Structural and magnetic properties of the solid solution () YMn1−x(Cu3/4Mo1/4)xO3

Recently, the ferroelectromagnet YMnO₃ has been the focus of interest because it exhibits both antiferromagnetism (Néel temperature 80 K) and ferroelectricity (Curie temperature 914 K). There have been no reports of complete YMn_1−xM_xO₃ solid solutions in which substitution of the foreign M cation preserves the hexagonal P6₃cm structure. In contrast there exist several homeotypic phases with the general formula, Ln_1+nCu_nMO_3+3n (n=1 (M=Ti), 2 (M=V) and 3 (M=Mo); Ln: lanthanide). Several YMn_1−x(Cu_3/4Mo_1/4)_xO₃ compounds have been synthesized. The solid solution, from YMnO₃ (x=0) to YCu_3/4Mo_1/4O₃ (x=1) has been characterized by X-ray diffraction and transmission electron microscopy study. For 0<x<0.9, the compounds are found to crystallize in the non-centrosymmetric structure, space group P6₃cm, of YMnO₃. The Mn-free end member, x=1, crystallizes in a complex multiple cell, the superstructure being associated to Cu³⁺/Mo⁶⁺ cationic ordering. Dilution of the Mn³⁺ magnetic array by the paramagnetic (Cu²⁺) and diamagnetic (Mo⁶⁺) cations is found to decrease the antiferromagnetic ordering temperature and it becomes undetectable for x0.5 compositions.     

Fluorescent polymer cubosomes and hexosomes with aggregation-induced emission

Fluorescent polymer cubosomes and hexosomes with aggregation-induced emission (AIE) were prepared from amphiphilic block copolymers PEG-b-PTPEMA where the hydrophobic block PTPEMA was a polymethacrylate with tetraphenylethene (TPE) as the AIE side group. Four highly asymmetric block copolymers with hydrophilic block weight ratio f_PEG ≤ 20% were synthesized. Cubosomes and hexosomes with strong fluorescence emission were obtained by nanoprecipitation of polymers with f_PEG < 9% in dioxane/water and THF/water systems. Their ordered internal structures were studied by electron microscopy (cryo-EM, SEM and TEM) and the X-ray scattering technique (SAXS). To elucidate the formation mechanisms of these inverted colloids, other parameters influencing the morphologies, like the water content during self-assembly and the organic solvent composition, were also investigated. This study not only inspires people to design novel building blocks for the preparation of functional cubosomes and hexosomes, but also presents the first AIE fluorescent polymer cubosome and hexosome with potential applications in bio-related fields.

Fluorescent Im$\bar{3}$m cubosome and P6mm hexosome with aggregation-induced emission (AIE) were reported, which were formed by amphiphilic block copolymers PEG-b-PTPEMA. The length of hydrophobic block PTPEMA was adjusted to control morphology formation.     

2,3,5,6‐Tetrakis[3,5‐bis(trifluoromethyl)phenoxy]‐2,5‐bis(dimethylamino)2,3,5,6‐tetrabora‐1,4‐dioxane diethyl ether 0.667‐solvate

The title compound, C₃₆H₂₆B₄F₂₄N₂O₆·0.667C₄H₁₀O, has centrosymmetric tetraboradioxane molecules, half each of three of these comprising the asymmetric unit together with a molecule of diethyl ether. Disorder affects most of the CF₃ groups and one ethyl group of the solvent molecule. The B₄O₂ rings are approximately planar and contain two B atoms with trigonal geometry and two with distorted tetrahedral geometry, the B—O bonds for the four‐coordinate B atoms being longer than those for the three‐coordinate B atoms. N—H...O hydrogen bonds link two of the crystallographically independent molecules together in chains, while the third molecule forms discrete trimolecular clusters with two solvent molecules via N—H...O hydrogen bonds. This is the first crystallographically characterized example of a tetrabora‐dioxane molecule containing both four‐ and three‐coordinate B atoms.     

Square‐Planar Carbonylchlororhodium(I) Complexes Containing trans‐Spanning Diphosphine Ligands as Catalysts for the Carbonylation of Methanol

The rhodium(I) complexes trans‐[Rh(diphos)(CO)Cl] 7 (diphos=pbpb), 8 (diphos=nbpb), and 9 (diphos=cbpb) were synthesized (Scheme 4) and used as catalysts for the carbonylation of MeOH to AcOH (Scheme 1). The trans coordination imposed by the rigid C‐spacer framework of the diphos ligands pbpb, nbpb, and cbpb, demonstrated by ³¹P‐NMR and IR spectroscopy of 7 – 9 and unambiguously confirmed by single‐crystal X‐ray structure analysis of 7 , improved the thermal stability of the rhodium(I) system under carbonylation conditions and, hence, the catalytic performance of the complexes. For the catalytic carbonylation of MeOH, the active catalyst could be prepared in situ from the mixture of [Rh(CO)₂Cl]₂ and the corresponding diphos ligand pbpb, nbpb, or cbpb, giving the same results as carbonylation in the presence of the isolated complexes 7, 8 or 9 (see Table). The highest activity was observed for complex 7 (or the mixture [Rh(CO)₂Cl]₂/pbpb, the catalytic turnover number (TON) being 950 after 15 min (170°, 22 bar).     

