Single-drop micro-extraction and diffuse reflectance Fourier transform infrared spectroscopic determination of chromium in biological fluids

The present paper deals with a new micro-extraction procedure for selective separation of Cr(VI) in the form of a metaloxy anionic species namely dichromate (Cr₂O₇²⁻) with N¹-hydroxy-N¹,N²-diphenylbenzamidine (HOA) in to dichloromethane and its subsequent and rapid diffuse reflectance Fourier transform infrared spectroscopic (DRS-FTIR) determination employing potassium bromide matrix. The diffuse reflectance Fourier transform infrared spectroscopy gives both qualitative and quantitative information about the dichromate. The determination of chromium is based on the analytical peak selection, among the various vibrational peaks, at 902 cm⁻¹. The micro-extraction was based on the liquid-liquid solvent extraction (LLSE) principle. The dichromate binds with the nitrogen and oxygen atoms of N¹-hydroxy-N¹,N²-diphenylbenzamidine (HOA) and forms 1:2, Cr(VI):HOA complex in 0.1 mol L⁻¹ HCl medium. The formation of above complex, in the acidic medium, is confirmed by the appearance of chocolate-brown color in the micro-extract. The speciation studies of Cr(III) and Cr(VI) is done by conversion of Cr(III) into Cr(VI) utilizing H₂O₂ as an oxidizing agent. The chemistry of pure dichromate and that of its HOA complex is discussed. The limit of detection (LoD) and the limit of quantification (LoQ) of the method are found to be 0.01 μg g⁻¹ Cr₂O₇²⁻ and 0.05 μg g⁻¹ Cr₂O₇²⁻, respectively. The standard deviation value and the relative standard value at a level of 10 μg Cr₂O₇²⁻/0.1 g KBr for n = 10 is found to be 0.26 μg Cr₂O₇²⁻ and 2.6%, respectively. The relative standard deviation (n = 8 and 6) for the determination of dichromate (Cr₂O₇²⁻) in real human biological fluid samples is observed to be in the range 3.1-7.8%.     

On the spectroscopic examination of printed documents by using a field emission scanning electron microscope with energy-dispersive X-ray spectroscopy (FE-SEM-EDS) and chemometric methods: application in forensic science

Analytical and Bioanalytical Chemistry - The detection of computer-generated document forgeries has always been a challenging task for forensic document examiners (FDE). With the aim to support the...     

Application of simulated standard spectra for the analysis of complex sample spectra from NaI(Tl) detectors

The most accurate method for the analysis of complex gamma ray spectra from scintillation detectors is least squares method. The major requirement of this method is individual standard spectra of all nuclides expected in the complex spectrum which is not possible and feasible for some nuclides. In the present work, an approach of using simulated standard spectrum of the radionuclides for the least squares analysis is studied. The paper describes the methodology used for the generation of simulated spectrum which is the main objective, and validation of results using standard sources in the Sodium Iodide (NaI(Tl)) based gamma ray spectrometer.     

Inter-conversion of Tb3+ and Tb4+ states and its fluorescence properties in MO–Al2O3: Tb (M = Mg,Ca, Sr,Ba) phosphor materials

Terbium ion doped MO–Al₂O₃ (M = Mg, Ca, Sr and Ba) series phosphors have been synthesized through combustion technique and their luminescence properties have been studied and compared. Terbium ion in different phosphors has shown different fluorescence properties due to the presence of different ratios of Tb³⁺ and Tb⁴⁺ states in different samples. The UV/Visible absorption and XPS techniques have been used to probe the existence of Tb³⁺ and Tb⁴⁺ states. The host sensitive 4f–5d and the charge transfer transitions enabled the use of terbium ion as an indicator of the structure.     

Noncovalent assembly of ferrocene on modified gold surfaces mediated by uracil–adenine base pairs

Redox-active ferrocene was assembled on gold surfaces through the hydrogen bonding interactions between adenine-substituted ferrocene and a uracil-terminated organothiol monolayer. The surface coverage of ferrocene Γ could be varied from ca. 4 × 10^? 11 to 2.0 × 10^? 10 mol cm^? 2 by diluting the thiol-modified uracil derivative with inert 1-octanethiol. A decrease in the apparent electron transfer rate constant for ferrocene, k_app, from ca. 50 to 10 s^? 1 was observed upon increasing Γ.     

