Comparative dielectric and thermotropic properties of liquid crystalline polyesters as a function of mesogen group and flexible thioether group length

Two polyesters containing rigid biphenyl and hydroquinone bisbenzoate groups and presenting flexible thioether moieties with different lengths (14 elements in the flexible group) have been carried out using a reaction of the Michaël type. The properties of these polyesters have been compared to those of polyesters of the same type presenting shorter flexible groups (11 elements). All these polymers present thermotropic properties: the biphenyl ones are smectic and the bisbenzoate ones are nematic. The biphenyl polyesters present two types of dielectric relaxations: α and β. The bisbenzoate ones show three relaxations, α and two β (β and β^′). The lengthening of the flexible group increases significantly the flexibility of the molecular chains.     

Synthesis and characterization of mannosyl mimetic derivatives based on a beta-cyclodextrin core

The synthesis of branched beta-cyclodextrins substituted with mannosyl mimetic derivatives at one primary hydroxy group is described. It was shown that the self-inclusion phenomenon observed for the target compounds in water did not preclude the inclusion properties of the cyclodextrin moiety.     

Bifurcated, modular syntheses of chiral annulet triazacyclononanes

Three chiral 2,6-disubstituted tri-N-methyl azamacrocycles have been prepared by modular methods. These macrocycles were accessed from three chiral 1,4,7-triazaheptanes intermediates that were prepared by two independent routes. The first of these routes involved the benzylamine opening of chiral tosyl aziridines followed by debenzylation but was problematic on solubility grounds. A second, more effective, route was developed which avoided debenzylation by using ammonia in the nucleophilic opening of chiral tosyl aziridines.     

Monomeric (dialkylamino)boranes: a new and efficient boron source in palladium catalyzed C-B bond formation with aryl halides

Thermal decomposition of hindered amine-borane adducts leads in high yields to monomeric (dialkylamino)boranes R1R2N-BH2 (R1 and R2 = alkyl) that are new and efficient boron-sources in the Pd0 catalyzed borylation reaction affording monomeric aryl(dialkylamino)boranes R1R2N-BHR3 (R3 = aryl).     

Structural insights into aluminum chlorofluoride (ACF)

The structure of the very strong solid Lewis acid aluminum chlorofluoride (ACF, AlCl(x)F(3-x), x = 0.05-0.3) was studied by IR, ESR, Cl K XANES, (19)F MAS NMR, and (27)Al SATRAS NMR spectroscopic methods and compared with amorphous aluminum fluoride conventionally prepared by dehydration of alpha-AlF(3) x 3H(2)O. The thermal behavior of both compounds was investigated by DTA and XRD. In comparison to ACF, amorphous AlF(3) prepared in a conventional way is not catalytically active for the isomerization reaction of 1,2-dibromohexafluoropropane, which requires a very strong Lewis acid. Both compounds are mainly built up of corner-sharing AlF(6) octahedra forming a random network. The degree of disorder in ACF is higher than in amorphous AlF(3). Terminal fluorine atoms were detected in ACF by (19)F NMR. The chlorine in ACF does not exist as a separate, crystalline AlCl(3) phase. Additionally, chlorine-containing radicals, remaining from the synthesis, are trapped in cavities of ACF. These radicals are stable at room temperature but do not take part in the catalytic reaction.     

Structurally Simple Osmium(II) Polypyridyl Complexes as Photosensitizers for Photodynamic Therapy in the Near Infrared**

Five osmium(II) polypyridyl complexes of the general formula [Os(4,7-diphenyl-1,10-phenanthroline)₂ L ]²⁺ were synthesized as photosensitizers for photodynamic therapy by varying the nature of the ligand L . Thanks to the pronounced π-extended structure of the ligands and the heavy atom effect provided by the osmium center, these complexes exhibit a high absorption in the near-infrared (NIR) region (up to 740 nm), unlike related ruthenium complexes. This led to a promising phototoxicity in vitro against cancer cells cultured as 2D cell layers but also in multicellular tumor spheroids upon irradiation at 740 nm. The complex [Os(4,7-diphenyl-1,10-phenanthroline)₂(2,2′-bipyridine)]²⁺ was found to be the most efficient against various cancer cell lines, with high phototoxicity indexes. Experiments on CT26 tumor-bearing BALB/c mice also indicate that the Os^II complexes could significantly reduce tumor growth following 740 nm laser irradiation. The high phototoxicity in the biological window of this structurally simple complex makes it a promising photosensitizer for cancer treatment.     

