Gas-to-Particle Partitioning of Products from Ozonolysis of Δ3-Carene and the Effect of Temperature and Relative Humidity.

Formation of oxidized products from Δ3-carene (C10H16) ozonolysis and their gas-to-particle partitioning at three temperatures (0, 10, and 20 °C) under dry conditions (<2% RH) and also at 10 °C under humid (78% RH) conditions were studied using a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) combined with a filter inlet for gases and aerosols (FIGAERO). The Δ3-carene ozonolysis products detected by the FIGAERO-ToF-CIMS were dominated by semivolatile organic compounds (SVOCs). The main effect of increasing temperature or RH on the product distribution was an increase in fragmentation of monomer compounds (from C10 to C7 compounds), potentially via alkoxy scission losing a C3 group. The equilibrium partitioning coefficient estimated according to equilibrium partitioning theory shows that the measured SVOC products distribute more into the SOA phase as the temperature decreases from 20 to 10 and 0 °C and for most products as the RH increases from <2 to 78%. The temperature dependency of the saturation vapor pressure (above an assumed liquid state), derived from the partitioning method, also allows for a direct way to obtain enthalpy of vaporization for the detected species without accessibility of authentic standards of the pure substances. This method can provide physical properties, beneficial for, e.g., atmospheric modeling, of complex multifunctional oxidation products.

The Cerebellar Mutism Syndrome: Risk Assessment, Prevention and Treatment.

Cerebellar mutism syndrome (CMS) has received increasing attention over the last decades as a complication of posterior fossa tumour surgery in children. Risk factors, aetiological aspects, and treatment measures of the syndrome have been investigated, yet the incidence of CMS remains unchanged. Overall, we are currently able to identify patients at risk, but we are unable to prevent it from occurring.Once CMS sets in, several symptomatic pharmacological treatments have been suggested, but only in smaller case series and not in randomized controlled trials, and it is not clear whether the treatment or time itself had a helpful effect.Within weeks to months, most patients regain their ability to speak after a phase with mutism or severely reduced speech; however, many patients continue to have speech and language deficits. At this point, anti-cancer treatment with chemotherapy and radiotherapy may be of focus more than the prognosis of CMS; however, many patients continue to have speech and language problems for months and years to come, and they are at high risk of other neurocognitive sequelae as well.Without reliable measures to prevent or treat the syndrome, we may look towards improving the prognosis of speech and neurocognitive functioning in these patients. As speech and language impairment is the cardinal symptom and late effect of CMS, the effect of intense and early-onset speech and language therapy as a standard of care in these patients should be investigated in relation to its effect on regaining speech capacity.

Does evidentiality support source monitoring and false belief understanding? A cross-linguistic study with Turkish- and English-speaking children.

This study investigates the impact of evidentiality on source monitoring and the impact of source monitoring on false belief understanding (FBU), while controlling for short-term memory, age, gender, and receptive vocabulary. One hundred (50 girls) monolingual 3- and 4-year-olds from Turkey and the UK participated in the study in 2019. In Turkish, children's use of direct evidentiality predicted their source monitoring skills, which, in turn, predicted their FBU. In English, FBU was not related to source monitoring. Combined results from both languages revealed that Turkish-speaking children had better FBU than English-speaking children, and only for Turkish-speaking children, better source monitoring skills predicted better FBU. This suggests an indirect impact of evidentiality on FBU by means of source monitoring in Turkish.

Ozonolysis of α-Pinene and Δ3-Carene Mixtures: Formation of Dimers with Two Precursors.

The formation of secondary organic aerosol (SOA) from the structurally similar monoterpenes, α-pinene and Δ3-carene, differs substantially. The aerosol phase is already complex for a single precursor, and when mixtures are oxidized, products, e.g., dimers, may form between different volatile organic compounds (VOCs). This work investigates whether differences in SOA formation and properties from the oxidation of individual monoterpenes persist when a mixture of the monoterpenes is oxidized. Ozonolysis of α-pinene, Δ3-carene, and a 1:1 mixture of them was performed in the Aarhus University Research on Aerosol (AURA) atmospheric simulation chamber. Here, ∼100 ppb of monoterpene was oxidized by 200 ppb O3 under dark conditions at 20 °C. The particle number concentration and particle mass concentration for ozonolysis of α-pinene exceed those from ozonolysis of Δ3-carene alone, while their mixture results in concentrations similar to α-pinene ozonolysis. Detailed offline analysis reveals evidence of VOC-cross-product dimers in SOA from ozonolysis of the monoterpene mixture: a VOC-cross-product dimer likely composed of the monomeric units cis-caric acid and 10-hydroxy-pinonic acid and a VOC-cross-product dimer ester likely from the monomeric units caronaldehyde and terpenylic acid were tentatively identified by liquid chromatography-mass spectrometry. To improve the understanding of chemical mechanisms determining SOA, it is relevant to identify VOC-cross-products.

