Gas-Phase Oxidation of Atmospherically Relevant Unsaturated Hydrocarbons by Acyl Peroxy Radicals.

This study assesses the atmospheric impact of reactions between unsaturated hydrocarbons such as isoprene and monoterpenes and peroxy radicals containing various functional groups. We find that reactions between alkenes and acyl peroxy radicals have reaction rates high enough to be feasible in the atmosphere and lead to high molar mass accretion products. Moreover, the reaction between unsaturated hydrocarbons and acyl peroxy radicals leads to an alkyl radical, to which molecular oxygen rapidly adds. This finding is confirmed by both theoretical calculations and experiments. The formed perester peroxy radical may either undergo further H-shift reactions or react bimolecularly. The multifunctional oxygenated compounds formed through acyl peroxy radical + alkene reactions are potentially important contributors to particle formation and growth. Thus, acyl peroxy radical-initiated oxidation chemistry may need to be included in atmospheric models.

Direct Measurements of Covalently Bonded Sulfuric Anhydrides from Gas-Phase Reactions of SO3 with Acids under Ambient Conditions.

Sulfur trioxide (SO3) is an important oxide of sulfur and a key intermediate in the formation of sulfuric acid (H2SO4, SA) in the Earth's atmosphere. This conversion to SA occurs rapidly due to the reaction of SO3 with a water dimer. However, gas-phase SO3 has been measured directly at concentrations that are comparable to that of SA under polluted mega-city conditions, indicating gaps in our current understanding of the sources and fates of SO3. Its reaction with atmospheric acids could be one such fate that can have significant implications for atmospheric chemistry. In the present investigation, laboratory experiments were conducted in a flow reactor to generate a range of previously uncharacterized condensable sulfur-containing reaction products by reacting SO3 with a set of atmospherically relevant inorganic and organic acids at room temperature and atmospheric pressure. Specifically, key inorganic acids known to be responsible for most ambient new particle formation events, iodic acid (HIO3, IA) and SA, are observed to react promptly with SO3 to form iodic sulfuric anhydride (IO3SO3H, ISA) and disulfuric acid (H2S2O7, DSA). Carboxylic sulfuric anhydrides (CSAs) were observed to form by the reaction of SO3 with C2 and C3 monocarboxylic (acetic and propanoic acid) and dicarboxylic (oxalic and malonic acid)-carboxylic acids. The formed products were detected by a nitrate-ion-based chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (NO3--CI-APi-TOF; NO3--CIMS). Quantum chemical methods were used to compute the relevant SO3 reaction rate coefficients, probe the reaction mechanisms, and model the ionization chemistry inherent in the detection of the products by NO3--CIMS. Additionally, we use NO3--CIMS ambient data to report that significant concentrations of SO3 and its acid anhydride reaction products are present under polluted, marine and polar, and volcanic plume conditions. Considering that these regions are rich in the acid precursors studied here, the reported reactions need to be accounted for in the modeling of atmospheric new particle formation.

Cost-effective approach for atmospheric accretion reactions: a case of peroxy radical addition to isoprene.

We present an accurate and cost-effective method for investigating the accretion reactions between unsaturated hydrocarbons and oxidized organic radicals. We use accretion between isoprene and primary, secondary and tertiary alkyl peroxy radicals as model reactions. We show that a systematic semiempirical transition state search can lead to better transition state structures than relaxed scanning with density functional theory with a significant gain in computational efficiency. Additionally, we suggest accurate and effective quantum chemical methods to study accretion reactions between large unsaturated hydrocarbons and oxidized organic radicals. Furthermore, we examine the atmospheric relevance of these types of reactions by calculating the bimolecular reaction rate coefficients and formation rates under atmospheric conditions from the quantum chemical reaction energy barriers.

DTI-MR fingerprinting for rapid high-resolution whole-brain T1 , T2 , proton density, ADC, and fractional anisotropy mapping.

