Revisiting the Discrepancy between Experimental and Theoretical Predictions of the Adiabaticity of Ti + CHOH.

We revisit the naked transition metal cation (Ti) and methanol reaction and go beyond the standard Landau-Zener (LZ) picture when modeling the intersystem crossing (ISC) rate between the lowest doublet and quartet states. We use both (i) unconstrained Born-Oppenheimer molecular dynamics (BOMD) calculations with an approximate two-state method to estimate population transfer between spin diabats and (ii) constrained dynamics to explore energetically accessible portions of the - 1 crossing seam, where is the total number of internal degrees of freedom. Whereas previous LZ calculations (that necessarily relied on the Condon approximation to be valid) fell short and predicted much slower crossing probabilities than shown in experiment, we show that ISC can occur rapidly because the spin-orbit coupling (SOC) between the doublet and quartet surfaces can vary by 2 orders of magnitude (depending on where in the seam the crossing occurs during dynamics) and the crossing region is revisited multiple times during a dynamics run of a few hundred femtoseconds.

KRAS mutations in advanced non-small cell lung cancer: From biology to novel therapeutic strategies.

Kristen rat sarcoma viral oncogene homolog (KRAS) mutations play a major role in the carcinogenesis of many types of solid tumors including non-small cell lung cancer (NSCLC). Among KRAS mutations, p.G12C single-nucleotide variant (KRAS) is the most frequently reported in NSCLC patients, with a prevalence of about 12-13 %.

Blinded independent central review versus local investigator assessment of PFS in RCTs of immunotherapy in advanced cancers: A systematic review and meta-analysis.

Background: Assessment of Progression-free survival (PFS) events by investigators might be inaccurate in randomized controlled trials (RCTs) with open-label design. We explored differences in PFS evaluated by blinded independent central review (BICR) or local investigator assessment (IA) in trials testing immunotherapy (IO) in advanced cancers.

Methods: We systematically reviewed articles of RCTs investigating IO in advanced tumors, published in PubMed-indexed journals up to December 2023.

Dissociative electron attachment and Ar+ reaction with chromium hexacarbonyl, 296-400 K.

Dissociative electron attachment rate constants have been measured for Cr(CO)6 under thermal conditions, 296-400 K, yielding Cr(CO)5- product. At 296 K, 2.92 ± 0.

Intersystem Crossing Control of the Nb + CO → NbO + CO Reaction.

The transfer of an oxygen atom from carbon dioxide (CO) to a transition metal cation in the gas phase offers atomic level insights into single-atom catalysis for CO activation. Given that these reactions often involve open-shell transition metals, they may proceed through intersystem crossing between different spin manifolds. However, a definitive understanding of such spin-forbidden reaction requires dynamical calculations on multiple global potential energy surfaces (PESs) coupled by spin-orbit couplings.

Putting the child in the driver's seat: Insights into language development from children's interactions in preschool classrooms.

Children's own language production has a role in structuring the language of their conversation partners and influences their own development. Children's active participation in their own language development is most apparent in the rich body of work investigating language in natural environments. The advent of automated measures of vocalizations and movement have made such in situ research increasingly feasible.

Depressive symptoms in children and adolescents with epilepsy and primary headache: a cross-sectional observational study.

Background: The primary aims of our cross-sectional observational study were: (i) to determine the prevalence of depressive symptoms in children and adolescents with epilepsy compared to controls and (ii) to explore the difference in depressive symptoms in patients with epilepsy only and those with epilepsy and primary headache as a comorbidity. The secondary objective was to explore parental stress levels.

Methods: 68 pediatric patients aged 6-18 years (44 with epilepsy only and 24 with epilepsy and headache) and 50 controls were recruited.

A Common Bottleneck for Metal Oxidation by Molecular Oxygen Across Size Regimes: Kinetics of Atomic Lanthanide Cations (La-Lu) with O.

Kinetics of the lanthanide cations (Ln = La-Lu excluding ) reacting with molecular oxygen were measured in a selected-ion flow tube apparatus from 300 to 600 K. Where exothermic, these reactions occur efficiently, producing LnO + O. The reactions display positive temperature dependences consistent with Arrhenius equation behavior and show small activation energies (0-2 kJ mol) that are strongly correlated to promotion energies of the Ln atoms.

Multistate Dynamics and Kinetics of CO Activation by Ta in the Gas Phase: Insights into Single-Atom Catalysis.

The activation of carbon dioxide (CO) by a transition-metal cation in the gas phase is a unique model system for understanding single-atom catalysis. The mechanism of such reactions is often attributed to a "two-state reactivity" model in which the high-energy barrier of a spin state correlating with ground-state reactants is avoided by intersystem crossing (ISC) to a different spin state with a lower barrier. However, such a "spin-forbidden" mechanism, along with the corresponding dynamics, has seldom been rigorously examined theoretically, due to the lack of global potential energy surfaces (PESs).

PLASTAMINATION: Outcomes on the Central Nervous System and Reproduction.