Chemical characteristics and sources of organosulfates, organosulfonates, and carboxylic acids in aerosols in urban Xi'an, Northwest China.

We investigated speciation and levels of organosulfates, organosulfonates as well as carboxylic acids in aerosol samples collected during summer (2014) and winter (2014/15) in Xi'an, Northwest China, to improve understanding of composition and sources of organic aerosols in this region heavily affected by air pollution. Organosulfates are formed from reactive gas-phase organic compounds and acidic sulfate aerosols, contributing to secondary organic aerosols, SOA. The aerosol samples show a large diversity in organosulfur species in line with other regions of China, reflecting the high levels and complexity of SOA precursors. In summer samples, organosulfates from isoprene are prevalent due to transport of air masses from southern regions with isoprene-emitting mountain forests. During winter, air masses are local or from areas north of the city with low population density and very low temperatures. The estimated levels of organosulfates and organosulfonates in summer (768 ± 346 ng m-3) and winter samples (938 ± 374 ng m-3) are more similar than expected given the high levels of sulfate and organic carbon in winter, indicating the complexity of organosulfur formation processes. We observed an organosulfonate with molecular weight 214 (C6H14O6S) at high estimated levels (254 ± 232 ng m-3) in winter, but much lower concentrations (12 ± 13 ng m-3) in summer. High levels of organosulfur compounds were mainly observed at aerosol pH below about 2.5. Concentrations of carboxylic acids from oxidation of monoterpenes were low (5.2 ± 2.7 ng m-3 in summer). Phthalic acid was as high as 90 ± 29 ng m-3 during winter and correlated highly with organic carbon, chloride and potassium, indicating a common origin, most likely burning of biomass and plastic-containing waste. Further research is needed to elucidate formation and sources of organosulfates and organosulfonates, as well as the impact on aerosol properties affecting e.g. health effects.

Do complement clauses really support false-belief reasoning? A longitudinal study with English-speaking 2- to 3-year-olds.

To examine whether children's acquisition of perspective-marking language supports development in their ability to reason about mental states, we conducted a longitudinal study testing whether proficiency with complement clauses around age 3 explained variance in false-belief reasoning 6 months later. Forty-five English-speaking 2- and 3-year-olds (23 female, Time 1 age range = 33-41 months) from middle-class families in the North-West of England took part in the study, which addresses a series of uncertainties in previous studies. We avoided the confound of using complement clauses in the false-belief tests, assessed complement-clause proficiency with a new comprehensive test designed to capture gradual development, and controlled for individual differences in executive functioning that could affect both linguistic and sociocognitive performance. Further, we aimed to disentangle the influence of two aspects of complement-clause acquisition: proficiency with the perspective-marking syntactic structure itself and understanding of the specific mental verbs used in this syntactic structure. To investigate direction of causality, we also tested whether early false-belief reasoning predicted later complement-clause proficiency. The results provide strong support for the hypothesis that complement-clause acquisition promotes development in false-belief reasoning. Proficiency with the general structure of complement-clause constructions and understanding of the specific mental verbs "think" and "know" in third-person complements at Time 1 both contributed uniquely to predicting false-belief performance at Time 2. However, false-belief performance at Time 1 also contributed uniquely to predicting complement-clause proficiency at Time 2. Together, these results indicate a bidirectional relationship between linguistic and sociocognitive development. (PsycInfo Database Record (c) 2021 APA, all rights reserved).

Single Solvent Molecules Induce Dual Nucleophiles in Gas-Phase Ion-Molecule Nucleophilic Substitution Reactions.

