Unusual Complexes of P(CH)3 with FH, ClH, and ClF

© 2020 by the authors.Ab initio MP2/aug’-cc-pVTZ calculations have been performed to determine the structures and binding energies of complexes formed by phosphatetrahedrane, P(CH)3, and HF, HCl, and ClF. Four types of complexes exist on the potential energy surfaces. Isomers A form at the P atom near the end of a P-C bond, B at a C-C bond, C at the centroid of the C-C-C ring along the C3 symmetry axis, and D at the P atom along the C3 symmetry axis. Complexes A and B are stabilized by hydrogen bonds when FH and ClH are the acids, and by halogen bonds when ClF is the acid. In isomers C, the dipole moments of the two monomers are favorably aligned but in D the alignment is unfavorable. For each of the monomers, the binding energies of the complexes decrease in the order A > B > C > D. The most stabilizing Symmetry Adapted Perturbation Theory (SAPT) binding energy component for the A and B isomers is the electrostatic interaction, while the dispersion interaction is the most stabilizing term for C and D. The barriers to converting one isomer to another are significantly higher for the A isomers compared to B. Equation of motion coupled cluster singles and doubles (EOM-CCSD) intermolecular coupling constants J(X-C) are small for both B and C isomers. J(X-P) values are larger and positive in the A isomers, negative in the B isomers, and have their largest positive values in the D isomers. Intramolecular coupling constants 1J(P-C) experience little change upon complex formation, except in the halogen-bonded complex FCl:P(CH3) AThis work was carried out with financial support from the Ministerio de Ciencia, Innovación y Universidades of Spain (Project No. PGC2018–094644-B-C22) and Comunidad Autónoma de Madrid (P2018/EMT–4329 AIRTEC-CM)

Redetermination of (E)-N,N′-bis­(4-bromo­phen­yl)formamidine

In comprison with the previous structural study [Anulewicz et al. (1991 ▶). Pol. J. Chem. 65, 465–471], for which only the coordinates of all non-H atoms and of some H atoms were reported, the current redetermination of the title compound, C13H10Br2N2, additionally reports anisotropic displacement parameters for all non-H atoms and the coordinates of all H atoms, accompanied by higher accuracy of the geometric parameters. Two independent half-mol­ecules are present in the asymmetric unit, which are completed by a twofold rotation axis as symmetry element. In the crystal, inter­molecular N—H⋯N hydrogen bonds link the mol­ecules into dimers. Linear chains parallel to [102] are formed by inter­molecular Br⋯Br inter­actions of 3.4328 (7) Å between two Br atoms of adjacent mol­ecules. The dihedral angles between the benzene rings are 50.05 (15) and 75.61 (11)° in the two independent molecules. Owing to the twofold symmetry of the mol­ecules, H atoms attached to the N atoms are only half-occupied, leading to them being disordered over two positions of equal occupancy

Neural Correlates of Multisensory Enhancement in Audiovisual Narrative Speech Perception: A fMRI investigation

This fMRI study investigated the effect of seeing articulatory movements of a speaker while listening to a nat- uralistic narrative stimulus. It had the goal to identify regions of the language network showing multisensory enhancement under synchronous audiovisual conditions. We expected this enhancement to emerge in regions known to underlie the integration of auditory and visual information such as the posterior superior temporal gyrus as well as parts of the broader language network, including the semantic system. To this end we presented 53 participants with a continuous narration of a story in auditory alone, visual alone, and both synchronous and asynchronous audiovisual speech conditions while recording brain activity using BOLD fMRI. We found multi- sensory enhancement in an extensive network of regions underlying multisensory integration and parts of the semantic network as well as extralinguistic regions not usually associated with multisensory integration, namely the primary visual cortex and the bilateral amygdala. Analysis also revealed involvement of thalamic brain regions along the visual and auditory pathways more commonly associated with early sensory processing. We conclude that under natural listening conditions, multisensory enhancement not only involves sites of multisensory in- tegration but many regions of the wider semantic network and includes regions associated with extralinguistic sensory, perceptual and cognitive processing

The dual developmental origin of spinal cerebrospinal fluid-contacting neurons gives rise to distinct functional subtypes.

Chemical and mechanical cues from the cerebrospinal fluid (CSF) can affect the development and function of the central nervous system (CNS). How such cues are detected and relayed to the CNS remains elusive. Cerebrospinal fluid-contacting neurons (CSF-cNs) situated at the interface between the CSF and the CNS are ideally located to convey such information to local networks. In the spinal cord, these GABAergic neurons expressing the PKD2L1 channel extend an apical extension into the CSF and an ascending axon in the spinal cord. In zebrafish and mouse spinal CSF-cNs originate from two distinct progenitor domains characterized by distinct cascades of transcription factors. Here we ask whether these neurons with different developmental origins differentiate into cells types with different functional properties. We show in zebrafish larva that the expression of specific markers, the morphology of the apical extension and axonal projections, as well as the neuronal targets contacted by CSF-cN axons, distinguish the two CSF-cN subtypes. Altogether our study demonstrates that the developmental origins of spinal CSF-cNs give rise to two distinct functional populations of sensory neurons. This work opens novel avenues to understand how these subtypes may carry distinct functions related to development of the spinal cord, locomotion and posture

Supersymmetric Homogeneous Quantum Cosmologies Coupled to a Scalar Field

Recent work on $N=2$ supersymmetric Bianchi type IX cosmologies coupled to a scalar field is extended to a general treatment of homogeneous quantum cosmologies with explicitely solvable momentum constraints, i.e. Bianchi types I, II, VII, VIII besides the Bianchi type IX, and special cases, namely the Friedmann universes, the Kantowski-Sachs space, and Taub-NUT space. Besides the earlier explicit solution of the Wheeler DeWitt equation for Bianchi type IX, describing a virtual wormhole fluctuation, an additional explicit solution is given and identified with the `no-boundary state'.Comment: 23 PAGE

Design of the fill/transfer station cryostat for the OMEGA cryogenic target system

General Atomics is designing, testing and fabricating a system for supplying cryogenic targets for the University of Rochester`s OMEGA laser system. A prototype system has demonstrated the filling of 1 mm diameter, 3 {micro}m wall plastic spheres to 111 MPa (1,100 atm) with deuterium and then cooling to 18 K to condense the fuel. The production design must be capable of routinely filling and cooling targets with a 50/50 mix of deuterium and tritium and transferring them to a device which places the targets into the focus of 60 laser beams. This paper discusses the design and analysis of the production Fill/Transfer Station cryostat. The cryostat has two major components, a fixed base and a removable dome. The joint between the base and the dome is similar to a bayonet fitting and is sealed by a room temperature elastomeric o-ring. Since the cryostat must be housed in a glovebox, its design is driven strongly by maintenance requirements. To reach the equipment inside the cryostat, the dome is simply unbolted and lifted. The inside of the cryostat is maintained at 16 K by a closed loop helium flow system. Gaseous helium at about 1.4 MPa (200 psi) flows through tubes which are brazed to the inner walls. Cooling is provided by several cryocoolers which are located external to the cryostat. Liquid nitrogen is used as a heat intercept and to precool the helium gas