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1.
ACS Appl Mater Interfaces ; 16(28): 36142-36156, 2024 Jul 17.
Article in English | MEDLINE | ID: mdl-38968001

ABSTRACT

There is an urgent need to develop phototherapeutic agents with imaging capabilities to assess the treatment process and efficacy in real-time during cancer phototherapy for precision cancer therapy. The safe near-infrared (NIR) fluorescent dyes have garnered significant attention and are desirable for theranostics agents. However, until now, achieving excellent photostability and fluorescence (FL) imaging capability in aggregation-caused quenching (ACQ) dyes remains a big challenge. Here, for the only FDA-approved NIR dye, indocyanine green (ICG), we developed a dual-ferrocene (Fc) chimeric nanonetwork ICG@HFFC based on the rigid-flexible strategy through one-step self-assembly, which uses rigid Fc-modified hyaluronic acid (HA) copolymer (HA-Fc) and flexible octadecylamine (ODA) bonded Fc (Fc-C18) as the delivery system. HA-Fc reserved the ability of HA to target the CD44 receptor of the tumor cell surface, and the dual-Fc region provided a rigid space for securely binding ICG through metal-ligand interaction and π-π conjugation, ensuring excellent photostability. Additionally, the alkyl chain provided flexible confinement for the remaining ICG through hydrophobic forces, preserving its FL. Thereby, a balance is achieved between outstanding photostability and FL imaging capability. In vitro studies showed improved photobleaching resistance, enhanced FL stability, and increased singlet oxygen (1O2) production efficiency in ICG@HFFC. Further in vivo results display that ICG@HFFC had good tumor tracing ability and significant tumor inhibition which also exhibited good biocompatibility.. Therefore, ICG@HFFC provides an encouraging strategy to realize simultaneous enhanced tumor tracing and photothermal/photodynamic therapy (PTT/PDT) and offers a novel approach to address the limitations of ACQ dyes.


Subject(s)
Ferrous Compounds , Hyaluronic Acid , Indocyanine Green , Metallocenes , Photochemotherapy , Ferrous Compounds/chemistry , Humans , Metallocenes/chemistry , Animals , Mice , Indocyanine Green/chemistry , Indocyanine Green/therapeutic use , Indocyanine Green/pharmacology , Hyaluronic Acid/chemistry , Photothermal Therapy , Female , Fluorescent Dyes/chemistry , Fluorescent Dyes/pharmacology , Mice, Inbred BALB C , Photosensitizing Agents/chemistry , Photosensitizing Agents/pharmacology , Photosensitizing Agents/therapeutic use , Mice, Nude , Cell Line, Tumor , Neoplasms/diagnostic imaging , Neoplasms/drug therapy , Neoplasms/therapy , Neoplasms/pathology , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Antineoplastic Agents/therapeutic use , Nanoparticles/chemistry , Nanoparticles/therapeutic use
2.
Chem Rec ; 24(7): e202300347, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38984727

ABSTRACT

The medicinal chemistry of ferrocene has gained its momentum after the discovery of biological activities of ferrocifen and ferroquine. These ferrocenyl drugs have been designed by replacing the aromatic moiety of the organic drugs, tamoxifen and chloroquine respectively, with a ferrocenyl unit. The promising biological activities of these ferrocenyl drugs have paved a path to explore the medicinal applications of several ferrocenyl conjugates. In these conjugates, the ferrocenyl moiety has played a vital role in enhancing or imparting the anticancer activity to the molecule. The ferrocenyl conjugates induce the cytotoxicity by generating reactive oxygen species and thereby damaging the DNA. In medicinal chemistry, the five membered nitrogen heterocycles (azoles) play a significant role due to their rigid ring structure and hydrogen bonding ability with the biomolecules. Several potent drug candidates with azole groups have been in use as chemotherapeutics. Considering the importance of ferrocenyl moiety and azole groups, several ferrocenyl azole conjugates have been synthesized and screened for their biological activities. Hence, in the view of a wide scope in the development of potent drugs based on ferrocenyl azole conjugates, herein we present the details of synthesis and the anticancer activities of ferrocenyl compounds bearing azole groups such as imidazole, triazoles, thiazole and isoxazoles.


