Measurement of K shell radiative transition probabilities and K, L2 and L3 shell/subshell fluorescence yields of some elements in the atomic number range 30 ≤ Z ≤ 40

K shell radiative transition probabilities and K, L₂ and L₃ shell/subshell fluorescence yields were measured using the K_β/K_α intensity ratio for seven elements in the atomic number range 30≤Z≤40 (Zn, As, Se, Rb, Sr, Y and Zr). The targets were irradiated with γ photons of energy 59.5 keV from Am-241. The obtained values were compared with the theoretical values. It was observed that the present values agree with previous theoretical results. The L₂ and L₃ subshell fluorescence yields were the first measured for the present elements.     

A method to determineL-subshell ionization cross sections for medium and heavy elements

We have developed a method to determineL-subshell ionization cross sections and report here on the first measurements of electron inducedL-subshell cross sections for target elements (29≦Z≦79) at electron bombarding energies between 50≦E ₀≦200 keV. The method involves the detection of characteristic X rays by means of a high resolution flat crystal spectrometer of known reflectivity and is based on the correlation of measured X ray intensities, Auger- and Coster-Kronig yields and radiative transition probabilities with theL-subshell cross section.     

Natural widths and Coster–Kronig transitions of L X-ray spectra in elements between Pd and Sb

The Lα and Lβ X-ray emission spectra in the elements between Pd (Z=46) and Sb (Z=51) were measured using a high-resolution double-crystal vacuum spectrometer. The relative intensities of satellite structures, which originate in L₁L₃M_4,5 Coster–Kronig transitions, were estimated to that of each diagram line, and compared with calculated values. According to the work of Chen et al. [1977a. Theoretical L-shell Coster–Kronig energies 11⩽Z⩽103. At. Data Nucl. Data Tables 19, 97–151], Salgueiro et al. [1987. J. Phys. (Paris) 48 Colloq. C9, 609] and Vlaicu et al. [1998. Investigation of the 74W L emission spectra and satellites. Phys. Rev. A 58, 3544] L₁L₃M₄ Coster–Kronig transition is forbidden for 50⩽Z⩽77, and L₁L₃M₅ Coster–Kronig transition is forbidden for 50⩽Z⩽73. The results suggest that L₁L₃M_4,5 Coster–Kronig transitions may be allowed even for Sn (Z=50) and Sb (Z=51).     

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.     

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.     

Electron affinities of the lanthanides

The electron affinities (EA's) of the lanthanides (La through Tm) have been determined from the expression EA = IP₁ ? C)r^?1)_n1, where IP₁ is the first ionization potential and (r^?1)_n1 is the relativistic radial integral of an electron in the unfilled shell, the constant C includes the quantum numbers n, 1 of the partly filled shells and the atomic number Z of each element. The EA's vary from +0.5 eV (La) to –0.2eV (Tm) which is consistent with other semi-empirical estimates for certain lanthanide elements.     

The preparation,crystal structure and electrochemistry of (5Z,5′Z)-2,2′-(alkane-α,ω-diylsulfanyldiyl)bis(5-(3-pyridylmethylene)-3,5-dihydro-4H-imidazol-4-ones) and their complexes with cobalt(II) chloride

A series of S-alkylated derivatives of 2-thiohydantoins, containing two 5-(3-pyridylmethylene)-3,5-dihydro-4H-imiazole-4-one fragments joined by polymethylene bridges with different numbers of carbon atoms, was synthesized. The title (5Z,5′Z)-2,2′-(alkane-α,ω-diylsulfanyldiyl)bis(5-(3-pyridylmethylene)-3,5-dihydro-4H-imidazol-4-ones) (L) were obtained by alkylation of 5-(3-pyridylmethylene)-3-phenyl-2-thiohydantoine by 1,2-dibromoethane, 1,6-dibromohexane or 1,10-dibromodecane in DMF in the presence of potassium carbonate. The complexes of ligands L with CoCl₂ · 6H₂O have been synthesized. It is shown that, regardless of the L:CoCl₂ ratio, complexes with LCoCl₂ composition are obtained in all cases. The structure of the cobalt(II) chloride complex with (5Z,5′Z)-2,2′-(ethane-1,2-diyldisulfanyldiyl)bis(5-(3-pyridylmethylene)-3-phenyl-3,5-dihydro-4H-imidazol-4-one) was determined by means of the RSA method. The cobalt atom in this complex has a tetrahedral ligand environment and it is coordinated by two chloride anions and two nitrogen atoms of pyridine fragments, forming a 19-membered metallocycle. Electrochemical investigations of the synthesized ligands and complexes have been made by CVA and RDE methods. It is established that the first stage of reduction for the complexes takes place on the metal, whereas the first stage of oxidation takes place on the coordinated chloride-anions.     

