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A ferrocene-substituted thiobarbituric acid (FT) has been synthesized to explore its photophysical properties and photodynamic and photoantimicrobial chemotherapy activities. FT has an intense metal-to-ligand charge transfer (MLCT) band at ca. 575 nm. The ferrocene moiety of FT undergoes photooxidation to form a ferrocenium species which in turn produces hydroxyl radical in an aqueous environment, which was confirmed via the bleaching reaction of p-nitrosodimethylaniline (RNO). FT exhibits efficient PDT activity against MCF-7 cancer cells with an IC 50 value of 5.6 μM upon irradiation with 595 nm for 30 min with a Thorlabs M595L3 LED (240 mW cm -2 ). Photodynamic inactivation of Staphylococcus aureus and Escherichia coli by FT shows significant activity with log reduction values of 6.62 and 6.16 respectively, under illumination for 60 min at 595 nm. These results demonstrate that ferrocene-substituted thiobarbituric acids merit further study for developing novel bioorganometallic PDT agents., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

FLASH radiotherapy delivers a high dose (≥10 Gy) at a high rate (≥40 Gy/s). In this way, particles are delivered in pulses as short as a few nanoseconds. At that rate, intertrack reactions between chemical species produced within the same pulse may affect the heterogeneous chemistry stage of water radiolysis. This stochastic process suits the capabilities of the Monte Carlo method, which can model intertrack effects to aid in radiobiology research, including the design and interpretation of experiments. In this work, the TOPAS-nBio Monte Carlo track-structure code was expanded to allow simulations of intertrack effects in the chemical stage of water radiolysis. Simulation of the behavior of radiolytic yields over a long period of time (up to 50 s) was verified by simulating radiolysis in a Fricke dosimeter irradiated by 60Co γ rays. In addition, LET-dependent G values of protons delivered in single squared pulses of widths, 1 ns, 1 µs and 10 µs, were obtained and compared to simulations using no intertrack considerations. The Fricke simulation for the calculated G value of Fe3+ ion at 50 s was within 0.4% of the accepted value from ICRU Report 34. For LET-dependent G values at the end of the chemical stage, intertrack effects were significant at LET values below 2 keV/µm. Above 2 keV/µm the reaction kinetics remained limited locally within each track and thus, effects of intertrack reactions remained low. Therefore, when track structure simulations are used to investigate the biological damage of FLASH irradiation, these intertrack reactions should be considered. The TOPAS-nBio framework with the expansion to intertrack chemistry simulation provides a useful tool to assist in this task., (©2020 by Radiation Research Society. All rights of reproduction in any form reserved.)

By taking advantage of the efficient Förster resonance energy transfer (FRET) between near-infrared (NIR)-responsive lanthanide-doped upconversion nanoparticles (UCNPs) and Fenton reagent ferrocenyl compounds ( Fc ), a series of Fc -UCNPs was designed by functionalizing NaYF 4 :Yb,Tm nanoparticles with Fc1 - Fc5 via surface-coordination chemistry. Fc -UCNP-Lipo nanosystems were then constructed by encapsulating Fc -UCNP inside liposomes for efficient delivery. Fc -UCNP can effectively release ·OH via a NIR-promoted Fenton-like reaction. In vitro and in vivo studies of Fc1 -UCNP-Lipo confirmed the preferential accumulation in a tumor site followed by an enhanced uptake of cancer cells. After cellular internalization, the released Fc1 -UCNP can effectively promote ·OH generation for tumor growth suppression. Such a Fc1 -UCNP-Lipo nanosystem exhibits advantages such as easy fabrication, low drug dosage, and no ferrous ion release.

Metal-organic frameworks (MOFs) have been identified as promising materials for the delivery of therapeutics to cure cancer owing to their intrinsic porous structure. However, in a majority of cases, MOFs act as only a delivery cargo for anticancer drugs while little attention has been focused on the utilization of their intriguing physical and chemical properties for potential anticancer purposes. Herein for the first time, an ultrathin (16.4 nm thick) ferrocene-based MOF (Zr-Fc MOF) nanosheet has been synthesized for synergistic photothermal therapy (PTT) and Fenton reaction-based chemodynamic (CDT) therapy to cure cancer without additional drugs. The Zr-Fc MOF nanosheet acts not only as an excellent photothermal agent with a prominent photothermal conversion efficiency of 53% at 808 nm but also as an efficient Fenton catalyst to promote the conversion of H 2 O 2 into hydroxyl radical ( • OH). As a consequence, an excellent therapeutic performance has been achieved in vitro as well as in vivo through this combinational effect. This work aims to construct an "all-in-one" MOF nanoplatform for PTT and CDT treatments without incorporating any additional therapeutics, which may launch a new era in the investigation of MOF-based synergistic therapy platforms for cancer therapy.

