Impulsivity profiles across five harmonized longitudinal childhood preventive interventions and associations with adult outcomes.

This study aimed to parse between-person heterogeneity in growth of impulsivity across childhood and adolescence among participants enrolled in five childhood preventive intervention trials targeting conduct problems. In addition, we aimed to test profile membership in relation to adult psychopathologies. Measurement items representing impulsive behavior across grades 2, 4, 5, 7, 8, and 10, and aggression, substance use, suicidal ideation/attempts, and anxiety/depression in adulthood were integrated from the five trials (N = 4,975). We applied latent class growth analysis to this sample, as well as samples separated into nonintervention (n = 2,492) and intervention (n = 2,483) participants. Across all samples, profiles were characterized by high, moderate, low, and low-increasing impulsive levels. Regarding adult outcomes, in all samples, the high, moderate, and low profiles endorsed greater levels of aggression compared to the low-increasing profile. There were nuanced differences across samples and profiles on suicidal ideation/attempts and anxiety/depression. Across samples, there were no significant differences between profiles on substance use. Overall, our study helps to inform understanding of the developmental course and prognosis of impulsivity, as well as adding to collaborative efforts linking data across multiple studies to better inform understanding of developmental processes.

Photoisomerization of (Cyanomethylene)cyclopropane (C5H5N) to 1-Cyano-2-methylenecyclopropane in an Argon Matrix.

Broad-band ultraviolet photolysis (λ > 200 nm) of (cyanomethylene)cyclopropane (5) in an argon matrix at 20 K generates 1-cyano-2-methylenecyclopropane (7), a previously unknown compound. This product was initially identified by comparison of its infrared spectrum to that predicted by an anharmonic MP2/6-311+G(2d,p) calculation. This assignment was unambiguously confirmed by the synthesis of 1-cyano-2-methylenecyclopropane (7) and observation of its authentic infrared spectrum, which proved identical to that of the observed photoproduct. We investigated the singlet and triplet potential energy surfaces associated with this isomerization process using density functional theory and multireference calculations. The observed rearrangement of compound 5 to compound 7 is computed to be endothermic (3.3 kcal/mol). We were unable to observe the reverse reaction (7 → 5) under the photochemical conditions.

Rotational Spectroscopy of 1-Cyano-2-methylenecyclopropane (C5H5N)─A Newly Synthesized Pyridine Isomer.

The gas-phase rotational spectrum of 1-cyano-2-methylenecyclopropane (C1, C5H5N), an isomer of pyridine, is presented for the first time, covering the range from 235 to 500 GHz. Over 3600 a-, b-, and c-type transitions for the ground vibrational state have been assigned, measured, and least-squares fit to partial-octic A- and S-reduced distorted-rotor Hamiltonians with low statistical uncertainty (σfit = 42 kHz). Transitions for the two lowest-energy fundamental states (ν27 and ν26) and the lowest-energy overtone (2ν27) have been similarly measured, assigned, and least-squares fit to single-state Hamiltonians. Computed vibration-rotation interaction constants (B0-Bv) using the B3LYP and MP2 levels of theory are compared with the corresponding experimental values. Based upon our preliminary analysis, the next few vibrationally excited states form one or more complex polyads of interacting states via Coriolis and anharmonic coupling. The spectroscopic constants and transition frequencies presented here form the foundation for both future laboratory spectroscopy and astronomical searches for 1-cyano-2-methylenecyclopropane.

Intergenerational Effects of the Fast Track Intervention on Next-Generation Child Outcomes: A Preregistered Randomized Clinical Trial.

