The role of Zn in the sustainable one-pot synthesis of dimethyl carbonate from carbon dioxide, methanol and propylene oxide

Dimethyl carbonate (DMC) can be applied as a greener alternative to more hazardous materials, e.g. phosgene or dimethyl sulfate. Herein, one-pot synthesis of DMC from propylene oxide, methanol and CO2 using alkali halide catalysts under mild conditions was studied. Addition of Zn powder to the K2CO3-NaBr-ZnO catalyst system was seen to increase DMC selectivity from 19.8% (TOF = 39.0 h-1) to 40.2% (TOF = 78.1 h-1) at 20 bar and 160 °C for 5 h. Catalyst characterisation showed that Zn powder increases the stability of the catalyst, preventing the active ingredients on the catalyst surface from leaching. An increase in propylene oxide conversion to DMC is attributed to the increase of Zn2+ ions in the reaction solution. Elevated pressure was not found to be a necessary reaction condition for transesterification. This study shows that increased selectivity to DMC can be achieved at mild conditions with the addition of Zn powder

The role of Zn in the sustainable one-pot synthesis of dimethyl carbonate from carbon dioxide, methanol and propylene oxide

Dimethyl carbonate (DMC) can be applied as a greener alternative to more hazardous materials, e.g. phosgene or dimethyl sulfate. Herein, one-pot synthesis of DMC from propylene oxide, methanol and CO2 using alkali halide catalysts under mild conditions was studied. Addition of Zn powder to the K2CO3-NaBr-ZnO catalyst system was seen to increase DMC selectivity from 19.8% (TOF = 39.0 h-1) to 40.2% (TOF = 78.1 h-1) at 20 bar and 160 °C for 5 h. Catalyst characterisation showed that Zn powder increases the stability of the catalyst, preventing the active ingredients on the catalyst surface from leaching. An increase in propylene oxide conversion to DMC is attributed to the increase of Zn2+ ions in the reaction solution. Elevated pressure was not found to be a necessary reaction condition for transesterification. This study shows that increased selectivity to DMC can be achieved at mild conditions with the addition of Zn powder

Berberine chloride pretreatment exhibits neuroprotective effect against 6-hydroxydopamine-induced neuronal insult in rat

Parkinson�s disease (PD) is a rather common movement disorder as a result of the degeneration of dopaminergic neurons within the substantianigra. Current treatments for PD afford symptomatic relief with no prevention of disease progression. Due to the neuroprotective and anti-apoptotic potential of the isoquinoline alkaloid berberine (BBR), this study was conducted to assess whether BBR pretreatment could attenuate behavioral and neuronal derangement in 6-hydroxydopamine (6-OHDA)-induced model of PD in the rat. Unilateral intrastriatal 6-OHDA-lesioned rats received BBR at doses of 25 and/or 50 mg/kg (i.p.) three times at an interval of 24 h, started 2 days before the surgery. After 1 week, apomorphine caused significant contralateral rotations and a significant reduction in the number of Nissl-stained and tyrosine-hydroxylase (TH)-positive neurons on the left side of the substantianigra. BBR pretreatment at a dose of 50 mg/kg significantly reduced rotations and prevented loss of TH-positive neurons. These results indicate pre-lesion administration of BBR could protect against 6-OHDA toxicity and this may be of benefit besides other available therapies in PD. © 2015 by School of Pharmacy Shaheed Beheshti University of Medical Sciences and Health Services

Synthesis of TiO2-x/W18O49 Hollow Double-shell and Core-shell Microspheres for CO2 Photoreduction under Visible Light

TiO2x/W18O49 with core–shell or double-shelled hollow microspheres were synthesized through a facile multi-step solvothermal method. The formation of the hollow microspheres with a doubleshell was a result of the Kirkendall effect during the solvothermal treatment with concentrated NaOH. The advanced architecture significantly enhanced the electronic properties of TiO2x/ W18O49, improving by more than 30 times the CO2 photoreduction efficiency compared to the pristine W18O49. Operando DRIFTS measurements revealed that the yellow TiO2x was a preferable CO2 adsorption and conversion site

Spinal Cord Imaging Markers and Recovery of Volitional Leg Movement With Spinal Cord Epidural Stimulation in Individuals With Clinically Motor Complete Spinal Cord Injury

Previous studies have shown that epidural stimulation of the lumbosacral spinal cord (scES) can re-enable lower limb volitional motor control in individuals with chronic, clinically motor complete spinal cord injury (SCI). This observation entails that residual supraspinal connectivity to the lumbosacral spinal circuitry still persisted after SCI, although it was non-detectable when scES was not provided. In the present study, we aimed at exploring further the mechanisms underlying scES-promoted recovery of volitional lower limb motor control by investigating neuroimaging markers at the spinal cord lesion site via magnetic resonance imaging (MRI). Spinal cord MRI was collected prior to epidural stimulator implantation in 13 individuals with chronic, clinically motor complete SCI, and the spared tissue of specific regions of the spinal cord (anterior, posterior, right, left, and total cord) was assessed. After epidural stimulator implantation, and prior to any training, volitional motor control was evaluated during left and right lower limb flexion and ankle dorsiflexion attempts. The ability to generate force exertion and movement was not correlated to any neuroimaging marker. On the other hand, spared tissue of specific cord regions significantly and importantly correlated with some aspects of motor control that include activation amplitude of antagonist (negative correlation) muscles during left ankle dorsiflexion, and electromyographic coordination patterns during right lower limb flexion. The fact that amount and location of spared spinal cord tissue at the lesion site were not related to the ability to generate volitional lower limb movements may suggest that supraspinal inputs through spared spinal cord regions that differ across individuals can result in the generation of lower limb volitional motor output prior to any training when epidural stimulation is provided

