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1.
Am Psychol ; 2024 May 02.
Artigo em Inglês | MEDLINE | ID: mdl-38695780

RESUMO

Dropout has been identified as a significant problem among military populations seeking psychotherapy (Goetter et al., 2015; Hoge et al., 2014), yet an overall estimate of its exact prevalence and predictors does not exist. The aims of the current meta-analysis were to estimate outpatient psychotherapy dropout rates for this population and evaluate potential moderators of this event. In total, 283 articles-comprising data from 719,465 U.S. service members and veterans-met all inclusion criteria and were included in the meta-analysis. The average weighted dropout rate for all outpatient therapies was 25.6%, 95% CI [22.4%, 29.2%], and prediction interval [1.9%, 85.9%]. Furthermore, dropout was 27.0% for cognitive behavioral therapies (CBTs), 25.3% for trauma treatments, 27.6% for the Department of Veterans Affairs (VA), 28.9% for individual therapies, and 9.8% for intensive outpatient settings. Findings from metaregression analyses using mixed-effects models indicated that higher dropout was linked with the following after accounting for other moderators: younger age, CBTs, nonmanualized approaches, VA versus Department of Defense settings, individual versus group therapies, and weekly versus intensive outpatient formats. Dropout was not linked with other client, therapist, treatment, and research variables. Taken together, dropout estimates were obtained for a range of military populations and treatment characteristics, including theoretical orientation, presenting concern, setting, and therapy formats. These estimates may provide potential benchmarks for therapists, administrators, and policymakers serving military populations. Leveraging dropout prevention strategies with at-risk groups highlighted in this study may enhance mental health care outcomes for this high-need population. (PsycInfo Database Record (c) 2024 APA, all rights reserved).

2.
J Phys Chem Lett ; 12(42): 10437-10443, 2021 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-34672587

RESUMO

In atom probe tomography of molecular organic materials, field ionization of either entire molecules or molecular fragments can occur, but the mechanism governing this behavior was not previously understood. This work explains when a doubly ionized small molecule organic material is expected to undergo fragmentation. We find that multiple detection events arising from post-ionization fragmentation of a parent molecular dication into two daughter ions is well explained by the free energy and geometries of the molecules computed using density functional theory. Of the systems studied, exergonic free energies for formation of the daughter ions, smaller activation energies for dissociation, and increases in bond length are all found to be quantitative predictors for ion fragmentation. This work expands the applicability of atom probe tomography to organic materials by increasing the fundamental understanding of processes occurring during this analysis technique.

3.
J Org Chem ; 86(21): 14553-14562, 2021 11 05.
Artigo em Inglês | MEDLINE | ID: mdl-34582209

RESUMO

Alloxan is an important toxic glucose analogue used to induce diabetes in lab test animals. Once regarded as a "problem structure," the condensed-phase structure of anhydrous alloxan has largely been settled, but literature inconsistencies remain for the structure of the typically employed reagent alloxan monohydrate. Due to the criticality of structure-function relationships, we have used 1H/13C{1H} NMR, IR spectroscopy, as well as quantum mechanical (QM) calculations to probe the liquid-phase structure and reactivity of alloxan monohydrate. In protic solvents (D2O and acetic acid-d4), hydration at the C5 carbonyl of alloxan monohydrate occurs quantitatively to form the C5 gem-diol (5,5'-dihydroxybarbituric acid). In the aprotic solvent dimethyl sulfoxide (DMSO)-d6, there exists a mixture of the C5 gem-diol and planar tetraketo form of alloxan monohydrate. QM calculations explain the solvent-dependent hydration reactivity, where a solvent-assisted H-atom transfer mechanism lowers the activation energy of water addition at the C5 carbonyl by ∼16 or 27 kcal/mol in water or acetic acid, respectively, compared to the unassisted hydration reaction. Prompt recrystallization of alloxan monohydrate from boiling water does not alter the structure of the reagent. These findings probe the exact structure of alloxan monohydrate to guide future research efforts in biological sciences and in organic synthesis.


Assuntos
Aloxano , Água , Animais , Dimetil Sulfóxido , Solventes , Termodinâmica
4.
Org Biomol Chem ; 18(44): 9044-9049, 2020 11 28.
Artigo em Inglês | MEDLINE | ID: mdl-33150911

RESUMO

A synthetic method towards fluorinated allylamines using allene precursors is reported. A variety of heterocyclic amines were employed as nucleophiles in a Selectfluor promoted intermolecular fluoroamination reaction. This strategy provides a novel synthetic route to access vinyl fluorides with a vicinal amine moiety.

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