Isotope shift in chromium

Thirty-three spectral lines of chromium atom in the blue-violet region (425–465 nm) have been investigated with the method of laser-induced resonance fluorescence on an atomic beam. For all the lines, the isotope shifts for every pair of chromium isotopes have been determined. The lines can be divided into six groups, according to the configuration of the upper and lower levels. Electronic factors of the field shift and the specific mass shift (F_ik and M_ik^SMS, respectively) have been evaluated and the values for each pure configuration involved have been determined. Comparison of the values F_ik and M_ik^SMS to the ab initio calculations results has been performed. The presence of crossed second order (CSO) effects has been observed.     

Determination of the local electron number density in laser-induced plasmas by Stark-broadened profiles of spectral lines: Comparative results from Hα, Fe I and Si II lines

Measurements of the local electron density in laser-induced plasma have been carried out from the Stark-broadened profiles of three reference lines (H_α, Fe I and Si II). The plasma has been generated from a Fe–Si sample in air using a Nd:YAG laser. Compatible values of the local electron density have been obtained from the three lines. The experiment is based on the use of an imaging spectrometer, the capability for spatial resolution of a charge-coupled device and the application of a spatial deconvolution procedure to the spectra. Distributions of the emission coefficient have been obtained, showing that the three lines are emitted from different regions of the plasma. The implications in the apparent electron density values obtained in spatially-integrated measurements are discussed: similar values are obtained for the H_α and Si II lines, while the Fe I line leads to a 25% lower value.     

Eigenschafts-Korrelationen bei Chalkogenidgläsern. I. Das System Germanium-Antimon-Schwefel

Correlations between Properties of Chalcogenide Glasses. I. The System Germanium—Antimony—Sulphur Glass formation and properties of the glasses in the system Ge–Sb–S are described. The limits of the glass-forming region correspond approximately to the lines joining GeS, GeS₃ and Sb₂S₃ in the composition diagram. The results indicate two regions of liquid immiscibility, both at high sulphur and high antimony contents. The densities increase linearly with the average molecular weights per formula-unit of the glasses. Glass transition temperatures are in the range from 200 to 350°C, and values of Vickers hardness between 150 and 300 kp/mm² have been measured. Both properties are in a linear relationship with the approximate values for the atomization energies of the glasses.     

Line shapes in electronic absorption spectra. Phenanthrene

The 3000 Å, (¹B₂ ← ¹A₁), absorption system of phenanthrene in durene crystals at 4°K illustrates an electronic transition, which is subject to near-resonance vibronic perturbations whose effect is intermediate to both the small (sparse intermediate) and large molecule (statistical) limits. Both broad (300 cm^?1) and narrow (10 cm^?1) lines are evident. A model is proposed which incorporates both these features by fast allowing for a consideration of the interaction between a small number of discrete levels, those associated with the largest coupling, followed by a treatment of the broadening of these levels through interaction with the remaining near continuum of states of the lower electronic state. Thus, one and the same electronic state provides both a sparse and dense manifold of levels. An important result of the model is that in terms of absorption intensities all the lines emerge with the same heights but differ in widths. When the intensities are summed with respect to energies this aspect is obscured. This approach has been shown to satisfactorily reproduce many of the features of the ¹B₂ absorption spectra of phenanthrene and phenanthrene-d₁₀. The ¹B₂ absorption systems have also been measured in the vapour phase and fine structure attributable to vibronic coupling and sequence band development are discussed.     

Study of the ν1, ν1 + ν3 and ν2 + ν3 infrared bands of ONCl

A type (ΔK_a = 0) rovibrational lines of the near-prolate asymmetric top ¹⁶O¹⁴N³⁵Cl have been assigned on high resolution Fourier transform spectra: 820 lines of the ν₁ band, centered around 1800 cm⁻¹, 435 lines of the ν₁ + ν₃ band, centered around 2131 cm⁻¹, and 257 lines of the ν₂ + ν₃ band, centered around 925 cm⁻¹. Least-squares calculations have been carried out over these lines, using the A reduced Watson's hamiltonian in I^r representation; r.m.s. standard deviations of 0.0016 cm⁻¹, 0.0016 cm⁻¹ and 0.006 cm⁻¹ have been respectively obtained, making it possible to measure molecular constants of the (001), (101) and (011) vibrational levels of ¹⁶O¹⁴N³⁵Cl.     

