Alkaline hydrolyses of anionic phenyl esters such as 4-acetoxy-3-nitrobenzoic acid and 4-butyryloxy-3-nitrobenzoic acid were examined in the presence of cationic and polymeric liposomes, liposomes of low molecular weight compounds, and micelles. All the additives accelerate the reaction due to the hydrophobic interaction between substrates and additives and the electrostatic interaction both between substrates and additives and between OH− and additives. In the Arrhenius plots of the reactions catalyzed by the liposomes, discontinuous regions were observed due to the phase transition of liposomes from the gel state to the liquid crystal state. Activation parameters ΔH≠, ΔS≠ and ΔV≠ for thes…

Specific recognition and formation of two- dimensional streptavidin domains in monolayers: applications to molecular devices

Abstract By virtue of the high-affinity specific interaction between the vitamin, biotin, and the protein, streptavidin, monolayers of synthetic lipids with biotin headgroups can tightly bind streptavidin at the lipid-water interface. Through this specific recognition fluorescently-labelled streptavidin spontaneously organizes in the plane of the interface to form large protein domains, directly visible in situ by fluorescence microscopy and exhibiting optical anisotropy. Further structural characterization has shown that these domains are two-dimensional protein crystals. Correlation with the known three-dimensional crystal structure of streptavidin indicates that two of streptavidin's fou…

Preparation de vesicules contenant une matrice polymere reticule hydrophile (couches bimoleculaires phospholipides revetues de microparticules polymeres)

Molecular Recognition via Hydrogen Bonding at the Air−Water Interface:  An Isotherm and Fourier Transform Infrared Reflection Spectroscopy Study

Molecular recognition in Langmuir monolayers at the air−water interface as a function of headgroup orientation and substrate using isotherms and in-situ Fourier transform infrared (FT-IR) reflection spectroscopy has been investigated. Isotherm measurements show that urea and 2,4,6-triaminopyrimidine (TAP) are specifically bound to barbituric acid lipid monolayers. As expected, TAP causes a larger shift in the limiting area of the isotherms than urea due to steric requirements. The peak positions of the CH stretching vibrations of the barbituric acid lipids indicate that the alkyl chains of barbituric acid lipids 1−3 are in a close-packed all-trans conformation both before and after the reco…

Surface functionalization and surface recognition: Plasmon optical detection of molecular recognition at self assembled monolayers

The synthesis of biotin- functionalized organic mercaptans and their chemisorption on gold surfaces is described. Biotin bound covalently to self assembled monolayers is recognized by streptavidin from aqueous buffer solutions. Spacer length and packing density of the biotin labels on the organic surface determine the docking kinetics. With a flexible and hydrophilic spacer very fast -diffusion controlled-docking is observed. As an alternative method of self assembly the spreading of organic mercaptans on water surfaces is established. Pressure-area diagrams of different functionalized mercaptans and disulfides are shown and their monolayer properties are discussed.

Polymerization of Lipid and Lysolipid Like Diacetylenes in Monolayers and Liposomes

The bilayer type lipid membrane has a variety of important functions that are necessary in order to sustain life. A lot of these functions have been studied with artificial model membranes such as black lipid membranes (BLM) or liposomes. A great disadvantage of all these models is their instability — BLM for instance can only exist for minutes or hours and only under the presence of water. Therefore, it was the aim of this work to produce simple model membranes that can retain their structure under a variety of test conditions. The route chosen to obtain such membranes was through the polymerization of lipid and lysolipid like molecules in monolayers at the gas-water interface or in liposo…

Langmuir films and Langmuir-Blodgett multilayers incorporating mechanically-threaded molecules-pseudorotaxanes

This paper describes the synthesis of a π-electron rich aromatic lipid containing a polyether thread intercepted by a 1,5-dioxynaphthalene moiety. The terminus of one end of the polyether is a methoxyl group and the other a glycerol unit linked via the 2-oxo position, while the 1,3-oxo functions are covalently attached to octadecyl chains. This compound, when cospread at the air-water interface with the tetracationic cyclophane, cyclobis(paraquat-p-phenylene), and the phospholipid, dimyristoylphosphatidic acid, as its monoanion, forms self-assembled pseudorotaxanes which are self-organized into a two-dimensional supramolecular array at the interface. The electrostatic interactions between t…

Structure et proprietes thermodynamiques de polyamides rigides portant ces groupes lateraux flexibles

Combined main chain/side chain polymers. A new class of liquid crystalline polymers with unusual structural, thermodynamic and dynamic properties

Abstract Combined main chain/side chain polymers carry rigid rod-like mesogenic units both in the side chain and along the chain backbone. The properties of such combined systems are expected to be controlled by the competition of the interactions between the mesogenic units in the side and main chains as well as the tendency of the chain backbones to maximize their entropy. The thermodynamic, structural and dynamic properties of such combined main chain/side chain liquid-crystalline polymers were investigated for various chain architectures. The combined systems were found to display properties corresponding in many cases to a favourable superposition of properties characteristic of both m…

Pharmakologisch aktive polymere, 9. Synthese und untersuchung makromolekularer derivate des 1-adamantanamins

Es wurden zwei Methacrylatmonomere (3 und 6) dargestellt, welche die 1-Adamantylamino-Gruppe mit verschiedenen Spacergruppen enthalten. Die neuen Monomeren wurden mit 2-Methylsulfinylathylmethacrylat zu wasserloslichen Produkten copolymerisiert. Die Copolymeren mit 1-Adamantylamino-Gruppen sowie eine Modellsubstanz ohne Adamantyl-Gruppe wurden in vitro und in vivo auf ihre Wirkung gegen InfluenzaViren untersucht. Two methacrylate monomers (3 and 6) containing 1-adamantylamino groups with different spacer groups were prepared. The new monomers were copolymerized with 2-methylsulfinylethyl methacrylate to yield water soluble products. The copolymers containing the 1-adamantylamino group and a…

Formation and Characterization of Self-Assembled Films of Thiol-Derivatized Poly(Dimethylsiloxane) on Gold

Poly(dimethylsiloxane) (PDMS) copolymers containing propanethiol side chain “stickers” for forming self-assembled films on gold surfaces have been studied by various experimental techniques including ellipsometry, contact angle measurements, FT-IR, angle-dependent XPS, and ToF−SIMS. The results show that the thiol-containing side chains do not all chemisorb to the gold surfaces. In addition, the concentration of these sticker units was found to have a dominant effect on the polymer film thickness, the surface wetting properties, and the orientation of the PDMS backbone. Ab initio calculations reveal that the IR-active PDMS Si−O stretching bands can be used as indications of chain orientatio…

Interaction between biotin lipids and streptavidin in monolayers: formation of oriented two-dimensional protein domains induced by surface recognition.

Highly specific ligand-receptor interactions generally characterize surface recognition reactions. Such processes can be simulated by streptavidin-biotin-specific binding. Biotin lipids have thus been synthesized, and their interaction with streptavidin (or avidin) at the air-water interface was directly shown by measurement of surface pressure isotherms and fluorescence microscopy. These proteins interact with the biotin lipid monolayer via specific binding or nonspecific adsorption. Both phenomena were clearly distinguished by use of the inactivated form of streptavidin. The binding of fluorescein-labeled streptavidin to monolayers was also directly observed by fluorescence microscopy. Th…

Poly[sulfadiazineacrylamide] (5), labeled with 14C in the main chain, was synthesized and its molecular weight viscosimetrically determined by comparison with unlabeled samples of poly[sulfadiazineacrylamide] with similar molecular weights which were determined by membrane osmometry. The material showed a polymer-specific prolongation of its systemic behaviour in mice. Rates of excretion of the polymer were negligibly low, whereas the toxicity was considerable. It was concentrated in the liver during the course of the experiment, but no affinity toward the PC6 plasmacytoma in mice could be detected. Poly[sulfadiazinacrylamid] (5) mit 14C-Hauptkettenmarkierung wurde synthetisiert und sein Mo…

Synthesis of a Fullerene Derivative of Benzo[18]crown-6 byDiels-Alder Reaction: Complexation Ability, Amphiphilic Properties, and X-Ray Crystal Structure of a Dimethoxy-1,9-(methano[1,2]benzenomethano)fullerene[60] Benzene Clathrate

A fullerene derivative 1 of benzo[18]crown-6 was obtained by Diels-Alder addition of fullerene[60](C60) to the ortho-quinodimethane prepared in situ from 4,5-bis(bromomethyl)benzo[18]crown-6 (3) with Bu4NI in toluene. Extraction experiments show that the complexation of K+ ions strongly increases the solubility of 1 in protic solvents like MeOH. Using Langmuir-Blodgett techniques, monolayers of the highly amphiphilic fullerene-derived crown ether 1 and its K+ ion complex were prepared. An X-ray crystal structure was obtained from a benzene clathrate of comparison compound 2, synthesized by Diels-Alder reaction of C60 with the ortho-quinodimethane derived from 1,2-bis(bromomethyl)-4,5-dimeth…

4-4-20 anti-fluorescyl IgG Fab' recognition of membrane bound hapten: direct evidence for the role of protein and interfacial structure.

The surface forces apparatus was used to identify the molecular forces that control the interactions of monoclonal 4-4-20 antifluorescyl IgG Fab' fragments with fluorescein-presenting supported planar bilayers. At long range, the electrostatic force between oriented Fab' and fluorescein monolayers was controlled by the composition of the protein exterior surrounding the antigen-combining site rather than by the overall protein charge. The measured positive electrostatic potential of the Fab' monolayer at pH > pI(Fab') was consistent with the structure of the exposed Fab' surface in which a ring of positive charge at the mouth of the antigen-combining site dominates the local electrostatic s…

The thermal degradation mechanisms of amphiphilic acrylic copolymers containing mesogenic pyrimidine side chains and hydrophilic 2-hydroxyethyl acrylate (HEA) main-chain spacer units were investigated by thermogravimetry (TG) and pyrolysis-field ionization mass spectrometry (Py-FIMS). The degradation behaviour of these polymers depends on the amount of HEA incorporated. Thermogravimetry revealed that the main decomposition occurs in a single step for the pyrimidine homopolymer, whereas with increasing HEA content a two-step process evolves. The major products identified by Py-FIMS are two alcohols and one olefin split from the aromatic side chains. Depolymerization is only a minor degradati…

The formation and behaviour of radiation-induced free radicals in statistical copolymers of ethoxyvinylthiomethane (1a) with N-vinylpyrrolidone (2) (1:2,5) and of ethylthiovinylthiomethane (1b) with 2 (1:3,5) has been studied using electron spin resonance spectroscopy. After a γ-irradiation of the copolymers at 77K Cα-radicals in the vinylpyrrolidone moieties could be detected. Investigations on the behaviour of these radicals with an annealing procedure revealed that only in the copolymer (3b) with the dithioacetal group a transfer reaction of hydrogen atoms to the Cα-radicals in the vinylpyrrolidone moieties occurs. This process may be regarded as a repair mechanism. Es wurde die Bildung …

Polymer therapeutics—polymers as drugs, drug and protein conjugates and gene delivery systems: Past, present and future opportunities

As the 21st century begins we are witnessing a paradigm shift in medical practice. Whereas the use of polymers in biomedical materials applications, for example as prostheses, medical devices, cont...

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.

