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1.
Molecules ; 29(9)2024 May 05.
Article in English | MEDLINE | ID: mdl-38731638

ABSTRACT

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.


Subject(s)
Alkynes , Azides , Click Chemistry , Copper , Cycloaddition Reaction , Copper/chemistry , Click Chemistry/methods , Ligands , Catalysis , Azides/chemistry , Alkynes/chemistry , Coumarins/chemistry , Ferrous Compounds/chemistry , Metallocenes/chemistry , Molecular Structure
2.
Anal Chim Acta ; 1309: 342685, 2024 Jun 22.
Article in English | MEDLINE | ID: mdl-38772667

ABSTRACT

The monitoring of heavy metal ions in ocean is crucial for environment protection and assessment of seawater quality. However, the detection of heavy metal ions in seawater with electrochemical sensors, especially for long-term monitoring, always faces challenges due to marine biofouling caused by the nonspecific adsorption of microbial and biomolecules. Herein, an electrochemical aptasensor, integrating both antifouling and antibacterial properties, was developed for the detection of Hg2+ in the ocean. In this electrochemical aptasensor, eco-friendly peptides with superior hydrophilicity served as anti-biofouling materials, preventing nonspecific adsorption on the sensing interface, while silver nanoparticles were employed to eliminate bacteria. Subsequently, a ferrocene-modified aptamer was employed for the specific recognition of Hg2+, leveraging the aptamer's ability to fold into a thymine-Hg2+-thymine (T-Hg2+-T) structure upon interaction, and bringing ferrocene nearer to the sensor surface, significantly amplifying the electrochemical response. The prepared electrochemical aptasensor significantly reduced the nonspecific adsorption in seawater while maintaining sensitive electrochemical response. Furthermore, the biosensor exhibited a linear response range of 0.01-100 nM with a detection limit of 2.30 pM, and realized the accurate monitoring of mercury ions in real marine environment. The research results offer new insights into the preparation of marine antifouling sensing devices, and it is expected that sensors with antifouling and antimicrobial capabilities will find broad applications in the monitoring of marine pollutants.


Subject(s)
Anti-Bacterial Agents , Biofouling , Biosensing Techniques , Electrochemical Techniques , Mercury , Seawater , Mercury/analysis , Seawater/chemistry , Seawater/microbiology , Electrochemical Techniques/methods , Anti-Bacterial Agents/analysis , Anti-Bacterial Agents/pharmacology , Biosensing Techniques/methods , Biofouling/prevention & control , Aptamers, Nucleotide/chemistry , Silver/chemistry , Water Pollutants, Chemical/analysis , Metal Nanoparticles/chemistry , Limit of Detection , Ferrous Compounds/chemistry , Metallocenes
3.
Int J Mol Sci ; 25(9)2024 Apr 28.
Article in English | MEDLINE | ID: mdl-38732028

ABSTRACT

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.


Subject(s)
Amino Acids , Ferrous Compounds , Metallocenes , Peptides , Ferrous Compounds/chemistry , Amino Acids/chemistry , Metallocenes/chemistry , Peptides/chemistry , Hydrogen Bonding , Stereoisomerism
4.
J Hazard Mater ; 471: 134451, 2024 Jun 05.
Article in English | MEDLINE | ID: mdl-38691935

ABSTRACT

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.


Subject(s)
Ferrous Compounds , Nitrobenzenes , Anaerobiosis , Nitrobenzenes/metabolism , Nitrobenzenes/chemistry , Ferrous Compounds/chemistry , Ferrous Compounds/metabolism , Water Pollutants, Chemical/metabolism , Water Pollutants, Chemical/chemistry , Nanoparticles/chemistry , Oxidation-Reduction , Waste Disposal, Fluid/methods , Aniline Compounds/chemistry , Aniline Compounds/metabolism , Wastewater/chemistry , Bioreactors
5.
Environ Sci Technol ; 58(16): 7186-7195, 2024 Apr 23.
Article in English | MEDLINE | ID: mdl-38598770

ABSTRACT

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.


