Synthesis and structure of novel copper(II) complexes with pyrazole derived ligands and metal–ligand interaction in solution

Two new ligands of the coumarin type have been synthesized and characterized by ¹H, ¹³C NMR, IR and MS. The crystal and molecular structures of ligand 2, determined by the X-ray diffraction method, are presented. With copper(II) these ligands create solid complexes of the type CuLCl₂, where L is 5-(2-hydroxybenzoyl)-3-methyl-1-(2-pyridinyl)pyrazol-4-carboxylic acid methyl ester (2) or 3-methyl-1-(2-pyridinyl)-1H-chromene[4,3-c]pyrazol-4-on (3). The new copper(II) complexes have been characterized by elemental analysis and solid state FT-IR. The protonation constants of ligands 2 and 3 have been determined in 5% v/v 1,4-dioxane–water solution (25 °C). The coordination modes in the complexes with copper(II) are discussed for 2 on the basis of potentiometric and UV–Vis data.     

Thermal and MS studies of silver(I) 2,2-dimethylbutyrate complexes with tertiary phosphines and their application for CVD of silver films

[Ag₂(CH₃CH₂C(CH₃)₂COO)₂] (1), [Ag₂(CH₃CH₂C(CH₃)₂COO)₂(PMe₃)₂] (2) and [Ag₂(CH₃CH₂C(CH₃)₂COO)₂(PEt₃)₂] (3) were prepared and characterized by MS-EI; ¹H, ¹³C, ³¹P NMR, variable temperature IR (VT-IR) spectroscopy and thermal analysis. MS and VT-IR data analysis suggests bidentate bridging carboxylates and monodentately bonded phosphines in the solid phase. The same methods used for gas phase analysis of 1–2 proved [(CH₃CH₂C(CH₃)₂COO)Ag₂]⁺ as the main ion, which could be transported in the gas phase during the CVD process. In the case of 3, similar intensity to the latter ion revealed [Ag{P(C₂H₅)}]⁺ and it is responsible for the CVD performance of 3. Thermal analysis results revealed that decomposition of 1–3 proceed in one endothermic process, with metallic silver formation between 197 and 220 °C. In the case of 1, VT-IR studies of the gaseous decomposition products demonstrate the presence of ester molecules and CO₂, whereas for 2 the main gaseous product appeared to be acid anhydride. Therefore, 2 was not used as a silver CVD precursor. Metallic layers were produced from 3 in hot-wall CVD experiments, (between 200 and 280 °C), under a total reactor pressure of 2.0 mbar, using argon as a carrier gas. Thin films deposited on Si(1 1 1) substrate were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Silver films obtained at moderate temperature (220–250 °C) revealed a thickness below 50 nm, and were whitish colored and slightly matt.     

Dynamics of thin periodic plates resting on a periodically inhomogeneous Winkler foundation

Summary The aim of the paper is to investigate the dynamic response of thin elastic plates having periodic substructure in planes parallel to the plates midplane and interacting with a Winkler foundation. The main goal of the analysis is to describe the effect of substructure size on the plates dynamics. For this purpose, the method proposed in [4, 5] is used. Two special cases are analysed: a plate band with a constant thickness interacting with a periodically inhomogeneous Winkler foundation, and a plate band with a periodically variable thickness interacting with a homogeneous Winkler foundation. The physical correctness conditions of the model are also discussed. Received 14 July 1998; accepted for publication 7 January 1999     

Oxyreactive Thermal Analysis of Dispersed Organic Matter, Kerogen and Carbonization Products A Tool for Investigation of the Heated Rock Masses

This paper presents the results of oxyreactive thermal analyses of organic matter in rocks, heated naturally during diagenetic to metamorphic processes. During the experiments we traced the reactions in the temperature range up to 900°C, it means from the very beginning of diagenetic transformations to the highest real temperatures acting in the Earth's crust as a solid phase. The results showed that TA could be a tool for the reconstruction of thermal regime in natural coal-bearing systems. This revised version was published online in August 2006 with corrections to the Cover Date.     

Du Bois–Reymond Type Lemma and Its Application to Dirichlet Problem with the p(t)–Laplacian on a Bounded Time Scale

This paper is devoted to study the existence of solutions and their regularity in the p(t)–Laplacian Dirichlet problem on a bounded time scale. First, we prove a lemma of du Bois–Reymond type in time-scale settings. Then, using direct variational methods and the mountain pass methodology, we present several sufficient conditions for the existence of solutions to the Dirichlet problem.     

