Acidity as Descriptor for Methanol Desorption in B-, Ga- and Ti-MFI Zeotypes

The isomorphous substitution of Si with metals other than Al in zeotype frameworks allows for tuning the acidity of the zeotype and, therefore, to tailor the catalyst’s properties as a function of the desired catalytic reaction. In this study, B, Ga, and Ti are incorporated in the MFI framework of silicalite samples and the following series of increasing acidity is observed: Ti-silicalite < B-silicalite < Ga-silicalite. It is also observed that the lower the acidity of the sample, the easier the methanol desorption from the zeotype surface. In the target reaction, namely the direct conversion of methane to methanol, methanol extraction is affected by the zeotype acidity. Therefore, the results shown in this study contribute to a more enriched knowledge of this reaction.

Direct photoelectrochemical oxidation of hydroxymethylfurfural on tungsten trioxide photoanodes

An important target reaction for solar-powered biomass valorization is the conversion of 2,5-hydroxymethylfurfural (HMF) into key monomers for polyester production.

Conversion of fructose into methyl lactate over SnO2/Al2O3 catalystin flow regime

In recent years, numerous researchers have focused on the development of catalytic methods for processing of biomass-derived sugars into alkyl lactates, which are widely used as non-toxic solvents and are the starting material for obtaining monomeric lactide. In this work, the transformation of fructose into methyl lactate on Sn-containing catalyst in the flow reactor that may be of practical interest was studied. The supported Sn-containing catalyst was ob-tained by a simple impregnation method of granular γ-Al2O3. The catalytic ex-periments were performed in a flow reactor at temperatures of 160-190 °C and pressure of 3.0 MPa. The 1.6-9.5 wt.% fructose solutions in 80% aqueous methanol were used as a reaction mixture. It was found that addition to a reac-tion mixture of 0.03 wt.% potassium carbonate leads to the increase in selec-tivity towards methyl lactate on 15% at 100% conversion of fructose. Prod-ucts of the target reaction С6Н12О6 + 2СН3ОН = 2С4Н8О3 + 2Н2О were ana-lyzed using 13C NMR method. The following process conditions for obtaining of 65 mol% methyl lactate yield at 100% fructose conversion were found: use of 4.8 wt.% fructose solution in 80% methanol, 180 °С, 3.0 МПа and a load on catalyst 1.5 mmol C6H12O6/mlcat/h at contact time of 11 minutes. The cata-lyst productivity is 2.0 mmol C4H8O3/mlcat/h and the by-productі are 1,3-dihydroxyacetone dimethyl acetal (20%) and 5-hydroxymethylfurfural (10%). It should be noted that a racemic mixture of L- and D-methyl lactates has been obtained by conversion of D-fructose on the SnO2/Al2O3 catalyst. The SnO2/Al2O3 catalyst was found to be stable for 6 h while maintaining full fruc-tose conversion at 55–70% methyl lactate selectivity. After regeneration the catalyst completely restores the initial activity.

Mechanistic insight into the organocalcium-mediated nucleophilic alkylation of benzene and further rational design

DFT calculations disclosed the mechanism of the target reaction and the origin of unusual nucleophilicity of organocalcium. More reactive analogues were designed.

New Developments on the Hirao Reactions, Especially from “Green” Point of View

Background: The Hirao reaction discovered ca. 35 years ago is an important P–C coupling protocol between dialkyl phosphites and aryl halides in the presence of Pd(PPh3)4 as the catalyst and a base to provide aryl phosphonates. Then, the reaction was extended to other Preagents, such as secondary phosphine oxides and H-phosphinates and to other aryl and hetaryl derivatives to afford also phosphinic esters and tertiary phosphine oxides. Instead of the Pd(PPh3)4 catalyst, Pd(OAc)2 and Ni-salts were also applied as catalyst precursors together with a number of mono- and bidentate P-ligands. Objective: In our review, we undertook to summarize the target reaction with a special stress on the developments attained in the last 6 years, hence this paper is an update of our earlier reviews in a similar topic. Conclusion: “Greener” syntheses aimed at utilizing phase transfer catalytic and microwave-assisted approaches, even under “P-ligand-free. or even solvent-free conditions are the up-to date versions of the classical Hirao reaction. The mechanism of the reaction is also in the focus these days.

