Effects of finite size nuclei in relativistic four-component calculations of hyperfine structure

The effect of a finite size model for both the nuclear charge and magnetic moment distributions on calculated EPR hyperfine structure have been studied using a relativistic four-component method based on density functional theory. This approach employs a restricted kinetically balanced basis (mDKS-RKB) and includes spin-polarization using noncollinear spin-density exchange-correlation functionals in the unrestricted fashion. Benchmark calculations have been carried out for a number of small molecules containing Zn, Cd, Ag, and Hg. The present results are compared with those obtained at the Douglas-Kroll-Hess second order (DKH-2) method. The dependence of the results on the quality of the orbital and auxiliary basis sets has been studied. It was found that some basis sets contain irregularities that deteriorate the results. Especial care has to be taken also on the construction of the auxiliary basis for fitting the total electron and spin-densities.     

Protective effect of mitochondrially targeted antioxidant MitoQ on oxidatively stressed fibroblasts

3T3 and VH10 cells were subjected to oxidative damage by hydroxyl radicals generated from Cu(II) ions and ascorbate. The presence of reactive oxygen and nitrogen species in cells was determined using fluorescent dyes. MitoQ—a mitochondrially targeted antioxidant—was examined to prevent cell death and was compared with trolox as a reference standard serving as an antioxidant. MitoQ at lower concentrations (up to 500 nM) prevented damage of mitochondria and thereby increased viability of cells. However, at higher concentrations (over 500 nM) MitoQ decreased the viability of both strains of cells. The last observation indicates that the application of MitoQ should be evaluated also from the point of its cell-destructive potential.     

Observation of a Doppler broadening of the 4438 keV gamma-line of12C in processes12C(n,n′γ)12C and9Be(α, nγ)12C

A Doppler broadening is described of the 4438 keV spectral gamma-line observed by means of a Ge(Li) detector during the deexcitation of nuclei of¹²C in an inelastic scattering¹²C(n, n′γ)¹²C using an²⁴¹Am−Be source as well as during the reaction⁹Be(α, nγ)¹²C taking place in the Am−Be source. The FWHM of the spectral line is equal to (90±4) keV in the latter reaction and (64±8) keV in the former process. Experimental values agree well with theoretical ones. Presented at the Instrumental Activation Analysis Conference, IAA 79, June 4–8, 1979, Klučenice, Czechoslovakia.     

Heterogeneous reactions of solid nickel(II) complexes. XVIII

The Stoichiometry of thermal decomposition was studied for the following compounds: Ni(NCS)₂(2-Mepy)₂ (I), (Me=methyl, py=pyridine), Ni(NCS)₂(2-Etpy)₂ (II) (Et=ethyl), Ni(NCS)₂(2-Clpy)₂ (III), Ni(NCS)₂(2-Brpy)₂ (IV), Ni(NCS)₂(2-NH₂py)₂ (V), Ni((NCS)₂(2-NH₂py)₂·3/4 (C₂H₅)₂O (VI). The release of volatile ligands 2-Rpy is a one-step process for complexes I, II, III and IV, while for V and VI it is a two-step process, Ni(NCS)₂(2-NH₂py)₁ (VII) being formed as an intermediate complex. It was found that complexes I and II are square-planar; the others exhibited pseudo-octahedral geometry. The differences in stereochemistry of the above complexes are explained by the different electronic properties of 2-Rpy.     

Metal chelate exchange in the organic phase-I Theory: application in spectrophotometry and complex chemistry

Metal chelates, extracted from an aqueous phase by organic solvents, can react with other chelating agents (or their metal chelates) dissolved in the same solvent. This exchange of metal chelates in the organic phase can be used for (1) investigation of the exchange equilibrium and composition of the metal chelates formed, (2) determination of the extraction constants, (3) preparation of new inner-complexes soluble in organic solvents, and (4) spectrophotometric determination of small amounts of metals. The theory and experimental verification of this phenomenon are given. The extraction constants of silver and zinc diethyldithiocarbamates in carbon tetrachloride have been determined by means of the extraction constants of the corresponding dithizonates. A mixed complex of arsenic(III) with dithizone and diethyldithiocarbamic acid has been prepared and its properties studied. A simple method for spectrophotometric determination of microgram quantities of arsenic is proposed.     

