Theoretical study of the effect of substituent and backbone conformation on the electronic properties of symmetrically substituted poly(di‐n‐alkylsilanes)

We present the results of ab initio 3‐21G∗ geometry optimizations and valence effective Hamiltonian (VEH) band structure calculations aimed at determining the evolution of the geometric and electronic (ionization potential, electron affinities, and band gaps) properties of all‐trans poly(dimethylsilane), poly(diethylsilane), poly(di‐n‐propylsilane), and poly(di‐n‐butylsilane) when increasing the size of the alkyl group. In the latter polymer, we have also studied the 7/3 conformation, in order to analyze the effect of the backbone conformation on the geometric and electronic structure. The VEH ionization potentials of all‐trans poly(di‐n‐alkylsilanes) are almost equal, and as experimental photoemission data show, only slight differences are appreciated. The band gap decreases in going from poly(di‐n‐butylsilane) to poly(di‐n‐propylsilane) and to poly(diethylsilane), and increases when passing to poly(dimethylsilane), which coincides with experimental evidences on poly(di‐n‐alkylsilanes). The change from all‐trans to 7/3 conformation of poly(di‐n‐butylsilane) implies an increase of both, ionization potential and band gap, in perfect agreement with experimental photoemission and absorption data. The applicability of VEH to deal with poly(di‐n‐alkylsilanes) is [email protected]

Electrical response of β-PVDF in a constant uniaxial strain rate deformation

The microstructure of β-PVDF has great influence on its piezo- and pyroelectric responses. The microstructure of β-PVDF drastically changes upon a mechanical deformation perpendicular to the preferred chain orientation, mainly above the yielding point. The voltage (open-circuit response) developed in β-PVDF films was monitored while the material is subjected to a constant strain rate programFundação para a Ciência e Tecnologia (FCT) - POCTI/CTM/33501/99

On the relevance of the polar β-phase of poly(vinylidene fluoride) for high performance lithium-Ion battery separators

Separator membranes based on poly(vinylidene fluoride), PVDF, poly(vinylidene fluoride-co-trifluoroethylene), PVDF-TrFE, poly(vinylidene fluoride-co-hexafluropropylene), PVDF-HFP and poly(vinylidene fluoride-co-chlorotrifluoroethylene), PVDF-CTFE were prepared by solvent casting method using N,N-dimethylformamide (DMF) as solvent. In all cases, the same polymer/solvent ratio and solvent evaporation temperature were used. For all membranes, porous microstructure is achieved with a degree of porosity larger than 50%. The β-phase content as well as degree of crystallinity were different for each membrane, which were lower for the co-polymer membranes when compared with PVDF. On the other hand, the observed ionic conductivity values, electrolyte uptake, tortuosity and MacMullin number were similar for all membranes. The electrochemical performance of the separator membranes was evaluated in Li/C–LiFePO4 half-cell configuration showing good cyclability and rate capability for all membranes. Among the all separator membranes, PVDF-TrFE demonstrate the best electrochemical performance, with a discharge capacity value of 87 mAh.g-1 after 50 cycles with a capacity retention of 78 % at 2C.Finally, the correlation between the β-phase content in the membranes and the cycling performance was demonstrated (which was significant at high-C rates): larger β-phase contents, leading higher polarity, facilitates faster lithium ion migration within the separator for similar microstructures.This work was supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UID/FIS/04650/2013. The authors thank FEDER funds through the COMPETE 2020 Programme and National Funds through FCT under the projects PTDC/CTM-ENE/5387/2014 and UID/CTM/50025/2013 and grants SFRH/BD/90215/2012 (J.C.D.) and SFRH/BPD/112547/2015 (C.M.C.). The authors acknowledge funding by the Spanish Ministry of Economy and Competitiveness (MINECO) through the project MAT2016-76039-C4-3-R (AEI/FEDER, UE) (including the FEDER financial support) and from the Basque Government Industry Department under the ELKARTEK Program. Authors are grateful to the Government of the Basque Country for financial support (Grupos de Investigación, IT718-13). The authors thank Solvay, Timcal and Phostech for kindly supplying the high quality materials.info:eu-repo/semantics/publishedVersio

Nucleation of the electroactive γ phase and enhancement of the optical transparency in low filler content poly(vinylidene)/clay nanocomposites

Poly(vinylidene fluoride), PVDF, based nanocomposites with different clays structures have been processed by solvent casting and melt crystallisation. Depending on the melting temperature of the polymer, the nanocomposite recrystalises in the electroactive or non electroactive β-phase of the polymer. This fact is related to the thermal behaviour of the clay. For montmorillonite clay, the full crystallisation of the electroactiveγ-phase occurs for clay contents lower than 0.5 wt%, allowing the nanocomposites to maintain the mechanical properties of the polymer matrix. The electroactivity of the material has been proven by measuring the piezoelectric d33 response of the material. The obtained value of d33 is -7 pC/N, lower than in β-PVDF obtained by mechanical stretching, but still among the largest coefficients obtained for polymers. Further, the optical transmittance in the visible range is strongly enhanced with respect to the transmittance of the pure polymer. Finally, it is demonstrated that the nucleation of the β-phase can be also obtained in other clays, such as in kaolinite and laponite.Fundação para a Ciência e a Tecnologia (FCT) - NANO/NMed-SD/0156/2007, PTDC/CTM/69316/2006, PTDC/CTM-NAN/112574/2009, SFRH/BD/62507/2009.FEDER funds through the "Programa Operacional Factores de Competitividade – COMPETECOST Action MP1003, the ‘European Scientific Network for Artificial Muscles’ (ESNAM)