MCS2: minimal coordinated supports for fast enumeration of minimal cut sets in metabolic networks

Motivation Constraint-based modeling of metabolic networks helps researchers gain insight into the metabolic processes of many organisms, both prokaryotic and eukaryotic. Minimal cut sets (MCSs) are minimal sets of reactions whose inhibition blocks a target reaction in a metabolic network. Most approaches for finding the MCSs in constrained-based models require, either as an intermediate step or as a byproduct of the calculation, the computation of the set of elementary flux modes (EFMs), a convex basis for the valid flux vectors in the network. Recently, Ballerstein et al. proposed a method for computing the MCSs of a network without first computing its EFMs, by creating a dual network whose EFMs are a superset of the MCSs of the original network. However, their dual network is always larger than the original network and depends on the target reaction. Here we propose the construction of a different dual network, which is typically smaller than the original network and is independent of the target reaction, for the same purpose. We prove the correctness of our approach, minimal coordinated support (MCS2), and describe how it can be modified to compute the few smallest MCSs for a given target reaction. Results We compare MCS2 to the method of Ballerstein et al. and two other existing methods. We show that MCS2 succeeds in calculating the full set of MCSs in many models where other approaches cannot finish within a reasonable amount of time. Thus, in addition to its theoretical novelty, our approach provides a practical advantage over existing methods. Availability and implementation MCS2 is freely available at https://github.com/RezaMash/MCS under the GNU 3.0 license. Supplementary information Supplementary data are available at Bioinformatics online.

Hydroxymethylation of Furfural to HMF with Aqueous Formaldehyde over Zeolite Beta Catalyst

Hydroxymethylation of 2-furaldehyde (furfural) toward 5-hydroxymethyl-2-furaldehyde (HMF) was examined in this work among various zeolites with an aqueous formaldehyde as a reagent in a batch and a flow reactor system. It was found that the zeolite beta gave high activity and good reusability with calcination treatment before each run for the target reaction in the batch system. The unique stability of the HMF yield in the liquid-flow system was also observed only in the case of zeolite beta. The effect of the SiO2/Al2O3 ratio in the zeolite beta suggested that hydrophobicity would be an important factor in faster hydroxymethylation with an aqueous formaldehyde reagent. The highest turnover frequency (TOF) for HMF production was found to be 2.4 h−1 in the case of zeolite beta with SiO2/Al2O3 = 440 in the batch reactor system. An approximately 30% yield for HMF was achieved under optimum conditions for zeolite beta catalysts.

Homogeneous Catalysts Based on Heteropoly Acid Solutions for Redox Processes. III. Development of an Effective Method for Synthesis of 2,3,5-trimethyl-1,4-benzoquinone

Various methods for preparation of 2,3,5-trimethyl-1,4-benzoquinone (TMQ) – the key semiproduct for synthesis of vitamin E – through catalytic oxidation of 2,3,6-trimethylphenol (TMP) are considered. Potentials of aqueous solutions of Mo-V-P heteropoly acids (HPA) as catalysts for oxidation of TMP with oxygen are shown. Various technological modes of application of HPA for the said reaction are analyzed, among which are a one-stage homogeneous acetic acid oxidation of TMP and a two-phase two-stage method. The efficiency of the two-stage method is demonstrated; it provides a high (up to 99.5 %) selectivity to TMQ and a high productivity of the catalyst for the target reaction (ca 600–800 g TMQ·Lcat–1·h–1).

Computing irreversible minimal cut sets in genome-scale metabolic networks via flux cone projection

Motivation Minimal cut sets (MCSs) for metabolic networks are sets of reactions which, if they are removed from the network, prevent a target reaction from carrying flux. To compute MCSs different methods exist, which may fail to find sufficiently many MCSs for larger genome-scale networks. Results Here we introduce irreversible minimal cut sets (iMCSs). These are MCSs that consist of irreversible reactions only. The advantage of iMCSs is that they can be computed by projecting the flux cone of the metabolic network on the set of irreversible reactions, which usually leads to a smaller cone. Using oriented matroid theory, we show how the projected cone can be computed efficiently and how this can be applied to find iMCSs even in large genome-scale networks. Availability and implementation Software is freely available at https://sourceforge.net/projects/irreversibleminimalcutsets/. Supplementary information Supplementary data are available at Bioinformatics online.