Studies on the interaction of selenite and selenium with sulphur donors. Part 2. A kinetic study of the reaction with 2-mercaptoethanol

1994 ◽  
Vol 72 (12) ◽  
pp. 2506-2515 ◽  
Author(s):  
Wimal Amaratunga ◽  
John Milne
Keyword(s):  
Reaction Mechanism ◽  
Nmr Spectroscopy ◽  
Nmr Spectra ◽  
Nucleophilic Attack ◽  
Elemental Selenium ◽  
Sulfinic Acid ◽  
Reaction Stage ◽  
Second Stage ◽  
Selenous Acid ◽  
Two Stages

Selenous acid is reduced by 2-mercaptoethanol in water to elemental selenium in two stages.[Formula: see text]The reactions have been followed by spectrophotometry and by proton and 77Se NMR spectroscopy. The mechanism of the first stage parallels that proposed for butyl thiols in 60% dioxane but nucleophilic attack by RS− rather than RSH on the Se(IV) intermediate, RSSeO2−, is of greater significance for 2-mercaptoethanol than for n-butylthiol. The signals of three intermediates are observed in the Se-77 NMR spectra of a mixture undergoing the first reaction stage. These arise from, HOC2H4SSeO2−, (HOC2H4S)2SeO, and an asymmetric intermediate that chemical shift evidence suggests is the sulfinic acid ester, HOC2H4S(O)SeSC2H4OH. The second stage involves coordination of the bis(thio)selenide by thiolate followed by decomposition to disulfide and selenium. Evidence is presented to support a reaction mechanism involving nucleophilic attack exclusively at Se(II) and not at S(II) as suggested in previous work. This stage is strongly accelerated at basic pH and, at pH 8.3 and above, both the first and second stages can take place simultaneously.

Studies on the interaction of selenite and selenium with sulfur donors. Part 3. Sulfite

1995 ◽  
Vol 73 (5) ◽  
pp. 716-724 ◽  
Author(s):  
Sheila Ball ◽  
John Milne
Keyword(s):  
Raman Spectroscopy ◽  
Aqueous Solutions ◽  
Nmr Spectra ◽  
Formation Constants ◽  
The Other ◽  
Elemental Selenium ◽  
Ambient Temperatures ◽  
Selenous Acid ◽  
First Time ◽  
Sulfite Solution

Elemental selenium dissolves in sulfite solution to form selenosulfate ion: Se + SO32− = SeSO32−.The formation constants for this equilibrium at temperatures from 0 to 35 °C are reported for the first time. The isomeric thioselenate anion, SSeO32−, is not, however, produced by the reaction of sulfur with selenite nor is the selenoselenate ion, Se2O32−, formed from selenium and selenite. Selenotrithionate is formed rapidly from the reaction of selenous acid with sulfite and hydrogen sulfite according to: HSeO3− + 3 HSO3− = Se(SO3)22− + SO42− + 2H2O.Two isomers of the selenotrithionate ion are observed by Se-77 NMR and Raman spectroscopy, one with O-bonded Se, Se(OSO2)22−, and the other with S-bonded Se, Se(SO3)22−. Both isomers are formed in reactions with hydrogen sulfite but only the O-bonded isomer is formed in sulfite solutions at ambient temperatures. The Raman and Se-77 NMR spectra of the various sulphur–selenium anions formed are given and the parallel with the reactions of selenous acid and thiols is discussed. Keywords: selenium, sulfite, selenosulfate, selenotrithionate, Se-77 NMR, Raman spectroscopy, equilibria, aqueous solutions.

Studies on the interaction of selenite and selenium with sulphur donors. Part 5. Thiocyanate

1996 ◽  
Vol 74 (10) ◽  
pp. 1889-1895 ◽  
Author(s):  
Christopher Milne ◽  
John Milne
Keyword(s):  
Raman Spectroscopy ◽  
Nmr Spectroscopy ◽  
Nmr Spectra ◽  
Chemical Exchange ◽  
Acid Oxidation ◽  
Relaxation Processes ◽  
Line Broadening ◽  
Linkage Isomerism ◽  
Selenous Acid ◽  
Scalar Relaxation

The oxidation of thiocyanic acid by selenous acid has been shown to take place in an analogous way to that found for selenous acid oxidation of most thiols and thiolates to give the corresponding selenotrisulfide and disulfide products[Formula: see text]The products of this reaction have been studied by IR, Raman, and Se-77, C-13, and N-15 NMR spectroscopy. The vibrational spectra of the solid Se(SCN)2 have been assigned based on S-bonded thiocyanate ligands and, through NMR and vibrational spectroscopy, both this linkage isomer and the isomer with N- and S-bonded thiocyanate have been identified and characterized in solutions of Se(SCN)2. A complex combination of scalar relaxation processes, involving chemical exchange and quadrupolar effects, accounts for the line broadening observed in the carbon-13 NMR spectra. Key words: selenite, thiocyanate, selenium dithiocyanate, Se-77, N-15, and C-13 NMR; Raman spectroscopy; linkage isomerism

