Mechanisms of inclusion of thallium-201 into Prussian blue nanoparticles for nuclear medicine applications.

Prussian blue is known for its high affinity for thallium and other univalent metal cations and has been used as a treatment for radiocaesium and thallium/radiothallium poisoning. While Prussian blue nanoparticles (PBNPs) show potential for binding radioactive thallium for further use in nuclear medicine applications, the inclusion mechanism remains elusive. Understanding the interaction between PBNPs and 201Tl is essential for identifying the physicochemical and radiochemical properties required for optimal in vivo performance. In this work, we evaluated the binding mechanism between Tl and PBNPs with different coatings and core shapes. Combining PBNPs with [201Tl] thallium(I) chloride provided high radiolabelling yields and radiochemical stabilities under physiological conditions. Comprehensive characterisation by different X-ray techniques confirmed that Tl ions are located in the interstitial sites within the crystal structure, maintaining the integrity of the iron (Fe) 4p electronic distribution and inducing local modifications in the nearby C-N ligands. Additionally, this inclusion does not impact the core or the shell of the nanoparticles but does alter their ionic composition. The PB ionic network undergoes significant changes, with a substantial drop in K+ content, confirming that Tl+ ions replace K+ and occupy additional spaces within the crystal structure. These results open new opportunities in nuclear medicine applications with 201Tl-PBNPs where the size, shape and composition of the particles can be specifically tuned depending on the desired biological properties without affecting the radiochemical performance as a vehicle for 201Tl.

Nanoporous YVO4 as a luminescent host for probing molecular encapsulation.

Control of phase separation of VO43- and rare earth precursors in reverse microemulsions afforded ∼35 nm YVO4 nanoparticles with functionalisable ∼7 ± 3 nm nanopores. Doping by Eu3+ allowed luminescent probing of interfacial crystallisation while xylenol orange absorption showed molecular encapsulation in particle cavities. This provides potential multifunctional systems combining UV-Vis-NIR luminescence and (photo)active molecules for optical sensing.

Highly Air Stable Tin Halide Perovskite Photovoltaics using a Bismuth Capped Copper Top Electrode.

An effective approach is reported to enhance the stability of inverted organo-tin halide perovskite photovoltaics based on capping the cathode with a thin layer of bismuth. Using this simple approach, unencapsulated devices retain up to 70% of their peak power conversion efficiency after up to 100 h testing under continuous one sun solar illumination in ambient air and under electrical load, which is exceptional stability for an unencapsulated organo-tin halide perovskite photovoltaic device tested in ambient air. The bismuth capping layer is shown to have two functions: First, it blocks corrosion of the metal cathode by iodine gas formed when those parts of the perovskite layer not protected by the cathode degrade. Second, it sequesters iodine gas by seeding its deposition on top of the bismuth capping layer, thereby keeping it away from the electro-active parts of the device. The high affinity of iodine for bismuth is shown to correlate with the high polarizability of bismuth and the prevalence of the (012) crystal face at its surface. Bismuth is ideal for this purpose, because it is environmentally benign, non-toxic, stable, cheap, and can be deposited by simple thermal evaporation at low temperature immediately after deposition of the cathode.

Sample Preparation of Atherosclerotic Plaque for SAXS/WAXS Experimentation.

Atherosclerosis is often described as a single disease entity; however, the morphology of each plaque is unique to the individual. The field currently lacks a technique that can discriminate stable from unstable plaques, to identify those at risk of a thromboembolic event. Small- and wide-angle X-ray scattering (SAXS/WAXS) holds the potential to be able to identify key materials present in a plaque, such as cholesterol species, collagen, low-density lipoproteins (LDLs), and hydroxyapatite. Protocols have been established for the preparation of excised human atherosclerotic tissue that are investigated herein. This includes the fixing, sectioning, and substrate selection of the sample. Through several sample preparation methods, vast improvements have been made to sample-to-noise ratio and background subtraction.

Exploring the Nanostructures Accessible to an Organic Surfactant Atmospheric Aerosol Proxy.