Subject(s)
Chromium , Groundwater , Oxidation-Reduction , Water Pollutants, Chemical , Groundwater/chemistry , Chromium/chemistry , Water Pollutants, Chemical/chemistry , Nanoparticles/chemistry , Environmental Restoration and Remediation/methods , Humic Substances , Ferrous Compounds/chemistry , Benzopyrans/chemistry
6.
ACS Sens ; 9(4): 2141-2148, 2024 Apr 26.
Article in English | MEDLINE | ID: mdl-38578241

ABSTRACT

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).


Subject(s)
Glycated Hemoglobin , Methylene Blue , Glycated Hemoglobin/analysis , Humans , Methylene Blue/chemistry , Graphite/chemistry , Gold/chemistry , Metal Nanoparticles/chemistry , Quantum Dots/chemistry , Hemoglobins/analysis , Hemoglobins/chemistry , Boronic Acids/chemistry , Ferrous Compounds/chemistry , Metallocenes/chemistry , Limit of Detection , Electrochemical Techniques/methods , Hydrogen Peroxide/chemistry
7.
Biosensors (Basel) ; 14(4)2024 Mar 28.
Article in English | MEDLINE | ID: mdl-38667154

ABSTRACT

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.


Subject(s)
Biosensing Techniques , Ferrous Compounds , Glucose , Graphite , Metallocenes , Polyethyleneimine , Graphite/chemistry , Metallocenes/chemistry , Ferrous Compounds/chemistry , Polyethyleneimine/chemistry , Glucose/analysis , Electrodes , Oxidation-Reduction
8.
Biosens Bioelectron ; 256: 116276, 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-38599073

ABSTRACT

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.


Subject(s)
Alpha-Ketoglutarate-Dependent Dioxygenase FTO , Biosensing Techniques , CRISPR-Cas Systems , DNA, Catalytic , Electrochemical Techniques , Limit of Detection , Luminescent Measurements , Metallocenes , Alpha-Ketoglutarate-Dependent Dioxygenase FTO/chemistry , Alpha-Ketoglutarate-Dependent Dioxygenase FTO/metabolism , Humans , DNA, Catalytic/chemistry , Electrochemical Techniques/methods , Nitriles/chemistry , Endodeoxyribonucleases/chemistry , Endodeoxyribonucleases/metabolism , CRISPR-Associated Proteins/chemistry , Adenosine/analogs & derivatives , Adenosine/analysis , Adenosine/chemistry , Nanostructures/chemistry , Ferrous Compounds/chemistry , Bacterial Proteins/chemistry , Bacterial Proteins/genetics
9.
J Inorg Biochem ; 256: 112551, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38678911

ABSTRACT

The solvated iron(II) salt [Fe(NCMe)6](BF4)2 (Me = methyl) is shown to be a bifunctional catalyst with respect to aziridination of styrene. The salt serves as an active catalyst for nitrene transfer from PhINTs to styrene to form 2-phenyl-N-tosylaziridine (Ph = phenyl; Ts = tosyl, -S{O}2-p-C6H4Me). The iron(II) salt also acts as a Lewis acid in non-coordinating CH2Cl2 solution, to catalyze heterolytic CN bond cleavage of the aziridine and insertion of dipolarophiles. The 1,3-zwitterionic intermediate is presumably supported by interaction of the metal dication with the anion, and by resonance stabilization of the carbocation. Nucleophilic dipolarophiles then insert to give a five-membered heterocyclic ring. The result is a two-step cycloaddition, formally [2 + 1 + 2], that is typically regiospecific, but not stereospecific. This reaction mechanism was confirmed by conducting a series of one-step, [3 + 2] additions of unsaturated molecules into pre-formed 2-phenyl-N-tosylaziridine, also catalyzed by [Fe(NCMe)6](BF4)2. Relevant substrates include styrenes, carbonyl compounds and alkynes. These yield five-membered heterocylic rings, including pyrrolidines, oxazolidines and dihydropyrroles, respectively. The reaction scope appears limited only by the barrier to formation of the dipolar intermediate, and by the nucleophilicity of the captured dipolarophile. The bifunctionality of an inexpensive, earth-abundant and non-toxic catalyst suggests a general strategy for one-pot construction of heterocyclic rings, as demonstrated specifically for pyrrolidine ring formation.


