Electron Excited L X-Ray Spectra of the Elements 14 ≤ Z ≤ 22

The L spectra of the elements 14 ≤ Z ≤ 22 were reinvestigated. Because of the limited energy resolution of the multilayer reflectors neither Ll and Lη nor Lα and Lβ₁ could be resolved. Nevertheless, the line Lβ_3,4 = L₁M_2,3 was observed for all elements Z ≥ 16, but not for ¹⁴Si and ¹⁵P. Exceptions to this are ¹⁸Ar and ²²Ti. For ¹⁸Ar no suitable sample is available. In the case of ²²Ti the Lβ_3,4 line is overlapped by the O Kα line which has its origin in the oxide surface layer of the Ti standard. In all cases the Lβ_3,4 line was observed near to the expected position which was determined by means of the known electron binding energies. The L spectrum of ²¹Sc was studied for various energies of the incident electrons, E₀. These measurements show that Lβ_3,4 is much more strongly absorbed in Sc than Ll,η and Lα,β₁. From these measurements approximate mass absorption coefficients (m.a.c.) were deduced. The relative net peak height I(Lβ_3,4)/I(Lα,β₁) decreases from 15% at E₀ = 4 keV to 4% at E₀ = 20 keV, whereas I(Ll,η)/I(Lα,β₁) remains nearly constant at 90%. The peak to background ratio of Ll,η is greater than that of Lα,β₁.     

The L Spectrum of Fe and Fe3O4

The intensities of the Fe L lines/bands l = L₃M₁, η = L₂M₁, α_1,2 = L₃M_4,5, β₁ = L₂M₄, and β_3,4 = L₁M_2,3 were measured for pure Fe and Fe₃O₄ using a TAP crystal as the dispersing element. The energy of the exciting electrons, E₀, was varied in the range 5 ≤ E₀ ≤ 25 keV. For pure Fe the following results were obtained. The net peak height ratio Ll/Lα remains relatively constant with varying E₀ at approximately 14%. The E₀ dependence of Lη is similar to that of Ll, although Lη is less intense than Ll by a factor of 7. Lβ₁/Lα decreases from 20% for E₀ = 5 keV to about 5% for 25 keV. Lβ_3,4 behaves like Lβ₁ but is weaker by a factor of 15. For Fe₃O₄ a much weaker intensity of Lα was observed which can be partially explained by its stronger absorption. Again, the E₀ dependence of Ll and Lη is similar with Ll/Lα = 19% and Lη/Lα = 4%. Lβ₁ and Lβ_3,4 show a comparable E₀ dependence. Lβ₁/Lα decreases from 50% for E₀ = 5 keV to 34% for 25 keV. Lβ_3,4 is weaker than Lβ₁ by a factor of about 25. The observed E₀ dependence of the different lines was used to estimate a set of mass absorption coefficients. Our value for Lα in Fe agrees well with other data which were deduced from variable E₀ measurements but differs considerably from data given by Heinrich and Henke.     

Comparisons of an external magnetic field effect and chemical effect on X-ray <Emphasis Type="Italic">Kβ</Emphasis>/<Emphasis Type="Italic">Kα</Emphasis> intensity ratio and line-shape of some Chromium compounds

The effect of chemical composition and external magnetic field on the Kβ/Kα intensity ratio and line-shape of some chromium compounds have been investigated using the energy dispersive X-ray fluorescence analysis. The measurements were done using the 22.69 keV photon energy and energy dispersive Si(Li) semiconductor detector. The samples are located in the external magnetic field of intensities 0.6 T and 1.2 T. The experimental results obtained for B = 0 are compared with other experimental and theoretical values. The results have shown that the X-ray Kβ/Kα intensity ratios, chemical shifts, asymmetry indices and full widths at half maximum (FWHM) values can change when irradiation is conducted in a magnetic field.     

Chemical shifts of Kα and Kβ<Subscript>1,3</Subscript> X-ray emission spectra for oxygen compounds of Ti,Cr, Fe,Co, Cu with WDXRF

Chemical shifts and full widths at half maximum intensity (FWHM) of Kα and Kβ_1,3 X-ray emission lines and differences of full widths at half maximum intensity (ΔFHWM) using metallic element as reference for these emission lines were measured for oxygen compounds of elements in the range 22≤Z≤29 with a Wavelength-Dispersive X-Ray Fluorescence Spectrometer (WDXRF). It was also found larger chemical shifts and FWHM for Kβ_1,3 lines than those of Kα ones. It should be noted that the magnitude of the chemical shifts increases with increasing number of ligand atom.     