The composition of atmospheric aerosols varies with time, season, location, and environment. This affects key aerosol properties such as hygroscopicity and reactivity, influencing the aerosol's impact on the climate and air quality. The organic fraction of atmospheric aerosol emissions often contains surfactant material, such as fatty acids. These molecules are known to form three-dimensional nanostructures in contact with water. Different nanostructures have marked differences in viscosity and diffusivity that are properties whose understanding is essential when considering an aerosol's atmospheric impact. We have explored a range of nanostructures accessible to the organic surfactant oleic acid (commonly found in cooking emissions), simulating variation that is likely to happen in the atmosphere. This was achieved by changing the amount of water, aqueous phase salinity and by addition of other commonly coemitted compounds: sugars and stearic acid (the saturated analogue of oleic acid). The nanostructure was observed by both synchrotron and laboratory small/wide angle X-ray scattering (SAXS/WAXS) and found to be sensitive to the proxy composition. Additionally, the spacing between repeat units in these nanostructures was water content dependent (i.e., an increase from 41 to 54 Šin inverse hexagonal phase d-spacing when increasing the water content from 30 to 50 wt %), suggesting incorporation of water within the nanostructure. A significant decrease in mixture viscosity was also observed with increasing water content from ∼104 to ∼102 Pa s when increasing the water content from 30 to 60 wt %. Time-resolved SAXS experiments on levitated droplets of this proxy confirm the phase changes observed in bulk phase mixtures and demonstrate that coexistent nanostructures can form in droplets. Aerosol compositional and subsequent nanostructural changes could affect aerosol processes, leading to an impact on the climate and urban air pollution.

Polymerisation-Induced Self-Assembly of Graft Copolymers.

We report the polymerisation-induced self-assembly of poly(lauryl methacrylate)-graft-poly(benzyl methacrylate) copolymers during reversible addition-fragmentation chain transfer (RAFT) grafting from polymerisation in a backbone-selective solvent. Electron microscopy images suggest the phase separation of grafts to result in a network of spherical particles, due to the ability of the branched architecture to freeze chain entanglements and to bridge core domains. Small-angle X-ray scattering data suggest the architecture promotes the formation of multicore micelles, the core morphology of which transitions from spheres to worms, vesicles, and inverted micelles with increasing volume fraction of the grafts. A time-resolved SAXS study is presented to illustrate the formation of the inverted phase during a polymerisation. The grafted architecture gives access to unusual morphologies and provides exciting new handles for controlling the polymer structure and material properties.

Controlled Synthesis of Well-Defined Polyaminoboranes on Scale Using a Robust and Efficient Catalyst.

The air tolerant precatalyst, [Rh(L)(NBD)]Cl ([1]Cl) [L = κ3-(iPr2PCH2CH2)2NH, NBD = norbornadiene], mediates the selective synthesis of N-methylpolyaminoborane, (H2BNMeH)n, by dehydropolymerization of H3B·NMeH2. Kinetic, speciation, and DFT studies show an induction period in which the active catalyst, Rh(L)H3 (3), forms, which sits as an outer-sphere adduct 3·H3BNMeH2 as the resting state. At the end of catalysis, dormant Rh(L)H2Cl (2) is formed. Reaction of 2 with H3B·NMeH2 returns 3, alongside the proposed formation of boronium [H2B(NMeH2)2]Cl. Aided by isotopic labeling, Eyring analysis, and DFT calculations, a mechanism is proposed in which the cooperative "PNHP" ligand templates dehydrogenation, releasing H2B═NMeH (ΔG‡calc = 19.6 kcal mol-1). H2B═NMeH is proposed to undergo rapid, low barrier, head-to-tail chain propagation for which 3 is the catalyst/initiator. A high molecular weight polymer is formed that is relatively insensitive to catalyst loading (Mn ∼71 000 g mol-1; D, of ∼ 1.6). The molecular weight can be controlled using [H2B(NMe2H)2]Cl as a chain transfer agent, Mn = 37 900-78 100 g mol-1. This polymerization is suggested to arise from an ensemble of processes (catalyst speciation, dehydrogenation, propagation, chain transfer) that are geared around the concentration of H3B·NMeH2. TGA and DSC thermal analysis of polymer produced on scale (10 g, 0.01 mol % [1]Cl) show a processing window that allows for melt extrusion of polyaminoborane strands, as well as hot pressing, drop casting, and electrospray deposition. By variation of conditions in the latter, smooth or porous microstructured films or spherical polyaminoboranes beads (∼100 nm) result.

