Fluorine containing phosphazene polymers

In this paper we highlighted the synthesis, characterization, and practical exploitation of different types of polyphosphazenes substituted with fluorinated groups. There are several ways in which fluorine atoms can be inserted into polyphosphazenes, all of which leading to different polymers showing a wide range of characteristics. In general it is true that the insertion of fluorine atoms into phosphazene macromolecules leads to an enhancement of the thermal stability, flame resistance, low-temperature elastomericity, and chemical inertness of the phosphazenes obtained. The contribution of Italian research groups to the preparation and exploitation of organic commercial macromolecules grafted onto fluorinated polyphosphazenes is also reviewed.     

Determination of residual monomers in acrylate dispersions by gas chromatography

The content of residual monomers is one of the most important characteristics of polymer dispersions. As a result of the similar physicochemical parameters of ethyl acrylate and methyl methacrylate, it is very difficult to determine the residual monomers in acrylate dispersions obtained by emulsion polymerization of both monomers. Gas chromatography with capillary columns, however, permits separation of these monomers and their quantitative determination in acrylate dispersions.     

Gravimetric determination of rhenium as 2,4,6-triphenylpyrylium perrhenate

A gravimetric method for determination of rhenium is based on formation of sparingly soluble 2,4,6-triphenylpyrylium perrhenate. The conditional solubility product in O.1N sulphuric acid medium was found to be (3.72 +/- 0.08) x 10(-9). The interference of foreign anions (simple or complex) is eliminated by preliminary extraction of perrhenate with acetone from strongly alkaline medium. The method is applied to the determination of rhenium in perrhenates and rhenium alloys.     

Understanding the catalytic role of flexible chiral δ-amino alcohols: the 1-(2-aminoethyl)norbornan-2-ol model

An empiric first approach to the knowledge about the structural factors influencing the catalytic behavior of conformationally flexible δ-amino-alcohol-based ligands, for the enantioselective addition of dialkylzincs to prochiral carbonyl groups, has been applied using the 1-(2-aminoethyl)norbornan-2-ol moiety as the model chiral system, and the asymmetrically catalyzed addition of diethylzinc to benzaldehyde as the test reaction. For this purpose, a selected small library of seven norbornane-based chiral ligands, bearing well-defined structural variations to allow a comparative study, that is, variation of the relative configuration and steric hindrance at the C(2), C(3) and/or C(7) norbornane positions, has been synthesized and probed in the mentioned test reaction. The experimental results obtained have been rationalized empirically using diastereomeric Noyori-like transition states, demonstrating that the conformational flexibility of the δ-amino-alcohol ligands, contrary to the more studied and rigid β-amino-alcohols, plays a crucial role on the catalytic behavior of such ligands (stereochemical sense and degree of the stereodifferentiation in the asymmetric process), which makes such structural factors, important for the improved design of new related chiral catalysts. In this sense, a robust crude empirical model for the prediction of the catalytic behavior of such δ-amino-alcohol-based ligands is proposed.     

Isoscalar factors for tetragonal,orthorhombic, monoclinic and triclinic shubnikov point groups

The relations between isoscalar factors for corepresentations of antiunitary magnetic point groups are discussed in the case of associated corepresentations. The tables of the isoscalar factors for the single- and double-valued corepresentations of all tetragonal, orthorhombic, monoclinic, and triclinic Shubnikov point groups are given. Some peculiarities of the calculation method of the isoscalar factors for corepresentations are considered.     

Photobiological Properties of 1'-Thieno-4,6,4'-trimethylangelicin

Some photobiological properties of l'-thieno-4,6,4′-tri-methylangelicin (TTMA), a new isoster of 4,6,4′-trimeth-ylangelicin (TMA) were studied in comparison with the parent compound. The TTMA absorbs UVA light and photobinds in vitro to DNA more efficiently than TMA; however, in Ehrlich cells in vivo TTMA linked to DNA to a lesser extent than the parent compound. In general, the formation of damage into DNA is in line with this last result: In fact, TTMA and TMA form equivalent amounts of interstrand cross-links (ISC) both in vitro in linearized PM2 DNA and in vivo in HeLa cells. In this system TTMA induces DNA-protein cross-links (DPC) more efficiently than TMA; on the contrary, no significant amounts of single-strand breaks were detected with both compounds. The antiproliferative activity of TTMA is consistent with these results, being only slightly more pronounced than that of TMA. Experiments carried out using double irradiation demonstrated that these drugs are capable of inducing antiproliferative effects by bi-photonic reactions, including the formation of both ISC and DPC. Thus, replacement of the oxygen atom by a sulfur increases the UV absorption of the drug and its capacity to photobind to DNA in vitro but does not yield a comparable enhancement of its photosensitizing properties in vivo; this might be due to various reasons, for instance to an increase in the lipophilic character that could modify the behavior in vivo.     