Pharmakologisch aktive polymere, 8.Poly[2-(methylsulfinyl)äthylacrylat]e und ihre vermittelnde wirkung auf die transkutane resorption von pharmaka

Poly[2-(methylsulfinyl)athylacrylat] (2a) und Poly[2-(methylsulfinyl)athylmethacrylat] (2b) wurden synthetisiert und auf ihre vermittelnde Wirkung bei transkutaner Resorption einiger Pharmaka untersucht. 2b verbesserte die Resorption der Phosphorsaureester Dimethoat® und Paraoxon® und der p-Aminohippursaure und war etwa mit der Wirksamkeit von DMSO vergleichbar. Ein geringer penetrationsfordernder Effekt ergab sich fur Dinitrochlorbenzol. Nicht beeinflust wurde die dermale Resorption von Isoprenalinsulfat. Die beiden Polymeren zeigten eine gute Lokalvertraglichkeit und 2b auch keine akute Allgemeintoxizitat bei systematischer Anwendung. Der fur DMSO charakteristische knoblauchartige Geruch …

Sanidics: A new class of mesophases, displayed by highly substituted rigid-rod polyesters and polyamides

Abstract The structure of rigid-chain polyesters and polyamides which possess flexible side chains consisting of methylene or 1,4,7-trioxaoctyl oxide units have been investigated by means of X-ray scattering. The X-ray studies were performed on fibres and monodomains. Additional information was gained from calorimetric, dilatometric and microscopic studies. The investigations revealed that these polymers display mesophases and that the structures of the mesophases differ from those observed for discotic and calamitic phases. They are characterized by the fact that in the ordered and disordered phases board-like molecules are stacked parallel on top of each other and that these stacks of mol…

Synthesis and Characterization of Liquid-Crystalline Polymers with Cholesteric Phase

Polymerization of Mono- and Bi-functional Diacetylene Derivatives in Monolayers at the Gas-Water Interface

The spreading and polymerization behaviour of long chain acids and phospholipid analogues containing diacetylene groups is described. Especially the polymerization in monolayers is followed spectroscopically with a new device used in connection with a commercial UV spectrometer. The polymerization is topochemically controlled. Sonification of the phospholipid analogues in water results in the formation of liposomes with multilayered membranes. Polymerization of the liposomes in water forms aqueous solutions of polymer vesicles.

Electric Field Effects and Miscibility in Cybotactic Micellar Nematic and Ordinary Nematic Polyesters

Abstract Miscibility behavior and electro-optical instabilities are reported for two main chain thermotropic nematic polyesters formed by regularly alternating a disubstituted azoxy-benzene mesogen with a flexible spacer containing either 7 or 10 methylene units (HEPTA-9 and DDA-9, respectively). Polymer HEPTA-9 displays an ordinary nematic organization and polymer DDA-9 forms a cybotactic nematic phase. Both are totally miscible with each other, and with PAA, in the nematic phase. Williams domains and dynamic scattering modes are observed in both cases.

Polyreaktionen in orientierten systemen. II.. Polymerisation von 4-vinylpyridinium-salzen in micellar geordneten lösungen

Die Kinetik der „spontanen” Polymerisation von 4-Vinylpyridiniumperchlorat in Wasser zeigt, das oberhalb einer „kritischen” Konzentration ein Wechsel des Polymerisationsmechanismus eintritt entsprechend einer Anderung in der Struktur des sich bildenden Polymeren. Untersuchungen der Viskositat und der Oberflachenspannung an Modellsubstanzen zeigen, das dieses Phanomen der Bildung von Micellen und der darin ablaufenden Polymerisation zuzuschreiben ist. Der alkalische Abbau der Polymeren wurde untersucht. The kinetics of the “spontaneous” polymerization of 4-vinylpyridiniumperchlorate in water proves that above a “critical” concentration the polymerization mechanism is changed. Correspondingly…

Phase Behaviour of Dye-Containing Liquid Crystalline Copolymers and their Mixtures with Low Molecular Weight Liquid Crystals

Liquid crystalline side-chain polymers can be obtained by connecting the mesogenic groups and the polymer chain via a flexible spacer. The liquid crystalline polymers combine the well-known properties of low molecular weight liquid crystals with those of polymers.1

Polymer-induced shape changes and capping in giant liposomes

We studied the coupling of a polymeric amphiphile undergoing a transition from an expanded to a collapsed state of the hydrophilic polymer chain upon heating above 29°C with free and solid supported lipid bilayers. Lateral diffusion measurements and studies of vesicle shape-changes confirmed previous calorimetric studies, suggesting that the amphiphile remains incorporated in the giant vesicles and the supported bilayer during the transition. The two-dimensional hydrodynamic radii of the amphiphile in the expanded and collapsed state was measured by making use of the strong quadratic dependence of the diffusion coefficient on the radius of the diffusant (D ∞ r−2) due to the frictional coupl…

Untersuchungen von polymeren im massenspektrometer, 4. Abbaureaktionen von polybenzylen

Die Abbaureaktionen von unsubstituierten Poly(1,4-phenylenmethylen)en (A) (Polybenzylen), Poly[(2,5-dimethyl-1,4-phenylen)methylen] [Poly(2,5-dimethylbenzyl)] (B), Poly[(2,3,5,6-tetramethyl-1,4-phenylen)methylen] [Poly(2,3,5,6-tetramethylbenzyl)] (C) und Poly(1,4-phenylenathyliden) [Poly(α-methylbenzyl)] (D) wurden durch direkte Pyrolyse im Massenspektrometer untersucht. Die Massenpyrogramme von unter verschiedenen Reaktionsbedingungen dargestellten Polybenzylen wurden verglichen, mit dem Ziel, direkt Informationen uber Strukturunterschiede wie Kettenverzweigung und unterschiedliche Verknupfung der Benzyleinheiten zu erhalten; hierbei konnten in einem Falle auf hohere Kettenverzweigung deut…

Polymeric Micelles and Liposomes as Potential Drug Carriers

In the past, a whole aray of polymeric carriers for biologically active substances have been reported. In this field the main interest has focused on the use of randomly solubilized polymers. Naturally occuring amphiphilic transport proteins can be modelled by synthetic micellar solubilized polymers. Poly(ethylene oxide)-polypeptide block copolymers with hydrophobic and cyclophosphamide-containing side groups are described. These micellar systems are able to transport different hydrophobic drugs.

Specific interaction of desthiobiotin lipids and water-soluble biotin compounds with streptavidin

As shown for biotin lipids (Ref. 1), the formation of perfect 2-D crystalline streptavidin domains can also be observed in the plane of desthiobiotin lipid monolayers. The binding constant of streptavidin with desthiobiotin (Ka = 5·1013 mol−1) is lower than that with biotin (Ka = 1015 mol−1) (Ref. 2). By adding free biotin into the subphase a competitive replacement and a detaching of the streptavidin domains from the desthiobiotin lipid monolayer takes place. Streptavidin domains built at receptor lipid monolayers are still functional. As could be shown, there are two biotin binding sites at each protein molecule that are fully accessible to biotin (Ref. 1). This can be proven by the inter…

Untersuchungen von Polymeren im Massenspektrometer. I. Fragmentierungsreaktionen von oligomeren β-Alaninen

Beim Abbau von Poly-β-alaninen entstehen unter milden Pyrolysebedingungen oligomere Carbonsaureamide. Die Fragmentierungsreaktionen derartiger Pyrolysebruchstucke werden an dimeren bis tetrameren β-Lactamen untersucht. Als Hauptfragmentierungsreaktionen werden nach Ionisation an einem der Heteroatome αN-, Keten-, αO-, und βO-Spaltung mit MCLAFFERTY-Umlagerung gefunden. The degradation of poly-β-alanines under mild pyrolytical conditions yields oligomeric amids. Dimeric, trimeric and tetrameric β-lactames were used to study the fragmentation reactions of those degradation products. After ionisation at one of the hetero atoms αN-, keten-, αO- and βO-cleavage (with MCLAFFERTY-rearrangement) we…

Molecular Recognition of Biotinyl Hydrophobic Helical Peptides with Streptavidin at the Air/Water Interface

Transient photoconductivity in a discotic hexagonal plastic crystal

The synthesis and phase behaviour of a series of polymers having liquid crystalline sidechains and a poly(acrylic acid) backbone are described. These polymers show a dependence of the phase transition temperatures on molecular weight. In copolymers of two liquid crystalline acrylic esters, induced smectic phases occur. A comparison of the phase transitions of the different polyacrylates, with those of liquid crystalline polymethacrylates and polysiloxanes, published elsewhere, establishes that the spacer group achieves partial “decoupling” of liquid crystalline and polymer properties.

Specific Protein Docking to Chelator Lipid Monolayers Monitored by FT-IR Spectroscopy at the Air–Water Interface

Resultats preliminaires sur les polysiloxanes discotiques avec des cycles triphenylene pentasubstitue fixes au squelette par des liaisons flexibles

Pharmakologisch aktive polymere, 4. Monomere und polymere alkylsulfinyl-alkylacrylate und -methacrylate als mögliche resorptionsvermittler

Relationship between microscopic and macroscopic structures of organic thin films for SHG

The experiments described in this paper were undertaken in order to obtain information about the relationship between the structure and non-linear optical properties (second-harmonic generation) of organic thin films. For this purpose, two closely related dyes, diones and tetrones, were compared, both of which are shown to have large hyperpolarisabilities. Their microscopic properties are investigated by conformational analysis and electron diffraction. It could be shown that detailed knowledge about the structure and the adjacent neighbour packing can be obtained from conformational analysis and electron diffraction in order to understand the non-linear optical properties of the two dyes.

Snap-together vesicles

The supramolecular self-organization of an amphotropic cholesterol derivative Micelles, liposomes and liquid-crystalline phases

Abstract The cholesterol derivative tetraethoxycholesteryl semisuccinate is both a mesogen and an amphiphile. This combination of both molecular prerequisites permits two types of supramolecular self-organization: the formation of a thermotropic liquid-crystalline phase and of various forms of aggregates in contact with water or other solvents. Depending on the pH of the aqueous medium the compound self organizes in micelles or liposomes. At high concentrations lyotropic liquid-crystalline phases are obtained. The formation of liposomes and lyotropic phases is not restricted to water as a solvent but can also be induced in pure organic media such as water-free diethyleneglycol. Due to the b…

Investigations of polymerizable multilayers as gas separation membranes

Abstract Polymerizable Langmuir—Blodgett (LB) multilayers of several diacetylenic amphiphiles were investigated on gas-permeable, polymeric supports. Macroscopically homogeneous multilayer films of hexacosa-10,12-diynoic acid and pentacosa-10,12-diyne phosphonate could be built up on polypropylene and polytetrafluoroethylene materials. As shown by scanning electron microscopy, the microscopic homogeneity of the built-up multilayers was mainly controlled by the surface structure of the support material, whereas the chemical nature of the support and photopolymerization of the layers did not affect the high order of the films. Such LB multilayers deposited on porous support materials are able…

The synthesis and the phase behaviour of liquid crystalline main chain polymers are described. In these poly- and copolyesters the mesogenic units are linked by highly flexible oligodimethylsiloxane spacers. The comparison of their phase behaviour with that of polyesters known from the literature shows that dimethylsiloxane spacers as a replacement for alkyl spacers are leading to a drastic decrease of the transition temperatures. Depending on the length of the spacer glass transitions as low as −111°C can be achieved. The widths of the liquid crystalline phases thereby are retained up to a spacerlength of 13 oxydimethylsilanediyl (dimethylsiloxane) units. The homopolyesters mainly show sme…

Microstructure of a Discotic Polymer as Revealed by Electron Diffraction and High-Resolution Imaging

Liquid crystalline side chain polymers containing photoreactive azobenzene chromophores in the dark-adapted trans form and phenylbenzoate groups as co-mesogens have been prepared and investigated as monomolecular layers at the water/air interface and as multilayer assemblies deposited onto solid supports by the Langmuir–Blodgett–Kuhn (LBK) technique. Pressure area isotherms at variable temperatures together with reflection absorption spectra and Brewster angle microscopic pictures have been taken and analyzed (i) to derive information about the structural order and the packing properties of the mesogenic side groups within the monolayers of different homo- and co-polymeric systems and ii) t…

Molecular organization via ionic interactions at interfaces. 1. Monolayers and LB films of cyclic bisbipyridinium tetracations and dimyristoylphosphatidic acid

Monolayer Properties of Hydrophobic .alpha.-Helical Peptides Having Various End Groups at the Air/Water Interface

Preparation d'oligosiloxanes et de polyarylates avec des groupes mesogenes fixes lateralement

Reaction kinetics in dense two-dimensional polymer solutions : an excimer probe study

We report measurements of the time dependent reaction rate of excimer formation in two-dimensional solutions of a polymerized amphiphile with partially pyrene-labelled chains in monolayers at the air-water-interface. We find a time dependent reaction rate for excimer formation obeying a power law r(t) ∞ t -β . The exponent β has a value of 0.22±0.12. This value is consistent with β=1/4, as has been predicted for bimolecular diffusion-controlled reactions in two-dimensional polymer melts by de Gennes. The measurements demonstrate the usefulness of the excimer technique to explore polymer dynamics

Electronic coupling responsible for energy transfer in columnar liquid crystals

Electronic coupling is the driving force for energy transfer in molecular materials and consists of several components. We determine the strength of dipolarrmultipolar coupling and coupling due to orbital overlap for excitation transport in triphenylene columnar liquid crystals. We use time-resolved fluorescence spectroscopy and computer simulations. The fit of the experimental and simulated fluorescence decays reveals that the transfer process is dominated by short range interactions .multipolar and orbital overlap but the contribution of long range dipolar interactions cannot be neglected. q 1999 Elsevier Science B.V. All rights reserved.