Tuning morphology, surface, and nanocrystallinity of rare earth vanadates by one-pot colloidal conversion of hydroxycarbonates.

We show that particle size, morphology, nanocrystallinity, surface area, and defect density of (Y,Eu)VO4 structures can be tuned by one-pot colloidal conversion of rare earth hydroxycarbonates in water/ethylene glycol (EG) suspensions. Using small angle X-ray scattering, transmission electron microscopy and dynamic light scattering, we show how volume fractions of EG direct the amorphous to crystalline conversion at 1 atm/95 °C by controlling size and aggregation of hydroxycarbonate precursors. A template effect due to a Kirkendall-type conversion occurs for low EG contents, yielding solids with high densities of oxygen defects, as demonstrated by O2 uptakes in thermogravimetry and X-ray photoelectron spectroscopy profiles. Starting from small and aggregated hydroxycarbonates high-porosity (Y,Eu)VO4 nanoparticles were produced with expanded unit cells and short-range (<100 Å) crystalline ordering. We explored the effects of synthesis on the textural, microstructure, and defects of (Y,Eu)VO4 solids, which were further correlated to the spectroscopic profiles of Eu3+-activated samples. We show that the ratios between Eu3+ 5D0 internal quantum yields and particle diameters can be directly correlated to the particle surface areas, opening new perspectives for theoretical detailing of f-f luminescence in YVO4 solids, and enabling accurate tuning of structure and applicability of colloidal vanadate nanoparticles for sensing and catalysis applications.

MAS NMR Investigation of Molecular Order in an Ionic Liquid Crystal.

The structure and molecular order in the thermotropic ionic liquid crystal (ILC), [choline][geranate(H)octanoate], an analogue of Choline And GEranate (CAGE), which has potential for use as a broad-spectrum antimicrobial and transdermal and oral delivery agent, were investigated by magic-angle spinning (MAS) nuclear magnetic resonance (NMR), polarizing optical microscopy, small-angle X-ray scattering (SAXS), and mass spectrometry. Mass spectrometry and the 1H NMR chemical shift reveal that CAGE-oct is a dynamic system, with metathesis (the exchange of interacting ions) and hydrogen exchange occurring between hydrogen-bonded/ionic complexes such as [(choline)(geranate)(H)(octanoate)], [(choline)(octanoate)2(H)], and [(choline)(geranate)2(H)]. These clusters, which are shown by mass spectrometry to be significantly more stable than expected for typical electrostatic ion clusters, involve hydrogen bonding between the carboxylic acid, carboxylate, and hydroxyl groups, with rapid hydrogen bond breaking and re-formation observed to average the 1H chemical shifts. The formation of a partial bilayer liquid crystal (LC) phase was identified by SAXS and polarizing optical microscopy at temperatures below ∼293 K. The occurrence of this transition close to room temperature could be utilized as a potential temperature-induced "switch" of the anisotropic properties for particular applications. The presence of an isotropic component of approximately 23% was observed to coexist with the LC phase, as detected by polarizing optical microscopy and quantified by both 1H-13C dipolar-chemical shift correlation (DIPSHIFT) and 1H double-quantum (DQ) MAS NMR experiments. At temperatures above the LC-to-isotropic transition, intermediate-range order (clustering of polar and nonpolar domains), a feature of many ILs, persists. Site-specific order parameters for the LC phase of CAGE-oct were obtained from the MAS NMR measurement of the partially averaged 13C-1H dipolar couplings (DCH) by cross-polarization (CP) build-up curves and DIPSHIFT experiments, and 1H-1H dipolar couplings (DHH) by double-quantum (DQ) build-up curves. The corresponding order parameters, SCH and SHH, are in the range 0-0.2 and are lower compared to those for smectic (i.e., layered) phases of conventional nonionic liquid crystals, resembling those of lamellar phases formed by lyotropic surfactant-solvent systems.

