Effects of Cr Doping and Water Content on the Crystal Structure Transitions of Ba2In2O5

Temperature-dependent crystal structure alterations in the brownmillerite-type material Ba2In2O5 play a fundamental role in its applications: i) photocatalytic CO2 conversion; ii) oxygen transport membranes; and iii) proton conduction. This is connected to a reversible uptake of up an equimolar amount of water. In this study, in situ X-ray and neutron diffraction were combined with Raman spectroscopy and solid-state nuclear magnetic resonance experiments to unravel the effects of Cr doping and water content on the crystal structure transitions of Ba2In2O5(H2O)x over a wide temperature range (10 K ≤ T ≤ 1573 K, x < 1). A mixture of isolated and correlated protons was identified, leading to a highly dynamic situation for the protons. Hence, localisation of the protons by diffraction techniques was not possible. Cr doping led to an overall higher degree of disorder and stabilisation of the tetragonal polymorph, even at 10 K. In contrast, a further disordering at high temperatures, leading to a cubic polymorph, was found at 1123 K. Cr doping in Ba2In2O5 resulted in severe structural changes and provides a powerful way to adjust its physical properties to the respective application.

Synthesis, characterization and antioxidant activity of 2-(4-Phenyl-6-p-Tolylpyrimidin-2-ylthio)-N-(4-substituted Phenyl)acetamides

A series of 2-(4-phenyl-6-p-tolylpyrimidin-2-ylthio)-N- (4-substituted phenyl)acetamide(4a-o) has been synthesized. Compounds have been characterized and tested for their antioxidant activity. The titled compounds (4a-o) have been synthesized by the reaction between 4-phenyl-6-p-tolylpyrimidine-2-thiol (2) with 2-chloro-N-substituted phenylacetamide (3ao) refluxed in acetone using catalytic amount of K2CO3. Compound (2) has been synthesized from (E)-1-phenyl- 3-p-tolylprop-2-en-1-one (1) with equimolar amount thiourea refluxed in alcoholic KOH to get compound (2). Starting compound chalcone was synthesized by Claisen-Schmidt condensation. All synthesized compounds have been characterized using spectroscopic techniques such as FT-IR, 1H NMR, 13C NMR, Mass Spectrometry and elemental analysis. Antioxidant assay has been performed by using DPPH radical scavenging method. Compounds 4-h and 4-o have shown good antioxidant activity.

INVESTIGATION OF THE DIRECTION OF THE REACTIONS OF MERCAPTOACETIC ACID ESTERS WITH EPI- AND THIOEPICHLOROHYDRINS

The reactions of mercaptoacetic acid ethers with epi- and thio-epichlorohydrin in alkaline medium have been investigated. It was found that the reaction of mercaptoacetic acid esters with epichlorohydrin in the presence of an equimolar amount of sodium hydroxide simultaneously produces 2,3-epoxy¬pro-pylalkoxycarbonylmethyl sulfides and 1-chlor-3-alkoxycarbonylmethylthiol-2-propanols. Under using sodium hydroxide is used as a catalyst, only 1-chlorine-3-alkoxycarbonylmethyltio-2-propa-nols are obtained the reaction of mercaptoacetic acid esters with epichlorohydrin. As a result of the interaction of mercapto-acetic acid esters with thioepichlorohydrin in the presence of equimolar amounts of sodium hydroxide, 2,3-epitiopropylalkoxycarbonylmethyl sulfides are formed as the only products of the reaction

Commentary on “time-dependent selected reaction monitoring-based GC-MS/MS method for estimation of genotoxic impurities in a new antibacterial agent: alalevonadifloxin mesylate”

The references cited in this article to justify the analysis of alkyl mesylates in alalevonadifloxin mesylate (ALA) are considered totally inappropriate since they all present evidence showing that such esters are not formed during the synthesis of a sulfonic-acid salt using an alcohol as solvent. Relevant mechanistic and kinetic data, first published over a decade ago, demonstrate that no alkyl-sulfonate impurities are produced when an equimolar amount of methanesulfonic acid is added to the base form of a drug substance dissolved in ethanol (or a similar alcohol solvent), and so confirmatory assay data should not be required.

Densities, Viscosities, and Thermal Conductivities of the Ionic Liquid 7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-enium Acetate and Its Mixtures with Water

7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-enium acetate (mTBD acetate) is a protic ionic liquid that is being investigated for use in industrial processes, such as for producing textiles from cellulose. To aid in designing such processes, we have measured the densities, viscosities, and thermal conductivities of mTBD acetate and aqueous mixtures containing mTBD acetate. We also investigated how excess amounts of mTBD or acetic acid affect the density, and found that in general an excess of either component decreases the density. However, when no water is present, the sample with excess acetic acid actually has a slightly higher density than when there is an equimolar amount of acid and base. The maximum density occurs when some water is present (around 30–40 mol%). We also modeled the density data using the ePC-SAFT equation of state and provide simple correlations for calculating the viscosity and thermal conductivity of these mixtures.