Reactions of fluorinated acid anhydrides, (CF3CO)2O, (CF3SO2)2O and (FSO2)2O, with organometallic substrates of group 15 (As, Sb and Bi)

(C₆H₅)₃MX₂ (M = As, Sb; X = OCOCF₃ and M = Sb, Bi; X = SO₃F, SO₃CF₃) compounds prepared by the interaction of triphenylmetal(V) substrates with (CF₃CO)₂O, (CF₃SO₂)₂O and (FSO₂)₂O have been characterized by molecular weight determination, elemental and spectroscopic (IR, ¹H and ¹⁹F NMR, mass) analyses.     

Determination of nitrite and mixtures of bromide and iodide with o-iodosobenzoate

Nitrite diazotizes sulphanilamide, which then does not undergo 3,5-dibromination. Nitrite can therefore be determined by reaction with excess of sulphanilamide, the surplus of which is then titrated with o-iodosobenzoate or chloramine-T in the presence of potassium bromide, with Methyl Red as indicator. Mixtures of iodide and bromide can be analysed by oxidation of the iodide with excess of o-iodosobenzoate at pH 4-6, followed by extraction of the iodine (which is then titrated with thiosulphate) and then oxidation of the bromide in dilute sulphuric acid medium in the presence of sulphanilamide as bromine scavenger, the residual oxidant being evaluated iodometrically.     

Synthesis of some new 4-imino-3,5,7-trisubstituted-pyrido[2,3-d]pyrimidine-2(1H)-thiones

The synthesis of 4-imino-3,5,7-trisubstituted-pyrido[2,3-d]pyrimidine-2(1H)-thiones is described. The elemental analysis, ir and nmr spectral data confirm the structure of the products.     

Systematic mutational analysis of an ubiquitin ligase (MDM2)-binding peptide: computational studies

To understand the importance of amino acids that comprise the peptide PMI (p53-MDM2/MDMX inhibitor), a p53-mimicking peptide with high affinity for the ubiquitin ligase MDM2, computational alanine scanning has been carried out using various protocols. This approach is very useful for identifying regions of a peptide that can be mutated to yield peptides that bind to their targets with higher affinities. Computational alanine scanning is a very useful technique that involves mutating each amino acid of the peptide in its complex with its target (MDM2 in the current study) to alanine, running short simulations on the mutated complex and computing the difference in interaction energies between the mutant peptides and the target protein (MDM2 in the current study) relative to the interaction energy of the original (wild-type) peptide and the target protein (MDM2 in the current study). We find that running multiple short simulations yield values of computed binding affinities (enthalpies) that are similar to those obtained from a long simulation and are well correlated with the trends in the data available from experiments that used Surface Plasmon Resonance to obtain dissociation constants. The p53-mimicking peptides contain three amino acids (F19, W23 and L26) that are major determinants of the interactions between the peptides and MDM2 and form an essential motif. We find in the current study that the trends amongst the contributions to experimental binding affinities of the hydrophobic residues F19, W23 and L26 are the best reproduced in all the computational protocols examined here. This study suggests that running such short simulations may provide a rapid method to redesign peptides to obtain high-affinity variants against a target protein. We further observe that modelling an extended conformation at the C-terminus of the helical PMI peptides, in accord with the conformation of the p53-peptide complexed to MDM2, reproduces the trends seen amongst the experimental affinities of the peptides that carry the alanine mutations at their C-termini. This suggests that some of the mutant peptides possibly interconvert between helical and extended states and can bind to MDM2 in either conformation. This novel feature, not obvious from the crystallographic data, if factored into modelling protocols, may yield novel high-affinity peptides. Our findings suggest that such protocols may enable rapid investigations of at least certain types of amino acid mutations, notably from large to small amino acids.