Chemical effect on L X-ray fluorescence cross-sections of Hg,Pb and Bi compounds

Chemical effect on the photon induced L X-ray fluorescence cross-sections (σ_Lα, σ_Lβ and σ_Lγ) for Hg, Pb and Bi compounds were investigated. The samples were excited by gamma rays with energy 59.5 keV from ²⁴¹Am radioisotope source. L X-rays emitted by samples were counted by a Si(Li) detector with resolution 160 eV at 5.9 keV. We observed chemical effect on the photon induced L X-ray fluorescence cross-sections (σ_Lα, σ_Lβ and σ_Lγ) for Hg, Pb and Bi compounds. Our values were compared with calculated theoretical values.     

Resonances in helium atoms associated with theN=4 andN=5 He+ thresholds

Some doubly excited autoionising states of helium atoms converging on theN=4 andN=5 He⁺ thresholds are calculated by use of a method of complex-coordinates. States withL≧2 and with parities of (?1) ^L and (?1) ^L+1 are calculated by using products of Slater-orbital type wave functions with expansion lengths up to 319 terms. Resonance parameters (both resonance energy and autoinoisation width) are calculated for states with angular momentum up toL=7 forN=4 resonances, andL=8 forN=5 resonances.     

Profile changes in barium Lα X-ray emission spectra due to excitation photon energies

New X-ray fluorescence satellites which are inside the natural width of the parent lines are observed in barium Lα_1,2 X-ray spectra. The measurements were performed with a double-crystal X-ray fluorescence spectrometer. Three X-ray tube anodes (Cr, W, Rh) were used in order to vary the excitation photon energy. As the photon energy of chromium Kα is between the L_III and the L_II threshold energies of barium, only an L_II electron of barium can be excited by the chromium anode tube. The narrowest profile was observed for Cr Kα excitation. Tungsten Lα and rhodium Kα photon energies are high enough to excite any L_I ,L_II or L_III electron of barium atom. Profile analysis shows that the satellite lines were produced by the excitation of W Lα or Rh Kα. It is concluded that the appearances of X-ray line-width satellites depend on primary photon energies, and that these satellites cause to smear the profiles of parent lines.     

New interpretation of the AgL-series x-ray spectrum

Based on the de-excitation model of atomicL-shell vacancies, recent put forward by us, a new interpretation of Paratt's AgL x-ray spectrum has been successfully carried out, by using experimental and semiempiricalL ₁-hole decay data reported in recent years. An initialL-vacancy distributionN ₁:N ₂:N ₃=1:1.44:3.14 has been calculated from the silver spectrum. Present value of AgM-electron shakeoff probability due to anL-shell hole isP _M =0.034, which is much larger than theoretical calculations and semiempirical data.     

Measurements of Coster–Kronig enhancement factors for Yb,Lu, Os and Pt elements

In this work X-ray production cross-sections’ measurements, L_ι, L_α, L_β and L_γ, of Yb, Lu, Os and Pt elements have been studied at energies in the range 9.572–14.384 keV and the effect of Coster–Kronig transitions on fluorescence cross-sections for L X-ray line has been obtained. From these studies absolute values of L X-ray cross-sections have been calculated with incorporation of the enhancement due to the Coster–Kronig effect. The experimental enhancement factors tend to be smaller than those predicted by theory.     

Determination of nanocellulose fibril length by shear viscosity measurement

The lengths of ten types of cellulose nanofibrils were evaluated by shear viscosity measurement of their dilute dispersions. Aqueous dispersions of surface-carboxylated cellulose nanofibrils with a uniform width of ~3 nm were prepared from wood cellulose by 2,2,6,6-tetramethylpiperidine-1-oxyl-mediated oxidation and successive mechanical treatment. Cellulose nanofibril samples with different average lengths were prepared by controlling the conditions of the oxidation or mechanical treatment. The viscosity-average lengths, L _visc, of the nanofibrils were calculated by applying the shear viscosities of the dilute dispersions to an equation for the dilute region flow behavior of rod-like polymer molecules. The obtained L _visc values ranged from 1,100 to 2,500 nm and showed a linear relationship to the length-weighted average length, L _w, measured by microscopic observation; the relation was described as L _visc = 1.764 × L _w + 764. The influences of the electric double-layer of the nanofibrils and surface-carboxylate content on the value of L _visc were also investigated.     

