Pyridine solvated dioxouranium complex with salen ligand: Synthesis,characterization and luminescence properties

A new derivative of dioxouranium(VI) salen complex, [UO2(L)(pyridine)], where [L = N,N′-Bis(2-hydroxybenzylidene)-2,2-dimethyl-1,3-propanediamine] is synthesized and characterized by elemental analysis (C, H, N), FT-IR, ESI-MS spectrometry, UV/Vis, fluorescence, ¹H and ¹³C NMR spectroscopy and thermal gravimetric (TG) study. Furthermore, the single crystal X-ray diffraction measurements of the complex were carried out at 100 and 273 K. The crystal structure measurements revealed that the complex has distorted pentagonal bipyramidal geometry with uranium atom located at the centre and bonded to two phenoxy oxygen and two azomethine nitrogen in tetradenate fashion and one nitrogen from pyridine making it seven coordinated. In addition, the photoluminescence property of the complex was also recorded.     

Platinum metallodrug-protein binding studies by capillary electrophoresis-inductively coupled plasma-mass spectrometry: characterization of interactions between Pt(II) complexes and human serum albumin

Characterizing how platinum metallocomplexes bind to human serum albumin (HSA) is essential in evaluating anticancer drug candidates. Using cisplatin as a reference complex, the application of capillary electrophoresis (CE) to reliably assess drug/HSA interactions was validated. Since this complex is small compared to the size of the protein, the binding response could only be recognized when applying CE coupled to a (platinum) metal-specific mode of detection, namely inductively coupled plasma-mass spectrometry (ICP-MS). This coupling allowed for confirmation of a specific affinity of cisplatin and novel Pt complexes to HSA, measurement of the kinetics of binding reactions, and determination of the number of drug molecules attached to the protein. As the cisplatin/HSA molar ratio increased, the reaction rate became faster with a maximum on the kinetic curve appearing at about 50 h of incubation at 20 times excess of cisplatin. The reaction was characterized as a pseudo-first order reaction with the rate constant k = 0.003 min(-1) at 37 degrees C. When incubated with a 20-fold excess of cisplatin, HSA bound up to 10 mol of Pt per mol of the protein. This is indicative for a strong metal-protein coordination occurring at several HSA sites other than the only protein cysteine residue. Structural analogs of cisplatin, bearing aminoalcohol ligands, showed comparable protein binding reactivity and stoichiometry but a common equilibrium was not reached even after one week of incubation. Also apparent was a two-step mechanism of the binding reaction. Results demonstrated the suitability of CE-ICP-MS as a rapid assay for high-throughput studying of drug/HSA interactions.     

Probability issues in molecular design: predictive and modeling ability in 3D-QSAR schemes

In the current work we investigated 3D-QSAR data by the use of the coupled leave-several-out (LSO) and leave-one-out (LOO) cross-validation (CV) procedures. We verified the above mentioned scheme using both simulated data and real 3D QSAR data describing a series of CoMFA steroids, heterocyclic azo dyes and styrylquinoline HIV integrase inhibitors. Unlike in standard analyses, this technique characterizes individual method not by a single performance metrics but screens a whole possible modeling space by sampling different molecules into the training and test sets, respectively. This allowed us for the discussion of the information included in the estimators validating cross-validation procedures, as well as the comparison of the efficiency of several 3D QSAR schemes, in particular, Comparative Molecular Field Analysis (CoMFA) and Comparative Molecular Surface Analysis (CoMSA). Moreover, it allows one to acquire some general knowledge about predictive and modeling ability in 3D QSAR method.     

