Amphiphilic dyes for NLO in LB-films

The influence of structural variations of phenyl-hydrazones and stilbazium salts on monolayer behaviour and second-harmonic generation in LB-monolayers is discussed. In contrast to the stilbazium salts the variation of the substituents of the phenylhydrazones does not influence the absorption maximum of the dyes in resonance enhancement of the nonlinearity. This allows a direct comparison of the substitution pattern on SHG.

Continuous fractionation of poly[(dimethylimino)decamethylene bromide] and molecular weight dependence of the glass transition

30 g of the ionene poly[(dimethylimino)decamethylene bromide] were fractionated by a continuous counter-current extraction method (CPF) using ethylene glycol monoethyl ether as the solvent and diisopropyl ether as the non-solvent component. The efficiency of the separation was checked by viscometry and gel-permeation chromatography (GPC) measurements. Eight fractions of different molar mass were prepared for differential scanning calorimetry (DSC) experiments. With bromide as counter-ion, the glass transition temperature of the ionene increases from ca. 60 to 85°C as the intrinsic viscosity of this material (in 0,4 M aqueous solutions of KBr at 25°C) rises from ca. 14 to 22 mL/g. When bromi…

Influence of chain length on the molecular dynamics of an aliphatic ionene

An aliphatic random copolymer ionene (a cationic polyelectrolyte with N + in the repeat unit), was fractionated with the continuous polymer fractionation and investigated for its molecular weight dependent properties. The fractions were analyzed with GPC and capillary viscometry for their molecular weight. Glass transition temperatures were determined with DSC and a strong molecular weight dependence was observed, but no influence in the ionic conductivity was observed. The temperature dependency of ionic conductivity in ionenes is described.

About 340 g of a cycloaliphatic ionene (see formula given in the introduction) were fractionated by a continuous countercurrent extraction method (CPF). The efficiency of the separation was checked by viscometry and gel permeation chromatography (GPC). Ten different fractions with number average molecular masses between 16 000 and 29 000 D were obtained and their glass transition temperatures T g determined by differential scanning calorimetry (DSC) for their bromide and tetrafluoroborate salts. No molecular weight dependence of T g was found, in contrast to recently reported results with aliphatic ionenes, where - in case of the bromide - T g increases with rising molecular weight.

Chemische charakterisierung des kettenaufbaus und kristallisationsverhaltens von copolymeren aus 3,3-bis(chlormethyl)oxetan und β-propiolacton

Aus 3,3-Bis(chlormethyl)oxetan (1) und β-Propiolacton (2) wurden durch kationische Polymerisation Copolymere hergestellt, in denen Propiolactoneinheiten bis zu einem Molenbruch von 0,16 eingebaut sind. Das Copolymerisationsverhalten wurde untersucht, und die Copolymerisationsparameter wurden bestimmt. Die Copolymeren wurden kristallisiert und die Einkristalle hinsichtlich ihrer Zusammensetzung und Morphologie charakterisiert. Durch selektive Umesterung in den amorphen Bereichen der suspendierten Einkristalle wurde die Verteilung der aus β-Propiolacton gebildeten Einheiten (PL) uber den Kristall untersucht, und die Ergebnisse mit Abbauversuchen an den gelosten Copolymeren wurden verglichen. …

Characterization of semicrystalline random copolymers by small-angle neutron scattering

A new method is introduced to determine the degree of partitioning of noncrystallizable comonomer units (B units) between the two phases of a semicrystalline random copolymer. The method is based on the comparison of the intensities of small-angle neutron and x-ray scattering (SANS and SAXS, respectively). By this technique two quantities can be evaluated: the difference Δρ of the mass densities between the crystalline and the disordered regions, and the concentration fluctuations of the B units in the two phases. It is found that SANS is very sensitive to the presence of small amounts of B units if their scattering length is sufficiently different from that of the A units. This will be the…

ZnO-latex hybrids obtained by polymer-controlled crystallization: a spectroscopic investigation.