OBJECTIVE: The authors sought to determine whether the Fast Track mental health intervention delivered to individuals in childhood decreased mental health problems and the need for health services among the children of these individuals. METHODS: The authors examined whether Fast Track assignment in one generation of children (generation 2; G2) from grades 1 through 10 reduced parent-reported mental health problems and health services use in these children's children (generation 3; G3) 18 years later relative to a control group. The Fast Track intervention blended parent behavior-management training, child social-cognitive skills tutoring, home visits, and classroom social-ecology changes across grades 1-10 to ameliorate emerging conduct problems among the G2 children. For this study, 1,057 G3 children of Fast Track participants (N=581 intervention group, N=476 control group) were evaluated. RESULTS: G3 children of G2 parents who were randomized to the Fast Track intervention group used fewer general inpatient services and fewer inpatient or outpatient mental health services compared with G3 children of G2 parents randomized to the control group. Some of these effects were mediated: randomization to Fast Track predicted fewer internalizing problems and less use of corporal punishment among G2 adults at age 25, which subsequently predicted less general inpatient service use and outpatient mental health service use among the G3 children by the time the G2 parents were 34 years old. There were no significant differences between G3 children from these two groups on the use of other health services or on mental health measures. CONCLUSIONS: Fast Track was associated with lower use of general inpatient services and inpatient and outpatient mental health services intergenerationally, but effects on parent-reported mental health of the children were not apparent across generations. Investing in interventions for the mental health of children could reduce service use burdens across generations.

Kindergarten conduct problems are associated with monetized outcomes in adolescence and adulthood.

BACKGROUND: Across several sites in the United States, we examined whether kindergarten conduct problems among mostly population-representative samples of children were associated with increased criminal and related (criminal + lost offender productivity + victim; described as criminal + victim hereafter) costs across adolescence and adulthood, as well as government and medical services costs in adulthood. METHODS: Participants (N = 1,339) were from two multisite longitudinal studies: Fast Track (n = 754) and the Child Development Project (n = 585). Parents and teachers reported on kindergarten conduct problems, administrative and national database records yielded indexes of criminal offending, and participants self-reported their government and medical service use. Outcomes were assigned costs, and significant associations were adjusted for inflation to determine USD 2020 costs. RESULTS: A 1SD increase in kindergarten conduct problems was associated with a $21,934 increase in adolescent criminal + victim costs, a $63,998 increase in adult criminal + victim costs, a $12,753 increase in medical services costs, and a $146,279 increase in total costs. In the male sample, a 1SD increase in kindergarten conduct problems was associated with a $28,530 increase in adolescent criminal + victim costs, a $58,872 increase in adult criminal + victim costs, and a $144,140 increase in total costs. In the female sample, a 1SD increase in kindergarten conduct problems was associated with a $15,481 increase in adolescent criminal + victim costs, a $62,916 increase in adult criminal + victim costs, a $24,105 increase in medical services costs, and a $144,823 increase in total costs. CONCLUSIONS: This investigation provides evidence of the long-term costs associated with early-starting conduct problems, which is important information that can be used by policymakers to support research and programs investing in a strong start for children.

The 235-360 GHz Rotational Spectrum of 1-Oxaspiro[2.5]octa-4,7-dien-6-one─Analysis of the Ground Vibrational State and Its 10 Lowest-Energy Vibrationally Excited States.

The millimeter-wave rotational spectrum of 1-oxaspiro[2.5]octa-4,7-dien-6-one (1) was collected from 235 to 360 GHz. With the rotational spectrum of this compound available for the first time, more than 5500 a- and c-type transitions were observed and assigned for the vibrational ground state. These transitions were least-squares fit to S- and A-reduced, sextic distorted-rotor Hamiltonians in the Ir representation (σfit = 37 kHz). Additionally, transitions of four fundamental states (ν22, ν21, ν39, and ν38), four overtone states (2ν22, 3ν22, 4ν22, and 5ν22), and two combination states (ν22 + ν21 and ν22 + ν39) were measured, assigned, and least-squares fit to single-state, S- and A-reduced, sextic distorted-rotor Hamiltonians in the Ir representation (σfit < 42 kHz). The computed vibration-rotation interaction constants (B0 - Bv) (MP2 and B3LYP/6-311+G(2d,p)) were compared to their corresponding experimental values, showing excellent agreement for all fundamental states. Based on the intensities of the transitions from six members of the v ν22 series, the fundamental frequency of ν22 was determined to be 79.0 (2.1) cm-1.

Photochemistry of 1-(2- and 3-Thienyl)diazoethanes: Spectroscopy and Tunneling Reaction of Triplet 1-(3-Thienyl)ethylidene.

