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Imaging CF3I conical intersection and photodissociation dynamics with ultrafast electron diffraction
(2018)
Conical intersections play a critical role in excited-state dynamics of polyatomic molecules because they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wave-packet trajectories through these intersections directly. Here, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF3I molecules using ultrafast gas-phase electron diffraction. In the two-photon channel, we have mapped out the real-space trajectories of a coherent nuclear wave packet, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitation of both the umbrella and the breathing vibrational modes in the CF3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab initio nonadiabatic dynamics calculations.
Drawing on the social-ecological perspective, this longitudinal study investigated the potential moderating effect of gender in the relationships among Machiavellianism, popularity goals, and cyberbullying involvement (i.e. victimization, perpetration) among adolescents from China, Cyprus, India, and the United States.
There were 2,452 adolescents (M-age = 14.85; SD = .53; 13-16 years old; 49.1% girls) from China, Cyprus, India, and the United States included in this study.
They completed surveys on Machiavellianism, popularity goals, and cyberbullying victimization and perpetration during the fall of 2014 (Time 1). One year later, during the fall of 2015, adolescents completed surveys on cyberbullying victimization and perpetration.
Findings revealed that Machiavellianism and popularity goals were both associated positively with Time 2 cyberbullying victimization and perpetration for all adolescents. The associations between Machiavellianism and Time 2 cyberbullying perpetration and between popularity goals and Time 2 cyberbullying perpetration were stronger for Chinese and Indian boys than girls.
Opposite patterns were found for popularity goals and Time 2 cyberbullying perpetration for adolescents from the United States.
Gender did not moderate any of the associations for Cypriot adolescents or for Time 2 cyberbullying victimization.
The social-ecological perspective provides a useful understanding of how various contexts influence bullying.
Distinct cellular roles for PDCD10 define a gut-brain axis in cerebral cavernous malformation
(2019)
Cerebral cavernous malformation (CCM) is a genetic, cerebrovascular disease. Familial CCM is caused by genetic mutations in KRIT1, CCM2, or PDCD10. Disease onset is earlier and more severe in individuals with PDCD10 mutations. Recent studies have shown that lesions arise from excess mitogen-activated protein kinase kinase kinase 3 (MEKK3) signaling downstream of Toll-like receptor 4 (TLR4) stimulation by lipopolysaccharide derived from the gut microbiome. These findings suggest a gut-brain CCM disease axis but fail to define it or explain the poor prognosis of patients with PDCD10 mutations. Here, we demonstrate that the gut barrier is a primary determinant of CCM disease course, independent of microbiome configuration, that explains the increased severity of CCM disease associated with PDCD10 deficiency. Chemical disruption of the gut barrier with dextran sulfate sodium augments CCM formation in a mouse model, as does genetic loss of Pdcd10, but not Krit1, in gut epithelial cells. Loss of gut epithelial Pdcd10 results in disruption of the colonic mucosal barrier. Accordingly, loss of Mucin-2 or exposure to dietary emulsifiers that reduce the mucus barrier increases CCM burden analogous to loss of Pdcd10 in the gut epithelium. Last, we show that treatment with dexamethasone potently inhibits CCM formation in mice because of the combined effect of action at both brain endothelial cells and gut epithelial cells. These studies define a gut-brain disease axis in an experimental model of CCM in which a single gene is required for two critical components: gut epithelial function and brain endothelial signaling.
