NAC-900 cathode electro-Fenton system at pH = levels ranging from 3 to 5 exceeded 90%; thus, extending the pH applicability of the electro-Fenton process. The degradation efficiency of phenol using the NAC-900 cathode electro-Fenton system in various water matrices approached 90%, indicating robust performance in real wastewater treatment scenarios. This research elucidates the impact of cathodic Fe(III) adsorption on Fe(II) regeneration within the electro-Fenton system, and clarifies the influence of different N- doping types on the cathodic adsorption of Fe(III).


Assuntos
Compostos Férricos , Poluentes Químicos da Água , Adsorção , Poluentes Químicos da Água/química , Carvão Vegetal/química , Conservação de Recursos Energéticos , Oxirredução , Eletrodos , Fenol , Compostos Ferrosos , Peróxido de Hidrogênio/química
19.
ACS Sens ; 9(4): 2141-2148, 2024 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-38578241

RESUMO

The glycated hemoglobin (HbA1c) level, which is defined as the ratio of HbA1c to total hemoglobin (tHb, including glycated and unglycated hemoglobin), is considered one of the preferred indicators for diabetes monitoring. Generally, assessment of the HbA1c level requires separate determination of tHb and HbA1c concentrations after a complex separation step. This undoubtedly increases the cost of the assay, and the loss or degradation of HbA1c during the separation process results in a decrease in the accuracy of the assay. Therefore, this study explored a dual-signal acquisition method for the one-step simultaneous evaluation of tHb and HbA1c. Quantification of tHb: graphene adsorbed carbon quantum dots and methylene blue were utilized as the substrate material and linked to the antibody. tHb was captured on the substrate by the antibody. The unique heme group on tHb catalyzed the production of •OH from H2O2 to degrade methylene blue on the substrate, and a quantitative relationship between the tHb concentration and the methylene blue oxidation current signal was constructed. Quantification of HbA1c: complex labels with HbA1c recognition were made of ZIF-8-ferrocene-gold nanoparticles-mercaptophenylboronic acid. The specific recognition of the boronic acid bond with the unique cis-diol structure of HbA1c establishes a quantitative relationship between the oxidation current of the label-loaded ferrocene and the concentration of HbA1c. Thus, the HbA1c level can be assessed with only one signal readout. The sensor exhibited extensive detection ranges (0.200-600 ng/mL for tHb and 0.100-300 ng/mL for HbA1c) and low detection limits (4.00 × 10-3 ng/mL for tHb and 1.03 × 10-2 ng/mL for HbA1c).


Assuntos
Hemoglobinas Glicadas , Azul de Metileno , Hemoglobinas Glicadas/análise , Humanos , Azul de Metileno/química , Grafite/química , Ouro/química , Nanopartículas Metálicas/química , Pontos Quânticos/química , Hemoglobinas/análise , Hemoglobinas/química , Ácidos Borônicos/química , Compostos Ferrosos/química , Metalocenos/química , Limite de Detecção , Técnicas Eletroquímicas/métodos , Peróxido de Hidrogênio/química
20.
J Anim Sci ; 1022024 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-38632976

RESUMO

This experiment aimed to investigate the effects of dietary iron supplementation from different sources on the reproductive performance of sows and the growth performance of piglets. A total of 87 sows with similar farrowing time were blocked by body weight at day 85 of gestation, and assigned to one of three dietary treatments (n = 29 per treatment): basal diet, basal diet supplemented with 0.2% ferrous sulfate (FeSO4), and basal diet supplemented with 0.2% iron sucrose, respectively, with 30% iron in both FeSO4 and iron sucrose. Compared with the control (CON) group, iron sucrose supplementation reduced the rate of stillbirth and invalid of neonatal piglets (P < 0.05), and the number of mummified fetuses was 0. Moreover, it also improved the coat color of newborn piglets (P < 0.05). At the same time, the iron sucrose could also achieve 100% estrus rate of sows. Compared with the CON group, FeSO4 and iron sucrose supplementation increased the serum iron content of weaned piglets (P < 0.05). In addition, iron sucrose increased serum transferrin level of weaned piglets (P < 0.05) and the survival rate of piglets (P < 0.05). In general, both iron sucrose and FeSO4 could affect the blood iron status of weaned piglets, while iron sucrose also had a positive effect on the healthy development of newborn and weaned piglets, and was more effective than FeSO4 in improving the performance of sows and piglets.


Sows need more iron to meet the requirements for their and offspring's growth during pregnancy and lactation. Exogenous iron supplementation may improve the reproductive performance of sows and the growth performance of piglets, but different sources of iron have different effects. This study facilitates the understanding of the effects of iron sucrose and ferrous sulfate on the reproductive performance of sows and the growth performance of piglets.


Assuntos
Ração Animal , Fenômenos Fisiológicos da Nutrição Animal , Dieta , Suplementos Nutricionais , Reprodução , Animais , Feminino , Ração Animal/análise , Dieta/veterinária , Suínos/crescimento & desenvolvimento , Suínos/fisiologia , Reprodução/efeitos dos fármacos , Gravidez , Animais Recém-Nascidos , Ferro/administração & dosagem , Ferro/farmacologia , Compostos Ferrosos/farmacologia , Compostos Ferrosos/administração & dosagem , Óxido de Ferro Sacarado/farmacologia , Óxido de Ferro Sacarado/administração & dosagem , Ferro da Dieta/administração & dosagem , Ferro da Dieta/farmacologia
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