22 research outputs found
On the ‘centre of gravity’ method for measuring the composition of magnetite/maghemite mixtures, or the stoichiometry of magnetite-maghemite solid solutions, via 57Fe Mössbauer spectroscopy
We evaluate the application of 57Fe Mössbauer spectroscopy to the determination of the composition of magnetite (Fe3O4)/maghemite (?-Fe2O3) mixtures and the stoichiometry of magnetite-maghemite solid solutions. In particular, we consider a recently proposed model-independent method which does not rely on a priori assumptions regarding the nature of the sample, other than that it is free of other Fe-containing phases. In it a single parameter, ?RT-the 'centre of gravity', or area weighted mean isomer shift at room temperature, T = 295 ± 5 K - is extracted by curve-fitting a sample's Mössbauer spectrum, and is correlated to the sample's composition or stoichiometry. We present data on high-purity magnetite and maghemite powders, and mixtures thereof, as well as comparison literature data from nanoparticulate mixtures and solid solutions, to show that a linear correlation exists between ?RT and the numerical proportion of Fe atoms in the magnetite environment: ? = Femagnetite/Fetotal = (?RT - ?o)/m, where ?o= 0.3206 ± 0.0022 mm s-1 and m = 0.2135 ± 0.0076 mm s-1. We also present equations to relate ? to the weight percentage w of magnetite in mixed phases, and the magnetite stoichiometry x = Fe2+/Fe3+ in solid solutions. The analytical method is generally applicable, but is most accurate when the absorption profiles are sharp; in some samples this may require spectra to be recorded at reduced temperatures. We consider such cases and provide equations to relate ?(T) to the corresponding ? value.This work was supported by the European Union Seventh Framework Programme through the NanoMag project ‘Nanometrology standardisation methods for magnetic nanoparticles’, under grant agreement no. 60444
Dipolar-coupled moment correlations in clusters of magnetic nanoparticles
Here, we investigate the nature of the moment coupling between 10-nm
DMSA-coated magnetic nanoparticles, in both colloidal dispersion and in powder
form. The individual iron oxide cores were composed of > 95% maghemite and
agglomerated to clusters. At room temperature the ensemble behaved as a
superparamagnet according to M\"ossbauer and magnetization measurements,
however, with clear signs of dipolar interactions at low temperatures. Analysis
of temperature-dependent AC susceptibility data in the superparamagnetic regime
indicates a tendency for dipolar coupled anticorrelations of the core moments
within the clusters. To resolve the directional correlations between the
particle moments we performed polarized small-angle neutron scattering and
determined the magnetic spin-flip cross-section of the powder in low magnetic
field at 300 K. We extract the underlying pair distance distribution function
of the magnetization vector field by an indirect Fourier transform of the
cross-section, and which suggests positive as well as negative correlations
between nearest neighbor moments, with anticorrelations clearly dominating for
next-nearest moments. These tendencies are confirmed by Monte Carlo simulations
of such core-clusters.Comment: 11 pages, 6 figure
Tailoring the surface charge of dextran-based polymer coated SPIONs for modulated stem cell uptake and MRI contrast
Tracking stem cells in vivo using non-invasive techniques is critical to evaluate the efficacy and safety of stem cell therapies. Superparamagnetic iron oxide nanoparticles (SPIONs) enable cells to be tracked using magnetic resonance imaging (MRI), but to obtain detectable signal cells need to be labelled with a sufficient amount of iron oxide. For the majority of SPIONs, this can only be obtained with the use of transfection agents, which can adversely affect cell health. Here, we have synthesised a library of dextran-based polymer coated SPIONs with varying surface charge from −1.5 mV to +18.2 mV via a co-precipitation approach and investigated their ability to be directly internalised by stem cells without the need for transfection agents. The SPIONs were colloidally stable in physiological solutions. The crystalline phase of the particles was confirmed with powder X-ray diffraction and their magnetic properties were characterised using SQUID magnetometry and magnetic resonance. Increased surface charge led to six-fold increase in uptake of particles into stem cells and higher MRI contrast, with negligible change in cell viability. Cell tracking velocimetry was shown to be a more accurate method for predicting MRI contrast of stem cells compared to measuring iron oxide uptake through conventional bulk iron quantification