Multiple P-T-d-t paths reveal the evolution of the final Nuna assembly in northeast Australia
(2020)
The final assembly of the Mesoproterozoic supercontinent Nuna was marked by the collision of Laurentia and Australia at 1.60 Ga, which is recorded in the Georgetown Inlier of NE Australia. Here, we decipher the metamorphic evolution of this final Nuna collisional event using petrostructural analysis, major and trace element compositions of key minerals, thermodynamic modelling, and multi-method geochronology. The Georgetown Inlier is characterised by deformed and metamorphosed 1.70-1.62 Ga sedimentary and mafic rocks, which were intruded byc. 1.56 Ga old S-type granites. Garnet Lu-Hf and monazite U-Pb isotopic analyses distinguish two major metamorphic events (M1 atc. 1.60 Ga and M2 atc. 1.55 Ga), which allows at least two composite fabrics to be identified at the regional scale-c. 1.60 Ga S1 (consisting in fabrics S1a and S1b) andc. 1.55 Ga S2 (including fabrics S2a and S2b). Also, three tectono-metamorphic domains are distinguished: (a) the western domain, with S1 defined by low-P(LP) greenschist facies assemblages; (b) the central domain, where S1 fabric is preserved as medium-P(MP) amphibolite facies relicts, and locally as inclusion trails in garnet wrapped by the regionally dominant low-Pamphibolite facies S2 fabric; and (c) the eastern domain dominated by upper amphibolite to granulite facies S2 foliation. In the central domain, 1.60 GaMP-medium-T(MT) metamorphism (M1) developed within the staurolite-garnet stability field, with conditions ranging from 530-550 degrees C at 6-7 kbar (garnet cores) to 620-650 degrees C at 8-9 kbar (garnet rims), and it is associated with S1 fabric. The onset of 1.55 GaLP-high-T(HT) metamorphism (M2) is marked by replacement of staurolite by andalusite (M2a/D2a), which was subsequently pseudomorphed by sillimanite (M2b/D2b) where granite and migmatite are abundant.P-Tconditions ranged from 600 to 680 degrees C and 4-6 kbar for the M2b sillimanite stage. 1.60 Ga garnet relicts within the S2 foliation highlight the progressive obliteration of the S1 fabric by regional S2 in the central zone during peak M2 metamorphism. In the eastern migmatitic complex, partial melting of paragneiss and amphibolite occurred syn- to post-S2, at 730-770 degrees C and 6-8 kbar, and at 750-790 degrees C and 6 kbar, respectively. The pressure-temperature-deformation-time paths reconstructed for the Georgetown Inlier suggest ac. 1.60 Ga M1/D1 event recorded under greenschist facies conditions in the western domain and under medium-Pand medium-Tconditions in the central domain. This event was followed by the regional 1.56-1.54 Ga low-Pand high-Tphase (M2/D2), extensively recorded in the central and eastern domains. Decompression between these two metamorphic events is ascribed to an episode of exhumation. The two-stage evolution supports the previous hypothesis that the Georgetown Inlier preserves continental collisional and subsequent thermal perturbation associated with granite emplacement.
This study investigated the role of medium (face-to-face, cyber) and publicity (public, private) in adolescents' perceptions of severity and coping strategies (i.e., avoidant, ignoring, helplessness, social support seeking, retaliation) for victimization, while accounting for gender and cultural values. There were 3432 adolescents (ages 11-15, 49% girls) in this study; they were from China, Cyprus, the Czech Republic, India, Japan, and the United States. Adolescents completed questionnaires on individualism and collectivism, and ratings of coping strategies and severity for public face-to-face victimization, private face-to-face victimization, public cyber victimization, and private cyber victimization. Findings revealed similarities in adolescents' coping strategies based on perceptions of severity, publicity, and medium for some coping strategies (i.e., social support seeking, retaliation) but differential associations for other coping strategies (i.e., avoidance, helplessness, ignoring). The results of this study are important for prevention and intervention efforts because they underscore the importance of teaching effective coping strategies to adolescents, and to consider how perceptions of severity, publicity, and medium might influence the implementation of these coping strategies.
In this study, we reassessed the taxonomic position of Typhlomys (Rodentia: Platacanthomyidae) from Huangshan, Anhui, China, based on morphological and molecular evidence. Results suggested that Typhlomys is comprised of up to six species, including four currently recognized species ( Typhlomys cinereus, T. chapensis, T. daloushanensis, and T. nanus), one unconfirmed candidate species, and one new species ( Typhlomys huangshanensis sp. nov.). Morphological analyses further supported the designation of the Huangshan specimens found at mid-elevations in the southern Huangshan Mountains (600 m to 1 200 m a.s.l.) as a new species.
