Catalytic Performance of One-Pot Synthesized Fe-MWW Layered Zeolites (MCM-22, MCM-36, and ITQ-2) in Selective Catalytic Reduction of Nitrogen Oxides with Ammonia

The application of layered zeolites of MWW topology in environmental catalysis has attracted growing attention in recent years; however, only a few studies have explored their performance in selective catalytic reduction with ammonia (NH₃-SCR). Thus, our work describes, for the first time, the one-pot synthesis of Fe-modified NH₃-SCR catalysts supported on MCM-22, MCM-36, and ITQ-2. The calculated chemical composition of the materials was Si/Al of 30 and 5 wt.% of Fe. The reported results indicated a correlation between the arrangement of MWW layers and the form of iron in the zeolitic structure. We have observed that one-pot synthesis resulted in high dispersion of Fe³⁺ sites, which significantly enhanced low-temperature activity and prevented N₂O generation during the reaction. All of the investigated samples exhibited almost 100% NO conversion at 250 °C. The most satisfactory activity was exhibited by Fe-modified MCM-36, since 50% of NO reduction was obtained at 150 °C for this catalyst. This effect can be explained by the abundance of isolated Fe³⁺ species, which are active in low-temperature NH₃-SCR. Additionally, SiO₂ pillars present in MCM-36 provided an additional surface for the deposition of the active phase.     

Regioselective Synthesis of 5- and 3-Hydroxy-N-Aryl-1H-Pyrazole-4-Carboxylates and Their Evaluation as Inhibitors of Plasmodium falciparum Dihydroorotate Dehydrogenase

In silico evaluation of various regioisomeric 5- and 3-hydroxy-substituted alkyl 1-aryl-1H-pyrazole-4-carboxylates and their acyclic precursors yielded promising results with respect to their binding in the active site of dihydroorotate dehydrogenase of Plasmodium falciparum (PfDHODH). Consequently, four ethyl 1-aryl-5-hydroxy-1H-pyrazole-4-carboxylates and their 3-hydroxy regioisomers were prepared by two-step syntheses via enaminone-type reagents or key intermediates. The synthesis of 5-hydroxy-1H-pyrazoles was carried out using the literature protocol comprising acid-catalyzed transamination of diethyl [(dimethylamino)methylene]malonate with arylhydrazines followed by base-catalyzed cyclization of the intermediate hydrazones. For the synthesis of isomeric methyl 1-aryl-3-hydroxy-1H-pyrazole-4-carboxylates, a novel two-step synthesis was developed. It comprises acylation of hydrazines with methyl malonyl chloride followed by cyclization of the hydrazines with tert-butoxy-bis(dimethylamino)methane. Testing the pyrazole derivatives for the inhibition of PfDHODH showed that 1-(naphthalene-2-yl)-5-hydroxy-1H-pyrazole-4-carboxylate and 1-(naphthalene-2-yl)-, 1-(2,4,6-trichlorophenyl)-, and 1-[4-(trifluoromethyl)phenyl]-3-hydroxy-1H-pyrazole-4-carboxylates (~30% inhibition) were slightly more potent than a known inhibitor, diethyl α-{[(1H-indazol-5-yl)amino]methylidene}malonate (19% inhibition).     

Raman Method in Identification of Species and Varieties,Assessment of Plant Maturity and Crop Quality—A Review

The present review covers reports discussing potential applications of the specificity of Raman techniques in the advancement of digital farming, in line with an assumption of yield maximisation with minimum environmental impact of agriculture. Raman is an optical spectroscopy method which can be used to perform immediate, label-free detection and quantification of key compounds without destroying the sample. The authors particularly focused on the reports discussing the use of Raman spectroscopy in monitoring the physiological status of plants, assessing crop maturity and quality, plant pathology and ripening, and identifying plant species and their varieties. In recent years, research reports have presented evidence confirming the effectiveness of Raman spectroscopy in identifying biotic and abiotic stresses in plants as well as in phenotyping and digital selection of plants in farming. Raman techniques used in precision agriculture can significantly improve capacities for farming management, crop quality assessment, as well as biological and chemical contaminant detection, thereby contributing to food safety as well as the productivity and profitability of agriculture. This review aims to increase the awareness of the growing potential of Raman spectroscopy in agriculture among plant breeders, geneticists, farmers and engineers.     

