Self-seeded coprecipitation flow synthesis of iron oxide nanoparticles via triphasic reactor platform: Optimising heating performance under alternating magnetic fields

Liquid-liquid segmentation is a common method to prevent reactor fouling when synthesising nanoparticles in flow, despite limiting synthetic protocols to single reagent addition steps before segmentation. This work demonstrates how a modular triphasic (gas–liquid–liquid) flow reactor platform overcomes this limitation, facilitating a continuous and fouling-free four-step co-precipitation flow synthesis of iron oxide nanoparticles (IONPs) for magnetically induced hyperthermia cancer treatment (MHCT). For this and other biomedical applications water-based IONP syntheses such as co-precipitation are favoured, but producing IONPs > 10 nm as needed for MHCT remains challenging. To overcome this size barrier for co-precipitation syntheses, a seeded growth co-precipitation strategy was employed here for the first time. After demonstrating the synthesis in batch, a triphasic flow reactor was developed to translate the multistep batch protocol into flow. Nitrogen gas was used to space the liquid–liquid segmented slugs evenly, enabling self-synchronised solution addition into the aqueous slugs dispersed in heptane. Three additions of the iron precursor solution followed by citric acid solution addition formed the seeds, grew them to larger IONPs and stabilised them. The flow platform was used for screening of the synthetic parameters to optimise the IONP heating performance in an alternating magnetic field, hence investigating their potential as MHCT heating agents. The optimal reactor settings identified made it possible to continuously synthesise 0.46 gIONPs/h colloidally stable IONPs in the aqueous phase of size ∼15 nm. The fouling-free flow reactor operated at short overall residence times (<5 min) using just ferric and ferrous salts, sodium carbonate and citric acid. The IONPs exhibited high heating performance, with an intrinsic loss power up to 3.76 nH m2 kgFe-1

Stable Iron Oxide Nanoflowers with Exceptional Magnetic Heating Efficiency: Simple and Fast Polyol Synthesis

Magnetically induced hyperthermia has reached a milestone in medical nanoscience and in phase III clinical trials for cancer treatment. As it relies on the heat generated by magnetic nanoparticles (NPs) when exposed to an external alternating magnetic field, the heating ability of these NPs is of paramount importance, so is their synthesis. We present a simple and fast method to produce iron oxide nanostructures with excellent heating ability that are colloidally stable in water. A polyol process yielded biocompatible single core nanoparticles and nanoflowers. The effect of parameters such as the precursor concentration, polyol molecular weight as well as reaction time was studied, aiming to produce NPs with the highest possible heating rates. Polyacrylic acid facilitated the formation of excellent nanoheating agents iron oxide nanoflowers (IONFs) within 30 min. The progressive increase of the size of the NFs through applying a seeded growth approach resulted in outstanding enhancement of their heating efficiency with intrinsic loss parameter up to 8.49 nH m2 kgFe-1. The colloidal stability of the NFs was maintained when transferring to an aqueous solution via a simple ligand exchange protocol, replacing polyol ligands with biocompatible sodium tripolyphosphate to secure the IONPs long-term colloidal stabilization

Magnetic zeolites: novel nanoreactors through radiofrequency heating

Many catalytic applications use conventional heating to increase the temperature to allow the desired reaction. A novel methodology is presented for the preparation of magnetic zeolite-based catalysts, allowing more efficient radiofrequency heating. These nanoreactors are tested in the isomerisation of citronellal with successful results and without any apparent deactivation

Magnetic monopole density and antiferromagnetic domain control in spin-ice iridates.

Magnetically frustrated systems provide fertile ground for complex behaviour, including unconventional ground states with emergent symmetries, topological properties, and exotic excitations. A canonical example is the emergence of magnetic-charge-carrying quasiparticles in spin-ice compounds. Despite extensive work, a reliable experimental indicator of the density of these magnetic monopoles is yet to be found. Using measurements on single crystals of Ho2Ir2O7 combined with dipolar Monte Carlo simulations, we show that the isothermal magnetoresistance is highly sensitive to the monopole density. Moreover, we uncover an unexpected and strong coupling between the monopoles on the holmium sublattice and the antiferromagnetically ordered iridium ions. These results pave the way towards a quantitative experimental measure of monopole density and demonstrate the ability to control antiferromagnetic domain walls using a uniform external magnetic field, a key goal in the design of next-generation spintronic devices

