Hydrogenation of Polyesters to Polyether Polyols

The amount of plastic waste is continuously increasing. Besides conventional recycling, one solution to deal with this problem could be to use this waste as a resource for novel materials. In this study, polyesters are hydrogenated to give polyether polyols by using in situ-generated Ru-Triphos catalysts in combination with Lewis acids. The choice of Lewis acid and its concentration relative to the ruthenium catalyst are found to determine the selectivity of the reaction. Monitoring of the molecular weight during the reaction confirms a sequential mechanism in which the diols that are formed by hydrogenation are etherified to the polyethers. To probe the applicability of this tandem hydrogenation etherification approach, a range of polyester substrates is investigated. The oligoether products that form in these reactions have the chain lengths that are appropriate for application in the adhesives and coatings industries. This strategy makes polyether polyols accessible that are otherwise difficult to obtain from conventional fossil-based feedstocks. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

Atypical dorsolateral prefrontal activity in females with conduct disorder during effortful emotion regulation

BACKGROUND: Conduct disorder (CD), which is characterized by severe aggressive and antisocial behavior, is linked to emotion processing and regulation deficits. However, the neural correlates of emotion regulation are yet to be investigated in adolescents with CD. Furthermore, it remains unclear whether CD is associated with deficits in emotional reactivity, emotion regulation, or both. METHODS: We used functional magnetic resonance imaging to study effortful emotion regulation by cognitive reappraisal in 59 female adolescents 15 to 18 years of age (30 with a CD diagnosis and 29 typically developing (TD) control adolescents). RESULTS: Behaviorally, in-scanner self-report ratings confirmed successful emotion regulation within each group individually but significant group differences in emotional reactivity and reappraisal success when comparing the groups (CD < TD). Functional magnetic resonance imaging results revealed significantly lower activation in left dorsolateral prefrontal cortex and angular gyrus in CD compared with TD adolescents during emotion regulation, but no group differences for emotional reactivity. Furthermore, connectivity between left dorsolateral prefrontal cortex and the bilateral putamen, right prefrontal cortex, and amygdala was reduced in CD compared with TD adolescents during reappraisal. Callous-unemotional traits were unrelated to neural activation, but these traits correlated negatively with behavioral reports of emotional reactivity. CONCLUSIONS: Our results demonstrate reduced prefrontal brain activity and functional connectivity during effortful emotion regulation in female adolescents with CD. This sheds light on the neural basis of the behavioral deficits that have been reported previously. Future studies should investigate whether cognitive interventions are effective in enhancing emotion-regulation abilities and/or normalizing prefrontal and temporoparietal activity in female adolescents with CD

Co-Oligomers of Renewable and "Inert" 2-MeTHF and Propylene Oxide for Use in Bio-Based Adhesives

Commercial polyether polyols are usually obtained by the ring-opening polymerization of epoxides or tetrahydrofuran. 2-Methyl-tetrahydrofuran (2-MeTHF) could be an alternative bio-based building block for the synthesis of these polyols. Although 2-MeTHF cannot be polymerized, we did achieve the copolymerization of 2-MeTHF with propylene oxide (PO) using Lewis and Brønsted acids as catalysts and water or diols as initiators. The resulting polyether polyols have a molecular weight range, which allows their use as components for adhesives. The molar content of 2-MeTHF in the oligomers can be up to 48%. A 1:1 copolymer of 2-MeTHF and PO is produced when stoichiometric amounts of BF3·OEt2 are used. Here, the monomeric units in the chains alternate, but also cyclic or other nondiol products are formed that are detrimental to its further use in adhesives. Linear dihydroxyl-terminated polyether chains were formed when the heteropolyacid H3PW12O40·24H2O was used as a catalyst and a diol as an initiator. The formation of cyclic products can be drastically reduced when the accumulation of propylene oxide during the reaction is avoided. 1H NMR experiments indicate that the step of 2-MeTHF incorporation is the alkylation of 2-MeTHF by protonated PO. It was shown that the 2-MeTHF/PO copolymer had increased tensile strength compared to polypropylene glycol in a two-component adhesive formulation

Neuroendocrine Stress Response in Female and Male Youths With Conduct Disorder and Associations With Early Adversity