Subject(s)
Aziridines , Styrene , Aziridines/chemistry , Catalysis , Styrene/chemistry , Ferrous Compounds/chemistry , Heterocyclic Compounds/chemistry , Cycloaddition Reaction , Imines
10.
Water Res ; 256: 121645, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38653093

ABSTRACT

Mercury contamination is a global concern, and the degradation and detoxification of methylmercury have gained significant attention due to its neurotoxicity and biomagnification within the food chain. However, the currently known pathways of abiotic demethylation are limited to light-induced photodegradation process and little is known about light-independent abiotic demethylation of methylmercury. In this study, we reported a novel abiotic pathway for the degradation of methylmercury through the oxidation of both mineral structural iron(II) and surface-adsorbed iron(II) in the absence of light. Our findings reveal that methylmercury can be oxidatively degraded by reactive oxygen species, specifically hydroxyl and superoxide radicals, which are generated from the oxidation of iron(II) minerals under dark conditions. Surprisingly, Hg(0) trapping experiments demonstrated that inorganic Hg(II) resulting from the oxidative degradation of methylmercury was rapidly reduced to gaseous Hg(0) by iron(II) minerals. The demethylation of methylmercury, coupled with the generation of Hg(0), suggests a potential natural attenuation process for methylmercury. Our results highlight the underappreciated roles of iron(II) minerals in the abiotic degradation of methylmercury and the release of gaseous Hg(0) into the atmosphere.


Subject(s)
Mercury , Methylmercury Compounds , Minerals , Oxidation-Reduction , Methylmercury Compounds/chemistry , Mercury/chemistry , Minerals/chemistry , Iron/chemistry , Ferrous Compounds/chemistry , Ferrous Compounds/metabolism
11.
Talanta ; 274: 126023, 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38583328

ABSTRACT

Dual-potential ratiometric electrochemiluminescence (ECL) is in favor of resistance to environmental interference. However, two kinds of emitters or coreactants, and a wide scan potential range (>2 V) are mandatory. This work developed a new dual-potential ratiometric ECL sensor for detection of carcinoembryonic antigen (CEA) using single emitter (luminol) and single coreactant (H2O2) with a mild potential range from -0.1 to 0.6 V. Luminol could produce a strong cathodic ECL (Ec) induced by hydroxyl radicals (HO‧) from the reduction of H2O2, and a relatively weak anodic ECL (Ea). After the ferrocene modified CEA aptamer (Apt-Fc) was attached, Fc could promote Ea by catalyzing the oxidation of H2O2, and reduce Ec by consuming HO‧. With the cycling amplification of the exonuclease I, CEA could substantially reduce the amount of Apt-Fc, resulting in the decrease of Ea and the rise of Ec. So, the ratio of Ec to Ea (Ec/Ea) was used as the detection signal, realizing the sensitive determination of CEA from 0.1 pg mL-1 to 10 ng mL-1 with a LOD of 41.85 fg mL-1 (S/N = 3). The developed sensor demonstrated excellent specificity, stability and reproducibility, with satisfactory results in practical detection.


Subject(s)
Aptamers, Nucleotide , Carcinoembryonic Antigen , Electrochemical Techniques , Hydrogen Peroxide , Luminescent Measurements , Luminol , Carcinoembryonic Antigen/analysis , Carcinoembryonic Antigen/blood , Electrochemical Techniques/methods , Humans , Luminescent Measurements/methods , Hydrogen Peroxide/chemistry , Hydrogen Peroxide/analysis , Luminol/chemistry , Aptamers, Nucleotide/chemistry , Limit of Detection , Biosensing Techniques/methods , Metallocenes/chemistry , Ferrous Compounds/chemistry
12.
Talanta ; 274: 125999, 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38583327

