Measurement of the frequency response induced by electrostriction in optical fibers

Accurate measurements of the frequency response of the nonlinear refractive index induced by the combined effects of Kerr nonlinearity with electrostrictional excitation of acoustic waves in optical fibers are presented. A detailed experimental investigation of both standard (zero-dispersion wavelength,lambda(0) approximately 1.31microm) and dispersion-shifted (lambda(0)=1.55microm) single-mode fibers showed the presence of several resonant peaks induced by the electrostrictive nonlinearity in the fiber structure. This investigation has provided better insight into the frequency behavior of the electrostriction-induced acoustic waves in optical fibers.     

Crystal structure of the complex between 7,7,8,8-tetracyanoquinodimethane and 1-oxide-2-phenyl-quinoline

A series of complexes between 1-oxide quinolines and 7,7,8,8-tetracyanoquinodimethane has been synthesized and one of them has been analyzed by x-ray diffraction methods. Crystals of the title compound are monoclinic (C₁₅H₁₁NO·C₁₂H₄N₄), space groupP2₁/n,a=44.525(4),b=7.326(2),c=6.531(2) Å,=90.23(3)°. The structure was solved by direct methods and refined by block-matrix least-squares to giveR=0.047 for 1865 reflections above 2(I). Molecular dimensions, interplanar distances, empirical method and IR spectra suggest a -^* interaction with very low charge-transfer in the complex.     

Monitoring the synthetic procedures of commercial drugs by 2H NMR spectroscopy: the case of ibuprofen and naproxen

We determined the D/H isotope ratios of some ibuprofen and naproxen samples by (2)H NMR spectroscopy. Some of these values were found to be useful for collecting hints on the synthetic procedures employed to prepare these drugs. Site-specific isotope ratio analysis shows great potentials in the fight against patent infringement.     

Do computed crystal structures of nonpolar molecules depend on the electrostatic interactions? The case of tetracene

We present a strategy for comparing the global properties of competing potential models. By systematically sampling the potential energy surface of crystalline tetracene, we assess how the number, energy and structure of its minima are modified by switching on (or off) the Coulombic interactions. The increased complexity of the Coulombic potential leads to a more "rugged" potential energy surface with a larger number of minima, but the effect is not large. In fact, we find a subset of minima stable only in presence of the Coulombic interactions, a smaller subset stable only in their absence, and a large majority stable in both cases. Among these, there is a very good, but not perfect, correlation between the energies and the structures computed with and without the electrostatic interactions. Although electrostatic interactions play a role even in a rigid nonpolar molecule such as tetracene, they are not as crucial as often believed, because altering the electrostatic model (or switching it off completely) leads, in most cases, to equivalent results.     

Assessment of water-soluble pi-extended squaraines as one- and two-photon singlet oxygen photosensitizers: design, synthesis, and characterization

Singlet oxygen sensitization by organic molecules is a topic of major interest in the development of both efficient photodynamic therapy (PDT) and aerobic oxidations under complete green chemistry conditions. We report on the design, synthesis, biology, and complete spectroscopic characterization (vis-NIR linear and two-photon absorption spectroscopy, singlet oxygen generation efficiencies for both one- and two-photon excitation, electrochemistry, intrinsic dark toxicity, cellular uptake, and subcellular localization) of three classes of innovative singlet oxygen sensitizers pertaining to the family of symmetric squaraine derivatives originating from pi-excessive heterocycles. The main advantage of pi-extended squaraine photosensitizers over the large number of other known photosensitizers is their exceedingly strong two-photon absorption enabling, together with sizable singlet oxygen sensitization capabilities, for their use at the clinical application relevant wavelength of 806 nm. We finally show encouraging results about the dark toxicity and cellular uptake capabilities of water-soluble squaraine photosensitizers, opening the way for clinical small animal PDT trials.     

Determination of alpha-amylase inhibitor activity of phaseolamin from kidney bean (Phaseolus vulgaris) in dietary supplements by HPAEC-PAD

Some dietary supplements, so-called 'starch-blockers', used to control overweight, are based on the protein concentrate of the kidney bean, known to contain high levels of the alpha-amylase inhibitor phaseolamin, which may hinder the digestion of complex carbohydrates, thereby promoting or supporting weight loss. Currently, methods to determine the levels of alpha-amylase inhibitor are based on the measurement of alpha-amylase activity using colorimetric methods that cannot be applied to dietary supplements because they are complex mixtures of different ingredients that may interfere with the measurement. The aim of this study was to develop an alternative method to determine the level of phaseolamin in dietary supplements, using high-performance anion-exchange chromatography coupled with pulsed amperometric detection (HPAEC-PAD) to measure the amount of maltose resulting from the action of the enzyme porcine alpha-amylase on soluble starch in the presence and absence of the inhibitor. The assay described proved sensitive and accurate for use with both dietary supplements and raw materials.     

Front Cover: Katritzky Salts for the Synthesis of Unnatural Amino Acids and Late-Stage Functionalization of Peptides (Eur. J. Org. Chem. 12/2023)

Peptide drug discovery often benefits from the large structural diversity permitted by unnatural amino acids (UAAs). Indeed, numerous approved peptide drugs include UAAs in their sequences. Therefore, innovative chemical approaches either to synthesize UAAs or to allow late-stage functionalization of peptides are emerging themes in peptide drug discovery. Thanks to the recent advances in deaminative strategies using alkylpyridiniums salts, often referred to as Katritzky salts, a variety of radical alkylation methods have been developed. In recent years the use of Katritzky salts have become popular in peptide chemistry due to their ease of preparation from a primary amine, which is a predominant functional group in amino acids. This review highlights the progress that has been made by using Katritzky salts in the synthesis of UAAs, late-stage peptide functionalization, and peptide macrocyclization.