Square-wave adsorptive stripping voltammetric approaches at two in situ modified electrodes as first analytical methods for the quantitative determination of a new anticancer drug candidate

The two adsorptive stripping voltammetric approaches for detection and quantitative determination of diethyl (2E)-2-{(2E)-[1-(4-methylphenyl)imidazolidin-2-ylidene]hydrazinylidene}butanedioate (DIB)—a novel molecule of medical importance—using two sensitive sensors based on modified glassy carbon electrodes as reusable sensors, were developed for the first time. The proposed electrochemical methods are based on adsorptive/reductive behaviour of DIB at two modified carbonic electrodes: a bismuth film-modified glassy carbon electrode (BiF/GCE) and a lead film-modified glassy carbon electrode (PbF/GCE). The electron gain mechanism for the electrochemical reduction of DIB on both developed sensors was proposed for the first time. To achieve the highest sensitivity in adsorptive stripping determinations, various experimental variables (e.g. the composition and pH of the supporting electrolytes, deposition conditions of bismuth and lead films, concentrations of plating solutions, accumulation times and potentials of DIB, etc.) were extensively examined. The comparison of validation parameters obtained during the determination of DIB at two sensors was presented. The excellent linear correlation was found between the monitored adsorptive stripping voltammetric peak current and the DIB concentration in the range of 15–600 μg L⁻¹ at an accumulation time of 30 s (with LOD = 4.2 μg L⁻¹ and LOQ = 14.0 μg L⁻¹) using the BiF/GCE as a sensor. Furthermore, the excellent linear relationship was confirmed between the monitored adsorptive stripping voltammetric peak current and the DIB concentration in the range of 9–900 μg L⁻¹ at an accumulation time of 10 s (with better LOD = 1.5 μg L⁻¹ and LOQ = 5.0 μg L⁻¹), employing the PbF/GCE as a sensor. The two optimized adsorptive stripping voltammetric approaches—as facile, sensitive, reliable and inexpensive—were successfully used as first methods for the quantitative analysis of a novel anticancer agent (DIB) in its pure pharmaceutically acceptable form. However, the practical applicability of square-wave adsorptive stripping voltammetric determination of the electroactive DIB molecule at a PbF/GCE, as the modified electrode of higher sensitivity, was presented after its successful solid phase extraction from a real serum sample.

     

Zinc oxide nanoparticles for improvement of thin film photovoltaic structures’ efficiency through down shifting conversion

The paper presents the idea to improve the performance of thin film photovoltaic cells by a light capture enhancement through the introduction of down shifting energy converters. Luminescent down shifting layers convert high-energy photons (UV light) into low-energy ones (visible light), which are more efficient in a photovoltaic conversion. For this purpose, the application of a thin layer composed of zinc oxide (ZnO) nanoparticles deposited onto a thin film solar cell is proposed. The paper presents both experimental and theoretical results of this approach. Conducted investigations include an analysis of ZnO nanoparticle layers, deposited in two independent technology methods. The results showed that ZnO nanoparticles have a great potential of application as down converting layers and can be implemented to improve the efficiency of photovoltaic cells, especially in the field of thin film PV structures. The proposed new deposition method can potentially be used in some industrial photovoltaic applications.     

Colloidal quantum dots conjugated with human serum albumin – interactions and bioimaging properties

Quantum dots, due to their unique optical properties, constitute significant materials for many areas of nanotechnology and bionanotechnology. This work presents a review of researches dedicated to the interaction between quantum dots (QDs) with human serum albumin (HSA) and human cell culture as important for nanomedicine applications. The optical properties of bio-nanocomplexes formed by nanoparticles including colloidal QDs (e.g., CdTe, CdS, CdCoS) and albumin are displayed. The absorption spectra show that adding HSA to colloidal QDs leads to a gradual decrease of absorption and broadening of the exciton structure. The photoluminescence quenching results indicate that the quenching effect of QDs on HSA fluorescence depends on the size and temperature. The nature of quenching is rather static, resulting in forming QD-HSA complexes. The CdTe QD-HSA complexes show chemical stability in a PBS buffer. Furthermore, it is stable in cytoplasm and suitable for cell labeling, tracking, and other bioimaging applications.     

Elastic shallow shells with functionally graded structure

Main objects of considerations are linear-elastic thin shallow shells with a tolerance-periodic structure along one direction. Moreover, their properties along the perpendicular direction can be described by continuous, slowly-varying functions. Hence, these objects can be treated as shells with a functionally graded structure. Here, the tolerance model of these shells is proposed. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of molecular water models on Molecular Dynamic simulation of nanoflows

We study an influence of the effect of water molecular models and thermostats on approaching equilibrium in Molecular Dynamics simulation of the nanoflows of water. Out of large number of existing models of water we present the results for four selected ones, i.e.: TIP4P, PPC, TIP4P-2005, TIP5P, and for two thermostats - Gaussian and Nosé-Hoover. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)