Direct dynamics simulation of singly hydrated peroxide ion reacting with CH3Cl reveals a new product channel that forms CH3OH + Cl- + HOOH, besides the traditional channel that forms CH3OOH + Cl- + H2O. This finding shows that singly hydrated peroxide ion behaves as a dual nucleophile through proton transfer between HOO-(H2O) and HO-(HOOH). Trajectory analysis attributes the occurrence of the thermodynamically and kinetically unfavored HO--induced pathway to the entrance channel dynamics, where extensive proton transfer occurs within the deep well of the prereaction complex. This study represents the first example of a single solvent molecule altering the nucleophile in a gas-phase ion-molecule nucleophilic substitution reaction, in addition to reducing the reactivity and affecting the dynamics, signifying the importance of dynamical effects of solvent molecules.

New Particle Formation and Growth from Dimethyl Sulfide Oxidation by Hydroxyl Radicals.

Dimethyl sulfide (DMS) is produced by plankton in oceans and constitutes the largest natural emission of sulfur to the atmosphere. In this work, we examine new particle formation from the primary pathway of oxidation of gas-phase DMS by OH radicals. We particularly focus on particle growth and mass yield as studied experimentally under dry conditions using the atmospheric simulation chamber AURA. Experimentally, we show that aerosol mass yields from oxidation of 50-200 ppb of DMS are low (2-7%) and that particle growth rates (8.2-24.4 nm/h) are comparable with ambient observations. An HR-ToF-AMS was calibrated using methanesulfonic acid (MSA) to account for fragments distributed across both the organic and sulfate fragmentation table. AMS-derived chemical compositions revealed that MSA was always more dominant than sulfate in the secondary aerosols formed. Modeling using the Aerosol Dynamics, gas- and particle-phase chemistry kinetic multilayer model for laboratory CHAMber studies (ADCHAM) indicates that the Master Chemical Mechanism gas-phase chemistry alone underestimates experimentally observed particle formation and that DMS multiphase and autoxidation chemistry is needed to explain observations. Based on quantum chemical calculations, we conclude that particle formation from DMS oxidation in the ambient atmosphere will most likely be driven by mixed sulfuric acid/MSA clusters clustering with both amines and ammonia.

Increased mortality among HIV infected patients with cryptococcal antigenemia in Guinea-Bissau.

Cryptococcal antigenemia may precede development of cryptococcal meningitis and death among patients with advanced HIV infection. Among 200 retrospectively and randomly selected ART-naïve patients with CD4 counts < 100 cells/µl from Guinea-Bissau, 20 (10%) had a positive cryptococcal antigen test. Self-reported headache and fever were predictors of a positive test, while cryptococcal antigenemia was a strong predictor of death within the first year of follow-up, MRR 2.22 (95% CI: 1.15-4.30). Screening for cryptococcal antigenemia should be implemented for patients with advanced HIV in Guinea-Bissau. Pre-emptive anti-fungal therapy should be initiated prior to ART-initiation if the screening is positive.

The influence of human leukocyte antigen-types on disease progression among HIV-2 infected patients in Guinea-Bissau.

OBJECTIVES: HIV-2 is endemic in West Africa and is characterized by lower transmissibility because of lower viral load, and HIV-2-infected persons usually have a slower progression to AIDS. The mechanisms behind the slower disease progression are unknown. The main objective was to identify specific HLA class I and II alleles that may influence the disease progression of HIV-2 infection. DESIGN: Cohort follow-up study. METHODS: We used high-resolution HLA typing of DNA from 437 antiretroviral naive HIV-2-infected patients from the Bissau HIV Cohort, Guinea-Bissau, to identify HLA alleles with an influence on HIV-2 disease progression. The effect of HLA-type on viral load and CD4 cell count was assessed initially by ranksum-test and t-test, followed by adjusted logistic regression and multivariable linear regression analysis, respectively. RESULTS: Three alleles (HLA-B58:01, HLA-DPB110:01 and HLA-DRB111:01) were associated with lower possibility of detectable baseline plasma viral load (P = 0.002, P = 0.044 and P = 0.033, respectively), and no alleles were associated with higher possibility of detectable plasma viral load. HLA-DPB110:01 and HLA-DRB111:01 were in linkage disequilibrium (P = 0.047). Patients with heterozygous HLA types in all their HLA class I loci or in one or two loci were not more likely to have undetectable viral load compared with patients that were homozygous in all their class I loci after adjusting for sex and CD4 cell count (P = 0.93 and P = 0.88, respectively). CONCLUSION: The three alleles HLA-B58:01, HLA-DPB110:01 and HLA-DRB111:01 may protect against HIV-2 disease progression towards AIDS.

Cue conflicts in context: interplay between morphosyntax and discourse context in Danish preschoolers' semantic role assignment.

