Mixed Oligoureas Based on Constrained Bicyclic and Acyclic β‐Amino Acids Derivatives: On the Significance of the Subunit Configuration for Folding

The combination of a non‐functionalized constrained bicyclo[2.2.2]octane motif along with urea linkages allowed the formation of a highly rigid 2.5_12/14 helical system both in solution and the solid state. In this work, we aimed at developing stable and functionalized systems as promising materials for biological applications in investigating the impact of this constrained motif and its configuration on homo and heterochiral mixed‐oligourea helix formation. Di‐, tetra‐, hexa‐, and octa‐oligoureas alternating the highly constrained bicyclic motif of (R) or (S) configuration with acyclic (S)‐β³‐amino acid derivatives were constructed. Circular dichroism (CD), NMR experiments, and the X‐ray crystal structure of the octamer unequivocally proved that the alternating heterochiral R/S sequences form a stable left‐handed 2.5‐helix in contrast to the mixed (S/S)‐oligoureas, which did not adopt any defined secondary structure. We observed that the (?)‐synclinal conformation around the C_α? C_β bond of the acyclic residues, although sterically less favorable than the (+)‐synclinal conformation, was imposed by the (R)‐bicyclic amino carbamoyl (BAC) residue. This highlighted the strong ability of the BAC residue to drive helical folding in heterochiral compounds. The role of the stereochemistry of the BAC unit was assessed and a model was proposed to explain the misfolding of the S/S sequences.     

AgNP-decorated SBA-15 for MWCNT Paste Modified Electrode: A Sensor for Simultaneous Voltammetric Determination of Paracetamol and Sulfamethoxazole

A new electrochemical sensor based on a carbon nanotube paste electrode modified with a Santa Barbara Amorphous material (SBA-15) decorated with silver nanoparticles, namely CNT/SBA/Ag-PE, was developed. It was successfully applied for individual and simultaneous determination of both paracetamol (PC) and sulfamethoxazole (SMZ) medicines. The electrode exhibited a linear dynamic range of 0.12–110 μmol L⁻¹ for paracetamol and 0.06–70 μmol L⁻¹ for sulfamethoxazole, and detection limits of 38 and 19 nmol L⁻¹, respectively. The proposed sensor offered high sensitivity, fast response time and the potential for detecting both drugs simultaneously. The CNT/SBA/Ag-PE enabled the simultaneous determination of PC and SMZ in urine samples with high recovery rates.     

Bose-Einstein condensation in semiconductors: the key role of dark excitons

Bose-Einstein condensation in semiconductors is controlled by the nonelementary-boson nature of excitons. Pauli exclusion between the fermionic components of composite excitons produces dramatic exchange couplings between bright and dark states. In microcavities, where bright excitons and photons form polaritons, they force the condensate to be linearly polarized, as observed. In bulk, they also force linear polarization, but of dark states, due to interband Coulomb scatterings. To evidence this dark condensate, indirect processes are thus needed.     

HPLC‐MS/MS method for quantitative determination of the novel dual inhibitor of FGF and VEGF receptors E‐3810 in tumor tissues from xenograft mice and human biopsies

We developed and validated a high‐performance liquid chromatography–tandem mass spectrometry analytical method to measure E‐3810, a novel dual inhibitor of fibroblast growth factor receptor 1 and vascular endothelial growth factor receptor 1–3 in tissues and determined the drug concentration in a biopsy of human breast cancer for the first time. The method is a modification of our previous one in plasma to study the clinical pharmacokinetics of the drug during the phase I/II trial. In view of the changes in matrix, we applied a partial validation protocol to determine recovery, sensitivity, range of linearity, precision, accuracy and stability of the method over three runs in a mouse tumor tissue and liver. The recovery of E‐3810 from liver or tumor homogenate was >69%, and the lower limit of quantification was 5 ng/ml. The method was linear in the concentration range 5.0–500.0 ng/ml, as demonstrated by a determination coefficient R² ≥ 0.9955. The range of the calibration curve was appropriate for the analysis, as demonstrated by the accuracy, which was between 91.4% and 106.7%. Interday precision and accuracy on quality control samples at 9, 30 and 300 ng/ml were 3.1‐11.2% and 98.3–111.4%, respectively. The assay was applied successfully to determine the intratumor concentration of E‐3810 in different mouse xenograft tumor models and in a biopsy of a patient with breast cancer included in the phase I/II trial of the drug. In mouse tumors, the concentrations of E‐3810 were higher than necessary to exert antitumor activity in vitro (1 µM). Even more of interest was the result obtained in a human biopsy of few milligrams, where E‐3810 reached 4.9 µg/g (11 µM). Copyright © 2014 John Wiley & Sons, Ltd.     