Study of Cyclization of 1-Benzoyl-3-methyl-3-(2-methoxycarbonylphenyl)thiourea to 1-Methyl-2-thioxo-4-quinazolone

1993 ◽  
Vol 58 (5) ◽  
pp. 1122-1132 ◽  
Author(s):  
Jaromír Kaválek ◽  
Vladimír Macháček ◽  
Miloš Sedlák ◽  
Vojeslav Štěrba
Keyword(s):  
Reaction Mechanism ◽  
Kinetic Study ◽  
Title Reaction ◽  
Initial Substance ◽  
Second Stage ◽  
Rate Determining Step ◽  
Benzoyl Group ◽  
Two Stages ◽  
The Given

The reaction mechanism of the title reaction was proposed on the bases of the kinetic study. The reaction takes place in two stages considerably differing in rates. In the first, faster stage, the anion of initial substance cyclizes to 1-methyl-3-benzoyl-2-thioxo-4-quinazolone. The reaction is reversible, the concentration of 1-methyl-3-benzoyl-2-thioxo-4-quinazolone decreases with increasing concentration of methanolate. In the second stage, the benzoyl group rearrangement in the given substance from nitrogen to sulfur and subsequent methanolysis to 1-methyl-2-thioxo-4-quinazolone take place. The rate-determining step is the methanolysis for [CH3O(-)] < 4 . 10-3 mol l-1 and the benzoyl group rearrangement for higher methanolate concentrations.

Spectroscopic Characterization of the Selenium-Rich Heterocycles Se5S, Se7S, and 1,5-Se6S2

1991 ◽  
Vol 46 (12) ◽  
pp. 1674-1678 ◽  
Author(s):  
Ralf Steudel ◽  
Maria Papavassiliou ◽  
Frank Baumgart
Keyword(s):  
Nmr Spectroscopy ◽  
Nmr Spectra ◽  
Spectroscopic Characterization ◽  
Reversed Phase ◽  
Nucleophilic Attack ◽  
Crystal Data ◽  
Reversed Phase Hplc ◽  
Cyclic Molecules ◽  
First Time

Se5S in CS2 solution at 20°C spontaneously decomposes to give a mixture of 8 selenium-rich cyclic molecules which have been identified by reversed-phase HPLC and 77Se NMR spectroscopy as Se6, Se7, Se8, Se6S, Se7S, 1,2-Se6S2, 1,5-Se6S2, and 1,4-Se4S2. NMR spectra of Se5S, Se7S, and 1,5-Se6S2 have been measured for the first time; Raman spectra of solid Se5S and Se7S as well as crystal data of Se7S are reported in addition. A mechanism based on nucleophilic attack on Se5S is proposed for the formation of the products.

Altered Fine Structure of B Lymphocytes Correlated with Defective Terminal Differentiation

1973 ◽  
Vol 31 ◽  
pp. 386-387
Author(s):  
Dale E. Bockman ◽  
L. Y. Frank Wu ◽  
Alexander R. Lawton ◽  
Max D. Cooper
Keyword(s):  
Immune Deficiency ◽  
B Lymphocytes ◽  
Plasma Cells ◽  
Present Report ◽  
Specific Antigen ◽  
Terminal Differentiation ◽  
Second Stage ◽  
Two Stages ◽  
Deficiency Diseases ◽  
Cell Line Generation

B-lymphocytes normally synthesize small amounts of immunoglobulin, some of which is incorporated into the cell membrane where it serves as receptor of antigen. These cells, on contact with specific antigen, proliferate and differentiate to plasma cells which synthesize and secrete large quantities of immunoglobulin. The two stages of differentiation of this cell line (generation of B-lymphocytes and antigen-driven maturation to plasma cells) are clearly separable during ontogeny and in some immune deficiency diseases. The present report describes morphologic aberrations of B-lymphocytes in two diseases in which second stage differentiation is defective.

