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Northern Koryakia belongs to two different vegetation zones: Beringian forest-tundra zone and East-Siberian larch forest subzone of the Eurasian boreal (taiga) zone. The territory of Northern Koryakia was subdivided into 3 geobotanical provinces and 14 districts. Most peculiar, the Siberian dwarf-pine ( Pinus pumila ) elfin woods occupy zonal mesic habitats of plains, plateaus and gentle mountain slopes. They form a zonal vegetation type of Beringian creeping woodland . Polar birch ( Betula middendorffii ) shrubs (up to 1.5 m tall) and dwarf-alder ( Alnus fruticosa ) thickets form another important vegetation type associated with Pinus pumila open woodlands. These two vegetation types form a distinctive subalpine vegetation belt at lower elevations (up to 150-300 m). The alpine vegetation belt (up to 400-450 m) is characterized by a complex of dwarf-shrub and lichen-rich tundra communities that occur under conditions of a heat deficit and very short growing season. Azonal habitats, such as wide river valleys, are occupied by flood-plain forests ( Chosenia arbutifolia, Populus suaveolens, Salix udensis, andS. schwerinii). In the floodplains of rivers and streams, shrubby willow thickets are widespread, predominated by Salix pulchra, S. alaxensis, S. krylovii and S. hastata. Several vegetation types, mainly coastal dwarf-shrub tundra, mires, salt marshes, mesic and hygric meadows, and isolated Betula ermanii groves are distributed on azonal sites. In waterlogged habitats of lowlands and depressions, sedge-moss mires, Sphagnum -rich oligotrophic bogs with 40-60 cm-thick peat layers, hillocky mires, and polygonal mires develop. Tussocky sedge-cottongrass mires developing in the intermountain depressions are characteristic to the Anadyr-Penzhina lowland. Typical components of them are Carex lugens , Eriohorum vaginatum , Betula exilis and other hyparctic dwarf-shrubs. In the western part of the Penzhina River Basin, larch ( Larix cajanderi ) open woodlands form the northern forest limit. In addition, there are groves of Japanese white birch ( Betula platyphylla ) in the river valleys.

Stone-birch (Betula ermanii) forests were studied at the northern limit of their range in the north of the Koryaksky District. The species composition, community structure, and habitats of stone-birch groves are described. Their altitudinal position and geographical distribution are discussed. A classification of stone-birch communities on Olyutorsky Gulf coast was developed using the dominant-determinant approach. Within the study area, the community diversity of stone-birch forests was represented by 5 associationsforming 3 groups of associations: Betuleta pteridosa (fern-rich stone-birch forests), Betuleta calamagrostidosa (grass-rich stone-birch forests), and Betuleta fruticosa (shrub-rich stone-birch forests). All the syntaxa have been previously described from the Kamchatka Peninsula. The Koryak communities differed from their Kamchatka analogues in the floristic composition, lower species diversity, and high density of the shrub layer. The most important characteristics of shrub-rich stone-birch communities were the high abundance of Sorbus sambucifolia and Alnus fruticosa, while for fern-rich communities it was the predominance of Dryopteris expansa in the herb layer. The intrazonal stone-birch groves are considered to be the remnants of widespread birch forests of the Holocene climate optimum, which ended ca. 5 Ka B. P. They have survived on the southern maritime slopes of the Koryak Upland ridges and turned into fragmentary and floristically impoverished communities. The relic stone-birch groves of the Koryak Upland are regarded as rare and endangered communities in need of special protection.

The distribution boundaries of the two birch species communities: Stone-birch (Betula ermanii Cham.) and White birch (Betula platyphylla Sukacz) forests have been firstly reliably established for the North of the Koryak Region. The remote sensing data, aerial observations, original relevés, and itinerary research data were used. A map of the Stone-birch and White-birch forests allocation in the mainland part of the Koryak Region was compiled. It was shown that Stone-birch groves were found in relatively warmer and wetter areas adjacent to the Bering Sea coast. They occupy Southern and South-Eastern slopes of the Koryak Upland spurs; whereas White birch forests are common in the continental districts. They are found in the valleys of the rivers Penzhina, Talovka, Belaya, Oklan, Apukvayam, on the Penzhinskiy Ridge slopes. Stone-birch forests do not occur North of 62° northern latitude, do not overcome the boggy depression of Parapolsky Dale, and do not occur to the West of 167° 30’ eastern longitude. The natural phytogeographical boundary between the areas of the two birch formations are the Southern and South-Eastern spurs of the Koryak Upland.

The flora of liverworts is described for the immediate vicinity of the thermal springs in Kamchatka. It is revealed that because of the hydrothermal phenomena widely spread in Kamchatka certain thermophilic taxa exist as relicts and a small group of species grows that occur only near the thermal fields over their whole range. In general, the taxonomic diversity of liverworts in thermal habitats is rather low with only 45 species being found.

