Simultaneous confidence bands for the integrated hazard function

The construction of the simultaneous confidence bands for the integrated hazard function is considered. The Nelson–Aalen estimator is used. The simultaneous confidence bands based on bootstrap methods are presented. Four methods of construction of such confidence bands are proposed. The weird and conditional bootstrap methods are used for resampling. Simulations are made to compare the actual coverage probability of the bootstrap and the asymptotic simultaneous confidence bands. It is shown that the equal-tailed bootstrap confidence band has the coverage probability closest to the nominal one. We also present application of our confidence bands to the data regarding survival after heart transplant. This research was partly supported by AGH grant No. 10.420.03.     

Application of arc-plasma discharges to coating of screw taps

The paper reports on results of technological research on the coating of standard screw taps with TiN layers deposited by means of arc-plasma discharges, which were carried out within a BULAT-type device equipped with three identical metal-plasma sources. Particular attention is paid to morphology of the coated surfaces. Some data about thickness and microhardness of the coating layers, as well as results of laboratory wear tests of the coated tools, are also presented.     

On photovoltaic effect in hybrid heterojunction formed from palladium phthalocyanine and titanium dioxide layers

The results of the research on the photovoltaic properties of a system formed from tin oxide, titanium dioxide, palladium phthalocyanine and gold (SnO₂:F/TiO₂/PdPc/Au) are presented. Films of TiO₂ were deposited using a sol–gel method, then PdPc and Au layers were subsequently evaporated under a high vacuum. The system exhibits a strong rectification effect in the dark, while an effective photogeneration of charge carriers within the TiO₂/PdPc junction is observed under illumination. The experimental relations of a short-circuit current and an open-circuit voltage against the light intensity suggest that trapping states participate in recombination processes.     

Coordination ability of insect kinin analogs

Spectroscopic data, including electronic absorption, CD and EPR results, as well as theoretical calculations have shown that the insertion of 4-aminopyroglutamate, a novel cis-peptide bond mimic, in the insect kinin peptide leads to an effective ligand towards Cu(II) ions at basic pH ranges. The 4-aminopyroglutamate motif induces a specific peptide conformation which favors the formation of one or two five-membered chelating rings stabilizing a bent structure, with the coordination of 3N-type or 4N-type in the metallopeptide molecule involving in metal bonding C-terminal of modified peptide. It is worth noting that the copper(II) bonding does not undergo hydrolysis even at a very high pH range.     

Novel Approach to Two-Component Analysis Based on the Generalized Calibration Strategy

The generalized calibration strategy (GCS), developed and previously applied to chemical analysis, has been adapted to two-component (2C) analysis. According to the 2C-GCS procedure, a set of 10 calibration solutions containing a sample and standards of two analytes in well-defined composition was diluted. The measurements performed at a given dilution stage allow the concentration of both analytes in a sample to be evaluated with six apparent concentrations calculated with various mathematical approaches. As a result, the method allows the detection, examination, and elimination of nonlinear and interference effects with multiplicative and additive characteristics. To perform 2C-GCS automatically and effectively, a dedicated flow sequential injection system was designed to be fully controlled by a computer. Caffeine and paracetamol were determined in synthetic and pharmaceutical samples using this calibration approach. The analytes were determined with good precision and accuracy with low consumption of sample and standard solutions. On the basis of this experimental model, the influence of effects and tendencies in the examined analytical system was detected and evaluated.     

Analytical Strategy for the Determination of Selenium in Biological Materials by Inductively Coupled Plasma-Mass Spectrometry with a Dynamic Reaction Cell

Selenium was determined in serum, hair, and tobacco by inductively coupled plasma-mass spectrometry using ⁷⁷Se, ⁷⁸Se, and ⁸²Se. The set of standards method (SSM) and the standard addition method (SAM) were applied to calibration with and without the use of internal standards (⁷²Ge and ¹⁰³Rh). In addition, the usefulness of the dynamic reaction cell (DRC) with methane as the reaction gas was characterized. The results obtained in different conditions were evaluated in terms of precision and accuracy. It was demonstrated theoretically and experimentally that an internal standard is a potential source of systematic errors as it can be influenced multiplicatively and additively by its own interferents (independently of selenium). Furthermore, it was shown that—against common opinion—an internal standard can fail in elimination of chemical interference effects influencing selenium and in increasing of precision of selenium determinations. The DRC was shown to be effective in the elimination of additive effects, although the results obtained by both SSM and SAM with DRC were systematically positively erroneous. Finally, selenium was determined accurately in each examined sample when SAM was applied to calibration, and signals were measured either for ⁸²Se without the use of the DRC, or for ⁷⁷Se or ⁷⁸Se with the use of the DRC. In addition, it has also been shown that samples should be diluted prior to analysis to the greatest acceptable extent.     

Photoredox reactions of Cr(III) mixed-ligand complexes

Irradiation of chromium(III) complexes with oxalate and pyridinedicarboxylate ligands (pda = 2,3-, 2,4-, or 2,5-dicarboxylate) leads to diverse behaviors, dictated by light energy, presence of oxygen and the ligand nature. Irradiation within the MC bands is unaffected by O₂ and results in ligand substitution. The LMCT excitation is effective only when oxalate is coordinated to Cr(III); then electron transfer from oxalate to central ion generates an intermediate, consisted of a Cr(II)species and the C₂O₄^? radicals. The species undergo fast redox reactions dependent on the presence of O₂ and the pda ligand.(1) In anoxic medium the fast outersphere electron transfer from Cr(II) to solvent, generates hydrated electrons and re-oxidizes the chromium centre to Cr^III. Then geminate recombination regenerates substrate, whereas competitive release of the C₂O₄^? radical leads to substitution of one oxalate ligand by two water molecules (aquation induced by the LMCT excitation). In the presence of the pda ligand the outersphere electron transfer is accompanied by the innersphere CT, generating Cr(III) coordinated to two radical ligands: C₂O₄^? and pda^3?; the intermediate releases also e_aq^?, but this reaction is slower than that of the homoleptic oxalate complex. Hydrated electrons are scavenged also by the released radicals. All these processes are completed within microseconds and in consequence, the Cr(III) complexes irradiated in deoxygenated solutions are insensitive to subsequent oxygenation.(2) When UV-irradiation is carried out in oxygenated medium reaction of Cr(II) species with molecular oxygen competes with the outer- or inner electron transfer observed in anoxic medium. Both these pathways result in generation of chromate(VI). Quantum yield of the Cr(VI) production is sensitive to the presence and structure of pda ligand, decreasing within the series 2,3-pda > 2,4-pda > 2,5-pda.