Objective: Conduct disorder (CD) involves aggressive and antisocial behavior and is associated with blunted cortisol stress response in male youths. Far less is known about cortisol stress responsivity in female youths with CD or other neuroendocrine responses in both sexes. Although CD is linked to early adversity, the possibility that neuroendocrine alterations may mediate the relationship between early adversity and CD has not been systematically investigated. Method: Within the European FemNAT-CD multi-site study, salivary cortisol, testosterone, the testosterone/cortisol ratio, oxytocin, and psychological stress response to a standardized psychosocial stress test (the Trier Social Stress Test [TSST]), together with common pre- and postnatal environmental risk factors, were investigated in 130 pubertal youths with CD (63% female, 9-18 years of age) and 160 sex-, age-, and puberty-matched healthy controls (HCs). Results: The TSST induced psychological stress in both CD and HCs. In contrast, female and male youths with CD showed blunted cortisol, testosterone, oxytocin, and testosterone/cortisol stress responses compared to HCs. These blunted stress responses partly mediated the relationship between environmental risk factors and CD. Conclusion: Findings from this unique sample, including many female youths with CD, provide evidence for a widespread attenuated stress responsivity of not only stress hormones, but also sex hormones and neuropeptides in CD and its subgroups (eg, with limited prosocial emotions). Results are the first to demonstrate blunted neuroendocrine stress responses in both female and male youths with CD. Early adversity may alter neuroendocrine stress responsivity. Biological mechanisms should be investigated further to pave the way for personalized intervention, thereby improving treatments for CD.</p

Testing the Ecophenotype Model:Cortical Structure Alterations in Conduct Disorder With Versus Without Childhood Maltreatment

Background:Childhood maltreatment is common in youths with conduct disorder (CD), and both CD and maltreatment have been linked to neuroanatomical alterations. Nonetheless, our understanding of the contribution of maltreatment to the neuroanatomical alterations observed in CD remains limited. We tested the applicability of the ecophenotype model to CD, which holds that maltreatment-related psychopathology is (neurobiologically) distinct from psychopathology without maltreatment.Methods:Surface-based morphometry was used to investigate cortical volume, thickness, surface area, and gyrification in a mixed-sex sample of participants with CD (n = 114) and healthy control subjects (HCs) (n = 146), ages 9 to 18 years. Using vertexwise general linear models adjusted for sex, age, total intracranial volume, and site, the control group was compared with the overall CD group and the CD subgroups with (n = 49) versus without (n = 65) maltreatment (assessed by the Children’s Bad Experiences interview). These subgroups were also directly compared.Results:The overall CD group showed lower cortical thickness in the right inferior frontal gyrus. CD youths with a history of maltreatment showed more widespread structural alterations relative to HCs, comprising lower thickness, volume, and gyrification in inferior and middle frontal regions. Conversely, CD youths with no history of maltreatment only showed greater left superior temporal gyrus folding relative to HCs. When contrasting the CD subgroups, those with maltreatment displayed lower right superior temporal gyrus volume, right precentral gyrus surface area, and gyrification in frontal, temporal, and parietal regions.Conclusions:Consistent with the ecophenotype model, findings indicated that CD youths with versus without maltreatment differ neurobiologically. This highlights the importance of considering maltreatment history in neuroimaging studies of CD and other disorders

Does the Relationship between Age and Brain Structure Differ in Youth with Conduct Disorder?

Conduct disorder (CD) is characterised by persistent antisocial and aggressive behaviour and typically emerges in childhood or adolescence. Although several authors have proposed that CD is a neurodevelopmental disorder, very little evidence is available about brain development in this condition. Structural brain alterations have been observed in CD, and some indirect evidence for delayed brain maturation has been reported. However, no detailed analysis of age-related changes in brain structure in youth with CD has been conducted. Using cross-sectional MRI data, this study aimed to explore differences in brain maturation in youth with CD versus healthy controls to provide further understanding of the neurodevelopmental processes underlying CD. 291 CD cases (153 males) and 379 healthy controls (160 males) aged 9–18 years (Mage = 14.4) were selected from the European multisite FemNAT-CD study. Structural MRI scans were analysed using surface-based morphometry followed by application of the ENIGMA quality control protocols. An atlas-based approach was used to investigate group differences and test for group-by-age and group-by-age-by-sex interactions in cortical thickness, surface area and subcortical volumes. Relative to healthy controls, the CD group showed lower surface area across frontal, temporal and parietal regions as well as lower total surface area. No significant group-by-age or group-by-age-by-sex interactions were observed on any brain structure measure. These findings suggest that CD is associated with lower surface area across multiple cortical regions, but do not support the idea that CD is associated with delayed brain maturation, at least within the age bracket considered here.</p

