Blue-LED Synthesis of Pummerer's Ketones by Peroxidase-Lignin-Catalyzed Oxidative Coupling of Substituted Phenols

Pummerer's ketones resembling the tricyclic scaffold of bioactive natural substances were synthesized by blue-LED driven Horseradish Peroxidase oxidative coupling of substituted phenols in 2-methyltetrahydrofuran by using meso-tetraphenylporphyrin as photosensitizer and dioxygen as primary oxidant. The application of functionalized lignin nanoparticles as a renewable and efficient platform for the immobilization of the enzyme extended the effectiveness of the overall process to heterogeneous catalysis under buffer limiting conditions.     

Vanishings for the cohomology of certain families of stable rank two vector bundles onP 3

Sunto Si analizzano delle condizioni per l'annullamento della coomologia di fibrati stabili di rango 2su P ³.Dopo i primi risultati di annullamento dovuti principalmente ad Hartshorne, Chang congetturò che alcune disuguaglianze sulle, classi di Chern fossero sufficienti per l'annullamento del primo gruppo di coomologia. La congettura finora è provata solo in alcuni casi particolari. Nel lavoro si dimostra la congettura in molti altri casi. In particolare si completano alcuni risultati recenti dovuti ad Ellia affrontando il caso in cui la prima classe di Chern è dispari.     

The Singularity of Kontsevich’s Solution for QH<Superscript>*</Superscript>(CP<Superscript>2</Superscript>)

In this paper we study the nature of the singularity of the Kontsevichs solution of the WDVV equations of associativity. We prove that it corresponds to a singularity in the change of two coordinates systems of the Frobenius manifold given by the quantum cohomology of CP². Mathematics Subject Classifications (2000) 53C99, 32D99, 14N35, 88A99.     

Topological defects and bulk melting of hexagonal ice

We use classical molecular dynamics combined with the recently developed metadynamics method [Laio, A.; Parrinello, M. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 20] to study the process of bulk melting in hexagonal ice. Our simulations show that bulk melting is mediated by the formation of topological defects which preserve the coordination of the tetrahedral network. Such defects cluster to form a defective region involving about 50 molecules with a surprisingly long lifetime. The subsequent formation of coordination defects triggers the transition to the liquid state.     

Orbital magnetization in periodic insulators

Working in the Wannier representation, we derive an expression for the orbital magnetization of a periodic insulator. The magnetization is shown to be comprised of two contributions, an obvious one associated with the internal circulation of bulklike Wannier functions in the interior, and an unexpected one arising from net currents carried by Wannier functions near the surface. Each contribution can be expressed as a bulk property in terms of Bloch functions in a gauge-invariant way. Our expression is verified by comparing numerical tight-binding calculations for finite and periodic samples.     

Diffraction and localization in low-dimensional photonic bandgaps

We show that, in low-dimensional photonic bandgaps, wave diffraction resulting from localization in the translational-invariant directions is strongly influenced by the photonic band structure of the periodic crystal, leading to new kinds of wave localization. In particular, for a periodic layered structure we show that, close to a bandgap edge, diffraction is enhanced, with a transition from a parabolic diffraction curve-typical of isotropic media and supporting Gaussian beams-to hyperbolic or elliptic diffraction curves. In the last two cases localization in the form of stationary X-shaped or sinc-shaped waves is possible.     

On the Generation of Certain Bundles of the Projective Space

Extending a result of Manivel, we prove the following: THEOREM. Suppose $\sum\limits_i {b_i \geqslant } \sum\limits_i {a_i } + n$ and $$\sum\limits_i {b_i } [n + d_i d_i - 1] \geqslant \sum\limits_i {a_i } [n + l_i l_i - 1] + n.$$ Then the kernel E(d) of the general morphism: $$\mathop \oplus \limits_{i = 1}^v (Bi \otimes O_{P^n } (d_i )) \to \mathop \oplus \limits_{j = 1}^v (A_j \otimes O_{P^n } (l_i ))$$ (l ₁>...>l _s>d ₁>...>d _v) is a globally generated vector bundle, except for at most finitely many sets $\left\{ {b_i ,a_i } \right\}$ .     

