Studies on the Regioselectivity of Horner-Wadsworth-Emmons (Hwe) Reactions on 3,4-Enuloses. Further Evidence of Phosphonate-Phosphate Rearrangements Through Five Membered Cyclic Intermediates.

ABSTRACT

The Horner-Wadsworth-Emmons (HWE) reaction was performed on methyl 3,6-di-O-benzoyl-2-deoxy-α-D-glycero-hex-2-enopyranosid-4-ulose (1) with the potassium enolates of dimethyl [(methoxycarbonyl)methyl]phosphonate (2) or diethyl [(ethoxycarbonyl) methyl]phosphonate (3) under different conditions (metallic cation and solvent) in order to study regio- and stereochemical aspects of the reaction. In the presence of lithium ions, no reaction took place. When sodium enolates were employed, 1,2-addition was the main reaction in chelating solvents, whereas the 1,4-adduct is favoured in the less polar, non chelating toluene. Only 1,2-addition was observed with potassium enolates. Evidence of phosphonate-phosphate rearrangements through five membered cyclic intermediates is described.     

Recycling solid supports – A head-to-tail linker

The concept of a `head-to-tail linker' designed to allow the regeneration and reuse of a variety of solid supports is introduced. The synthesis of this linker, its coupling to various solid supports, its application in a number of standard solid phase reactions and resin regeneration are presented.     

Three-dimensional microfabrication by two-photon-initiated polymerization with a low-cost microlaser

Fabrication of submicrometer structures by two-photon-initiated polymerization is performed with an inexpensive and low-power microlaser. This is made possible by the design of photoinitiators with strong two-photon absorption cross sections. We analyze the influence of both material properties and irradiation conditions on the two-photon polymerization rate and show that resins based on our highly sensitive two-photon photoinitiator can be solidified with microlaser excitation, whereas commercial UV photoresins require ultrashort and intense laser pulses.     

Tuning high-power laser diodes with as much as 0.38 W of power and M(2) = 1.2 over a range of 32 nm with 3-GHz bandwidth

Gain-guided diode lasers usually have emission wavelengths determined by the manufacturing process, with typically 0.5-1-nm bandwidth. Furthermore, their beam quality is rather poor. We show that external cavities allow for tunable narrow-bandwidth operation of gain-guided diode lasers. At the same time the beam quality is drastically improved; almost diffraction-limited light of more than 200 mW has been achieved over the whole tuning range from 910 to 942 nm with narrow bandwidth.     

Adding Prior Information in FWI through Relative Entropy

Full waveform inversion is an advantageous technique for obtaining high-resolution subsurface information. In the petroleum industry, mainly in reservoir characterisation, it is common to use information from wells as previous information to decrease the ambiguity of the obtained results. For this, we propose adding a relative entropy term to the formalism of the full waveform inversion. In this context, entropy will be just a nomenclature for regularisation and will have the role of helping the converge to the global minimum. The application of entropy in inverse problems usually involves formulating the problem, so that it is possible to use statistical concepts. To avoid this step, we propose a deterministic application to the full waveform inversion. We will discuss some aspects of relative entropy and show three different ways of using them to add prior information through entropy in the inverse problem. We use a dynamic weighting scheme to add prior information through entropy. The idea is that the prior information can help to find the path of the global minimum at the beginning of the inversion process. In all cases, the prior information can be incorporated very quickly into the full waveform inversion and lead the inversion to the desired solution. When we include the logarithmic weighting that constitutes entropy to the inverse problem, we will suppress the low-intensity ripples and sharpen the point events. Thus, the addition of entropy relative to full waveform inversion can provide a result with better resolution. In regions where salt is present in the BP 2004 model, we obtained a significant improvement by adding prior information through the relative entropy for synthetic data. We will show that the prior information added through entropy in full-waveform inversion formalism will prove to be a way to avoid local minimums.     

Chiodo formulas for the <Emphasis Type="Italic">r</Emphasis>-th roots and topological recursion

We analyze Chiodo’s formulas for the Chern classes related to the r-th roots of the suitably twisted integer powers of the canonical class on the moduli space of curves. The intersection numbers of these classes with \(\psi \)-classes are reproduced via the Chekhov–Eynard–Orantin topological recursion. As an application, we prove that the Johnson-Pandharipande-Tseng formula for the orbifold Hurwitz numbers is equivalent to the topological recursion for the orbifold Hurwitz numbers. In particular, this gives a new proof of the topological recursion for the orbifold Hurwitz numbers.     

Soliton-based Y-branch in photorefractive crystals induced through dispersion-shifted optical fiber

We experimentally demonstrate for what is believed to be the first time that a dispersion-shifted fiber can be used to electro-optically induce a soliton Y-branch structure in a photorefractive centrosymmetric paraelectric crystal (potassium lithium tantalate niobate). The application of a nonstationary external bias field enables us to stabilize the spatially partially coherent behavior of the optical beam at the fiber output. Furthermore, we show the switching capabilities of this soliton-based device in the optical communication field guiding a probe beam at a nonphotorefractive wavelength (1557 nm).     

Approximate chemical analysis of volcanic glasses using Raman spectroscopy

The effect of chemical composition on the Raman spectra of a series of natural calcalkaline silicate glasses has been quantified by performing electron microprobe analyses and obtaining Raman spectra on glassy filaments (~450 µm) derived from a magma mingling experiment. The results provide a robust compositionally‐dependent database for the Raman spectra of natural silicate glasses along the calcalkaline series. An empirical model based on both the acquired Raman spectra and an ideal mixing equation between calcalkaline basaltic and rhyolitic end‐members is constructed enabling the estimation of the chemical composition and degree of polymerization of silicate glasses using Raman spectra. The model is relatively insensitive to acquisition conditions and has been validated using the MPI‐DING geochemical standard glasses 1 as well as further samples. The methods and model developed here offer several advantages compared with other analytical and spectroscopic methods such as infrared spectroscopy, X‐ray fluorescence spectroscopy, electron and ion microprobe analyses, inasmuch as Raman spectroscopy can be performed with a high spatial resolution (1 µm²) without the need for any sample preparation as a nondestructive technique. This study represents an advance in efforts to provide the first database of Raman spectra for natural silicate glasses and yields a new approach for the treatment of Raman spectra, which allows us to extract approximate information about the chemical composition of natural silicate glasses using Raman spectroscopy. We anticipate its application in handheld in situ terrestrial field studies of silicate glasses under extreme conditions (e.g. extraterrestrial and submarine environments). © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd