Hidden Resources of Coordinated XPS and DFT Studies

Electronic configuration of chemically bound atoms, at the surface or in the bulk of a solid, contains the traps for energy absorption provided by the valence band electron transitions; the core-level excitation of any origin is coupled with traps forming the multichannel route for energy dissipation. This chapter displays tracing over these channels by means of X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT). Conformity between energy losses in the XPS spectra and electron transitions in relevant unit cells is verified by the examples of the pristine and half fluorinated graphite C2F, and the Br2-embedded C2F. Perfect XPS-DFT combination can be useful for material science providing exhaustive data on state and geometry of the atoms in a sample, regardless the field of its application. The valence band is insensitive to the energy source for its excitation. It makes the behavior of energy losses in XPS spectra of the atoms to be a descriptor of bonding between these atoms in multicomponent materials. Moreover, the state of any component can be tracked through change or invariability of satellites in the relevant XPS spectra, obtained in the course of the external influence, thus revealing a wear performance of the material

Freezing-out of heavy isotopes of Kr

The separation of isotopes of natural Krypton at the gas-liquid and liquid-solid phase interfaces was studied under nonequilibrium conditions using a cryogenic cell and mass spectrometry. The formation of condensate upon cooling Kr from the ambient temperature begins at an equilibrium temperature, which corresponds to the partial pressure of the dominant isotope 84Kr, and is accompanied by depletion of the gas phase 84Kr with a separation coefficient of ~0.92; but the isotopic composition returns to the original under conditions close to equilibrium. The formation of a solid phase near the freezing point is accompanied by depletion of the gas phase by heavy isotopes. The separation coefficients 86Kr and 84Kr are ~2 and ~12, respectively, when ~3.2% of the atoms pass into the solid phase. The solid phase with its fraction below 8.8%, 5.8% and 5.7% does not contain 80Kr, 82Kr and 83Kr with separation coefficients above ~90, ~110 and ~70, respectively, to compensate for the enrichment of the gas and liquid phases. Pressure-selective condensation can be used to separate components with close boiling points when distillation and temperature-selective condensation methods are ineffective, and freezing-out of heavy isotopes can be used to enrich elements with practically important isotopes.Comment: 11 pages; 3 Figures; 3 Tables; 26 Reference