Electron Excited L X-Ray Spectra of the Elements 24 ≤ Z ≤ 33

A reinvestigation was undertaken in order to obtain reliable data of the relative intensities of the L spectra for the elements 24 ≤ Z ≤ 33. A TAP crystal with a periodicity of 25.757 ? was used as the dispersing element. With this crystal one is able to resolve the lines/bands Ll = L₃M₁, Lη = L₂M₁, Lα_1,2 = L₃M_4,5, Lβ₁ = L₂M₄, and Lβ_3,4 = L₁M_2,3. Among the investigated elements ³³As is the only one for which the energy of the lines Lα_1,2 and Lβ₁ is below the L₃ absorption edge. For all the other elements the lines Ll, Lη, and Lα_1,2 are below the L₃ edge, whereas Lβ₁ and Lβ_3,4 are above this edge. This difference leads to effects of differential absorption, where the absorption is stronger for decreasing line energy. For the net peak height ratio β₁/α we obtained results which are of the same order of magnitude as those given by White and Johnson (W&J) in their popular tables. But for l/α and β_3,4/β₁ our results show an atomic number dependence which is completely different from those given by W&J.     

The Observation of Strong Absorption of the Yttrium Lα Line in Sialon Ceramics

 β-sialon ceramics sintered with yttria additives have been studied with the use of an electron probe X-ray analysis (EPMA). Sialon ceramics were prepared from a carbothermally derived β-sialon powder and then sintered in a nitrogen atmosphere with yttria admixture. The above process was followed by annealing in flowing nitrogen. Scanning electron microscope (SEM) observations have shown that the sintered material contains a glassy phase (Y-Si-Al-O-N) on the grain boundaries. X-ray diffraction (XRD) after annealing in nitrogen revealed the presence of a considerable amount of yttrium aluminium garnet (YAG). The higher voltage of 30 kV was used in order to excite the yttrium K_α radiation (14.96 keV) at an appropriate overvoltage ratio because in some phases of the material, the disappearance of the yttrium L_α line has been observed during EPMA examination at an accelerating voltage of 15 kV in energy dispersive spectra (EDS). The intensity of the yttrium K_α line was sufficiently high, while the Y L_α line was not seen in the ED spectrum. Because the position of the yttrium L_α line (1.922 keV) is very close to the Si (K) absorption edge (1.84 keV), the strong absorption at this edge is probably responsible for the effect. This result should be considered as a serious warning in the case of EPMA (EDS) studies on compounds or mixtures suspected to contain both silicon and yttrium, because at electrons energies lower than 15 keV, the presence of yttrium in materials can go unnoticed. In wavelength dispersive spectra (WDS) obtained at 15 keV the intensity of the yttrium L_α line was also very low but measurable.     

Fluorescence and photochemical properties of crystalline boron difluorides β-diketonato

The fluorescence and photochemical properties of crystalline β-diketonatoboron difluorides (DBD) RCOCHCOR¹BF₂ were studied. These compounds are characterized by relatively high photochemical stability. The introduction of electron-donating groups into the aromatic α-substituent of the chelate ring increases and the introduction of electron-withdrawing groups decreases the fluorescence intensity of DBD. Anisoylbenzoylmethanotoboron difluoride was found to exhibit the highest fluorescence intensity. The substituents were shown to influence the relative arrangement of singlet and triplet ηπ^* and ππ^* levels and luminescence properties of compounds. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1030–1033, June, 2000.     

Dependence of the Kβ/Kα intensity ratio on the oxidation state

The K/K X-ray intensity ratios were measured for pure Cr, Mn, Co and Cu belonging to the 3 d shell as well as in their compounds, to look for the influence of the chemical environment on the fluorescence yield ratios. The vacancies in the K shell created by 59.5 keV -rays from an²⁴¹Am source and the X-rays were measured using a Ge(Li) detector. A steady increase of the K/K intensity ratio was observed with increasing oxidation. The present results agree with previously published experimental data.     

