The use of advanced electroactive catalysts enhances the performance of electrochemical biosensors in real-time biomonitoring and has received much attention owing to its excellent physicochemical and electrochemical possessions. In this work, a novel biosensor was developed based on the electrocatalytic activity of functionalized vanadium carbide (VC) material, including VC@ruthenium (Ru), VC@Ru-polyaniline nanoparticles (VC@Ru-PANI-NPs) as non-enzymatic nanocarriers for the fabrication of modified screen-printed electrode (SPE) to detect acetaminophen in human blood. As-prepared materials were characterized using SEM, TEM, XRD, and XPS techniques. Biosensing was carried out using cyclic voltammetry and differential pulse voltammetry techniques and has revealed imperative electrocatalytic activity. A quasi-reversible redox method of the over-potential of acetaminophen increased considerably compared with that at the modified electrode and the bare SPE. The excellent electrocatalytic behaviour of VC@Ru-PANI-NPs/SPE is attributed to its distinctive chemical and physical properties, including rapid electron transfer, striking ᴫ-ᴫ interface, and strong adsorptive capability. This electrochemical biosensor exhibits a detection limit of 0.024 μM, in a linear range of 0.1-382.72 μM with a reproducibility of 2.45 % relative standard deviation, and a good recovery from 96.69 % to 105.59 %, the acquired results ensure a better performance compared with previous reports. The enriched electrocatalytic activity of this developed biosensor is mainly credited to its high surface area, better electrical conductivity, synergistic effect, and abundant electroactive sites. The real-world utility of the VC@Ru-PANI-NPs/SPE-based sensor was ensured via the investigation of biomonitoring of acetaminophen in human blood samples with satisfactory recoveries.
The constant increase in cardiovascular disease rate coupled with significant drawbacks of existing therapies emphasise the necessity to improve therapeutic strategies. Natural flavonoids exert innumerable pharmacological effects in humans. Here, we demonstrate the effects of chrysin, a natural flavonoid found largely in honey and passionflower on the modulation of platelet function, haemostasis and thrombosis. Chrysin displayed significant inhibitory effects on isolated platelets, however, its activity was substantially reduced under physiological conditions. In order to increase the efficacy of chrysin, a sulfur derivative (thio-chrysin), and ruthenium-complexes (Ru-chrysin and Ru-thio-chrysin) were synthesised and their effects on the modulation of platelet function were evaluated. Indeed, Ru-thio-chrysin displayed a 4-fold greater inhibition of platelet function and thrombus formation in vitro than chrysin under physiologically relevant conditions such as in platelet-rich plasma and whole blood. Notably, Ru-thio-chrysin exhibited similar efficacy to chrysin in the modulation of haemostasis in mice. Increased bioavailability and cell permeability of Ru-thio-chrysin compared to chrysin were found to be the basis for its enhanced activity. Together, these results demonstrate that Ru-thio-coupled natural compounds such as chrysin may serve as promising templates for the development of novel anti-thrombotic agents.
Despite the importance of studying the instability of delithiated cathode materials, it remains difficult to underpin the degradation mechanism of lithium-rich cathode materials due to the complication of combined chemical and structural evolutions. Herein, we use state-of-the-art electron microscopy tools, in conjunction with synchrotron X-ray techniques and first-principle calculations to study a 4d-element-containing compound, Li2Ru0.5Mn0.5O3. We find surprisingly, after cycling, ruthenium segregates out as metallic nanoclusters on the reconstructed surface. Our calculations show that the unexpected ruthenium metal segregation is due to its thermodynamic insolubility in the oxygen deprived surface. This insolubility can disrupt the reconstructed surface, which explains the formation of a porous structure in this material. This work reveals the importance of studying the thermodynamic stability of the reconstructed film on the cathode materials and offers a theoretical guidance for choosing manganese substituting elements in lithium-rich as well as stoichiometric layer-layer compounds for stabilizing the cathode surface.