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.     

Intermolecular interactions in dioxane-water solutions of substituted coumarins according to ultrasonic data

Density, ultrasonic velocity of pure dioxane (Dx) and ligands, 4,6-dimethyl-7-hydroxycoumarin (L₁), 6-ethyl-7-hydroxy-4-methylcoumarin (L₂), and 3-chloro-7-hydroxy-4-methylcoumarin (L₃) in different percent of Dx-water mixture have been investigated at 303.15 K. Acoustical parameters such as adiabatic compressibility (β), intermolecular free length (L _f ), acoustical impedance (Z), relative association (R _A ), apparent molar compressibility (Φ_β), and apparent molar volume (Φ _V ) have also been evaluated from the experimental data of density and ultrasonic velocity. An excellent correlation between a given parameters is observed at all percent of dioxane-water and the result suggests nature of intermolecular interactions between the components.     

Structure and stability of AuXe n Z (n = 1–3, Z = −1, 0, +1) clusters

We have explored the structures and stabilities of AuXe _n ^Z (n = 1–3, Z = ?1, 0, +1) cluster series at CCSD(T) theoretical level. The electron affinities and ionization potentials are correlated to the HOMO–LUMO gaps. The role of the interaction was investigated using the natural bond orbital analysis.     

Cu(I) cloride complexes with 4,5-(2-pyridylethylene)dithio-1,3-dithiol-2-thione and triphenylphosphine

Heteroligand binuclear complexes of CuCl with triphenylphosphine and 5-pyridine-2-yl-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione (L¹) of the compositions [CuCl(PPh₃)(L¹)]₂ (I) and [CuCiL¹]₂ (II) are synthesized and studied by X-ray diffraction method. Crystals I are monoclinic; space group P2₁/n, a=8.9520(18) Å, b=18.926(4) Å, c=16.841(3) Å, β=94.96(3)°, Z=2. The Cu(I) atom has a quasi-tetrahedral surrounding involving the tetraphenylphosphine P atom, the pyridyl N atom of the molecule L¹, and two bridging Cl atoms. Crystals II are monoclinic; space group P2₁/c, a=9.3520(19) Å, b=8.1490(16) Å, c=18.660(4) A, β = 104.43(3)°, Z = 2. Both L¹ ligands in complex II act as bridges. The Cu(I) atom also has a quasi-tetrahedral surrounding formed by the Cl atoms, the pyridyl N atoms and thiol S atom of one L¹ ligand, and the thione S atom of the second L¹ ligand. Similar binuclear complexes with the bridging function of the L¹ ligand were also detected in a solution of II by the ESI method.     

Crystal structures of new isostructural oxovanadium(V) complexes with hydrazone ligands

Two new isostructural methoxide-bridged dimeric oxovanadium(V) complexes [VO(L¹)(OMe)]₂ (1) and [VO(L²)(OMe)]₂ (2), where L¹ and L² are the deprotonated forms of 3-bromo-N′-[1-(2-hydroxyphenyl)×ethylidene]benzohydrazide (H₂L¹) and 3-chloro-N′-[1-(2-hydroxyphenyl)ethylidene]benzohydrazide (H₂L²) respectively, are synthesized and characterized by elemental analyses, IR spectra, and single crystal X-ray determination. Both crystals crystallize in the triclinic space group P-1. For 1, a = 7.5237(15) Å, b = 10.846(3) Å, c = 11.195(3) Å, α = 84.143(3)°, β = 72.244(3)°, γ = 77.869(3)°, V = 849.9(4) ų, Z = 1, R ₁ = 0.0634, wR ₂ = 0.1373. For 2, a = 7.493(2) Å, b = 10.740(3) Å, c = 11.109(3) Å, α = 84.569(2)°, β = 71.783(2)°, γ = 79.822(2)°, V = 835.0(4) ų, Z = 1, R ₁ = 0.0511, wR ₂ = 0.1076. Each V atom in the complexes is octahedrally coordinated.     

An iterative method for obtaining accurate atomic inner shell binding energies

A new method based on an iterative procedure for obtaining accurate atomic inner shell binding energies is described. The method makes use of the doubly modi-fied Moseley plot as the starting point. As an illustration accurate binding energies for the M ₁ shell in the atomic number range 57 ≤ Z ≤ 71 have been obtained. This has also resulted in the removal of the anomaly in the M ₁ binding energy of Z = 68. Our calculations point to a need for a fresh look at the theoretical calculations of inner shell binding energies for Z = 57 to 71 in which some unsuspected effects appear to occur when the 4f shell is opened, half filled and closed.     

