Complexing processes in M(II)-dithiomalonamide-diacetyl triple systems (M= Ni,Cu) in ethanol solution and in a metal(II)hexacyanoferrate(II) gelatin-immobilized matrix materials

The complexing processes in the M ^II -dithiomalonamide-diacetyl triple system (M=Ni, Cu) occuring in the nickel(II)- and copper(II)hexacyanoferrate(II) gelatin-immobilized matrix in contact with aqueous alkaline solutions (pH~12) containing dithiomalonamide and diacetyl at room temperature, and between MCl₂, dithiomalonamide and diacetyl in EtOH solutions upon heating to$80°C, have been studied. In the Ni ^II -dithiomalonamide-diacetyl system, template synthesis occurs in EtOH solution but does not occur in the gelatin-immobilized matrix, whereas in the Cu ^II -dithiomalonamide-diacetyl system, template synthesis occurs in the gelatin-immobilized matrix but not in EtOH solution. Dithiomalonamide and diacetyl are the ligand synthons in the processes indicated.     

Blood lead monitoring in Italy: Assessment of the quality of results obtained between 1992 and 1994

Between 1992 and 1994, a new screening campaign for blood Pb monitoring in the Italian general population was carried out. Since the first campaign (started in 1978, in accomplishment of the European Community Directive 77/312/EEC) a working group of the Laboratory of Clinical Biochemistry at the Italian National Institute of Health (Istituto Superiore di Sanità), as the Reference Centre (RC), has coordinated the activity of various laboratories spread over the national territory. Appropriate quality assurance procedures, including an external quality assessment scheme (EQAS), were elaborated. Within the EQAS, three or four trials were carried out every year. Each laboratory participating in the trial analyzed eight control samples prepared from cow blood at different Pb concentrations. The results obtained by each peripheral laboratory and the RC between 1992 and 1994 have been compared by regression analysis. The same statistical method was adopted to compare the results obtained by each peripheral laboratory and the RC in the duplicate analysis of about 10 per cent of the human samples collected during the 1992–1994 monitoring campaign. There was no evidence of systematic differences between the regression lines obtained on control and human samples. In spite of the lower Pb concentration in the control samples analyzed during the 1992–1994 campaign, the analytical performance of the laboratories was better than that obtained in the previous screening campaign (1985–1986). Blood Pb levels observed in human samples collected between 1992 and 1994, confirm the downward time trend observed in the campaigns carried out in 1978–1979, 1980–1981 and 1985–1986. This study confirms that the results obtained in an EQAS are representative of the actual performance in the analysis of real (human) samples.     

Rigid optically-active D2 and D3 macrocycles

The synthesis and characterization of novel optically-active macrocycles, obtained by esterification reaction from a binaphthyl-containing diol and phthalic or terephthalic acids, and possessing overall D2 or D3 symmetry, is described.     

Photochemical study of [3(3)](1,3,5)cyclophane and emission spectral properties of [3n]cyclophanes (n = 2-6)

Thephotochemical reaction of [3(3)](1,3,5)cyclophane 2, which is a photoprecursor for the formation of propella[3(3)]prismane 18, was studied using a sterilizing lamp (254 nm). Upon photolysis in dry and wet CH2Cl2 or MeOH in the presence of 2 mol/L aqueous HCl solution, the cyclophane 2 afforded novel cage compounds comprised of new skeletons, tetracyclo[6.3.1.0.(2,7)0(4,11)]dodeca-5,9-diene 43, hexacyclo[6.4.0.0.(2,6)0.(4,11)0.(5,10)0(9,12)]dodecane 44, and pentacyclo[6.4.0.0.(2,6)0.(4,11)0(5,10)]dodecane 45. All of these products were confirmed by the X-ray structural analyses. A possible mechanism for the formation of these photoproducts via the hexaprismane derivative 18 is proposed. The photophysical properties in the excited state of the [3n]cyclophanes ([3n]CP, n = 2-6) were investigated by measuring the emission spectra and determining the quantum yields and lifetimes of the fluorescence. All [3n]CPs show excimeric fluorescence without a monomeric one. The lifetime of the excimer fluorescence becomes gradually longer with the increasing number of the trimethylene bridges. The [3n]CPs also shows excimeric phosphorescence spectra without vibrational structures for n = 2, 4, and 5, while phosphorescence is absent for n = 3 and 6. With an increase in symmetry of the benzene skeleton in the [3(3)]- and [3(6)]CPs, the probability of the radiation (phosphorescence) process from the lowest triplet state may drastically decrease.     