Fungicidal properties of meso-arylglycosylporphyrins: influence of sugar substituents on photoinduced damage in the yeast Saccharomyces cerevisiae

A series of neutral meso-arylglycosylporphyrins has been tested in order to evaluate their potency as antifungal agents against the yeast Saccharomyces cerevisiae. Photodynamic activity of these molecules results in intracellular damage as evidenced by the loss of clonogenicity and DNA fragmentation. The ability of these photosensitizers to permeate yeast cells is determined by microspectrofluorimetry and is correlated with their antifungal potency. Amphiphilic porphyrin derivatives are shown to exhibit the more pronounced photoactivity.     

Settling of paraffin crystals in cooled middle distillate fuels

The mechanism of action of additives that control the sedimentation of paraffin crystals after their crystallization in model diesel oil has been studied by means of a new experimental approach. The chemical analysis of the crystals and detailed measurements of the sedimentation phenomenon give new insights into this complex process. Thus, the wax antisettling additives used for preventing wax crystal sedimentation adsorb at the surfaces of wax particles and provide them with enhanced colloidal stability. The settling rate is not related to the size of the crystals or the viscosity of the liquid medium, but to the ability of the additives to prevent the aggregation of wax crystals. The reported methodology makes it possible to investigate the fundamental mechanisms, but also to evaluate structure-activity relationships of the various additives used in the petroleum industry.     

Synthesis of chiral N-protected 1,2-dihydro-quinoline-2-carbonitrile and 1,2-dihydro-isoquinoline-1-carbonitrile via an asymmetric Reissert reaction

Addition of cyanide ion to chiral N-acyl-quinolinium and N-acyl-isoquinolinium salts led selectively to 1,2-addition products. Removal of the chiral auxiliary affords the title compounds in pure enantiomeric form.     

A convenient synthesis of new aminomethylenedioxypyrroloindoles via an iminium salt

Cyclization of 2-(1-pyrrolyl)piperonylcarboxamide derivatives gave iminium perchlorates which afforded 9-(N-substituted-imino) and 9-(N-substituted amino)-6,7-methylenedioxypyrrolo[1,2-a]indoles.     

Crystal and molecular structures ofp-(1,1,3,3-tetramethylbutyl)calix[5]arene and its 1 : 1 complex with toluene

A cyclic pentamer was obtained fromp-(1,1,3,3-tetramethylbutyl) phenol. It crystallizes from a mixture of acetone and toluene at room temperature giving a 1 : 1 complex with toluene (compound A), whereas at 50°C the empty form (compound B) is obtained. Crystals of A are orthorhombic, space groupPna2₁,a = 20.083(2),b = 12.936(6),c = 28,423(1) Å,Z = 4, finalR value = 0.067. The empty form, B, is monoclinicP2₁/c,a = 18.695(2),b = 11.673(5),c = 35.100(4) Å, = 114.33(1),Z = 4, finalR value = 0.135. The macrocycle is in the cone conformation for both compounds; the toluene molecule lies in the cone as often found for calix[4]arenes.     

Galactose oxidase models: solution chemistry, and phenoxyl radical generation mediated by the copper status

Galactose oxidase (GO) is an enzyme that catalyzes two-electron oxidations. Its active site contains a copper atom coordinated to a tyrosyl radical, the biogenesis of which requires copper and dioxygen. We have recently studied the properties of electrochemically generated mononuclear Cu(II)-phenoxyl radical systems as model compounds of GO. We present here the solution chemistry of these ligands under various copper and dioxygen statuses: N(3)O ligands first chelate Cu(II), leading, in the presence of base, to [Cu(II)(ligand)(CH(3)CN)](+) complexes (ortho-tert-butylated ligands) or [(Cu(II))(2)(ligand)(2)](2+) complexes (ortho-methoxylated ligands). Excess copper(II) then oxidizes the complex to the corresponding mononuclear Cu(II)-phenoxyl radical species. N(2)O(2) tripodal ligands, in the presence of copper(II), afford directly a copper(II)-phenoxyl radical species. Addition of more than two molar equivalents of copper(II) affords a Cu(II)-bis(phenoxyl) diradical species. The donor set of the ligand directs the reaction towards comproportionation for ligands possessing an N(3)O donor set, while disproportionation is observed for ligands possessing an N(2)O(2) donor set. These results are discussed in the light of recent results concerning the self-processing of GO. A path involving copper(II) disproportionation is proposed for oxidation of the cross-linked tyrosinate of GO, supporting the fact that both copper(I) and copper(II) activate the enzyme.