Subject(s)
Antineoplastic Agents , Azoles , Ferrous Compounds , Heterocyclic Compounds , Metallocenes , Azoles/chemistry , Azoles/pharmacology , Azoles/chemical synthesis , Ferrous Compounds/chemistry , Ferrous Compounds/pharmacology , Ferrous Compounds/chemical synthesis , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/chemical synthesis , Humans , Metallocenes/chemistry , Metallocenes/pharmacology , Metallocenes/chemical synthesis , Heterocyclic Compounds/chemistry , Heterocyclic Compounds/pharmacology , Heterocyclic Compounds/chemical synthesis
3.
Bioelectrochemistry ; 160: 108774, 2024 Jul 06.
Article in English | MEDLINE | ID: mdl-38981325

ABSTRACT

Salivary α-amylase (α-ALS) has drawn attention as a possible bioindicator for dental caries. Herein, combining the synergistic properties of multi-walled carbon nanotubes (MWCNTs), ß-cyclodextrin (ß-CD) and starch, an electrochemical sensor is constructed employing ferrocene (FCN) as an electrochemical indicator to oversee the progression of the enzymatic catalysis of α-ALS. The method involves a two-step chemical reaction sequence on a screen-printed carbon electrode (SPCE). X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Field emission scanning electron microscope (FE-SEM), and Dynamic light scattering (DLS) were used to characterize the synthesized material, while Static water Contact angle measurements, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) were performed to monitor each step of sensor fabrication. The electrochemical sensor permitted to detect α-ALS within the linear range of 0.5-280 U mL-1, revealing detection (LOD), and quantification (LOQ) values of 0.041 U mL-1, and 0.159 U mL-1, respectively. Remarkably, the sensor demonstrated exceptional specificity and selectivity, effectively discriminating against other interfering substances in saliva. Validation of the method involved analyzing α-ALS levels in artificial saliva with an accuracy range of 97 % to 103 %, as well as in real clinical saliva samples across various age groups.

4.
Adv Mater ; : e2405747, 2024 Jun 19.
Article in English | MEDLINE | ID: mdl-38898683

ABSTRACT

To meet the growing demand for energy storage, lithium-ion batteries (LIBs) with fast charging capabilities has emerged as a critical technology. The electrode materials affect the rate performance significantly. Organic electrodes with structural flexibility support fast lithium-ion transport and are considered promising candidates for fast-charging LIBs. However, it is a challenge to create organic electrodes that can cycle steadily and reach high energy density in a few minutes. To solve this issue, accelerating the transport of electrons and lithium ions in the electrode is the key. Here, it is demonstrated that a ferrocene-based polymer electrode (Fc-SO3Li) can be used as a fast-charging organic electrode for LIBs. Thanks to its molecular architecture, LIBs with Fc-SO3Li show exceptional cycling stability (99.99% capacity retention after 10 000 cycles) and reach an energy density of 183 Wh kg-1 in 72 seconds. Moreover, the composite material through in situ polymerization with Fc-SO3Li and 50 wt % carbon nanotube (denoted as Fc-SO3Li-CNT50) achieved optimized electron and ion transport pathways. After 10 000 cycles at a high current density of 50C, it delivered a high energy density of 304 Wh kg-1. This study provides valuable insights into designing cathode materials for LIBs that combine high power and ultralong cycle life.