X-ray diffraction to probe the kinetics of ice recrystallization inhibition.

Understanding the nucleation and growth of ice is crucial in fields ranging from infrastructure maintenance, to the environment, and to preserving biologics in the cold chain. Ice binding and antifreeze proteins are potent ice recrystallization inhibitors (IRI), and synthetic materials that mimic this function have emerged, which may find use in biotechnology. To evaluate IRI activity, optical microscopy tools are typically used to monitor ice grain size either by end-point measurements or as a function of time. However, these methods provide 2-dimensional information and image analysis is required to extract the data. Here we explore using wide angle X-ray scattering (WAXS/X-ray powder diffraction (XRD)) to interrogate 100's of ice crystals in 3-dimensions as a function of time. Due to the random organization of the ice crystals in the frozen sample, the number of orientations measured by XRD is proportional to the number of ice crystals, which can be measured as a function of time. This method was used to evaluate the activity for a panel of known IRI active compounds, and shows strong agreement with results obtained from cryo-microscopy, as well as being advantageous in that time-dependent ice growth is easily extracted. Diffraction analysis also confirmed, by comparing the obtained diffraction patterns of both ice binding and non-binding additives, that the observed hexagonal ice diffraction patterns obtained cannot be used to determine which crystal faces are being bound. This method may help in the discovery of new IRI active materials as well as enabling kinetic analysis of ice growth.

Metallic iron in cornflakes.

Iron is an essential element, and cornflake-style cereals are typically fortified with iron to a level up to 14 mg iron per 100 g. Even single cornflakes exhibit magnetic behaviour. We extracted iron microparticles from samples of two own-brand supermarket cornflakes using a strong permanent magnet. Synchrotron iron K-edge X-ray absorption near-edge spectroscopic data were consistent with identification as metallic iron, and X-ray diffraction studies provided unequivocal identification of the extracted iron as body-centred cubic (BCC) α-iron. Magnetometry measurements were also consistent with ca. 14 mg per 100 g BCC iron. These findings emphasise that attention must be paid to the speciation of trace elements, in relation to their bioavailability. To mimic conditions in the stomach, we suspended the iron extract in dilute HCl (pH 1.0-2.0) at 310 K (body temperature) and found by ICP-MS that over a period of 5 hours, up to 13% of the iron dissolved. This implies that despite its metallic form in the cornflakes, the iron is potentially bioavailable for oxidation and absorption into the body.

Unprecedented phase transition sequence in the perovskite Li0.2Na0.8NbO3.

The perovskite Li0.2Na0.8NbO3 is shown, by powder neutron diffraction, to display a unique sequence of phase transitions at elevated temperature. The ambient temperature polar phase (rhombohedral, space group R3c) transforms via a first-order transition to a polar tetragonal phase (space group P42mc) in the region 150-300°C; these two phases correspond to Glazer tilt systems a-a-a- and a+a+c-, respectively. At 500°C a ferroelectric-paraelectric transition takes place from P42mc to P42/nmc, retaining the a+a+c- tilt. Transformation to a single-tilt system, a0a0c+ (space group P4/mbm), occurs at 750°C, with the final transition to the aristotype cubic phase at 850°C. The P42mc and P42/nmc phases have each been seen only once and twice each, respectively, in perovskite crystallography, in each case in compositions prepared at high pressure.

Growth of crystalline garnet mixed films, superlattices and multilayers for optical applications via shuttered combinatorial pulsed laser deposition.

A range of crystalline garnet multilayer structures have been fabricated via multi-beam, multi-target PLD in conjunction with a system of mechanical shutters. Structures grown consisted of alternating Gd3Ga5O12 (GGG) and Gd3Sc2Ga3O12 (GSGG) layers on Y3Al5O12 (YAG) substrates, with both simple and chirped designs. Distinct layers are observed where layer thickness is around 2 nm or greater, although some layering may also be present at a sub-unit cell level. These structures demonstrate the viability of the shutter technique as a quick, simple fabrication method for a variety of optical multilayer structures.