On the metabolites produced by Colletotrichum gloeosporioides a fungus proposed for the Ambrosia artemisiifolia biocontrol; spectroscopic data and absolute configuration assignment of colletochlorin A

Ambrosia artemisiifolia L. is responsible for serious allergies induced on humans. Different approaches for its control were proposed during the COST Action FA1203 “Sustainable management of Ambrosia artemisiifolia in Europe” (SMARTER). Fungal secondary metabolites often show potential herbicidal activity. Three phytotoxins were purified from the fungal culture filtrates of Colletotrichum gloeosporioides, isolated from infected leaves of A. artemisiifolia. They were identified by spectroscopic and chemical methods as colletochlorin A, orcinol and tyrosol (1, 2 and 3). The absolute configuration 6’R to colletochlorin A was assigned for the first time applying the advanced Mosher’s method. When assayed by leaf-puncture on A. artemisiifolia only 1 caused the appearance of large necrosis. The same symptoms were also induced by 1 on ambrosia plantlets associated with plant wilting. On Lemna minor, colletochlorin A caused a clear fronds browning, with a total reduction in chlorophyll content.     

Analysis of spectral Hamiltonian boundary value methods (SHBVMs) for the numerical solution of ODE problems

Numerical Algorithms - Recently, the numerical solution of stiffly/highly oscillatory Hamiltonian problems has been attacked by using Hamiltonian boundary value methods (HBVMs) as spectral methods...     

β-N-Heterocyclic Cyclobutane Carboximides: Synthesis through a Tandem Base-Catalyzed Amidation/aza-Michael Addition Protocol and Facile Transformations

A stereoselective one-pot double derivatization of cyclobutene-1-carboxylic acid via a mild organic base catalyzed amidation/aza-Michael addition of benzo[d]oxazol-2(3H)-ones has been developed. This unprecedented tandem reaction provides access to novel β-N-heterocyclic cyclobutane carboximide derivatives with a trans geometry. The carboximide moiety reacts smoothly with nucleophiles, allowing access to diverse derivatives of trans-β-N-heterocyclic cyclobutanecarboxylic acid, including peptidomimetic structures.     

Tunable Linear and Nonlinear Optical Properties from Room Temperature Phosphorescent Cyclic Triimidazole-Pyrene Bio-Probe

Organic materials with multiple emissions tunable by external stimuli represent a great challenge. TTPyr, crystallizing in different polymorphs, shows a very rich photophyisics comprising excitation-dependent fluorescence and phosphorescence at ambient conditions, and mechanochromic and thermochromic behavior. Transformation among the different species has been followed by thermal and X-ray diffraction analyses and the emissive features interpreted through structural results and DFT/TDDFT calculations. Particularly intriguing is the polymorph TTPyr(HT), serendipitously obtained at high temperature but stable also at room temperature, whose non-centrosymmetric structure guarantees an SHG efficiency 10 times higher than that of standard urea. Its crystal packing, where only the TT units are strongly rigidified by π-π stacking interactions while the Pyr moieties possess partial conformational freedom, is responsible for the observed dual fluorescence. The potentialities of TTPyr for bioimaging have been successfully established.     

Forecasting the integration of immigrants

In this research, we develop and introduce a theoretical and mathematical forecasting framework of immigrant integration using immigrant density as a single driver. First, we introduce the integration concepts we aim at forecasting. Thereafter, we introduce a theoretical and mathematical model of the relationship between integration and immigrant density. Based on this model, we develop a methodological forecasting framework. We test the framework using immigrant integration data from Spain. We produce the forecasts, and conduct the proper evaluation of them. Finally, we conclude with a brief discussion of the wider implications of our results.     

The Mechanism of 2-Furaldehyde Formation from d-Xylose Dehydration in the Gas Phase. A Tandem Mass Spectrometric Study

The mechanism of reactions occurring in solution can be investigated also in the gas phase by suited mass spectrometric techniques, which allow to highlight fundamental mechanistic features independent of the influence of the medium and to clarifying controversial hypotheses proposed in solution studies. In this work, we report a gas-phase study performed by electrospray triple stage quadrupole mass spectrometry (ESI-TSQ/MS) on the dehydration of d-xylose, leading mainly to the formation of 2-furaldehyde (2-FA). It is generally known in carbohydrate chemistry that the thermal acid catalyzed dehydration of pentoses leads to the formation of 2-FA, but several aspects on the solution-phase mechanism are controversial. Here, gaseous reactant ions corresponding to protonated xylose molecules obtained from ESI of a solution containing d-xylose and ammonium acetate as protonating reagent were allowed to undergo collisionally activated decomposition (CAD) into the triple stage quadrupole analyzer. The product ion mass spectra of protonated xylose are characterized by the presence of ionic intermediates arising from xylose dehydration, which were structurally characterized by their fragmentation patterns. As expected, the xylose triple dehydration leads to the formation of the ion at m/z 97, corresponding to protonated 2-FA. On the basis of mass spectrometric evidences, we demonstrated that in the gas phase, the formation of 2-FA involves protonation at the OH group bound to the C1 atom of the sugar, the first ionic intermediate being characterized by a cyclic structure. Finally, energy resolved product ion mass spectra allowed to obtain information on the energetic features of the d-xylose→2-FA conversion.

$$\pi $$π-Formulas and Gray code

In previous papers we introduced a class of polynomials which follow the same recursive formula as the Lucas–Lehmer numbers, studying the distribution of their zeros and remarking that this distribution follows a sequence related to the binary Gray code. It allowed us to give an order for all the zeros of every polynomial \(L_n\). In this paper, the zeros, expressed in terms of nested radicals, are used to obtain two formulas for \(\pi \): the first can be seen as a generalization of the known formula

$$\begin{aligned} \pi =\lim _{n\rightarrow \infty } 2^{n+1}\cdot \sqrt{2-\underbrace{\sqrt{2+\sqrt{2+\sqrt{2+\cdots +\sqrt{2}}}}}_{n}}, \end{aligned}$$

related to the smallest positive zero of \(L_n\); the second is an exact formula for \(\pi \) achieved thanks to some identities valid for \(L_n\).

     

A Novel Coherent Multilevel Combined Phase and Polarization Shift Keying Modulation in Twisted Fibers

This article proposes a novel coherent multilevel modulation model that exploits polarization and phase of the field. This model is based on the possibility of coherent systems to use all the four degrees of freedom of the electromagnetic field. The proposed scheme is able, by applying a suitable twisting process to the optical fiber, to physically confine the polarization and the phase of the transmitted field within the phase sphere. In this way, with the same performances of existing systems, the receiver is considerably simplified because there is no longer need of birefringence tracking circuits.