Nd,Yb, Au and UL-subshell ionization probabilities for 92 MeV Ar impact

The Nd, Yb, Au and UL-subshell X-ray emission probabilities as function of the impact parameter have been measured by X-ray—particle coincidence for 92 MeV Ar impact. The derivedL-subshell ionization probabilities show severe deviations from first order perturbation theory (SCA + corrections), although the totalL-shell ionization probabilities are still fairly well described by this approach. As is obvious from the data analysis, the discrepancy is due toL-substate coupling during the collision, which has a strong influence on the subshell ionization process, but is neglected in this theoretical approach. The observed influence of the multiple outer shell ionization on the measured data is also discussed.     

Further studies on the taumerization of the hydrido (alkynyl) cluster Ru3Pt(μ-H) {μ4-ν2-C ≡ C1Bu} (CO)9(L2) to the vinylidene cluster Ru3Pt{μ4-ν2-C ≡ C(H)tBu} (CO)9(L2): X-ray structures of Ru3Pt(μ-H){μ4-ν2-C = C(H)tBu} (CO)9(L2); L2 = dppet,dppp, andS,S-dppb

The first order rate constants for the tautomerization of the hydrio(alkynyl) clusters Ru₃Pt(μ-H){μ₄-ν²-C ≡ C¹Bu}(CO)₉(L₂);1a: L₂ = dppe,1b; L₂ = dppet,1c; L₂ = dppp and1d; L₂ =S,S-dppb to the corresponding vinylidene clusters Ru₃Pt{μ₄-ν²-C = C(H)^tBu}(CO)₉(L₂)2 have been measured, and they follow the orser1d <1a <1b ～1c. The reactions involving1a and1d exhibit an inverse kinetic deuterium isotope effect. The structures of1b, 2b, 2c, and2d were determined by X-ray crystallography, and are compared with those of1a and2a which have been previously reported. Crystal data for1b, space groupPbca,a = 13.338(4) Å,b = 17.771(6) Å,c = 36.092(8) Å,Z = 8,R(R _w) = 0.059(0.058) for 2342 absorption corrected, observed data; for2b, space group P2₁/n,a = 10.566(2) Å,b = 20.234(5) Å,c = 20.270(3) Å,β = 96.11(1)°,Z = 4,R(R _w) = 0.043(0.053) for 5865 absorption corrected, observed data; for2c, space group P2₁/n,a = 14.211(5) Å,b = 19.534(2) Å,c = 15.870(2) Å,β = 100.81(2)°,Z = 4,R(R _w) = 0.055(0.031) for 6566 absorption corrected, observed data: for2d, space group P2₁2₁2₁,a = 12.309(4) Å,b = 19.047(6) Å,c = 19.206(4) Å,Z = 4,R(R _w) = 0.055(0.053) fpr 2151 absorption corrected, observed data. The fluxional behavior of1d and1e (which consists of two interconverting isomers) has been examined by variable temperature¹³C NMR spectroscopy and by³¹P EXSY.     

CZE and ESI-MS of Borate-Sugar Complexes

Capillary zone electrophoresis (CZE) with electrospray ionization (ESI) mass spectrometry (MS) was used to study borate (B^?1) and sugar (L) complexes (L _x B^?1). Boric acid was adjusted to pH 10 with ammonium hydroxide to create an ESI-MS compatible CZE background electrolyte. We show for the first time that the electrophoretic peaks for each injected sugar contained both the substrates (i.e., sugar and/or multimers) and products (i.e., L _x B^?1). The effects of sheath liquid, temperature, and borate concentration were studied. The molecular mass information obtained from the ESI-MS provided new evidence on the mechanisms of borate-sugar complexation. Direct infusion ESI-MS and CZE-ESI-MS experiments strongly suggest that the formation of L _x B^?1 was from the direct reaction of a sugar or sugar multimer (L _x ) and B^?1. Larger L _x B^?1, where x > 2 were observed. Separation in the CZE dimension allows for the simultaneous analysis of a sugar mixture and simplified the ESI-MS analysis of sugars of the same molecular mass. The increase in sugar electrophoretic mobility caused by the increase in borate concentration was discussed in terms of the formation of L _x B^?1 complexes. In addition, the separation of five nucleosides by CZE using a borate electrolyte and detection using ESI-MS is demonstrated.     