Raman and resonance-Raman spectra of CsI/I−3

Raman and resonance-Raman spectra of the I^?₃ ion isolated within CsI crystals have been studied using 647 nm and 488 nm exciting radiation. Sample temperatures between 300 and 20 K have been used. Eleven overtones of the symmetric stretching mode (nν₁) have been observed in the resonance-Raman spectrum excited by the 488 nm Ar⁺ laser line. Bands centred at 153, 170, 264 and 304 cm^?1 have been assigned as ν₃, 2ν₂, ν₁+ν₃ and 2ν₃(Σ⁺) respectively. The remaining structure between the nν₁ lines has been assigned as due to combinations of these lines with the lattice vibrations of the CsI crystal.     

A molecular beam study of a van der Waals complex; vibration-inversion transitions in NH3-Ar

Three ν₂ vibration-inversion transitions of NH₃-Ar have been found with linewidths smaller than 2 MHz, yielding a minimum predissociation lifetime of 80 ns. While one of these lines was previously identified as a low frequency inversion doublet transition, the other two lines belong to the high frequency component of the ν₂ vibration-inversion doublet.     

Measurement of L subshell photoionisation cross sections of Th and U at 22.6, 25.8, 29.2 and 32.9 kev

Bremsstrahlung from an X-ray tube was used to excite secondary targets of Ag, Sn, I and Ba to get nearly monochromatic excitation energies of 22.6, 25.8, 29.2 and 32.9 keV, respectively. Th and U were used as targets. The L X-ray fluorescence cross sections of different lines from the targets have been measured. Of the several methods to obtain L subshell photoionisation cross sections from these fluorescence data, the merits and demerits of four common methods have been explained and the method with least uncertainty was suggested as the best one for such analysis. Following this method, with intensities of the resolved L_γ lines, three L subshell photoionisation cross sections have been obtained using six different sets of atomic parameters. The variation of these cross sections with different atomic parameters has been discussed. For σ₁, all the derived values are within 30% of one other while for σ₂ and σ₃, they are within 12%. Measured cross sections have been compared with the data of others and with the theoretical values of Scofield. Finally, the intensity ratios of different L lines have also been compared with available data and the theoretical values. Within experimental errors, our data are in good agreement with the data of others and with the theoretical predictions.     

Metal benzoylpivaloylmethanates. Part II. 1,4-dioxane adducts of copper(II) chelates

Summary 1 : 1 Dioxane adducts of Copper(II) chelates withpara-subtituted benzoylpivaloylmethanes have been synthesized and their u.v., vis., i.r., mass, e.p.r. spectra as well as their magnetic moments and thermal stabilities investigated. Powdered samples of undiluted magnetically adducts were found to give well resolved e.p.r. spectra; the (S = 1) g_| signal being split into nine lines. Magnetic susceptibilities measured down to 4 K did not reveal exchange interactions. The uncommon structure of the e.p.r. spectra is believed to be due to the dimeric structure of the adduct in which an interion dipolar zero-field splitting of the triplet state occurs. The Cu-Cu distance estimated from the e.p.r. D_dd parameter is found to be 7.4 Å.     

Antitumor activity of stilbenoids and flavonoids isolated from Acanthopanax brachypus

This report is the first to detail the antitumor activity of Acanthopanax brachypus, a species well recognized by eastern folk medicine. Four stilbeniods and nine flavonoids have been isolated from stem bark of the plant. The isolates have been tested for their antitumor activity against selected human cancer cell lines (HgpG-2, MCF-7, K-562, and A-549). Even though three of the compounds have shown high to moderate cytotoxicity against certain cell lines (IC₅₀ of 4.5 to 6.5 μg/mL), in most of the experiments little or no anticancer activity has been revealed.     