Mixtures of lecithin with polymerizable derivatives of cholesterol. A monolayer film balance study.

One of the best investigated binary lipid mixtures is the lecithin-cholesterol system. We show here that it is possible to modify the cholesterol in such a way that it can be polymerized without changing its behaviour in mixtures with lecithin. The polymerizable derivatives exhibit a very similar phase diagram in the mixture with dipalmitoyl-phosphatidylcholine as the cholesterol itself. This is demonstrated by filmbalance measurements.

Autopolymerisation de ce monomere ionique dans l'eau ou dans un solvant organique par addition d'acide protique. Suivant la concentration du monomere, il se forme un sel diyl-1,4 ou yl-4

Studies of Molecular Orientation and Order in Self-Assembled Semifluorinated n-Alkanethiols:  Single and Dual Component Mixtures

The structure, orientation and morphology of self-assembled monolayers of a semifluorinated n-alkanethiol, F(CF2)8(CH2)11SH (F8H11SH), have been investigated by polarized IR, angular dependent XPS, ToF-SIMS, contact angle, and ellipsometric measurements. The orientation of the all trans hydrocarbon segment was found to be tilted much less from the surface normal than the 30° tilt found for octadecanethiol. This has been attributed to the steric constraints imposed by the larger cross section fluorocarbon helices that subsequently are tilted from the surface normal. In addition, studies of dual component mixtures of F8H11SH/F8SH and F8SH/F8H2SH have revealed that competitive adsorption occur…

Tradition and innovation in science

A Commentary on the paper ”Self‐organization of substituted azacrowns based on their discoid and amphiphilic nature„, by C. Mertesdorf and H. Ringsdorf. First published in Liquid Crystals, 5, 1757‐1772 (1989).

Fluorescence studies of hydrophobically-modified poly(N-isopropylacrylamides) or how to play accordion on a liposome

The coil/globule transition of polymers in solution is a favourite topic of discussion among polymer theoreticians. Here, this phenomenon is used to play a “molecular accordion” built with a thermosensitive polymer anchored to liposomes, a tune which mimics a natural process occuring in cell membranes.

End-Group-Dominated Molecular Order in Self-Assembled Monolayers

Phase identification of triphenylene-based discotic monomer and its main chain polymers

Abstract A monomer, 2,3,6,7,10,11-hexakispentyloxy triphenylene (HPT) possesses a triphenylene core as a discotic mesogen. Polymers containing this discotic mesogen have been studied using wide-angle X-ray and electron diffraction. HPT is known to show a discotic liquid crystal phase, noted as Dho (h for hexagonal bidimensional lattice, o for ordered molecular spacing in each column). In this paper, however, HPT liquid crystalline phases, heated up from the crystalline state and cooled down from the isotropic state, were characterized in the diameter dimensions. In addition. the diameters of the columns are close to a parameter of two separate crystals. A core orientation was, therefore, pr…

Domain Structures in Langmuir-Blodgett Films Investigated by Atomic Force Microscopy

Investigations of phase-separated Langmuir-Blodgett films by atomic force microscopy reveal that on a scale of 30 to 200 micrometers, these images resemble those observed by fluorescence microscopy. Fine structures (less than 1 micrometer) within the stearic acid domains were observed, which cannot be seen by conventional optical microscopic techniques. By applying the force modulation technique, it was found that the elastic properties of the domains in the liquid condensed phase and grains observed within the liquid expanded phase were comparable. Small soft residues in the domains could also be detected. The influence of trace amounts of a fluorescence dye on the micromorphology of monol…

Polymeric monolayers and liposomes as models for biomembranes. How to bridge the gap between polymer science and membrane biology?

This contribution deals with the stabilization of membrane model systems, especially vesicles. The desired further biological functionalization of these stabilized polymeric membranes is possible via the incorporation of proteins. Addition of natural lipids to polymerizable membranes and degradation of the unpolymerized component after polymerization allows selective opening of otherwise stable compartments. Finally, first attempts are made to combine biological properties of natural cells and the durability of polymerized membranes via fusion of synthetic vesicles with natural cells.

Synthesis and Characterization of Fluorescent, Low-Symmetry Triphenylene Discotic Liquid Crystals:  Tailoring of Mesomorphic and Optical Properties

A series of monofunctionalized triphenylene-based discotic liquid crystals were synthesized starting from 2-hydroxy-3,6,7,10,11-pentakis(pentyloxy)triphenylene. These compounds are unique in that they possess a single electron-withdrawing group (and consequently a large dipole moment) connected directly to the polyaromatic core. All of the new liquid crystals show a significantly broader range of mesogenicity relative to the parent compound 2,3,6,7,10,11-hexakis(pentyloxy)triphenylene. Moreover, some of the new mesogens exhibit a more ordered mesophase relative to the hexagonal columnar phase (Dh) at lower temperatures. Monofunctionalization of the triphenylene core has a dramatic effect on…

2H NMR studies of phase behaviour and molecular motions of doped discotic liquid-crystalline systems

Abstract A discotic triphenylene monomer as well as a dimer and a main chain polymer, all substituted with heptyloxy side groups, were doped with an electron acceptor (2,4,7-trinitrofluorenone (TNF)) to give charge transfer complexes. These doped systems were aligned in a magnetic field, thus proving their liquid crystallinity. 2H NMR measurements show that the electron acceptor molecules are incorporated into the columns built of triphenylene cores. In the charge transfer complex with the triphenylene monomer almost all the electron acceptor molecules stack in the columns even close to the clearing temperature T 1, while for the dimer and especially for the polymer a significant fraction o…

Small unilamellar liposomes from mixed natural and polymeric phospholipids: stability and susceptibility to phospholipase A2.

The concept of the uncorkable liposome composed of phase-separated mixtures of a polymerized phospholipid and an enzymically digestible phospholipid has been investigated, using small unilamellar vesicles composed of mixtures of (polymerized) dienoylphosphatidylcholine (DENPC) and dimyristoylphosphatidylcholine (DMPC). Mixed liposomes, even those containing only 10% DENPC, were much more stable than DMPC liposomes, as indicated by the release of entrapped [3H]inulin or [14C]glucose. DMPC liposomes released entrapped solute on exposure to phospholipase A2, whereas mixed vesicles were resistant. The results are compared with those of an earlier study on monolayers of similar compositions. It …

Etude de deux systemes differents avec de l'hydroxy-4 benzoate de phenyle comme unite mesogene. Les separateurs sont formes de 6 unites methylene et le squelette est de l'acide poly(meth)acrylique

Molecular dynamics of discotic charge-transfer complexes, dielectric spectroscopy and2H NMR studie

Abstract Using a combination of solid state 2H NMR spectroscopy on selectively deuteriated samples and dielectric spectroscopy, the molecular dynamics of discotic charge-transfer (CT) complexes were investigated. These complexes show particular thermodynamic and flow properties. Considered were mixtures of low molar mass donors and acceptors, low molar mass donors with main chain acceptor polymers and covalently linked donor-acceptor twins with different lengths of the spacer. A main result is that correlated rotational motions of discotic molecules or groups about the columnar axis are observed in all systems except for the twin with the short spacer. This type of motion seems to be a gene…

Specific recognition, 2-d-crystallization and function of proteins in monolayers

Second harmonic generation in self-assembled alternating multilayers of hemicyanine containing polymers and polyvinylamine

Abstract Assembly of noncentrosymmetric multilayers is a facile technique for preparing noncentrosymmetric films avoiding electrical poling procedures and problems from subsequent relaxation of the induced orientational order. A maximum Xzzz of 13 × 10−9 esu was achieved for the assembly of up to six layers. Current problems are the long-term hydrolysation of the hemicyanine nonlinear optical chromophores and the reduction of polar orientation with increasing layer thickness.

Polymeric gegenions induced variability and mobility of amphiphilic supramolecular structures on solid substrates

Abstract The micromorphological variations of amphiphilic L -glutamate derivatives at air-substrate interfaces due to an adjacent mobile polymer matrix have been investigated via fluorescence microscopy. Adjusted monolayers of the L -glutamate derivatives have been transferred by LB technique out of different aggregation states onto various substrates. The substrates have been prepared by successive polymer preadsorption to the solid support. The influence of the adjacent polymer layers on the domain morphology as a function of water content and temperature has been examined intensively. Moreover, reversible domain changes induced by temperature variation of the transferred films have been …

Fluoroalkylated discotic liquid crystals

Abstract The concept of mesophase stabilization by partial fluorination of side chains has been extended to discotic systems. The mesophase structure is essentially unchanged, whereas the temperature range of the mesophase is strongly affected by the fluorinated side chains. Triphenylene substituted with only one partially fluorinated side chain exhibits a decrease of the clearing temperature, whereas for symmetrically substituted systems a broad range mesophase has been observed. This behaviour can be attributed to a segregation of the incompatible parts of the molecule giving rise to a stabilized columnar structure for the symmetrical substitution pattern.

Synthesis of a Fullerene[60] Cryptate and Systematic Langmuir-Blodgett and Thin-Film Investigations of Amphiphilic Fullerene Derivatives

The synthesis of the first fullerene cryptate 7 with a sodium ion bound to a benzo[2.2.2]cryptand covalently attached to a methanofullerene[60] is described. The amphiphilic properties of 7 as well as of a variety of other covalent fullerene derivatives with polar functional groups and the ability of these compounds to form Langmuir monolayers at the air-water interface were investigated in a systematic study. Among these derivatives are Diels-Alder adducts of C60 and methanofullerenes, four of which are fullerene C-glycosides. The films at the water surface were characterized by their surface pressure versus molecular area isotherms, compression and expansion cycles, and optical light micr…

Untersuchung von vinylpyridiniumverbindungen IV. Polyreaktionen von 2-vinylpyridiniumsalzen

Spontaneous domain formation of phospholipase A2 at interfaces: fluorescence microscopy of the interaction of phospholipase A2 with mixed monolayers of lecithin, lysolecithin and fatty acid.

Abstract Fluorescence microscopy has recently been proven to be an ideal tool to investigated the specific interaction of phospholipase A 2 with oriented substrate monolayers. Using a dual labeling technique, it could be shown that phospholipase A 2 can specifically attack and hydrolyze solid analogous l -α-DPPC domains. After a critical extent of monolayer hydrolysis the enzyme itself starts to aggregate forming regular shaped protein domains (Grainger et al. (1990) Biochim. Biophys. Acta 1023. 365–379). In order to confirm that the existence of hydrolysis products in the mononlayer is necessary for the observed aggregation of phospholipase A 2 , mixed monolayers of d - and l -α-DPPC, l -α…

Langmuir-Blodgett films from a polymer with triphenylene moieties in the side groups deposited on a quartz substratum with aluminium and gold electrodes show a dark conductivity in the plane of the Langmuir-Blodgett film. This dark conductivity is increased using gold electrodes as compared with aluminium electrodes. It depends in a superlinear way upon the applied electric field and is not enhanced by oxygen. The dark conductivity can be enhanced by doping the Langmuir-Blodgett films with iodine but it is not influenced by doping the Langmuir-Blodgett films with 2,4,7-trinitro-9-fluorenone. Upon excitation in the absorption band of the triphenylene moiety an in-plane photocurrent, which is…

Deuteron Magnetic Resonance Study of Order and Dynamics in Liquid Crystal Polymers

Abstract Thermotropic nematic polyesters, specifically deuterated at different positions of the polymer chain are studied by multiple pulse dynamic NMR. Analysis of the NMR experiments is achieved, employing a comprehensive model, based on the stochastic Liouville equation. Computer simulations provide the orientational distributions and conformations of the polymer chains and the correlation times of the various motions. In the anisotropic melt the correlation times for chain reorientation and trans-gauche-isomerization are in the range of 0.1–10 ns. Decreasing the temperature of the solid polymer first freezes the intermolecular motions. Thus, below the glass transition only intramolecula…

A series of liquid-crystalline copolymers 1 with a chiral azobenzene moiety as photoreactive mesogenic unit was prepared. The polymers were fractionated and the mesophase behaviour of the high- and low-molecular weight fractions was examined. The copolymers display smectic A and cholesteric phases. For the cholesteric phases the pitch of the helix was determined, which ranges from 3 to 20 μm. Stable monolayers at the air-water interface were obtained from two monomers and one of the homopolymers. Multilayer assemblies of the azobenzene-containing polymers can be used to study photo-induced order/disorder transitions.