5.
Molecules ; 29(11)2024 May 25.
Article in English | MEDLINE | ID: mdl-38893381

ABSTRACT

Desalination is considered a promising solution to alleviate water shortages, yet current methods are often restricted, due to challenges like high energy consumption, significant cost, or limited desalination capacity. In this study, we present a novel approach of redox flow desalination (RFD) utilizing the highly aqueous-soluble and reversible redox-active compound, potassium 1,1'-bis(sulfonate) ferrocene (1,1'-FcDS). This water-soluble organic compound yielded stable and rapid desalination, sustaining extended operation without notable decay and achieving an impressive desalination rate of up to 457.5 mmol·h-1·m-2 and energy consumption as low as 40.2 kJ·molNaCl-1. Specifically, the RFD device effectively desalinated a 50 mM NaCl solution to potable standards within 6000 s using 1,1'-FcDS. It maintained an average energy consumption of 178.16 kJ·molNaCl-1 and exhibited negligible deterioration in desalination rate, energy efficiency, and charge efficiency throughout a rigorous 12,000 s cycling test. Furthermore, the versatility of this method was demonstrated by effectively treating saline water with varying initial concentrations from 10 mM to 50 mM, showcasing its potential across a broad spectrum of applications.

6.
Water Res ; 260: 121915, 2024 Aug 15.
Article in English | MEDLINE | ID: mdl-38878309

ABSTRACT

The effective removal of trace levels of the highly toxic arsenite (As(Ⅲ)) from groundwater is crucial to address the threat to drinking water supply. Herein, we developed an electrochemical separation system utilizing redox-active ferrocene-based metal-organic frameworks (termed Fe-DFc) for selective removal of As(III). This system leveraged 1,1'-ferrocenedicarboxylic acid as a ligand coordinated with iron, enabling the highly selective capture and conversion of As(III) from groundwater. The Fe-DFc electrode-based electrochemical system not only effectively removed As(III) even in the presence of a 1250-fold excess of competing electrolytes, but also converted about 96 % of the adsorbed As(III) into the less toxic As(V), surpassing the results of those documented in the current literature. X-ray absorption fine structure analysis and density functional theory calculations demonstrated that the high selectivity of Fe-O6 moiety and the exceptional redox activity of Fc synergistically contributed to the efficient removal of As(III). Moreover, the electrochemical separation system enabled the remediation of arsenic-contaminated groundwater at a low energy cost of 0.033 kWh m-3 during long-term operation, highlighting the application potential of the electrochemical technology for arsenic removal from contaminated water.


Subject(s)
Arsenic , Electrochemical Techniques , Ferrous Compounds , Metal-Organic Frameworks , Water Pollutants, Chemical , Metal-Organic Frameworks/chemistry , Water Pollutants, Chemical/chemistry , Ferrous Compounds/chemistry , Metallocenes/chemistry , Groundwater/chemistry , Water Purification/methods , Adsorption , Oxidation-Reduction
7.
Sci Rep ; 14(1): 13847, 2024 Jun 15.
Article in English | MEDLINE | ID: mdl-38879584

ABSTRACT

A series of 4-ferrcenylbutyl carboxylate esters with different alkyl chain length (C2-C4) of carboxylic acids were synthesized using Fe3O4@SiO2@(CH2)3-Im-bisEthylFc[I] nanoparticles as catalyst and have been characterized with FT-IR, 1H NMR, and 13C NMR. Ferrocenyl-based esters were used as corrosion inhibitors of mild steel in the 1M HCl solution as corrosive media. The corrosion inhibition efficiency of the synthesized ferrocenyl-based esters has been assessed by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The 4-ferrocenylbutyl propionate showed a more effective corrosion inhibition behavior among the studied esters with 96% efficiency after immersion in the corrosive media for 2 weeks. The corrosion inhibition mechanism is dominated by formation of passive layer of inhibitor on the surface of the mild steel by adsorption. Moreover, the adsorption characteristics of 4-butylferrcenyl carboxylate esters on mild steel were thoroughly explored using density functional theory calculations. It was found that the Fe atoms located around the C impurity in the mild steel are the most efficient and active sites to adsorb 4-butylferrcenyl carboxylate esters.

