Impact of precursors and bioaccessibility on childhood PFAS exposure from house dust.

This study investigated the impact of precursors and bioaccessibility on childhood per- and polyfluoroalkyl substances (PFAS) exposure in house dust (n = 28) from Adelaide, Australia. Sum PFAS concentration (∑38) ranged from 3.0 to 2640 µg kg-1 with PFOS (1.5-675 µg kg-1), PFHxS (1.0-405 µg kg-1) and PFOA (1.0-155 µg kg-1) constituting the major perfluoroalkyl sulfonic (PFSA) and carboxylic acids (PFCA). The total oxidizable precursor (TOP) assay was applied to estimate concentrations of unmeasurable precursors that may undergo oxidation to measurable PFAS. Sum PFAS concentration post-TOP assay changed 3.8-112-fold (91.5-62,300 µg kg-1) with median post-TOP assay PFCA (C4-C8) concentrations (92.3-170 µg kg-1) increasing significantly (13.7-48.5-fold). As incidental dust ingestion is a significant exposure pathway for young children, PFAS bioaccessibility was determined using an in vitro assay. Sum PFAS bioaccessibility ranged from 4.6 to 49.3 % with significantly (p < 0.05) higher PFCA (10.3-83.4 %) bioaccessibility compared to PFSA (3.5-51.5 %). When in vitro extracts were assessed post-TOP assay, PFAS bioaccessibility changed (7-1060 versus 137-3900 µg kg-1) although percentage bioaccessibility decreased (2.3-14.5 %) due to the disproportionately higher post-TOP assay PFAS concentration. PFAS estimated daily intake (EDI) was calculated for a 'stay-at-home' 2-3-year-old child. Inclusion of dust specific bioaccessibility values resulted in a 1.7-20.5-fold decrease in ∑PFOA, PFOA and PFHxS EDI (0.02-1.23 ng kg bw-1 day-1) compared to default absorption assumptions (0.23-5.4 ng kg bw-1 day-1). However, when 'worst-case scenario' precursor transformation was considered, EDI calculations were 4.1-187-fold higher that the EFSA tolerable weekly intake value (equivalent to 0.63 ng kg bw-1 day-1), although this was moderated when exposure parameters were refined through PFAS bioaccessibility incorporation (0.35-17.0-fold higher than the TDI). Irrespective of exposure scenario, EDI calculations were below the FSANZ tolerable daily intake values for PFOS (20 ng kg bw-1 day-1) and PFOA (160 ng kg bw-1 day-1) for all dust samples analysed.

Mass Spectrometry Imaging Can Distinguish on a Proteomic Level Between Proliferative Nodules Within a Benign Congenital Nevus and Malignant Melanoma.

Histopathological interpretation of proliferative nodules occurring in association with congenital melanocytic nevi can be very challenging due to their similarities with congenital malignant melanoma and malignant melanoma arising in association with congenital nevi. We hereby report a diagnostically challenging case of congenital melanocytic nevus with proliferative nodules and ulcerations, which was originally misdiagnosed as congenital malignant melanoma. Subsequent histopathological examination in consultation by one of the authors (R.L.) and mass spectrometry imaging analysis rendered a diagnosis of congenital melanocytic nevus with proliferative nodules. In this case, mass spectrometry imaging, a novel method capable of distinguishing benign from malignant melanocytic lesions on a proteomic level, was instrumental in making the diagnosis of a benign nevus. We emphasize the importance of this method as an ancillary tool in the diagnosis of difficult melanocytic lesions.

Spectroscopy and thermometry of drumhead modes in a mesoscopic trapped-ion crystal using entanglement.