Nanoparticles for imaging, sensing, and therapeutic intervention
Nanoparticles have the potential to contribute to new modalities in molecular imaging and sensing as well as in therapeutic interventions. In this Nano Focus article, we identify some of the current challenges and knowledge gaps that need to be confronted to accelerate the developments of various applications. Using specific examples, we journey from the characterization of these complex hybrid nanomaterials; continue with surface design and (bio)physicochemical properties, their fate in biological media and cells, and their potential for cancer treatment; and finally reflect on the role of animal models to predict their behavior in humans
Exploring precision polymers to fine-tune magnetic resonance imaging properties of iron oxide nanoparticles
The use of bio-polymers as stabilising agents for iron oxide-based negative magnetic resonance imaging (MRI) contrast agents has become popular in recent years, however the wide polydispersity of biologically-derived and commercially available polymers limits the ability to produce truly tuneable and reproducible behaviour, a major challenge in this area. In this work, stable colloids of iron oxide nanoparticles were prepared utilising precision-engineered bio-polymer mimics, poly(2-acrylamido-2-methylpropane sodium sulfonate) (P(AMPS)) polymers, with controlled narrow polydispersity molecular weights, as templating stabilisers. In addition to producing magnetic colloids with excellent MRI contrast capabilities (r values reaching 434.2 mM s at 25 °C and 23 MHz, several times higher than similar commercial analogues), variable field relaxometry provided unexpected important insights into the dynamic environment of the hydrated materials, and hence their exceptional MRI behaviour. Thanks to the polymer's templating backbone and flexible conformation in aqueous suspension, nanocomposites appear to behave as "multi-core" clustered species, enhancing interparticle interactions whilst retaining water diffusion, boosting relaxation properties at low frequency. This clustering behaviour, evidenced by small-angle X-ray scattering, and strong relaxometric response, was fine-tuned using the well-defined molecular weight polymer species with precise iron to polymer ratios. By also showing negligible haemolytic activity, these nanocomposites exhibit considerable potential for MRI diagnostics. [Abstract copyright: Crown Copyright © 2020. Published by Elsevier Inc. All rights reserved.
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Prenormative verification and validation of a protocol for measuring magnetite–maghemite ratios in magnetic nanoparticles
An important step in establishing any new metrological method is a prenormative interlaboratory study, designed to verify and validate the method against its stated aims. Here, the 57Fe Mössbauer spectrometric ‘centre of gravity’ (COG) method was tested as a means of quantifying the magnetite/maghemite (Fe3O4/γ-Fe2O3) composition ratio in biphasic magnetic nanoparticles. The study involved seven laboratories across Europe and North and South America, and six samples—a verification set of three microcrystalline mixtures of known composition, and a validation set of three nanoparticle samples of unknown composition. The spectra were analysed by each participant using in-house fitting packages, and ex post facto by a single operator using an independent package. Repeatability analysis was performed using Mandel’s h statistic and modified Youden plots. It is shown that almost all (83/84) of the Mandel h statistic values fall within the 0.5% significance level, with the one exception being borderline. Youden-based pairwise analysis indicates the dominance of random uncertainties; and in almost all cases the data analysis phase is only a minor contributor to the overall measurement uncertainty. It is concluded that the COG method is a robust and promising candidate for its intended purpose
Colloidal Flower-Shaped Iron Oxide Nanoparticles: Synthesis Strategies and Coatings
