Role of the metal cation in the dehydration of the microporous metal–organic frameworks CPO-27-M

The dehydration of the CPO-27-M (M-MOF-74, M = Zn, Co, Ni, Mg, Mn, Cu) metal-organic framework series has been investigated comprehensively using in situ variable temperature powder X-ray diffraction (VT-PXRD) and thermal analysis (TG) coupled with mass spectrometry (MS). Significant differences in the order of water desorption from different adsorption sites on heating are found with varying metal cation in the otherwise isostructural material. For all CPO-27-M (except M = Cu), water is bonded significantly more strongly to the accessible open metal sites, and these water molecules are only desorbed at higher temperatures than the other water molecules. CPO-27-Cu is an exception, where all water molecules desorb simultaneously and at much lower temperatures (below 340 K). MS and TG data show that all CPO-27-M start to release traces of CO2 already at 300–350 K, and thus long before bulk thermal decomposition is observed. Only for CPO-27-Co, the CO2 release is essentially constant on its baseline between 450 and 700 K, and it is the only CPO-27-M member that shows a stable plateau in the TG in this region. Additional rehydration studies on CPO-27-Co show that the MOF incorporates any water molecules present until the pores are fully loaded. CPO-27-Co consequently behaves as an efficient trap for any water present

Visualization of Dissolution‐Precipitation Processes in Lithium–Sulfur Batteries

In this work, light is shed on the dissolution and precipitation processes S8 and Li2S, and their role in the utilization of active material in Li-S batteries. Combining operando X-ray Tomographic Microscopy and optical image analysis, in real-time; sulfur conversion/dissolution in the cathode, the diffusion of polysulfides in the bulk electrolyte, and the redeposition of the product of the electrochemical reaction, Li2S, on the cathode are followed. Using a custom-designed capillary cell, positioning the entire cathode volume within the field of view, the conversion of elemental sulfur to soluble polysulfides during discharge is quantitatively followed. The results show the full utilization of elemental sulfur in the cathode in the initial stage of discharge, with all solid sulfur converted to soluble polysulfide species. Optical image analysis shows a rapid diffusion of polysulfides as they migrate from the cathode to the bulk electrolyte at the start of discharge and back to the cathode in the later stages of discharge, with the formation and precipitation of Li2S. The results point to the redeposition of Li2S on all available surfaces in the cathode forming a continuous insulating layer, leaving polysulfide species remaining in the electrolyte, and this is the process limiting the cell\u27s specific capacity

Neural activation in the ventromedial prefrontal cortex precedes conscious experience of being in or out of a transient hallucinatory state

Background and Hypotheses Auditory verbal hallucinations (AVHs) is not only a common symptom in schizophrenia but also observed in individuals in the general population. Despite extensive research, AVHs are poorly understood, especially their underlying neuronal architecture. Neuroimaging methods have been used to identify brain areas and networks that are activated during hallucinations. A characteristic feature of AVHs is, however, that they fluctuate over time, with varying frequencies of starts and stops. An unanswered question is, therefore, what neuronal events co-occur with the initiation and inhibition of an AVH episode. Study Design We investigated brain activation with fMRI in 66 individuals who experienced multiple AVH-episodes while in the scanner. We extracted time-series fMRI-data and monitored changes second-by-second from 10 s before to 15 s after participants indicated the start and stop of an episode, respectively, by pressing a hand-held response-button. Study Results We found a region in the ventromedial prefrontal cortex (VMPFC) which showed a significant increase in activation initiated a few seconds before participants indicated the start of an episode, and a corresponding decrease in activation initiated a few seconds before the end of an episode. Conclusions The consistent increase and decrease in activation in this area in advance of the consciously experienced presence or absence of the “voice” imply that this region may act as a switch in turning episodes on and off. The activation is unlikely to be confounded by motor responses. The findings could have clinical implications for brain stimulation treatments, like transcranial magnetic stimulation.publishedVersio

Sex differences in antipsychotic efficacy and side effects in schizophrenia spectrum disorder:results from the BeSt InTro study

Current guidelines for patients with schizophrenia spectrum disease do not take sex differences into account, which may result in inappropriate sex-specific treatment. In the BeSt InTro study, a total of 144 patients (93 men and 51 women) with a schizophrenia spectrum diagnosis and ongoing psychosis were included and randomized to amisulpride, aripiprazole, or olanzapine in flexible dose. This trial is registered with ClinicalTrials.gov (NCT01446328). Primary outcomes were sex differences in dose, dose-corrected serum levels, efficacy, and tolerability. Dosing was higher for men than for women in the aripiprazole group (p = 0.025) and, at trend level, in the olanzapine group (p = 0.056). Dose-corrected serum levels were 71.9% higher in women than in men for amisulpride (p = 0.019) and 55.8% higher in women than in men for aripiprazole (p = 0.049). In the amisulpride group, men had a faster decrease in psychotic symptoms than women (p = 0.003). Moreover, amisulpride was more effective than the other medications in men but not in women. Prolactin levels were higher in women than in men, especially for amisulpride (p < 0.001). Also, women had higher BMI increase on amisulpride compared to the two other antipsychotics (p < 0.001). We conclude that clinicians should be aware of the risks of overdosing in women, especially for amisulpride and aripiprazole. Amisulpride is highly effective in men, but in women, amisulpride showed more severe side effects and may thus not be the drug of first choice. Our study shows that sex differences should be taken into account in future studies on antipsychotics. Future research is warranted to evaluate these preliminary results