548 research outputs found
Overcoming the engineering constraints for scaling-up the state-of-the-art catalyst for tail-gas N2O decomposition
An efficient process is reported for preparing a state-of-the-art Fe-ferrierite catalyst for N2O decomposition under industrial tail-gas conditions. In the synthesis procedure we evaluate the very demanding constraints for scale-up; i.e. large reactor volumes are typically needed, long processing times and considerable amounts of waste water is generated. The proposed synthesis minimizes the amount of water used, and therefore the amount produced waste water is minimal; in this approach there is no liquid residual water stream that would need intensive processing. This has remarkable benefits in terms of process design, since the volume of equipment is reduced and the energy-intensive filtration is eliminated. This route exemplifies the concept of process intensification, with the ambition to re-engineer an existing process to make the industrial catalyst manufacture more sustainable. The so-obtained catalyst is active, selective and very stable under tail gas conditions containing H2O, NO and O2, together with N2O; keeping a high conversion during 70 h time on stream at 700 K, with a decay of 0.01%/h, while the standard reference catalyst decays at 0.06%/h; hence it deactivates six times slower, with ~5% absolute points of higher conversion. The excellent catalytic performance is ascribed to the differential speciation
Soft Templating and Disorder in an Applied 1D Cobalt Coordination Polymer Electrocatalyst
Disordered materials with resilient and soft-templated functional units bear the
potential to fill the pipeline of robust catalysts for renewable energy storage.
However, for novel materials lacking long-range order, the ability to discern
local structure with atomic resolution still pushes the boundaries of current
analytical and modeling approaches. We introduce a two-pillar strategy to
monitor the formation and unravel the structure of the first disordered onedimensional cobalt coordination polymer catalyst, Co-dppeO2. This target
material excels through proven high performance in commercial alkaline
electrolyzers and organic transformations. We demonstrate that the key architecture behind this activity is the unconventional embedding of hydrated
{H2O-Co2(OH)2-OH2} edge-site motifs, nested into a flexible organic matrix of
highly oxidized and bridging hydrophobic dppeO2 ligands. Our combination
of in situ spectroscopy and computational modeling of X-ray scattering and
absorption spectra, backed with complementary experimental techniques,
holds the key to understanding the atomic-range structure of important
disordered materials
Scope and Mechanistic Study of the Coupling Reaction of α,ÎČ-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways
The cationic ruthenium-hydride complex [(C6H6)(PCy3)(CO)RuH]+BF4â (1) was found to be a highly effective catalyst for the intermolecular conjugate addition of simple alkenes to α,ÎČ-unsaturated carbonyl compounds to give (Z)-selective tetrasubstituted olefin products. The analogous coupling reaction of cinnamides with electron-deficient olefins led to the oxidative coupling of two olefinic CâH bonds in forming (E)-selective diene products. The intramolecular version of the coupling reaction efficiently produced indene and bicyclic fulvene derivatives. The empirical rate law for the coupling reaction of ethyl cinnamate with propene was determined as follows: rate = k[1]1[propene]0[cinnamate]â1. A negligible deuterium kinetic isotope effect (kH/kD = 1.1 ± 0.1) was measured from both (E)-C6H5CHâC(CH3)CONHCH3 and (E)-C6H5CDâC(CH3)CONHCH3 with styrene. In contrast, a significant normal isotope effect (kH/kD = 1.7 ± 0.1) was observed from the reaction of (E)-C6H5CHâC(CH3)CONHCH3 with styrene and styrene-d8. A pronounced carbon isotope effect was measured from the coupling reaction of (E)-C6H5CHâCHCO2Et with propene (13C(recovered)/13C(virgin) at CÎČ = 1.019(6)), while a negligible carbon isotope effect (13C(recovered)/13C(virgin) at CÎČ = 0.999(4)) was obtained from the reaction of (E)-C6H5CHâC(CH3)CONHCH3 with styrene. Hammett plots from the correlation of para-substituted p-X-C6H4CHâCHCO2Et (X = OCH3, CH3, H, F, Cl, CO2Me, CF3) with propene and from the treatment of (E)-C6H5CHâCHCO2Et with a series of para-substituted styrenes p-Y-C6H4CHâCH2 (Y = OCH3, CH3, H, F, Cl, CF3) gave the positive slopes for both cases (Ï = +1.1 ± 0.1 and +1.5 ± 0.1, respectively). Eyring analysis of the coupling reaction led to the thermodynamic parameters, ÎH⧧ = 20 ± 2 kcal molâ1 and ÎS⧧ = â42 ± 5 eu. Two separate mechanistic pathways for the coupling reaction have been proposed on the basis of these kinetic and spectroscopic studies
Facile access to a heterocyclic, sp3-rich chemical scaffold via a tandem condensation/intramolecular nitroneâalkene [3+2] cycloaddition strategy
A heterocyclic, sp3-rich chemical scaffold was synthesised in just 6 steps via a highly regio- and diastereo-selective tandem nitrone formation/intramolecular nitroneâalkene [3+2] cycloaddition reaction. A library of 543 lead-like compounds based on the scaffold core has been produced
WNT signalling in prostate cancer
Genome sequencing and gene expression analyses of prostate tumours have highlighted the potential importance of genetic and epigenetic changes observed in WNT signalling pathway components in prostate tumours-particularly in the development of castration-resistant prostate cancer. WNT signalling is also important in the prostate tumour microenvironment, in which WNT proteins secreted by the tumour stroma promote resistance to therapy, and in prostate cancer stem or progenitor cells, in which WNT-ÎČ-catenin signals promote self-renewal or expansion. Preclinical studies have demonstrated the potential of inhibitors that target WNT receptor complexes at the cell membrane or that block the interaction of ÎČ-catenin with lymphoid enhancer-binding factor 1 and the androgen receptor, in preventing prostate cancer progression. Some WNT signalling inhibitors are in phase I trials, but they have yet to be tested in patients with prostate cancer
Authors' Reply to the Letter to the Editor: Reply to "Non green perspective on biodegradable polymer nanocomposites"
MicroRNA profiling of cisplatinresistant oral squamous cell carcinoma cell lines enriched withcancer-stem-cell-like and epithelial-mesenchymal transition-type features
Oral cancer is of major public health problem in India. Current investigation was aimed to identify
the specific deregulated miRNAs which are responsible for development of resistance phenotype
through regulating their resistance related target gene expression in oral squamous cell carcinoma
(OSCC). Cisplatin-resistant OSCC cell lines were developed from their parental human OSCC cell lines
and subsequently characterised. The resistant cells exhibited enhanced proliferative, clonogenic
capacity with significant up-regulation of P-glycoprotein (ABCB1), c-Myc, survivin, ÎČ-catenin and a
putative cancer-stem-like signature with increased expression of CD44, whereas the loss of E-cadherin
signifies induced EMT phenotype. A comparative analysis of miRNA expression profiling in parental
and cisplatin-resistant OSCC cell lines for a selected sets (deregulated miRNAs in head and neck cancer)
revealed resistance specific signature. Moreover, we observed similar expression pattern for these
resistance specific signature miRNAs in neoadjuvant chemotherapy treated and recurrent tumours
compared to those with newly diagnosed primary tumours in patients with OSCC. All these results
revealed that these miRNAs play an important role in the development of cisplatin-resistance mainly
through modulating cancer stem-cell-like and EMT-type properties in OSCC
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