Photolysis (λ > 613 nm) of 1-(3-thienyl)diazoethane (21) yields the s-E rotamer of triplet 1-(3-thienyl)ethylidene (3), as characterized by UV/vis and EPR spectroscopy. The s-Z rotamer of 3 was not observed. EPR and UV/vis signals attributed to carbene 3 decrease by approximately 50% upon standing in the dark for 68 h at 10 K. Although formally spin-forbidden, an intramolecular [1,2]-hydrogen shift in triplet carbene 3 to afford singlet s-E 3-vinylthiophene (8) is presumed to occur via quantum mechanical tunneling. The behavior of the CD3 analogue supports this interpretation. Photolysis (λ > 613 nm) of 1-(3-thienyl)diazoethane-d3 (21-d3) yields triplet 1-(3-thienyl)ethylidene-d3 (3-d3), as characterized by IR, UV/vis, and EPR spectroscopy. No change in the signal intensity of EPR and UV/vis signals of triplet 3-d3 is observed upon standing in the dark for 68 h at 10 K. In a series of 2-substituted thienyl derivatives, irradiation of 1-(2-thienyl)diazoethane (22), 1-(2-thienyl)diazoethane-d3 (22-d3), or (3-methyl-2-thienyl)diazomethane (23) does not yield triplet carbene intermediates. Positioning and labeling of the methyl group proved to have a large effect on products observed for these species. 1-(2-Thienyl)diazoethane (22) yields the products of [1,2]-hydrogen migration, s-Z and s-E 2-vinylthiophene (7), while 22-d3 and 23 give products derived from opening of the thiophene ring.

Child and Adolescent Psychopathology and Subsequent Harmful Behaviors Associated with Premature Mortality: A Selective Review and Future Directions.

In the United States (U.S.), premature mortality in adulthood from suicide, alcohol-related disease, and substance overdoses has increased steadily over the past two decades. To better understand these trends, it is necessary to first examine the harmful behaviors that often precede these preventable deaths (i.e., suicidal ideation and attempts, and harmful alcohol and substance use). Representing critical developmental periods in which psychopathology is most likely to emerge, childhood and adolescence provide an informative lens through which to investigate susceptibility to harmful behaviors. This article synthesizes current evidence describing these rising U.S. mortality rates and the prevalence rates of harmful behaviors linked to these types of mortality. A brief selective review of longitudinal research on harmful behaviors in relation to the most relevant categories of child and adolescent psychopathology is then provided. Finally, recommendations for future research and implications for prevention are discussed.

Precise Equilibrium Structure of Benzene.

Recent advances in gas-phase structure determination afford outstanding agreement between the CCSD(T)/cc-pCVTZ-corrected semi-experimental (reSE) equilibrium structures and their corresponding best theoretical estimates (BTEs) of the equilibrium structures (re) based upon corrections to the CCSD(T)/cc-pCV5Z geometries for the aromatic heterocycles pyrimidine and pyridazine. Herein, that same analysis is extended to the fundamental aromatic molecule benzene, using published experimental spectroscopic data for a total of 11 available isotopologues. The incorporation of rotational constants from all of these isotopologues and CCSD(T) corrections to address the impacts of both the vibration-rotation interaction and electron-mass distribution results in a highly precise and accurate reSE structure. The CCSD(T)/cc-pCV5Z optimized geometry has been further corrected to address a finite basis set, untreated electron correlation, relativistic effects, and a breakdown of the Born-Oppenheimer approximation. This analysis achieves outstanding agreement between the re (BTE) and reSE structural parameters of benzene to a highly satisfying level (0.0001 Å), an agreement that surpasses our recently published structures of the aforementioned nitrogen-substituted benzene analogues. The D6h geometry of benzene is now known to an unprecedented precision: RC-C = 1.3913 (1) Å and RC-H = 1.0809 (1) Å. The mutual agreement between theory and experiment presented in this work validates both, substantially resolving all discrepancies between the reSE and theoretical re structures available in the literature.

Improved semi-experimental equilibrium structure and high-level theoretical structures of ketene.