Formation of protein multilayers and their competitive replacement based on self-assembled biotinylated phospholipids.

Based on specific recognition processes the build-up of protein multilayers was achieved using streptavidin layers as a docking matrix. For this purpose, streptavidin was organized at biotin-containing monolayers, liposomes, and self-assembled layers on gold. Thus, mixed double and triple layers of streptavidin, Con A, Fab fragments, and hormones were prepared and characterized by fluorescence microscopy and plasmon spectroscopy. Using biotin analogues with lower binding constants several cycles of multilayer formation followed by competitive replacement could be achieved.

Thermotropic polyesters with mesogenic groups based on substituted hydroquinone units and highly flexible siloxan spacer in the main chain

New thermotropic Polyesters having mesogenic groups based on substituted hydroquinone units and highly flexible oligosiloxan spacer in the main chain, are synthesized and characterized. The mesophase formed at low temperature are studied by differential scanning calorimetry (DSC) and polarized light microscopy. The liquid crystalline behaviour of these polyesters, particulary their transition temperatures and the mesophase width could be explained on the basis of their structural features.

Photophysical Properties of Discotic Dibenzopyrenes

Abstract The photophysical properties of three discogenic dibenzopyrenes substituted by eight pentyloxy (O5DPB), heptyloxy (O7DBPP) or decyloxy (O10DBP) side chains are studied in solution and thin films. It is shown that the absorption and fluorescence spectra of the columnar mesophases are clearly distinguishable from those of the corresponding crystalline phases, allowing the study of phase transitions. Thus, it is found that the shorter the lateral chain length, the slower the crystallisation process. For O5DBP, the supercooled mesophase is stable over a period of at least one year; it crystallises after cooling below the glassy transition. Such a behaviour gives rise to temperature con…

Incorporation of ATP synthetase into long-term stable liposomes of a polymerizable synthetic sulfolipid

Molecular Recognition-Induced Function and Competitive Replacement by Hydrogen-Bonding Interactions:  Amphiphilic Barbituric Acid Derivatives, 2,4,6-Triaminopyrimidine, and Related Structures at the Air−Water Interface

The phenomenon of molecular recognition inducing further function is common in nature. However, there are few synthetic systems which achieve this cascade type mechanism, and those are generally ca...

Superconducting hollow and solid fibers and thin films of YBa2Cu3OX from a polymeric precursor

Tetraethynylethene molecular scaffolding: Nonlinear optical, redox, and amphiphilic properties of donor functionalized polytriacetylene and expanded radialenes

Photoconductivity in the columnar phases of a glassy discotic twin

Surface characterization of functional poly(diacetylene) and poly(butadiene) mono- and multilayers

The surface properties of Langmuir-Blodgett mono- and multilayers of a variety of amphiphilic poly(diacetylene)s and poly(butadiene)s were investigated by contact angle, streaming potentialζ, ellipsometry, and X-ray photoelectron spectroscopic (XPS) measurements. Captive air and octane angles varied between approximately 60° and 105° for hydrophobicx-layers and 31° to 46° for hydrophilic surfaces depending on the particular head group, whereas advancing angles determined via the vertical plate method are considerably higher. Negative streaming potentials were obtained for all surfaces. Positively charged monolayers yielded less negativeζ- potential values (−28 mV) than negatively charged (−…

A radical mechanism is proposed for the formation of the 1,2-polymer 2 in the “spontaneous” polymerization of 4-vinylpyridinium salts 4-VP.HX (X=NO3, ClO4, HSO4, I) in aqueous solution on the basis of strong inhibition by oxygen and other radical inhibitors. Quantitative investigation of the influence of oxygen on the formation of the 1,2-polymer allowed the derivation of a formal kinetic scheme for the initiation and polymerization steps which is consistent with a free radical mechanism. Dependence of the average molecular weight of 2 on monomer concentration is in agreement with this model. Dependence of the inhibition time on the oxygen concentration as well as an acceleration of the fin…

Influence des groupes mesogenes sur le polymorphisme de polyphenylene-1,4 terephtalate et differents polyesters a chaine principale semi-flexible

Polyreaktionen in orientierten Systemen, 3. Polymerisation ungesättigter Benzylidenaniline mit flüssig-kristallinen Eigenschaften

Die Acrylsaure- und Methacrylsaureester 3a–m wurden synthetisiert und auf ihr nematogenes Verhalten untersucht. Zwei Monomertypen wurden zur Untersuchung des Polymerisationsverhaltens herangezogen. Dabei zeigte sich, das die Polymerisationsgeschwindigkeit beim ubergang vom nematischen in den isotropen Bereich sprungartig ansteigt. In Abhangigkeit von der Darstellungsweise des Polymeren ergaben sich Unterschiede in der Struktur. Polymere, die bei 20°C in Losung dargestellt werden, sind amorph, wahrend Losungsmittel-polymerisate, die bei −78°C hergestellt und anschliesend getempert wurden, eine Struktur aufweisen, die mit der der Polymeren aus der nematischen Phase nahezu ubereinstimmt. Diese…

Synthesis of activated cyclophosphamide derivatives bearing functional groups

Aus Cyclophosphamid (I) erhalt man mit Ozon das Hydroperoxid (IIa), das mit Triethylphosphit zu (IIb) reduziert und dann in Trifluoressigsaure mit entsprechenden Thioverbindungen zu zahlreichen Thioethern (III) mit funktionellen Gruppen substituiert werden kann . Diese werden auf Antitumorwirkung untersucht.

Study of the micro-phase separation in LC-polymers with paired mesogens

Differential scanning calorimetry and miscibility investigations were used to study the micro-phase separation of liquid-crystalline dimesogenic side-group polysiloxanes. Diluted co-polysiloxanes exhibit two glass transition temperatures and an unusual miscibility behavior. The observed biphasic character is compared with that of certain amphiphilic systems.

The photochemical rearrangement of polymeric N-(1-pyridinio) amidates. A novel, aqueous photoresist system

Microstructure and lateral diffusion in monolayers of polymerizable amphiphiles

Lipid analogue amphiphilic molecules containing polymerizable units were investigated in monolayers at the air/water interface by using film balance measurements, fluorescence microscopy, and photobleaching techniques. The polymerizable groups (diene-, diyne-, and methacrylate units) were introduced into the hydrophobic alkyl chains or into the polar head of the amphiphilic molecules. In the case of the diene- and diyne-containing compounds the polymerizable units are incorporated into the hydrophobic alkyl chains, enabling them to form a two-dimensional network. Due to the free chain flexibility of the monomers the lateral mobility was comparable to that of saturated lipid analogues and de…

Polymerization of diacetylene carbonic acid monolayers at the gas-water interface

Polymer therapeutics: clinical applications and challenges for development.

Differentiation of isomeric cyclic diamides by electron impact mass spectra

The behaviour under electron impact of two series of isomeric cyclopentane- and cyclohexane-1, 2- and -1, 3-dicarboxylic acid dipiperidides was studied. Diagnostic fragmentation pathways were found to differentiate the isomeric diamides. Additional evidence was obtained from the metastable transitions.

Polyreaktionen in orientierten Medien, 4. Fotoreaktionen von Fumar- und Maleinsäurederivaten in Multischichten

Discotic Liquid Crystals - A New Class of Fast Photoconductors

We showed for the first time that discotic liquid crystals are well suited for a new class of fast photoconducting materials. Due to their spontaneous orientation and their dynamical fluctuations in the mesophase, they show exceptionally high mobilities of 1·10−3 cm2/Vs, about two to three orders of magnitude higher than those obtained for conventional amorphous polymers. Further on, the Gaussian transport (for holes in the mesophase) is remarkable, which is characterized by the existence of a conduction band and the absence of trapping states. In contrast, the charge carrier transport in amorphous photoconductors is generally trap-dominated which limits technical properties, leading to low…

Protein interactions with ordered lipid films: Specific and unspecific binding

Bilayer Formation of Streptavidin Bridged by Bis(biotinyl) Peptide at the Air/Water Interface

Dynamic behaviors of fractal-like domains in monolayers

In this paper we report our recent investigations on the morphological evolution of fractal-like domains of the liquid-condensed (LC) phase in lipid monolayers. It is demonstrated that the dimension of the LC domains increases upon continuous illumination of microscope light. The experimental data indicate that the increasing rate of fractal dimension of the LC domains depends on the concentration of fluorescence probes. By analyzing the domain growth process we find that the self-similarity of the pattern disappears gradually during its growth. The possible mechanism behind the observed phenomena is discussed.

In-Plane Anisotropy and Phase Change in Langmuir-Blodgett Films of a Triphenylene Derivative

Abstract The “in-plane anisotropy” of a triphenylene derivative in Langmuir-Blodgett (L.B.) films has been investigated. Upon heating, L.B. films exhibit a reversible phase transition appearing as an abrupt increase from a low to a high “in-plane anisotropy” corresponding to the formation of the same hexagonal liquid crystal phase observed in the bulk material at almost the same temperature, with the columnar axis aligned along the dipping direction.

Pharmakologisch-aktive polymere, 21. Orientierende Untersuchungen zur körperverteilung und Ausscheidung von poly[2-(methylsulfinyl)ethylacrylat]en bei der Ratte

Poly[2-(methylsulfinyl)ethyl acrylate] (1) was synthesized as well as derivatives 14C-labelled in side groups (6) or 14C-labelled in the main chain (11). Polymer 11 with the 14C-labelled main chain was fractionated by precipitation. The η-M-relation determined by measurements of unlabelled polymers in the ultracentrifuge for comparison was used to establish the viscosimetrically determined molecular weights of the labelled fractions. After intravenous application of aqueous solutions of the polymer in rats the excretion rate up to 72 h after treatment was ascertained to ca. 50%; the concentration in the blood serum was found to be strikingly high. A tendency to reinforced storage in organs …

Reversible Digital And Holographic Optical Storafe In Polymeric Liquid Crystals (PLC)

A new reversible optical storage technique based on azo dye containing liquid crystalline polymers and copolymers is described. Monodomain films of the polymers were used as storage medium. Digital and holographic information was stored and reconstructed. The stored information can be erased and the writing process is repeatable. The storage process is explained in terms of a transcis isomerization of the mesogen inducing local director field distortions.

Nachweis der spezifischen Proteinadsorption an Chelatorlipidmonoschichten mit FT-IR-Spektroskopie an der Wasser/Luft-Grenzfläche

Polymerization in black lipid membranes. Influence on ion transport

A variety of different lipids containing dienoyl groups in the side chains were tested for membrane formation using the planar lipid bilayer approach. One of these lipids formed stable bilayers which could be polymerized using UV-illumination. The influence of the polymerization was studied in monolayers, lipid vesicles and planar bilayers. The stability of the lipid bilayer membranes was increased by polymerization. Thus, the lifetime of the membranes increased from about 1 h to 4–5 h or longer. Furthermore, the specific conductance of unmodified membranes and of carrier-mediated transport is reduced. The transport of lipophilic ions was investigated as a function of polymerization using t…

Feinstrukturanalyse eines diskotischen Polymers durch Elektronenbeugung und hochauflösende Elektronenmikroskopie

Polyhydrogenomethylsiloxanes ayant la meme paire de groupes lateraux mesogenes mais un bras ecarteur different

X-ray investigation of combined main-chain/side-chain liquid-crystalline polymers

Abstract Structural investigations on six combined liquid-crystalline polymers using the X-ray technique are described. The measurements have allowed a characterization of the liquid-crystalline phases and have led to our first ideas about the phase structures. All mesogenic groups are arranged parallel to each other, the shortest segment in the main-chain or in the side-chain determines the smectic layer spacing. A modified designation for liquid-crystalline phases of high polymers is proposed.