The assembly of magnetic cores into regular structures may notably influence the properties displayed by a magnetic colloid. Here, key synthesis parameters driving the self-assembly process capable of organizing colloidal magnetic cores into highly regular and reproducible multi-core nanoparticles are determined. In addition, a self-consistent picture that explains the collective magnetic properties exhibited by these complex assemblies is achieved through structural, colloidal, and magnetic means. For this purpose, different strategies to obtain flower-shaped iron oxide assemblies in the size range 25-100 nm are examined. The routes are based on the partial oxidation of Fe(OH)(2), polyol-mediated synthesis or the reduction of iron acetylacetonate. The nanoparticles are functionalized either with dextran, citric acid, or alternatively embedded in polystyrene and their long-term stability is assessed. The core size is measured, calculated, and modeled using both structural and magnetic means, while the Debye model and multi-core extended model are used to study interparticle interactions. This is the first step toward standardized protocols of synthesis and characterization of flower-shaped nanoparticles
Standardisation of magnetic nanoparticles in liquid suspension
Suspensions of magnetic nanoparticles offer diverse opportunities for technology innovation, spanning a large number of industry sectors from imaging and actuation based applications in biomedicine and biotechnology, through large-scale environmental remediation uses such as water purification, to engineering-based applications such as position-controlled lubricants and soaps. Continuous advances in their manufacture have produced an ever-growing range of products, each with their own unique properties. At the same time, the characterisation of magnetic nanoparticles is often complex, and expert knowledge is needed to correctly interpret the measurement data. In many cases, the stringent requirements of the end-user technologies dictate that magnetic nanoparticle products should be clearly defined, well characterised, consistent and safe; or to put it another way—standardised. The aims of this document are to outline the concepts and terminology necessary for discussion of magnetic nanoparticles, to examine the current state-of-the-art in characterisation methods necessary for the most prominent applications of magnetic nanoparticle suspensions, to suggest a possible structure for the future development of standardisation within the field, and to identify areas and topics which deserve to be the focus of future work items. We discuss potential roadmaps for the future standardisation of this developing industry, and the likely challenges to be encountered along the way
The spotted gar genome illuminates vertebrate evolution and facilitates human-teleost comparisons
To connect human biology to fish biomedical models, we sequenced the genome of spotted gar (Lepisosteus oculatus), whose lineage diverged from teleosts before teleost genome duplication (TGD). The slowly evolving gar genome has conserved in content and size many entire chromosomes from bony vertebrate ancestors. Gar bridges teleosts to tetrapods by illuminating the evolution of immunity, mineralization and development (mediated, for example, by Hox, ParaHox and microRNA genes). Numerous conserved noncoding elements (CNEs; often cis regulatory) undetectable in direct human-teleost comparisons become apparent using gar: functional studies uncovered conserved roles for such cryptic CNEs, facilitating annotation of sequences identified in human genome-wide association studies. Transcriptomic analyses showed that the sums of expression domains and expression levels for duplicated teleost genes often approximate the patterns and levels of expression for gar genes, consistent with subfunctionalization. The gar genome provides a resource for understanding evolution after genome duplication, the origin of vertebrate genomes and the function of human regulatory sequences
Nanoparticles for imaging, sensing, and therapeutic intervention
Nanoparticles have the potential to contribute to new modalities in molecular imaging and sensing as well as in therapeutic interventions. In this Nano Focus article, we identify some of the current challenges and knowledge gaps that need to be confronted to accelerate the developments of various applications. Using specific examples, we journey from the characterization of these complex hybrid nanomaterials; continue with surface design and (bio)physicochemical properties, their fate in biological media and cells, and their potential for cancer treatment; and finally reflect on the role of animal models to predict their behavior in humans.L.B. and R.L. thank EPSRC (EP/H046143/1) for funding. G.P. thanks the European Union (ERDF European Regional Development Fund) via the INTERREG Upper Rhine program (Nanomatrix). C.M. acknowledges the National Science Foundation (CHE-1240151: Centre for Sustainable Nanotechnology). T.P. acknowledges the financial support of the European project Magnifyco (Contract NMP4-SL-2009-228622). D.P. acknowledges support from INNI, FTA: Nanomedicine for Personalized Theranostics, and from The Leona M. and Harry B. Helmsley Nanotechnology Research Fund.Peer Reviewe