Claisen rearrangement induced by low-energy collision of ESI-generated, protonated benzyloxy indoles

The Claisen rearrangement is a well-known process occurring in condensed phase. In the gas-phase protonated allyl phenyl ethers, propargyl phenyl ethers, and N-allyl aniline produced by positive ion chemical ionization undergo Claisen rearrangement. This reaction has been observed even in the case of odd-electron molecular ions. Phenyl allenyl ether molecular ions actually undergo Claisen rearrangement, producing intense [M - CO](+*) ions. In this investigation, the behavior of protonated benzyloxy indole and some of its derivatives, obtained in electrospray conditions, is described. Low-energy MS/MS experiments carried out on [M + H](+) species show CO loss and an unexpected water loss: both can be justified only by the occurrence of Claisen rearrangement. Deuterium labeling experiments confirm this mechanism. The influence of different substituents in the indole moiety is discussed.     

Voltammetric Detection of Free Sulfhydryl Compounds in Food Flours

Cyclic voltammetry has been applied to the rapid measurement of free SH‐compounds in food flours samples. The protocol is based on the electrochemical adaptation of the Ellman's test, where the DTNB reacts with SH‐compounds present in food flour extracts, resulting in the equimolar production of the electroactive compound TNBA which, in turns, reacts with phenylendiamine. The reaction is found to provide an analytical signal from which to quantify indirectly free sulfhydryl compounds in flours extracts.     

Electrospinning of poly(lactic acid): Theoretical approach for the solvent selection to produce defect‐free nanofibers

In this study an integrated methodology was proposed for the selection of solvent systems to produce electrospinnable solutions that form defect‐free poly(lactic acid) (PLA) fibers with narrow diameter distributions. The solvent systems were chosen using a thermodynamic approach, combined with electrical and rheological property criteria. More specifically, the three step methodology includes (1) initial choice of solvent by solubility evaluation to meet thermodynamic criteria, (2) electrical properties, that is, conductivity and dielectric constant adjustment by using solvent mixtures to meet electrical property criteria, and (3) critical entanglement concentration (C_e) determination by viscosity measurements, supported by elastic and plastic moduli measurements, followed by concentration adjustment to meet rheological criteria. All three criteria need to be met to ensure defect‐free nanofiber morphology. The methodology was demonstrated using PLA solutions that were characterized in terms of thermodynamic properties, conductivity, surface tension, and viscosity measurements. These data were analyzed and related to the nanofiber morphology and diameter as determined from scanning electron microscopy (SEM). Measurements of the elastic (G′) and the plastic (G″) moduli of PLA solutions showed a sharp increase of G′ at the chain entanglement concentration. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1483–1498     

Study of the elastic stiffness constants of thiourea by Brillouin scattering

All the elastic stiffness constants of thiourea have been measured at room temperature. The value of C₆₆(0.7 × 10¹⁰dynes/cm²) is very low. The C₁₁ and C₃₃ constants exhibit discontinuities at 169 and 202 K. The longitudinal acoustic phonons propagating in the c direction are very strongly damped in the vicinity of 202 K.     

Measurement of axisymmetric temperature fields using reference beam and shearing interferometry for application to flames

A unified methodology for the application of reference beam and shearing interferometry to measure axisymmetric temperature fields within flames is proposed. Sensitivity and accuracy of the techniques are analyzed basing on interferograms of reference temperature profiles and CARS measurements obtained in test laminar flames. The rapid decay of temperature measurements accuracy with increasing both intensity of errors sources and uncertainty on independent parameters is assessed. The spatial variation of mixture composition in diffusive combusting flows requires the application of complementary methods to obtain a satisfactory accuracy, while flow fields with lean premixed combustion can be treated as optically-homogeneous media. The temperature maps resulting from the investigation of the test laminar flames are presented and discussed. The capability to disclose the thermal structure and to provide reliable quantitative data is demonstrated. Received: 15 March 1999/Accepted: 29 July 1999     

Thiazole Analogues of the Marine Alkaloid Nortopsentin as Inhibitors of Bacterial Biofilm Formation

Anti-virulence strategy is currently considered a promising approach to overcome the global threat of the antibiotic resistance. Among different bacterial virulence factors, the biofilm formation is recognized as one of the most relevant. Considering the high and growing percentage of multi-drug resistant infections that are biofilm-mediated, new therapeutic agents capable of counteracting the formation of biofilms are urgently required. In this scenario, a new series of 18 thiazole derivatives was efficiently synthesized and evaluated for its ability to inhibit biofilm formation against the Gram-positive bacterial reference strains Staphylococcus aureus ATCC 25923 and S. aureus ATCC 6538 and the Gram-negative strain Pseudomonas aeruginosa ATCC 15442. Most of the new compounds showed a marked selectivity against the Gram-positive strains. Remarkably, five compounds exhibited BIC₅₀ values against S. aureus ATCC 25923 ranging from 1.0 to 9.1 µM. The new compounds, affecting the biofilm formation without any interference on microbial growth, can be considered promising lead compounds for the development of a new class of anti-virulence agents.     

The Pharmaceutical Use of Captisol®: Some Surprising Observations

The purpose of this paper is to share some recent observations on the pharmaceuticaluses and properties of Captisol^® or SBE_7M--CD in controlled porosity osmotic pump tablets (CP-OPT) and the underlying mechanism/sthat lead to apparent zero-order drug release pattern. It would have been simple toattribute the apparent zero-order release mechanism/s of poorly water-soluble drugsfrom CP-OPTs and pellets utilizing Captisol^®as both a solubilizing andosmotic agent, to purely osmotic and diffusional components. However, the mechanismmay be more related to a counterbalancing of physical properties as the concentration of Captisol^®changes within the matrix. Specifically, the initial concentration of Captisol^®within a core is 0.3–0.4M. When this drops to lower values an osmotic pressure drop occurs across the membrane. Therefore, drug release should not follow apparent zero-order kinetics if all the drug is solubilized. However, as the viscosity within the tablet also drops, the apparent diffusion coefficient of both Captisol^® and drug increases. Therefore, it appears that there is an initial resistance (hydraulic pressure) to fluid flow from the tablet through the rate-limiting microporous membrane. This resistance decreases so that even as osmotic pressure and concentration differences drop with time, counterbalancing faster release occurs. Osmotic driving force appears to be the most important initial driving force but a diffusional component becomes more significant with time.     

Synthesis of Insect Sex Pheromones and Their Homologues I. (Z,E)-9, 11-Alkadienyl Acetates

(Z, E)-9, 11-Tetradecadienyl-l-acetate (1), a major component of the sex pheromone of Spodoptera litura (F.), and (Z, E}-9, 11-pentadecadienyl-1-acetate (2) were synthesized by the Wittig reaction between (E)-2-alkenal (3) and the ylid derived from 9-hydroxynonyltriphenylphosphonium bromide (4).