PEG-modified glucose oxidase immobilized on a PVA cryogel membrane for amperometric biosensor applications

Poly(ethylene glycol)-modified glucose oxidase was immobilized in a poly(vinyl alcohol) cryogel membrane, obtained by a freezing-thawing cyclic process, to obtain a suitable amperometric glucose sensor. The covalent linkage between PEG and GOD molecule improved the physical immobilization of enzyme in the polymeric matrix, by decreasing its loss in time. Sensor behaviour was evaluated electrochemically with a hydrogen peroxide electrode. The glucose content in standard solutions was determined and linear calibration curves in the 5x10(-5)-5x10(-3) mol l(-1) range were obtained. The kinetic parameters in the immobilized system were evaluated and analytical characteristics of sensor, including stability and influence of pH and temperature, were determined.     

A novel Cu,Zn superoxide dismutase from the fungal strain Humicola lutea 110: isolation and physico-chemical characterization

The fungal strain Humicola lutea 110 produces a mangan- and a copper zinc-containing superoxide dismutases (SOD). In this study, the purification, N-terminal sequence and spectroscopic properties of the new Cu,Zn SOD are described. The preparation of the pure metalloenzyme was achieved via treatment of the strain with acetone followed by gel and ion exchange chromatography. The protein consists of 302 amino acid residues and has a molecular mass of approximately 32 kDa, as determined by PAG electrophoresis and 3100 U mg-1 protein-specific activity. It is a dimeric enzyme with two identical subunits of 15,950 Da, as indicated by SDS-PAGE, mass spectroscopic and amino acid analysis. The N-terminal sequence analysis of the Cu,Zn SOD from the fungal strain revealed a high degree of structural homology with enzymes from other eukaryotic sources. Conformational stability and reversibility of unfolding of the dimeric enzyme were determined by fluorescence and circular dichroism (CD) spectroscopy. The critical temperature of deviation from linearity (Tc) of the Arrhenius plot ln (Q-1(-1)) vs. 1/T was calculated to be 68 degrees C and the respective activation energy for the thermal deactivation of the excited indole chromophores is 42 kcal mol-1. The melting temperatures (Tm) were determined by CD measurements to be 69 degrees C for the holo- and 61 degrees C for the apo-enzyme. The fluorescence emission of the Cu,Zn SOD is dominated by 'buried' tryptophyl chromophores. Removal of the copper-dioxygen system from the active site caused a 4-fold increase of the fluorescence quantum yield and a 10 nm shift of the emission maximum position towards higher wavelength.     

The role of a vector-valued field in multidimensional universe geometry

For a model of the multidimensional universe we take a smooth manifold S which under the action of a compact Lie group G fibres into orbits of the same type G/H acquiring the structure of a fibre bundle with typical fibre G/H and base-the orbit space S/G (identified with the four-dimensional spacetime). The notion of a connection form on the fibre bundle SS/G is defined and its role for some geometrical structures on S is considered. In the framework of a theory of G-invariant tensor-type fields on S, it is shown that -being itself a field of this type-determines a dimensional reduction of the objects on S to objects on S/G.     

Manganese(II) and copper(II) hexafluoroacetylacetonate 1:1 complexes with 5-(4-[N-tert-butyl-N-aminoxyl]phenyl)pyrimidine: regiochemical parity analysis for exchange behavior of complexes between radicals and paramagnetic cations

Mn(hfac)(2) and Cu(hfac)(2) form coordination complexes with 5-(4-[N-tert-butyl-N-aminoxyl]phenyl)pyrimidine, PyrimPh-NIT. (Mn[PyrimPh-NIT](hfac)(2))(2) and (Cu[PyrimPh-NIT](hfac)(2))(2), 1 and 2, respectively, are cyclic M(2)L(2) dimers that exhibit strong exchange coupling between the coordinated paramagnetic dication (M) and nitroxide (NIT) unit. The M-NIT exchange is strongly antiferromagnetic (AFM) in 1 and strongly ferromagnetic (FM) in 2. Magnetic susceptibility measurements for 1 were fitted to an AFM spin pairing model with J/k = -0.25 K between Mn-NIT spin sites units. Complex 2 also exhibits AFM spin pairing between S = 1 Cu-NIT spin units that is somewhat field dependent at low temperature. The fit of corrected paramagnetic susceptibility chi(T) to an AFM spin pairing model at 200 Oe yields J/k = (-)3.8 K, quite similar to earlier measurements at 1000 Oe yielding J/k = (-)5.0 K. At 1.40 K, the magnetization of 2 does not approach saturation until somewhat above 170 kOe, giving an S-shaped curve; at 0.55 K, the magnetization curve shows steps characteristic of field-induced crossover between the S = 0 ground state and excited spin states. From the steps in the 0.55 K data, we estimate J/k = (-)3.8-4.0 K for 2, in good agreement with the analysis of chi(T).