The umpolung of substituent effect in nucleophilic aromatic substitution. A new approach to the synthesis of N,N-disubstituted melamines (triazine triskelions) under mild reaction conditions

By the umpolung of substituent effect 1,3,5-triazines substituted with three dialkylamino groups were prepared under mild reaction conditions by treatment of cyanuric chloride with tertiary amines. Quaternary N-triazinylammonium salts were identified as reactive intermediates activating the triazine ring and strongly promoting the persubstitution of all chlorine atoms. The final degradation of intermediate N-triazinylammonium chlorides proceeded at room temperature or in boiling dichloromethane spontaneously within irreversible evolution of appropriate chloroalkane.     

Small Noncytotoxic Carbon Nano‐Onions: First Covalent Functionalization with Biomolecules

Small carbon nano‐onions (CNOs, 6–8 shells) were prepared in high yield and functionalized with carboxylic groups by chemical oxidation. After functionalization these nanostructures were soluble in aqueous solutions. 3‐(4,5‐dimethylthiazol‐2‐yl)‐5‐(3‐carboxymethoxyphenyl)‐2‐(4‐sulfophenyl)‐2 tetrazolium (MTS) tests showed excellent cytocompatibility of all CNOs analyzed at 30 and 300 μg mL^?1, so these carbon nanostructures can be safely used for biological applications. The first covalent functionalization of oxidized CNOs (ox‐CNOs) with biomolecules, by using biotin–avidin interactions is reported here. Multilayers were prepared on a gold surface by layer‐by‐layer assembly and the process was monitored by surface plasmon resonance (SPR) spectroscopy and atomic force microscopy (AFM). Covalent binding of molecules to the short amine‐terminated organosulfur monolayers was assessed by Fourier transform infrared spectroscopy using total attenuated reflactance mode (FT‐IR/HATR).     

Nonsingular bilinear forms on direct sums of ideals

In the paper we formulate a criterion for the nonsingularity of a bilinear form on a direct sum of finitely many invertible ideals of a domain. We classify these forms up to isometry and, in the case of a Dedekind domain, up to similarity.     

Tautomerism, structure and properties of 1,1′,1″-(2,4,6-trihydroxybenzene-1,3,5-triyl)triethanone

According to computational predictions 1,1′,1″-(2,4,6-trihydroxybenzene-1,3,5-triyl)triethanone (triacetylphloroglucinol) (TTT, form a) can exist in five tautomeric forms, among which 2,4,6-tris(1-hydroxyethylidene)-1,3,5-cyclohexanetrione (form e) exhibits thermodynamic stability comparable to that of form a. X-ray investigations reveal that the compound exists in form a in the crystalline solid phase. Analysis of the arrangement of atoms involved in the three intramolecular H-bonds, responsible for the stabilization of tautomer a by 55.4 kcal/mol, suggests that there could be fast H atom (proton) transfer within the hydrogen bonds, bringing about the transformation of a into e and vice versa. Such an effect could explain the unique behaviour and spectral properties of TTT in solutions.     

Liquid chromatography tandem mass spectrometry with ion trap and triple quadrupole analyzers for determination of thyreostatic drugs in urine and muscle tissue

Liquid chromatography tandem mass spectrometry methods were developed and validated to screen for and confirm residues of the thyreostatic drugs: tapazole, thiouracil, methylthiouracil, propylthiouracil, and phenylthiouracil in bovine and porcine urine and muscle tissues using dimethylthiouracil as internal standard. Thyreostats were extracted from urine samples with diethyl ether after derivatisation with 3-iodobenzylbromide in basic medium (pH 8.0) and analyzed by gradient elution on a Nucleosil C18 column with ion trap mass spectrometry detection using an electrospray source and triple quadrupole MS detection with turbo spray source. Thyreostats were extracted from muscle tissue with methanol, the denaturation of matrix protein was performed and then the same steps as for the urine samples were carried out. The methods were validated in accordance with the Commission Decision 2002/657/EC. Good thyreostats recoveries were obtained (from 82% to 117%) as well as acceptable within-lab reproducibility. The values of the decision limit CCα and the detection capability CCβ of five thyreostatic drugs are found to be below the recommended concentration set at 10 μg L(-1) (kg(-1)). The results of the validation demonstrate that liquid chromatography mass spectrometry with ion trap detection does not meet the criteria for confirmation for some thyreostats and therefore was applied for screening purpose only.     

