High molecular weight SOA formation during limonene ozonolysis: insights from ultrahigh-resolution FT-ICR mass spectrometry characterization

The detailed molecular composition of laboratory generated limonene ozonolysis secondary organic aerosol (SOA) was studied using ultrahigh-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Approximately 1200 molecular formulas were identified in the SOA over the mass range of 140 to 850 Da. Four characteristic groups of high relative abundance species were observed; they indicate an array of accretion products that retain a large fraction of the limonene skeleton. The identified molecular formulas of each of the groups are related to one another by CH2, O and CH2O homologous series. The CH2 and O homologous series of the low molecular weight (MW) SOA (m/z \u3c 300) are explained with a combination of functionalization and fragmentation of radical intermediates and reactive uptake of gas-phase carbonyls. They include isomerization and elimination reactions of Criegee radicals, reactions between alkyl peroxy radicals, and scission of alkoxy radicals resulting from the Criegee radicals. The presence of compounds with 10–15 carbon atoms in the first group (e.g. C11H18O6) provides evidence for SOA formation by the reactive uptake of gas-phase carbonyls during limonene ozonolysis. The high MW compounds (m/z \u3e 300) were found to constitute a significant number fraction of the identified SOA components. The formation of high MW compounds was evaluated by molecular formula trends, fragmentation analysis of select high MW compounds and a comprehensive reaction matrix including the identified low MW SOA, hydroperoxides and Criegee radicals as building blocks. Although the formation of high MW SOA may occur via a variety of radical and non-radical reaction channels, the combined approach indicates a greater importance of the non-condensation reactions over aldol and ester condensation reaction channels. Among these hemi-acetal reactions appear to be most dominant followed by hydroperoxide and Criegee reaction channels

Naturally Occurring Stable Calcium Isotope Ratios in Body Compartments Provide a Novel Biomarker of Bone Mineral Balance in Children and Young Adults

Serum calcium (Ca), bone biomarkers, and radiological imaging do not allow accurate evaluation of bone mineral balance (BMB), a key determinant of bone mineral density (BMD) and fracture risk. We studied naturally occurring stable (non‐radioactive) Ca isotopes in different body pools as a potential biomarker of BMB. {42}^Ca and {44}^Ca are absorbed from our diet and sequestered into different body compartments following kinetic principles of isotope fractionation; isotopically light {42}^Ca is preferentially incorporated into bone, whereas heavier {44}^Ca preferentially remains in blood and is excreted in urine and feces. Their ratio (δ^{44/42}Ca) n serum and urine increases during bone formation and decreases with bone resorption. In 117 healthy participants, we measured Ca isotopes, biomarkers, and BMD by dual‐energy X‐ray absorptiometry (DXA) and tibial peripheral quantitative CT (pQCT). {44}^Ca and 42Ca were measured by multi‐collector ionization‐coupled plasma mass‐spectrometry in serum, urine, and feces. The relationship between bone Ca gain and loss was calculated using a compartment model. δ^{44/42}Ca_{serum} and δ^{44/42}Ca_{urine} were higher in children (n = 66, median age 13 years) compared with adults (n = 51, median age 28 years; p < 0.0001 and p = 0.008, respectively). δ^{44/42}Ca_{serum} increased with height in boys (p < 0.001, R^{2} = 0.65) and was greatest at Tanner stage 4. δ^{44/42}Ca_{serum} correlated positively with biomarkers of bone formation (25‐hydroxyvitaminD [p < 0.0001, R^{2} = 0.37] and alkaline phosphatase [p = 0.009, R^{2} = 0.18]) and negatively with bone resorption marker parathyroid hormone (PTH; p = 0.03, R^{2} = 0.13). δ^{44/42}Ca_{serum} strongly positively correlated with tibial cortical BMD Z‐score (n = 62; p < 0.001, R^{2} = 0.39) but not DXA. Independent predictors of tibial cortical BMD Z‐score were δ^{44/42}Ca_{serum} (p = 0.004, β = 0.37), 25‐hydroxyvitaminD (p = 0.04, β = 0.19) and PTH (p = 0.03, β = −0.13), together predicting 76% of variability. In conclusion, naturally occurring Ca isotope ratios in different body compartments may provide a novel, non‐invasive method of assessing bone mineralization. Defining an accurate biomarker of BMB could form the basis of future studies investigating Ca dynamics in disease states and the impact of treatments that affect bone homeostasis