In vitro human growth hormone increases human chorionic gonadotropin and progesterone secretion by human placenta at term: evidence of a modulatory role by opioids

We examined the in vitro effect of human growth hormone (hGH) on hormone placental production and the modulation by opioids of this function. Small placental fragments from 12 term placentas were incubated at 37 degrees C in a 95% air and 5% CO2 atmosphere for 4 h with various concentrations of hGH (1-1000 ng/ml) or naloxone (3-500 ng/ml). Both hGH and naloxone increased the concentrations of human chorionic gonadotropin (hCG) and progesterone in the media. The effect of the hGH was dose-dependent and statistically significant at 10 ng/ml, while naloxone was able to increase hCG and progesterone production only at the highest doses (250-500 ng/ml). The concomitant treatment with ineffective doses of naloxone and hGH was able to enhance hCG and progesterone secretion reaching levels similar to those obtained with the highest doses of hGH alone. High naloxone concentrations significantly decreased both hCG and progesterone secretion induced by high doses of hGH. This study confirms the relevance of growth hormone in sustaining placental endocrine activities and indicates an effect of opioids in modulating these function

Activation of mGlu3 Receptors Stimulates the Production of GDNF in Striatal Neurons

Metabotropic glutamate (mGlu) receptors have been considered potential targets for the therapy of experimental parkinsonism. One hypothetical advantage associated with the use of mGlu receptor ligands is the lack of the adverse effects typically induced by ionotropic glutamate receptor antagonists, such as sedation, ataxia, and severe learning impairment. Low doses of the mGlu2/3 metabotropic glutamate receptor agonist, LY379268 (0.25–3 mg/kg, i.p.) increased glial cell line-derived neurotrophic factor (GDNF) mRNA and protein levels in the mouse brain, as assessed by in situ hybridization, real-time PCR, immunoblotting, and immunohistochemistry. This increase was prominent in the striatum, but was also observed in the cerebral cortex. GDNF mRNA levels peaked at 3 h and declined afterwards, whereas GDNF protein levels progressively increased from 24 to 72 h following LY379268 injection. The action of LY379268 was abrogated by the mGlu2/3 receptor antagonist, LY341495 (1 mg/kg, i.p.), and was lost in mGlu3 receptor knockout mice, but not in mGlu2 receptor knockout mice. In pure cultures of striatal neurons, the increase in GDNF induced by LY379268 required the activation of the mitogen-activated protein kinase and phosphatidylinositol-3-kinase pathways, as shown by the use of specific inhibitors of the two pathways. Both in vivo and in vitro studies led to the conclusion that neurons were the only source of GDNF in response to mGlu3 receptor activation. Remarkably, acute or repeated injections of LY379268 at doses that enhanced striatal GDNF levels (0.25 or 3 mg/kg, i.p.) were highly protective against nigro-striatal damage induced by 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine in mice, as assessed by stereological counting of tyrosine hydroxylase-positive neurons in the pars compacta of the substantia nigra. We speculate that selective mGlu3 receptor agonists or enhancers are potential candidates as neuroprotective agents in Parkinson's disease, and their use might circumvent the limitations associated with the administration of exogenous GDNF

Alterations in ethanol-induced behaviors and consumption in knock-in mice expressing ethanol-resistant NMDA receptors

Ethanol's action on the brain likely reflects altered function of key ion channels such as glutamatergic N-methyl-D-aspartate receptors (NMDARs). In this study, we determined how expression of a mutant GluN1 subunit (F639A) that reduces ethanol inhibition of NMDARs affects ethanol-induced behaviors in mice. Mice homozygous for the F639A allele died prematurely while heterozygous knock-in mice grew and bred normally. Ethanol (44 mM; ∼0.2 g/dl) significantly inhibited NMDA-mediated EPSCs in wild-type mice but had little effect on responses in knock-in mice. Knock-in mice had normal expression of GluN1 and GluN2B protein across different brain regions and a small reduction in levels of GluN2A in medial prefrontal cortex. Ethanol (0.75-2.0 g/kg; IP) increased locomotor activity in wild-type mice but had no effect on knock-in mice while MK-801 enhanced activity to the same extent in both groups. Ethanol (2.0 g/kg) reduced rotarod performance equally in both groups but knock-in mice recovered faster following a higher dose (2.5 g/kg). In the elevated zero maze, knock-in mice had a blunted anxiolytic response to ethanol (1.25 g/kg) as compared to wild-type animals. No differences were noted between wild-type and knock-in mice for ethanol-induced loss of righting reflex, sleep time, hypothermia or ethanol metabolism. Knock-in mice consumed less ethanol than wild-type mice during daily limited-access sessions but drank more in an intermittent 24 h access paradigm with no change in taste reactivity or conditioned taste aversion. Overall, these data support the hypothesis that NMDA receptors are important in regulating a specific constellation of effects following exposure to ethanol. © 2013 den Hartog et al