L-shell ionization in Au by O5+-and Ni5+-ion impact

TheL X-ray production cross sections in gold by 60 to 72 MeV O⁵⁺ ions and 58 to 87 MeV Ni⁵⁺-ions have been measured. TheL-subshell ionization cross sections derived from these experimental results have been compared with the direct ionization theories viz. plane wave Born approximation (PWBA) theory and modified perturbed-stationary-state theory with energy loss, Coulomb deflection and relativistic effects (MECPSSR). A new procedure has been described to account for the change in the yield ratioLβ₁/Lβ_{2, 15} with energy, for Ni⁵⁺-ion impact on gold. TheL sub-shell ionization cross sections have been derived fromLβ₁,Lβ₄ andLβ_{2, 15} lines of theLβ group in addition to those calculated by the conventional Datz TRY3 technique usingLα,Lγ₁ andLγ_{2, 3} X-ray lines. From the shift in the energies of variousL X-ray lines and changes in their intensities, 3 and 5 spectator vacancies in theM- andN-shells in gold have been estimated with O⁵⁺-ion impact while 7, 20 and 4 to 6 spectator vacancies have been inferred in theM-,N-andO-shells respectively with Ni⁵⁺-ion impact in the energy range of the projectiles undertaken in the present studies.     

Enthalpy characteristics of dissolution of L-tryptophan in water + formamides binary solvents at 298.15 K

Enthalpies of dissolution of L-tryptophan in aqueous solutions of formamide (FA), N-methylformamide (MFA), and N,N-dimethylformamide (DMF) are measured according to calorimetry at the concentration of amides x ₂ = 0?0.4 mole fraction. Standard values of enthalpies of dissolution and transfer Δ_tr H ^o of L-tryptophan from water to binary solvent, as well as enthalpy coefficients of pair-wise interactions h _xy of L-tryptophan with formamide molecules are calculated. The effect the composition of a waterorganic mixture has on the enthalpy characteristics of L-tryptophan is considered. The relation of Δ_tr H ^o of L-tryptophan with the structure of amides is shown. A quantitative estimation of the contributions to the energy of L-tryptophan-formamide pair-wise interactions determined by polarity/polarizability, acidity, and basicity of organic solvent is performed using the four-parameter Kamlet-Taft correlation equation.     

Measurements ofL-subshell fluorescence yields for light and medium heavy elements (28≤Z≤47)

We report on the first determination ofL-subshell fluorescence yields, ω_Li, for various elements with 28≤Z≤47. The method applied is based on the subshell ionization by relativistic electron impact with an electron energy ofE ₀=50 keV and the detection of characteristic X rays by means of a high resolution crystal spectrometer calibrated absolutely with respect to its transmission and reflectivity. The number of initialL vacancies and its subshell distribution as well as the normalized X-ray transition probabilities, the Coster-Kronig yields and theK-shell Auger transition rates are taken from theory. The results obtained for ω_Li yield values that are for all three subshells in agreement with the predictions of a widely used semi-empirical formula and for ω _L2 and ω _L3 also with theoretical calculations. The values of ω _L1, however, exceed the theory systematically.     

Impact parameter dependence of theL-subshell ionization probabilities and of theL 3-subshell alignment tensor components in 4 MeVp-Sm collisions

The ionization of theL-subshells of Samarium by the impact of 4 MeV protons was examined by measuring the coincidence between x rays and scattered protons. TheL ₃-subshell ionization probability agrees well with the SCA predictions, for theL ₁-subshell and theL ₂-subshell ionization probabilities and also for theL ₃-alignment tensor components the results are not in agreement with SCA. Possible reasons for these deviations could be a neglect of collisional coupling between theL-substates.     

Measurement of L x-ray production cross sections by 60 keV photons and average L shell fluorescence yields of lanthanides

L x-ray production cross sections have been measured for lanthanides with 60 keV. The measured L x-ray production cross section values for the lanthanides are in good agreement with the theoretical ones evaluated using L _i subshell fluorescence yields ω_i, Coster-Kronig transition probabilities ? _ij based on the Relativistic-Hartree-Slater theory, K to L _i subshell vacancy transfer probabilities n _KLi, fractions of the ratiative width of the subshell F _ny and L _i subshell photoionisation cross section σ_Pi. The average L shell fluorescence yields ω_L have also been derived using the presently measured total L x-ray production cross section values and the theoretical K to L shell vacancy transfer probabilities. These results are compared with theoretically predicted values.     