Vacancy Contents in MnZn Ferrites From TG Curves

Expressions for calculating the cation vacancy contents of MnZn ferrites from thermogravimetric curves are presented together with some experimental data. In a single-phase MnZn ferrite synthesized by conventional ceramic procedures, the O₂ evolution accompanying ferrite formation follows the formal equation. Mn²⁺ _σα Zn_σβ Fe³⁺ _2σ(1–γ) [V ]_{σ/4(1–2γ)} O₄ =σ'/σ Mn²⁺ _σ(α–2ϕ) Zn_σβ Fe²⁺ _2σθ Mn³⁺ _2σϕ Fe³⁺ _{2σ(1–γ–θ)} [V ]_{σ/4(1–2γ–3ϕ)} O₄ +σ'φ/2O₂ (g) where α and β denote the MnO and ZnO mole fractions in the primary mixture γ=α+β, θ and ϕ depend on the quantities of Fe²⁺ and Mn³⁺ formed, respectively, φ=θ–ϕ and σ'/σ is a function of the former parameters. Even though the relative amounts of Fe²⁺ /Fe³⁺ and Mn²⁺ /Mn³⁺ remain uncertain, the vacancy content [V ] of the ferrite can be determined because it depends on φ alone, which is related to the change in mass of the sample as the synthesis takes place through the equation φ=(1.5–γ) μ_β /μ_O2 (1–m _f /m _i ) Here, m _i and m _f are the masses of the sample before and after O₂ evolution, μ_B is the formula mass of the ferrite and μ_O2 is the O₂ molar mass. Practically vacancy-free single-phase MnZn ferrite samples were obtained by sintering in air at 1250°C and cooling in pure N₂ . This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of chemical effect on the Kβ/Kα X-ray intensity ratios for calcium and potassium compounds

K_β/K_α X-ray intensity ratios of some K and Ca compounds were studied. The samples were excited by 5.96 keV γ-rays emitted from (50 mCi ⁵⁵Fe filtered annular) radioisotope source and characteristic K X-ray from the samples were measured by a Si(Li) detector, with a resolution of 0.16 keV at 5.9 keV. The experimental values were compared with the calculated theoretical values for K and Ca.     

Positional selectivity in electrophilic substitution reactions of π-excessive heterocycles (review)

Existing experimental data on positional selectivity in electrophilic substitution reactions of π-excessive heterocycles are classified. These data are discussed basing on the results of the authors' quantum-chemical calculations [RHF/6-31G(d), MP2/6-31G(d), and B3LYP/6-31G(d)] of the σ-complexes formed during attack of electrophiles such as H⁺, Me⁺, Me₃Si⁺, Br⁺, NO₂ ⁺, MeCO⁺, and SO₃ at the α- and β-positions of furan, thiophene, selenophene, pyrrole and its N-substituted derivatives, N-R-pyrroles (R = Me, t-Bu, SiMe₃, Si(i-Pr)₃, C₆H₄(p-NO₂), SO₂Ph, CHO, CO₂Me), and the corresponding α- and β-substituted electrophilic substitution products. The differences in energies of the α-and β-isomers of the σ-complexes characterize the preferred direction of electrophilic attack, while the differences in the energies of the isomeric products make it possible to assess the energy preference of one of them. Analysis of the obtained data demonstrates the effects of the studied heterocycles' structure, the nature of the electrophile, and the thermal and steric factors on the positional selectivity (α/β ratio) in electrophilic substitution reactions of π-excessive five-membered heteroaromatic compounds.     

Experimental X-ray intensity ratios of the Lα Lβ, Lγ, Lℓ and Lη lines

Experimental, relative intensities for the components of L X-rays have been collected from the literature, and the atomic number dependence has been found for the L_β/L_α, L_γ/L_α, L_ℓ/L_α and L_η/L_α ratios. Among the L X-ray components L_α is predominant if Z<40, L_β/L_α≈1.0 if 50≤Z≤90, L_γ/L_β≈1.0 if 94≤Z≤100, and L_γ/L_α>1.0 if Z≈100.     

First ionization potentials and conjugation in molecules of ethylene derivatives containing organoelemental substituents of Group IV elements

Unlike theE _HOMO energies, the first vertical ionization potentials (I ₁) of monosubstituted ethylenes dependen not only on both the inductive and resonance effects but also on the polarizability of the substituents, which can be characterized by the σ_α parameters. The σ _R ⁺ , σ _p ⁺ , and σ_α parameters for 12 silicon-, germanium-, and tin-containing groups were determined using the equations relating theI ₁ values and the σ_I, σ _R ⁺ , σ _p ⁺ and σ_α parameters of the substituents in the molecules of organic compounds. The conjugation of organoelemental substituents with the double bond is stronger than that with benzene ring; the σ _R ⁺ parameters in the ethylene and benzene series are related by a linear dependence. Translated fromIzvestiya Akademii Nauk Seriya Khimicheskaya, No. 9, pp. 1626–1631, September, 1997.     