ФЕНОЛОГІЧНІ СПОСТЕРЕЖЕННЯ ЗА РОЗВИТКОМ ВЕРОНІКИ ЛІКАРСЬКОЇ

THE PHENOLOGICAL OBSERVATIONS OF VERONICA OFFICINALIS DEVELOPMENT1 I.I. Milian, 2 M.V. Melnyk, 1 S.M. Marchyshyn, 1 S. Yu. Cholach1SHEI "Ternopil State Medical University byI. Ya. Gorbachevskogo Ministry of Health ofUkraine "2SHEI "Ivano-FrankivskNationalMedicalUniversity"Veronica officinalis - wild plant of plantain family (Plantaginaceae). It grows on sandy soils in light forests throughoutUkraine. Veronica belongs to the species that are found on the edges, clearings, glades, forest meadows and among shrubs.Natural reserves of Veronica Officinalis decrease every year, while the demand of pharmaceutical industry inUkrainefor raw materials of wild medicinal plants remains high. The purpose of our work is to study the features of Veronica Officinalis in the terms of culture.Phenological observations were conducted by the methodics of the State Commission agricultural crops species-analysis on the research areas and in natural plant communities in the 3 - 10 - multiple repetition.Analyzing the structure of morphogenesis of Veronica Officinalis, peculiarities of the formation and life of the parent bush were studied. Plants were planted ( on April 16) in the ground with the aisle 45h70 cm.Gradual change of the shape of leaves of the plants was observed. The appearance of the first buds coincides with the period of intensive growth - from early June until the third decade of June. Budding phase continues until the first blooming flower. During this period, growing activity of the plant is reduced.Change of day rhythm of bloom depends on temperature and humidity. Optimum conditions for flowers blooming can be considered air temperature 18 -22 Cand humidity 50 - 60%, while in the morning hours there is a maximum number of flowers in bloomThe average duration of flowering in nature conditions is 20 days. In natural plant communities in late phases of development of Veronica Officinalis begins.If after flowering generative shoots are removed comes the second, less intense wave of flowering begins in the end of August.Phase of growth and formation begins after fertilization, and further ripening and seed maturation take place. Maturation is accompanied by gradual dehydration of a plant leaves and stems become dry.Fructification phase comprises three stages: milk, wax and full ripeness. Milk maturity is characterized by wreath shedding and the formation of ovaries.Maturation of boxes takes place in stages. Average time of maturation boxes on experimental plots on average is - 26 days, in the natural plant communities - 36 days. Seeds storage is carried in the stage of full maturity. Height of the plant the ranged from 15 -30 cm.Depending on the place of growth and meteorological conditions significant differences in all phenological phases are observed. Thus, plants Veronica Officinalis that grow in natural condition beginning of regrowth and flowering delay ruiting period for 10 - 15 days. During phenological observations on experimental plots of Veronica Officinalis differences in the onset phase of development are not significant. This indicates that the plants that grow in the same abiotic and edaphic conditions have the same type of occurrence of all phases of organogenesis.Conclusion. As a result of phenological observations it was found that to create favorable conditions for the development of Veronica Officinalis on research areas it is important to take into account the soil type, the availability of moisture, lighting and so on. Beydeman Y..N. Metodyka yzuchenyya fenolohyy rastenyy y rastytelʹnykh soobshchestv / Y..N. Beydeman. – Novosybyrsk : Nauka, 1974. – 155 s. 2. Yzotova M. A. Travnyk. Luchshye retsepty narodnoy medytsyny / M. A. Yzotova, T. F. Plotnykova, YU. Y. Kyrova, N. A. Sarafanova. ― M. : Éksmo, 2009. ― 896 s.Minarchenko V. M. Resursna znachushchistʹ vydiv likarsʹkykh roslyn Ukrayiny / V. M. Minarchenko, T. P. Harnyk // Fitoterapiya. ― 2013. ― № 4. ― S. 37―40.Morozyuk S. S. Alʹbom z botaniky / S. S. Morozyuk, V. V. Protopopova . – K. : Radyansʹka shkola, 1979. – 151s.Pro vnesennya zmin do nakazu MOZ Ukrayiny vid 16 lyutoho 2009 roku № 95: nakaz MOZ Ukrayiny № 118 vid 14.02.2013r. [Elektronnyy resurs] Rezhym dostupu do inf.: https://www.moz.gov.ua/ua/portal/dn_ 20130214 _0118. htmlRoslynnyy svit ta lisovi resursy [Elektronnyy resurs] Rezhym dostupu do inf.: http://ukrmodno.com.ua/health/1-roslinnij-svit-ta-lisovi-resursi/ main.htm

INVESTIGATION OF ACUTE TOXICITY AND NEUROTROPIC PROPERTIES OF THE FLOWERS' DENSE EXTRACTS OF TAWNY DAYLILY (HEMEROCALLIS FULVA L.) AND HYBRID DAYLILY (HEMEROCALLIS HYBRIDA VAR. «STELLA DE ORO»)