Distributed Entropy Energy-Efficient Clustering algorithm for cluster head selection (DEEEC)

2020 ◽  
Vol 39 (6) ◽  
pp. 8139-8147
Author(s):  
Ranganathan Arun ◽  
Rangaswamy Balamurugan
Keyword(s):  
Energy Efficient ◽  
Clustering Algorithm ◽  
Cluster Head ◽  
Residual Energy ◽  
Energy Utilization ◽  
Sensor Nodes ◽  
Second Stage ◽  
Energy Efficient Clustering ◽  
Two Stages ◽  
Ch Selection

In Wireless Sensor Networks (WSN) the energy of Sensor nodes is not certainly sufficient. In order to optimize the endurance of WSN, it is essential to minimize the utilization of energy. Head of group or Cluster Head (CH) is an eminent method to develop the endurance of WSN that aggregates the WSN with higher energy. CH for intra-cluster and inter-cluster communication becomes dependent. For complete, in WSN, the Energy level of CH extends its life of cluster. While evolving cluster algorithms, the complicated job is to identify the energy utilization amount of heterogeneous WSNs. Based on Chaotic Firefly Algorithm CH (CFACH) selection, the formulated work is named “Novel Distributed Entropy Energy-Efficient Clustering Algorithm”, in short, DEEEC for HWSNs. The formulated DEEEC Algorithm, which is a CH, has two main stages. In the first stage, the identification of temporary CHs along with its entropy value is found using the correlative measure of residual and original energy. Along with this, in the clustering algorithm, the rotating epoch and its entropy value must be predicted automatically by its sensor nodes. In the second stage, if any member in the cluster having larger residual energy, shall modify the temporary CHs in the direction of the deciding set. The target of the nodes with large energy has the probability to be CHs which is determined by the above two stages meant for CH selection. The MATLAB is required to simulate the DEEEC Algorithm. The simulated results of the formulated DEEEC Algorithm produce good results with respect to the energy and increased lifetime when it is correlated with the current traditional clustering protocols being used in the Heterogeneous WSNs.

Analisis Kebutuhan Petunjuk Praktikum Berbasis Keterampilan Proses Sains untuk Mencapai Kemampuan Merancang Eksperimen

2019 ◽  
Vol 2 (2) ◽  
Author(s):  
Fitriah Khoirunnisa ◽  
Friska Septiani Silitonga ◽  
Veri Firmansyah
Keyword(s):  
Core Competence ◽  
Process Skills ◽  
Learning Materials ◽  
Science Process Skills ◽  
Second Stage ◽  
The Core ◽  
The Core Competence ◽  
Two Stages ◽  
Practical Instruction ◽  
Design Experiments

Penelitian ini bertujuan menganalisis kebutuhan petunjuk praktikum berbasis Keterampilan Proses Sains (KPS) untuk mencapai kemampuan merancang eksperimen pada materi kalor reaksi kalorimetri. Penelitian dilakukan terhadap peserta didik kelas XI SMA Negeri 2 Kota Tanjungpinang. Variabel penelitian mencakup analisis kebutuhan bahan ajar dan analisis kesesuaian Kompetensi Inti (KI) dan Kompetensi Dasar (KD). Jenis penelitian yang dilakukan adalah penelitian deskriptif kualitatif. Tahapan pertama dalam penelitian ini adalah menganalisis kebutuhan bahan ajar dengan cara membandingkan dua petunjuk praktikum yang selama ini telah digunakan di sekolah tersebut, ditinjau dari aspek struktur format penulisan, aspek kreativitas, dan aspek keterampilan proses sains yang terdapat dalam petunjuk praktikum. Sehingga didapatkan kesimpulan bahwa petunjuk praktikum yang selama ini digunakan tidak memberikan kesempatan kepada peserta didiknya untuk merancang eksperimen yang telah ditentukan. Tahapan kedua yaitu menganalisis kesesuaian kompetensi inti dan kompetensi dasar, yang bertujuan untuk menentukan indikator pencapaian kompetensi (IPK) yang akan menjadi acuan dalam mengembangkan petunjuk praktikum berbasis keterampilan proses sains. Dari kedua tahapan yang telah dilakukan maka dapat disimpulkan bahwa peserta didik memerlukan petunjuk praktikum yang mampu mengonstruksi pikiran dan mengaktifkan kinerja mereka, sehingga pendekatan Keterampilan Proses Sains menjadi pilihan dalam mengembangkan petunjuk praktikum yang sesuai dengan karakteristik kurikulum 2013.   This research aims to analyze the needs of Science Process Skills based Practical Instruction to achieve the ability to design experiments on the calor of reaction. This research was done to the students of class XI SMA Negeri 2 Tanjungpinang City. Research Variable includes the analysis of the needs of the learning materials and analysis of the suitability of the Core Competence (KI) and Basic Competence (KD). The type of research conducted is descriptive qualitative research. The first stages in this research is to analyze the needs of learning materials by comparing two practical instructions that had been implementing in the school, from the aspects of the structure of writing format, creativity, and science process skills embedded in practical instructions. The conclusion of this research that current practical instructions does not give an opportunity to the participants to design determined experiments. The second stage, namely analyzing the suitability of core competence and basic competence, which aims to determine the indicators of achievement of the competencies (GPA) which will be a reference in developing process skills-based teaching instructions science. Of the two stages that has been done then it can be concluded that learners need practical instructions to construct  thinking and and their performance, so the Science Process Skills approach is an option in developing practical instruction suitable for the characteristics of the curriculum of 2013.