PURPOSE: This study aims to develop a high-efficiency and high-resolution 3D imaging approach for simultaneous mapping of multiple key tissue parameters for routine brain imaging, including T1 , T2 , proton density (PD), ADC, and fractional anisotropy (FA). The proposed method is intended for pushing routine clinical brain imaging from weighted imaging to quantitative imaging and can also be particularly useful for diffusion-relaxometry studies, which typically suffer from lengthy acquisition time. METHODS: To address challenges associated with diffusion weighting, such as shot-to-shot phase variation and low SNR, we integrated several innovative data acquisition and reconstruction techniques. Specifically, we used M1-compensated diffusion gradients, cardiac gating, and navigators to mitigate phase variations caused by cardiac motion. We also introduced a data-driven pre-pulse gradient to cancel out eddy currents induced by diffusion gradients. Additionally, to enhance image quality within a limited acquisition time, we proposed a data-sharing joint reconstruction approach coupled with a corresponding sequence design. RESULTS: The phantom and in vivo studies indicated that the T1 and T2 values measured by the proposed method are consistent with a conventional MR fingerprinting sequence and the diffusion results (including diffusivity, ADC, and FA) are consistent with the spin-echo EPI DWI sequence. CONCLUSION: The proposed method can achieve whole-brain T1 , T2 , diffusivity, ADC, and FA maps at 1-mm isotropic resolution within 10 min, providing a powerful tool for investigating the microstructural properties of brain tissue, with potential applications in clinical and research settings.

High-resolution myelin-water fraction and quantitative relaxation mapping using 3D ViSTa-MR fingerprinting.

PURPOSE: This study aims to develop a high-resolution whole-brain multi-parametric quantitative MRI approach for simultaneous mapping of myelin-water fraction (MWF), T1, T2, and proton-density (PD), all within a clinically feasible scan time. METHODS: We developed 3D visualization of short transverse relaxation time component (ViSTa)-MRF, which combined ViSTa technique with MR fingerprinting (MRF), to achieve high-fidelity whole-brain MWF and T1/T2/PD mapping on a clinical 3T scanner. To achieve fast acquisition and memory-efficient reconstruction, the ViSTa-MRF sequence leverages an optimized 3D tiny-golden-angle-shuffling spiral-projection acquisition and joint spatial-temporal subspace reconstruction with optimized preconditioning algorithm. With the proposed ViSTa-MRF approach, high-fidelity direct MWF mapping was achieved without a need for multicompartment fitting that could introduce bias and/or noise from additional assumptions or priors. RESULTS: The in vivo results demonstrate the effectiveness of the proposed acquisition and reconstruction framework to provide fast multi-parametric mapping with high SNR and good quality. The in vivo results of 1 mm- and 0.66 mm-isotropic resolution datasets indicate that the MWF values measured by the proposed method are consistent with standard ViSTa results that are 30× slower with lower SNR. Furthermore, we applied the proposed method to enable 5-min whole-brain 1 mm-iso assessment of MWF and T1/T2/PD mappings for infant brain development and for post-mortem brain samples. CONCLUSIONS: In this work, we have developed a 3D ViSTa-MRF technique that enables the acquisition of whole-brain MWF, quantitative T1, T2, and PD maps at 1 and 0.66 mm isotropic resolution in 5 and 15 min, respectively. This advancement allows for quantitative investigations of myelination changes in the brain.

Iodine oxoacids enhance nucleation of sulfuric acid particles in the atmosphere.

The main nucleating vapor in the atmosphere is thought to be sulfuric acid (H2SO4), stabilized by ammonia (NH3). However, in marine and polar regions, NH3 is generally low, and H2SO4 is frequently found together with iodine oxoacids [HIOx, i.e., iodic acid (HIO3) and iodous acid (HIO2)]. In experiments performed with the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we investigated the interplay of H2SO4 and HIOx during atmospheric particle nucleation. We found that HIOx greatly enhances H2SO4(-NH3) nucleation through two different interactions. First, HIO3 strongly binds with H2SO4 in charged clusters so they drive particle nucleation synergistically. Second, HIO2 substitutes for NH3, forming strongly bound H2SO4-HIO2 acid-base pairs in molecular clusters. Global observations imply that HIOx is enhancing H2SO4(-NH3) nucleation rates 10- to 10,000-fold in marine and polar regions.