INVESTIGATION OF ACUTE TOXICITY AND NEUROTROPIC PROPERTIES OF THE FLOWERS' DENSE EXTRACTS OF TAWNY DAYLILY (HEMEROCALLIS FULVA L.) AND HYBRID DAYLILY (HEMEROCALLIS HYBRIDA VAR. «STELLA DE ORO»)S. M. Marchyshyn1, O. V. Zarichanska2, S. Yu. Cholach1I. Horbachevsky Ternopil State Medical University1Vinnytsia National Memorial Medical University by M. I. Pyrohov2Introduction.  In modern conditions almost no one person is able to avoid stressful situations that lead to manifestations of functional disorders of the central nervous system - neuroses. Anxiety, depression, sleep disturbances and disorder of emotional sphere due to the prevalence among the population gain significant measures. In accordance with the urgency of the problem, the search for safety and effective remedies for correction of mild neurosis’ manifestations among the preparations of plant origin is promising. From the literature sources, it is known that preparations from flowers of Daylily genus plants (Hemerocallis L.) show effects on the nervous system and are used in traditional medicine in China, Japan and North America for the treatment of depression, insomnia and other psycho-emotional disorders. Previously we performed a comprehensive phytochemical study of plant raw materials of two species of daylilies – tawny daylily (Hemerocallis fulva L.) and hybrid daylily (Hemerocallis hybrida var. “Stella De Oro”). Analysis of quantitative composition and qualitative content of biologically active substances of two investigated daylilies’ species demonstrates the appropriateness of the creation of phytosubstances on their base and investigation of phytosubstances’ pharmacological properties. The purpose of these studies was to determine the safety of thick extracts from flowers of tawny daylily and hybrid daylily, to establish the influence of extracts on behavioral responses and emotional state, depressive behavior and physical endurance of laboratory mice.Investigation methods. The investigation was conducted on 48 male white nonlinear mice weighing 18-25 grams, which were divided into 8 groups (n = 6): Group 1 – intact control; 2-5 groups – animals, injected with thick extracts from flowers of tawny daylily and hybrid daylily variety “Stella De Oro” in the form of aqueous solutions intragastric at doses 100 and 250 mg / kg. 6-7 comparison groups received medication according to the behavioral model: imipramine (solution for injection “Melipramine”, Egis, Hungary) 25 mg / kg (for Porsolt’s test of antidepressant activity); 2-etyltiobenzimidazole hydrobromide – the active component of actoprotective drugs “Bemityl” and “Metaprot” at dose 50 mg / kg (for test of actoprotective effect). To determine the effect of daylilies flowers’ extracts on behavioral responses and emotional state of intact animals common open field test was used without medicinal preparation’s control.Results and discussions. Investigation of acute toxicity has shown safety of both extracts samples – at dose 5000 mg / kg these substances did not cause any symptoms of poisoning. In open field behavioral test extract from tawny daylily’s flowers in dose 100 mg / kg shown pronounce stimulating effect; extract from hybrid daylily’s flowers in dose 250 mg / kg elucidated sedative activity. In behavioral despair’s test with immobilization the extract of hybrid daylily’s flowers in dose of 250 mg / kg shown distinct antidepressant properties, which are close to the level of activity of tricyclic antidepressant imipramine.Tawny daylily and hybrid daylily flowers’ extracts at both investigated doses had no effect on physical endurance of mice in the forced swim test with a load, whereas reference-medication shown expressive actoprotective effect.Conclusions. The acute toxicity of the dense extracts from flowers of tawny daylily and hybrid daylily of “Stella De Oro” variant has been determined for the first time; the investigated substances were assigned to the 5th classof substances’ toxicity according to the classification of Hodge and Sterner (practically non-toxic substances – LD50 > 5000 mg/kg). The effect of investigated extracts on behavioral reactions and emotional condition, depressive behavior and physical endurance of laboratory mice has been defined using behavioral tests. Diverse and expressive influence of investigated thick extracts on central nervous system and physical endurance of laboratory mice has been elucidated.ReferencesAzymova Yu. E. Depresiya i yiyi somatychni proyavy / Yu. E. Azymova, G. R. Tabyeyeva // Lechashhyj vrach. – 2009. – [Elektronyj resurs]. – Rezhym dostupu: http://www.lvrach.ru/2009/09/10637387/Akimova M. S. Eksperymentalne doslidzhennya stresprotektornyx vlastyvostej kriopodribnenogo poroshku aroniyi chornoplidnoyi pry gipokinetychnomu stresi: avtoref. dys. na zdobuttya nauk. stupenya kand. farm. nauk : specz. 14.03.05 «Farmakologiya» / M. S. Akimova; Nacionalnyj farmacevtychnyj universytet. – Kharkiv, 2014. – 20 s.Eksperymentalne vyvchennya novyh adaptogennyh zasobiv: metod. rekomendaciyi / L. V. Yakovlyeva, O. Ya. Mishhenko, Yu. B. Laryanovska, O. Yu. Koshova ta in. – K.: DFCz, 2009. – 38 s.Konovalova O. Yu. Analiz rynku antydepresyvnyh preparativ na osnovi zviroboyu zvychajnogo, yaki zareyestrovani v Ukrayini / O. Yu. Konovalova, T. K. Shurayeva, T. V. Dzhan, T. A. Groshovyj, N. P. Darzuli // Farmacevtychnyj chasopys. – 2010. – № 2. – S. 52-57.Kurkin V. A. Izuchenie nejrotropnoj aktyvnosty novyh lekarstvennyh preparatov iz travy zveroboya / V. A. Kurkyn, A. V. Dubyshhev, O. E. Pravdyvceva, L. N. Zymyna // Medycynskyj almanah. – 2009. – № 4 (9). – S. 33-36.Marchyshyn S. M. Vmist aminokyslot u pidzemnyh i nadzemnyh organax lilijnyka buro-zhovtogo (Hemerocallis fulva L.) ta lilijnyka gibrydnogo (Hemerocallis hybrida var. “Stella De Oro”) / S. M. Marchyshyn, O. V. Zarichanska //  Farmacevtychnyj chasopys. – 2015. – № 1 (33). – S. 11-14.Marchyshyn S. M. Vmist karbonovyx kyslot u pidzemnyh i nadzemnyh organah lilijny` buro-zhovtogo (Hemerocallis fulva L.) ta lilijnyka gibrydnogo (Hemerocallis hybrida var. “Stella De Oro”)  / S. M. Marchyshyn, S. S. Kozachok, O. V. Zarichanska // Farmacevtychnyj zhurnal. – 2015. – № 2. – S. 53-57.Marchyshyn S. M. Doslidzhennya flavonoyidiv nadzemnyx organiv lilijnyka buro-zhovtogo (Hemerocallis fulva L.) ta lilijnyka gibrydnogo (Hemerocallis hybrida var. “Stella De Oro”) / S. M. Marchyshyn, O. V. Zarichanska, M. S. Garnyk // Fitoterapiya. Chasopys. – 2015. – № 3. – S. 52-55. Rukovodstvo po provedenyyu doklynycheskyh issledovanyj lekarstvennyh sredstv / Pod red. dokt. med. nauk A. N. Myronova. – Chast pervaya. – M.: Gryf i K, 2012. – 944 s. Czokalo I. Ye. Eksperymentalne vyvchennya stresprotektornoyi j aktoprotektornoyi diyi kompozyciyi exinaceyi ta burshtynovoyi kysloty / I. Ye. Czokalo, O. I. Zajcev, K. G. Shhokina // Farmakom. – 2010. – № 4. – S. 72-75.Deacon R. M. Housing, husbandry and handling of rodents for behavioral experiments / R. M. Deacon // Nature Protocols. – 2006. – V. 1. – № 2. – P. 936–946.Eico Uezu. Effects of Hemerocallis on sleep in mice / College of Education, University of the Ryukyus, Okinawa, Japan. Psychiatry and Clinical Neurosciences, –1998 Apr.; 52(2). – P. 136-137.Handbook of medicinal herbs / James A. Duke, Mary Jo Bogenschutz-Godwin, Judi duCellier, Peggy-Ann K. Duke. – 2nd ed. – CRC Press LLC, 2002. – P. 246.Hodge Н.С. Tabulation of toxicity classes / Н.С. Hodge, L.H. Sterner // Am. Industr. Hyg. Ass. Quart. – 1943. – Vol. 10. – № 4. – P. 93.Porsolt R.D. Behavioral models of depression / R.D. Porsolt, A. Lenegre, J.M. Elliot [et al.] // Experimental Approaches to Anxiety and Depression. – Chichester New York, 1992. – P. 73-85.Zarichanska Olena. Investigation of the volatile oil in modified roots, flowers and leaves of Hemerocallis species / Olena Zarichanska, Svitlana Marchyshyn, Myroslava Garnyk // 46th International Symposium on Essential Oils 2015 Abstracts. Natural Volatiles and Essential Oils – 2015. – №2(3) – Lublin (Poland), September 13-16, 2015. – PP-099. Zarichanska O. V. Qualitative composition and quantitative content of macro- and microelements in plant raw materials of plants of Hemerocallis L. genus / O. V. Zarichanska // Topical issues of new drugs development. International Scientific And Practical Conference Of Young Scientists And Student, NUPh – April 23, 2015. – P.111-112