The photodissociation of physisorbed alkyl nitrites.: Λ-doublet population and alignment of desorbed NO

The photolysis of thin layers of tert- and iso-butyl nitrite, physisorbed on a transparent insulating MgF₂ surface, has been investigated. (1+1′)-Resonance-enhanced multiphoton ionization (REMPI) spectroscopy was used to characterize the desorbed NO. For high-J rotational levels, a preference for the Π(A″) Λ-doublet and a small degree of alignment is observed. The axis of alignment is found to be parallel to the plane of polarization of the photolysis laser and perpendicular to the surface normal, indicating a cartwheeling mode of desorption. The photofragment yield (PHOFRY) spectrum of iso-butyl nitrite is also reported.     

STUDIES ON ACOUSTICAL PROPERTIES OF POLY(4,4′-CYCLOPENTYLIDENE DIPHENYLENE TOLUENE-2,4-DISULFONATE) IN DIFFERENT SOLVENTS AT 30°C

Various acoustical parameters of poly(4,4′-cyclopentylidene diphenylene toluene-2,4-disulfonate) (PSBPT) in chloroform, 1,2-dichloroethane, 1,4-dioxane and tetrahydrofuran were evaluated at 30°C using an interferometer operating at a frequency of 3 MHz. Some of these parameters, except the internal pressure, relaxation time, classical absorption coefficient and solvation number, were correlated with concentration. Excellent linear correlations between the parameters U, Z, K_s, R, b, L_f and r and concentration are observed. The increase of U, Z, R, b, P and decrease of K_s, r and L_f with increasing solute concentration C indicated polymer-solvent interaction. The positive values of the solvation number further supported the structure forming tendency of PSBPT. The relative viscosity against C plots indicated structural changes take place after 1% concentration except for the tetrahydrofuran system where it is observed at about 2% concentration; due to polymer-polymer entanglement. © 1997 Elsevier Science Ltd     

Highly-controllable imprinted polymer nanoshell at the surface of silica nanoparticles based room-temperature phosphorescence probe for detection of 2,4-dichlorophenol

This paper reports a facile and general method for preparing an imprinted polymer thin shell with Mn-doped ZnS quantum dots (QDs) at the surface of silica nanoparticles by stepwise precipitation polymerization to form the highly-controllable core–shell nanoparticles (MIPs@SiO₂–ZnS:Mn QDs) and sensitively recognize the target 2,4-dichlorophenol (2,4-DCP). Acrylamide (AM) and ethyl glycol dimethacrylate (EGDMA) were used as the functional monomer and the cross-linker, respectively. The MIPs@SiO₂–ZnS:Mn QDs had a controllable shell thickness and a high density of effective recognition sites, and the thickness of uniform core–shell 2,4-DCP-imprinted nanoparticles was controlled by the total amounts of monomers. The MIPs@SiO₂–ZnS:Mn QDs with a shell thickness of 45 nm exhibited the largest quenching efficiency to 2,4-DCP by using the spectrofluorometer. After the experimental conditions were optimized, a linear relationship was obtained covering the linear range of 1.0–84 μmol L⁻¹ with a correlation coefficient of 0.9981 and the detection limit (3σ/k) was 0.15 μmol L⁻¹. The feasibility of the developed method was successfully evaluated through the determination of 2,4-DCP in real samples. This study provides a general strategy to fabricate highly-controllable core–shell imprinted polymer-contained QDs with highly selective recognition ability.     

Structure of a new schiff base cobalt(III) complex with antibacterial activity

A new Schiff base cobalt(III) complex with the formula [CoL¹L²(N₃)]·NO₃ (L¹ is 2-[1-(2-phenylaminoethylimino)ethyl]phenolate, L² is N-phenylethane-1,2-diamine) is prepared and characterized by physicochemical methods and single crystal X-ray determination. The complex crystallizes in the triclinic system space group P-1, with a = 8.504(2) Å, b = 14.973(3) Å, c = 20.676(4) Å, α = 100.021(3)°, β = 90.005(3)°, γ = 103.084(2)°, V = 2523.0(9) ų, Z = 4, R ₁ = 0.0732, and wR ₂ = 0.1182. Single crystal X-ray diffraction analysis reveals that the complex contains two mononuclear [CoL¹L²(N₃)]⁺ cations and two nitrate anions. The Co atom is six-coordinated in an octahedral geometry. The ligands and the cobalt(III) complex are screened in vitro for their antibacterial activity against Bacillus subtillis, Staphylococcus aureus, Escherichia coli, and Pseudomonas aereuguinosa.