A general NMR method for rapid, efficient, and reliable biochemical screening

High-throughput screening is usually the method of drug-lead discovery. It is now well accepted that, for a functional assay, quality is more important than quantity. The ligand-based or protein-based NMR screening methodologies for detecting compounds binding to the macromolecular target of interest are now well established. A novel and sensitive NMR method for rapid, efficient, and reliable biochemical screening is presented. The method named 3-FABS (three fluorine atoms for biochemical screening) requires the labeling of the substrate with a CF(3) moiety and utilizes (19)F NMR spectroscopy for the detection of the starting and enzymatically modified substrates. The method allows for high-quality screening of large compound or natural product extract collections and for measuring their IC(50) values. Applications of this technique to the screening of inhibitors of the Ser/Thr kinase AKT1 and the protease trypsin are presented. In addition, an interesting application of 3-FABS to functional genomics is also presented.     

Direct catalytic aldol-type reactions using RCH2CN

[reaction: see text] A copper fluoride-catalyzed cyanomethylation that can be applied to a wide range of ketones and aldehydes was developed using TMSCH(2)CN as a nucleophile. The reaction was extended to a conceptually more advanced copper alkoxide-catalyzed direct addition of alkylnitriles to aldehydes, which can act as a surrogate direct catalytic aldol reaction of esters. These reactions can be applied to the first catalytic enantioselective cyanomethylation of ketones and direct catalytic enantioselective cyanomethylation of aldehydes.     

Structural characterization techniques for the analysis of semiconductor strained heterostructures

A combined method for structural characterization of strained epitaxial heterostructures involving different techniques such as Rutherford backscattering spectrometry (RBS), multiple crystal X-ray diffractometry (MCD) and transmission electron microscopy (TEM) is presented. In order to obtain a complete characterization of the analysed structure, three different quantities are measured independently: the epilayer thickness, the density of misfit dislocations which may appear at the interface, and the significant components of the strain tensor, mainly the tetragonal distortion, affecting the epilayer lattice. In this way the thermodynamic state and the mechanisms of plastic deformation of the structures can be fully investigated. In this contribution we present and discuss the experimental results concerning a set of InP/GaAs samples having different layer thicknesses ranging from 5 to 500 nm. The thickness of the samples has been determined by RBS. Measurements of in-plane strain and tetragonal distortion have been performed by MCD and RBS-channelling respectively, finally TEM has been used for determining the defects densities and distribution.     

High-intensity ultrasound and microwave, alone or combined, promote Pd/C-catalyzed aryl-aryl couplings

Pd-catalyzed homo- and cross-couplings of boronic acids and aryl halides were successfully carried out both in aqueous media under high-intensity ultrasound (US) and in DME under microwave (MW). Heterogeneous catalysis with Pd/C was employed, avoiding phosphine ligands and phase-transfer catalysts. In a trial series involving 15 different iodo- and bromoaryls and 7 boronic acids, both energy sources drastically reduced reaction times affording biaryls in acceptable to good yields. With palladium(II) acetate as catalyst, electron-deficient aryl chlorides also reacted, affording a few biaryls in acceptable yields. Ullmann-type zinc-mediated homocoupling of iodo- and bromoaryls in the presence of Pd/C under CO₂ atmosphere was achieved in aqueous media under US, though not under MW. Suzuki homo- and cross-couplings were also carried out in a new reactor developed in our laboratory, featuring combined US and MW irradiation, further improving a green synthetic method.     

Fluorine-NMR competition binding experiments for high-throughput screening of large compound mixtures

High-throughput ligand-based NMR screening with competition binding experiments is extended to (19)F detection. Fluorine is a favorable nucleus for these experiments because of the significant contribution of the Chemical Shift Anisotropy (CSA) to the (19)F transverse relaxation of the ligand signal when bound to a macromolecular target. A low to moderate affinity ligand containing a fluorine atom is used as a reference molecule for the detection and characterization of new ligands. Titration NMR experiments with the selected reference compound are performed for finding the optimal set-up conditions for HTS and for deriving the binding constants of the identified NMR hits. Rapid HTS of large chemical mixtures and plant or fungi extracts against the receptor of interest is possible due to the high sensitivity of the (19)F nucleus and the absence of overlap with the signals of the mixtures to be screened. Finally, a novel approach for HTS using a reference molecule in combination with a control molecule is presented.     

BLUE and NEAR ULTRAVIOLET REVERSIBLE PHOTOREACTION IN THE INDUCTION OF FUNGAL CONIDIATION

Abstract— The effects of blue light and near UV light on the induction of conidiation in the fungus, Aliernuriu tomato, were investigated. Induction of conidiation was repeatedly controlled by alternating doses of near UV light and blue light. When the final light was near UV, conidiation was induced and conidia developed in the following darkness; when it was blue, the induction of conidiation was suppressed. When conidiation was induced by irradiation with a light mixed with near UV and blue, not only the time lag for inducing conidiation but also the amount of conidia formed were regulated by the fluence rates of both those lights.
Thus, 'mycochrome' is considered to function as a photoreceptor system in the induction of conidiation of this fungus.