X-ray Crystal Structure, ab Initio Calculations, and Reactivity of 1,3,2lambda(5)-Diazaphosphetes: A New Type of 4-pi-Electron 4-Membered Heterocycle

The structure of P,P-bis(diisopropylamino)-4-phenyl-1,3,2lambda(5)-diazaphosphete, 1a, has been determined by a single-crystal X-ray diffraction study (C(19)H(33)N(4)P, monoclinic system, space group P2(1), a = 9.482(1) ?, b = 11.374(3) ?, c = 9.668(2) ?, beta = 97.16(1) degrees, Z = 2). According to quantum chemical calculations at an RHF level of optimization utilizing the 6-31g(d,p) basis set, 1a has a zwitterionic structure with the negative charge delocalized on the NCN allylic fragment and the positive charge localized at the phosphorus. Heterocycle 1a reacts with water and benzaldehyde affording N-phosphoranylbenzamidine 3 (95% yield) and the expected aza-Wittig adduct 4 (85% yield), respectively. Addition of 1 equiv of methyl trifluoromethanesulfonate and of 2 equiv of BH(3).THF to 1a affords cyclic phosphonium salt 5 (94% yield) and the bis(borane) adduct 6a (90% yield), respectively. Dimethyl acetylenedicarboxylate slowly reacts with 1a giving rise to 1,3,4lambda(5)-diazaphosphinine, 9, in 70% yield. The X-ray crystal structures of products 2,3, and 6a are reported (2: C(26)H(38)N(5)P, monoclinic system, space group C2/c, a = 16.337(8) ?, b = 19.810(2) ?, c = 8.800(2) ?, beta = 117.68(2) degrees, Z = 4. 3: C(19)H(35)N(4)OP, orthorhombic system, space group P2(1)2(1)2(1), a = 9.090(1) ?, b = 12.955(2) ?, c = 17.860(3) ?, Z = 4. 6a: C(19)H(39)B(2)N(4)P, orthorhombic system, space group P2(1)2(1)2(1), a = 10.340(1) ?, b = 13.247(1) ?, c = 16.996(1) ?, Z = 4).     

Effect of pH on interface composition and on quality of oil-in-water emulsions made with hen egg yolk

Constituents of egg yolk are key ingredients of many food emulsions. They contribute to create an interfacial film between oil and water, which determines largely the characteristics of the emulsions. Food emulsions prepared with yolk are made at various pHs. However, the effect of pH on the adsorption of yolk constituents and on the composition of the interfacial film is not known. The present study deals with the influence of pH (3, 6 and 9), on protein interface concentration and composition, change in interfacial tension, and oil droplet diameter, of emulsions made with yolk. Emulsions were prepared as follows: 0.5% w/v of yolk; oil volume fraction: 0.375, homogenisation rate: 20 000 rpm/2 min. pH 6 provided the best conditions to prepare emulsion with yolk. The average diameter of oil droplets was lower at pH 6 (8.5 μm) than at pH 3 (11.8 μm) and pH 9 (13.5 μm). The interfacial protein concentration was higher at pH 6 (1.7 mg m⁻²) than at pH 3 and pH 9 (0.5 mg m⁻²). At pH 6, all the proteins of yolk, except phosvitin, were adsorbed at the interface and the interfacial tension at steady-state was lower (10 mN m⁻¹) than at pH 3 (15 mN m⁻¹) and pH 9 (30 mN m⁻¹). At pH 3, proteins at the interface are mainly phosvitin, and, at pH 9, some apoproteins of LDL and HDL. The pH modulates the composition of yolk proteins at the interface, mainly by modifying the net charge of the proteins causing their repulsion or dimerisation.