Parental Age in Relation to Offspring's Neurodevelopment.

Objective: Advanced parenthood increases the risk of severe neurodevelopmental disorders like autism, Down syndrome and schizophrenia. Does advanced parenthood also negatively impact offspring's general neurodevelopment?Method: We analyzed child-, father-, mother- and teacher-rated attention-problems (N = 38,024), and standardized measures of intelligence (N = 10,273) and educational achievement (N = 17,522) of children from four Dutch population-based cohorts. The mean age over cohorts varied from 9.73-13.03. Most participants were of Dutch origin, ranging from 58.7%-96.7% over cohorts. We analyzed 50% of the data to generate hypotheses and the other 50% to evaluate support for these hypotheses. We aggregated the results over cohorts with Bayesian research synthesis.Results: We mostly found negative linear relations between parental age and attention-problems, meaning that offspring of younger parents tended to have more attention problems. Maternal age was positively and linearly related to offspring's IQ and educational achievement. Paternal age showed an attenuating positive relation with educational achievement and an inverted U-shape relation with IQ, with offspring of younger and older fathers at a disadvantage. Only the associations with maternal age remained after including SES. The inclusion of child gender in the model did not affect the relation between parental age and the study outcomes.Conclusions: Effects were small but significant, with better outcomes for children born to older parents. Older parents tended to be of higher SES. Indeed, the positive relation between parental age and offspring neurodevelopmental outcomes was partly confounded by SES.

Testing sampling bias in estimates of adolescent social competence and behavioral control.

In 5 of the 6 large Dutch developmental cohorts investigated here, lower SES adolescents are underrepresented and higher SES adolescents overrepresented. With former studies clearly revealing differences between SES strata in adolescent social competence and behavioral control, this misrepresentation may contribute to an overestimation of normative adolescent competence. Using a raking procedure, we used national census statistics to weigh the cohorts to be more representative of the Dutch population. Contrary to our expectations, in all cohorts, little to no differences between SES strata were found in the two outcomes. Accordingly, no differences between weighted and unweighted mean scores were observed across all cohorts. Furthermore, no clear change in correlations between social competence and behavioral control was found. These findings are most probably explained by the fact that measures of SES in the samples were quite limited, and the low SES participants in the cohorts could not be considered as representative of the low SES groups in the general population. Developmental outcomes associated with SES may be affected by a raking procedure in other cohorts that have a sufficient number and sufficient variation of low SES adolescents.

Robust longitudinal multi-cohort results: The development of self-control during adolescence.

Longitudinal data from multiple cohorts may be analyzed by Bayesian research synthesis. Here, we illustrate this approach by investigating the development of self-control between age 13 and 19 and the role of sex therein in a multi-cohort, longitudinal design. Three Dutch cohorts supplied data: the Netherlands Twin Register (NTR; N = 21,079), Research on Adolescent Development and Relationships-Young (RADAR-Y; N = 497), and Tracking Adolescents' Individual Lives Survey (TRAILS; N = 2229). Self-control was assessed by one measure in NTR and RADAR-Y, and three measures in TRAILS. In each cohort, we evaluated evidence for competing informative hypotheses regarding the development of self-control. Subsequently, we aggregated this evidence over cohorts and measures to arrive at a robust conclusion that was supported by all cohorts and measures. We found robust evidence for the hypothesis that on average self-control increases during adolescence (i.e., maturation) and that individuals with lower initial self-control often experience a steeper increase in self-control (i.e., a pattern of recovery). From self-report, boys have higher initial self-control levels at age 13 than girls, whereas parents report higher self-control for girls.

Long range coupling between defect centres in inorganic nanostructures: valence alternation pairs in nanoscale silica.