We have investigated the structural dynamics in photoexcited 1,2-diiodotetrafluoroethane molecules (C2F4I2) in the gas phase experimentally using ultrafast electron diffraction and theoretically using FOMO-CASCI excited-state dynamics simulations. The molecules are excited by an ultraviolet femtosecond laser pulse to a state characterized by a transition from the iodine 5p perpendicular to orbital to a mixed 5p parallel to sigma hole and CF2 center dot antibonding orbital, which results in the cleavage of one of the carbon-iodine bonds. We have observed, with sub-Angstrom resolution, the motion of the nuclear wave packet of the dissociating iodine atom followed by coherent vibrations in the electronic ground state of the C2F4I radical. The radical reaches a stable classical (nonbridged) structure in less than 200 fs.
Sugar amino acids (SAAs), as biologically interesting structures bearing both amino and carboxylic acid functional groups represent an important class of multifunctional building blocks. In this study, we develop an easy access to novel SAAs in only three steps starting from nitro compounds in high yields in analytically pure form, easily available by ceric (IV) mediated radical additions. Such novel SAAs have been applied in the assembly of total nine carbopeptoids with the form of linear homo-and heterooligomers for the structural investigations employing circular dichroism (CD) spectroscopy, which suggest that the carbopeptoids emerge a well-extended, left (or right)-handed conformation similar to polyproline II (PPII) helices. NMR studies also clearly demonstrated the presence of ordered secondary structural elements. 2D-ROESY spectra were acquired to identify i+1NH <-> (C1H)-C-i, (C2H)-C-i correlations which support the conformational analysis of tetramers by CD spectroscopy. These findings provide interesting information of SAAs and their oligomers as potential scaffolds for discovering new drugs and materials.
As national efforts to reduce CO2 emissions intensify, policy-makers need increasingly specific, subnational information about the sources of CO2 and the potential reductions and economic implications of different possible policies. This is particularly true in China, a large and economically diverse country that has rapidly industrialized and urbanized and that has pledged under the Paris Agreement that its emissions will peak by 2030. We present new, city level estimates of CO2 emissions for 182 Chinese cities, decomposed into 17 different fossil fuels, 46 socioeconomic sectors, and 7 industrial processes. We find that more affluent cities have systematically lower emissions per unit of gross domestic product (GDP), supported by imports from less affluent, industrial cities located nearby. In turn, clusters of industrial cities are supported by nearby centers of coal or oil extraction. Whereas policies directly targeting manufacturing and electric power infrastructure would drastically undermine the GDP of industrial cities, consumption based policies might allow emission reductions to be subsidized by those with greater ability to pay. In particular, sector based analysis of each city suggests that technological improvements could be a practical and effective means of reducing emissions while maintaining growth and the current economic structure and energy system. We explore city-level emission reductions under three scenarios of technological progress to show that substantial reductions (up to 31%) are possible by updating a disproportionately small fraction of existing infrastructure.
During the past decade, self-assembly of saccharide-containing amphiphilic molecules toward bioinspired functional glycomaterials has attracted continuous attention due to their various applications in fundamental and practical areas. However, it still remains a great challenge to prepare hierarchical glycoassemblies with controllable and diversiform structures because of the complexity of saccharide structures and carbohydrate-carbohydrate interactions. Herein, through hierarchical self-assembly of modulated amphiphilic supramolecular metallocarbohydrates, we successfully prepared various well-defined glyco-nanostructures in aqueous solution, including vesicles, solid spheres, and opened vesicles depending on the molecular structures of metallocarbohydrates. More attractively, these glyco-nanostructures can further transform into other morphological structures in aqueous solutions such as worm-like micelles, tubules, and even tupanvirus-like vesicles (TVVs). It is worth mentioning that distinctive anisotropic structures including the opened vesicles (OVs) and TVVs were rarely reported in glycobased nano-objects. This intriguing diversity was mainly controlled by the subtle structural trade-off of the two major components of the amphiphiles, i.e., the saccharides and metallacycles. To further understand this precise structural control, molecular simulations provided deep physical insights on the morphology evolution and balancing of the contributions from saccharides and metallacycles. Moreover, the multivalency of glyco-nanostructures with different shapes and sizes was demonstrated by agglutination with a diversity of sugarbinding protein receptors such as the plant lectins Concanavalin A (ConA). This modular synthesis strategy provides access to systematic tuning of molecular structure and self-assembled architecture, which undoubtedly will broaden our horizons on the controllable fabrication of biomimetic glycomaterials such as biological membranes and supramolecular lectin inhibitors.