N-ALKOXYMETHYL DERIVATIVES OF 2-AMINOTHIAZOLE AND THEIR PROTECTIVE PROPERTIES

Conditions for alkoxymethylation of 2-aminothiazole with semiformals obtained by the interaction of aliphatic alcohols with formaldehyde were worked out. Alkoxymethylation was performed by means of preliminary preparation of the semiformal of appropriate hydroxylcontaining compounds followed by interaction of semiformal with equimolar amount of 2- aminothiazole. The structure of the obtained compounds was acknowledged by means of IR and NMR 1 H spectroscopy. It was established that the reaction of the alkoxymethylation proceeds in the amino form of the starting 2-aminothiazole to form an appropriate monosubstituted Nalkoxymethyl derivative. As a result of microbiological tests, it was established that these compounds have high bactericidal properties against microorganisms which affect petroleum products and, at a concentration of 0.5%, completely protect both M-8 lubricating oil and diesel fuel from damage by bacteria even in terms of their forced infection. It found that at a concentration of 100 mg/l the obtained compounds protect the CT-3 steel from acid corrosion, moreover N-(isopropoxymethyl)thiazol-2-amine has the greatest protection effect.

Densities, viscosities, and thermal conductivities of the ionic liquid 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-enium acetate and its mixtures with water

7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-enium acetate (mTBD acetate) is a protic ionic liquid that is being investigated for use in industrial processes, such as for producing textiles from cellulose. To aid in designing such processes, we have measured the densities, viscosities, and thermal conductivities of mTBD acetate and aqueous mixtures containing mTBD acetate. We also investigated how excess amounts of mTBD or acetic acid affect the density, and found that in general an excess of either component decreases the density. However, when no water is present, the sample with excess acetic acid actually has a slightly higher density than when there is an equimolar amount of acid and base. The maximum density occurs when some water is present (around 30-40 mol%). We also modeled the density data using the ePC-SAFT equation of state and provide simple correlations for calculating the viscosity and thermal conductivity of these mixtures.

Comparison of Blood Profiles of γ-Oryzanol and Ferulic Acid in Rats after Oral Intake of γ-Oryzanol

γ-Oryzanol (OZ), a bioactive phytochemical abundant in cereals such as rice, has been reported to be mainly hydrolyzed to ferulic acid (FA) in the body. Meanwhile, in our previous study, we revealed that a part of OZ is absorbed into the body and exists in its intact form. However, the comprehensive absorption profile of OZ and its metabolites (e.g., FA) after OZ intake has not been fully elucidated yet. Therefore, in this study, we measured the concentrations of OZ, FA, and FA conjugates (i.e., FA sulfate and glucuronide) in the blood of rats with the use of HPLC-MS/MS after a single oral administration of 300 µmol/kg body weight of rice bran OZ (RBOZ). As a result, intact OZ along with FA and FA conjugates existed in the blood, which implied that these constituents may all contribute to the physiological effects under OZ intake. Additionally, when an equimolar amount of FA (300 µmol/kg body weight) was administered, it was found that the absorption profile of FA was significantly different from that when RBOZ was administered.

Catalytic Hydrogenation of Carboxamides with a Bifunctional Cp*Ru Catalyst Bearing an Imidazol-2-ylidene with a Protic Aminoethyl Side Chain

Synthesis of a Cp*Ru complex bearing an NH2-functionalized N-heterocyclic carbene (C–NH) was achieved by treatment of Cp*RuBr(isoprene) with an equimolar amount of a silver complex, which was generated from Ag2O and 1-(2-aminoethyl)-3-methylimidazolium bromide, in CH3CN at room temperature. The new Cp*RuBr(C–NH) complex showed a higher catalytic performance than the related Cp*RuCl(P–NH) and Cp*RuCl(N–NH) complexes. In the reaction of N-arylcarboxamides, the amine products were obtained in satisfactory yields under mild temperature conditions.

Cycloaddition reactions of acetylenic iminium salts and diazoacetates leading to pyrazole iminium salts

Acetylenic iminium triflates with the general formula [R–C≡ C–C(Ar)=N+R2 TfO−] were found to be excellent dipolarophiles in [3+ 2] cycloaddition reactions with diazoacetates leading to (1H-pyrazol-3(5)-yl)methanaminium triflates in high yields. The terminal acetylenic iminium salt (propyne iminium salt) [HC≡C–C(Ph)=N+Me2 TfO−] reacted with an equimolar amount of methyl diazoacetate instantaneously at 20°C to form the expected pyrazole in almost quantitative yield. When a 2:1 stoichiometry was applied, subsequent Michael addition of the pyrazole at the alkyne occurred and the bis(iminium) ditriflate 4 was obtained in high yield. By hydride reduction or hydrolysis of the iminium group, some of the highly hygroscopic pyrazole iminium salts were converted into neutral, twofold functionalized, di- and tri-C-substitued 1H-pyrazoles.