Reactivity of silyl-substituted heterobimetallic iron-platinum hydride complexes towards unsaturated molecules: Part II. Insertion of trifluoropropyne and hexafluorobutyne into the platinum-hydride bond

Insertion of hexafluorobutyne into the Pt-H bond of the heterobimetallic complexes [(OC)₃Fe{Si(OMe)₃}(μ-Ph₂PXPPh₂)Pt(H)(PPh₃)] (1a X = CH₂; 1b X = NH) yields the σ-alkenyl complexes [(OC)₃Fe{μ-Si(OMe)₂(OMe)}(μ-Ph₂PXPPh₂)Pt{C(CF₃)C(H)CF₃}] (3a X = CH₂; 3b X = NH). This insertion reaction is accompanied by dissociation of the platinum bound PPh₃ ligand and saturation of the vacant coordination site by a dative μ−η²-Si-O → Pt interaction. Addition of the Pt-H bond of 1a across the triple bond of 3,3,3-trifluoropropyne affords in a regiospecific manner [(OC)₃Fe{μ-Si(OMe)₂(OMe)}(μ-dppm)Pt{C(CF₃)CH₂}] (2) having the trifluoromethyl substituent on the α-carbon. Addition of RNC to 3 affords the isocyanide adducts [(OC)₃Fe{Si(OMe)₃}(μ-Ph₂PXPPh₂)Pt(CNR){C(CF₃)C(H)CF₃}] (4a R = t-Bu, X = CH₂; 4b R = 2,6-xylyl, X = CH₂; 4c R = 2,6-xylyl, X = NH). In dichloromethane solution 3a is gradually transformed into the C₄F₆-bridged compound [(OC)₃Fe(μ-dppm)(μ-CF₃CCCF₃)Pt(CO)] 5. The Pt-bound carbonyl ligand of 5 is displaced by xylylisocyanide or trimethylphosphite affording the derivatives [(OC)₃Fe(μ-dppm)(μ-CF₃CCCF₃)Pt(CNxylyl)] 6 and [(OC)₃Fe(μ-dppm)(μ-CF₃CCCF₃)Pt{P(OMe)₃}] 7. The molecular structures of 4a, 5 and 6 have been determined by X-ray diffraction studies.     

EVALUATION OF NEW BENZOPORPHYRIN DERIVATIVES WITH ENHANCED PDT EFFICACY*

Abstract— A first report on the biological evaluation of a series of isomerically pure benzoporphyrin derivatives ( cis- and frarcs-isomers) as methyl esters is described. In preliminary in vivo studies, the n- bexyl ether analogues of both cis- and trans -isomers of benzoporphyrin derivatives were found to be more active than the industrially prepared benzoporphyrin derivative, a mixture of monocarboxylic acids (BPDMA, Quadralogic Technologies, Vancouver). Further studies with 4-de-vinyl-4-(I-hexyloxyethyl) benzoporphyrin derivative showed that, like BPDMA, it had reduced residual skin phototoxicity compared in mice with Photofrin®. The uptake and clearance characteristics of BPDMA were also compared with the 4-(1-hexyloxyethyl)-derivative by in vivo reflection spectroscopy.     

Influence of the aggregation state in solution on the supramolecular organization of adsorbed type I collagen layers

In the last years, adsorbed collagen was shown to form layers with a supramolecular organization depending on the substrate surface properties and on the preparation procedure. If the concentration of collagen and the duration of adsorption are sufficient, fibrillar collagen structures are formed, corresponding to assemblies of a few molecules. This occurs more readily on hydrophobic compared to hydrophilic surfaces. This study aims at understanding the origin of such fibrillar structures and in particular at determining whether they result from the deposition of fibrils formed in solution or from the building of assemblies at the interface. Therefore, type I collagen solutions with an increasing degree of aggregation were prepared, using the “neutral-start” approach, by ageing pH 5.8 solutions at 37 °C for 15 min, 2 or 7 days. The obtained solutions were used to investigate the influence of collagen aggregation in solution on the supramolecular organization of adsorbed collagen layers, which was characterized by X-ray photoelectron spectroscopy and atomic force microscopy. Polystyrene and plasma-oxidized polystyrene were chosen as substrates for the adsorption. The size and the density of collagen fibrils at the interface decreased upon increasing the degree of aggregation of collagen in solution. This is explained by a competitive adsorption process between monomers and aggregates of the solution, turning at the advantage of the monomers. More aggregated solutions, which are thus depleted in free monomers, behave like less concentrated solutions, i.e. lead to a lower adsorbed amount and less fibril formation at the interface. This study shows that the supramolecular fibrils observed in adsorbed collagen layers, especially on hydrophobic substrates, are not formed in the solution, prior to adsorption, but are built at the interface, through the assembly of free segments of adsorbed molecules.     