When learning their first language, children develop strategies for assigning semantic roles to sentence structures, depending on morphosyntactic cues such as case and word order. Traditionally, comprehension experiments have presented transitive clauses in isolation, and cross-linguistically children have been found to misinterpret object-first constructions by following a word-order strategy (Chan, Lieven & Tomasello, 2009; Dittmar, Abbot-Smith, Lieven & Tomasello, 2008; Hakuta, 1982; McDonald, 1989; Slobin & Bever, 1982). In an act-out study, we replicated this finding with Danish preschoolers. However, object-first clauses may be context-sensitive structures, which are infelicitous in isolation. In a second act-out study we presented OVS clauses in supportive and unsupportive discourse contexts and in isolation and found that five- to six-year-olds' OVS comprehension was enhanced in discourse-pragmatically felicitous contexts. Our results extend previous findings of preschoolers' sensitivity to discourse-contextual cues in sentence comprehension (Hurewitz, 2001; Song & Fisher, 2005) to the basic task of assigning agent and patient roles.

The α-effect in gas-phase SN2 reactions of microsolvated anions: methanol as a solvent.

The α-effect, an enhanced reactivity of nucleophiles with a lone-pair adjacent to the reaction center, has been studied in solution for several decades. The gas-phase α-effect has recently been documented in studies of SN2 reactions as well as in competing reactions for both bare and microhydrated anions. In the present work we extend our studies of the significance of microsolvation on the α-effect, employing methanol as the solvent, in the expectation that the greater stability of the methanol cluster relative to the water cluster will lower the reactivity and thereby allow studies over a wider efficiency range. We compare the gas-phase reactivity of the microsolvated α-nucleophile HOO(-)(CH3OH) to that of microsolvated normal alkoxy nucleophiles, RO(-)(CH3OH) in reactions with CH3Cl and CH3Br. The results reveal enhanced reactivity of HOO(-)(CH3OH) toward both methyl halides relative to the normal nucleophiles, and clearly demonstrate the presence of an α-effect for the microsolvated α-nucleophile. The highly exothermic reactions with methyl bromide result in a smaller Brønsted ßnuc value than observed for methyl chloride, and the α-effect in turn influences the reactions with methyl chloride more than with methyl bromide. Computational investigations reveal that reactions with methyl bromide proceed through earlier transition states with less advanced bond formation compared to the related reactions of methyl chloride. In addition, solvent interactions for HOO(-) are quite different from those with the normal nucleophiles at the transition state, indicating that differential solvation may well contribute to the α-effect. The greater thermodynamic and kinetic stability of the anion-methanol clusters relative to the anion-water clusters accounts well for the differences in the influence of solvation with the two protic polar solvents.

The α-effect and competing mechanisms: the gas-phase reactions of microsolvated anions with methyl formate.

The enhanced reactivity of α-nucleophiles, which contain an electron lone pair adjacent to the reactive site, has been demonstrated in solution and in the gas phase and, recently, for the gas-phase S(N)2 reactions of the microsolvated HOO(-)(H2O) ion with methyl chloride. In the present work, we continue to explore the significance of microsolvation on the α-effect as we compare the gas-phase reactivity of the microsolvated α-nucleophile HOO(-)(H2O) with that of microsolvated normal alkoxy nucleophiles, RO(-)(H2O), in reactions with methyl formate, where three competing reactions are possible. The results reveal enhanced reactivity of HOO(-)(H2O) towards methyl formate, and clearly demonstrate the presence of an overall α-effect for the reactions of the microsolvated α-nucleophile. The association of the nucleophiles with a single water molecule significantly lowers the degree of proton abstraction and increases the S(N)2 and B(AC)2 reactivity compared with the unsolvated analogs. HOO(-)(H2O) reacts with methyl formate exclusively via the B(AC)2 channel. While microsolvation lowers the overall reaction efficiency, it enhances the B(AC)2 reaction efficiency for all anions compared with the unsolvated analogs. This may be explained by participation of the solvent water molecule in the B(AC)2 reaction in a way that continuously stabilizes the negative charge throughout the reaction.

Investigating the α-effect in gas-phase S(N)2 reactions of microsolvated anions.