Correction: Ring-opening yields and auto-oxidation rates of the resulting peroxy radicals from OH-oxidation of α-pinene and ß-pinene.

[This corrects the article DOI: 10.1039/D2EA00133K.].

Evidence of nitrate-based nighttime atmospheric nucleation driven by marine microorganisms in the South Pacific.

Our understanding of ocean-cloud interactions and their effect on climate lacks insight into a key pathway: do biogenic marine emissions form new particles in the open ocean atmosphere? Using measurements collected in ship-borne air-sea interface tanks deployed in the Southwestern Pacific Ocean, we identified new particle formation (NPF) during nighttime that was related to plankton community composition. We show that nitrate ions are the only species for which abundance could support NPF rates in our semicontrolled experiments. Nitrate ions also prevailed in the natural pristine marine atmosphere and were elevated under higher sub-10 nm particle concentrations. We hypothesize that these nucleation events were fueled by complex, short-term biogeochemical cycling involving the microbial loop. These findings suggest a new perspective with a previously unidentified role of nitrate of marine biogeochemical origin in aerosol nucleation.

Calcium Sulfate Microparticle Size Modification for Improved Alginate Hydrogel Fabrication and Its Application in 3D Cell Culture.

Calcium ion-crosslinked alginate hydrogels are widely used as a materials system for investigating cell behavior in 3D environments in vitro . Suspensions of calcium sulfate particles are often used as the source of Ca 2+ to control the rate of gelation. However, the instability of calcium sulfate suspensions can increase chances of reduced homogeneity of the resulting gel and requires researcher's proficiency. Here, we show that ball-milled calcium sulfate microparticles with smaller sizes can create more stable crosslinker suspensions than unprocessed or simply autoclaved calcium sulfate particles. In particular, 15 µm ball-milled calcium sulfate microparticles result in gels that are more homogeneous with a balanced gelation rate, which facilitates fabrication of gels with consistent mechanical properties and reliable performance for 3D cell culture. Overall, these microparticles represent an improved method for alginate hydrogel fabrication that can increase experimental reliability and quality for 3D cell culture.

A systematic study on the kinetics of H-shift reactions in pristine acyl peroxy radicals.

A series of acyl peroxy radical H-shifts were systematically studied using computational approaches. Acyl peroxy radicals were categorized into small- (ethanal-pentanal), medium- (hexanal and heptanal) and large-sized (octanal and nonanal) molecules. The H-shifts spanning from 1,4 to 1,9 were inspected for each studied system. For all acyl peroxy radicals, it is the combination of barrier heights and quantum mechanical tunneling that explains the yield of the peracid alkyl radical product. We used the ROHF-ROCCSD(T)-F12a/VDZ-F12//ωB97X-D/aug-cc-pVTZ level of theory to estimate the barrier heights and the subsequent rate coefficients with the exception of the smallest acyl peroxy radical ethanal, for which MN15 density functional was applied. The estimated multiconformer H-shift rate coefficients were found to be in the range of 10-2 s-1 to 10-1 s-1 for the fastest H-migrations. The determined rates imply that these H-shift reactions are often competitive with other RO2 loss processes and should be considered as a path to functionalization in modelling not only rural but also urban air quality.

Molecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics.

The oxidation of aromatics contributes significantly to the formation of atmospheric aerosol. Using toluene as an example, we demonstrate the existence of a molecular rearrangement channel in the oxidation mechanism. Based on both flow reactor experiments and quantum chemical calculations, we show that the bicyclic peroxy radicals (BPRs) formed in OH-initiated aromatic oxidation are much less stable than previously thought, and in the case of the toluene derived ipso-BPRs, lead to aerosol-forming low-volatility products with up to 9 oxygen atoms on sub-second timescales. Similar results are predicted for ipso-BPRs formed from many other aromatic compounds. This reaction class is likely a key route for atmospheric aerosol formation, and including the molecular rearrangement of BPRs may be vital for accurate chemical modeling of the atmosphere.

