Optical design of a toroidal grating monochromator based beam line on Indus-1

In this paper, we discuss the detailed optical design of a beam line that is under construction on the synchrotron radiation source, Indus-1. Toroidal mirrors are used as pre-and post- focusing elements and a toroidal grating monochromator as a dispersing element. Using three interchangeable gratings, this monochromator will give, at a moderate resolution, a good throughput on the sample in the wavelength range 40 to 1000 Å. Effect of various parameters and their optimization on the resolution and throughput characteristics have been studied by ray tracing calculations, and presented.     

The utilization of chemical shift and spin-lattice (T1) relaxation time data for the discrimination of isomeric indenoisoxazoles

Treatment of 2-pivaloyl-1,3-indandione with hydroxylamine leads to the formation of a pair of isomeric indenoisoxazoles, the product formed dependent upon the cyclization conditions. Under acidic conditions, 8-t-butylindeno[1,2-c]isoxazol-7-one ( 5 ) is formed while under neutral or basic conditions, an oxime, 2 , is generated which may then be cyclized under acidic conditions to give 3-t-butylindeno[1,2-c]isoxazol-4-one ( 4 ). Although these isomeric indenoisoxazoles may be discriminated by chemical means, we were interested in developing an unequivocal method for distinguishing these and potentially other isomeric pairs by spectroscopic means. A ¹³C-nmr based method for the discrimination of these isomers which is based on the utilization of chemical shift arguments and spin-lattice relaxation data is thus presented.     

Studies on the interaction of Eu(III) with lawsone (2-hydroxy-1,4-naphthoquinone), lapachol (2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphthoquinone), juglone (5-hydroxy-1,4-naphthoquinone) and plumbagin (2-methyl-5-hydroxy-1,4-naphthoquinone)

pH-metric studies show that one mole of Eu(III) interacts with three molecules of each of juglone, plumbagin, lawsone and lapachol in solution. The stability and thermodynamics of these systems (50% aqueous acetone, 0.1 M KNO₃ ionic strength) are discussed and explained.     

A reinvestigation of the bamberger-ham phenazine. Synthesis: A limitation

The Bamberger-Ham condensation of 4-substituted nitrosobenzenes in concentrated sulfuric acid reported as a method of synthesis for phenazine N-oxides has been found to be limited to electron donating substituents. Methyl 4-nitrosobenzoale has been found to react under these conditions to give dimethyl 2-nitrodiphenylamine-4, 5-diearboxylate ( 2 ). Compounds of unknown structure previously reported to arise from acid treatment of 4-bromo- and 4-chloronilrosobenzene have been shown to be 4, 5-dibromo-2-nitrosophenylamine ( 10 ) and the analogous dichloro compound. Treatment under stronger acidic conditions (oleum) converted 10 but not 2 into the corresponding phenazine N-oxide. Mechanistic implications are discussed.     

Stability and thermodynamics of La(III)-, Pr(III)-, Nd(III)-, Gd(III)- and Eu(III)-p-nitrobenzaldehyde thiosemicarbazone systems

Three complexes containing bidentate N-2,3-dimethylphenylglycine, (2,3-HDPG), N-2,4-dimethylphenylglycine, (2,4-HDPG) and N-2-ethylphenylglycine, (2-HEPG) acids have been prepared and characterized. These compounds have the general formula Zn(2,3-DPG)₂·2 H₂O, Zn(2,4-DPG)₂ and Zn(2-EPG)₂·2 H₂O, respectively. The structure of the complexes as inferred from their chemistries have been found to be compatible with the infrared spectral data. The thermal behaviour of these complexes has been studied from their TG, DTG and DSC diagrams obtained in a dynamic atmosphere of pure air. Heats of dehydration have been calculated from DSC curves.     

Kinetics of non-isothermal decomposition of acid maleato complexes of some bivalent metals

McGinn et al. [1] and Misra and Naik [2] studied the complexing capacity of maleic acid with metals. Edge [3] reported his findings on the pyrolysis of normal nickel maleato. This note is concerned with the estimation of kinetic parameters of the non-isothermal decomposition of acid maleato complexes of Co(II), Cu(II), Ni(II) and Cd(II).     

Multilayer mirror as a substrate for total reflection X-ray fluorescence spectrometry

X-ray field intensity generated over a multilayer surface during a strong Bragg reflection condition has been used to analyze the particulate matter deposited on its surface, for the average particles size distribution and detection sensitivity of various elements. The elemental detection sensitivities achieved at Bragg reflection condition are compared to those obtained at incidence angles below critical angle, under total external reflection condition. The results obtained indicate that when big size particles (> 1 μm) are distributed over a large surface area, the observed fluorescence yields deteriorate by 15–18% in the total external reflection condition, due to strong sample absorption effects. In such a case, use of a multilayer mirror as a sample carrier and fluorescence excitation under Bragg reflection condition provides better fluorescence yield and hence improved detection sensitivity for an element.     

Characterization of trace embedded impurities in thin multilayer structures using synchrotron X‐ray standing waves

X‐ray standing wave (XSW) field generated under Bragg reflection condition in a periodic Mo/Si multilayer structure has been used to determine the concentration and location of various trace element contaminants embedded in different layers of that multilayer structure. We have used intense synchrotron X rays for XSW analysis. It is observed that various trace element impurities such as Cr, Fe, Ni and W get embedded unintentionally in the multilayer structure during the deposition process. Consequences of such impurity incorporation on the optical properties of the multilayer structure are discussed in hard and soft X‐ray regions. Present measurements are important in order to optimize the deposition methods on one hand and to better correlate the measured optical properties of a multilayer structure with theoretical models on the other. Copyright © 2010 John Wiley & Sons, Ltd.     

Sample preparation for evaluation of detection limits in X-ray fluorescence spectrometry.

The influence of analyte mass concentration on determination of detection limits in X-ray fluorescence spectrometry has been investigated experimentally. Both the total reflection X-ray fluorescence (TXRF) and the conventional energy-dispersive X-ray fluorescence techniques have been used to derive the dependence of analyte mass concentration on the values of detection limits. Results obtained indicate that values of detection limits are optimum, or in other words, they are closer to the true detection limit of the technique, when analyte concentrations are in the range of 10 times of the detection limit.