Highly selective CO₂ photoreduction to CO on MOF-derived TiO₂

Metal–Organic Framework (MOF)-derived TiO2, synthesised through the calcination of MIL-125-NH2, is investigated for its potential as a CO2 photoreduction catalyst. The effect of the reaction parameters: irradiance, temperature and partial pressure of water was investigated. Using a two-level design of experiments, we were able to evaluate the influence of each parameter and their potential interactions on the reaction products, specifically the production of CO and CH4. It was found that, for the explored range, the only statistically significant parameter is temperature, with an increase in temperature being correlated to enhanced production of both CO and CH4. Over the range of experimental settings explored, the MOF-derived TiO2 displays high selectivity towards CO (98%), with only a small amount of CH4 (2%) being produced. This is notable when compared to other state-of-the-art TiO2 based CO2 photoreduction catalysts, which often showcase lower selectivity. The MOF-derived TiO2 was found to have a peak production rate of 8.9 × 10−4 μmol cm−2 h−1 (2.6 μmol g−1 h−1) and 2.6 × 10−5 μmol cm−2 h−1 (0.10 μmol g−1 h−1) for CO and CH4, respectively. A comparison is made to commercial TiO2, P25 (Degussa), which was shown to have a similar activity towards CO production, 3.4 × 10−3 μmol cm−2 h−1 (5.9 μmol g−1 h−1), but a lower selectivity preference for CO (3 : 1 CH4 : CO) than the MOF-derived TiO2 material developed here. This paper showcases the potential for MIL-125-NH2 derived TiO2 to be further developed as a highly selective CO2 photoreduction catalyst for CO production

GCK-MODY diabetes associated with protein misfolding, cellular self-association and degradation

AbstractGCK-MODY, dominantly inherited mild fasting hyperglycemia, has been associated with >600 different mutations in the glucokinase (GK)-encoding gene (GCK). When expressed as recombinant pancreatic proteins, some mutations result in enzymes with normal/near-normal catalytic properties. The molecular mechanism(s) of GCK-MODY due to these mutations has remained elusive. Here, we aimed to explore the molecular mechanisms for two such catalytically ‘normal’ GCK mutations (S263P and G264S) in the F260-L270 loop of GK. When stably overexpressed in HEK293 cells and MIN6 β-cells, the S263P- and G264S-encoded mutations generated misfolded proteins with an increased rate of degradation (S263P>G264S) by the protein quality control machinery, and a propensity to self-associate (G264S>S263P) and form dimers (SDS resistant) and aggregates (partly Triton X-100 insoluble), as determined by pulse-chase experiments and subcellular fractionation. Thus, the GCK-MODY mutations S263P and G264S lead to protein misfolding causing destabilization, cellular dimerization/aggregation and enhanced rate of degradation. In silico predicted conformational changes of the F260-L270 loop structure are considered to mediate the dimerization of both mutant proteins by a domain swapping mechanism. Thus, similar properties may represent the molecular mechanisms for additional unexplained GCK-MODY mutations, and may also contribute to the disease mechanism in other previously characterized GCK-MODY inactivating mutations

Efficient low-loaded ternary Pd-In2O3-Al2O3 catalysts for methanol production

Pd-In2O3 catalysts are among the most promising alternatives to Cu-ZnO-Al2O3 for synthesis of CH3OH from CO2. However, the intrinsic activity and stability of In2O3 per unit mass should be increased to reduce the content of this scarcely available element and to enhance the catalyst lifetime. Herein, we pro -pose and demonstrate a strategy for obtaining highly dispersed Pd and In2O3 nanoparticles onto an Al2O3 matrix by a one-step coprecipitation followed by calcination and activation. The activity of this catalyst is comparable with that of a Pd-In2O3 catalyst (0.52 vs 0.55 gMeOH h-1 gcat-1 at 300 & DEG;C, 30 bar, 40,800 mL h-1 gcat-1 ) but the In2O3 loading decreases from 98 to 12 wt% while improving the long-term stability by three-fold at 30 bar. In the new Pd-In2O3-Al2O3 system, the intrinsic activity of In2O3 is highly increased both in terms of STY normalized to In specific surface area and In2O3 mass (4.32 vs 0.56 g gMeOH h-1 gIn2O3-1 of a Pd-In2O3 catalyst operating at 300 & DEG;C, 30 bar, 40,800 mL h-1 gcat-1).The combination of ex situ and in situ catalyst characterizations during reduction provides insights into the interaction between Pd and In and with the support. The enhanced activity is likely related to the close proximity of Pd and In2O3, wherein the H2 splitting activity of Pd promotes, in combination with CO2 activation over highly dispersed In2O3 particles, facile formation of CH3OH