Refined inequalities on graded Lie groups

We construct a Littlewood–Paley decomposition associated to a Rockland operator on graded Lie groups, which allows us to deduce refined Gagliardo–Nirenberg, Sobolev and Hardy inequalities.     

FAIMS-MS-IR spectroscopy workflow: a multidimensional platform for the analysis of molecular isoforms

An original workflow allowing inline FAIMS separation, electrospray ionization, mass analysis and ion spectroscopy (IRMPD: InfraRed Multiple Photon Dissociation) is presented for multidimensional molecular analysis. This new instrument consists of an ultraFAIMS (Owlstone) device interfaced to a linear ion trap (LTQ XL Thermo Scientific) which was modified for IRMPD spectroscopy. Two modes of operation are demonstrated on an isomeric mixture of paracetamol and 2-phenylglycine. In the first mode a FAIMS (high-Field Asymmetric waveform Ion Mobility Spectrometry) separation of the isomers is performed with a static compensation field for mass- and isomer- selective ion spectroscopy. In the second mode, the compensation field is scanned while the ions are irradiated at a fixed wavenumber. The advantages of this workflow as compared to traditional FAIMS-MS and IRMPD spectroscopy are described. The potential of the two modes for molecular spectroscopy and analytical applications, in particular the new “omics” are discussed.     

Access to New Endoperoxide Derivatives by Electrochemical Oxidation of Substituted 3‐Azabicyclo[4.1.0]hept‐4‐enes

A series of substituted 3‐azabicyclo[4.1.0]hept‐4‐ene derivatives were prepared and analysed by cyclic voltammetry. Preparative aerobic electrochemical oxidation reactions were then carried out. Three original endoperoxides were isolated, characterised and subjected to antimalarial and cytotoxicity activity assays.     

Paper strengthening by polyaminoalkylalkoxysilane copolymer networks applied by spray or immersion: a model study

Two di-alkoxysilanes, with (AMDES, aminopropylmethyldiethoxysilane) or without (DMDES, dimethyldiethoxysilane) an amine function, and a tri-alkoxy aminosilane (APTES, aminopropyltriethoxysilane) as well as their mixtures were introduced in paper as fiber strengthening agents. The polymerization and copolymerization of these polysiloxanes in the paper were investigated. In all the cases where APTES was present, the formation of networks was established by measuring the soluble fraction amount extracted from the treated papers. A slight decrease of the opacity of the paper sheets when AMDES was part of the treatment was noted. The presence of APTES reduced this opacity loss. The study of the physicochemical properties of the treated paper (mechanical strength and alkalinity) demonstrated that, besides the required deacidification feature, the different treatments allowed an efficient strengthening of the cellulose fibers to various extents. Contact angle measurements indicated a decrease of the hydrophilic character of papers treated with the mixture APTES/AMDES and the occurrence of a hydrophobic character of the papers treated with APTES alone. These results were consistently obtained for both spray and immersion treatment processes.     

New Chiral Ortho-P,S-Difunctionalized Aromatic Compounds

Abstract

A new method to prepare enantioenriched sulfinates was developed to obtain optically active ortho-methylsulfinyl(phenylphosphonates). It consists of a diastereoselective oxidation of sulfenates to sulfinates. Additionally, preliminary results concerning the synthesis of ortho-phophonylated benzylic thiol derivatives via a new P═S to P═C [1,4]-rearrangement and a first synthetic application of these compounds are also described.