Electronic and structural peculiarities of Br2-embedded C2F: XPS and DFT study

The prospects of the complementary use of X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) have been demonstrated by the examples of highly oriented pyrolytic graphite, half-fluorinated graphite C2F, and half-fluorinated graphite C2F intercalated with Br C2FBr0.15. It has been shown that the photoelectron energy losses in XPS spectra conform well to valence band electron transitions resulted from the DFT calculations for relevant unit cells. This conformity justified the other results of joined XPS and DFT studies, which have revealed two arrangements of the Br2 embedded into the C2F framework. The first arrangement corresponds to separate Br pairs in which the Br state is similar to a free Br2 molecule, whereas the second one is an ultra-dense Br chain in which the Br state is between free Br2−1 and Br10 species. The specific energy losses in the XPS Br3d spectrum of C2FBr0.15 indicate a comparable content of both Br arrangements in a sample. Besides, a distinct structure in the difference F1s XPS spectrum is assigned to the expected strengthening of the C-F bond in a C2F matrix under the Br2 intercalation. The state and orientation of intercalated Br2 are juxtaposed with experimental studies by Near Edge and Extended X-ray Absorption Fine Structure spectroscopy and by Raman spectroscopy. A successful confluence of XPS and DFT can be useful in the field of material science, providing the local geometry, the state and bonding between atoms in a sample, and thereby revealing the wear performance of the material, regardless of its application