A procedure is developed for the gas-chromatographic determination of 1,2,3-benzotriazole including preliminary derivatization with acetic anhydride in an aqueous solution followed by the extraction the derivative with toluene. The procedure is applied to the analysis of water samples, process solutions for treating metals, air of the working zone, and industrial emissions. Determination limits in water media are 0.01 mg/L and in the air of the working zone, 0.1 mg/m3.

Zol-gel process was used to synthesize equilibrium mixtures of mono-, di-, and trimester derived from trimethylolpropane and perfluorocarboxylic acids. The elution order of the components of the mixtures from a weakly polar HP-5 column was established. The mass spectra of the synthesized compounds were studied. The GC-MS parameters of the products were compared with the respective parameters of their nonfluorinated analogs. The characteristics of the fluorinated esters have features determined by the esterification degree and the nature of the perfluoroalkyl groups, due to which these compounds can be identified in mixtures.

The reaction of fluorine-containing glycidyl ethers with various alcohols (i-PrOH, MeOH, PhOH, 2,2,3,3-tetrafluoropropanol) in basic medium resulted in products of regioselective opening of the oxirane ring. In reaction of 2,2,3,3-tetrafluoropropyloxymethyloxirane with 2-propanol under conditions of phase-transfer catalysis the main product was the corresponding 1,2-diol (yield 42%).

The reaction of 2,3-epoxyoctafluorobutane with 2-aminobenzenethiol in N,N-dimethylacetamide gave 3-(2-aminophenylsulfanyl)-1,1,1,3,4,4,4-heptafluorobutane-2,2-diol. In the reaction of the same compounds in dioxane, 2,3-bis(trifluoromethyl)-3,4-dihydro-2H-1,4-benzothiazin-2-ol was formed as a result of primary attack by the amino group in 2-aminobenzenethiol on the epoxy ring. The same product was obtained by treatment with 2-aminobenzenethiol of 2,3-bis(trifluoromethyl)-2H-1,4-benzoxazin-2-ol which was synthesized from 2,3-epoxyoctafluorobutane and 2-aminophenol.

The reaction of a technical mixture of polychlorinated biphenyls with ethanol and potassium hydroxide in dimethyl sulfoxide was studied. The composition of the products formed in the process was determined by gas chromatography and gas chromatography mass spectrometry.

The reactions of epoxy derivatives of internal perfluoroolefins with o-phenylenediamine and 2-aminophenol in dioxane gave 23–67% of the corresponding 2,3-bis(perfluoroalkyl)quinoxalines and 2,3-bis(perfluoroalkyl)-2H-1,4-benzoxazin-2-ols, respectively. When N,N-dimethylacetamide was used as a solvent, the main reaction pathway was anionic isomerization of epoxides into ketones which were then converted into 2-perfluoroalkylbenzimidazoles (in the reactions with o-phenylenediamine) or 2-hydroxy-N-perfluoroalkanoylanilines (in the reactions with 2-aminophenol). The reaction of 3,4-epoxydodecafluorohexane with 2-aminophenol in N,N-dimethylacetamide was accompanied by unusual cyclization to afford 2-pentafluoropropanoyl-2-pentafluoroethyl-1,3-benzoxazolidine.

The reactions of oxides of internal trans -, cis -perfluoroolefins with o -phenylenediamine and 2-aminophenol in dioxane gave 2,3-bis(perfluoroalkyl)quinoxalines and 2,3-bis(perfluoroalkyl)-2H-1,4-benzoxazin-2-ols respectively in yields of 23–67%. When N , N -dimethylacetamide was used as a solvent an anionic isomerization of the oxides into ketones, which further yielded 2-(perfluoroalkyl)benzimidazoles in the case of o -phenylenediamine and 2-hydroxy- N -perfluoroalkanoylanilines in the case of 2-aminophenol, became the main path of these reactions. Unusual cyclization resulting in 2-pentafluoroethyl-2-pentafluoropropanoylbenzoxazolidine occurs on interaction between dodecafluoro-3,4-epoxyhexane and 2-aminophenol in N , N -dimethylacetamide.

The reaction of Sovol technical mixture of polychlorobiphenyls with sodium methoxide in bipolar aprotic solvents was studied. The reactivity of polychlorobiphenyls was evaluated using gas chromatography and gas chromatography-mass spectrometry.

A procedure was developed for determining chloroacetic acids in drinking water. The procedure is based on solid-phase extraction followed by the conversion of chloroacetic acids to trifluoroacetic esters and their separation and determination by gas–liquid chromatography with an electron capture detector. Esterification conditions were optimized. The procedure was used for analyzing samples of drinking water.

