Time-resolved gas-phase kinetic and quantum chemical studies of the reaction of silylene with oxygen

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with O-2. The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at five temperatures in the range 297-600 K. The second order rate constants at 10 Torr were fitted to the Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-11.08 +/- 0.04) + (1.57 +/- 0.32 kJ mol(-1))/RT ln10 The decrease in rate constant values with increasing temperature, although systematic is very small. The rate constants showed slight increases in value with pressure at each temperature, but this was scarcely beyond experimental uncertainty. From estimates of Lennard-Jones collision rates, this reaction is occurring at ca. 1 in 20 collisions, almost independent of pressure and temperature. Ab initio calculations at the G3 level backed further by multi-configurational (MC) SCF calculations, augmented by second order perturbation theory (MRMP2), support a mechanism in which the initial adduct, H2SiOO, formed in the triplet state (T), undergoes intersystem crossing to the more stable singlet state (S) prior to further low energy isomerisation processes leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are H2O + SiO. The decomposition of the intermediate cyclo-siladioxirane, via O-O bond fission, plays an important role in the overall process. The bottleneck for the overall process appears to be the T -> S process in H2SiOO. This process has a small spin orbit coupling matrix element, consistent with an estimate of its rate constant of 1 x 10(9) s(-1) obtained with the aid of RRKM theory. This interpretation preserves the idea that, as in its reactions in general, SiH2 initially reacts at the encounter rate with O-2. The low values for the secondary reaction barriers on the potential energy surface account for the lack of an observed pressure dependence. Some comparisons are drawn with the reactions of CH2 + O-2 and SiCl2 + O-2

Influence of Phytoestrogens on Skeletal Muscle Structure

Constant increase of meat quantity along with ensuring its high quality are nowadays being the priority requirements of the market towards modern meat production. With selection and animal nutrition as the basic mechanisms regulating the quantity and quality of meat, in recent years more attention has been devoted to investigations of the effects of different chemical compounds on muscle tissue, while monitoring their potential negative effects on both animals and humans as the end consumers. A group of compounds that is being increasingly studied in the last years are phytoestrogens – substances of plant origin with chemical structure very similar to estrogen, capable of causing either estrogenic or anti-estrogenic reactions in the organism. The most studied phytoestrogens are daidzein and genistein, and due to their ability to mimic estrogen in the body, they are thought to be able of influencing growth and carcass composition in farm animals. This paper gives an overview of the newer results on the effects of phytoestrogens genistein and daidzein on skeletal muscle tissue in farm animals

The Effective Fragment Molecular Orbital Method for Fragments Connected by Covalent Bonds

We extend the effective fragment molecular orbital method (EFMO) into treating fragments connected by covalent bonds. The accuracy of EFMO is compared to FMO and conventional ab initio electronic structure methods for polypeptides including proteins. Errors in energy for RHF and MP2 are within 2 kcal/mol for neutral polypeptides and 6 kcal/mol for charged polypeptides similar to FMO but obtained two to five times faster. For proteins, the errors are also within a few kcal/mol of the FMO results. We developed both the RHF and MP2 gradient for EFMO. Compared to ab initio, the EFMO optimized structures had an RMSD of 0.40 and 0.44 {\AA} for RHF and MP2, respectively.Comment: Revised manuscrip

Importance of Early Intervention in Reducing Autistic Symptoms and Speech–Language Deficits in Children with Autism Spectrum Disorder

The intervention focused on starting treatment at an early age to develop the child’s full potential, which is known as early intervention. Given that autistic symptoms and language deficits occur at an early age and affect other areas of development in children with autistic spectrum disorder, we wanted to examine if early intervention is more effective in the reduction in autistic symptoms and language deficits in children aged 36–47 months old when compared to children 48–60 months old. The sample consisted of 29 children diagnosed with ASD who were admitted for integrative therapy. All participants were divided into two groups based on age: G1: 36–47 months old children, and G2: 48–60 months old children. To estimate the presence of autistic symptoms, we used the GARS-3, and for the assessment of speech–language abilities, we used the subscale Estimated Speech and Language Development (ESLD). Our results regarding the effect of the group on the difference in the scores at two time points showed that there was a statistically significant effect of the group on the reduction in autistic symptoms (p 0.05). Our study highlights the importance of emphasizing the exact age when using the terms “early intervention” and “early development” in future studies and practice because it is necessary to determine and establish guidelines about which particular ages are crucial for starting treatment in certain developmental aspects

PHIP - a novel candidate breast cancer susceptibility locus on 6q14.1

Most non-BRCA1/2 breast cancer families have no identified genetic cause. We used linkage and haplotype analyses in familial and sporadic breast cancer cases to identify a susceptibility locus on chromosome 6q. Two independent genome-wide linkage analysis studies suggested a 3 Mb locus on chromosome 6q and two unrelated Swedish families with a LOD > 2 together seemed to share a haplotype in 6q14.1. We hypothesized that this region harbored a rare high-risk founder allele contributing to breast cancer in these two families. Sequencing of DNA and RNA from the two families did not detect any pathogenic mutations. Finally, 29 SNPs in the region were analyzed in 44,214 cases and 43,532 controls from BCAC, and the original haplotypes in the two families were suggested as low-risk alleles for European and Swedish women specifically. There was also some support for one additional independent moderate-risk allele in Swedish familial samples. The results were consistent with our previous findings in familial breast cancer and supported a breast cancer susceptibility locus at 6q14.1 around the PHIP gene.Peer reviewe