Synthesis and Antiproliferative Effect of Halogenated Coumarin Derivatives

A series of 6- and 6,8-halocoumarin derivatives have been investigated as potential antiproliferative compounds against a panel of tumor and normal cell lines. Cytotoxic effects were determined by the MTT method. To investigate the potential molecular mechanism involved in the cytotoxic effect, apoptosis assay, cell cycle analysis, reactive oxygen species (ROS), and reduced glutathione analysis were performed. Among the screened compounds, coumarins 6,8-dibromo-2-oxo-2H-chromene-3-carbonitrile 2h and 6,8-diiodo-2-oxo-2H-chromene-3-carbonitrile 2k exhibited the most antiproliferative effect in thyroid cancer-derived cells TPC-1. The apoptosis assay showed that both 2h and 2k induced apoptosis in TPC-1 thyroid cancer cells. According to these experiments, both coumarins induced a slight increase in TPC-1 cells in the G2/M phase and a decrease in the S phase. A significant increase in ROS levels was observed in TPC-1 treated with diiodocoumarin 2k, while the dibromocoumarin 2h induced a decrease in ROS in a dose and time-dependent manner.     

Rapid Classification and Recognition Method of the Species and Chemotypes of Essential Oils by ATR-FTIR Spectroscopy Coupled with Chemometrics

In the present work, the applicability of attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, coupled with chemometric tools in recognizing essential oils (EOs) for routine control, was evaluated. EOs belonging to Mentha, Cymbopogon, and Lavandula families and to S. rosmarinus and T. vulgaris species were analyzed, and the performance of several untargeted approaches, based on the synergistic combination of ATR-FTIR and Partial Least Squares Discriminant Analysis (PLS-DA), was tested to classify the species and chemotypes. Different spectra pre-processing methods were employed, and the robustness of the built models was tested by means of a Receiver Operating Characteristic (ROC) curve and random permutations test. The application of these approaches revealed fruitful results in terms of sensitivity and specificity, highlighting the potentiality of ATR-FTIR and chemometrics techniques to be used as a sensitive, cost-effective, and rapid tool to differentiate EO samples according to their species and chemotype.     

Secondary Formation of Aromatic Nitroderivatives of Environmental Concern: Photonitration Processes Triggered by the Photolysis of Nitrate and Nitrite Ions in Aqueous Solution

Aromatic nitroderivatives are compounds of considerable environmental concern, because some of them are phytotoxic (especially the nitrophenols, and particularly 2,4-dinitrophenol), others are mutagenic and potentially carcinogenic (e.g., the nitroderivatives of polycyclic aromatic hydrocarbons, such as 1-nitropyrene), and all of them absorb sunlight as components of the brown carbon. The latter has the potential to affect the climatic feedback of atmospheric aerosols. Most nitroderivatives are secondarily formed in the environment and, among their possible formation processes, photonitration upon irradiation of nitrate or nitrite is an important pathway that has periodically gained considerable attention. However, photonitration triggered by nitrate and nitrite is a very complex process, because the two ionic species under irradiation produce a wide range of nitrating agents (such as ^•NO₂, HNO₂, HOONO, and H₂OONO⁺), which are affected by pH and the presence of organic compounds and, in turn, deeply affect the nitration of aromatic precursors. Moreover, aromatic substrates can highly differ in their reactivity towards the various photogenerated species, thereby providing different behaviours towards photonitration. Despite the high complexity, it is possible to rationalise the different photonitration pathways in a coherent framework. In this context, this review paper has the goal of providing the reader with a guide on what to expect from the photonitration process under different conditions, how to study it, and how to determine which pathway(s) are prevailing in the formation of the observed nitroderivatives.