Chemical utilization (conversion) of polychlorobiphenyls by nitration of their industrial mixture was studied. Reduction of the nitro derivatives gave mixtures of aminopolychlorobiphenyls.

A method for the metrological certification of reference samples (RS) of solutions of organic compounds was proposed. The method is based on a procedure of sample preparation that uses both calculated and experimental data and involves the evaluation of the purity of the reagents employed. Impurity components were identified. Procedures for the determination of impurity components in source materials by gas chromatography with flame-ionization detection were developed. Calibration coefficients for halogen-containing impurity components in reference to an internal standard were determined experimentally or calculated. Certified reference samples of solutions of trichloromethane, bromodichloromethane, dibromochloromethane, and tribromomethane were designed for the quality control of drinking water

A procedure was proposed for the metrological certification of reference samples (RS) of solutions of organic compounds. The procedure consists in the determination of performance characteristics of RSs using the developed and certified procedures for the determination of mass concentrations by gas chromatography with flame ionization detection using internal standards. The selection of the internal standards and calibration procedures and the calculation of the errors of determination are considered. Certified reference samples (CRS) of tetrachloromethane, tetrachloroethylene, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol solutions in ethanol are developed for the quality control of drinking water

Perfluorocarboxylic thioesters RFC(O)SR (RF=CF3(CF2)j, R=CH3(CH2)i, i andj=0–5) were studied for the first time by GLC on packed columns using SE-30, SKTFT-50X, and XE-60 as the stationary phase. The values of thermodynamics functions of sorption were calculated. The correlations between these functions and the molecular structures as well as the conditions of analysis were established. The insertion of the S atom into the molecules of derivatives of perfluorocarboxylic acids causes a decrease in the contribution of the orientation interaction and an increase in the dispersion interaction of thioesters with the stationary phases compared to esters and amides of perfluorocarboxylic acids studied previously.

The dependence of the variations in the differential molar free energy of sorption of polyfluorocarboxamides RFC(O)NR2 (RF = CF3(CF2)i,i=0 to 5, R=H or Me) on capillary columns on the molecular structure of the amides, the temperature of analysis, and the nature of the stationary phases (OV-101, XE-60, and PEG-40M) were investigated by GLC. The peculiarities of the variation of the sorption characteristics of amides in XE-60 and PEG-40M polar phases, which cause the inversion of the order of retention of the members of pseudohomologous series, were found.

The contributions of methylene and difluoromethylene units of six homologous and six pseudohomologous series of esters ofn-perfluoroalkanoic acids to the differential molar free energy, enthalpy, and entropy of sorption on stationary phases of different polarities in glass capillary columns under isothermal conditions were calculated. The features observed characterize the peculiarities of the sorption of esters of polyfluorinated carboxylic acids on phases of different polarities and make it possible to estimate the enthalpy and entropy contributions to the energy of sorption of the esters, the effect of the temperature of the analysis and the length of the alkyl or polyfluoroalkyl chain on the retention parameters of the compound analyzed. The inversion of the retention order of trifluoroacetates and pentafluoropropionates in XE-60 nitrile-containing phase was found.

Retention indices and dI/dT values were obtained for members of six homologous and six pseudohomologous series of polyfluorinated saturated carboxylic esters on capillary columns with OV-101 or XE-60 as stationary phase. There was a nonlinear dependence of retention indices of fluorinated fatty acid esters on carbon chain length of homologs with m, n=1–6. A universal correlation equation was shown to describe the chromatographic behavior of polyfluorinated carboxylic esters.

In six homologous (RFC(O)O(CH2)mCH3, m=0–5) and six pseudohomologous (CF3-(CF2)nC(O)OR, n=0–5) of saturated, fluorinated carboxylic acid esters the effect of analysis temperature (Ta) in the range 60–160°C on the values of retention indexes (I) and on the differential molar free energy, enthalpy, and entropy of sorption of methylene and difluoromethylene groups when using SE-30 and SKTFT-50Kh as the stationary phase (SP) was studied. For each homolog I decreases linearly as Ta increases, but the values of dI/dTa are different for different homologs and increase as the length of the fluorinated chain increases. The sorption parameters ΔHm (CH2) and ΔSm(CH2) are constant when m > 3 and ΔHn (CF2) and ΔSn(CF2) vary regularly as n varies. The values of ΔHm (CH2) and ΔSm (CH2) exceed those of the corresponding ΔHn (CF2) and ΔSn (CF2) for m=n when adsorbed on both SPs. The thermodynamic sorption parameters of the esters for m=1 and n=1 differ sharply from the corresponding parameters for m > 2 and n > 2.