ESTIMATING GAS AND ROCK OUTBURST RISK ON THE BASIS OF KNOWLEDGE AND EXPERIENCE – THE EXPERT SYSTEM BASED ON FUZZY LOGIC

2014 ◽  
Vol 59 (1) ◽  
pp. 41-52 ◽  
Author(s):  
Norbert Skoczylas
Keyword(s):  
Fuzzy Logic ◽  
Expert System ◽  
Mining Industry ◽  
Automatic Assessment ◽  
Science Field ◽  
Second Stage ◽  
Two Stages ◽  
Outburst Hazard

Abstract The Author endeavored to consult some of the Polish experts who deal with assessing and preventing outburst hazards as to their knowledge and experience. On the basis of this knowledge, an expert system, based on fuzzy logic, was created. The system allows automatic assessment of outburst hazard. The work was completed in two stages. The first stage involved researching relevant sources and rules concerning outburst hazard, and, subsequently, determining a number of parameters measured or observed in the mining industry that are potentially connected with the outburst phenomenon and can be useful when estimating outburst hazard. Then, the Author contacted selected experts who are actively involved in preventing outburst hazard, both in the industry and science field. The experts were anonymously surveyed, which made it possible to select the parameters which are the most essential in assessing outburst hazard. The second stage involved gaining knowledge from the experts by means of a questionnaire-interview. Subjective opinions on estimating outburst hazard on the basis of the parameters selected during the first stage were then systematized using the structures typical of the expert system based on fuzzy logic.

Integrated assessment and mapping of the environmental situation in the Russian Federation regions

2017 ◽  
Vol 924 (6) ◽  
pp. 6-16
Author(s):  
V.S. Tikunov ◽  
O.Yu. Chereshnia
Keyword(s):  
Russian Federation ◽  
Pollution Index ◽  
Pollution Level ◽  
Anthropogenic Pressure ◽  
Environmental Capacity ◽  
Environmental Friendliness ◽  
Second Stage ◽  
Environmental Situation ◽  
The Russian Federation ◽  
Two Stages

The article presents a methodology for a comprehensive assessment of the environmental situation in Russian Federation regions based on the pollution index and the index of the ecological tension. The evaluation was carried out in two stages. At the first stage, the degree of pollution of the atmosphere, hydrosphere and lithosphere of the regions was estimated on the basis of the emission of pollutants into the atmosphere, departing from stationary sources, the formation of solid domestic wastes (SDW) and the discharge of contaminated wastewater. Based on these three indicators, a pollution index was constructed that estimates aggregate pollution level. In the second stage, the authors made the estimation of loads generated by atmospheric emissions, solid waste and waste water discharged into the territory of each region, per capita and in relation to the environmental capacity of the economy. This allows us to take into account the area of pollution, anthropogenic pressure and environmental responsibility of the population, as well as the environmental friendliness of production. On the basis of relative indicators, the index of ecological tension was created.

NMR spectroscopic investigation of p-substituted 2,4,4,6-tetraphenyl-1,4-dihydropyridines and their oxa and thia analogues

1989 ◽  
Vol 54 (7) ◽  
pp. 1854-1869 ◽  
Author(s):  
Marián Schwarz ◽  
Petr Trška ◽  
Josef Kuthan
Keyword(s):  
Nmr Spectroscopy ◽  
Trifluoroacetic Acid ◽  
Spectroscopic Investigation ◽  
Nmr Spectra ◽  
Dynamic Equilibrium

The 1H, 13C and 19F NMR spectra of photochromic p-substituted 2,4,4,6-tetraphenyl-1,4-dihydropyridines IIa-IIg, 1-methyl-2,4,4,6-tetraphenyl-1,4-dihydropyridines IIIa-IIIg, 2,4,4,6-tetraphenyl-4H-pyrans IVa-IVh, and 2,4,4,6-tetraphenyl-4H-thiopyran V were inspected; it was found that compounds IIa-IIg occur in a dynamic equilibrium with their dihydro tautomer VIa-VIg. Also deuteriodeprotonation of IIa and IIIa and their reaction with trifluoroacetic acid were investigated by NMR spectroscopy.

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