The millimeter-wave rotational spectrum of ketene (H2C=C=O) has been collected and analyzed from 130 to 750 GHz, providing highly precise spectroscopic constants from a sextic, S-reduced Hamiltonian in the Ir representation. The chemical synthesis of deuteriated samples allowed spectroscopic measurements of five previously unstudied ketene isotopologues. Combined with previous work, these data provide a new, highly precise, and accurate semi-experimental (reSE) structure for ketene from 32 independent moments of inertia. This reSE structure was determined with the experimental rotational constants of each available isotopologue, together with computed vibration-rotation interaction and electron-mass distribution corrections from coupled-cluster calculations with single, double, and perturbative triple excitations [CCSD(T)/cc-pCVTZ]. The 2σ uncertainties of the reSE parameters are ≤0.0007 Å and 0.014° for the bond distances and angle, respectively. Only S-reduced spectroscopic constants were used in the structure determination due to a breakdown in the A-reduction of the Hamiltonian for the highly prolate ketene species. All four reSE structural parameters agree with the "best theoretical estimate" (BTE) values, which are derived from a high-level computed re structure [CCSD(T)/cc-pCV6Z] with corrections for the use of a finite basis set, the incomplete treatment of electron correlation, relativistic effects, and the diagonal Born-Oppenheimer breakdown. In each case, the computed value of the geometric parameter lies within the statistical experimental uncertainty (2σ) of the corresponding semi-experimental coordinate. The discrepancies between the BTE structure and the reSE structure are 0.0003, 0.0000, and 0.0004 Å for rC-C, rC-H, and rC-O, respectively, and 0.009° for θC-C-H.

Carbon Condensation via [4 + 2] Cycloaddition of Highly Unsaturated Carbon Chains.

We present computational studies of reaction pathways for alkyne/polyyne dimerization that represent plausible early steps in mechanisms for carbon condensation. A previous computational study of the ring coalescence and annealing model of C60 formation revealed that a 1,4-didehydrobenzocyclobutadiene intermediate (p-benzyne derivative) has little to no barrier to undergoing an unproductive retro-Bergman cyclization, which brings into question the relevance of that reaction pathway. The current study investigates an alternative model, which proceeds through an initial [4 + 2] cycloaddition instead of a [2 + 2] cycloaddition. In this pathway, the problematic intermediate is avoided, with the reaction proceeding via a (potentially) more kinetically stable tetradehydronaphthalene derivative. The computational studies of the [2 + 2] and [4 + 2] model systems, with increasing alkyne substitutions, reveal that the para-benzyne diradical of the [4 + 2] pathway has a significantly greater barrier to ring opening than the analogous intermediates of the [2 + 2] pathway and that alkyne substitution has little effect on this important barrier. These studies employ spin-flip, time-dependent density functional theory (SF-TDDFT) to provide suitable treatment of open-shell diradical intermediates.

Parent Management Training Augmentation to Address Coercive and Disruptive Behavior in Cognitive-Behavioral Therapy for Pediatric Obsessive-Compulsive Disorder.

Coercive and disruptive behaviors commonly interfere with cognitive-behavioral therapy (CBT) trials among youths with obsessive-compulsive disorder (OCD). Although evidence supports parent management training (PMT) for reducing disruptive behavior, no group-based PMT interventions exist for OCD-related disruptive behaviors. We studied feasibility and effectiveness of group-based adjunctive PMT among non-randomized, OCD-affected families receiving family-based group CBT. Linear mixed models estimated treatment effects across OCD-related and parenting outcomes at post-treatment and 1-month follow-up. Treatment response for 37 families receiving CBT + PMT (Mage = 13.90) was compared to 80 families receiving only CBT (Mage = 13.93). CBT + PMT was highly accepted by families. Families who received CBT + PMT had improved disruptive behaviors, parental distress tolerance, and other OCD-related outcomes. OCD-related outcomes did not significantly differ between groups. Results support CBT + PMT as effective treatment for pediatric OCD that may not provide incremental benefits beyond CBT alone. Future research should determine feasible and effective ways to incorporate key PMT components into CBT-based interventions.

Millimeter-Wave and High-Resolution Infrared Spectroscopy of 2-Furonitrile─A Highly Polar Substituted Furan.