Optical magnetic imaging of living cells

Magnetic imaging is a powerful tool for probing biological and physical systems. However, existing techniques either have poor spatial resolution compared to optical microscopy and are hence not generally applicable to imaging of sub-cellular structure (e.g., magnetic resonance imaging [MRI]1), or entail operating conditions that preclude application to living biological samples while providing sub-micron resolution (e.g., scanning superconducting quantum interference device [SQUID] microscopy2, electron holography3, and magnetic resonance force microscopy [MRFM]4). Here we demonstrate magnetic imaging of living cells (magnetotactic bacteria) under ambient laboratory conditions and with sub-cellular spatial resolution (400 nm), using an optically-detected magnetic field imaging array consisting of a nanoscale layer of nitrogen-vacancy (NV) colour centres implanted at the surface of a diamond chip. With the bacteria placed on the diamond surface, we optically probe the NV quantum spin states and rapidly reconstruct images of the vector components of the magnetic field created by chains of magnetic nanoparticles (magnetosomes) produced in the bacteria, and spatially correlate these magnetic field maps with optical images acquired in the same apparatus. Wide-field sCMOS acquisition allows parallel optical and magnetic imaging of multiple cells in a population with sub-micron resolution and >100 micron field-of-view. Scanning electron microscope (SEM) images of the bacteria confirm that the correlated optical and magnetic images can be used to locate and characterize the magnetosomes in each bacterium. The results provide a new capability for imaging bio-magnetic structures in living cells under ambient conditions with high spatial resolution, and will enable the mapping of a wide range of magnetic signals within cells and cellular networks5, 6

Theorem on the Distribution of Short-Time Particle Displacements with Physical Applications

The distribution of the initial short-time displacements of particles is considered for a class of classical systems under rather general conditions on the dynamics and with Gaussian initial velocity distributions, while the positions could have an arbitrary distribution. This class of systems contains canonical equilibrium of a Hamiltonian system as a special case. We prove that for this class of systems the nth order cumulants of the initial short-time displacements behave as the 2n-th power of time for all n>2, rather than exhibiting an nth power scaling. This has direct applications to the initial short-time behavior of the Van Hove self-correlation function, to its non-equilibrium generalizations the Green's functions for mass transport, and to the non-Gaussian parameters used in supercooled liquids and glasses.Comment: A less ambiguous mathematical notation for cumulants was adopted and several passages were reformulated and clarified. 40 pages, 1 figure. Accepted by J. Stat. Phy

Spectral line shape of resonant four-wave mixing induced by broad-bandwidth lasers

We present a theoretical and experimental study of the line shape of resonant four-wave mixing induced by broad-bandwidth laser radiation that revises the theory of Meacher, Smith, Ewart, and Cooper (MSEC) [Phys. Rev. A 46, 2718 (1992)]. We adopt the same method as MSEC but correct for an invalid integral used to average over the distribution of atomic velocities. The revised theory predicts a Voigt line shape composed of a homogeneous, Lorentzian component, defined by the collisional rate Γ, and an inhomogeneous, Doppler component, which is a squared Gaussian. The width of the inhomogeneous component is reduced by a factor of √2 compared to the simple Doppler width predicted by MSEC. In the limit of dominant Doppler broadening, the width of the homogeneous component is predicted to be 4Γ, whereas in the limit of dominant homogeneous broadening, the predicted width is 2Γ. An experimental measurement is reported of the line shape of the four-wave-mixing signal using a broad-bandwidth, "modeless", laser resonant with the Q1 (6) line of the A2 Σ - X2 Π(0,0) system of the hydroxyl radical. The measured widths of the Voigt components were found to be consistent with the predictions of the revised theory