Potentiometric response and mechanism of anionic recognition of heterocalixarene-based ion selective electrodes

The ion selective electrode (ISE)-based potentiometric approach is shown to be an effective means of characterizing the anion recognition sites in the molecular receptor calix[2]pyridino[2]pyrrole (CPP). In particular, potentiometric pH-measurements involving the use of experimental PVC-membranes based on CPP revealed the existence of both mono- and diprotonated forms of the receptor under readily accessible conditions. Based on these analyses, apparent surface protonation constants for this heterocalixarene were found to lie between 8.5-8.9 (pK_B1) and 3.3-3.8 (pK_B2). CPP was found to interact with targeted anionic analytes based on both coulombic and hydrogen bond interactions, as inferred from varying the kinds of ionic sites present within the membrane phase. Potentiometric selectivity studies revealed that CPP preferred “Y-shaped” anions (e.g. acetate, lactate, benzoate) over spherical anions (e.g. fluoride and chloride), fluoride over chloride within the set of spherical anions, and the ortho-isomer over the corresponding meta- and para-isomers in the case of hydroxybenzoate (salicylate and congeners). In the context of this study, the advantages of potentiometric determinations of acetylsalicylic acid using optimized PVC-membranes based on CPP relative to more conventional PVC-membrane ISEs based on traditional anion exchanger were also demonstrated.     

Stereospecific Synthesis of D-Glycero-D-ido-oct-2-ulose

Summary.  D-Glycero-D-gulo-heptose reacted with 2,2-dimethoxypropane to give its 2,3:6,7-di-O-isopropylidene derivative. Its base-catalyzed addition to formaldehyde resulted in the formation of 2,3:6,7-di-O-isopropylidene-2-C-(hydroxymethyl)-D-glycero-D-gulo-heptofuranose. After acid hydrolysis of this aldolization product, a new branched-chain aldose, 2-C-(hydroxymethyl)-D-glycero-D-gulo-heptose, was obtained, which was stereospecifically rearranged under the catalytic action of molybdic acid to D-glycero-D-ido-oct-2-ulose. Received October 17, 2000. Accepted December 4, 2000     

Voltage enhancement in dye-sensitized solar cell using (001)-oriented anatase TiO2 nanosheets

A nanocrystalline TiO₂ (anatase) nanosheet exposing mainly the (001) crystal faces was tested as photoanode material in dye-sensitized solar cells. The nanosheets were prepared by hydrothermal growth in HF medium. Good-quality thin films were deposited on F-doped SnO₂ support from the TiO₂ suspension in ethanolic or aqueous media. The anatase (001) face adsorbs a smaller amount of the used dye sensitizer (C101) per unit area than the (101) face which was tested as a reference. The corresponding solar cell with sensitized (001)-nanosheet photoanode exhibits a larger open-circuit voltage than the reference cell with (101)-terminated anatase nanocrystals. The voltage enhancement is attributed to the negative shift of flatband potential for the (001) face. This conclusion rationalizes earlier works on similar systems, and it indicates that careful control of experimental conditions is needed to extract the effect of band energetic on the current/voltage characteristics of dye-sensitized solar cell.     

Perimidine-based synthetic receptors for determination of copper(II) in water solution

Perimidine-based chelators 1 and 2 were prepared, and their structures were confirmed by ¹H and ¹³C NMR, MS spectroscopy and elemental analysis. These compounds were studied as specific synthetic receptors for the recognition of transition metal ions. They exhibited high affinity and selectivity towards Cu(II) ions. The conditional binding constants, linear dynamic range and detection limit were determined by UV–vis spectroscopy. These parameters demonstrated high potential of the prepared synthetic receptors for the recognition and determination of Cu(II) ions. The minimum detectable concentrations of Cu(II) ions for the synthetic receptors 1 and 2 were 270 and 75 nM (R ² = 0.9915 and 0.9964) in aqueous medium (water/DMSO; 99:1 (v/v)), respectively.     

Development of piezoelectric immunosensors for measurement of albuminuria

The development of piezoelectric immunosensors for human serum albumin (HSA) is reported. The piezoelectric crystals were modified either with monoclonal antibody AL-01 (direct assay) or with HSA (competitive assay). Measurements were carried out in the flow-through mode. Affinity interaction between albumin and the antibody was characterised. With immobilised antibody and HSA in solution, the kinetic association rate constant k(a) was 18 100 l mol(-1) s(-1) and the dissociation constant k(d) was 0.00369 s(-1). For the opposite arrangement (immobilised HSA), a slower dissociation was observed, k(d) was 0.00085 s(-1). A competitive assay for HSA was developed with working range of 1-5 mug ml(-1) and a total time for one analysis equal to 17 min. Samples of urine were analysed after tenfold dilution. The developed system was successfully evaluated on real samples from diabetic patients and the obtained results correlated well with the standard reflectometric assay of proteins in urine.