The effect of small micropores on methane adsorption of coals from Northern China

In this study, the effect of coal micropores on the adsorption properties, especially the Langmuir pressure (P _L ), was investigated by testing 11 coal samples from Northern China. The adsorption of CO₂ at 273 K was utilized to analyze the pore size distribution. The results of these coals show that micropore volume and micropore surface area are the major factors affecting the Langmuir volume (V _L ) but have weaker effects on P _L . Micropore filling theory considers that some smaller micropores with an obvious overlapping adsorption force cause volume filling adsorption. These micropores firstly reach saturated adsorption, controlling the adsorption volume at the low-pressure stage and thus have a great effect on P _L . Four times the methane molecular diameter, 1.5 nm, was assumed as the critical pore size with obvious overlapping adsorption force. The relationship between P _L and the proportion of the pore volume below 1.5 nm to the micropore volume was investigated, and it was found that the higher the volume proportion of these small micropores was, the smaller the P _L was, though two data points deviated from this trend. The reason for the anomalous coal samples could be the deviation from the assumed critical pore size of 1.5 nm for volume filling and the effects of the various micropore surface properties, which await further study. The micropore surface increases with increasing coal rank, as does V _L . The proportion of pore volume below 1.5 nm increases with coal rank, and P _L reverses. However, these relationships are discrete.     

Construction of metal-organic frameworks through coordination and hydrogen bonding interactions: Syntheses, structures and photoluminescent properties of metal complexes with macrocyclic ligand

A macrocyclic ligand L with two diethylenetriamine units linked by two rigid biphenylene spacers was used as building block for construction of metal-organic frameworks. A silver(I) complex with macrocyclic and open-chain mix-type ligands [Ag₂(L)(L′)](ClO₄)₂ (1) [L′=1,6-bis(4-imidazol-1′-ylmethylphenyl)-2,5-diazahexane] was obtained by reaction of L and L′ together with AgClO₄·H₂O. It is interesting that the open-chain tetradentate ligand L′ only served as a bidentate ligand to bridge the Ag₂L units into an infinite one-dimensional (1D) cationic chain. Neutral 1D chain coordination polymer [Cu₂(L)(μ-SO₄)₂]·3H₂O·3MeOH (2) is formed by sulfate bridges between the neighboring Cu₂L units. When L reacted with nickel(II) sulfate instead of copper(II) sulfate, a monomacrocycle molecular complex [Ni₂(L)(H₂O)₄(SO₄)₂] (3) was obtained in which the sulfate anion acts as monodentate ligands rather than as bridges. When Cd(II) salts were used for the reactions with L, another two neutral 1D coordination polymers, [Cd₂(L)(μ-Cl)₂Cl₂]·2H₂O (4) and [Cd₂(L)(μ-Br)₂Br₂] (5), with the same structure were isolated. All the synthesized complexes exhibit three-dimensional framework structures linked by various hydrogen bonds. The photoluminescent properties of the synthesized complexes were studied in the solid state at room temperature, and the Ag(I) and Cd(II) complexes were found to show strong blue luminescence.     

Energy and CKT dependence of proton induced L subshell X-ray intensity ratios in elements 57⩽Z⩽92

The dependence of L subshell X-ray intensity ratios on incident proton energy and the CK transitions has been investigated in elements 57⩽Z⩽92. The intensity ratio I(L_α)/I(L_l) neither shows variation with energy nor any dependence on the CK transitions. In general, the ratios I(L_α)/I(L_β) and I(L_α)/I(L_γ), first increase with incident proton energy, attain a maximum value, then start decreasing and attain an almost constant value after a particular energy (ranging from about 4.6 MeV for La to 5.8 MeV for U). A comparison has been made among the intensity ratios evaluated using three different sets of parameters. A maximum difference of about 18% has been observed among the different values.     