Multivariate Time Series Imputation: An Approach Based on Dictionary Learning

The problem addressed by dictionary learning (DL) is the representation of data as a sparse linear combination of columns of a matrix called dictionary. Both the dictionary and the sparse representations are learned from the data. We show how DL can be employed in the imputation of multivariate time series. We use a structured dictionary, which is comprised of one block for each time series and a common block for all the time series. The size of each block and the sparsity level of the representation are selected by using information theoretic criteria. The objective function used in learning is designed to minimize either the sum of the squared errors or the sum of the magnitudes of the errors. We propose dimensionality reduction techniques for the case of high-dimensional time series. For demonstrating how the new algorithms can be used in practical applications, we conduct a large set of experiments on five real-life data sets. The missing data (MD) are simulated according to various scenarios where both the percentage of MD and the length of the sequences of MD are considered. This allows us to identify the situations in which the novel DL-based methods are superior to the existing methods.     

Advantages of ethane oxidative dehydrogenation on the MoVNbTeOx catalyst under elevated pressure

1. Download : Download high-res image (97KB)
2. Download : Download full-size image

     

Development of Non-Hydrolysable Oligosaccharide Activity-Based Inactivators for Endoglycanases: A Case Study on α-1,6 Mannanases

There is a vast genomic resource for enzymes active on carbohydrates. Lagging far behind, however, are functional chemical tools for the rapid characterization of carbohydrate-active enzymes. Activity-based probes (ABPs) offer one chemical solution to these issues with ABPs based upon cyclophellitol epoxide and aziridine covalent and irreversible inhibitors representing a potent and widespread approach. Such inhibitors for enzymes active on polysaccharides are potentially limited by the requirement for several glycosidic bonds, themselves substrates for the enzyme targets. Here, it is shown that non-hydrolysable trisaccharide can be synthesized and applied even to enzymes with challenging subsite requirements. It was found that incorporation of carbasugar moieties, which was accomplished by cuprate-assisted regioselective trans-diaxial epoxide opening of carba-mannal synthesised for this purpose, yields inactivators that act as powerful activity-based inhibitors for α-1,6 endo-mannanases. 3-D structures at 1.35–1.47 Å resolutions confirm the design rationale and binding to the enzymatic nucleophile. Carbasugar oligosaccharide cyclophellitols offer a powerful new approach for the design of robust endoglycosidase inhibitors, while the synthesis procedures presented here should allow adaptation towards activity-based endoglycosidase probes as well as configurational isosteres targeting other endoglycosidase families.     

Oxidative dehydrogenation of ethane to ethylene with carbon dioxide over supported Ga,Fe, and Cr-containing catalysts

Oxydative dehydrogenation of ethane to ethelene over Ga-, Fe- and Cr-oxide systems has been investigated. CO₂ was used as an oxidizing agent. The activity and stability of the synthesized catalysts were studied. The most efficient catalytic system was selected and the experimental conditions for the optimal conversion/selectivity ratio were found.     

On toric face rings

Following a construction of Stanley we consider toric face rings associated to rational pointed fans. This class of rings is a common generalization of the concepts of Stanley-Reisner and affine monoid algebras. The main goal of this article is to unify parts of the theories of Stanley-Reisner and affine monoid algebras. We consider (non-pure) shellable fan’s and the Cohen-Macaulay property. Moreover, we study the local cohomology, the canonical module and the Gorenstein property of a toric face ring.     

Silylation of silanols with vinylsilanes catalyzed by a ruthenium complex

A new ruthenium complex-catalyzed O-silylation of silanols with vinylsilanes leading to siloxane bond formation with the evolution of ethylene is described. A maximum conversion of silanol is reached using an excess of vinylsilane to also yield the product of the homo-coupling of the latter. Under the optimum conditions, when vinylsilane with at least one ethoxy substituent is used, the reaction gives exclusively unsymmetrical siloxanes.