ABSTRACT

The construction of efficient methods for highly sensitive and rapid detection of disease markers is essential for the early diagnosis of serious diseases. In this paper, taking advantage of the UiO-66-NH2 signal molecule in combination with a waste-free entropy-driven DNA machine, a novel homogeneous electrochemical ratiometric platform is developed to detect MircoRNA (miRNA). Metal-organic framework materials (UiO-66-NH2 MOF) and ferrocene were utilized as electrochemical signal tags and reference probes, respectively. The target-initiated waste-free three-dimensional (3D) entropy-driven DNA nanomachine is activated in the presence of miRNA, resulting in DNA-labeled-UiO-66-NH2 falling off from the electrode, leading to a decrease in the signal of UiO-66-NH2 at 0.83V. Our strategy can mitigate false positive responses induced by the DNA probes immobilized on electrodes in traditional distance-dependent signal adjustment ratiometric strategies. The proposed ratiometric platform demonstrates superior sensitivity (a detection limit of 9.8 fM), simplified operation, high selectivity, and high repeatability. The ratiometric biosensor is also applied to detect miRNA content in spiked serum samples.


Subject(s)
Biosensing Techniques , Electrochemical Techniques , Entropy , Metal-Organic Frameworks , MicroRNAs , MicroRNAs/blood , MicroRNAs/analysis , Biosensing Techniques/methods , Electrochemical Techniques/methods , Humans , Metal-Organic Frameworks/chemistry , DNA/chemistry , Limit of Detection , Electrodes , DNA Probes/chemistry , DNA Probes/genetics , Ferrous Compounds/chemistry , Metallocenes/chemistry
13.
Chem Commun (Camb) ; 60(36): 4773-4776, 2024 Apr 30.
Article in English | MEDLINE | ID: mdl-38602162

ABSTRACT

A small-molecule Fenton reagent, integrating ferrocene with a carbonic anhydrase inhibitor, was designed to intelligently regulate intracellular acidosis for self-augmented chemodynamic therapy. Acidosis coupled with up-regulated ROS levels demonstrated potent cytotoxicity and effective tumor suppression.


Subject(s)
Ferrous Compounds , Hydrogen Peroxide , Iron , Metallocenes , Humans , Ferrous Compounds/chemistry , Ferrous Compounds/pharmacology , Hydrogen Peroxide/chemistry , Hydrogen Peroxide/pharmacology , Iron/chemistry , Metallocenes/chemistry , Metallocenes/pharmacology , Reactive Oxygen Species/metabolism , Carbonic Anhydrase Inhibitors/chemistry , Carbonic Anhydrase Inhibitors/pharmacology , Acidosis/drug therapy , Animals , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemical synthesis , Cell Line, Tumor , Mice
14.
Bioorg Med Chem ; 105: 117716, 2024 May 01.
Article in English | MEDLINE | ID: mdl-38608329

ABSTRACT

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.


Subject(s)
Cell Survival , Cyclohexylamines , Drug Design , Ferroptosis , Human Umbilical Vein Endothelial Cells , Piperazines , Humans , Ferroptosis/drug effects , Piperazines/pharmacology , Piperazines/chemical synthesis , Piperazines/chemistry , Human Umbilical Vein Endothelial Cells/drug effects , Structure-Activity Relationship , Cyclohexylamines/pharmacology , Cyclohexylamines/chemistry , Cyclohexylamines/chemical synthesis , Cell Survival/drug effects , Molecular Structure , Phenylenediamines/pharmacology , Phenylenediamines/chemistry , Phenylenediamines/chemical synthesis , Dose-Response Relationship, Drug , Reactive Oxygen Species/metabolism , Ferrous Compounds/pharmacology , Ferrous Compounds/chemistry , Ferrous Compounds/chemical synthesis , Membrane Potential, Mitochondrial/drug effects
15.
Ultrason Sonochem ; 106: 106884, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38677267

