Enantioselective synthesis of (+)-gossonorol and related systems using organozinc reagents

The sesquiterpene (+)-gossonorol is prepared in only three synthetic steps in 60% overall yield and 82% ee from commercially available reagents. The key asymmetric step is the catalytic enantioselective addition of dimethylzinc to 5-methyl-1-(2-methylphenyl)hex-4-en-1-one catalyzed by chiral isoborneolsulfonamide ligands in the presence of titanium tetraisopropoxide. The modular approach allows the synthesis not only of the aforementioned natural product but also other products arising from the corresponding processes of ethylation, phenylation, and ethynylation, just by changing the final nucleophilic reagent and using the same isoborneol type ligand.     

Thermal evaluation of cashew nutshell liquid as new bioadditives for poly(methyl methacrylate)

In this study, the thermal-oxidative stability of poly(methyl methacrylate), PMMA, 1 % additivated with replenishable phenolic lipids is evaluated by thermogravimetric (TG/DTG) analyses and differential scanning calorimetry (DSC) analyses. Since technical cashew nutshell liquid (CNSL), a byproduct from the cashew industry, is composed basically of two phenolic lipids, cardanol and cardol, the utilization of this industrial waste and its main components as a new source of bioadditives for use as antioxidants is evaluated. The TG analyses revealed that addition of the phenolic constituent of CNSL increased the thermal stability of PMMA films considerably. The results obtained were also confirmed by DSC analyses.     

Development of new high‐performance visible light photoinitiators based on carbazole scaffold and their applications in 3d printing and photocomposite synthesis

In this article, new compounds based on the carbazole scaffold (DMs = DM1 and DM2, constituted by a carbazole unit connected on positions 3 and 6 to a two 4,4′‐dimethoxydiphenylamine groups and differing by the substituent present on the nitrogen heteroatom of the carbazole core) were synthesized and proposed as high‐performance visible light photoinitiators/photosensitizers for both the free‐radical polymerization of methacrylates and the cationic polymerization of epoxides upon visible light exposure using LED@405 nm. Remarkably, DM2 leads to higher final conversions than DM1. In order to study the photophysical and photochemical properties of the carbazole derivatives, different parameters were taken into account such as the light absorption, the steady‐state photolysis, and the fluorescence spectroscopy. Using different techniques such as fluorescence quenching, redox behavior, and cyclic voltammetry, we are able to discuss the photosensitization/photoinitiation reactions providing a full coherent picture of the involved chemical mechanisms. The photosensitization of the carbazole derivatives occurred predominantly via singlet excited states at the rate of the diffusion limit. Upon exposure to laser diode at 405 nm, DMs show high performance in initiating systems for 3D resins. Remarkably, DM2 can also be used in photocomposite synthesis using light‐emitting diode conveyor. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2081–2092     

Large deflection of a non-linear,elastic, asymmetric Ludwick cantilever beam subjected to horizontal force,vertical force and bending torque at the free end

The investigated cantilever beam is characterized by a constant rectangular cross-section and is subjected to a concentrated constant vertical load, to a concentrated constant horizontal load and to a concentrated constant bending torque at the free end. The same beam is made by an elastic non-linear asymmetric Ludwick type material with different behavior in tension and compression. Namely the constitutive law of the proposed material is characterized by two different elastic moduli and two different strain exponential coefficients. The aim of this study is to describe the deformation of the beam neutral surface and particularly the horizontal and vertical displacements of the free end cross-section. The analysis of large deflection is based on the Euler–Bernoulli bending beam theory, for which cross-sections, after the deformation, remain plain and perpendicular to the neutral surface; furthermore their shape and area do not change. On the stress viewpoint, the shear stress effect and the axial force effect are considered negligible in comparison with the bending effect. The mechanical model deduced from the identified hypotheses includes two kind of non-linearity: the first due to the material and the latter due to large deformations. The mathematical problem associated with the mechanical model, i.e. to compute the bending deformations, consists in solving a non-linear algebraic system and a non-liner second order ordinary differential equation. Thus a numerical algorithm is developed and some examples of specific results are shown in this paper.     

Mixing method influence on compatibility and polymorphism studies by DSC and statistical analysis

Most of the pharmaceutical products are formulated as solid dosage form, which may present drug–excipient interactions that lead to changes in the chemical nature of the drug, such as solubility and bioavailability and may compromise its safety and effectiveness. Differential scanning calorimetry (DSC) is a widely used method for the rapid evaluation of the drug-excipient compatibility and the stability of the mixture formed; however, there is no consensus on the preparation methods of the drug–excipient mixtures. The aim of this study was to investigate the influence of the mixing method on the drug–excipient compatibility studies by means of DSC analysis, using tenofovir disoproxil fumarate as a drug model. Statistical analysis revealed significant differences in the heat of fusion of the drug in the mixtures prepared by several mixing methods. Vortex Mixer with a Pop-Off Cup used for 3 min proved to be very satisfactory for these studies. A polymorphic transition was observed in the mixture prepared with the mortar and pestle. Therefore, this method should be avoided since it may induce errors in the interpretation of DSC results. In this way, the mixing method used to prepare a mixture for studies of interactions between the API and the excipients in a pharmaceutical formulation has a great influence on the results and it must be chosen carefully.     

On cardinal characteristics of Yorioka ideals

Yorioka introduced a class of ideals (parametrized by reals) on the Cantor space to prove that the relation between the size of the continuum and the cofinality of the strong measure zero ideal on the real line cannot be decided in . We construct a matrix iteration of c.c.c. posets to force that, for many ideals in that class, their associated cardinal invariants (i.e., additivity, covering, uniformity and cofinality) are pairwise different. In addition, we show that, consistently, the additivity and cofinality of Yorioka ideals does not coincide with the additivity and cofinality (respectively) of the ideal of Lebesgue measure zero subsets of the real line.