Valence alternation pair (VAP) states are formed by a closed-shell combination of two space- and charge-separated topological defect centres. These pairs of defects, although historically invoked to explain the electronic properties of bulk inorganic glassy materials (e.g., amorphous silicon dioxide) via the concept of negative-U defects, have more recently been found in a number of theoretical studies of silica surfaces and nanoscale silica clusters. Using density functional theory we systematically probe the structure and internal stability of VAPs in a number of silica nanoclusters with respect to the separation of the two constituent defect centres. We find that VAP states in nanosilica are strongly stabilised by the attractive electrostatic interaction between their separated oppositely charged component defects such that VAPs can persist up to an internal separation of a least 1.5 nanometres. Beyond this distance VAPs become unstable with respect to an open-shell combination of topological defects, virtually indistinguishable from two isolated open-shell defect centres. Finally, we theoretically analyse the possibility of experimental observation of VAP states through their infra-red vibrational spectra.

The effect of local environment on photoluminescence: a time-dependent density functional theory study of silanone groups on the surface of silica nanostructures.

The optical absorption spectrum and lowest photoluminescence (PL) signal for silanone terminated silica nanostructures are studied using time-dependent density functional theory calculations on a range of realistic low energy silica nanocluster models. We show that the broad experimental absorption spectrum for silanone centers [V. A. Radtsig and I. M. Senchenya Russ. Chem. Bull. 45, 1849 (1996)] is most likely the result of a synergetic combination of inhomogeneous broadening, thermal broadening and the small energy differences between different excitations. We further demonstrate that upon relaxation of the excited state the excited electron and hole localize on only one silanone center, and that there is a clear and distinct link between the local environment of a silanone center and its absorption and PL spectra. Finally, we provide strong evidence that the silanone center does not have a double bond between the constituent silicon and oxygen atoms but rather can be probably more aptly described as the =Si(+)-O(-) charge-transfer species.

Optical excitations of defects in realistic nanoscale silica clusters: comparing the performance of density functional theory using hybrid functionals with correlated wavefunction methods.

Optical excitations of low energy silica (SiO(2))(4) clusters obtained by global optimization, as opposed to constructed by hand, are studied using a range of theoretical methods. By focusing on the lowest energy silica clusters we hope to capture at least some of the characteristic ways by which the dry surfaces of silica nanosystems preferentially terminate. Employing the six lowest energy (SiO(2))(4) cluster isomers, we show that they exhibit a surprisingly wide range of geometries, defects, and associated optical excitations. Some of the clusters show excitations localized on isolated defects, which are known from previous studies using hydrogen-terminated versions of the defect in question. Other clusters, however, exhibit novel charge-transfer excitations in which an electron transfers between two spatially separated defects. In these cases, because of the inherent proximity of the constituent defects due to the small cluster dimensions, the excitation spectrum is found to be very different from that of the same defects in isolation. Excitation spectra of all clusters were calculated using time-dependent density functional theory (TD-DFT) and delta-SCF DFT (DeltaDFT) methods employing two different hybrid density functionals (B3LYP and BB1K) differing essentially in the amount of incorporated Hartree-Fock-like exchange (HFLE). In all cases the results were compared with CASPT2 calculated values which are taken as a benchmark standard. In line with previous work, the spatially localized excitations are found to be well described by TD-DFT/B3LYP but which gives excitation energies that are significantly underestimated in the case of the charge-transfer excitations. The TD-DFT/BB1K combination in contrast is found to give generally good excitation energies for the lowest excited states of both localized and charge-transfer excitations. Finally, our calculations suggest that the increased quality of the predicted excitation spectra by adding larger amounts of HFLE is mainly due to an increased localization of the excited state associated with the elimination of spurious self-interaction inherent to (semi-)local DFT functionals.

Fully coordinated silica nanoclusters: (SiO2)N molecular rings.

A new form of finite silica with edge-sharing SiO2 units connected in a ring is proposed. High-level density-functional calculations for (SiO2)(N), N=4-14, show the rings to be energetically more stable than the corresponding (SiO2)(N) linear chains for N>11. The rings display frequency modes in remarkable agreement with infrared bands measured on dehydrated silica surfaces indicating their potential as models of strained extended silica systems. Silica rings, if synthesized, may also be useful precursors for new bulk-silica polymorphs with tubular or porous morphologies.