Conjugated Azoalkenesi Part III. Synthesis of Sone Phosphorous Azoalkenes

Recently, some of us reviewed the synthes is and chemical reactions of conjugated azoalkenes.¹ Emphasis was placed on the fact that these derivatives represent at the same time interesting products and useful intermediates in organic chemistry. In fact, conjugated azoolefins undergo a wide range of 1,4-additions, (3+2)- and (4+2)-cycloadditions allowing various functionalizations of the carbon atom adjacent to the carbonyl group, and the construction of many types of interesting five - and six-membered heterocycles, such as widely substituted pyrrole and pyridazine rings. These relevant synthetic objectives appear not to be smoothly obtained by other procedures. In addition, many of the compounds produced from conjugated azoalkenes can profitably be employed in the preparation of natural, pharmaceutical, and phytopharmaceutical products.¹     

Modified Guanines as Constituents of Smart Ligands for Nucleic Acid Quadruplexes

Repetitive guanine‐rich nucleic acid sequences play a crucial role in maintaining genome stability and the cell life cycle and represent potential targets for regulatory drugs. Recently, it has been demonstrated that guanine‐based ligands with a porphyrin core can be used as markers of G‐quadruplex assemblies in cell tissues. Herein, model systems of guanine‐based ligands are explored by DFT methods. The energies of formation of modified guanine tetrads and those of modified tetrads stacked on the top of natural guanine tetrads have been calculated. The interaction energy has been decomposed into contributions from hydrogen bonding, stacking, and ion coordination and a twist–rise potential energy scan has been performed to find the individual local minima. Energy decomposition analysis reveals the impact of various substituents (F, Cl, Br, I, Me, NMe₂) on individual energy terms. In addition, cooperative reinforcement in forming the modified and stacked tetrads, as well as the frontier orbitals participating in the hydrogen‐bonding framework involving the HOMO–LUMO gap between the occupied σ_HOMO on the proton‐accepting C=O and =N? groups and unoccupied σ_LUMO on the N?H groups, has been studied. The investigated systems are demonstrated to have a potential in ligand development, mainly due to stacking enhancement compared with natural guanine, which is used as a reference.     

Biodegradable aromatic copolyesters made from bicyclic acetalized galactaric acid

Random poly(hexamethylene terephthalate‐co‐galactarate)s and poly(dodecamethylene terephthalate‐co‐galactarate)s copolyesters covering the whole range of compositions were obtained with weight‐average molecular weights of ～30,000–50,000 g mol^?1 by melt polycondensation. They were thermally stable above 300 °C, and displayed T_g in the +20 to ?20 °C range with values steadily decreasing with the content in galactarate units. All the copolyesters were semicrystalline with T_m between 50 and 150 °C and those made from dodecanediol were able to crystallize from the melt at a crystallization rate depending on composition. Copolyesters containing up to 50% of galactaric units retained the crystal structure of their respective polyterephthalate homopolyesters, whereas they adopted the structure of the respective polygalactarates when the content in Galx units reached 70%. Stress‐strain essays revealed decay in the mechanical parameters as the aromatic units were replaced by Galx. Incubation in aqueous buffer revealed that hydrolysis of the polyesters were largely enhanced by copolymerization and evidenced the capacity of the Galx unit for making aromatic polyesters susceptible to biodegradation. A detailed NMR analysis complemented by SEM observations indicated that hydrolysis took place by preferred splitting of galactarate ester bonds with releasing of alkanediol and Galx‐diacid. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Nature of Alkali- and Coinage-Metal Bonds versus Hydrogen Bonds

We have quantum chemically studied the structure and nature of alkali- and coinage-metal bonds (M-bonds) versus that of hydrogen bonds between A−M and B⁻ in archetypal [A−M⋅⋅⋅B]⁻ model systems (A, B=F, Cl and M=H, Li, Na, Cu, Ag, Au), using relativistic density functional theory at ZORA-BP86-D3/TZ2P. We find that coinage-metal bonds are stronger than alkali-metal bonds which are stronger than the corresponding hydrogen bonds. Our main purpose is to understand how and why the structure, stability and nature of such bonds are affected if the monovalent central atom H of hydrogen bonds is replaced by an isoelectronic alkali- or coinage-metal atom. To this end, we have analyzed the bonds between A−M and B⁻ using the activation strain model, quantitative Kohn-Sham molecular orbital (MO) theory, energy decomposition analysis (EDA), and Voronoi deformation density (VDD) analysis of the charge distribution.     

Bis[N,N′‐diisopropylbenzamidinato(−)]silicon(II): Lewis Acid/Base Reactions with Triorganylboranes

Reaction of the donor‐stabilized silylene 1 (which is three‐coordinate in the solid state and four‐coordinate in solution) with BEt₃ and BPh₃ leads to the formation of the Lewis acid/base complexes 2 and 3 , respectively, which are the first five‐coordinate silicon compounds with an Si?B bond. These compounds were structurally characterized by crystal structure analyses and by multinuclear NMR spectroscopic studies in the solid state and in solution. Additionally, the bonding situation in 2 and 3 was analyzed by quantum chemical studies.     

An Edible Oil Enriched with Lycopene from Pink Guava (Psidium guajava L.) Using Different Mechanical Treatments

According to the regulations of the United States Food and Drug Administration (FDA), organic solvents should be limited in pharmaceutical and food products due to their inherent toxicity. For this reason, this short paper proposes different mechanical treatments to extract lycopene without organic solvents to produce an edible sunflower oil (SFO) enriched with lycopene from fresh pink guavas (Psidium guajava L.) (FPGs). The methodology involves the use of SFO and a combination of mechanical treatments: a waring blender (WB), WB+ high-shear mixing (HSM) and WB+ ultrafine friction grinding (UFFG). The solid:solvent (FPG:SFO) ratios used in all the techniques were 1:5, 1:10 and 1:20. The results from optical microscopy and UV–vis spectroscopy showed a correlation between the concentration of lycopene in SFO, vegetable tissue diameters and FPG:SFO ratio. The highest lycopene concentration, 18.215 ± 1.834 mg/g FPG, was achieved in WB + UFFG with an FPG:SFO ratio of 1:20. The yield of this treatment was 66% in comparison to the conventional extraction method. The maximal lycopene concentration achieved in this work was significantly higher than the values reported by other authors, using high-pressure homogenization for tomato peel and several solvents such as water, SFO, ethyl lactate and acetone.