Antimicrobial nanocomposite films made of poly(lactic acid)-cellulose nanocrystals (PLA-CNC) in food applications: part A—effect of nisin release on the inactivation of Listeria monocytogenes in ham

New bioactive nanocomposite films were prepared by compression molding method for food applications. Film matrix was composed of poly(lactic acid) containing cellulose nanocrystals (PLA-CNC). Nanocomposite films were converted to bioactive films using nisin as an antimicrobial agent by an adsorption coating method. Resulting antimicrobial films were then introduced in packages containing sliced cooked ham as a food model and stored for 14 days at 4 °C to determine their inhibiting capacity against Listeria monocytogenes and their physicochemical and structural properties. The study also focused on the nisin release from the films by using an agar diffusion bioassay. It was observed that mechanical properties such as tensile strength, tensile modulus, elongation at break and water vapor permeability values of the bioactive films were stable after 14 days of storage. Fourier transform infrared spectroscopy analysis allowed characterizing the adsorption of nisin onto PLA-CNC surface. Microbiological analysis of sliced cooked ham inoculated with L. monocytogenes (3 log CFU/g) allowed determining the potentiality of nisin as a strong antimicrobial agent in PLA-CNC-based films. Bioactive PLA-CNC-nisin films showed a significant reduction of L. monocytogenes in ham from day 1 and a total inhibition from day 3. The percentage of nisin release increased continuously from day 0 to day 14, up to 21 % at day 14. These results demonstrated the potential application of PLA-CNC-nisin films on controlling the growth of food pathogens in meat products.     

Optimization of microfluidization for the homogeneous distribution of cellulose nanocrystals (CNCs) in biopolymeric matrix

Microfluidization, which is a high-pressure homogenization technique, was used to develop highly dispersed cellulose nanocrystal (CNC) reinforced chitosan based nanocomposite films. A three factor central composite design with five levels was designed to systematically optimize the microfluidization process. The three factors were the CNC content, the microfluidization pressure and the number of microfluidization cycles. Response surface methodology was used to obtain relationship between the mechanical properties of the nanocomposite films and the factors. Polynomial equations were generated based on the regression analysis of the factors and the predicted properties of the nanocomposite films were in good agreement with the experimental results. Microfluidization effectively reduced the CNC–chitosan aggregates and improved the mechanical properties of the nanocomposite films. Microscopic analysis of the microfluidized nanocomposite films revealed a 10–15 times reduction in the size of the aggregates compared to the non-microfluidized CNC/chitosan films and an increase in the root mean square surface roughness (Rq).     

Modular approach for modeling a multi-energy district boiler

The present paper deals with the modeling of a district boiler (city of La Rochelle, west coast of France), as part of the OptiEnR research project. This “multi-energy” boiler supplies domestic hot water and heats residential and public buildings, using mainly wood and sometimes fuel or gas if necessary. The OptiEnR research project focuses on optimizing the performance of the boiler. Its main objective is to minimize the use of fossil energy, stocking renewable energy during low-demand periods and using it when peak-demand is high. Because of both the complexity of the plant as a whole and the strong interactions between the sub-systems (the wood boiler, the gas-fuel oil boiler, the breaking pressure bottle, the cogeneration plant, the hot water distribution network), a modular approach has been proposed. According to what information is available, a combination of white, grey and black boxes (Hammerstein–Wiener models) has been used to carry out the modeling task. To answer for the lack of information, additional parameters were proposed and identified. The model has been first used in simulation during heating periods, with the aim of optimizing both the parameters of the boilers control systems and the use of wood, gas and fuel oil. Next, it will be used, when adding to the plant a thermal storage unit and implementing a model predictive controller, to improve its functioning, especially reducing the coverage rate of the fossil energy boiler.     

1H and31P ENDOR of the isotropic CO2 − signal atg=2.0007 in the EPR spectra of precipitated carbonated apatites

The isotropic EPR signal atg=2.0007 in X-irradiated carbonated apatites, precipitated from aquaeous solutions and dried at 25°C, is investigated with Electron Nuclear Double Resonance (ENDOR). The²³Na,³¹P and¹H ENDOR results indicate that the precursor of this radical is most probably located in an aqueous phase entrapped between the crystallites (the so-called occluded water). Other experimental features, such as the correlation between the appearance of the signal in the EPR spectrum and the presence of some residual (adsorbed and/or occluded) water in the sample seem to strengthen our hypothesis.