8.
ChemSusChem ; : e202400829, 2024 Jun 17.
Article in English | MEDLINE | ID: mdl-38884174

ABSTRACT

Ferrocene (Fc) and Fc derivatives have gained popularity in recent years due to their unique structure and characteristics. Among Fc's diverse performances, photothermal conversion, as a primary source of energy conversion, has sparked substantial study attention. This review summaries Fc and Fc derivatives with photothermal characteristics, as well as their applications developed recently. First, methods for the synthesis of Fc-based materials are systematically discussed. Then, the photothermal conversion mechanism based on nonradiative relaxation is summarized. Furthermore, the most recent advances in Fc-based materials in photothermal applications are described, including photothermal degradation, photothermal antibacterial, photothermal therapies, photothermal catalysis, solar-driven water production, and photothermal CO2 separation. Finally, a summary and insights on the photothermal application of Fc-based materials are provided. This paper seeks to provide researchers with a better knowledge of photothermal behavior while also highlighting the potential of Fc and its derivatives in photothermal fields.

9.
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
10.
Int J Biol Macromol ; 268(Pt 2): 131944, 2024 May.
Article in English | MEDLINE | ID: mdl-38692531

ABSTRACT

Efficient removal and recycling of phosphorus from complex water matrices using environmentally friendly and sustainable materials is essential yet challenging. To this end, a novel bio-based adsorbent (DX-FcA-CS) was developed by coupling oxidized dextran-crosslinked chitosan with ferrocene carboxylic acid (FcA). Detailed characterization revealed that the incorporation of FcA reduced the total pore area of DX-FcA-CS to 7.21 m2·g-1, one-third of ferrocene-free DX-CS (21.71 m2·g-1), while enhancing thermal stability and PO43- adsorption performance. Adsorption kinetics and isotherm studies demonstrated that the interaction between DX-FcA-CS and PO43- followed a pseudo-second-order kinetic model and Langmuir model, indicating chemical and monolayered adsorption mechanisms, respectively. Moreover, DX-FcA-CS exhibited excellent anti-interference properties against concentrated co-existing inorganic ions and humic acid, along with high recyclability. The maximum adsorption capacity reached 1285.35 mg·g-1 (∼428.45 mg P g-1), three times that of DX-CS and surpassing many other adsorbents. PO43--loaded DX-FcA-CS could be further carbonized into electrode material due to its rich content of phosphorus and nitrogen, transforming waste into a valuable resource. These outstanding characteristics position DX-FcA-CS as a promising alternative for phosphate capture and recycling. Overall, this study presents a viable approach to designing environmentally friendly, recyclable, and cost-effective biomaterial for wastewater phosphate removal and value-added applications.


Subject(s)
Chitosan , Phosphates , Chitosan/chemistry , Adsorption , Porosity , Phosphates/chemistry , Kinetics , Water Purification/methods , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Wastewater/chemistry , Phosphorus/chemistry
11.
J Agric Food Chem ; 72(21): 11917-11927, 2024 May 29.
Article in English | MEDLINE | ID: mdl-38743609

ABSTRACT

An unprecedented study of the application of planar chiral compounds in antiviral pesticide development is reported. A class of multifunctional planar chiral ferrocene derivatives bearing α-amino phosphonate moieties was synthesized. These compounds, exhibiting superior optical purities, were subsequently subjected to antiviral evaluations against the notable plant pathogen potato virus Y (PVY). The influence of the absolute configurations of the planar chiral compounds on their antiviral bioactivities was significant. A number of these enantiomerically enriched planar chiral molecules demonstrated superior anti-PVY activities. Specifically, compound (Sp, R)-9n displayed extraordinary curative activities against PVY, with a 50% maximal effective concentration (EC50) of 216.11 µg/mL, surpassing the efficacy of ningnanmycin (NNM, 272.74 µg/mL). The protective activities of compound (Sp, R)-9n had an EC50 value of 152.78 µg/mL, which was better than that of NNM (413.22 µg/mL). The molecular docking and defense enzyme activity tests were carried out using the planar chiral molecules bearing different absolute configurations to investigate the mechanism of their antiviral activities against PVY. (Sp, R)-9n, (Sp, R)-9o, and NMM all showed stronger affinities to the PVY-CP than the (Rp, S)-9n. Investigations into the mechanisms revealed that the planar chiral configurations of the compounds played pivotal roles in the interactions between the PVY-CP molecules and could augment the activities of the defense enzymes. This study contributes substantial insights into the role of planar chirality in defending plants against viral infections.