Analyse vibrationnelle et structurale en série aliphatique insaturée: I. Étude des fumarate et maléate neutres de potassium

The Raman and infrared spectra of potassium maleate and fumarate in aqueous solutions have been studied from 100 to 3500 cm^?1.The analysis of the polarization ratio of the Raman lines allows us to corroborate the symmetries C_2v (maleate) and C_2h (fumarate) previously found for these two organic ions by other authors who had, however, studied a narrower spectral range.A more complete assignment concerning nearly all the fundamentals is proposed.     

Characterization of laser-induced plasmas by emission spectroscopy with curve-of-growth measurements. Part I: Temporal evolution of plasma parameters and self-absorption

Laser-induced plasmas have been characterized by emission spectroscopy, including the measurement of curves of growth. The plasmas have been generated in air at atmospheric pressure using an infrared Nd:YAG laser from a set of Fe–Ni alloys with varying Fe concentrations. The procedure used provides, in addition to the apparent temperature T and electron density N_e, a parameter N′l (the atom number density for 100% concentration times the length of the plasma along the line-of-sight), relevant to obtain the self-absorption and the intensity of the emission lines. The temporal evolution of the plasma parameters has been deduced from the measurement and fitting of the curves of growth. A fast temporal decrease of N′l is obtained for ions, whereas a gradual increase takes place for neutral atoms. The temporal evolution of the line intensity in the optically thin limit and the self-absorption of neutral atom and ion lines have been obtained experimentally and calculated from the evolution of the plasma parameters. The usefulness of the curve-of-growth method in measurements with time integration, in spite of the fast variation of the plasma parameters, has been demonstrated.     

Solubility in the system Na2Cr2O7 + 2NH4Cl ⇆ (NH4)2Cr2O7 + 2NaCl-H2O

The solubility in the water-salt quaternary reciprocal system Na₂Cr₂O₇ + 2NH₄Cl ⇆ (NH₄)₂Cr₂O₇ + 2NaCl-H₂O has been investigated for the first time at 25, 50, and 75°C. Using a formal analytical model, the boundaries of the phase fields have been determined, and the univariant lines and invariant points have been calculated. The experimental data have been used to calculate the temperature and concentration parameters of the circular isohydric process of potassium dichromate preparation with the participation of ammonium salts as intermediates.     

Isotope shifts in spectral lines of Yb+ in 322-615nm region and term shifts of odd and even parity energy levels of Yb II

Isotope shift Δσ(¹⁷²Yb - ¹⁷⁶Yb) has been measured in 79 classified lines of Yb II in the region 3225-6155 Å. Earlier studies provide isotope shift data in just six lines of Yb II. Term isotope shift ΔT (¹⁷²Yb-¹⁷⁶Yb) have been evaluated for 38 even and 30 odd parity levels of Yb II, using the present isotope shift data. The ΔT values have been discussed and correlated with the purity of the configuration assigned to an energy level, which enabled to check the reported eigenvector percentages of different configurations for some of the levels of Yb II. ΔT values of different levels resulting from J_IL_II couplings are also discussed.     

Fluorine core esca linewidths in CH3F and CF4

Ab initio calculations within the Hartree-Fock formation have been carried out on potential energy surfaces of the ground and the F_1s hole states of CH₃F and CF₄ in order to investigate linewidths of their ESCA spectra. The calculations show that potential energy surfaces of both hole states have dissociative character and can be approximated by straight lines in the region of interest. A simple formula for the ESCA fwhm linewidth is derived which yields results in good agreement with experiment. Theoretically derived relaxation and Koopmans' energies have been investigated as a function of geometry.     

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.     

Anion radicals of [60]fullerenes. An EPR study

Photochemically induced electron transfer in homogeneous systems (using triethylamine donor) and heterogeneous systems (using photoexcited TiO₂ suspension) was applied in in situ reduction of [60]fullerene. The anion radicals generated were characterized by means of EPR and VIS/near-IR spectroscopy. Narrow EPR lines were found. Radical A with g_A=2.0000 and peak-to-peak width, pp_A=0.09mT was observed as the primary product; followed by its consecutive product B with g_B=2.0006, pp_B=0.04mT, and in some cases product C with g_C=2.0009 and pp_c<0.1 mT. Radical A was assigned to [60]fullerene mono-anion, also characterized by a near-IR band at 1077 nm. B is presumably di-anion or a dimeric form of mono-anion. Identical results were also obtained using cathodic in situ reduction. Applying these generation techniques to [60]fullerene derivatives produced narrow EPR lines analogous to those described for pristine [60]fullerene. This was the case not only in organic solvents, but also in aqueous solutions. The results obtained present a contrast with the original ex situ EPR investigations describing [60]fullerene mono-anion with wide lines. According to the results presented here, the narrow and wide EPR lines do not represent contradictory phenomena, but are an integral part of the relatively complicated manifestations of various fullerene states and both will have to be seriously considered in the future.     