How to Bridge the Gap Between Membrane Biology and Polymer Science

Can polymer chemists contribute to the understanding or even mimicking of cell membrane functions and cell-cell interactions? Fascinated by the specificity and efficiency of, for example, the destruction of tumor cells by lymphocytes (1) and having in mind what biochemical analyses tell us about membrane composition, we may try to “synthesize” membrane and cell models. The commonly used model systems, such as planar lipid monolayers at the gas-water interface, bimolecular lipid membranes and spherical liposomes, are much less stable than natural membrane systems (Figure 1).

Compound Membranes of Linearly Polymerized and Cross-Linked Macrolipids with Phospholipids: Preparation, Microstructure and Applications

Methods for the assembly and for studying the structural and dynamic properties of partially polymerized membranes are described. Mixtures of two classes of polymerizable amphiphiles with diacyl phosphatidylcholines are studied: (1) phosphatidylcholines carrying a diacetylene group per chain (abbreviated as (m,n)-DIINPC (where m + n + 6 equals number of C-Atoms per chain) and (2) a phospholipid-like molecule with a polymerizable methacryl ligand connected to the phosphate head group via (CH2CH2O)m spacers which is abbreviated as (m.n)-POMECY (n = number of C-atoms per chain). — Phase diagrams of the lipid mixtures are established by static light scattering in combination with freeze fractur…

Untersuchungen von polymeren im massenspektrometer, 6. Poly(oxy-1,4-phenylen), poly(thio-1,4-phenylen) und poly(dithio-1,4-phenylen)

Der thermische Abbau von Poly(oxy-1,4-phenylen), Poly(thio-1,4-phenylen) und Poly(dithio-1,4-phenylen) wurde durch direkte Pyrolyse in der Ionenquelle des Massenspektrometers untersucht. Bei verringerter Elektronenenergie (15 eV) konnten die elektronenstosinduzierten Fragmentierungen der Pyrolysebruchstucke weitgehend zuruckgedrangt und die thermischen Abbaumechanismen ermittelt werden. In Abhangigkeit von den Bruckenatomen werden charakteristische Unterschiede im Abbauverhalten und in der Art der gebildeten Bruchstucke gefunden. Am Beispiel des Poly(dithio-1,4-phenylen)s kann gezeigt werden, das temperaturprogrammierte Pyrolyse und Verwendung eines Datensystems zur Ermittlung von thermisch…

Pharmakologisch aktive Polymere, 14. Modellsysteme zur Untersuchung der Abspaltung niedermolekularer Komponenten von polymeren Pharmaka

Fast photoconduction in the highly ordered columnar phase of a discotic liquid crystal

THE search for organic materials suitable for electronic applica-tions dates back to the early 1950s. But the only organic systems known so far to show electronic charge-carrier mobilities comparable to the amorphous inorganic semiconductors that are the main-stay of the microelectronics industry are zone-refined organic single crystals1–4. Single crystals are difficult and costly to process, however, and are not suitable for device applications. Here we show that a highly ordered columnar (stacked) phase of disk-like organic molecules can exhibit high mobilities for photoinduced charge carriers, of the order of 0.1 cm2 V-1 s-1—higher than for any organic material other than single-crystal …

Binding, Interaction, and Organization of Proteins with Lipid Model Membranes

Model membrane systems are used to investigate protein recognition and binding at interfaces. Fluorescence microscopy results are presented for interactions of the proteins, phospholipase A2 and antifluorescyl IgG, at lipid monolayer interfaces. Total internal reflection fluorescence measurements are used to quantify albumin and IgG adsorption to supported lipid monolayers.

Reduced protein adsorption on plastics via direct plasma deposition of triethylene glycol monoallyl ether

The direct plasma-induced deposition of tri(ethylene glycol) monoallyl ether is reported. RF plasma polymerization of this monomer was carried out under both continuous wave (CW) and pulsed plasma operation. The major focus of this work was optimization of the degree of retention of the C-O-C bonds of the starting monomer during the deposition process. This successfully was accomplished using low RF power during the CW runs and low RF duty cycles during the pulsed plasma experiments. Spectroscopic analysis of the plasma films revealed a strong dependence of film composition on the RF power and duty cycles employed. In particular, an unusually high level of film chemistry compositional contr…

Light Induced Modifications of Langmuir-Blodgett-Multilayer Assemblies Containing Amphotropic Azocopolymer

Abstract Photochromic LB-multilayers of amphotropic copolymers having rod-like azobenzene moieties as side groups which exhibit thermotropic liquid crystalline behaviour in the bulk have been characterized by UV-VIS spectroscopy as well as by angular dependent and energy dispersive SAXS. Upon irradiation with UV-light the initial optical in-plane anisotropy and the vertical layered structure of LB-films can be destroyed. A new layered structure can be rebuilt on irradiation with visible light or by annealing. Using linearly polarized light for the irradiation an optical anisotropy (POA) has been induced or reversibly modified by a photoselection process.

Polymer-supported bilayer on a solid substrate

The synthesis and polymerization of 2-cyanoethyl N-vinylcarbamate (3b) and of the corresponding 2-trimethylsilylethyl isomer 3c are reported. The homopolymers 4b and 4c, derived from 3b and 3c, could be deblocked under mild conditions (ethanolamine for 4b and trifluoroacetic acid or tetraethylammonium fluoride for 4c) with essentially 100% unmasking of the amino function. Treatment of such unmasked amino groups in a copolymer derived from N-vinyl-2-pyrrolidone and 3b with 4-{4-[bis(2-chloroethyl)amino]phenyl}butyryl chloride (13) (chlorambucil chloride) gave the corresponding amide, a potential antitumor agent. Kinetic studies showed that fluoride ion cleavage of poly(2-trimethylsilylethyl …

To obtain a carrier polymer for pharmacologically active components, linear polyethyleneimine (LPEI) was chemically modified by reactions with acrylic acid (1a), acrylamide (1b), acrylic acid esters (1c and 1d), sodium chloroacetate, and hydrochloric acid. All product polymers 2a – 2e are soluble in water. Among these, 2a and 2e, β- and α-amino acid derivatives, respectively, show no acute toxicity in mice up to dosages of 1 g/kg i. v. Similar types of polymers 5a and 5b and a polymer containing phosphonic acid moieties (5d) derived from branched polyethyleneimine (BPEI) were prepared. 5a and 5b are also nontoxic regardless of the molecular weight of four kinds of BPEI and of the wide range…

Illumination-related pattern formations in lipid monolayers

We report on the phenomenon that in the two phase coexistence region (LC-LE) of a lipid monolayer film the fractal-like solid domains may grow simply by continuous illumination of a fluorescence microscope. The mechanism of this 2D domain growth is discussed. This phenomenon gives insight into the two-dimensional ramified crystallization in monolayers.

Stability of liposomes composed of polymerizable and/or natural phospholipids

Structure and phase transitions of a liquid crystalline polymer

The structures, textures as well as thermodynamic properties of a side chain polymer exhibiting a liquid crystalline phase in addition to a partially crystalline state and the isotropic fluid state were investigated. Furthermore the kinetics of phase transitions between these states were analyzed. It was found that the properties of this polymer are intermediate between that of low molecular weight liquid crystals and common polymers. In particular it was observed that the relation between the liquid crystalline texture and the structure is different from that of low molecular weight liquid crystals and that the properties of the crystalline and liquid crystalline state depend strongly on t…

Polyreactions in oriented systems, VIII.. Polymerization of a liquid crystalline monomer under the influence of a high magnetic field

Monolayers of Bolaform Amphiphiles: Influence of Alkyl Chain Length and Counterions

We have prepared self-assembled monolayers of novel cationic bolaform amphiphiles on negatively charged substrates. Most of these amphiphiles form smooth, defect-free monolayers which can be used to reverse the substrate surface charge and thus allow subsequent adsorption of anionic molecules and construction of multilayers. Atomic force microscopy, surface force measurement, and surface plasmon spectroscopy were combined to probe the molecular orientation and ordering, mechanical properties, and surface electrical properties of the monolayers. In addition, the amphiphile aggregation behavior at an air-water interface was studied by surface tension measurement, and lyotropic phase behavior …

Force probe measurements of antibody-antigen interactions.

The surface force apparatus has been used to quantify directly the forces that govern the interactions between proteins and ligands. In this work, we describe the measured interactions between the antigen fluorescein and the Fab' fragment of the monoclonal 4-4-20 anti-fluorescyl IgG antibody. Here we first describe the use of the surface force apparatus to demonstrate directly the impact of the charge composition in the region of the antibody binding site on the antibody interactions. Several approaches are described for immobilizing antigens, antibodies, and proteins in general for direct force measurements. The measured force profiles presented are accompanied by an extensive discussion o…

Hermann Staudinger and the Future of Polymer Research Jubilees — Beloved Occasions for Cultural Piety

Polymeric amphiphiles with hydrophilic main chain spacers: Studies in monolayers and Langmuir-Blodgett multilayers

A methacrylic lipid was polymerized to form an amphiphilic homopolymer and random copolymers with various levels of acrylic acid comonomers. The behavior of these polymeric lipids was investigated in monolayers at the air-water interface and in Langmuir-Blodgett multilayers on polymer foil supports. The acrylic acid acts as a hydrophilic spacer along the polymer backbone, and improves the ability of the polymer to self-organize into highly ordered monolayers and ultimately LB multilayers. It is shown that the quality and stability of the multilayers increase substantially with the increase in comonomer content.

Influence of molecular weight and polydispersity on phase behaviour of polyesters with laterally fixed or cross-shaped mesogens

Abstract To supplement previous studies of polyesters with laterally attached and cross-shaped mesogens the influence of molecular weight and molecular weight distribution on the phase behaviour has been investigated. For that purpose two polyesters have been fractionated by preparative gel permeation chromatography under high pressure and observed by polarizing microscopy and DSC measurements. A monotropic nematic polyester with laterally attached mesogens shows changing phase transitions up to a molecular weight of 10 000 (Mw); at higher molecular weight only the clearing transition is still slightly influenced. The molecular weight distribution at an average molecular weight of 15 000 (M…

Electronic and mechanical characterization of self-assembled alkanethiol monolayers by scanning tunneling microscopy combined with interaction-force-gradient sensing.

We have used scanning tunneling microscopy to study self-assembled monolayers of mercaptohexadecanol in ultrigh vacuum. In addition to tunneling, the interaction force gradient acting between tip and sample was measured. Analysis of the force-gradient data shows that the tip is in mechanical contact with the surface of the monolayer which, in turn, is elastically compressed. The lateral dimensions of the mechanical contact are substantially (approximately five times) larger than the width of the tunneling-current filament. The results suggest that the compression of the monolayer constitutes an integral part of tunneling through the molecules

An emotional contribution to the Festschrift of the Journal of Biomaterials Science for Teiji Tsuruta

AbstractIt is a honor for me to contribute to the ‘Festschrift for Teiji Tsuruta’! Being old, it is much easier for me to look back than to think ahead. Thus, please allow me to make a few ‘historical remarks’ about Biomaterials and Biotechnology, long before Science stepped in. Remarks about Georg Christoph Lichtenberg, the Gottinger physicist and philosopher, and his relation to Teiji Tsuruta. And talking about him as teacher, one cannot do it without looking at Hermann Staudinger and his dreams.

Photoreactions in Langmuir-Blodgett-Kuhn multilayer assemblies of liquid crystalline azo-dy side-chain polymers

Reversible and persistent optical data storage in Langmuir-Blodgett-Kuhn liquid crystalline systems has been reported recently. Depending on the molecular structure, the trans-cis isomerization in these systems (induced by illumination with UV- and VIS-light) leads to different macroscopic behavior of the chromophore percentage on the photo-induced structural changes in a series of statistical copolymers.