Subject(s)
Antiviral Agents , Molecular Docking Simulation , Organophosphonates , Plant Diseases , Potyvirus , Solanum tuberosum , Antiviral Agents/pharmacology , Antiviral Agents/chemical synthesis , Antiviral Agents/chemistry , Plant Diseases/virology , Organophosphonates/pharmacology , Organophosphonates/chemistry , Organophosphonates/chemical synthesis , Solanum tuberosum/virology , Solanum tuberosum/chemistry , Potyvirus/drug effects , Structure-Activity Relationship , Stereoisomerism , Molecular Structure
12.
J Inorg Biochem ; 257: 112615, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38772187

ABSTRACT

A series of bis-naphthyl ferrocene derivatives were synthesized and characterized. Based on the results obtained from UV-visible absorption titration and ethidium bromide (EB) displacement experiments, it was observed that the synthesized compounds exhibited a strong binding ability to dsDNA. In comparison to the viscosity curve of EB, the tested compounds demonstrated a bisintercalation binding mode when interacting with CT-DNA. Differential pulse voltammetry (DPV) was employed to assess the binding specificity of these indicators towards ssDNA and dsDNA. All tested indicators displayed more pronounced signal differences before and after hybridization between probe nucleic acids and target nucleic acids compared to Methylene Blue (MB). Among the evaluated compounds, compound 3j containing an ether chain showed superior performance as an indicator, making it suitable for constructing DNA-based biosensors. Under optimized conditions including probe ssDNA concentration and indicator concentration, this biosensor exhibited good sensitivity, reproducibility, stability, and selectivity. The limit of detection was calculated as 4.53 × 10-11 mol/L. Furthermore, when utilizing 3j as the indicator in serum samples, the biosensor achieved satisfactory recovery rates for detecting the BRCA1 gene.


Subject(s)
Biosensing Techniques , DNA , Ferrous Compounds , Metallocenes , Ferrous Compounds/chemistry , Biosensing Techniques/methods , Metallocenes/chemistry , DNA/chemistry , Electrochemical Techniques/methods , Humans , DNA, Single-Stranded/chemistry
13.
J Colloid Interface Sci ; 671: 78-87, 2024 Oct.
Article in English | MEDLINE | ID: mdl-38795536

ABSTRACT

Aqueous ammonium ion batteries (AAIBs) are garnering increasing attention due to their utilization of abundant resources, cost-effectiveness, safety, and unique energy storage mechanism. The pursuit of high-performance cathode materials has become a pressing issue. In this study, we propose and synthesize ferrocene-embedded hydrated vanadium pentoxide (Fer/VOH) for implementation in AAIBs. The inclusion of ferrocene serves to expand the interlayer spacing, mitigate interlayer forces, and introduce the electron-rich environment characteristic of ferrocene. This augmentation facilitates the creation of additional oxygen vacancies, substantially enhancing the capacity and efficiency of ammonium ion storage. Notably, our investigation reveals that the incorporation of ferrocene attenuates the hydrogen bonding interactions associated with ammonium ions, rendering them more amenable to the interlayer embedding and release processes. Building upon these advantages, Fer/VOH exhibits a specific capacity of 313 mAh/g at a current density of 0.2 A/g, representing the highest reported performance among vanadium oxides utilized in AAIBs to date. Even after 2000 charge/discharge cycles at a current density of 2 A/g, Fer/VOH maintains a reversible specific capacity of 89 mAh/g, with a capacity retention rate of 54.8%. This study confirms the viability of Fer/VOH as a cathode material for AAIBs and offers a novel approach to enhancing the electrical conductivity and diminishing the hydrogen bonding forces in vanadium oxide intercalation through the embedding of electron-rich species and positronic groups.