The α-effect-enhanced reactivity of nucleophiles with a lone-pair adjacent to the attacking center-was recently demonstrated for gas-phase S(N)2 reactions of HOO(-), supporting an intrinsic component of the α-effect. In the present work we explore the gas-phase reactivity of microsolvated nucleophiles in order to investigate in detail how the α-effect is influenced by solvent. We compare the gas-phase reactivity of the microsolvated α-nucleophile HOO(-)(H2O) to that of microsolvated normal alkoxy nucleophiles, RO(-)(H2O), in reaction with CH3Cl using a flowing afterglow-selected ion flow tube instrument. The results reveal enhanced reactivity of HOO(-)(H2O) and clearly demonstrate the presence of an α-effect for the microsolvated α-nucleophile. The association of the nucleophile with a single water molecule results in a larger Brønsted ßnuc value than is the case for the unsolvated nucleophiles. Accordingly, the reactions of the microsolvated nucleophiles proceed through later transition states in which bond formation has progressed further. Calculations show a significant difference in solvent interaction for HOO(-) relative to the normal nucleophiles at the transition states, indicating that differential solvation may well contribute to the α-effect. The reactions of the microsolvated anions with CH3Cl can lead to formation of either the bare Cl(-) anion or the Cl(-)(H2O) cluster. The product distributions show preferential formation of the Cl(-) anion even though the formation of Cl(-)(H2O) would be favored thermodynamically. Although the structure of the HOO(-)(H2O) cluster resembles HO(-)(HOOH), we demonstrate that HOO(-) is the active nucleophile when the cluster reacts.

Intramolecular interactions in 2-aminoethanol and 3-aminopropanol.

Gas-phase vibrational spectra of 2-aminoethanol and 3-aminopropanol were recorded up to the third OH-stretching overtone using Fourier transform infrared spectroscopy, cavity ringdown spectroscopy, and intracavity laser photoacoustic spectroscopy. The experimental investigation was supplemented by local mode calculations, and the intramolecular interactions were investigated using atoms in molecules (AIM) and noncovalent interactions (NCI) theories. All calculations were performed at the CCSD(T)-F12a/VDZ-F12 level of theory. For both compounds the most abundant conformer has a structure that allows for hydrogen bond interaction from the OH group to the N atom of the amino group (OH-N). The spectra show signals from both hydrogen bonded and free OH stretches, implying the presence of several conformers. We observe hydrogen-bond-like interactions in both compounds. The red shift of the bonded OH-stretching frequency and intensity enhancement of the fundamental transition suggest that the hydrogen bond interaction is more pronounced in 3-aminopropanol. AIM analysis supports the presence of a hydrogen bond in 3-aminopropanol but not in 2-aminoethanol, whereas NCI analysis shows hydrogen bonding in both compounds with the stronger interaction found in 3-aminopropanol.

On the possible catalysis by single water molecules of gas-phase hydrogen abstraction reactions by OH radicals.

The gas phase hydrogen abstraction reaction between OH and CY(2)XH, where X = H, F, OH, or NH(2) and Y = H, CH(3) or F, in the absence and presence of a single water molecule is investigated using both density function theory, B3LYP, and explicitly correlated coupled cluster theory, CCSD(T)-F12. We find that a single water molecule could have a catalytic effect at low temperatures possible in laboratory experiments, but does not seem to catalyze these reactions at 298 K, and will not play a role under relevant atmospheric conditions.

Pseudo-bimolecular [2+2] cycloaddition studied by time-resolved photoelectron spectroscopy.

The first study of pseudo-bimolecular cycloaddition reaction dynamics in the gas phase is presented. We used femtosecond time-resolved photoelectron spectroscopy (TRPES) to study the [2+2] photocycloaddition in the model system pseudo-gem-divinyl[2.2]paracyclophane. From X-ray crystal diffraction measurements we found that the ground-state molecule can exist in two conformers; a reactive one in which the vinyl groups are immediately situated for [2+2] cycloaddition and a nonreactive conformer in which they point in opposite directions. From the measured S(1) lifetimes we assigned a clear relation between the conformation and the excited-state reactivity; the reactive conformer has a lifetime of 13 ps, populating the ground state through a conical intersection leading to [2+2] cycloaddition, whereas the nonreactive conformer has a lifetime of 400 ps. Ab initio calculations were performed to locate the relevant conical intersection (CI) and calculate an excited-state [2+2] cycloaddition reaction path. The interpretation of the results is supported by experimental results on the similar but nonreactive pseudo-para-divinyl[2.2]paracyclophane, which has a lifetime of more than 500 ps in the S(1) state.