The rotational spectrum of 2-furonitrile (2-cyanofuran) has been obtained from 140 to 750 GHz, capturing its most intense rotational transitions at ambient temperature. 2-Furonitrile is one of two isomeric cyano-substituted furan derivatives, both of which possess a substantial dipole moment due to the cyano group. The large dipole of 2-furonitrile allowed over 10 000 rotational transitions of its ground vibrational state to be observed and least-squares fit to partial octic, A- and S-reduced Hamiltonians with low statistical uncertainty (σfit = 40 kHz). The high-resolution infrared spectrum, obtained at the Canadian Light Source, allowed for accurate and precise determination of the band origins of its three lowest-energy fundamental modes (ν24, ν17, and ν23). Similar to other cyanoarenes, the first two fundamental modes (ν24, A″, and ν17, A', for 2-furonitrile) form an a- and b-axis Coriolis-coupled dyad. More than 7000 transitions from each of these fundamental states were fit to an octic A-reduced Hamiltonian (σfit = 48 kHz), and the combined spectroscopic analysis determines fundamental energies of 160.1645522 (26) cm-1 and 171.9436561 (25) cm-1 for ν24 and ν17, respectively. The least-squares fitting of this Coriolis-coupled dyad required 11 coupling terms, Ga, GaJ, GaK, GaJJ, GaKK, Fbc, FbcJ, FbcK, Gb, GbJ, and FacK. Using both the rotational and high-resolution infrared spectra, a preliminary least-squares fit was obtained for ν23, providing its band origin of 456.7912716 (57) cm-1. The transition frequencies and spectroscopic constants provided in this work, when combined with theoretical or experimental nuclear quadrupole coupling constants, will provide the foundation for future radioastronomical searches for 2-furonitrile across the frequency range of currently available radiotelescopes.

Vibrationally excited states of 1H- and 2H-1,2,3-triazole isotopologues analyzed by millimeter-wave and high-resolution infrared spectroscopy with approximate state-specific quartic distortion constants.

In this work, we present the spectral analysis of 1H- and 2H-1,2,3-triazole vibrationally excited states alongside provisional and practical computational predictions of the excited-state quartic centrifugal distortion constants. The low-energy fundamental vibrational states of 1H-1,2,3-triazole and five of its deuteriated isotopologues ([1-2H]-, [4-2H]-, [5-2H]-, [4,5-2H]-, and [1,4,5-2H]-1H-1,2,3-triazole), as well as those of 2H-1,2,3-triazole and five of its deuteriated isotopologues ([2-2H]-, [4-2H]-, [2,4-2H]-, [4,5-2H]-, and [2,4,5-2H]-2H-1,2,3-triazole), are studied using millimeter-wave spectroscopy in the 130-375 GHz frequency region. The normal and [2-2H]-isotopologues of 2H-1,2,3-triazole are also analyzed using high-resolution infrared spectroscopy, determining the precise energies of three of their low-energy fundamental states. The resulting spectroscopic constants for each of the vibrationally excited states are reported for the first time. Coupled-cluster vibration-rotation interaction constants are compared with each of their experimentally determined values, often showing agreement within 500 kHz. Newly available coupled-cluster predictions of the excited-state quartic centrifugal distortion constants based on fourth-order vibrational perturbation theory are benchmarked using a large number of the 1,2,3-triazole tautomer isotopologues and vibrationally excited states studied.

Predictors of problematic adult alcohol, cannabis, and other substance use: A longitudinal study of two samples.

This study examined whether a key set of adolescent and early adulthood risk factors predicts problematic alcohol, cannabis, and other substance use in established adulthood. Two independent samples from the Child Development Project (CDP; n = 585; 48% girls; 81% White, 17% Black, 2% other race/ethnicity) and Fast Track (FT; n = 463; 45% girls; 52% White, 43% Black, 5% other race/ethnicity) were recruited in childhood and followed through age 34 (CDP) or 32 (FT). Predictors of substance use were assessed in adolescence based on adolescent and parent reports and in early adulthood based on adult self-reports. Adults reported their own problematic substance use in established adulthood. In both samples, more risk factors from adolescence and early adulthood predicted problematic alcohol use in established adulthood (compared to problematic cannabis use and other substance use). Externalizing behaviors and prior substance use in early adulthood were consistent predictors of problematic alcohol and cannabis misuse in established adulthood across samples; other predictors were specific to the sample and type of substance misuse. Prevention efforts might benefit from tailoring to address risk factors for specific substances, but prioritizing prevention of externalizing behaviors holds promise for preventing both alcohol and cannabis misuse in established adulthood.

Predictive Validity of Adolescent Callous-Unemotional Traits and Conduct Problems with Respect to Adult Outcomes: High- and Low-Risk Samples.