A Study of Haloperidol Inclusion Complexes with <Emphasis Type="Italic">β</Emphasis>-Cyclodextrin Using Phase Solubility,NMR Spectroscopy and Molecular Modeling Techniques

Guest-host interactions of haloperidol (Halo) with β-cyclodextrin (β-CD) have been investigated using several techniques including phase solubility diagrams (PSD), proton nuclear magnetic resonance (¹H-NMR), X-ray powder diffractometry (XRPD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and molecular mechanical modeling (MM⁺). From an analysis of the PSDs, both protonated and neutral Halo (pK _a=8.5) form soluble 1:1 and 1:2 Halo/β-CD complexes, while the insoluble complex has 1:2 (Halo:β-CD) stoichiometry (B_S-type PSD). Ionization of Halo reduces its tendency to complex with β-CD, where the protonated species at pH=4.6 and 6.0 have K ₁₁ values of 100 L⋅mol⁻¹ and 298 L⋅mol⁻¹, respectively, compared with 2000 L⋅mol⁻¹ for neutral species at pH=10.6. The hydrophobic character of Halo was found to provide 32% of the driving force for complex stability, whereas other factors including specific interactions contribute −15 kJ⋅mol⁻¹. ¹H-NMR and MM⁺ studies indicate the formation of isomeric 1:1 and 1:2 complexes, where the chlorophenyl, flurophenyl, piperidine and butanone moieties become included into separate β-CD cavities. The dominant driving force for complexation is evidently van der Waals with very little electrostatic contribution. PSD, ¹H-NMR, XRPD, DSC and SEM studies indicate the formation of inclusion complexes in solution and in the solid state.     

Measurement of dispersion numbers for 36 and 100% tri-isoamyl phosphate solvents equilibrated with aqueous nitric acid solutions

The cross sections for the ¹¹⁸Sn (n, α)¹¹⁵Cd, ¹²⁰Sn (n, α)^117gCd and ¹²⁰Sn (n, α)^117mCd reactions have been measured in the neutron energy range of 13.5–14.6 MeV using the activation technique and a coaxial HPGe γ-ray detector. The fast neutrons were produced by the T (d, n) ⁴He reaction. The neutron energies in the measurements were determined by cross section ratios for ⁹³Nb(n,2n)^92mNb and ⁹⁰Zr(n, 2n)^89m+gZr reactions. The results of present work were discussed and compared with theoretical calculation data, measurement results found in the literature and with the comprehensive evaluation data in ENDF/B-VII.0, CENDL-3.1, JENDL-4.0 libraries.     

Study on the Inclusion Compounds of Eugenol with α-, β-, γ- and Heptakis (2,6-di-O-methyl)-β-cyclodextrins

Several host–guest inclusion compounds of eugenol as a guest molecule and cyclodextrins (α-,β-,γ-CD) and heptakis (2,6-di-O-methyl)-β-cyclodextrin (DMβ-CD) as hosts were investigated in the solid state and in aqueous solution. The one-to-one solid inclusion compounds of eugenol and β-CD or γ-CD were prepared, but those of eugenol with α- or DMβ-CD were not obtained under the same condition. However, the UV-visible absorption spectroscopy data indicated that the liquid guest could form a 1:1 inclusion compound with all four hosts respectively in aqueous solution. The two solid inclusion compounds were characterized by powder X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TG), differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR). The association constants (K), calculated from the modified Benesi–Hidebrand equation, of eugenol with α-, β-, γ- and DMβ-CD is 4.95 × 10⁴, 3.96 × 10⁵, 1.47 × 10⁵ and 9.33 × 10⁴ mol⁻¹ dm³, respectively.     