14.
J Inorg Biochem ; 257: 112586, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38728860

ABSTRACT

Ferrocene, ruthenium(II) and iridium(III) organometallic complexes, potential substitutes for platinum-based drugs, have shown good application prospects in the field of cancer therapy. Therefore, in this paper, six ferrocene-modified half-sandwich ruthenium(II) and iridium(III) propionylhydrazone complexes were prepared, and the anticancer potential was evaluated and compared with cisplatin. These complexes showed potential in-vitro anti-proliferative activity against A549 cancer cells, especially for Ir-based complexes, and showing favorable synergistic anticancer effect. Meanwhile, these complexes showed little cytotoxicity and effective anti-migration activity. Ir3, the most active complex (ferrocene-appended iridium(III) complex), could accumulate in the intracellular mitochondria, disturb the cell cycle (S-phase), induce the accumulation of reactive oxygen species, and eventually cause the apoptosis of A549 cells. Then, the design of these complexes provides a good structural basis for the multi-active non­platinum organometallic anticancer complexes.


Subject(s)
Antineoplastic Agents , Apoptosis , Coordination Complexes , Ferrous Compounds , Hydrazones , Iridium , Metallocenes , Ruthenium , Humans , Ferrous Compounds/chemistry , Ferrous Compounds/pharmacology , Iridium/chemistry , Iridium/pharmacology , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/chemical synthesis , Metallocenes/chemistry , Metallocenes/pharmacology , Ruthenium/chemistry , Coordination Complexes/pharmacology , Coordination Complexes/chemistry , Coordination Complexes/chemical synthesis , Hydrazones/chemistry , Hydrazones/pharmacology , Hydrazones/chemical synthesis , A549 Cells , Apoptosis/drug effects , Reactive Oxygen Species/metabolism , Cell Proliferation/drug effects
15.
Beilstein J Org Chem ; 20: 1011-1019, 2024.
Article in English | MEDLINE | ID: mdl-38711587

ABSTRACT

Ferrocene (FeCp2) was introduced as a non-magnetic guest molecule to activated carbon fibers (ACFs) as a nanographene-based host having localized spins originating from zigzag edges of graphene. The introduction of the guest molecule was confirmed by FTIR for ACFs-FeCp2 introduced at 55 (150) °C (FeCp2-ACFs-55(150)). The appearance of satellite Fe2p peaks and the increase in shake-up peak intensity of the C1s in the XPS spectrum proved the emergence of charge-transfer host-guest interaction in FeCp2-ACFs-150, supported by the red-shift of the G-band in the Raman spectrum. The six-times enhancement in the spin concentration in FeCp2-ACFs-150 compared with ACFs indicates the spin magnetism of the non-magnetic guest FeCp2+ molecule induced by a charge-transfer host-guest interaction in the nanographene host. The larger ESR linewidth than that expected from the dipolar interaction estimated by the localized spin concentration suggests the exchange interaction between the nanographene and FeCp2 spins. The narrowing of the ESR linewidth of FeCp2-ACFs-55 upon higher excitation microwave power suggests the inhomogeneity of the environment for FeCp2+ molecules in the nanographene host. The observed induction of spin magnetism by the interfacial interactions between the nanographene host and the guest molecules will be a promising strategy for developing a new class of molecular magnets.

16.
Spectrochim Acta A Mol Biomol Spectrosc ; 318: 124448, 2024 Oct 05.
Article in English | MEDLINE | ID: mdl-38763019

ABSTRACT

Mononuclear phosphinite Iridium complexes based on ferrocene group have been prepared and characterized by various spectroscopic techniques. The complexes were subjected to cyclic voltammetry studies in order to determine the energies of HOMO and LUMO levels and to estimate their electrochemical and some electronic properties. Organic complex-based memory substrates were immobilized using TiO2-modified ITO electrodes, and the memory functions of phosphinite-based organic complexes were verified by chronoamperometry (CA) and open-circuit potential amperometry (OCPA). Extensive theoretical and experimental investigations were directed to gain a more profound understanding of the chemical descriptors and the diverse electronic transitions taking place within the iridium complexes, as well as their electrochemical characteristics. The quantum chemical calculations were carried out for the iridium complexes at the DFT/CAM-B3LYP level of theory in the gas phase. Furthermore, the antioxidant, antimicrobial, DNA binding, and DNA cleavage activities of the complexes were tested. Complex 2 exhibited the highest radical scavenging activity (67.5 ± 2.24 %) at 200.0 mg/L concentration. It was observed that the complexes formed an inhibition zone in the range of 8-15 mm against Gram + bacteria and in the range of 0-13 mm against Gram - bacteria. The agarose gel electrophoresis method was used to determine the DNA binding and DNA cleavage activities of the complexes. All of the tested complexes had DNA binding activity; however, complexes 1, 2, and 8 showed better binding activity than the others.


