Use of PLS Discriminant Analysis for Revealing the Absence of a Compound in an Electron Ionization Mass Spectral Database

A mathematical model is proposed for revealing the absence of a compound to be identified in an electron impact mass spectral library. The mathematical model (developed based on PLS Discriminant Analysis) can be represented as a “black box” which provides an answer whether a compound to be sought is absent or present in a database. The match factors of top ten candidates among the possible ones were used as input data. More than 5000 objects (mass spectra) were used at the steps of training, validation, and testing. The developed classification model provides correct prediction (of whether a compound is absent from the library) in 28.4% cases, while only 1.2% of compounds present in the database were incorrectly classified as the absent ones.     

Determination of explosive vapor concentrations with remote sampling in the control of objects

A procedure is proposed for the determination of the vapor concentration of 2,4,6-trinitrotoluene (TNT) in air at a level of 10^–16 g/cm³ in the control of objects for the presence of TNT. The procedure includes preconcentration of TNT vapors and gas chromatographic determination with a limit of TNT detection at a level of 0.08 ± 0.02 pg in a sample. The procedure was applied to the control objects in cells of typical automatic luggage locker with sampling through sampling air ducts. A measure of sample losses as the breakthrough of vapors through sampling air ducts and gas dynamic conditions for the reduction of vapor losses as the ratio of diffusion coefficient to the air duct flow rate were proposed. The time constant of the saturation of the sampling system with TNT vapors and the time constant of its cleaning were determined. It was shown that TNT vapors can be detected virtually satisfactorily near TNT-containing objects with sampling through long channels.     

Primary photophysical and photochemical processes for Pt(SCN)<Subscript>6</Subscript><Superscript>2–</Superscript> complex

Photosolvation of a Pt^IV hexathiocyanate complex Pt(SCN)₆ ^2– in water and ethanol was studied by steady-state photolysis, nanosecond laser flash photolysis, and ultrafast kinetic spectroscopy. Complexes Pt(SCN)₅(H₂O)^– and Pt(SCN)₅(C₂H₅OH)^– were found to be the only reaction products. The quantum yields of photosolvation are independent of the excitation wavelength, being equal to 0.25 and 0.5 for the solutions of the complex in water and ethanol, respectively. Photosolvation proceeds by the mechanism of heterolytic metal—ligand bond dissociation without involvement of redox processes. The characteristic time of formation of the end products for both solvents is about 10 ps. Three successive intermediates detected on the picosecond time scale were interpreted as Pt^IV complexes. The nature of the intermediates and possible mechanisms of photosolvation are discussed.     

Solution state and complexing ability of 1,4-bis(amidomethylsulfinyl)butane toward iron(III), copper(II), cobalt(II), nickel(II), and manganese(II)

The solution state and thermodynamic stability of complexes of the new antituberculosis agent 1,4-bis(amidomethylsulfinyl)butane (L) with iron(III), copper(II), cobalt(II), nickel(II), and manganese(II) in an aqueous solution in the presence and in the absence of the nonionic surfactant Brij 35 were studied by spectrophotometry, pH potentiometry, NMR relaxation technique (T = 25 °C; variable ionic strength), and mathematical simulation. The geometry optimization of all structures was carried out by the molecular mechanics method MM2 in order to obtain data on coordination modes. In addition, the structure of 1,4-bis(amidomethylsulfinyl)butane was refined by the DFT/B3LYP/6-311++G(d,p) quantum chemical method using the IEFPCM model to take into account solvent effects. In an aqueous solution (in the concentration range of 1.3?10^–5—1?10^–3 mol L–1) and in the presence of Brij 35, 1,4-bis(amidomethylsulfinyl)butane exists as a neutral monomer. The Beer—Lambert—Bouguer law is obeyed in a wide concentration range for compound L in an aqueous solution, as well as in the presence of the surfactant, which can be used for the quantification of compound L. Iron(III), cobalt(II), and nickel(II) were shown to form 1: 1 mononuclear complexes with L; and copper(II) forms, 1: 1 and 2: 2 complexes. The presence of Brij 35 in the Cu²⁺—L system at a micellar concentration promotes the formation of a dinuclear complex.     