Photometric determination of copper(II) in nickel alloys using azoderivatives of ethyl acetoacetate

1-Ethoxy-2-(2-hydroxy-3-sulfo-5-chlorophenylazo)butane-1,3-dion (L₁), 1-ethoxy-2-(2-hydroxy-3,5-disulfophenylazo)butane-1,3-dion (L₂), 1-ethoxy-2-(2-hydroxy-4-nitrophenylazo)butane-1,3-dion (L₃), and 1-ethoxy-2-(2-hydroxyphenylazo)butane-1,3-dion (L₄) were synthesized on the basis of ethyl acetoacetate, and their analytical characteristics were studied. The following dissociation constants of the reagents were determined by potentiometric titration: pK ₁ = 5.94 ± 0.04 and pK ₂ = 9.75 ± 0.04 (L₁), pK ₁ = 5.78 ± 0.02 and pK ₂ = 9.55 ± 0.03 (L₂), pK ₁ = 6.03 ± 0.03 and pK ₂ = 9.86 ± 0.05 (L₃), and pK ₁ = 6.19 ± 0.05 and pK ₂ = 9.98 ± 0.06 (L₄). The chemical analytical characteristics of copper(II) complexes of L₁–L₄ were determined by spectrophotometry. It was found that, with an increase in the elecrophilic properties of the substituents introduced into the aromatic ring of the molecule, the sensitivity of the reaction increased; the substituents had no effect on the ratio of Cu : L = 1 : 2. A photometric procedure was developed for determining copper in nickel-based alloys.     

Concerning the Role of σ-Hole in Non-Covalent Interactions: Insights from the Study of the Complexes of ArBeO with Simple Ligands

The structure, stability, and bonding character of some exemplary LAr and L-ArBeO (L = He, Ne, Ar, N₂, CO, F₂, Cl₂, ClF, HF, HCl, NH₃) were investigated by MP2 and coupled-cluster calculations, and by symmetry-adapted perturbation theory. The nature of the stabilizing interactions was also assayed by the method recently proposed by the authors to classify the chemical bonds in noble-gas compounds. The comparative analysis of the LAr and L-ArBeO unraveled geometric and bonding effects peculiarly related to the σ-hole at the Ar atom of ArBeO, including the major stabilizing/destabilizing role of the electrostatic interactionensuing from the negative/positive molecular electrostatic potential of L at the contact zone with ArBeO. The role of the inductive and dispersive components was also assayed, making it possible to discern the factors governing the transition from the (mainly) dispersive domain of the LAr, to the σ-hole domain of the L-ArBeO. Our conclusions could be valid for various types of non-covalent interactions, especially those involving σ-holes of respectable strength such as those occurring in ArBeO.     

Ionic salt permeabilities and membrane potentials of asymmetric polypeptide membrane

Asymmetric membrane potentials and transport properties of polypeptide membrane consisting of two layers with poly(L-glutamic acid) and poly (γ-methylL-glutamate) were studied in the pH range of 2 to 6 at 25 °C. Under the condition adopted, the poly (L-glutamic acid) layer of the membrane underwentα helix to coil transition which was confirmed by ATR-IR measurements. The membrane potentials of the asymmetric membrane between two identical solutions of KCl,Δψ _asym, which is called asymmetric potential, were observed.Δψ _asym values were effected by the structural transition of poly (L-glutamic acid) layer. As a result, the effective charge density of the membrane, which was derived by the asymmetric membrane potential measurements, had a maximum at the transition region of pH=4.8. On the other hand, the permeation coefficient of KCl,P _i, was higher in the direction from poly (L-glutamic acid) side to poly (γ-methylL-glutamate) side, “G →M direction”, than in the oppositeM →G direction. Furthermore,P _i inG →M direction was dependent on the solution pH, that is,P _i decreased when pH was increased to 4.8 and increased on further increasing of pH These membrane behaviors were described in terms of the competition between structural transition and variation of fixed charge density owing to the helix to coil transition of the asymmetric polypeptide membrane.     

Molecular dynamics investigations on Lennard–Jones systems near the gas–liquid critical point

NVT simulations on Lennard–Jones (L–J) systems near the gas–liquid critical point were performed by a direct approach. As a result, the two necessary conditions for simulating the systems in accordance with the thermodynamic limit were proposed: (i) L/ξ≳20 (L: the box-length, ξ: the correlation length), (ii) the total time of evolution, t_E>500 L–J units, for ξ≈3.5. The proposed conditions are probably very close to the sufficient ones. The influence of finite-size effects on pressure and density of small systems was qualitatively predicted. The prediction was confirmed by the simulations but only for L markedly lower than the length of typical critical wave, 2πξ. For L markedly higher, the evolutions were dominated by an effect called here the instability effect. The effect became negligible just when the condition for L/ξ was fulfilled. The ξ₀′ constant for L–J fluid was estimated from direct measurements of ξ to be 0.27±0.02 (L–J units). The thermodynamic parameters of the critical point, obtained from extrapolation, were in agreement with the results of other authors. The β_C exponent was estimated from minimization for a high range of temperatures to be 0.346. A comparison of the efficiency of NVT and NpT methods was also performed and no distinct differences were noted.     