EELS measurements of boron concentration profiles in p-a-Si and nip a-Si solar cells

The p-type Si layer in a-Si and μc-Si solar cells on foil needs to fulfil several important requirements. The layer is necessary to create the electric field that separates the photo-generated charge carriers; the doping also increases the conductivity to conduct the photocurrent to the front contact; on the other hand, the p-layer should transmit the incident light efficiently to the intrinsic absorber layer. We show that it is possible to study TEM samples prepared, for analysis of possible layer defects, by focussed ion beam milling to detect boron and carbon concentrations as low as 10²⁰ cm^-3, using core-loss EELS combined with numerical analysis. We control the band gap and activation energy of p-a-SiC by varying the B₂H₆ and CH₄ flow during deposition in the process chamber. We have found a linear relation between the activation energy of the dark conductivity E_act and the optical band gap E₀₄. Modelling shows that the optimum efficiency in nip solar cells is obtained when the p-a-SiC band gap is slightly larger than the band gap of the absorber layer. We have assessed the potential of core-loss EELS for detecting B and C concentrations as low as 10²⁰ cm^-3 in a spatially resolved manner, and of low-loss EELS as a probe of the local variations in plasmon energy.     

Elimination of autofluorescence background from fluorescence tissue images by use of time-gated detection and the AzaDiOxaTriAngulenium (ADOTA) fluorophore

Sample autofluorescence (fluorescence of inherent components of tissue and fixative-induced fluorescence) is a significant problem in direct imaging of molecular processes in biological samples. A large variety of naturally occurring fluorescent components in tissue results in broad emission that overlaps the emission of typical fluorescent dyes used for tissue labeling. In addition, autofluorescence is characterized by complex fluorescence intensity decay composed of multiple components whose lifetimes range from sub-nanoseconds to a few nanoseconds. For these reasons, the real fluorescence signal of the probe is difficult to separate from the unwanted autofluorescence. Here we present a method for reducing the autofluorescence problem by utilizing an azadioxatriangulenium (ADOTA) dye with a fluorescence lifetime of approximately 15 ns, much longer than those of most of the components of autofluorescence. A probe with such a long lifetime enables us to use time-gated intensity imaging to separate the signal of the targeting dye from the autofluorescence. We have shown experimentally that by discarding photons detected within the first 20 ns of the excitation pulse, the signal-to-background ratio is improved fivefold. This time-gating eliminates over 96 % of autofluorescence. Analysis using a variable time-gate may enable quantitative determination of the bound probe without the contributions from the background.     

A study on adsorption of metals by activated carbon in a large-scale (municipal) process of surface water purification

Elements that enter the aquatic environment may pose a health risk to wildlife and humans. The aims of this study were: to determine how the introduction of activated carbon for a water purification system will improve the quality of the water produced; and to investigate the sorption of metals on activated carbons, including determination of the accumulation, as well as changes in concentrations of elements in carbons. The tests were carried out on three types of activated carbons with different granular structure. All samples were collected from Water Treatment Plant Goczalkowice, Poland. Concentrations of elements were measured using an optical emission spectrometer with inductively coupled plasma. The experiment showed that metals accumulating in the activated carbons during the operation included: Ca, Mn, Zn, and Cu. In each of the three types of carbons, it can distinguish such elements as Ba, Al, Cr, Ni, Ti, which are characterized by irregular accumulation during the operation of the filter. The introduction of carbon sorbent for water treatment largely contributed to improvement in the quality of raw material supplied to customers, mainly with regard to taste and smell, as well as to reduction of basic parameters: color, absorbance in the UV range and oxidability.      

Tunable negative index metamaterial employing in-plane switching mode at terahertz frequencies

We analysed the response of a tunable liquid crystal metamaterial transducer in the terahertz frequency range. Tunability of scattering parameters is achieving by an in-plane switching (IPS) effect. The metamaterial structure is based on Ω-shape resonators. A full-wave analysis technique based on the finite-difference time-domain (FDTD) method was performed using the QuickWave 3D electromagnetic solver. Terahertz transmission properties of the metamaterial structure can be controlled by the director of the liquid crystal layer. The effective refractive index for operation frequency varies from negative to positive values. A novel approach to switching of metamaterial transducer by IPS mode is presented.