Reactivite et distribution moleculaire dans les copolycondensats lineaires-I: Reactivite intrinseque

The effect of unequal intrinsic reactivity of functional groups on the molecular distribution in a linear step polymerization system is studied. In an R(A)₂/R′(B)₂ copolycondensate, the dependence of the polydispersity index on the relative reactivities of the two A-functional groups, at different extents of reaction, is examined in detail.     

Molecular mechanics (MM2) calculations and cone angles of phosphine ligands

Molecular mechanics (MM2) calculations were performed on 54 conformations of 18 phosphines (PH₃; PH_3−nR_n, where n = 1,…3, and R = Me and Et, n = 1 or 2 and R =ⁱPr, and n = 1 and R =^tBu, PMe₂Et, PMeEt₂, and PPhMe₂, and PPh₂R where R = Me, Et, ⁱPr, ^tBu and Ph). The results are compared to those previously obtained from MINDO/3 and MNDO calculations, and to experimental data. Single conformer cone angles and weighted average cone angles were calculated from MM2 optimized geometries employing Tolman's general definition, and they are compared to Tolman's values, MINDO/3 results, and T.L. Brown's E_R values. Of the cone angle definitions used, the weighted average values are suggested as the best single representation of phosphine ligand sizes. The steric parameters (cone angle and E_R values) alone, and in conjunction with electronic parameters, are correlated with experimental data.     

Periodic Mesoporous Organosilica Nanoparticles for CO2 Adsorption at Standard Temperature and Pressure

(1) Background: Due to human activities, greenhouse gas (GHG) concentrations in the atmosphere are constantly rising, causing the greenhouse effect. Among GHGs, carbon dioxide (CO₂) is responsible for about two-thirds of the total energy imbalance which is the origin of the increase in the Earth’s temperature. (2) Methods: In this field, we describe the development of periodic mesoporous organosilica nanoparticles (PMO NPs) used to capture and store CO₂ present in the atmosphere. Several types of PMO NP (bis(triethoxysilyl)ethane (BTEE) as matrix, co-condensed with trialkoxysilylated aminopyridine (py) and trialkoxysilylated bipyridine (Etbipy and iPrbipy)) were synthesized by means of the sol-gel procedure, then characterized with different techniques (DLS, TEM, FTIR, BET). A systematic evaluation of CO₂ adsorption was carried out at 298 K and 273 K, at low pressure. (3) Results: The best values of CO₂ adsorption were obtained with 6% bipyridine: 1.045 mmol·g⁻¹ at 298 K and 2.26 mmol·g⁻¹ at 273 K. (4) Conclusions: The synthetized BTEE/aminopyridine or bipyridine PMO NPs showed significant results and could be promising for carbon capture and storage (CCS) application.     

Strain relaxation in the epitaxy of La2/3Sr1/3MnO3 grown by pulsed-laser deposition on SrTiO3(001)

With a Curie point at 370?K, the half-metal (La_0.7Sr_0.3)MnO₃ (LSMO) is one of the most interesting candidates for electronic devices based on tunnel magnetoresistance. SrTiO₃ (STO) is up to now the best substrate for the epitaxy of suitable thin films of LSMO. The pseudocubic unit cell of rhombohedral LSMO has a parameter a _LSMO such that (a _STO ? a _LSMO)/a _LSMO = +?0.83% (where a _STO is the parameter of cubic STO) and an angle of 90.26°. As strained growth is tetragonal, relaxation implies recovery of both the pseudocubic parameter and of the original angle. In the LSMO layers that we prepare by pulsed-laser deposition, we show that these two processes are quite independent. The angular distortion is partially recovered by twinning in films 25?nm thick, while recovery of the parameter never occurs in the thickness range that we explored (up to 432?nm). A relaxation, however, takes place above a thickness of 100?nm, associated with a transition from two-dimensional to three-dimensional columnar growth. It is accompanied by chemical fluctuations. Our magnetic measurements exhibit Curie temperatures and magnetic moments very close to the bulk values in those layers where the crystal parameter is strained but the angle partially relaxed.     