Two-Dimensional Assembly Formation of Hydrophobic Helical Peptides at the Air/Water Interface: Fluorescence Microscopic Study

Monolayer formation of hydrophobic α-helical peptides, X-(Ala-Aib) 8 -Y (X=Boc-, HOOCCH 2 CH 2 CO-, biotinyl, biotinyl-(Sar) 3 -; Y=OMe, OBzl, OH), at the air/water interface was studied by the fluorescence microscopic method. Some peptides showed a mound in the π-A isotherm. When the monolayer containing a small amount of FITC-labeled peptide was held at the surface pressure corresponding to the top of the mound, bright and dark domains were observed by fluorescence microscopy. Domain formation was also observed by the addition of a cationic dye (DiIC 1 ) into the subphase underneath the peptide monolayer. The mound in the π-A isotherm is, therefore, ascribed to the phase transition from a…

Nonlinear optical self diffraction effects for a light beam in a liquid crystalline polymer in its isotropic fluid state was observed. This effect is characterized by the absence of a threshold intensity, a diffraction pattern that does not depend on the polarization of the reading beam relative to that of the writing beam and which cannot be disturbed by transversally applied static electrical fields. This effect is attributed to a thermally induced spatial refractive index modulation. The time constants of the response are of the order of ms.

Incorporation of Membrane Proteins in Solid-Supported Lipid Layers

The electro-optical properties of liquid crystalline polymers with polar mesogenic units in the side chain were investigated. It could be shown, that in an electric field, they show all effects known from low molecular weight liquid crystals, e.g. the Freedericksz-transition, the DAP-effect, the formation of William's domain, and the dynamic scattering. The optical response times are slightly longer than for low molecular weight liquid crystals, but in some cases at higher temperatures as short as 200 ms. By comparison of different polymers and some corresponding liquid crystalline monomers, it is found that: (1) the difference between the measuring temperature and the glass transition temp…

Cinnamic acid moieties were incorporated into amphiphilic compounds containing one and two alkyl chains. These lipid-like compounds with photoreactive units undergo self-organization to form monolayers at the gas-water interface and bilayer structures (vesicles) in aqueous solutions. The photoreaction of the cinnamic acid moiety induced by 254 nm UV light was investigated in the crystalline state, in monolayers, in vesicles and in solution in organic solvents. The single-chain amphiphiles undergo dimerization to yield photoproducts with twice the molecular weight of the corresponding monomers in organized systems. The photoreaction of amphiphiles containing two cinnamic acid groups occurs v…

Monolayers of rod-shaped and disc-shaped liquid crystalline compounds at the air-water interface

Calamitic (rod-shaped) and discotic (disc-shaped) thermotropic liquid crystalline (LC) compounds were spread at the air-water interface, and their ability to form monolayers was studied. The calamitic LCs investigated were found to form monolayers which behave analogously to conventional amphiphiles such as fatty acids. The spreading of the discotic LCs produced monolayers as well, but with a behaviour different from classical amphiphiles. The areas occupied per molecule are too small to allow the contact of all hydrophilic groups with the water surface and the packing of all hydrophobic chains. Various molecular arrangements of the discotics at the water surface to fit the spreading data a…

Complex Ordering in Thin Films of Di- and Trifunctionalized Hexaalkoxytriphenylene Derivatives

We have used pressure−area isotherms, X-ray diffraction, atomic force microscopy, and infrared dichroism to study Langmuir and Langmuir−Blodgett films of 2,3,6,7,10,11-hexaalkoxytriphenylenes which...

Molecular recognition in biotin-streptavidin systems and analogues at the air-water interface

Abstract Specific interaction between biotin and the protein streptavidin in monolayers of synthetic lipids with biotin headgroups has been shown to lead to formation of highly ordered two-dimensional streptavidin crystals. The same behaviour is observed when using desthiobiotin as lipid headgroup which exhibits a significantly lower binding constant compared with biotin (5 × 10 13 M -1 compared with 10 15 M -1 ). This offers the possibility of detaching competetively the 2D crystalline streptavidin layer by addition of free biotin to the aqueous phase. Use of lipoic acid as lipid headgroup ( K a = 7 × 10 7 M −1 ) leads to formation of small snisotropic protein domains indicating a crystall…

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.

Modeling of Cell Membrane Targeting: Specific Recognition, Binding, and Protein Domain Formation in Ligand-Containing Model Biomembranes

Drug delivery systems are designed to assist, accelerate, and control transport of pharmacologically active agents from sites of administration to specified targets in organs and tissues. So-called controlled drug delivery systems are intended to maintain continuously efficacious drug concentrations in vivo, either locally or systemically, over longer time periods. They should provide constant dosage levels above a minimum level of efficacy yet below mandated toxicity levels — a significant advantage over many conventional systemically administered formulations. Site-specific targeting of drugs, particularly those agents which prove highly toxic in small doses, can be utilized to maintain t…

ChemInform Abstract: Synthesis of a Fullerene Derivative of Benzo(18)crown-6 by Diels-Alder Reaction: Complexation Ability, Amphiphilic Properties, and X-Ray Crystal Structure of a Dimethoxy-1,9-(methano(1,2)benzenomethano) fullerene(60) Benzene Clathrate

A fullerene derivative 1 of benzo[18]crown-6 was obtained by Diels-Alder addition of fullerene[60](C60) to the ortho-quinodimethane prepared in situ from 4,5-bis(bromomethyl)benzo[18]crown-6 (3) with Bu4NI in toluene. Extraction experiments show that the complexation of K+ ions strongly increases the solubility of 1 in protic solvents like MeOH. Using Langmuir-Blodgett techniques, monolayers of the highly amphiphilic fullerene-derived crown ether 1 and its K+ ion complex were prepared. An X-ray crystal structure was obtained from a benzene clathrate of comparison compound 2, synthesized by Diels-Alder reaction of C60 with the ortho-quinodimethane derived from 1,2-bis(bromomethyl)-4,5-dimeth…

Structural variations of liquid crystalline polymers with phasmidic-type mesogens

Abstract The fixation of phasmidic-type mesogens through spacer groups to polysiloxane backbones provided a method of obtaining liquid crystalline polymers with phasmidic mesogens as side groups. The polymer 6b showed a bilayer structure in the mesophase range. The tendency to form liquid-crystalline phase depends on the number and the length of alkoxy substituents.

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

Hermann Staudinger und die Zukunft der Polymerforschung Jubiläumsfeiern– selbstbestimmter Anlass kultureller Frömmigkeit

Light-driven proton transport of bacteriorhodopsin incorporated into long-term stable liposomes of a polymerizable sulfolipid

Abstract The chromoprotein bacteriorhodopsin from Halobacterium halobium has been incorporated into liposomes made of a fully synthetic, polymerizable lipid. Bacteriorhodopsin is found to be active in these polymer liposomes. The advantage in the use of such polymer systems concerning long-term stability in comparison with liposomes made of natural lipid is demonstrated.

Second-harmonic generation in Langmuir–Blodgett monolayers of stilbazium salt and phenylhydrazone dyes

The second-order nonlinear optical susceptibilities χ(2) of several phenylhydrazone and stilbazium salt dyes in Langmuir–Blodgett monolayers have been determined from second-harmonic-generation measurements. Three of the substances demonstrated χ(2) values greater than 10−6 electrostatic units, although two of the three did not absorb light significantly at the second-harmonic wavelength.

Drug carriers were prepared by combining oligopeptidic sequences with synthetic polymeric chains. Soluble copolymers of N-(2-hydroxypropyl)methacrylamide (HPMA) were synthesized containing oligopeptidic side chains terminating in a drug model (p-nitroaniline). The susceptibility of these oligopeptidic sequences to degradation on incubation with lysosomal enzymes and human serum was evaluated by monitoring the p-nitroaniline liberation. It was shown that the drug model can be attached to the polymer carrier by means of an oligopeptidic spacer stable in blood serum and degradable after the polymer has been in contact with intracellular lysosomal enzymes. The studied polymer carriers were used…

Untersuchungen von polymeren im massenspektrometer, 5. Fragmentierungsreaktionen oligomerer oxy- und thio-1,4-phenylene

Als Modellverbindungen zur Differenzierung von thermischen und elektronenstosinduzierten Abbaureaktionen von entsprechenden Polymeren im Massenspektrometer wurden die Fragmentierungsreaktionen oligomerer 1,4-Phenylene mit Sauerstoff-, Schwefel- und Disulfidbrucken sowie eine Reihe alternierender Co-oligomersysteme untersucht. Bei verringerter Ionisationsenergie (15 eV) treten in den Massenspektren aller unzersetzt fluchtigen Oligomeren die Molekulionen als intensivste Peaks auf, so das–bei strukturell gleichen Polymeren–eine eindeutige Identifizierung von thermischen Abbauprodukten erwartet werden kann. In Abhangigkeit von den Bruckenatomen werden charakteristische Unterschiede in den Inten…

Epifluorescence microscopy studies of fatty acid monolayers: Domain formation induced by polymeric gegenions

The monolayer behavior of long-chain fatty acids at the air/water interface on a poly(ethyleneimine) containing subphase was investigated. The interaction of the polymeric gegenions in the subphase leads to expanded states and permits the visualization of the aggregation behavior of different long-chain fatty acids via fluorescence microscopy. The monolayer morphologies and their variability were intensively studied by fluorescence microscopy. In addition, the transfer of the complexed fatty acid monolayers to solid substrates has been investigated.

Ylide als polymerisationsinitiatoren. I. Salzhaltige und salzfreie phosphoniumylide

Phosphorylide, R3PCHX und R3PCH2·LiBr, konnen eine anionische Polymerisation von Vinylmonomeren starten. Dabei werden im Falle des Methacrylnitrils und des Methylmethacrylats die Ylide als Endgruppen in die Polymeren eingebaut. Bei den salzfreien Yliden hangt die Startwirksamkeit von der Basizitat des Ylidcarbanions ab, die Struktur dieser Ylide hat aber keinen mesbaren Einflus auf das Molekulargewicht und die Taktizitat der entstehenden Polymeren. Im Gegensatz dazu wird bei der Initiierung mit den salzhaltigen Yliden auch die Taktizitat der Polymeren von den Substituenten der Phosphorylide beeinflust. Phosphorous ylids, R3PCHX and R3PCH2·LiBr, are able to start an anionic polymerization of…

Molecular mechanisms determining the strength of receptor-mediated intermembrane adhesion

The strength of receptor-mediated cell adhesion is directly controlled by the mechanism of cohesive failure between the cell surface and underlying substrate. Unbinding can occur either at the locus of the specific bond or within the bilayer, which results in tearing the hydrophobic anchors from the membrane interior. In this work, the surface force apparatus has been used to investigate the relationship between the receptor-ligand bond affinities and the dominant mechanism of receptor-coupled membrane detachment. The receptors and ligands used in this study were membrane-bound streptavidin and biotin analogs, respectively, with solution affinities ranging over 10 orders of magnitude. With …

Liquid-crystalline copolymers with covalently attached dichroic dyes were synthesized and characterized. Copolymers with high anthraquinone and trisazo-dye content were obtained by copolymerization of dye monomers with 4-cyanophenyl 4-(6-acryloyloxyhexyloxy)benzoate (1) and 6-acryloyloxyhexyl 4-(trans-4-propylcyclohexyl)benzoate (2). Particular attention is given to the influence of the dye content and the dye structure on the liquid-crystalline behavior of the copolymers.

Formation of supramolecular aggregates by hydrogen bonding based on bispyrimidine and bisbarbituric acid

Hydrogen bonds between bispyrimidine and bisbarbituric acid in equal molar ratio can lead to the formation of supramolecular aggregates. This is established by TEM, IR and DSC measurements. Additionally, WAXS pattern showed that the aggregate is of laminar structure. Both the hydrolysis of this system and termination of the aggregate's growth were studied.

DOMAIN AND MOLECULAR SUPERLATTICE STRUCTURE OF DODECANETHIOL SELF-ASSEMBLED ON AU(111)

Annealed organic monolayers of dodecanethiol (CH3(CH2)11SH) self-assembled on Au(111) have been investigated by scanning tunnelling microscopy. By using very high tunnelling resistances (TOMEGA) we find evidence of well-ordered molecular domains at room temperature and observe two different types of c(4 x 2) superlattice structures with the same rectangular unit cell. In contrast to theoretical calculations each unit cell contains four inequivalent molecules. Possible reasons for this discrepancy are discussed.