Current understanding of the predictive validity of callous-unemotional (CU) traits is limited by (a) the focus on externalizing psychopathology and antisocial behaviors, (b) a lack of long-term prospective longitudinal data, (c) samples comprised of high-risk or low-risk individuals. We tested whether adolescent CU traits and conduct problems were associated with theoretically relevant adult outcomes 12-18 years later. Participants were drawn from two studies: higher-risk Fast Track (FT; n = 754) and lower-risk Child Development Project (CDP; n = 585). FT: conduct problems positively predicted externalizing and internalizing psychopathology and partner violence, and negatively predicted health, wellbeing, and education. Three conduct problems × CU traits interaction effects were also found. CDP: CU traits positively predicted depression and negatively predicted health and education; conduct problems positively predicted externalizing and internalizing psychopathology and substance use, and negatively predicted wellbeing. CU traits did not provide incremental predictive validity for multiple adult outcomes relative to conduct problems.

Latent classes of oppositional defiant disorder in adolescence and prediction to later psychopathology.

Current conceptualizations of oppositional defiant disorder (ODD) place the symptoms of this disorder within three separate but related dimensions (i.e., angry/irritable mood, argumentative/defiant behavior, vindictiveness). Variable-centered models of these dimensions have yielded discrepant findings, limiting their clinical utility. The current study utilized person-centered latent class analysis based on self and parent report of ODD symptomatology from a community-based cohort study of 521 adolescents. We tested for sex, race, and age differences in the identified classes and investigated their ability to predict later symptoms of depression and conduct disorder (CD). Diagnostic information regarding ODD, depression, and CD were collected annually from adolescents (grades 6-9; 51.9% male; 48.7% White, 28.2% Black, 18.5% Asian) and a parent. Results provided evidence for three classes of ODD (high, medium, and low endorsement of symptoms), which demonstrated important developmental differences across time. Based on self-report, Black adolescents were more likely to be in the high and medium classes, while according to parent report, White adolescents were more likely to be in the high and medium classes. Membership in the high and medium classes predicted later increases in symptoms of depression and CD, with the high class showing the greatest risk for later psychopathology.

Developmental Precursors of Primary and Secondary Callous-Unemotional Traits in Youth.

There is growing evidence of diverse etiological pathways to the development of callous-unemotional (CU) traits, known as primary and secondary CU variants. The purpose of the present study was to extend previous cross-sectional research and examine theoretical predictors of CU variants prospectively from childhood to adolescence. Participants included high-risk control and normative samples from the Fast Track project (N = 754, male = 58%, Black = 46%). Using structural equation modelling, primary CU traits, identified in early adolescence, were associated with higher levels of childhood emotion regulation and lower levels of prosocial behavior. Secondary CU traits were associated with lower levels of childhood emotion regulation and low parental warmth, but not prosocial behaviour. Neither CU variant was related to harsh parenting. Parental warmth moderated emotion regulation and prosocial behavior on secondary CU traits. Results were not moderated by sex. A greater understanding of theoretical developmental precursors of CU variants may better guide intervention efforts.

Primary and secondary callous-unemotional traits in adolescence are associated with distinct maladaptive and adaptive outcomes in adulthood.

While phenotypically indistinguishable with respect to callousness, individuals with primary and secondary callous-unemotional (CU) traits may show different developmental outcomes. This research predominantly comprised cross-sectional studies of male participants with a focus on maladaptive correlates. Thus, the present study examined whether youth with primary and secondary CU traits identified in Grade 7 reported distinct maladaptive outcomes (internalizing, externalizing, and substance use problems; criminal offenses; and sexual and partner experiences) and adaptive outcomes (health and wellbeing, education, and employment) in adulthood at age 25. We also examined sex differences. Participants included the high-risk control and normative samples from the Fast Track project (N = 754, male = 58%, Black = 46%). Youth with secondary CU traits reported higher levels of adult internalizing and externalizing psychopathology, a greater number of sexual partners and risky sexual behavior, and a greater number of violent offenses, compared with individuals with primary CU traits and those with low CU and anxiety symptoms. Conversely, youth with primary CU traits and low symptoms had higher wellbeing and happiness scores than those with secondary CU traits. Finally, there was differentiation on outcomes between female primary and secondary CU variants and male primary and secondary CU variants.