We present an electrochemical long period fiber grating (LPFG) sensor for electroactive species with an optically transparent electrode. The sensor was fabricated by coating indium tin oxide onto the surface of LPFG using a polygonal barrel-sputtering method. LPFG was produced by an electric arc-induced technique. The sensing is based on change in the detection of electron density on the electrode surface during potential application and its reduction by electrochemical redox of analytes. Four typical electroactive species of methylene blue, hexaammineruthenium(III), ferrocyanide, and ferrocenedimethanol were used to investigate the sensor performance. The concentrations of analytes were determined by the modulation of the potential as the change in transmittance around the resonance band of LPFG. The sensitivity of the sensor, particularly to methylene blue, was high, and the sensor responded to a wide concentration range of 0.001 mM to 1 mM.
A non-enzymatic glucose sensor of multi-walled carbon nanotube-ruthenium oxide/composite paste electrode (MWCNT-RuO(2)/CPE) was developed. The electrode was characterized by using XRD, SEM, TEM and EIS. Meanwhile, cyclic voltammetry and amperometry were used to check on the performances of the MWCNT-RuO(2)/CPE towards glucose. The proposed electrode has displayed a synergistic effect of RuO(2) and MWCNT on the electrocatalytic oxidation of glucose in 3M NaOH. This was possible via the formation of transitions of two redox pairs, viz. Ru(VI)/Ru(IV) and Ru(VII)/Ru(VI). A linear range of 0.5-50mM glucose and a limit of detection of 33 μM glucose (S/N=3) were observed. There was no significant interference observable from the traditional interferences, viz. ascorbic acid and uric acid. Indeed, results so obtained have indicated that the developed MWCNT-RuO(2)/CPE would pave the way for a better future to glucose sensor development as its fabrication was without the use of any enzyme.
Platinum drugs are heavily used first-line chemotherapeutic agents for many solid tumours and have stimulated substantial interest in the biological activity of DNA-binding metal complexes. These complexes generate DNA lesions which trigger the activation of DNA damage response (DDR) pathways that are essential to maintain genomic integrity. Cancer cells exploit this intrinsic DNA repair network to counteract many types of chemotherapies. Now, advances in the molecular biology of cancer has paved the way for the combination of DDR inhibitors such as poly (ADP-ribose) polymerase (PARP) inhibitors (PARPi) and agents that induce high levels of DNA replication stress or single-strand break damage for synergistic cancer cell killing. In this review, we summarise early-stage, preclinical and clinical findings exploring platinum and emerging ruthenium anti-cancer complexes alongside PARPi in combination therapy for cancer and also describe emerging work on the ability of ruthenium and gold complexes to directly inhibit PARP activity.
A novel bimetallic double thiocyanate-bridged ruthenium and tungsten metal complex containing bipyridyl and dithiolene co-ligands was synthesized and the behavior of the complex as a dye-sensitizer for a photoelectrochemical (PEG) cell for a direct water splitting reaction was investigated. The ligands and metal complexes were characterized on the basis of elemental analysis as well as uv-Vis, Fourier transform infrared ( Pim) and nuclear magnetic resonance (11I and 13C NMR) spectroscopy. Cyclic voltammetry of the bimetallic complex showed multiple redox couples, in which half potentials E 112 at 0 .625 , 0.05 and 0.61 V were assigned as the formal redox processes of Ru(III)IRu(II) reduction, W(IV)IW(V) and W(V)IW(VI) oxidations, respectively. Photocurrent measurements were performed in homogeneous system and TiO2 was used as the photoanode for photocurrent measurements. Current density generated by the bimetallic complex was higher than that of N3 commercial dye which suggested that the bimetallic complex donated more electrons to the semiconductor.