An enzyme caught in action: Direct imaging of hydrolytic function and domain formation of phospholipase A2 in phosphatidylcholine monolayers

AbstractPhospholipase A2, a ubiquitous lipolytic enzyme that actively catalyses hydrolysis of phospholipids, has been studied as a model for enzyme-substrate reactions, as a membrane structural probe, and as a model for lipid-protein interactions. Its mechanism of action remains largely controversial. We report here for the first time direct microscopic observation of the lipolytic action of fluorescently marked phospholipase A2 (Naja naja naja) against phosphatidylcholine monolayers in the lipid phase transition region. Under these conditions, phospholipase A2 is shown to target and hydrolyse solid-phase lipid domains of L-α-dipalmitoylphosphatidylcholine. In addition, after a critical ext…

Micellar and lyotropic behavior of three isomeric bola-amphiphiles with pyridinium groups

The micellar and lyotropic phase behavior of three isomeric bola-amphiphiles 1, 2 and 3 based on para-, meta- and ortho-phenylene derivatives with hydrophilic pyridinium headgroups was investigated. The micellar behavior was characterized by surface-tension and conductivity measurements: while the para-substituted amphiphile 1 and the ortho isomer 3 aggregated to micelles, the meta-substituted amphiphile 2 exhibited stepwise, but discontinous self-association. This is explained by the mass-action and phase-separation model. The existence of “premicellar” aggregates and the discontinous aggregation of 2 is evidenced in addition by a difference-spectro-photometric measurement. The low surface…

Covalently attached polymer mono- and multilayers on silanized glass substrates

Abstract Applying grazing incidence FTIR and ellipsometry, the reaction of poly [(1-methyl-vinyl isocyanate)-alt-(maleic anhydride)](IAP) with amino-silanized glass and silicon oxide surfaces has been investigated. A reactive surface containing isocyanate and anhydride groups was formed after the adsorption of the polymer. The layer could be further functionalized using 2-aminoethanol. Multilayers could be built up by adsorbing a second layer of IAP onto an already reacted first layer of IAP.

The synthesis and phase behaviour of azo dye containing liquid crystalline side group copolymers are described. These Copolymers show the same electro-optical effects as low molar mass guest-host systems. Their macroscopic oriented nematic structure can be frozen in below the glass transition temperature resulting in a polymer film with dichroic properties. The behaviour of the copolymers (phase behaviour, surface and electric field orientation) can be improved via mixtures with low molar mass liquid crystals.

Molecular dynamics in liquid crystalline N-acylated oligoethylenimines as studied by broadband dielectric spectroscopy

The molecular dynamics and the charge transport in six liquid crystalline N-acylated oligoethylenimines were investigated by dielectric spectroscopy. The dielectric spectra in the temperature range from 125 K up to 400 K and in the frequency range between 10 -2 Hz and 10 7 Hz could be described by a conductivity contribution and three relaxation processes. The molecular assignment of the α-process is a relaxation of the rigid benzamide unit. Its mean relaxation time is influenced by the length of the alkoxy side chains, the spacer length (ethylene or propylene groups) and the neighboring repeating units. In the columnar mesophase this process is cooperative due to sterical hindrance. A norm…

Supramolecular assembly using helical peptides

Abstract We investigated supramolecular assemblies of various hydrophobic helical peptides. The assemblies were formed at the air/water interface or in aqueous medium. The hexadecapeptide, Boc-(Ala-Aib)8-OMe (BA16M), was reported to take α-helical structure by X-ray analysis. Several derivatives were prepared, which have the repeating sequence of Ala-Aib, Lys(Z)-Aib or Leu-Aib, or have the terminal chemically modified. CD spectra of the peptides indicated helical conformation in ethanol solution. The surface pressure-area isotherms of the peptide monolayers showed an inflection at the surface area corresponding to the cross section along the helix axis, and the monolayers were collapsed by …

Neural cell pattern formation on glass and oxidized silicon surfaces modified with poly(N-isopropylacrylamide)

Control over the adsorption of proteins and over the adsorption and spatial orientation of mammalian cells onto surfaces has been achieved by modification of glass and other silicon oxide substrates with poly(N-isopropylacrylamide) (PNIPAM). The functionalization of the substrates was achieved either by a polymer-analogous reaction of aminosilanes with reactive N-(isopropylacrylamide) (NIPAM)-copolymers and by copolymerization of NIPAM with surface-bound methacrylsilane. The obtained coatings were characterized by FT-1R, ellipsometry, and surface plasmon resonance measurements. The adsorption of two proteins-fibrinogen and ribonuclease A-on these surfaces was studied in situ by real time su…

Material transport and organizing phenomena of Langmuir—Blodgett membranes from polymerizable built up diacetylene amphiphiles on hydrophobic supports

Abstract Langmuir—Blodgett multilayers of polymerized diin amphiphiles on different porous, hydrophobic ultrafilters have been studied as composite membranes under the conditions of reverse osmosis. Influences of differently structured surfaces of the supports on structure and phase change occurring during polymerization have been investigated by scanning electron microscopy and X-ray diffraction and are discussed with reverse osmosis data. When conditioned, fine porous hydrophobic supports become permeable to aqueous solutions at low pressures. Under these conditions permeate flux and retention were found to depend on the number of layers deposited.

Pharmakologisch-aktive polymere, 19. Polymere mit kovalent gebundenem streptomycinsulfat

Polymerizable phospholipid analogues--new stable biomembrane and cell models.

Giant liposomes as model membranes for immunological studies: spontaneous insertion of purified K1-antigen (poly-alpha-2,8-NeuAc) of Escherichia coli.

A flow chamber has been constructed to use giant liposomes (diameter 5-50 microns) as model membranes for immunological studies and other experiments involving the interaction with water-soluble compounds. As an example of immunological importance, the insertion of purified K-antigen from Escherichia coli K1 has been studied. Despite its large hydrophilic part (poly-alpha-2,8-NeuAc), which is capped at its potential reducing end with phosphatidic acid acting as a lipid anchor group, this water-soluble material is readily incorporated into liposomal membranes of dimyristoylphosphatidylcholine (DMPC). The incorporation has been proven by immunofluorescence using a FITC-labeled monoclonal anti…

The stability and functional properties of proteoliposomes mixed with dextran derivatives bearing hydrophobic anchor groups

Liposomes composed of Escherichia coli phospholipid were coated with polysaccharides bearing hydrophobic palmitoyl anchors. The effect on the stability of liposomes without or with integral membrane proteins was investigated. A high concentration of hydrophobized dextrans protected the liposomes against detergent degradation, decreased the fluidity of the membranes, prevented fusion of the liposomes and enhanced their stability. Proteoliposomes containing beef heart cytochrome-c oxidase and the lactose transport carrier of E. coli were similarly affected by coating with the dextrans. Under these conditions both membrane proteins were still active. Long-term stability of the coated liposomes…

Mixed monolayers of natural and polymeric phospholipids: structural characterization by physical and enzymatic methods

This study has focused on physical characterization and enzymatic hydrolysis of mixed monolayers of a natural phospholipid substrate and a polymerizable phospholipid analogue. Such a mixed system presents the possibility to stabilize model biomembranes, vary the molecular environment within the layer through polymerization and simultaneously examine these influences on monolayer structure. Phospholipase A2 was used here as a sensitive probe of the molecular environment within these mixed, polymerizable monolayers to complement information obtained from isotherm and isobar data. The results clearly show a strong influence of molecular environment on phospholipase A2 activity, even if differe…

Structure formation in doped discotic polymers and low molar mass model systems

Abstract Doping of low molar mass materials or polymers, possessing disc-like units, with electron acceptors leads to the stabilization of columnar discotic phases or even to the induction of such phases in compounds which either display a nematic discotic phase or only an amorphous phase in the absence of the electron acceptor. The induced columnar phase corresponds frequently to a hexagonally ordered one. We have observed, however, in addition the induction of new columnar phases such as the rectangularly ordered (Dro) and the columnar nematic phase (Nc). The enhancement of the tendency towards the formation of columnar phases is a consequence of electron acceptor—electron donor complex f…

Etude de polyesters avec du triphenylene ou du benzene comme cœur du discogene et des espaces flexibles alkylene

Riding tandems with nature

A number of acryl and methacryl derivatives of different sulfanilamides (1a—I) were prepared and polymerized. The fixation of the sulfonamide to the polymerizable group was carried out directly, using the acryl- and methacrylamides, and by means of spacer groups, to favour the enzymatic or hydrolytic release of the drug moiety. Selected sulfonamide types of different pKA values were used, and the pH-dependant solubility of the corresponding polymers was studied. The monomeric acryloyl and methacryloyl sulfonamides were homopolymerized radically by AIBN. For distribution studies polysulfadiazineacrylamide, 14C-labelled in the main chain (2e'), was synthesized. Copolymerization with 2-methyls…

The dielectric relaxation properties of a combined main-chain/side-chain liquid-crystalline polymer were investigated. It was found that the rotation of the side chain about the main chain (δ-process) is not as strongly restricted as in side-chain liquid-crystalline polymers. This is attributed to the facts that the side chain is attached to the flexible spacer within the chain backbone and that the concentration of the side chains is comparatively small. Two low-temperature relaxation processes were observed to occur in the glassy smectic and the crystalline state. They are attributed to intramolecular motions with in the mesogenic groups.

Infrared absorption study of hexapentyloxytriphenylene A discotic liquid crystal

Abstract Fourier transform infrared absorption (FTIR) spectroscopy has been used to study a discotic liquid crystal. IR spectra are reported as a function of temperature for hexapentyloxytriphenyle...

Inkorporation von Membranproteinen in festkörperunterstützte planare Lipidfilme

Structural variations in amphiphiles: Discoidal multivalent cations

Fourteen cationic multipolar amphiphiles have been synthesized with pyridinium or trimethylammonium head groups. The hydrophobic cores are planar ring systems (benzene or triphenylene) to which two, three, four, or six decylene or undecylene alkyl chains are attached by ester linkages. The hydrophilic head groups are bound to the outer ends of the alkyl chains.

Komplexierung von Übergangsmetall-Ionen mit substituierten Azamakrocyclen: Induktion columnarer Mesophasen durch molekulare Erkennung

Structure and Dynamics of Liquid Crystalline Polymers from Deuteron NMR

The molecular structures of thermotropic liquid crystalline polymers, which have been synthesized systematically in recent years, are described according to the model of decoupling the molecular motions of the mesogenic groups and the polymer chain by inserting a flexible spacer. The molecular structure is related to the properties of these systems, e.g., phase transition temperatures, mesophases formed, etc. The structure and mobility of a specific side chain, liquid crystalline polyacrylate with phenyl benzoate as a mesogenic group is investigated by deuteron NMR and compared with the behaviour of low molecular weight analogues selectively deuterated at equivalent positions, i.e., at the …

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

Molecular Recognition by Hydrogen Bonding in Polyelectrolyte Multilayers

Functional polyanions were prepared by copolymerization of sulfopropyl acrylate and sulfopropyl methacrylate with monomers bearing triaminopyrimidine or barbituric acid functionalities, respectively. Functionalized polyelectrolyte multilayers were assembled from these copolymers by stepwise alternating adsorption with poly(choline methacrylate). These multilayers are suited for molecular recognition of substrates that are complementary to the functional groups incorporated. Thus, multilayers containing triaminopyrimidine moieties selectively bind barbituric acid, and vice versa, when exposed to solutions of the 1:1 complex of barbituric acid and triaminopyrimidine. The molecular recognition…

The molecular order and mobility of two liquid-crystalline polyacrylates with phenyl benzoate moieties as mesogenic side groups and (CH2)m spacers (m = 2 and m = 6) were investigated by pulsed 2H NMR. The mesogenic side groups were isotopically labelled at the terminal phenylene ring. In the glassy state the orientational distribution function was characterized from the angular dependence of the 2H NMR line shape of samples macroscopically ordered in their nematic phase by the 8,4 T magnetic field of an NMR spectrometer. It was found to be Gaussian with widths of ± 18,5° and ± 10,5° for the m = 2 frozen nematic and m = 6 frozen smectic system, respectively. The phenylene rings undergo 180° …

The formation and the behaviour of radiation induced free radicals in poly[1-(tert-butoxy carbonylthio)ethylene] (2) and in a statistical copolymer 4 from O-tert-butyl S-vinyl thiocarbonate (1) with N-vinylpyrrolidone (1:1) was studied, using ESR spectroscopy. After γ-irradiation at 77 K, tert-butyl radicals and other species were detected in the polymers. The yield for the homopolymer was evaluated to be Gtert-butyl = 0.18. Investigations on the behaviour of radicals with an annealing procedure revealed, that at first the tert-butyl radicals disappear with increasing temperature and that a further warming up leads to a concentration rise of this radical species. A radical cation localized …

Donor-acceptor substituted polyenes : orientation in mono- and multilayers

Large molecules containing different chemical units whose interactions within the molecule result in new macroscopically observable effects, have become increasingly important.The organization of molecules of this type in ordered structures leads to functional molecular materials.Their use in molecular electronics requires that the units exhibit specific electronic properties. Recently, we reported on the intramolecular energy transfer through terminally substituted conjugated polyenes. An intramolecular electron transfer within donor-acceptor substituted polyenes can be achieved by introducing suitable terminal groups.

