Association of congenital heart disease and neurodevelopmental disorders: an observational and Mendelian randomization study.

BACKGROUND: This study aims to thoroughly study the connection between congenital heart disease (CHD) and neurodevelopmental disorders (NDDs) through observational and Mendelian randomization (MR) designs. METHODS: This observational study uses data from the National Survey of Children's Health (2020-2021). Multivariable logistic regression and propensity score matching (PSM) were performed to analyze the association. PSM was used to minimize bias for covariates such as age, race, gender, maternal age, birth weight, concussion or brain injury, preterm birth, cerebral palsy, Down syndrome, and other inherited conditions. In MR analyses, inverse variance-weighted measures, weighted median, and MR-Egger were employed to calculate causal effects. RESULTS: A total of 85,314 children aged 0-17 were analyzed in this study. In regression analysis, CHD (p = 0.04), the current heart condition (p = 0.03), and the severity of current heart condition (p < 0.05) had a suggestive association with speech or language disorders. The severity of current heart condition (p = 0.08) has a potential statistically significant association with attention deficit hyperactivity disorder(ADHD). In PSM samples, ADHD(p = 0.003), intellectual disability(p = 0.012), and speech or language disorders(p < 0.001) were all significantly associated with CHD. The severity of current heart condition (p < 0.001) also had a significant association with autism. MR analysis did not find causality between genetically proxied congenital cardiac malformations and the risk of NDDs. CONCLUSIONS: Our study shows that children with CHD have an increased risk of developing NDDs. Heart conditions currently and severity of current heart conditions were also significantly associated with these NDDs. In the future, we need to try more methods to clarify the causal relationship between CHD and NDDs.

Structure sensitivity of CO oxidation on Co3O4: a DFT study.

The reaction mechanism of CO oxidation on the Co(3)O(4) (110) and Co(3)O(4) (111) surfaces is investigated by means of spin-polarized density functional theory (DFT) within the GGA+U framework. Adsorption situation and complete reaction cycles for CO oxidation are clarified. The results indicate that 1) the U value can affect the calculated energetic result significantly, not only the absolute adsorption energy but also the trend in adsorption energy; 2) CO can directly react with surface lattice oxygen atoms (O(2f)/O(3f)) to form CO(2) via the Mars-van Krevelen reaction mechanism on both (110)-B and (111)-B; 3) pre-adsorbed molecular O(2) can enhance CO oxidation through the channel in which it directly reacts with molecular CO to form CO(2) [O(2)(a)+CO(g)→CO(2)(g)+O(a)] on (110)-A/(111)-A; 4) CO oxidation is a structure-sensitive reaction, and the activation energy of CO oxidation follows the order of Co(3)O(4) (111)-A(0.78 eV)>Co(3)O(4) (111)-B (0.68 eV)>Co(3)O(4) (110)-A (0.51 eV)>Co(3)O(4) (110)-B (0.41 eV), that is, the (110) surface shows higher reactivity for CO oxidation than the (111) surface; 5) in addition to the O(2f), it was also found that Co(3+) is more active than Co(2+), so both O(2f) and Co(3+) control the catalytic activity of CO oxidation on Co(3)O(4), as opposed to a previous DFT study which concluded that either Co(3+) or O(2f) is the active site.

Selective oxidation of styrene on an oxygen-adsorbed Cu(111): a comparison with Au(111).

The reaction mechanism for the styrene selective oxidation on the oxygen preadsorbed Cu(111) surface has been studied by the density functional theory calculation with the periodic slab model. The calculated result indicated that the process includes two steps: forming the oxametallacycle intermediate (OMMS) and then producing the products. In addition, it was found that the second step, from OMMS to the product, is the rate-controlling step, which is similar to the previous work of ethylene selective oxidation. The present result indicated that the selectivity towards the formation of styrene epoxide on Cu(111) is much higher than that on Au(111). More importantly, we found that the mechanism via the OMMS (2) (i.e., the preadsorbed atomic oxygen bound to the CH(2) group involved in C(6)H(5)-CH=CH(2)) to produce styrene epoxide is kinetically favored than that of OMMS (1). We also found that the selectivity toward the styrene epoxide formation on Cu(2)O is similar to that of Cu(111).

Selective oxidation of styrene on an oxygen-adsorbed Au(111): A density functional theory study.

The reaction mechanism for the styrene selective oxidation on the oxygen preadsorbed Au(111) surface has been studied by the density functional theory calculation with the periodic slab model. The calculated results showed that the process of reaction includes two steps: forming the oxametallacycle intermediate (OMME) and then producing the products. It was found that the second step, from OMME to product is the rate-controlling step, which is similar to ethylene selective oxidation on Ag. Importantly, the present density-functional-theory calculation results suggested that the mechanism via the OMME (2) (i.e. the preadsorbed atomic oxygen bound to the CH2 group involved in C6H5--CH=CH2) to produce styrene epoxide is kinetically favored than that of OMME (1).