Subject(s)
Coordination Complexes , Density Functional Theory , Iridium , Phosphines , Iridium/chemistry , Phosphines/chemistry , Coordination Complexes/chemistry , Coordination Complexes/pharmacology , Electrochemical Techniques/methods , Antioxidants/chemistry , Antioxidants/pharmacology , DNA/chemistry , DNA/metabolism , Microbial Sensitivity Tests , Models, Molecular , Anti-Infective Agents/pharmacology , Anti-Infective Agents/chemistry , Bacteria/drug effects , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry
17.
Chemistry ; 30(35): e202400730, 2024 Jun 20.
Article in English | MEDLINE | ID: mdl-38634285

ABSTRACT

We present herein the synthesis, characterization and complexation of ferrocenyl-substituted MIIs (mesoionic imines) and their metal complexes. In the free MIIs, strong hydrogen bonding interactions are observed between the imine-N and the C-H bonds of the ferrocenyl substituents both in the solid state and in solution. The influence of this hydrogen bonding is so strong that complexation of the MIIs with [IrCp*Cl2]2 yields unique six-membered iridacycles via C-H-activation of the corresponding C-H-site at the Fc-substituent and not the Ph-substituent. This result is in contrast to previous reports in which always a preferential C-H activation at the phenyl substituent is observed in competitive reactions in the presence of ferrocenyl substituents. The corresponding Ir complexes formed after in-situ halide exchange reaction exist in either [Ir-I] contact or as [Ir]+I- solvent separated ion-pairs depending on the solvent polarity. The iodide coordinated and solvent separated ion-pairs display drastically different physical properties. The TEP (Tolman-electronic-parameter) of these ligands was determined and lines up with previously reported MII-ligands. The redox properties were investigated by a combination of electrochemical and spectroelectrochemical methods. We show here how non-covalent interactions can have a drastic influence on the physical and chemical properties of these new class of compounds.

18.
Heliyon ; 10(7): e28929, 2024 Apr 15.
Article in English | MEDLINE | ID: mdl-38601696

ABSTRACT

Volatile sulfur compounds (VSCs) are important aroma and flavour characters in food and beverage products. The identification and quantification of these extremely reactive and volatile compounds pose analytical challenges which demand selective and sensitive methods. In this study, a novel quantification method was developed to analyse sulfhydryls as well as the total pool of sulfhydryls which can be released after tris(2-carboxyethyl)phosphine (TCEP) addition from disulfides, polysulfides, metal-bound and other yet to be identified sources naturally present in wine. The majority of methods for VSC quantification analyse VSCs in wine headspace, whereas this method measures sulfhydryls and TCEP-releasable sulfhydryl species, which likely include free and metal-bound sulfhydryl forms, in the liquid phase of wine using UHPLC-MS/MS. Sulfhydryls were derivatised with N-(2-ferroceneethyl) maleimide (FEM), subsequently, followed by differential labelling of sulfhydryls released after TCEP addition with ferrocenecarboxylic acid-(2-maleimidoyl)ethylamide (FMEA). Analysis of commercial wines revealed the presence of hydrogen sulfide, methanethiol, ethanethiol, and 2-mercaptoethanol at aroma-active concentrations. Significant positive correlations were found between MeSH and CH3-S-R TCEP-releasable species, and significant positive correlations were found between EtSH and CH3-CH2-S-R TCEP-releasable species. This method provides important information on sulfhydryls, and may also provide insights into a wine's risk of developing 'reductive' faults post-bottling from latent sources.

19.
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
20.
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
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