X-ray fluorescence determination of the FeO/Fe<Subscript>2</Subscript>O<Stack><Subscript>3</Subscript><Superscript>tot</Superscript></Stack> ratio in rocks

Chances for estimating the FeO/Fe₂O₃^tot ratio in rocks by the K and L series of X-ray fluorescence spectra are studied. The errors in the determination of FeO/Fe₂O₃^tot by the intensity ratio of the Kβ_2,5/Kβ_1,3 and Lβ/Lα_1,2 lines are compared. The relative standard deviation of determining FeO using a set of 49 standard samples of eruptive rocks varies in the range 5–16%, depending on the ratio FeO/Fe₂O₃^tot and the concentration of FeO. The better precision is attainable for a ratio above 0.45 at a FeO concentration in the range 5–15%. For samples of andesites and basalts, the relative standard deviation is better than 4%, for rocks of the granite family it is 23% at FeO concentrations below 3%. For samples of metamorphic and sedimentary rocks, the error of FeO determination is higher than that for the eruptive ones. For samples with the ratio FeO/Fe/Fe₂O₃^tot < 0.25, the deviation may exceed 30 rel %. In contrast to chemical analysis, the X-ray fluorescence method appears advantageous in time and cost of sample preparation and can be used for routine analysis in geochemical research.     

Comparative Study of the Inclusion Complexation of Pizotifen and Ketotifen with Native and Modified Cyclodextrins

The interaction of two benzocycloheptanes namely, pizotifen (Pizo) and ketotifen (Keto), with cyclodextrins (CDs: α-, β-, γ-, and HP-β-CDs) has been investigated by several techniques including phase solubility, X-ray powder diffractometry, ¹H-nuclear magnetic resonance and molecular mechanical modeling. The effects of CD type, pH, ionic strength and temperature on complex stability were also explored. The complex formation constant (K ₁₁) values for the Pizo/CD system follows the decreasing order β-CD > γ-CD > HP-β-CD > α-CD. However, for the Keto/CD system it follows the decreasing order γ-CD > β-CD > HP-β-CD > α-CD. The tendency of Pizo and Keto to complex with β-CD is driven to the extent of 70% by the hydrophobic effect. Complex formation of Keto and Pizo was substantially driven by entropy (>100 J⋅mol⁻¹⋅K⁻¹) but slightly retarded by enthalpy (3–8 kJ⋅mol⁻¹). ¹H-NMR and MM⁺ studies indicate multimodal inclusion of the methylpiperadine, thiophene and phenyl moieties into the β-CD cavity.     

The investigations on K and L X-ray fluorescence parameters of gold compounds

The study aimed to determine the chemical effects on the K and L X-ray intensity ratios and the K and L X-ray production cross sections for gold compounds. The K shell fluorescence yields and L shell average yields were also investigated. The samples were excited by 59.5 keV γ-rays from an ²⁴¹Am annular radioactive source and 123.6 keV γ-rays from a ⁵⁷Co annular radioactive source. K and L X-rays emitted from samples were counted by an Ultra-LEGe detector with a resolution of 0.150 keV at 5.9 keV. The experimental values were compared with theoretical, the semi-empirical and other experimental values.     

Probing hemoglobin structure by means of traveling-wave ion mobility mass spectrometry

Hemoglobin (Hb) is a tetrameric noncovalent complex consisting of two α- and two β-globin chains each associated with a heme group. Its exact assembly pathway is a matter of debate. Disorders of hemoglobin are the most common inherited disorders and subsequently the molecule has been extensively studied. This work attempts to further elucidate the structural properties of the hemoglobin tetramer and its components. Gas-phase conformations of hemoglobin tetramers and their constituents were investigated by means of traveling-wave ion mobility mass spectrometry. Sickle (HbS) and normal (HbA) hemoglobin molecules were analyzed to determine whether conformational differences in their quaternary structure could be observed. Rotationally averaged collision cross sections were estimated for tetramer, dimer, apo-, and holo-monomers with reference to a protein standard with known cross sections. Estimates of cross section obtained for the tetramers were compared to values calculated from X-ray crystallographic structures. HbS was consistently estimated to have a larger cross section than that of HbA, comparable with values obtained from X-ray crystallographic structures. Nontetrameric species observed included apo- and holo- forms of α- and β-monomers and heterodimers; α- and β-monomers in both apo- and holo- forms were found to have similar cross sections, suggesting they maintain a similar fold in the gas phase in both the presence and the absence of heme. Heme-deficient dimer, observed in the spectrum when analyzing commercially prepared Hb, was not observed when analyzing fresh blood. This implies that holo-α-apo-β is not an essential intermediate within the Hb assembly pathway, as previously proposed.