Maltreatment and parenting in youth with primary and secondary callous‐unemotional traits:Anxiety matters

Background: Youth with conduct disorder (CD) and high callous‐unemotional (CU) traits are not a homogenous group and can be disaggregated into primary and secondary subgroups. However, there are inconsistencies in defining primary and secondary subgroups, with some studies using anxiety, others using maltreatment and still others using both features to identify subgroups. There is a paucity of work comparing primary and secondary subgroups with typically developing (TD) youth on experiences of maltreatment and parenting as well as a lack of studies investigating sex differences. Methods: In a large sample of TD youth (n = 946, 66% female) and youth with CD (n = 885, 60% female), we used latent profile analysis in youth with CD aged between 9 and 18 years to address four aims: (i) to demonstrate how primary and secondary subgroup membership differs when anxiety, maltreatment, or both are used as continuous indicators, (ii) to compare primary and secondary subgroups with TD youth on abuse and neglect measures, and (iii) to compare primary and secondary subgroups with TD youth on parenting experiences, and (iv) to examine whether the results were consistent across sexes. Results: Anxiety without maltreatment yielded the best fitting and most theoretically interpretable classification of primary and secondary subgroups across both sexes (Bayesian information criterion = 17832.33, Entropy = 0.75, Lo‐Mendell‐Rubin: p &lt; 0.01). Compared with TD youth, youth with primary and secondary CU traits experienced greater levels of abuse and neglect (p &lt; 0.001, η2p = 0.04−0.16) and maladaptive parenting practices (p &lt; 0.001, η2p = 0.04−0.13). Youth with primary and secondary CU traits were equally high on levels of abuse, neglect, and maladaptive parenting (all p values &gt;0.05). Conclusions: We provide evidence that anxiety and maltreatment cannot be used interchangeably to identify youth with primary versus secondary CU traits. Anxiey yielded the best fitting and most theoretically interpretable classifications across both sexes. Our results signify the need for researchers and clinicians to adopt a unified approach to defining primary and secondary subgroups of CU traits using anxiety in both sexes

Sex-specific associations of basal steroid hormones and neuropeptides with Conduct Disorder and neuroendocrine mediation of environmental risk

Conduct Disorder (CD) is characterized by severe aggressive and antisocial behavior. The stress hormone system has frequently been investigated as a neurobiological correlate of CD, while other interacting neuroendocrine biomarkers of sex hormone or neuropeptide systems have rarely been studied, especially in females. We examined multiple basal neuroendocrine biomarkers in female and male adolescents with CD compared to healthy controls (HCs), and explored whether they mediate effects of environmental risk factors on CD. Within the FemNAT-CD study, salivary cortisol, alpha-amylase, testosterone, dehydroepiandrosterone-sulfate (DHEA-S), estradiol, progesterone, oxytocin, and arginine-vasopressin were measured under basal conditions in 166 pubertal adolescents with CD, and 194 sex-, age-, and puberty-matched HCs (60% females, 9-18 years). Further, environmental risk factors were assessed. Single hormone analyses showed higher DHEA-S, and lower estradiol and progesterone levels in both females and males with CD relative to HCs. When accounting for interactions between neuroendocrine systems, a male-specific sex hormone factor (testosterone/DHEA-S) predicted male CD, while estradiol and a stress-system factor (cortisol/alpha-amylase) interacting with oxytocin predicted female CD. Estradiol, progesterone, and oxytocin partly explained associations between early environmental risk and CD. Findings provide evidence for sex-specific associations between basal neuroendocrine measures and CD. Especially altered sex hormones (androgen increases in males, estrogen reductions in females) robustly related to CD, while basal stress-system measures did not. Early environmental risk factors for CD may act partly through their effects on the neuroendocrine system, especially in females. Limitations (e.g., basal neuroendocrine assessment, different sample sizes per sex, pubertal participants, exploratory mediation analyses) are discussed