Temperature effects on fluorescence line narrowing spectra of tetracene in amorphous solid solutions. Analytical implications

Temperature effects in the highly specific vibrationally resolved fluorescence line-narrowing (FLN) spectra of tetracene as a model compound have been investigated with emphasis on analytical implications.Contrary to what is generally observed in conventional solid state methods, in FLN when excitation in the 0-0 region is employed, the lowest temperatures in most cases do not produce the largest peak heights and intensities. For excitation in the vibronic S₁ region the conventional behaviour is observed. The analytically useful temperature interval in FLN spectroscopy generally is more limited than in techniques that use crystalline matrix materials.The spectral bands in FLN have a predominantly Lorentzian shape for excitation in the 0-0 region in our experimental set-up where, at the temperatures used, the excitation source does not contribute significantly to the lineshape. For excitation in the vibronic S₁ region a stronger Gaussian contribution to the lineshape is observed. No temperature dependent shift of the narrow lines occurs, contrary to what is generally found in the conventional solid state methods. In addition, the position of the lines in FLN is not solvent dependent.To explain these observations it is crucial to realize that in FLN, high resolution is achieved via selective excitation, so that the spectral emission features are determined by the excitation as well as the emission process.     

Synthesis of novel xanthone and acridone carboxamides with potent antiproliferative activities

Several new amino-substituted acridone and xanthone derivatives have been designed and synthesized, using an efficient methodology from suitable acridone- or xanthone-carboxylic acid intermediates. The antiproliferative activity of the target compounds has been evaluated against four cancer cell lines, namely breast adenocarcinoma MCF-7, acute lymphocytic leukemia CCRF-CEM, and its doxorubicin-resistant variant CEM/ADR5000 and prostate cancer PC-3 cell lines. Selected derivatives have also been tested against the urinary bladder T24 and metastatic melanoma WM266-4 cancer cell lines. Two nitro substituted acridones, bearing a basic side chain as well, were endowed with a remarkable profile against the majority of the cell lines tested, with IC₅₀ values in the low micromolar range. Both compounds cause accumulation at G0/G1 phase, induce apoptosis, and act as potent autophagy inhibitors in PC-3 cells, suggesting their further evaluation in various pathophysiological environments, conditions, and regimens.     

Correction of characteristic mass in Zeeman graphite furnace atomic absorption spectrometry

A systematic study has been made of the effect of hollow-cathode lamp current and slit width (SW) of the 4100ZL spectrometer on characteristic mass m₀, Zeeman sensitivity ratio R, and roll-over absorbance A_r, for nine elements: Au, Bi, Cd, Co, Cu, Mn, Ni, Pb and Tl. The lamp spectra near the recommended analytical lines have been investigated for these elements. The data obtained have been combined with a theoretical analysis to show that the self-absorption of the analytical lines observed with increasing current and the rise of non-absorbable radiation with increasing SW affect m₀ and the A_r and R parameters differently. It is shown that a separate correction requiring additional narrow-slit measurement of the A_r parameter is necessary to take into account the SW effect on m₀. A separate-correction method built upon this basis offers a substantial improvement of the accuracy of taking into account the SW effect on m₀ compared with the method of combined correction proposed earlier (E.G. Su, A.I. Yuzefovsky, R.G. Michel, J.T. McCaffrey and W. Slavin, Microchem. J., 48 (1993) 278). Exceptions are the Mn and Ni analytical lines, for which the m₀ correction has turned out to be ineffective both in the separate- and combined-correction procedures because of adjacent absorption-sensitive lines passing through the wider slit.