Energy transfer between conjugated polyelectrolytes in layer-by-layer assembled films

We present a study of Fo?rster resonance energy transfer (FRET) between two emissive conjugated polyelectrolytes (CPEs) in layer-by-layer (LbL) self-assembled films as a means of examining their organization and architecture. The two CPEs are a carboxylic acid functionalized polyfluorene (PFl-CO(2)) and thienylene linked poly(phenylene ethynylene) (PPE-Th-CO(2)). The PFl-CO(2) presents a maximum emission at 418 nm, while the PPE-Th-CO(2) has an absorption λ(max) centered at 431 nm, in sufficient proximity for effective FRET. Several LbL films have been constructed using varied concentrations of the deposition solutions and identity of the buffer layers separating the two emissive layers, using a system of either weak polyelectrolytes, poly(allylamine hydrochloride) (PAH)/poly(sodium methacrylate) (PMA), or strong polyelectrolytes, poly(diallylammonium chloride) (PDDA)/poly(styrene sulfonate) sodium (PSS). The efficiency of FRET has been monitored using fluorescence spectroscopy. Initially, the fluorescence of the PFl-CO(2) (E(g) ～ 3.0 eV), which emits at 420 nm, is quenched by the lower band gap PPE-Th-CO(2) (E(g) ～ 2.5 eV). For films using the PAH/PMA system as buffer bilayers and deposited from 1 mM solutions, the PFl-CO(2) fluorescence is progressively recovered as the number of intervening buffer bilayers is increased. Ellipsometry measurements indicate that energy transfer between the two emissive layers is efficient to a distance of ca. 7 nm.     

Rhodium(I)-catalyzed addition of arylboronic acids to (benzyl-/arylsulfonyl)acetonitriles: efficient synthesis of (Z)-β-sulfonylvinylamines and β-keto sulfones

An efficient rhodium(I)-catalyzed addition of arylboronic acids to (benzyl-/arylsulfonyl)acetonitrile is described. Novel β-sulfonylvinylamine products are formed in a stereoselective fashion (Z-alkene). Upon hydrolysis, useful β-keto sulfones are obtained with a broad scope of aryl and sulfonyl substituents.     

Thermal characteristics of bitumen pyrolysis

The pyrolysis behavior of bitumen was investigated using a thermogravimetric analyzer–mass spectrometer system (TG–MS) and a differential scanning calorimeter (DSC) as well as a pyrolysis-gas chromatograph/mass spectrometer system (Py-GC/MS). TG results showed that there were three stages of weight loss during pyrolysis—less than 110, 110–380, and 380–600 °C. Using distributed activation energy model, the average activation energy of the thermal decomposition of bitumen was calculated at 79 kJ mol⁻¹. The evolved gas from the pyrolysis showed that organic species, such as alkane and alkene fragments had a peak maximum temperature of 130 and 480 °C, respectively. Benzene, toluene, and styrene released at 100 and 420 °C. Most of the inorganic compounds, such as H₂, H₂S, COS, and SO₂, released at about 380 °C while the CO₂ had the maximum temperature peaks at 400 and 540 °C, respectively. FTIR spectra were taken of the residues of the different stages, and the results showed that the C–H bond intensity decreased dramatically at 380 °C. Py-GC/MS confirmed the composition of the evolved gas. The DSC revealed the endothermic nature of the bitumen pyrolysis.     

Atroposelective arylation of biaryls by C-H activation

Axial chirality of biaryls is found in natural products, bioactive molecules, ligands and catalysts and their synthesis is therefore highly appealing. Thus, the atroposelective palladium-catalyzed C-H functionalization of chiral biaryl sulfoxides was extended to a direct arylation reaction, affording ortho-terphenyls bearing one atropisomeric axis. The high stereoselectivities, good yields and operational simplicity, along with the traceless character of the sulfoxide moiety allows access to a wide range of optically active o-terphenyls.     

Geometric Inference for Probability Measures

Data often comes in the form of a point cloud sampled from an unknown compact subset of Euclidean space. The general goal of geometric inference is then to recover geometric and topological features (e.g., Betti numbers, normals) of this subset from the approximating point cloud data. It appears that the study of distance functions allows one to address many of these questions successfully. However, one of the main limitations of this framework is that it does not cope well with outliers or with background noise. In this paper, we show how to extend the framework of distance functions to overcome this problem. Replacing compact subsets by measures, we introduce a notion of distance function to a probability distribution in ℝ ^d . These functions share many properties with classical distance functions, which make them suitable for inference purposes. In particular, by considering appropriate level sets of these distance functions, we show that it is possible to reconstruct offsets of sampled shapes with topological guarantees even in the presence of outliers. Moreover, in settings where empirical measures are considered, these functions can be easily evaluated, making them of particular practical interest.     

High-spin nuclear states and persistent currents in mesoscopic rings

An analogy is presented between periodic persistent currents in mesoscopic rings and staggerings of gamma energy transitions from some nuclear high-spin states. Various sources of damping of the expected periodic structures in both physical systems are compared. This discussion provides, in the nuclear case, a tentative explanation of the scarcity of such staggerings, their appearance near ¹⁵⁰Gd and the existence of a spin-window for their observation. Received: 21 July 1997 / Revised version: 13 October 1997