Pesticide Residue Fast Screening Using Thermal Desorption Multi-Scheme Chemical Ionization Mass Spectrometry (TD-MION MS) with Selective Chemical Ionization.

In this work, the detection characteristics of a large group of common pesticides were investigated using a multi-scheme chemical ionization inlet (MION) with a thermal desorption unit (Karsa Ltd.) connected to an Orbitrap (Velos Pro, Thermo Fisher Scientific) mass spectrometer. Standard pesticide mixtures, fruit extracts, untreated fruit juice, and whole fruit samples were inspected. The pesticide mixtures contained 1 ng of each individual target. Altogether, 115 pesticides were detected, with a set of different reagents (i.e., dibromomethane, acetonylacetone, and water) in different polarity modes. The measurement methodology presented was developed to minimize the common bottlenecks originating from sample pretreatments and nonetheless was able to retrieve 92% of the most common pesticides regularly analyzed with standardized UHPLC-MSMS (ultra-high-performance liquid chromatography with tandem mass spectrometry) procedures. The fraction of detected targets of two standard pesticide mixtures generally quantified by GC-MSMS (gas chromatography with tandem mass spectrometry) methodology was much less, equaling 45 and 34%. The pineapple swabbing experiment led to the detection of fludioxonil and diazinon below their respective maximum residue levels (MRLs), whereas measurements of untreated pineapple juice and other fruit extracts led to retrieval of dimethomorph, dinotefuran, imazalil, azoxystrobin, thiabendazole, fludioxonil, and diazinon, also below their MRL. The potential for mutual detection was investigated by mixing two standard solutions and by spiking an extract of fruit with a pesticide's solution, and subsequently, individual compounds were simultaneously detected. For a selected subgroup of compounds, the bromide (Br-) chemical ionization characteristics were further inspected using quantum chemical computations to illustrate the structural features leading to their sensitive detection. Importantly, pesticides could be detected in actual extract and fruit samples, which demonstrates the potential of our fast screening method.

High-fidelity mesoscale in-vivo diffusion MRI through gSlider-BUDA and circular EPI with S-LORAKS reconstruction.

PURPOSE: To develop a high-fidelity diffusion MRI acquisition and reconstruction framework with reduced echo-train-length for less T2* image blurring compared to typical highly accelerated echo-planar imaging (EPI) acquisitions at sub-millimeter isotropic resolution. METHODS: We first proposed a circular-EPI trajectory with partial Fourier sampling on both the readout and phase-encoding directions to minimize the echo-train-length and echo time. We then utilized this trajectory in an interleaved two-shot EPI acquisition with reversed phase-encoding polarity, to aid in the correction of off-resonance-induced image distortions and provide complementary k-space coverage in the missing partial Fourier regions. Using model-based reconstruction with structured low-rank constraint and smooth phase prior, we corrected the shot-to-shot phase variations across the two shots and recover the missing k-space data. Finally, we combined the proposed acquisition/reconstruction framework with an SNR-efficient RF-encoded simultaneous multi-slab technique, termed gSlider, to achieve high-fidelity 720 µm and 500 µm isotropic resolution in-vivo diffusion MRI. RESULTS: Both simulation and in-vivo results demonstrate the effectiveness of the proposed acquisition and reconstruction framework to provide distortion-corrected diffusion imaging at the mesoscale with markedly reduced T2*-blurring. The in-vivo results of 720 µm and 500 µm datasets show high-fidelity diffusion images with reduced image blurring and echo time using the proposed approaches. CONCLUSIONS: The proposed method provides high-quality distortion-corrected diffusion-weighted images with ∼40% reduction in the echo-train-length and T2* blurring at 500µm-isotropic-resolution compared to standard multi-shot EPI.

Deep Learning Initialized Compressed Sensing (Deli-CS) in Volumetric Spatio-Temporal Subspace Reconstruction.