Cluster and periodic DFT calculations: the adsorption of atomic nitrogen on M(111) (M = Cu, Ag, Au) surfaces.

First-principle density functional calculations with cluster and slab models have been performed to investigate adsorption and thermally activated atomic nitrogen on M(111) (M = Cu, Ag, Au) surfaces. Optimized results indicate that the basis set of the N atom has a distinct effect on the adsorption energy but an indistinct one on the equilibrium distance. For the N/M(111) adsorption systems studied here, the threefold face centered cubic (fcc) hollow site is found to be the most stable adsorption site. The reason for the fcc site is that the perfected adsorption site has been explained by the density of states (DOS) analysis, that is, that N(2p) has the smallest DOS population near the Fermi level on the fcc site as compared with other adsorption sites. The variations of the adsorption energy as a function of adsorption site are similar and in the following order of N-M(111) binding strengths on a given site: Cu(111) > Ag(111) > Au(111). It is found that the N atom forms essentially an ionic bond for the most stable site. Large contributions between the M(ns) and N(2p) orbitals (n = 4, 5, and 6 for Cu, Ag, and Au, respectively) are found for the cluster model at the B3LYP/LANL2DZ-6-31G(d,p) level and also found in the slab DFT-GGA calculation results, which are the main characteristics of M-N bonds. At last, the dissociation of N2 on Cu(111) and Au(111) has also been obtained in this work, and the results showed that the dissociation of N2 on Cu(111) is more active than that on the Au(111) surface.

Selective oxidation of propylamine on oxygen-covered Au(111): a DFT study.

The reaction mechanism for selective oxidation of propylamine on oxygen-covered gold has been studied by the density functional theory (DFT) and generalized gradient approximation (GGA) with slab model. Our calculation results indicated that the adsorption energy of propylamine decreases with the increasing oxygen coverage, that is -0.38, -0.20 and -0.10 eV on clean, 2/9 monolayer (ML) and 2/3 monolayer (ML) oxygen, respectively. The adsorption energies of the intermediates also have the trend of the gradual lower. The present work also indicated that the final product distribution depends on the oxygen coverage: propylamine undergoes N-H bond and C-H bond cleavage to produce propionitrile and water at low-oxygen-coverage (θ(o) = 2/9 ML), and to yield propionitrile, propionaldehyde and water at high-oxygen-coverage (θ(o) = 2/3 ML). The energy barrier of the first step of propyamine oxidation (CH(3)CH(2)CH(2)NH(2) → CH(3)CH(2)CH(2)NH) is 0.16 eV (θ(o) = 2/9 ML) and 0.38 eV (θ(o) = 2/3 ML). On the second step, the barrier energy is 0.16 (θ(o) = 2/9 ML) and 0.25 (θ(o) = 2/3 ML) eV of CH(3)CH(2)CH(2)NH → CH(3)CH(2)CH(2)N, next both C-H breakage and the barrier energy is 0.20 eV (CH(3)CH(2)CH(2)N → CH(3)CH(2)CHN) and 0.25 eV (CH(3)CH(2)CHN → CH(3)CH(2)CN) on low oxygen coverage, and 0.15 eV (CH(3)CH(2)CH(2)N → CH(3)CH(2)CHN) and 0.26 eV(CH(3)CH(2)CHN → CH(3)CH(2)CN) on the high oxygen coverage. The additional reaction step of CH(3)CH(2)CHN → CH(3)CH(2)CHO occurs on the high oxygen coverage, and the associated barrier is 0.41 eV. The calculation results show that the oxidation of propylamine can occur at room temperature due to the lower energy barrier. Furthermore, it was found that the energy barrier for the possible reaction steps at the low oxygen coverage is generally smaller than that on high oxygen coverage, which agrees with the experimental results.

Adsorption of atoms on cu surfaces: a density functional theory study.

The chemisorption of atoms (H, N, S, O, and C) on Cu surfaces has been systematically studied by the density functional theory generalized gradient approximation method with the slab model. Our calculated results indicate that the orders of the adsorption energy are H < N < S < O < C on Cu(111) and H < N < O < S < C on Cu(110) and Cu(100). Furthermore, the adsorption energies of the given atoms on Cu(100) are larger than those on Cu(111) and Cu(110). The preferred adsorption sites are a 3-fold hollow site on Cu(111) and a 4-fold hollow site on Cu(100), but the preferred adsorption sites on Cu(110) are different for different adatoms. The energy, as well as the geometry, is in good agreement with the experimental and other theoretical data. In addition, this study focuses on the electronic and geometric properties of the metal-atom (M-A) bond to explain the difference in adsorption energies among adatoms. A detailed investigation of the density of states curves explains the nature of the most stable site. Finally, we test the effect of the coverage and find that the surface coverage has no influence on the preferred adsorption sites of the given adatoms on Cu(110) with the exception of hydrogen and oxygen, but has much influence on the value of the adsorption energy.