ABSTRACT

The purpose of this study was to investigate ferroptosis in Escherichia coli O157:H7 caused by ferrous sulfate (FeSO4) and to examine the synergistic effectiveness of FeSO4 combined with ultrasound-emulsified cinnamaldehyde nanoemulsion (CALNO) on inactivation of E. coli O157:H7 in vitro and in vivo. The results showed that FeSO4 could cause ferroptosis in E. coli O157:H7 via generating reactive oxygen species (ROS) and exacerbating lipid peroxidation. In addition, the results indicated that FeSO4 combined with CALNO had synergistic bactericidal effect against E. coli O157:H7 and the combined treatment could lead considerable nucleic acids and protein to release by damaging the cell membrane of E. coli O157:H7. Besides, FeSO4 combined with CALNO had a strong antibiofilm ability to inhibit E. coli O157:H7 biofilm formation by reducing the expression of genes related on biofilm formation. Finally, FeSO4 combined with CALNO exhibited the significant antibacterial activity against E. coli O157:H7 in hami melon and cherry tomato.


Subject(s)
Acrolein , Emulsions , Escherichia coli O157 , Ferroptosis , Ferrous Compounds , Escherichia coli O157/drug effects , Acrolein/analogs & derivatives , Acrolein/pharmacology , Acrolein/chemistry , Ferrous Compounds/pharmacology , Ferrous Compounds/chemistry , Ferroptosis/drug effects , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Biofilms/drug effects , Ultrasonic Waves , Reactive Oxygen Species/metabolism
16.
Eur J Med Chem ; 271: 116429, 2024 May 05.
Article in English | MEDLINE | ID: mdl-38663284

ABSTRACT

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.


Subject(s)
Amodiaquine , Antimalarials , Ferrous Compounds , Metallocenes , Plasmodium falciparum , Antimalarials/pharmacology , Antimalarials/chemistry , Antimalarials/chemical synthesis , Ferrous Compounds/chemistry , Ferrous Compounds/pharmacology , Plasmodium falciparum/drug effects , Metallocenes/chemistry , Metallocenes/pharmacology , Amodiaquine/pharmacology , Amodiaquine/chemistry , Structure-Activity Relationship , Molecular Structure , Humans , Parasitic Sensitivity Tests , Dose-Response Relationship, Drug
17.
Int J Mol Sci ; 25(8)2024 Apr 10.
Article in English | MEDLINE | ID: mdl-38673758

ABSTRACT

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.


Subject(s)
Ditiocarb , Hemoglobins , Nitric Oxide , Animals , Nitric Oxide/metabolism , Ditiocarb/pharmacology , Ditiocarb/chemistry , Mice , Hemoglobins/metabolism , Hemoglobins/chemistry , Electron Spin Resonance Spectroscopy/methods , Spin Trapping/methods , Neovascularization, Pathologic/metabolism , Cell Line, Tumor , Disease Models, Animal , Mice, Inbred DBA , Ferrous Compounds/chemistry
18.
ACS Macro Lett ; 13(5): 475-482, 2024 May 21.
Article in English | MEDLINE | ID: mdl-38591821

ABSTRACT

The development of antioxidant wound dressings to remove excessive free radicals around wounds is essential for wound healing. In this study, we developed an efficient strategy to prepare antioxidant self-healing hydrogels as wound dressings by combining multicomponent reactions (MCRs) and postpolymerization modification. A polymer containing ferrocene and phenylboronic acid groups was developed via the Biginelli reaction, followed by efficient modification. This polymer is antioxidant due to its ferrocene moieties and can rapidly cross-link poly(vinyl alcohol) to realize an antioxidant self-healing hydrogel through dynamic borate ester linkages. This hydrogel has low cytotoxicity and is biocompatible. In in vivo experiments, this hydrogel is superior to existing clinical dressings in promoting wound healing. This study demonstrates the value of the Biginelli reaction in exploring biomaterials, potentially offering insights into the design of other multifunctional polymers and related materials using different MCRs.


