Structure and stability of the sH binary hydrate cavity and host-guest versus guest-guest interactions therein: A DFT approach.

The intrinsic ability of clathrate hydrates to encage gaseous molecules is explored. Encapsulation ability depends on the cavity size and the type of guest gaseous species in addition to the physical parameters, temperature and pressure. Here we have reported the structure, stability and nature of interaction in dissimilar guest occupied sH hydrate cavity. Diatomic gas molecules and small polyatomic hydrocarbons are considered as guests. The irregular icosahedron (512 68 ) cavity of sH hydrate is the host. Different thermodynamic parameters for the guest molecules encapsulation were calculated using three different hybrid DFT functionals, B3LYP, M05-2X, M06, and moreover using dispersion correction (PBE0-D3). With the consideration of large H-bonded systems the 6-31G* and cc-pVTZ basis sets were used for two set of computations. To disclose the nature of interaction between the host-guest systems as well as the interaction between the guest molecules inside the host the non-covalent interaction (NCI) indices and energy decomposition analysis (EDA) were done. Impact of host-guest and guest-guest interactions are discussed.

Parallel Lemniscal and Non-Lemniscal Sources Control Auditory Responses in the Orbitofrontal Cortex (OFC).

The orbitofrontal cortex (OFC) controls flexible behavior through stimulus value updating based on stimulus outcome associations, allowing seamless navigation in dynamic sensory environments with changing contingencies. Sensory cue driven responses, primarily studied through behavior, exist in the OFC. However, OFC neurons' sensory response properties, particularly auditory, are unknown in the mouse, a genetically tractable animal. We show that mouse OFC single neurons have unique auditory response properties showing pure oddball detection and long timescales of adaptation resulting in stimulus-history dependence. Further, we show that OFC auditory responses are shaped by two parallel sources in the auditory thalamus, lemniscal and non-lemniscal. The latter underlies a large component of the observed oddball detection and additionally controls persistent activity in the OFC through the amygdala. The deviant selectivity can serve as a signal for important changes in the auditory environment. Such signals, if coupled with persistent activity, obtained by disinhibitory control from the non-lemniscal auditory thalamus or amygdala, will allow for associations with a delayed outcome related signal, like reward prediction error, and potentially forms the basis of updating stimulus outcome associations in the OFC. Thus, the baseline sensory responses allow the behavioral requirement-based response modification through relevant inputs from other structures related to reward, punishment, or memory. Thus, alterations in these responses in neurologic disorders can lead to behavioral deficits.