Introduction: Spatio-temporal MRI methods enable whole-brain multi-parametric mapping at ultra-fast acquisition times through efficient k-space encoding, but can have very long reconstruction times, which limit their integration into clinical practice. Deep learning (DL) is a promising approach to accelerate reconstruction, but can be computationally intensive to train and deploy due to the large dimensionality of spatio-temporal MRI. DL methods also need large training data sets and can produce results that don't match the acquired data if data consistency is not enforced. The aim of this project is to reduce reconstruction time using DL whilst simultaneously limiting the risk of deep learning induced hallucinations, all with modest hardware requirements. Methods: Deep Learning Initialized Compressed Sensing (Deli-CS) is proposed to reduce the reconstruction time of iterative reconstructions by "kick-starting" the iterative reconstruction with a DL generated starting point. The proposed framework is applied to volumetric multi-axis spiral projection MRF that achieves whole-brain T1 and T2 mapping at 1-mm isotropic resolution for a 2-minute acquisition. First, the traditional reconstruction is optimized from over two hours to less than 40 minutes while using more than 90% less RAM and only 4.7 GB GPU memory, by using a memory-efficient GPU implementation. The Deli-CS framework is then implemented and evaluated against the above reconstruction. Results: Deli-CS achieves comparable reconstruction quality with 50% fewer iterations bringing the full reconstruction time to 20 minutes. Conclusion: Deli-CS reduces the reconstruction time of subspace reconstruction of volumetric spatio-temporal acquisitions by providing a warm start to the iterative reconstruction algorithm.

Widespread detection of chlorine oxyacids in the Arctic atmosphere.

Chlorine radicals are strong atmospheric oxidants known to play an important role in the depletion of surface ozone and the degradation of methane in the Arctic troposphere. Initial oxidation processes of chlorine produce chlorine oxides, and it has been speculated that the final oxidation steps lead to the formation of chloric (HClO3) and perchloric (HClO4) acids, although these two species have not been detected in the atmosphere. Here, we present atmospheric observations of gas-phase HClO3 and HClO4. Significant levels of HClO3 were observed during springtime at Greenland (Villum Research Station), Ny-Ålesund research station and over the central Arctic Ocean, on-board research vessel Polarstern during the Multidisciplinary drifting Observatory for the Study of the Arctic Climate (MOSAiC) campaign, with estimated concentrations up to 7 × 106 molecule cm-3. The increase in HClO3, concomitantly with that in HClO4, was linked to the increase in bromine levels. These observations indicated that bromine chemistry enhances the formation of OClO, which is subsequently oxidized into HClO3 and HClO4 by hydroxyl radicals. HClO3 and HClO4 are not photoactive and therefore their loss through heterogeneous uptake on aerosol and snow surfaces can function as a previously missing atmospheric sink for reactive chlorine, thereby reducing the chlorine-driven oxidation capacity in the Arctic boundary layer. Our study reveals additional chlorine species in the atmosphere, providing further insights into atmospheric chlorine cycling in the polar environment.

Enhancing CAR-T cell functionality in a patient-specific manner.

Patient responses to autologous CD19 chimeric antigen receptor (CAR) T-cell therapies are limited by insufficient and inconsistent cellular functionality. Here, we show that controlling the precise level of stimulation during T-cell activation to accommodate individual differences in the donor cells will dictate the functional attributes of CAR-T cell products. The functionality of CAR-T cell products, consisting of a diverse set of blood samples derived from healthy donors, acute lymphoblastic leukemia (ALL), and chronic lymphocytic lymphoma (CLL) patient samples, representing a range of patient health status, is tested upon culturing on artificial antigen-presenting cell scaffolds to deliver T-cell stimulatory ligands (anti-CD3/anti-CD28) at highly defined densities. A clear relationship is observed between the dose of stimulation, the phenotype of the T-cell blood sample prior to T-cell activation, and the functionality of the resulting CAR-T cell products. We present a model, based on this dataset, that predicts the precise stimulation needed to manufacture a desired CAR-T cell product, given the input T-cell attributes in the initial blood sample. These findings demonstrate a simple approach to enhance CAR-T functionality by personalizing the level of stimulation during T-cell activation to enable flexible manufacturing of more consistent and potent CAR-T cells.

The gas-phase formation mechanism of iodic acid as an atmospheric aerosol source.