Readily-available and efficient catalyst is essential for activating oxidants to produce reactive species for deeply remediating water bodies contaminated by antibiotics. In this study, Ferrocene (Fc) was introduced to establish a heterogeneous photo-Fenton system for the degradation of sulfonamide antibiotics, taking sulfamethoxazole as a representative. Results showed that the removal of sulfamethoxazole was effective in Fc-catalyzed photo-Fenton system. Electron spin resonance and radical scavenging experiments verified that there was a photoindued electron transfer process from Fc to H 2 O 2 and dissolved oxygen resulting in the formation of OH that was primarily responsible for the degradation of sulfamethoxazole. The reactions of OH with substructure model compounds of sulfamethoxazole unveiled that aniline moiety was the preferable reaction site of sulfamethoxazole, which was verified by the formation of hydroxylated product and the dimer of sulfamethoxazole in Fc-catalyzed photo-Fenton system. This heterogeneous photo-Fenton system displayed an effective degradation efficiency even in a complex water matrices, and Fc represented a long-term stability by using the catalyst for multiple cycles. These results demonstrate that Fc-catalyzed photo-Fenton oxidation may be an efficient approach for remediation of wastewater containing antibiotics., (Copyright © 2018. Published by Elsevier B.V.)

The photo-Fenton process is recognized as a promising technique towards microorganism disinfection in wastewater, but its efficiency is hampered at near-neutral pH operating values. In this work, we overcome these obstacles by using the heterogeneous photo-Fenton process as the default disinfecting technique, targeting MS2 coliphage in wastewater. The use of low concentrations of iron oxides in wastewater without H 2 O 2 (wüstite, maghemite, magnetite) has demonstrated limited semiconductor-mediated MS2 inactivation. Changing the operational pH and the size of the oxide particles indicated that the isoelectric point of the iron oxides and the active surface area are crucial in the success of the process, and the possible underlying mechanisms are investigated. Furthermore, the addition of low amounts of Fe-oxides (1mgL -1 ) and H 2 O 2 in the system (1, 5 and 10mgL -1 ) greatly enhanced the inactivation process, leading to heterogeneous photo-Fenton processes on the surface of the magnetically separable oxides used. Additionally, photo-dissolution of iron in the bulk, lead to homogeneous photo-Fenton, further aided by the complexation by the dissolved organic matter in the solution. Finally, we assess the impact of the presence of the bacterial host and the difference caused by the different iron sources (salts, oxides) and the Fe-oxide size (normal, nano-sized)., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The aim of this project was to develop an absorbed dose to water primary standard for Ir-192 brachytherapy based on the Fricke dosimeter. To achieve this within the framework of the existing TG-43 protocol, a determination of the absorbed dose to water at the reference position, D(r0,θ0), was undertaken. Prior to this investigation, the radiation chemical yield of the ferric ions (G-value) at the Ir-192 equivalent photon energy (0.380 MeV) was established by interpolating between G-values obtained for Co-60 and 250 kV x-rays.An irradiation geometry was developed with a cylindrical holder to contain the Fricke solution and allow irradiations in a water phantom to be conducted using a standard Nucletron microSelectron V2 HDR Ir-192 afterloader. Once the geometry and holder were optimized, the dose obtained with the Fricke system was compared to the standard method used in North America, based on air-kerma strength.Initial investigations focused on reproducible positioning of the ring-shaped holder for the Fricke solution with respect to the Ir-192 source and obtaining an acceptable type A uncertainty in the optical density measurements required to yield the absorbed dose. Source positioning was found to be reproducible to better than 0.3 mm, and a careful cleaning and control procedure reduced the variation in optical density reading due to contamination of the Fricke solution by the PMMA holder. It was found that fewer than 10 irradiations were required to yield a type A standard uncertainty of less than 0.5%.Correction factors to take account of the non-water components of the geometry and the volume averaging effect of the Fricke solution volume were obtained from Monte Carlo calculations. A sensitivity analysis showed that the dependence on the input data used (e.g. interaction cross-sections) was small with a type B uncertainty for these corrections estimated to be 0.2%.The combined standard uncertainty in the determination of absorbed dose to water at the reference position for TG-43 (1 cm from the source on the transverse axis, in a water phantom) was estimated to be 0.8% with the dominant uncertainty coming from the determination of the G-value. A comparison with absorbed dose to water obtained using the product of air-kerma strength and the dose rate constant gave agreement within 1.5% for three different Ir-192 sources, which is within the combined standard uncertainties of the two methods.