Large-Scale Controls of the Surface Water Balance Over Land-Insights From a Systematic Review and Meta-Analysis

The long-term surface water balance over land is described by the partitioning of precipitation (P) into runoff and evapotranspiration (ET), and is commonly characterized by the ratio ET/P. The ratio between potential evapotranspiration (PET) and P is explicitly considered to be the primary control of ET/P within the Budyko framework, whereas all other controls are often integrated into a single parameter, ω. Although the joint effect of these additional controlling factors of ET/P can be significant, a detailed understanding of them is yet to be achieved. This study therefore introduces a new global dataset for the long-term mean partitioning of P into ET and runoff in 2733 catchments, which is based on in-situ observations and assembled from a systematic examination of peer-reviewed studies. A total of 26 controls of ET/P that are proposed in the literature are assessed using the new dataset. Results reveal that: (i) factors controlling ET/P vary between regions with different climate types; (ii) controls other than PET/P explain at least 35% of the ET/P variance in all regions, and up to ∼90% in arid climates; (iii) among these, climate factors and catchment slope dominate over other landscape characteristics; and (iv) despite the high attention that vegetation-related indices receive as controls of ET/P, they are found to play a minor and often non-significant role. Overall, this study provides a comprehensive picture on factors controlling the partitioning of P, with valuable insights for model development, watershed management, and the assessment of water resources around the globe

Singular Support of a Vertex Algebra and the Arc Space of Its Associated Scheme

Book Subtitle: In Honour of the 75th Birthday of Tony JosephSeries Title: Progress in Mathematics (vol. 330)Attached to a vertex algebra V are two geometric objects. The associated scheme of V isthespectrum of Zhu's Poisson algebra Rv.Thesingular support of V is the spectrum of the associated graded algebra gr(V) with respect to Li's canonical decreasing filtration. There is a closed embedding from the singular support to the arc space of the associated scheme, which is an isomorphism in many interesting cases. In this note we give an example of a non-quasi-lisse vertex algebra whose associated scheme is reduced, for which the isomorphism is not true as schemes but true as varieties

Introduction to a culturally sensitive measure of well-being: Combining life satisfaction and interdependent happiness across 49 different cultures

How can one conclude that well-being is higher in country A than country B, when well-being is being measured according to the way people in country A think about well-being? We address this issue by proposing a new culturally sensitive method to comparing societal levels of well-being. We support our reasoning with data on life satisfaction and interdependent happiness focusing on individual and family, collected mostly from students, across forty-nine countries. We demonstrate that the relative idealization of the two types of well-being varies across cultural contexts and are associated with culturally different models of selfhood. Furthermore, we show that rankings of societal well-being based on life satisfaction tend to underestimate the contribution from interdependent happiness. We introduce a new culturally sensitive method for calculating societal well-being, and examine its construct validity by testing for associations with the experience of emotions and with individualism-collectivism. This new culturally sensitive approach represents a slight, yet important improvement in measuring well-being.info:eu-repo/semantics/publishedVersio

Design and Implementation of Scientific Software Components to Enable Multiscale Modeling: The Effective Fragment Potential (QM/EFP) Method

The design and development of scientific software components to provide an interface to the effective fragment potential (EFP) methods are reported. Multiscale modeling of physical and chemical phenomena demands the merging of software packages developed by research groups in significantly different fields. Componentization offers an efficient way to realize new high performance scientific methods by combining the best models available in different software packages without a need for package readaptation after the initial componentization is complete. The EFP method is an efficient electronic structure theory based model potential that is suitable for predictive modeling of intermolecular interactions in large molecular systems, such as liquids, proteins, atmospheric aerosols, and nanoparticles, with an accuracy that is comparable to that of correlated ab initio methods. The developed components make the EFP functionality accessible for any scientific component-aware software package. The performance of the component is demonstrated on a protein interaction model, and its accuracy is compared with results obtained with coupled cluster methods

Self-construals predict personal life satisfaction with different strengths across societal contexts differing in national wealth and religious heritage

We explore to what extent previously observed pan-cultural association between dimensions of self-construal and personal life satisfaction (PLS) may be moderated by three national-contextual variables: national wealth, economic inequality, and religious heritage. The results showed that Self-reliance (vs. dependence on others) predicted PLS positively in poorer countries but negatively in richer countries. Connectedness to others (vs. self-containment) predicted PLS more strongly in Protestant-heritage countries. Self-expression (vs. harmony) predicted PLS more weakly (and non-significantly) in Muslim-heritage countries. In contrast, previously reported associations of self-direction (vs. reception-to-influence), consistency (vs. variability), and decontextualized (vs. contextualized) self-understanding with personal life satisfaction were not significantly moderated by these aspects of societal context. These results show the importance of considering the impact of national religious and economic context.info:eu-repo/semantics/acceptedVersio