Background: Environmental exposures to non-biodegradable and biodegradable plastics are unavoidable. Microplastics (MPs) and nanoplastics (NPs) from the manufacturing of plastics (primary sources) and the degradation of plastic waste (secondary sources) can enter the food chain directly or indirectly and, passing biological barriers, could target both the brain and the gonads. Hence, the worldwide diffusion of environmental plastic contamination (PLASTAMINATION) in daily life may represent a possible and potentially serious risk to human health.

The associative ionization of N(2P) + O(3P).

The rate constant of the associative ionization reaction N(2P) + O(3P) → NO+ + e- was measured using a flow tube apparatus. A flowing afterglow source was used to produce an ion/electron plasma containing a mixture of ions, including N2+, N3+, and N4+. Dissociative recombination of these species produced a population of nitrogen atoms, including N(2P).

Temperature-Dependent Kinetics for the Reactions of Fe ( = 2-17) and FeNi ( + = 3-9) with O: Comparison of Pure and Mixed Metal Clusters with Relevance to Meteor Radio Afterglows and Surface Oxidation.

Rate constants and product branching fractions were measured from 300-600 K for Fe + O ( = 2-17) and for 300-500 K for FeNi + O ( + = 3-9) using a selected-ion flow tube (SIFT) apparatus. Rate constants for 46 species are reported. All rate constants increased with increasing temperature, and several were in excess of the Langevin-Gioumousis-Stevenson (LGS) capture rate at elevated temperatures.

Kinetics of associative detachment of O + N and dissociative attachment of e + NO up to 1300 K: chemistry relevant to modeling of transient luminous events.

The rate constants of O + N → NO + e from 800 K to 1200 K and the reverse process e + NO → O + N from 700 K to 1300 K are measured using a flowing afterglow - Langmuir probe apparatus. The rate constants for O + N are well described by 3 × 10 e cm s. The rate constants for e + NO are somewhat larger than previously reported and are well described by 7 × 10 e cm s.

Kinetics for the Reactions of Ar, O, and NO with Isoprene (2-Methyl-1,3-butadiene) as a Function of Temperature (300-500 K).

Rate constants and product branching fractions were measured for reactions of Ar, O, and NO with isoprene (2-methyl-1,3-butadiene CH) as a function of temperature. The rate constants are large (∼2 × 10 cm s) and increase with temperature, exceeding the ion-dipole/induced dipole capture rate. Adding a hard sphere term to the collision rate provides a more useful upper limit and predicts the positive temperature dependences.

Electron and Ar+ interaction with Mo(CO)6 at thermal energies; energetic limit on removal of 5 ligands from Mo(CO)6.

The rate constant for electron attachment to Mo(CO)6 was determined to be ka = 2.4 ± 0.6 × 10-7 cm3 s-1 at 297 K in a flowing-afterglow Langmuir-probe experiment.

Ion-molecule studies of energetic oxygen allotropes in flow tubes: .

Starting in the 1960s, flow tube apparatuses have played a central role in the study of ion-molecule kinetics, allowing for immense chemical diversity of cationic, anionic, and neutral reactants. Here, we review studies of oxygen allotropes, excluding ground state O ( ), and focusing instead on reactions of cations, anions, and metal chemi-ionization reactions with ground state atomic oxygen (O P), vibrationally excited molecular oxygen (O (v)), electronically excited molecular oxygen (O ( )), and ozone (O ). Historical outlines of work over several decades are given along with a focus on more recent work by our group at the Air Force Research Laboratory.

Remote monitoring of implantable loop recorders reduces time to diagnosis in patients with unexplained syncope: a multicenter propensity score-matched study.

Background: There are little data on remote monitoring (RM) of implantable loop recorders (ILRs) in patients with unexplained syncope and whether it confers enhanced diagnostic power.

Objective: To evaluate the effect of RM in ILR recipients for unexplained syncope for early detection of clinically relevant arrhythmias by comparison with a historical cohort with no RM.

Methods: SyncRM is a propensity score (PS)-matched study prospectively including 133 consecutive patients with unexplained syncope and ILR followed up by RM (RM-ON group).

Digital Devices Use and Fine Motor Skills in Children between 3-6 Years.

(1) Background: The principal aim of our research was to explore the relationship between digital devices use and fine motor skills in children aged three to six years and to explore the effect of some socio-demographic factors. (2) Methods: we enrolled 185 children aged between three to six years. The parents of all the participants fulfilled a questionnaire to explore the digital device use, and their children performed a standardized test to assess fine motor skills (APCM-2).

Kinetics of O with Ca and Its Higher Oxides CaO ( = 1-3) and Updates to a Model of Meteoric Calcium in the Mesosphere and Lower Thermosphere.

The room-temperature rate constants and product branching fractions of CaO ( = 0-3) + O are measured using a selected ion flow tube apparatus. Ca + O produces CaO + O with = 9 ± 4 × 10 cm s, within uncertainty equal to the Langevin capture rate constant. This value is significantly larger than several literature values.