The kinetics of hydrolysis of fluoroalkyl-containing Β-aminovinyl ketones R1C(O)CHC(NHR3)R2, in which the substituents CF3 and HCF2CF2 are in the ketone (R1) or enamine parts of the molecule (R2), was studied. In acid (pH 10) media, they hydrolyze with the formation of the corresponding amines and Β-diketones. In an alkaline medium, the Β-diketones undergo cleavage to fluorinated acids and methyl ketones. The rate constants of hydrolysis in an acid medium change within a range of four orders, depending on the nature of the substituents. The presence of a fluoroalkyl group at the enamine reaction center increases the hydrolysis rate. In an alkaline medium, the rate constants vary within one order.

GLC has been used to determine the contribution of the methylene and difluoromethylene units to the sorption energy of the members of twelve homologous and pseudohomologous series of esters of n-polyfluorinated carboxylic acids for the SE-30 and SKTFT-50Kh stationary phases at 60–160‡C. An unusual increase in the energy of sorption of the methylene and difluoromethylene units with the increasing mass of the homolog has been observed. It has been found that, in distinction from the contributions of the methylene units, the sorption energy of the difluoromethylene units in the pseudohomologs is higher on the fluorinecontaining phase SKTFT-50Kh than on the nonpolar SE-30 phase, except the first unit. It has been shown that an increase in the temperature of the analysis reduces the energy contributions but that it has no influence on the general character of change of the sorption energy of the ester homologs and pseudohomologs.

The retention times were determined for the first time for the members of 12 homologous and pseudohomologous series of polyfluorinated carboxylic acid esters on SE-30 and SKTFT-50Kh phases in isothermal conditions in the 60–160°C temperature range. It was found that the contributions of the methylene and difluoromethylene groups to the retention times change nonlinearly with an increase in the atomic number of the homolog. The suitability of three correlation equations for describing the Chromatographic behavior of polyfluorocarboxylic acid esters was assessed.

The reaction of octafluoro-2,3-epoxybutane 1 with 2-aminothiophenol gave three kinds of novel fluorocontaining N,S-heterocyclic compounds depending on the solvent nature: 2,3-bis(trifluoromethyl)-3,4-dihydro-2H-1,4-benzothiazin-2-ol 2, 2-trifluoromethyl-2-[1-(2-aminophenylthio)-2,2,2-trifluoroethyl]-1,3-benzothiazolidine 6 and 5a,11a-bis(trifluoromethyl)-5a,6,11a,12-tetrahydro-5,11-dithia-6,12-diazanaphthacene 5. Use of the toluene, dioxane, tetrahydrofuran, acetonitrile and dimethoxyethane gave the unexpected dihydrobenzothiazine 2 (RS,SR > RR,SS) in good to moderate yields. In dimethylsulfoxide and N,N-dimethylacetamide, unusual cyclization occurred resulting in benzothiazolidine 6 (RS,SR/RR,SS ∼ 1:1) in moderate yields. Formation of minor 1,1,1,3,4,4,4-heptafluoro-3-(2-aminophenylthio)-2,2-dihydroxybutane 4 which was converted into bis(benzothiazine) 5 was observed in all solvents tested with the exception of toluene and dioxane. The molecular structure of the RS,SR-diastereomer of dihydrobenzothiazine 2, bis(benzothiazine) 5 and the RS,SR-diastereomer of benzothiazolidine 6 has been established by X-ray crystallography.

Quaternary salts of 9-acridinylhetarylmethanes were obtained by condensation of acridine with alkiodides of 2- and 4-methyl derivatives of nitrogen heterocycles in the presence of air oxygen. A study of the spectra of the acridinylhetarylmethanes and their quaternary salts and anhydro bases indicates tautomeric transfer of the hydrogen atom of the methylene group to the nitrogen atom of the acridine fragment in monoquaternized acridinylhetarylmethanes.

The kinetics of the reaction of acridine hydrochloride with the alkiodides of 2- and 4-picolines, 2- and 4-methylquinolines, 2-methylbenzothiazole, and 1,2-dimethylbenzimidazole in the presence of air oxygen were investigated. It is shown that the reaction is second order overall and first order in each of the components at a constant oxygen concentration. The reaction rate constants were calculated, and a mechanism is proposed for the reaction.

1. In the gas-liquid chromatography of microquantities of nickel β-aminovinyl-ketonates, the interphase adsorption does not introduce an appreciable contribution to the retention data. 2. The influence of the enthalpy and entropy factors on the dissolution of fluoroalkyl-containing nickel β-aminovinyl-ketonates in stationary liquid phases was analyzed, and it was shown that entropy of solution plays a dominant role in the determination of the order of retention of these chelates on the siloxane phases, depending on the number of difluoromethylene groups in the chain.