Iodine is a reactive trace element in atmospheric chemistry that destroys ozone and nucleates particles. Iodine emissions have tripled since 1950 and are projected to keep increasing with rising O3 surface concentrations. Although iodic acid (HIO3) is widespread and forms particles more efficiently than sulfuric acid, its gas-phase formation mechanism remains unresolved. Here, in CLOUD atmospheric simulation chamber experiments that generate iodine radicals at atmospherically relevant rates, we show that iodooxy hypoiodite, IOIO, is efficiently converted into HIO3 via reactions (R1) IOIO + O3 → IOIO4 and (R2) IOIO4 + H2O → HIO3 + HOI + (1)O2. The laboratory-derived reaction rate coefficients are corroborated by theory and shown to explain field observations of daytime HIO3 in the remote lower free troposphere. The mechanism provides a missing link between iodine sources and particle formation. Because particulate iodate is readily reduced, recycling iodine back into the gas phase, our results suggest a catalytic role of iodine in aerosol formation.

High-resolution myelin-water fraction and quantitative relaxation mapping using 3D ViSTa-MR fingerprinting.

Purpose: This study aims to develop a high-resolution whole-brain multi-parametric quantitative MRI approach for simultaneous mapping of myelin-water fraction (MWF), T1, T2, and proton-density (PD), all within a clinically feasible scan time. Methods: We developed 3D ViSTa-MRF, which combined Visualization of Short Transverse relaxation time component (ViSTa) technique with MR Fingerprinting (MRF), to achieve high-fidelity whole-brain MWF and T1/T2/PD mapping on a clinical 3T scanner. To achieve fast acquisition and memory-efficient reconstruction, the ViSTa-MRF sequence leverages an optimized 3D tiny-golden-angle-shuffling spiral-projection acquisition and joint spatial-temporal subspace reconstruction with optimized preconditioning algorithm. With the proposed ViSTa-MRF approach, high-fidelity direct MWF mapping was achieved without a need for multi-compartment fitting that could introduce bias and/or noise from additional assumptions or priors. Results: The in-vivo results demonstrate the effectiveness of the proposed acquisition and reconstruction framework to provide fast multi-parametric mapping with high SNR and good quality. The in-vivo results of 1mm- and 0.66mm-iso datasets indicate that the MWF values measured by the proposed method are consistent with standard ViSTa results that are 30x slower with lower SNR. Furthermore, we applied the proposed method to enable 5-minute whole-brain 1mm-iso assessment of MWF and T1/T2/PD mappings for infant brain development and for post-mortem brain samples. Conclusions: In this work, we have developed a 3D ViSTa-MRF technique that enables the acquisition of whole-brain MWF, quantitative T1, T2, and PD maps at 1mm and 0.66mm isotropic resolution in 5 and 15 minutes, respectively. This advancement allows for quantitative investigations of myelination changes in the brain.

High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures.

Dimethyl sulfide (DMS) influences climate via cloud condensation nuclei (CCN) formation resulting from its oxidation products (mainly methanesulfonic acid, MSA, and sulfuric acid, H2SO4). Despite their importance, accurate prediction of MSA and H2SO4 from DMS oxidation remains challenging. With comprehensive experiments carried out in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at CERN, we show that decreasing the temperature from +25 to -10 °C enhances the gas-phase MSA production by an order of magnitude from OH-initiated DMS oxidation, while H2SO4 production is modestly affected. This leads to a gas-phase H2SO4-to-MSA ratio (H2SO4/MSA) smaller than one at low temperatures, consistent with field observations in polar regions. With an updated DMS oxidation mechanism, we find that methanesulfinic acid, CH3S(O)OH, MSIA, forms large amounts of MSA. Overall, our results reveal that MSA yields are a factor of 2-10 higher than those predicted by the widely used Master Chemical Mechanism (MCMv3.3.1), and the NOx effect is less significant than that of temperature. Our updated mechanism explains the high MSA production rates observed in field observations, especially at low temperatures, thus, substantiating the greater importance of MSA in the natural sulfur cycle and natural CCN formation. Our mechanism will improve the interpretation of present-day and historical gas-phase H2SO4/MSA measurements.