Experimental estimation of velocities and anisotropy of a series of Swedish crystalline rocks and ores

To provide a guide for future deep (<1.5 km) seismic mineral exploration and to better understand the nature of reflections imaged by surface reflection seismic data in two mining camps and a carbonatite complex of Sweden, more than 50 rock and ore samples were collected and measured for their seismic velocities. The samples are geographically from the northern and central parts of Sweden, ranging from metallic ore deposits, meta-volcanic and meta-intrusive rocks to deformed and metamorphosed rocks. First, ultrasonic measurements of P- and S-wave velocities at both atmospheric and elevated pressures, using 0.5 MHz P- and S-wave transducers were conducted. The ultrasonic measurements suggest that most of the measured velocities show positive correlation with the density of the samples with an exception of a massive sulphide ore sample that shows significant low P- and S-wave velocities. The low P- and S-wave velocities are attributed to the mineral texture of the sample and partly lower pyrite content in comparison with a similar type sample obtained from Norway, which shows significantly higher P- and S-wave velocities.Later, an iron ore sample from the central part of Sweden was measured using a low-frequency (0.1–50 Hz) apparatus to provide comparison with the ultrasonic velocity measurements. The low-frequency measurements indicate that the iron ore sample has minimal dispersion and attenuation. The iron ore sample shows the highest acoustic impedance among our samples suggesting that these deposits are favourable targets for seismic methods. This is further demonstrated by a real seismic section acquired over an iron ore mine in the central part of Sweden. Finally, a laser-interferometer device was used to analyse elastic anisotropy of five rock samples taken from a major deformation zone in order to provide insights into the nature of reflections observed from the deformation zone. Up to 10% velocity-anisotropy is estimated and demonstrated to be present for the samples taken from the deformation zone using the laser-interferometery measurements. However, the origin of the reflections from the major deformation zone is attributed to a combination of anisotropy and amphibolite lenses within the deformation zone

Crack density tensor inversion for analysis of changes in rock frame architecture

This paper presents a development of the use of multi-axial ultrasonic data for the quantification of extrinsic, crack or grain-contact induced elastic anisotropy in core samples with application to a UKCS oil field. An approach for inversion of multi-axial velocity measurements is presented, which extends the previous work by Sayers (2002) for the determination of second- and fourth-order crack density tensors from inversion of multi-axial ultrasonic velocity data. The extensions to the inversion approach provide improved consideration of data uncertainties, by using all available P- and S-wave data and also permit the inclusion of an orthorhombic background anisotropy in the inversion [e.g. due to intrinsic lattice preferred orientation(LPO) effects]. The latter aspect leads to estimates of the extrinsic anisotropy, that is, the quantified crack density tensors, that are 'unpolluted' by the effects of the intrinsic anisotropy, thus permitting extrinsic and intrinsic anisotropies to be distinguished. For the samples considered, the extrinsic crack-induced anisotropy is strong relative to that of the intrinsic LPO effects, and the pre-dominant crack-set is commonly aligned parallel to the depositional fabric (which is generally horizontal). However, the LPO and extrinsic anisotropies are in general aligned, which indicates a linked origin. Furthermore, a strong correlation is observed between the degree of VTI anisotropy and the modal content of micas in the samples, which cannot be explained solely by the LPO effect. In fact, it is shown that increased horizontal (grain parallel) crack densities are associated with higher mica content. These horizontal cracks in the mica-rich samples often show moderate-to-strong variations in crack density with loading that might be detected in situ with non-hyperbolic moveout. Additionally, three samples show significant pressure sensitivity of the vertical crack sets indicating that loading-induced azimuthal anisotropy might also exist in some layers in situ and be detectable using azimuthal AVO type analyses. Analysis of the fourth-order crack density tensor allows insight into the relative sizes of the normal and tangential crack compliances, B-N and B-T. For one case it is found that B-N >= B-T (i. e. the crack-sets are more compliant in compression than in shear). For another sample B-N < B-T; this sample had been cleaned prior to the analysis, which appears to facilitate shear in the cracks. This conclusion may have significant implications for the use of analogue samples acquired at the surface where organic products, which lead to the reduced shear compliance, are not present