Micro- and submicrosized ZnO-polymer hybrid materials were synthesized by precipitating zinc oxide from an aqueous medium in the presence of poly(styrene-acrylic acid) latex nanoparticles, prepared by miniemulsion polymerization. Up to 10 wt % of the latex becomes incorporated into the crystals. Although the long-range order of the inorganic material is essentially not altered by the polymer, studies by photoluminescence (PL) spectroscopy and electron paramagnetic resonance (EPR) show that the latex particles influence the optical and paramagnetic properties of the hybrids, which can be correlated with changes in the defect structure. Typical PL emission spectra showed a narrow UV peak and …

Polymides 3a and 3b with stiff-chains bearing trioxaoctyl or tetraoxaundecyl side chains were synthesized and characterized. The polycondensation was done with pyromellitic anhydride and N,N′-bis(1-imidazolylcarbonyl)-2,5-(1,4,7-trioxaoctyl)- or 2,5-(1,4,7,10-tetraoxaundecyl)-1,4-phenylenediamine (2a or 2b). 3b, being sufficiently soluble, was characterized by 13C NMR spectroscopy. The results of IR and 13C NMR spectroscopy prove the presence of the correct imide structure. In solid state 3a and 3b form layered structures with the side chains being in a disordered state.

Low temperature plasma treatment of monomolecular Langmuir-Blodgett films

Abstract The structure of the surface layer of materials is usually quite different from the bulk. Detailed information about the surface structure is often not available. This, together with the complex nature of low temperature plasma treatment, hinders the investigations of plasma chemical processes on solid surfaces. Monomolecular Langmuir-Blodgett (LB) structures offer a unique opportunity to prepare model surfaces with known thickness and molecular architecture. From the data obtained, the depth of the Ar plasma influence on solid organic surfaces was estimated to be about 400–1000 A depending on the nature of the surface layer. An oxygen plasma penetrates deeper with a penetration li…

ChemInform Abstract: Preformed Polymers for Langmuir-Blodgett Films - Molecular Concepts

The use of preformed polymers for the preparation of Langmuir-Blodgett (LB) multilayers is reviewed. Principles for polymer self-organization are outlined and the appropriate molecular designs are discussed. Recent developments in the different classes of polymers for LB multilayers are presented, and their outstanding properties highlighted.

Photosensitive polymeric amphiphiles: Irradiation-induced structural changes in langmuir-blodgett multilayers

ChemInform Abstract: Amphiphilic Dyes for Nonlinear Optics: Dependence of Second Harmonic Generation on Functional Group Substitution.

Integrated Linear and Nonlinear Optics with Novel Macromolecular Systems

ABSTRACTThis paper deals with the application of some recently developed evanescent waveoptical techniques for the characterization of novel macromolecular host-guest systems. In particular, surface plasmon- and guided optical wave-spectroscopies and -microscopies are used to determine the linear and nonlinear optical properties of these materials in thin film form.

Surface-Functionalized Latex Particles as Controlling Agents for the Mineralization of Zinc Oxide in Aqueous Medium

Polystyrene latex particles modified at the surface with different hydrophilic functional groups were prepared by miniemulsion polymerization and used as controlling agents in the crystallization of zinc oxide from aqueous medium. The effects of the chemical nature of the surface functionalization and the latex concentration on the crystal growth, morphology, and crystalline structure of the resulting zinc oxide were analyzed. Micro- and submicrosized crystals with a broad variety of morphologies depending on the functionalization were obtained. Among the different latexes studied, the acrylic-acid-derived particles were shown to be a convenient system for further quantitative investigation…

Preformed polymers for Langmuir-Blodgett films- molecular concepts

The use of preformed polymers for the preparation of Langmuir-Blodgett (LB) multilayers is reviewed. Principles for polymer self-organization are outlined and the appropriate molecular designs are discussed. Recent developments in the different classes of polymers for LB multilayers are presented, and their outstanding properties highlighted.

Amphiphilic dyes for nonlinear optics: Dependence of second harmonic generation on functional group substitution