Alkylation of phenol with olefins in the presence of catalysts based on mesoporous aromatic frameworks

Mesoporous polyaromatic frameworks (PAFs) based on tetraphenylmethane were obtained and modified with sulfonic acid groups. The compounds were characterized by solid-state ¹³C NMR and IR spectroscopy, low-temperature nitrogen adsorption-desorption, and transmission electron microscopy. The acidities of the PAF-1-SO₃H and PAF-2-SO₃H samples determined by titration were 3.99 mmol g^–1 and 0.91 mmol g^–1, respectively. The catalytic activity of PAF-SO₃H for alkylation of phenol with linear terminal olefins was investigated. The reaction products were isomeric monoalkylphenols (C-alkylates), and alkyl phenyl ethers (O-alkylates).     

A comparative study of the reactions of fluorinated oxi- and thiiranes with acyl chlorides

The CoCl₂-catalyzed reactions of fluorinated 1,2-oxi- and thiiranes with acyl chlorides were studied. It was found that a regioselective heterocycle opening reaction resulted in two isomers having normal and abnormal structure in a ratio predetermined by the substituents in both the starting heterocycles and acyl chlorides.     

<Emphasis Type="Italic">N</Emphasis>-Allyl-substituted aminomethylene-1,1-bisphosphonates in 1,3-dipolar cycloaddition reaction with aromatic nitrile <Emphasis Type="Italic">N</Emphasis>-oxides

A reaction of N-allyl-substituted aminomethylene-1,1-bisphosphonates with aromatic nitrile N-oxides was used to obtain new aminomethylenebisphosphonates with one or two 3-arylisoxazoline rings at the nitrogen atom. NMR spectroscopy studies showed that the bisphosphonates with two isoxazoline fragments in the molecule exist in solution as a mixture of two diastereomers.     

Synthesis and properties of 1-(R-adamant-1-yl)-3-(1-propionylpiperidin-4-yl)ureas and 4-({4-[3-(R-adamant-1-yl)ureido]cyclohexyl}oxy)benzoic acids,efficient target-oriented human soluble epoxide hydrolase inhibitors

A reaction of R-adamant-1-yl isocyanates with 4-[(4-aminocyclohexyl)oxy]benzoic acid and 1-(4-aminopiperidin-1-yl)propan-1-one in DMF afforded corresponding ureas in 90—95% yield, the target-oriented inhibitors of epoxide hydrolase sEH. The ureas are characterized by reduced melting points and increased solubility in water, as well as by inhibitory activity in the range of 0.5—4.0 nmol L^–1.     

Heterocyclization of carboxy- and sulfonamides in the course of oxidative addition to unsaturated substrates

Formation of heterocyclic compounds in the course of oxidative addition of carboxamides and sulfonamides to alkenes and dienes is reviewed. Main attention is focused on reactions proceeding in the presence of halo-containing oxidative systems and reagents. Features of behavior of fluorine-substituted sulfonamides and carboxamides are discussed.     

Polyethylenimine and tris(2-aminoethyl)amine modified p(GA–EGMA) microbeads for sorption of uranium ions: equilibrium,kinetic and thermodynamic studies

Poly(glycidyl methacrylate-ethyleneglycol dimethacrylate), p(GA–EGMA), microbeads were prepared through suspension polymerization. It was decorated with polyethylene imine (PEIM) and tris(2-aminoethyl)amine (TAEA) ligands to decorate with polyamine groups. These microbeads were used for sorption of uranium ions from aqueous solution. The maximum sorption of uranium ions on the PEIM and TAEA modified microbeads was observed at pH 6.0. The maximum sorption capacity of acid hydrolyzed p(GA–EGMA)–OH, p(GA–EGMA)–PEIM and p(GA–EGMA)–TAEA microbeads was found to be 7.21, 87.8 and 64.3 mg g^?1. The sorption process conforms to the pseudo-second order kinetic model and the Langmuir and Temkin isotherm models well.