Subject(s)
Antioxidants , Ferrous Compounds , Hydrogels , Metallocenes , Wound Healing , Ferrous Compounds/chemistry , Metallocenes/chemistry , Hydrogels/chemistry , Hydrogels/pharmacology , Wound Healing/drug effects , Antioxidants/pharmacology , Antioxidants/chemistry , Animals , Mice , Boronic Acids/chemistry , Polyvinyl Alcohol/chemistry , Humans , Biocompatible Materials/chemistry , Biocompatible Materials/pharmacology
19.
Chemosphere ; 358: 142151, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38679169

ABSTRACT

Herein, MXene-based composite aerogel (MXene-Fe2+ aerogel) are constructed by a one-step freeze-drying method, using Ti3C2Tx MXene layers as substrate material and ferrous ion (Fe2+) as crosslinking agent. With the aid of the Fe2+ induced Fenton reaction, the synthesized aerogels are used as the particle electrodes to remove phenol from wastewater with three-dimensional electrode technology. Combined with the dual roles of Fe2+ and the highly conductive MXene, the obtained particle electrode possesses extremely effective phenol degradation. The effects of experiment parameters such as Fe2+ to MXene ratio, particle electrode dosage, applied voltage, and initial pH of solution on the removal of phenol are discussed. At pH = 2.5, phenol with 50 mg/L of initial concentration can be completely removed within 50 min at 10 V with the particle electrode dosage of 0.56 g/L. Finally, the mechanism of degradation is explored. This work provides an effective way for phenol degradation by MXene-based aerogel, which has great potential for the degradation of other organic pollutants in wastewater.


Subject(s)
Gels , Phenol , Waste Disposal, Fluid , Wastewater , Water Pollutants, Chemical , Wastewater/chemistry , Water Pollutants, Chemical/chemistry , Phenol/chemistry , Gels/chemistry , Waste Disposal, Fluid/methods , Iron/chemistry , Electrodes , Hydrogen-Ion Concentration , Ions/chemistry , Ferrous Compounds/chemistry , Titanium/chemistry
20.
Environ Pollut ; 350: 124004, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38641039

ABSTRACT

The Fe(II)/Fe(III) cycle is an important driving force for dissolution and transformation of jarosite. Divalent heavy metals usually coexist with jarosite; however, their effects on Fe(II)-induced jarosite transformation and different repartitioning behavior during mineral dissolution-recrystallization are still unclear. Here, we investigated Fe(II)-induced (1 mM Fe(II)) jarosite conversion in the presence of Cd(II), Mn(II), Co(II), Ni(II) and Pb(II) (denoted as Me(II), 1 mM), respectively, under anaerobic condition at neutral pH. The results showed that all co-existing Me(II) retarded Fe(II)-induced jarosite dissolution. In the Fe(II)-only system, jarosite first rapidly transformed to lepidocrocite (an intermediate product) and then slowly to goethite; lepidocrocite was the main product. In Fe(II)-Cd(II), -Mn(II), and -Pb(II) systems, coexisting Cd(II), Mn(II) and Pb(II) retarded the above process and lepidocrocite was still the dominant conversion product. In Fe(II)-Co(II) system, coexisting Co(II) promoted lepidocrocite transformation into goethite. In Fe(II)-Ni(II) system, jarosite appeared to be directly converted into goethite, although small amounts of lepidocrocite were detected in the final product. In all treatments, the appearance or accumulation of lepidocrocite may be also related to the re-adsorption of released sulfate. By the end of reaction, 6.0 %, 4.0 %, 76.0 % 11.3 % and 19.2 % of total Cd(II), Mn(II), Pb(II) Co(II) and Ni(II) were adsorbed on the surface of solid products. Up to 49.6 %, 44.3 %, and 21.6 % of Co(II), Ni(II), and Pb(II) incorporated into solid product, with the reaction indicating that the dynamic process of Fe(II) interaction with goethite may promote the continuous incorporation of Co(II), Ni(II), and Pb(II).


Subject(s)
Ferric Compounds , Metals, Heavy , Minerals , Ferric Compounds/chemistry , Minerals/chemistry , Metals, Heavy/chemistry , Cations, Divalent , Sulfates/chemistry , Ferrous Compounds/chemistry , Manganese/chemistry , Iron/chemistry , Soil Pollutants/chemistry
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