Sensing the Anti-Epileptic Drug Perampanel with Paper-Based Spinning SERS Substrates

The applications of SERS in therapeutic drug monitoring, or other fields of analytical chemistry, require the availability of sensitive sensors and experimental approaches that can be implemented in affordable ways. In this contribution, we show the production of cost-effective SERS sensors obtained by depositing Lee-Meisel Ag colloids on filter paper either by natural sedimentation or centrifugation. We have characterized the morphological and plasmonic features of the sensors by optical microscopy, SEM, and UV-Vis spectroscopy. Such sensors can be used to quantify by SERS the anti-epileptic drug Perampanel (in the concentration range 1 × 10⁻⁴–5 × 10⁻⁶ M) by spinning them during the micro-Raman measurements on the top of a custom device obtained from spare part hard disk drives. This approach minimizes laser-induced heating effects and allows averaging over the spatial non-uniformity of the sensor.     

Fisetin as a Senotherapeutic Agent: Biopharmaceutical Properties and Crosstalk between Cell Senescence and Neuroprotection

Like other organs, brain functions diminish with age. Furthermore, for a variety of neurological disorders—including Alzheimer’s disease—age is one of the higher-risk factors. Since in many Western countries the average age is increasing, determining approaches for decreasing the effects of aging on brain function is taking on a new urgency. Neuroinflammation and oxidative stress are two convoluted key factors in brain aging and chronic neurodegenerative diseases. The diverseness of factors, causing an age-related decrease in brain functions, requires identifying small molecules that have multiple biological activities that can affect all these factors. One great source of these small molecules is related to polyphenolic flavonoids. Recently, 3,3′,4′,7-tetrahydroxyflavone (fisetin) has been reported as a potent senotherapeutic capable of extending lifespan by reducing peroxidation levels and enhancing antioxidant cell responses. The neuroprotective effects of fisetin have been shown in several in vitro and in vivo models of neurological disorders due to its actions on multiple pathways associated with different neurological disorders. The present work aims to collect the most recent achievements related to the antioxidant and neuroprotective effects of fisetin. Moreover, in silico pharmacokinetics, pharmacodynamics, and toxicity of fisetin are also comprehensively described along with emerging novel drug delivery strategies for the amelioration of this flavonol bioavailability and chemical stability.     

The Potential of 2-Substituted Quinolines as Antileishmanial Drug Candidates

There is a need for new, cost-effective drugs to treat leishmaniasis. A strategy based on traditional medicine practiced in Bolivia led to the discovery of the 2-substituted quinoline series as a source of molecules with antileishmanial activity and low toxicity. This review documents the development of the series from the first isolated natural compounds through several hundred synthetized molecules to an optimized compound exhibiting an in vitro IC₅₀ value of 0.2 µM against Leishmania donovani, and a selectivity index value of 187, together with in vivo activity on the L. donovani/hamster model. Attempts to establish structure–activity relationships are described, as well as studies that have attempted to determine the mechanism of action. For the latter, it appears that molecules of this series act on multiple targets, possibly including the immune system, which could explain the observed lack of drug resistance after in vitro drug pressure. We also show how nanotechnology strategies could valorize these drugs through adapted formulations and how a mechanistic targeting approach could generate new compounds with increased activity.     

One-pot synthesis of stable NIR tetracene diimides via double cross-coupling

Tetracene tetracarboxylic diimides have been synthesized based on direct double ring extension of electron-deficient naphthalene diimides involving metallacyclopentadienes. Atomic structure and electronic transitions responsible for their NIR absorption spectra are investigated with quantum-chemical calculations. In light of their unique structure and admirable photophysical and electronic properties, this new molecular skeleton is promising candidate for n-type semiconductors.     

Structure of optimal transport networks subject to a global constraint

The structure of pipe networks minimizing the total energy dissipation rate is studied analytically. Among all the possible pipe networks that can be built with a given total pipe volume (or pipe lateral surface area), the network which minimizes the dissipation rate is shown to be loopless. Furthermore, such an optimal network is shown to contain at most N-2 nodes in addition to the N sources plus sinks that it connects. These results are valid whether the possible locations for the additional nodes are chosen freely or from a set of nodes (such as points of a grid). Applications of these results to various physical situations and to the efficient computation of optimal pipe networks are also discussed.