Heparin-stabilised iron oxide for MR applications: a relaxometric study

Superparamagnetic nanoparticles have strong potential in biomedicine and have seen application as clinical magnetic resonance imaging (MRI) contrast agents, though their popularity has plummeted in recent years, due to low efficacy and safety concerns, including haemagglutination. Using an in situ procedure, we have prepared colloids of magnetite nanoparticles, exploiting the clinically approved anti-coagulant, heparin, as a templating stabiliser. These colloids, stable over several days, produce exceptionally strong MRI contrast capabilities particularly at low fields, as demonstrated by relaxometric investigations using nuclear magnetic resonance dispersion (NMRD) techniques and single field r1 and r2 relaxation measurements. This behaviour is due to interparticle interactions, enhanced by the templating effect of heparin, resulting in strong magnetic anisotropic behaviour which closely maps particle size. The nanocomposites have also reliably prevented protein-adsorption triggered thrombosis typical of non-stabilised nanoparticles, showing great potential for in vivo MRI diagnostics

Evidence for global cooling in the Late Cretaceous

PublishedArticleThe Late Cretaceous ‘greenhouse’ world witnessed a transition from one of the warmest climates of the past 140 million years to cooler conditions, yet still without significant continental ice. Low-latitude sea surface temperature (SST) records are a vital piece of evidence required to unravel the cause of Late Cretaceous cooling, but high-quality data remain illusive. Here, using an organic geochemical palaeothermometer (TEX86), we present a record of SSTs for the Campanian–Maastrichtian interval (~83–66 Ma) from hemipelagic sediments deposited on the western North Atlantic shelf. Our record reveals that the North Atlantic at 35 °N was relatively warm in the earliest Campanian, with maximum SSTs of ~35 °C, but experienced significant cooling (~7 °C) after this to <~28 °C during the Maastrichtian. The overall stratigraphic trend is remarkably similar to records of high-latitude SSTs and bottom-water temperatures, suggesting that the cooling pattern was global rather than regional and, therefore, driven predominantly by declining atmospheric pCO2 levels.We gratefully acknowledge funding from the German Science Foundation (DFG Research Stipend Li 2177/1-1 to C.L.), a Royal Society (UK) URF (S.A.R.), a NERC (UK) grant (J.A.L.), a NERC (UK) studentship (K.L.), The Curry Fund of UCL (C.L.), the Cushman Foundation for Foraminiferal Research (J.M. Resig Fellowship to F.F.) and the Spanish Ministerio de Ciencia e Innovación project CGL2011-22912, co-financed by the European Regional Development Fund (I.P.-R., J.A.A., J.A.L.). We thank T. Dunkley-Jones and J. Young for assistance in collecting the samples and S. Schouten for providing TEX86L data from Demerara Rise. This paper is dedicated to Ernie Russell, who sadly died after submission of the manuscript

Investigations of the size distribution and magnetic properties of nanoparticles of Cu<inf>2</inf>OSeO<inf>3</inf>

Skyrmions in confined geometries have been a subject of increasing interest due to the different properties that they exhibit compared to their bulk counterparts. In this study, nanoparticles of skyrmion-hosting $\text{Cu}_{2}\text{OSeO}_{3}$ have been synthesised using a precipitation method followed by thermal treatment. This enables us to produce nanoparticles whose mean size varies from tens of nanometers to a few micrometers by varying the temperature and duration of the thermal decomposition of the precursor. These sizes span the $\sim 63$~nm diameter of skyrmions in $\text{Cu}_{2}\text{OSeO}_{3}$, allowing investigations into how the magnetic state changes when the size of the geometrical confinement is similar to and smaller than the size of an isolated magnetic skyrmion. AC susceptibility measurements performed on nanoparticles with a size distribution from 15 to 250 nm show a change in the magnetic phase diagram compared to bulk $\text{Cu}_{2}\text{OSeO}_{3}$

The enhancement of direct amide synthesis reaction rate over TiO 2 @SiO 2 @NiFe 2 O 4 magnetic catalysts in the continuous flow under radiofrequency heating

A series of TiO2@SiO2@NiFe2O4 composite magnetic catalyst with a core-double shell structure was synthesized by a sol-gel method. The morphology of the catalysts was studied by XRD, SEM, N2 physisorption and their magnetic properties were examined with magnetometry, and specific absorption rate measurements. The catalytic activity was determined in a direct amide synthesis reaction between aniline and phenylbutyric acid at 150 °C in a fixed bed flow reactor under radiofrequency heating. The intermediate silica layer of the catalyst increased the porosity of the outer titania layer and the specific absorbance rate of the catalyst. The initial reaction rate increased by 61% as compared to a similar core-shell TiO2@NiFe2O4 catalyst showing the detrimental effect of nickel ferrite on titania. The reaction rate was further increased by a factor of 3.5 after a sulfation treatment due to an optimum Lewis acid site strength. The highest specific reaction rate over TiO2@SiO2@NiFe2O4 was observed at a 7.5 wt% sulfate loading which was 2.6 times higher as compared to a mechanical mixture of the same composition. The initial reaction rate decreased by 36% after a period of 55 h on stream. The catalyst activity was restored after a treatment with a H2O2 solution