The ruthenium polypyridyl complex [Ru(dppz)2PIP]2+ (dppz: dipyridophenazine, PIP: (2-(phenyl)-imidazo[4,5-f ][1,10]phenanthroline), or Ru-PIP, is a potential anticancer drug that acts by inhibiting DNA replication. Due to the poor dissolution of Ru-PIP in aqueous media, a drug delivery agent would be a useful approach to overcome its limited bioavailability. Mesoporous silica nanoparticles (MSNs) were synthesized via a co-condensation method by using a phenanthrolinium salt with a 16 carbon length chain (Phen-C16) as the template. Optimization of the synthesis conditions by Box-Behnken design (BBD) generated MSNs with high surface area response at 833.9 m2g-1. Ru-PIP was effectively entrapped in MSNs at 18.84%. Drug release profile analysis showed that Ru-PIP is gradually released, with a cumulative release percentage of approximately 50% at 72 h. The release kinetic profile implied that Ru-PIP was released from MSN by diffusion. The in vitro cytotoxicity of Ru-PIP, both free and MSN-encapsulated, was studied in Hela, A549, and T24 cancer cell lines. While treatment of Ru-PIP alone is moderately cytotoxic, encapsulated Ru-PIP exerted significant cytotoxicity upon all the cell lines, with half maximal inhibitory concentration (IC50) values determined by MTT (([3-(4,5-dimethylthiazol-2-yl)-2,5-dephenyltetrazolium bromide]) assay at 48 h exposure substantially decreasing from >30 µM to <10 µM as a result of MSN encapsulation. The mechanistic potential of cytotoxicity on cell cycle distribution showed an increase in G1/S phase populations in all three cell lines. The findings indicate that MSN is an ideal drug delivery agent, as it is able to sustainably release Ru-PIP by diffusion in a prolonged treatment period.
Three novel ruthenium(II) complexes of the general formula [Ru(II)(bpy)2
L]2+ were synthesized, where L =
1,10-phenanthroline derivatives of position 2 imidazole having 3,4-didecyloxy-phenyl (ddip), 3,4-ditetradecyloxy-phenyl
(dtip) and 3,4-dihexadecyloxy-phenyl (dhip). All complexes were characterized by elemental analysis, 1
H-NMR and ESI-MS.
Their photophysical properties have also been studied by UV-visible spectroscopy and fluorescence spectroscopy. The
complexes exhibit Ru(II) metal centered emission at approximately 610 nm in acetonitrile solution at room temperature. DNA
binding studies were carried out by UV-visible titration, luminescence titration and viscosity studies. The results indicated
that [Ru(bpy)2
(ddip)]2+ binds to CT-DNA by partial intercalation mode, while [Ru(bpy)2
(dtip)]2+ and [Ru(bpy)2
(dhip)]2+
bind intercalatively via extended ligands.
Ruthenium(II) polypyridyl complexes can intercalate DNA with high affinity and prevent cell proliferation; however, the direct impact of ruthenium-based intercalation on cellular DNA replication remains unknown. Here we show the multi-intercalator [Ru(dppz)2(PIP)](2+) (dppz = dipyridophenazine, PIP = 2-(phenyl)imidazo[4,5-f][1,10]phenanthroline) immediately stalls replication fork progression in HeLa human cervical cancer cells. In response to this replication blockade, the DNA damage response (DDR) cell signalling network is activated, with checkpoint kinase 1 (Chk1) activation indicating prolonged replication-associated DNA damage, and cell proliferation is inhibited by G1-S cell-cycle arrest. Co-incubation with a Chk1 inhibitor achieves synergistic apoptosis in cancer cells, with a significant increase in phospho(Ser139) histone H2AX (γ-H2AX) levels and foci indicating increased conversion of stalled replication forks to double-strand breaks (DSBs). Normal human epithelial cells remain unaffected by this concurrent treatment. Furthermore, pre-treatment of HeLa cells with [Ru(dppz)2(PIP)](2+) before external beam ionising radiation results in a supra-additive decrease in cell survival accompanied by increased γ-H2AX expression, indicating the compound functions as a radiosensitizer. Together, these results indicate ruthenium-based intercalation can block replication fork progression and demonstrate how these DNA-binding agents may be combined with DDR inhibitors or ionising radiation to achieve more efficient cancer cell killing.