Measurements of radiative vacancy transfer probabilities from L3 subshells to M,N and O shells and subshells in the atomic range 72⩽Z⩽92

The probabilities of vacancy transfer, η_L3M, ηL₃M₁, ηL₃M₄, ηL₃M₅, η_L3N, ηL₃N₁, ηL₃N₄, ηL₃N₅, ηL₃O₁ and ηL₃O_4,5 from L₃ subshell to M, N and O shells and subshells for the elements Hf, Ta, W, Re, Pt, Au, HgO, Tl, Pb, Bi, Th, U have been measured using L shell fluorescence yields and X-ray intensity ratios. These experimental values were obtained from samples excited by 59.5-keV γ-rays, which were emitted from an ²⁴¹Am radioisotope source. Also K and L X-rays emitted from samples were measured by means of Si(Li) detector with a resolution of 155 at 5.9 keV. The results obtained from this study are compared with the results of other studies.     

Synthesis and structure of diamine bis(phenolate) complexes containing the Ti(OEt)–O–Ti(OEt) function

Reaction of diamine-bis(phenol) ligands containing a mixture of N-methyl and N,N′-dimethyl-N,N-bis(2-hydroxy-3,5-dimethylbenzyl)ethylenediamine, H₂L¹ and H₂L³, with [Ti(OCHMe₂)₄ in absolute ethanol under reflux without exclusion of air and moisture gives [(L¹)Ti (OEt–O–Ti(OEt)(L¹)] (1). [(L³)Ti(OEt)–O–Ti(OEt)(L³)] (2) forms when the remaining solution containing [(L³)Ti(OEt)₂] (3) (characterised by X-ray crystallography) is hydrolysed with H₂O. For the N-methyl and N,N′-dimethyl ligand mixture H₂L² and H₂L⁴, which contain tert-butyl groups on the ortho-positions of the aryl rings, [(L²)Ti(OEt)–O–Ti(OEt)(L²)] (4) forms much more slowly and [(L⁴)Ti(OEt)₂] (5) does not hydrolyse when H₂O is added. When the N-protonated ligand N,N-bis(2-hydroxy-3-methyl-5-tert-butylbenzyl)ethylenediamine, H₂L⁵, is used, rapid hydrolysis to two isomers of [(L⁵)Ti(OEt–O–Ti(OEt)(L⁵)] (6) occurs without addition of water. For N,N-bis(2-hydroxy-3,5-di-tert-butylbenzyl)ethylenediamine, H₂L⁶, hydrolysis to [(L⁶)Ti(OEt)–O–Ti(OEt)(L⁶)] (7) occurs slowly when H₂O is added. For pendant NMe₂ ligand N,N-dimethyl-N′,N′-bis(2-hydroxy-3-methyl-5-tert-butylbenzyl)ethylenediamine, H₂L⁷, the hydrolysis reaction readily gives [(L⁷)Ti(OEt)–O–Ti(OEt)(L⁷)] (8) for which an X-ray crystal structure was obtained. The ortho-tert-butyl ligand derivative H₂L⁸ formed a complex analysing as [(L⁸)Ti(OEt)–O–Ti(OEt)(L⁸)] (9) which could not be studied further due to insolubility. Pendant pyridine ligand N-(2-pyridylmethyl)-N,N-bis(2′-hydroxy-3′-methyl-5′-tert-butylbenzyl)amine, H₂L⁹, apparently forms isomers of [(L⁹)Ti(OEt)–O–Ti(OEt)(L⁹)] and possibly [{(L⁹)Ti(O)}₂] from [(L⁹)Ti(OEt)₂] (10). The ortho-tert-butyl ligand derivative H₂L¹⁰ formed [(L¹⁰)Ti(OEt)–O–Ti(OEt)(L¹⁰)] (11) for which an X-ray crystal structure was obtained.