Bottom-up assembly of high density molecular nanowire cross junctions at a solid/liquid interface

A monoalkylated tetrathiafulvalene derivative forms multilayer structures at the solid-liquid interface, with high density of cross junctions, which are interesting for molecular electronic circuit self-assembly.     

Influence of the macromolecular architecture on the self-assembly of amphiphilic copolymers based on poly(N,N-dimethylamino-2-ethyl methacrylate) and poly(epsilon-caprolactone)

The self-assembly of amphiphilic copolymers consisting of poly( N, N-dimethylamino-2-ethyl methacrylate) (PDMAEMA) and poly(-caprolactone) (PCL) segments arranged in graft and linear diblock architectures was investigated in this work by means of dynamic light scattering (DLS) in aqueous solution and by atomic force microscopy (AFM) on thin deposits. The solid-state deposits of the micelles were generated by a "freeze-drying" technique that preserves the initial micelle morphology in solution. A comparison between the morphological properties of graft copolymers with corresponding diblock copolymers was established to demonstrate the effect of the copolymer architecture on the micelle structure and organization.     

Nanorubbing of polythiophene surfaces

This work describes a new orientation method for semicrystalline poly(3-hexylthiophene) (P3HT) thin films, coupling nanorubbing and subsequent crystallization. Using the stylus of an atomic force microscope, we align the polymer chains on P3HT surfaces with a spatial and geometrical control of the oriented domains (nanorubbing). These chain-aligned structures can be made permanent thanks to the crystallization process, which propagates the orientation obtained at the surface to the bulk.     

Donor/acceptor-substituted anthradithiophene materials: synthesis, optical and electrochemical properties

The synthesis and characterization of two new anthradithiophene (ADT) derivatives bearing electron donating (triphenylamine) or accepting (5-formylthiophen-2-yl unit) moieties have been performed to assess their potential as materials for organic photovoltaics. Optical spectroscopy was used to evaluate the effect of electron rich/poor substituents on the visible absorption spectrum and on the stability towards photo-oxidation. The results are interpreted with the assistance of quantum-chemical calculations and cyclic voltammetry experiments.     

Evidence of the synergetic role of charged species and atomic oxygen in the molecular etching of PTFE surfaces for hydrophobic surface synthesis

The transformation of a poly(tetrafluoroethylene) (PTFE) hydrophobic surface into a superhydrophobic one using a low pressure RF plasma is explored using optical emission spectrometry (OES), X-ray photoelectron spectroscopy (XPS), water contact angle (WCA) measurements, mass measurements, and atomic force microscopy (AFM). It is shown that the increase in contact angle is due to an increase of roughness provoked by a chemical etching of the surface. We propose a molecular mechanism for etching that requires the simultaneous presence of atomic oxygen and negatively charged species (electrons) at the PTFE surface.     

Noncovalent control for bottom-up assembly of functional supramolecular wires

Noncovalent bonds have been used to assemble stacks of pi-electron-rich moieties at a surface, generating a pathway for charge transport. The system is comprised of a tetrathiafulvalene (TTF) derivative incorporating two amide groups which fasten the relative orientations of the electroactive moieties in the supramolecular polymer that is formed at the surface of graphite in octanoic acid. Scanning tunneling microscopy (STM) combined with molecular mechanics calculations has been used to prove the structure of the wires, and theory, corroborated with STS experiments, predicts that they are promising superstructures for charge transport.     

Chiral amphiphilic self-assembled alpha,alpha'-linked quinque-, sexi-, and septithiophenes: synthesis, stability and odd-even effects

The synthesis, characterization, and self-assembly in butanol of a series of well-defined alpha,alpha'-linked quinqui-, sexi-, and septithiophenes substituted, via ester links at their termini, by chiral oligo(ethylene oxide) chains carrying an alpha, beta, delta, and epsilon methyl, respectively, are reported. Studies of the self-assembly of these molecules using UV/visible absorption, luminescence, and circular dichroism spectroscopies reveal, for the sexithiophene case, that the magnitude of the observed Cotton effect in the aggregates diminishes progressively as the chiral substituent is moved away from the thiophene segment. The stability of the assemblies increases with the length of the oligothiophene and as the substituent chiral unit is moved away from the aromatic core, being greatest for the unsubstituted case. The sign of the Cotton effect alternates in an "odd/even" manner as the position of the chiral substituent is moved along the oligo(ethylene oxide) chain and on going from the quinquethiophene to the septithiophene having the same side chain. Atomic force microscopy on materials deposited from solution on an aluminum or glass surface and optical measurements show that capsules are formed from the oligothiophenes with H-type packing of the aromatic segments.     

Substrate-directed asymmetric induction in the rhodium catalyzed hydroformylation of C-allyl-sugars: The influence of the glycoside-moiety on the selectivity of the reaction

α- and β-C-allylgalactopyranosides 1c and 1d, α-C-allylazaglucopyranoside 1e and α-C-allylfruttofuranoside 1f were hydroformylated at low temperatures affording a mixture of linear and branched aldehydes in regioisomeric and diastereoisomeric ratios depending on the starting alkene. The results obtained have allowed us to study the influence of the different structural features of the sugar moiety on the regio- and diastereoselectivity of the hydroformylation reaction.     

Sheath and electron density dynamics in the normal and self-pulsing regime of a micro hollow cathode discharge in argon gas

A microplasma is generated in the microhole (400 μm diameter) of a molybdenum-alumina-molybdenum sandwich (MHCD type) at medium pressure (30–200 Torr) in pure argon. Imaging and emission spectroscopy have been used to study the sheath and electron density dynamics during the stationary normal regime and the self-pulsing regime. Firstly, the evolution of the microdischarge structure is studied by recording the emission intensity of the Ar (5p[3/2]₁–4s[3/2]₁)_{1}) line at 427.217 nm, and Ar⁺ (4p′ ²P_3/2–4s′ ²D_5/2)_{5/2}) line at 427.752 nm. The maximum of the Ar⁺ line is located in the vicinity of the sheath-plasma edge. In both regimes, the experimental observations are consistent with the position of the sheath edge calculated with an ionizing sheath model. Secondly, the electron density is recorded by monitoring the Stark broadening of the H_b_\beta-line. In the self-pulsing regime at 150 Torr, the electron density reaches its maximum value of 4 × 10¹⁵ cm^-3, a few tens of ns later than the discharge current maximum. The electron density then decays with a characteristic decay time of about 2 μs, while the discharge current vanishes twice faster. The electron density in the steady-state regime is two orders of magnitude lower, at about 6–8 × 10¹³ cm^-3.     

PLA-PMMA blends: A study by XPS and ToF-SIMS

This paper reports which are the possibilities of quantification by time of flight secondary ion mass spectrometry (ToF-SIMS) for some polymer blends. In order to assess the composition of the mixtures, we studied first different poly(l-lactide)/polymethylmethacrylate (PLA/PMMA) blends by X-ray photoelectron spectroscopy (XPS), this technique being quantitative. By XPS fitting of the C 1s level, we found a very good agreement of the measured concentrations with the initial compositions. Concerning ToF-SIMS data treatment, we used principal component analysis (PCA) on negative spectra allowing to discriminate one polymer from the other one. By partial least square regression (PLS), we found also a good agreement between the ToF-SIMS predicted and initial compositions. This shows that ToF-SIMS, in a similar way to XPS, can lead to quantitative results. In addition, the observed agreement between XPS (60-100 Å depth analyzed) and ToF-SIMS (10 Å depth analyzed) measurements show that there is no segregation of one of the two polymers onto the surface.