Tuning the Dipolar Second‐Order Nonlinear Optical Properties of Cyclometalated Platinum(II) Complexes with Tridentate N^C^N Binding Ligands

Appropriate functionalization of the cyclometalated ligand, L , and the choice of the ancillary ligand, X, allows the dipolar second‐order nonlinear optical response of luminescent [Pt L X] complexes—in which L is an N^C^N‐coordinated 1,3‐di(2‐pyridyl)benzene ligand and X is a monodentate halide or acetylide ligand—to be controlled. The complementary use of electric‐field‐induced second‐harmonic (EFISH) generation and harmonic light scattering (HLS) measurements demonstrates how the quadratic hyperpolarizability of this appealing family of multifunctional chromophores, characterized by a good transparency throughout much of the visible region, is dominated by an octupolar contribution.     

Cinchoninium l-tartrate tetrahydrate

The title compound, (3R,4S,8R,9S)-cinchoninium (2R,3R)-tartrate tetrahydrate, C₁₉H₂₃N₂O⁺·C₄H₅O₆⁻·4H₂O, is a hydrated salt of cinchonine. In the cinchoninium cation, the geometry around the quinuclidinic N atom is typical of a protonated N atom, and the bond lengths and angles in the tartrate moiety clearly indicate the mono-ionized form. The relative orientation of the quinoline and quinuclidine systems is that most frequently observed in structures of cinchona salts and corresponds to one of the energy minima calculated for this type of mol­ecule in the gas phase. An extended network of intermolecular hydrogen bonds spreads parallel to the bc plane separating apolar layers.     

Energy estimate and fundamental solution for degenerate hyperbolic Cauchy problems

The aim of this paper is to give an uniform approach to different kinds of degenerate hyperbolic Cauchy problems. We prove that a weakly hyperbolic equation, satisfying an intermediate condition between effective hyperbolicity and the C^∞ Levi condition, and a strictly hyperbolic equation with non-regular coefficients with respect to the time variable can be reduced to first-order systems of the same type. For such a kind of systems, we prove an energy estimate in Sobolev spaces (with a loss of derivatives) which gives the well-posedness of the Cauchy problem in C^∞. In the strictly hyperbolic case, we also construct the fundamental solution and we describe the propagation of the space singularities of the solution which is influenced by the non-regularity of the coefficients with respect to the time variable.     

ACMA (9-amino-6-chloro-2-methoxy acridine) forms three complexes in the presence of DNA

The interaction of ACMA (9-amino-6-chloro-2-methoxy acridine) (D) with DNA (P) has been studied by absorbance, fluorescence, circular dichroism, spectrophotometry, viscometry and unwinding electrophoresis. A T-jump kinetic study has also been undertaken. The experimental data show that, totally unlike other drugs, ACMA is able to form with DNA three complexes (PD(I), PD(II), PD(III)) that differ from each other by the characteristics and extent of the binding process. The main features of PD(I) fulfil the classical intercalation pattern and the formation/dissociation kinetics have been elucidated by T-jump techniques. PD(II) and PD(III) are also intercalated species but, in addition to the dye units lodged between base pairs, they also bear dye molecules externally bound, more in PD(III) relative to PD(II). A reaction mechanism is put forward here. Comparison between absorbance, fluorescence and kinetic experiments has enabled us to determine the binding constants of the three complexes, namely (6.5 ± 1.1) × 10(4) M(-1) (PD(I)), (5.5 ± 1.5) × 10(4) M(-1) (PD(II)) and (5.7 ± 0.03) × 10(4) M(-1) (PD(III)). The Comet assay reveals that the ACMA binding to DNA brings about genotoxic properties. The mutagenic potential studied by the Ames test reveals that ACMA can produce frameshift and transversion/transition mutations. ACMA also is able to produce base-pair substitution in the presence of S9 mix. Moreover, the MTT assays have revealed cytotoxicity. The biological effects observed have been rationalized in light of these features.     

Recent advances in vanadium catalyzed oxygen transfer reactions

Vanadium complexes have proven to be effective catalysts for the activation of peroxides and the selective oxidation of substrates like bromides, sulfides and alkenes. Besides their capability to form metalloperoxo species, which effectively transfer oxygen atoms to the substrate, these systems are synthetically useful for obtaining valuable oxidized molecules on a preparative scale, with a high degree of selectivity and TONs. Furthermore, the use of environmentally friendly oxidants like hydrogen and alkyl hydroperoxides increases significantly their potential application at an industrial level.Here we report a critical survey on the most effective homogeneous vanadium catalysts reported in the last decade concerning their synthetic application in oxygen transfer reactions (sulfoxidation, epoxidation, haloperoxidation) using hydrogen peroxide or alkyl hydroperoxides, demonstrating the different classes of ligands and complexes, their catalytic performances, their reactivity, chemo, stereo and substrate selectivity. Some examples of the use of non conventional reaction media or techniques and catalyst recycling studies will be also discussed.     