Fourier Magnetic Imaging with Nanoscale Resolution and Compressed Sensing Speed-up using Electronic Spins in Diamond

Optically-detected magnetic resonance using Nitrogen Vacancy (NV) color centres in diamond is a leading modality for nanoscale magnetic field imaging, as it provides single electron spin sensitivity, three-dimensional resolution better than 1 nm, and applicability to a wide range of physical and biological samples under ambient conditions. To date, however, NV-diamond magnetic imaging has been performed using real space techniques, which are either limited by optical diffraction to 250 nm resolution or require slow, point-by-point scanning for nanoscale resolution, e.g., using an atomic force microscope, magnetic tip, or super-resolution optical imaging. Here we introduce an alternative technique of Fourier magnetic imaging using NV-diamond. In analogy with conventional magnetic resonance imaging (MRI), we employ pulsed magnetic field gradients to phase-encode spatial information on NV electronic spins in wavenumber or k-space followed by a fast Fourier transform to yield real-space images with nanoscale resolution, wide field-of-view (FOV), and compressed sensing speed-up.Comment: 31 pages, 10 figure

Immune phenotypes and checkpoint molecule expression of clonally expanded lymph node-infiltrating T cells in classical Hodgkin lymphoma

Lymph node-infiltrating T cells have been of particular interest in classical Hodgkin lymphoma (cHL). High rates of complete therapeutic responses to antibody-mediated immune checkpoint blockade, even in relapsed/refractory patients, suggest the existence of a T cell-dominated, antigen-experienced, functionally inhibited and lymphoma-directed immune microenvironment. We asked whether clonally expanded T cells (1) were detectable in cHL lymph nodes, (2) showed characteristic immune phenotypes, and (3) were inhibited by immune checkpoint molecule expression. We applied high-dimensional FACS index sorting and single cell T cell receptor αβ sequencing to lymph node-infiltrating T cells from 10 treatment-naïve patients. T cells were predominantly CD4(+) and showed memory differentiation. Expression of classical immune checkpoint molecules (CTLA-4, PD-1, TIM-3) was generally low (< 12.0% of T cells) and not different between CD4(+) and CD8(+) T cells. Degrees of clonal T cell expansion varied between patients (range: 1-18 expanded clones per patient) and was almost exclusively restricted to CD8(+) T cells. Clonally expanded T cells showed non-naïve phenotypes and low checkpoint molecule expression similar to non-expanded T cells. Our data suggest that the therapeutic effects of immune checkpoint blockade require mechanisms in addition to dis-inhibition of pre-existing lymphoma-directed T cell responses. Future studies on immune checkpoint blockade-associated effects will identify molecular T cell targets, address dynamic aspects of cell compositions over time, and extend their focus beyond lymph node-infiltrating T cells

Coupling of magnetic order and charge transport in the candidate Dirac semimetal EuCd2_2As2_2

We use resonant elastic x-ray scattering to determine the evolution of magnetic order in EuCd$_2$As$_2$ below $T_\textrm{N}=9.5$\,K, as a function of temperature and applied magnetic field. We find an A-type antiferromagneticstructure with in-plane magnetic moments, and observe dramatic magnetoresistive effects associated with field-induced changes in the magnetic structure and domain populations. Our \textit{ab initio} electronic structure calculations indicate that the Dirac dispersion found in the nonmagnetic Dirac semimetal Cd$_3$As$_2$ is also present in EuCd$_2$As$_2$, but is gapped for $T < T_\textrm{N}$ due to the breaking of $C_3$ symmetry by the magnetic structure.Comment: Supplemental information attached to preprin