We demonstrate spectroscopy and thermometry of individual motional modes in a mesoscopic 2D ion array using entanglement-induced decoherence as a method of transduction. Our system is a ~400 µm-diameter planar crystal of several hundred 9Be(+) ions exhibiting complex drumhead modes in the confining potential of a Penning trap. Exploiting precise control over the 9Be(+) valence electron spins, we apply a homogeneous spin-dependent optical dipole force to excite arbitrary transverse modes with an effective wavelength approaching the interparticle spacing (~20 µm). Center-of-mass displacements below 1 nm are detected via the entanglement of spin and motional degrees of freedom.

Effect of milling on particle shape and surface energy heterogeneity of needle-shaped crystals.

PURPOSE: Milling and micronization of particles are routinely employed in the pharmaceutical industry to obtain small particles with desired particle size characteristics. The aim of this study is to demonstrate that particle shape is an important factor affecting the fracture mechanism in milling. METHODS: Needle-shaped crystals of the ß polymorph of D-mannitol were prepared from recrystallization in water. A portion of the recrystallized materials was ball-milled. Unmilled and milled sieved fractions of recrystallized D-mannitol were analyzed by dynamic image analysis (DIA) and inverse gas chromatography (IGC) at finite concentration to explain the breakage/fracture behavior. RESULTS: In the process of ball-milling, D-mannitol preferentially fractured along their shortest axis, exposing (011) plane with increased hydrophilicity and increased bounding rectangular aspect ratio. This is in contrary to attachment energy modeling which predicts a fracture mechanism across the (010) plane with increased hydrophobicity, and small change in particle shape. CONCLUSIONS: Crystal size, and more importantly, crystal shape and facet-specific mechanical properties, can dictate the fracture/cleavage behavior of organic crystalline materials. Thorough understanding of the crystal slip systems, combining attachment energy prediction with particle shape and surface characterization using DIA and IGC, are important in understanding fracture behavior of organic crystalline solids in milling and micronization.

Engineered two-dimensional Ising interactions in a trapped-ion quantum simulator with hundreds of spins.

The presence of long-range quantum spin correlations underlies a variety of physical phenomena in condensed-matter systems, potentially including high-temperature superconductivity. However, many properties of exotic, strongly correlated spin systems, such as spin liquids, have proved difficult to study, in part because calculations involving N-body entanglement become intractable for as few as N ≈ 30 particles. Feynman predicted that a quantum simulator--a special-purpose 'analogue' processor built using quantum bits (qubits)--would be inherently suited to solving such problems. In the context of quantum magnetism, a number of experiments have demonstrated the feasibility of this approach, but simulations allowing controlled, tunable interactions between spins localized on two- or three-dimensional lattices of more than a few tens of qubits have yet to be demonstrated, in part because of the technical challenge of realizing large-scale qubit arrays. Here we demonstrate a variable-range Ising-type spin-spin interaction, J(i,j), on a naturally occurring, two-dimensional triangular crystal lattice of hundreds of spin-half particles (beryllium ions stored in a Penning trap). This is a computationally relevant scale more than an order of magnitude larger than previous experiments. We show that a spin-dependent optical dipole force can produce an antiferromagnetic interaction J(i,j) proportional variant d(-a)(i,j), where 0 ≤ a ≤ 3 and d(i,j) is the distance between spin pairs. These power laws correspond physically to infinite-range (a = 0), Coulomb-like (a = 1), monopole-dipole (a = 2) and dipole-dipole (a = 3) couplings. Experimentally, we demonstrate excellent agreement with a theory for 0.05 ≲ a ≲ 1.4. This demonstration, coupled with the high spin count, excellent quantum control and low technical complexity of the Penning trap, brings within reach the simulation of otherwise computationally intractable problems in quantum magnetism.

Pyrrole syntheses based on titanium-catalyzed hydroamination of diynes.

Titanium-catalyzed hydroamination of 1,4- and 1,5-diynes by primary amines leads to imino-alkynes that undergo in situ 5-endo dig and 5-exo dig cyclization reactions, respectively. The products are 1,2,5-trisubsituted pyrroles accessed directly from readily available diyne starting materials.