Mechanistic aspects of vanadium catalysed oxidations with peroxides

The enhancement of the reactivity of peroxides, particularly hydrogen peroxide and alkylhydroperoxides, in the presence of vanadium catalysis is a very well known process. The catalytic effect is determined by the formation of an intermediate whose nature depends on the peroxides used and on its interaction with the metal precursor, high-valent peroxo vanadium species being usually the reactive oxidants. During the last decades the mechanistic details for several types of oxidation reactions have been elucidated. Interestingly, in a number of cases theoretical calculations offered support to the proposed reaction pathways.In general, V(V) peroxo species behave as electrophilic oxygen transfer reagents thus reacting preferentially with the more nucleophilic functional group present in the molecule. In several instances the chemoselectivity observed in such processes is very high when not absolute. As far as vanadium peroxides are concerned, a radical oxidative reactivity toward alkanes and aromatics has been also observed; also for this latter chemistry, diverse research groups studied in detail the mechanism. On the other hand, no clear-cut evidence of nucleophilic reactivity of vanadium peroxo complexes has been obtained.Here we collect a selection of recent achievements concerning the reaction mechanisms in the vanadium catalysed oxidation and bromination reactions with peroxides.     

Fast approximation to pixelwise relaxivity maps: Validation in iron overloaded subjects

Purpose

Liver iron quantification by MRI has become routine. Pixelwise (PW) fitting to the iron-mediated signal decay has some advantages but is slower and more vulnerable to noise than region-based techniques. We present a fast, pseudo-pixelwise mapping (PPWM) algorithm.

Materials and Methods

The PPWM algorithm divides the entire liver into non-contiguous groups of pixels sorted by rapid relative relaxivity estimates. Pixels within each group of like-relaxivity were binned and fit using a Levenberg–Marquadt algorithm.

Results

The developed algorithm worked about 30 times faster than the traditional PW approach and generated R2* maps qualitatively and quantitatively similar. No systematic difference was observed in median R2* values with a coefficient of variability (CoV) of 2.4%. Intra-observer and inter-observer errors were also under 2.5%. Small systematic differences were observed in the right tail of the R2* distribution resulting in slightly lower mean R2* values (CoV of 4.2%) and moderately lower SD of R2* values for the PPWM algorithm. Moreover, the PPWM provided the best accuracy, giving a lower error of R2* estimates.

Conclusion

The PPWM yielded comparable reproducibility and higher accuracy than the TPWM. The method is suitable for relaxivity maps in other organs and applications.     

Polygons in Minkowski three space and parabolic Higgs bundles of rank 2 on \mathbb{C}{{\mathbb{P}}^1}

Consider the moduli space of parabolic Higgs bundles (E, Φ) of rank two on ??¹ such that the underlying holomorphic vector bundle for the parabolic vector bundle E is trivial. It is equipped with the natural involution defined by $ \left( {E,\varPhi } \right)\mapsto \left( {E,-\varPhi } \right) $ . We study the fixed point locus of this involution. In [GM], this moduli space with involution was identified with the moduli space of hyperpolygons equipped with a certain natural involution. Here we identify the fixed point locus with the moduli spaces of polygons in Minkowski 3-space. This identification yields information on the connected components of the fixed point locus.     

GAP-43 mRNA detection by in situ hybridization, direct and indirect in situ RT-PCR in hippocampal and cerebellar tissue sections of adult rat brain

The growth-associated protein GAP-43 is a presynaptic membrane phosphoprotein that is expressed at high levels during development and axonal growth. To evaluate the cellular distribution of GAP-43 mRNA in the hippocampus and cerebellum of adult rats we applied in situ hybridization (ISH) as well as direct and indirect in situ RT-PCR using biotin as a reporter molecule. ISH resulted in a positive signal in most cerebellar granular cells and in 30% of hippocampal CA3 neurons. Direct in situ RT-PCR yielded cells with strong signals in every region investigated, with elevated background levels most likely related to incorporation of labeled nucleotides into non-specific amplicons through internal priming and DNA repair activity. Indirect in situ RT-PCR turned out to be the best approach for detecting GAP-43 mRNA positive cells. Cerebellar cells exhibiting a positive signal for GAP-43 mRNA were of the granular cell type (98%). Hippocampal neurons with a positive reaction for GAP-43 mRNA included all the neuron groups analyzed, namely CA1 (99%) and CA3 pyramidal cells (94%) and dentate gyrus granule cells (92%). Dentate gyrus granule cells have not tested positive for GAP-43 mRNA detection by molecular morphology analysis. These data show that in normal rats GAP-43 mRNA is present in different cell populations of hippocampal formation, supporting the role of this protein in the ongoing processes of synaptic plasticity.