Microporous {[Ni(cyclam)]3[W(CN)8]2}n affording reversible structural and magnetic conversions

Methanol adsorption into the porous 2D bimetallic coordination network {[Ni(cyclam)](3)[W(CN)(8)](2)}(n) (cyclam = 1,4,8,11-tetraazacyclotetradecane) causes significant modification of its structure and magnetic properties. Fully reversible transformations between the three states of the network: anhydrous, hydrated and methanol-modified are observed with the transition to the magnetic ordered state at T(c) equal to 4.9 K, 8.3 K and 11.4 K respectively. All three phases have a metamagnetic character but the methanol-modified one most easily turns to ferromagnetic and shows a hysteresis loop with coercivity field of 250 Oe. The differences in magnetic behaviour of the anhydrous and guest-induced forms of the compound are discussed in terms of changes in the structure: CN-bridge geometry and distance between the layers.     

Electron ionization and electrospray mass spectra of diaryl-substituted enaminoketones and their thio analogs

Electron ionization (EI) and positive electrospray ionization (ESI) mass spectra of selected diaryl enaminoketones and enaminothiones have been studied. In the EI mass spectra of both classes of compound, molecular ion peaks are accompanied by the peaks corresponding to the [M-H](+) ions. The formation of these ions can be rationalized by a cyclization reaction resulting in the formation of the respective isoxazolium and isothiazolium cations. Under positive ESI conditions, in the spectra recorded for the enaminoketones peaks corresponding to the [M+H](+), [M+Na](+) and [2M+Na](+) ions appeared, while in the spectra recorded for the enaminothiones, peaks corresponding to the [M-H](+) ions were dominant. These ions are most likely formed by oxidation of the neutral enaminothione molecules on the surface of the positively charged stainless steel capillary in the ESI ion source (anodic oxidation).     

N- Hydroxyphthalimide and transition metal salts as catalysts of the liquid-phase oxidation of 1-methoxy-4-(1-methylethyl)benzene with oxygen

The oxidation process of 1-methoxy-4-(1-methylethyl)benzene catalysed by N-hydroxyphthalimide (NHPI) or NHPI in combination with Cu(II), Co(II), Mn(II) and Fe(II) salts was studied. The effects of the amount of catalyst and the temperature were determined. 1-Methyl-1-(4-methoxyphenyl)ethyl hydroperoxide was obtained in a yield of 73 mol% when 1-methoxy-4-(1-methylethyl)benzene was oxidised for 3 h at 60°C in acetonitrile as a solvent in the presence of NHPI. 1-(4-Methoxyphenyl)ethanone with high selectivity up to 68–75 mol%, but low yield amounting to 11 mol% was obtained when 1-methoxy-4-(1-methylethyl)benzene was oxidised in the presence of the NHPI/Cu(II) system at 120°C.      

Carbon Dioxide Adsorption over Activated Carbons Produced from Molasses Using H2SO4, H3PO4, HCl,NaOH, and KOH as Activating Agents

Cost-effective activated carbons for CO₂ adsorption were developed from molasses using H₂SO₄, H₃PO₄, HCl, NaOH, and KOH as activating agents. At the temperature of 0 °C and a pressure of 1 bar, CO₂ adsorption equal to 5.18 mmol/g was achieved over activated carbon obtained by KOH activation. The excellent CO₂ adsorption of M-KOH can be attributed to its high microporosity. However, activated carbon prepared using HCl showed quite high CO₂ adsorption while having very low microporosity. The absence of acid species on the surface promotes CO₂ adsorption over M-HCl. The pore size ranges that are important for CO₂ adsorption at different temperatures were estimated. The higher the adsorption temperature, the more crucial smaller pores were. For 1 bar pressure and temperatures of 0, 10, 20, and 30 °C, the most important were pores equal and below: 0.733, 0.733, 0.679, and 0.536 nm, respectively.     

Nutritional and Polyphenolic Composition of Agrimonia procera Wallr. from Experimental Cultivation with Different Levels of Nitrogen Fertilization

Plants of the genus Agrimonia, including fragrant agrimony Agrimonia procera Wallr., mainly used as pharmaceutical raw material, perfectly fit into the current trends in nutrition and food technology that are searching for organic raw materials with high contents of bioactive compounds, such as dietary polyphenols and fiber. The aim of the research was to determine the nutritional and polyphenolic composition of fragrant agrimony Agrimonia procera Wallr. from experimental cultivation with varying levels of nitrogen fertilization in the nitrate, ammonium, or amide forms. In the experimental cultivation of fragrant agrimony in a seeding medium with a moderately high level of mineral content, the aerial parts, especially the leaves, were characterized by contents protein, dietary fiber, fat, and polyphenols at levels of 11.5, 58.0, 3.0, and 10.5% of dry matter, respectively, and an energy value of about 260 kcal/100 g of dry matter. The effect of additional nitrogen fertilization, in the form of ammonium nitrate and urea, on the content and yield of nutrients and polyphenol in fragrant agrimony depends both on the dose and the form of nitrogen, as well as the morphological part, of the plant.