Methacryloyloxyalkyltrimethylammonium chlorides (1a–c) with different alkyl chain lengths were synthesized and polymerized radically with 4,4′-azobis(4-cyanovalerianic acid) and K2S2O8 as initiators. With K2S2O8 as initiator, reaction orders of 0,5 and 1 with respect to initiator and monomer, were found. For the ionic monomers with longer alkyl chains the ratio of rate constants kp(2fkd/kt)0,5 was determined over a wide concentration range. It was found that with decreasing monomer concentration the ratio of rate constants increases, which is caused by a diminished termination rate because of an increased electrostatic repulsion of the ionic polymer radicals in dilute solution (increase of …

Investigation of polymers in the mass spectrometer, 7. Pyrolysis-gas chromatography-mass spectrometry of low molecular and high polymeric sulfanilamides

A number of low molecular, monomeric and polymeric sulfanilamide derivatives, which have found interest as possibly selective antitumour agents, were investigated by pyrolysis-gas chromatography (GC)-mass spectrometry (MS). Thermal degradation mechanisms were studied using also direct polymer pyrolysis in the ion source of the mass spectrometer. Thermal degradation products as well as low molecular weight sulfanilamides and related model compounds were characterized in their fragmentation behaviour by low and high resolution electron impact and field desorption mass spectrometry. Thermal fragments of structural significance were found, and a differentiation of the low and high molecular sul…

Polymeric monolayers and liposomes as models for biomembranes

Polymer chemists as poachers in foreign grounds? Why not? Macromolecular chemistry has become a mature science with all advantages and handicaps of a well-established scientific discipline: many heights are conquerred and the harvest is abundant, but adventures and the future might be elsewhere. Besides, in these times of bottomed out industrial profits in common plastics, future polymer chemistry cannot be limited to repetitive improvement of already successful mass polymers but should rather expand into neighboring fields of material science as well as life science where “polymer thinking” might help to overcome difficulties. — First hesitant steps on the bridge towards membrane biology h…

The synthesis and the thermotropic phase behavior of the dipolar amphiphiles C 5 H 5 N + (CH 2 ) m OCOPhPHCOO(CH 2 ) m N + C 5 H 5 and the polymeric amphiphile [(CH 2 ) 6 OPhPhO(CH 2 ) 6 OCOCH([CH 2 ] 6 N + C 5 H 5 )COO] n are described

Pharmakologisch-aktive polymere, 18. Körperverteilung und ausscheidungsverhalten von monomerem und polymerem sulfadiazinacrylamid

Sulfadiazinacrylamid was absorbed after oral and intraperitoneal application in rats to a high extent; the absorption from the intraperitoneum was retarded. Glucose treatment delayed the absorption after both application forms. At comparatively high renal and enteral excretion rates the biological half life time of the monomer was estimated to 8 h. A tumouraffinity was not found but there were indications for a preferred storage in the RES. Poly[sulfadiazinacrylamide] was absorbed after intraperitoneal injection to a clear extent, where at the beginning of the treatment under simultaneous glucose load the absorption was delayed. 24 h after injection higher concentrations in metabolic organs…

Quadratic Nonlinear Behaviour of Various Langmuir-Blodgett Molecules

The Langmuir-Blodgett (L-B) technique is well known as a method of building-up ordered arrays of organic molecules, and especially as a means of imposing a noncentrosymmetric structure from molecules that crystallize in a centrosymmetric space group(1–3). L-B films for use in quadratic nonlinear optics can be ordered in a statistically noncentrosymmetric lattice. The method involves the compression of a mono-layer of the organic molecule, spread on top of a water surface, into a two-dimensional solid, followed by the repeated dipping of the substrate to be coated into and out of the subphase. Monolayers may be deposited onto the substrate both on immersion and withdrawal, resulting in a cen…

Structure and properties of pharmacologically active polymers

Although the concept of using pharmacologically active macromolecular compounds as drugs is still regarded with much skepticism for both theoretical and practical reasons, interest in this field has grown in recent years because of the opportunity to take advantage of the specific properties of polymeric materials. For low molecular weight drugs, changes in structure often lead to a loss of specific activity. On the other hand, the properties of macromolecular drugs depend on the structure of the polymer used and this can be varied over a wide range by the incorporation of comonomer units, by the application of polymer-analogous reactions, or by related structural changes. A new model is pr…

Mixed polymeric monolayers and Langmuir-Blodgett multilayers with functional low molecular weight guest compounds

Abstract Mixed monolayers and Langmuir-Blodgett multilayers of functional low molecular weight guest compounds, especially nonlinear optical (NLO) dyes, within the matrix of an amphotropic spacer polymer have been prepared. The polymer matrix enabled the transfer of guest compounds not capable of self-organizing at the air-water interface by themselves. The structure of the LB multilayers and the transfer process were studied by small angle X-ray scattering and UV-visible spectroscopy. Good NLO coefficients were found in the mixed films.

PYROLYSIS-MASS SPECTROMETRY OF TRUXILLIC AND TRUXINIC POLYAMIDES AND RELATED COPOLYAMIDES

Phase behavior of discotic liquid crystalline polymers and related model compounds

Detection of phase transitions in thin films with a quartz crystal microbalance

Abstract The quartz crystal microbalance (QCM) is used to determine the phase transition point of thin films by measuring the change in frequency as a function of temperature. To elucidate this relationship, two types of polymers were studied where the bulk phase transitions were known. We investigated a casted thin film of an amphiphilic polyoxazoline and a Langmuir-Blodgett film comprised of fifteen double layers of an amphotropic polyacrylate. The phase transition points of the thin films could be detected by the QCM which were in the same range as for the bulk materials.

Polymeric Oriented Monolayers and Multilayers as Model Surfaces

All living cells are surrounded by a lipid bilayer membrane in which a variety of proteins (e.g., enzymes) are embedded (fluid mosaic model; Figure 1). Phospholipids and cholesterol represent the major part of the lipids of a biomembrane. Figure 2 illustrates the structure of some typical amphiphilic membrane components with hydrophobic alkyl chains and hydrophilic head groups. The amount of protein in biological membranes varies between 40 and 60%(3); however, in highly specialized membranes values between 20% (myelin sheath of nerve axons; electrical isolator) and 75% (mitochondrial inner membrane; enzyme system of the respiratory chain) may occur. Furthermore, the incorporation of protei…

X-ray scattering experiments on oriented polysiloxanes with paired mesogens and different distances between these swallow-tailed side groups show a remarkable dependence of the smectic monolayer thickness on the degree of dilution, whereas the interplanar distance of the side groups remain nearly constant. Due to the dominating interaction of the mesogenic moieties, the flexible main chain is forced to take part in the layer formation. A packing model is proposed to explain the results of the X-ray studies. For polymers with five or more dimethylsiloxane copolymer segments, a diffuse scattering appears in the smectic as well as in the isotropic phase. This scattering is independent of the o…

Dielectric Relaxation Measurements and X-Ray Investigations of Liquid Crystalline Side-Chain Polymers

In the last few years several liquid crystalline side-chain polymers have been synthesized,1 – 4 which combine the properties of low molecular weight liquid crystals with those of polymers.5 – 9

Scanning tunneling microscopy investigation of tricycloquinazoline liquid crystals on gold

Self-assembled monolayers (SAMs) of hexaalkylthioether derivatives of tricycloquinazoline (TCQ) on Au(111) and tungsten diselenide (WSe2) were investigated by scanning tunneling microscopy (STM). The Au(111) surfaces were found to be etched by the thioether containing solutions. Corroded surfaces which are similar to gold surfaces that were coated with SAMs of thiols or disulfides were revealed by STM. Atomic adsorption spectroscopy proved that an amount of gold that corresponds to ca. 30% of a monolayer was dissolved in the assembly solutions. On gold, the aromatic cores of the molecules were found to be in face-on orientation. The alkyl substituents were in most cases folded upwards and s…

Self-organization of substituted azacrowns based on their discoid and amphiphilic nature

Abstract Cyclame and hexacyclene derivatives, bearing four and six long-chain substituents respectively, were synthesized. They are discussed as monolayer-forming amphiphiles as well as liquid-crystalline-phase-forming thermotropic mesogens. The compounds investigated form ordered monolayers at the gas/water interface. In the monolayer the hydrophilic cyclic head group lies flat on the water surface, whereas the hydrophobic substituents are oriented perpendicularly with respect to the interface. Most derivatives fitted with aromatic substituents exhibit a solid condensed state exclusively. In contrast with this, solid condensed as well as expanded phases can be found when spreading the alip…

Deuteron NMR Relaxation Studies of Combined Main-Chain/Side-Chain Polymers in the Liquid Crystalline and Glassy State

Etude du polymere [O−Ph−CO 2 −Ph(R)−O−CO−Ph−O-(CH 2 ) 10 −] n (R=(CH 2 ) 6 −O−Ph−N=N−Ph−OMe) qui est caracterise par des parametres d'ordre des mesogenes de la chaine principale tres superieurs a ceux des chaines laterales. On observe une biaxialite moleculaire dans toutes les mesophases et dans la phase smectique A

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.

Thiopeptide-Supported Lipid Layers on Solid Substrates

The sequential layer-by-layer formation of peptide-supported bimolecular lipid membranes at solid supports is described. In the first step, thiol-derivatized peptide sequences of 5 and 7 amino acids are assembled on a Au substrate. After activation of their COOH-terminus phospholipid molecules (DMPE) are covalently attached via an amid bond to form a tethered monolayer on the Au electrode. The different preparation steps are analyzed by Fourier transform IR, X-ray reflectometry, and surface plasmon spectroscopy. The latter technique is then also used to on-line monitor at the solid/solution interface the formation of a bilayer by fusion of vesicles prepared from a fluid lipid mixture with a…

Properties of amphiphilic terminally substituted conjugated nonaene- and 2-docosylnonaene carboxylic acids in monolayers at the air-water interface

was a lo-' M Co(NO,), + lo-' M CH,COONa solution, with pH 7.5; the counter electrode was a Pt sheet, conveniently located in the electrochemical cell. After deposition, the electrochemical/electrochromic properties of the films were analyzed in degassed lo-' M KOH electrolyte, in a three electrode cell (Pt wire counter electrode, saturated calomel reference electrode) with optical windows. A PAR 173 potentiostat-galvanostat associated with a PAR 175 function generator was used in the electrochemical experiments. Data were recorded in a analogical X-Y (X-T) recorder. Monochromatic transmission (He-Ne laser, A = 632.8 nm) was recorded in situ, by means of a versatile optical bench; spectral t…

Modes of Structure Formation in Doped Discotic Polymers and Low Molar Mass Model Systems

By doping low molar mass or polymeric liquid crystals containing flat disc-like units with electron acceptors one achieves a stabilization of columnar phases, the induction of a columnar phases in otherwise discotic nematic or even in amorphous systems. Theoretical models based on the assumption of strong electron donator-acceptor (EDA) complex formation are able to account for the structure formation on a molecular level and the thermodynamic properties of the mixtures and the model of diffusion limited aggregation (DLA) for the structure formation on a supermolecular structure.

Synthesis of New Functionalized Discotic Liquid Crystals for Photoconducting Aplications

Abstract The columnar structure of discotic liquid crystals has been shown to be well suited for electronic transport parallel to the columnar axis. To tailor the processibility and mesophase behavior of such materials, several hydroxytriphenylene derivatives were synthesized. These hydroxytriphenylenes can be converted into oligomers, networks or polymers. Further, they can be reduced to arenes which posses reactive sites for classical aromatic substitutions. A number of mixed tail triphenylene derivatives and fluorescent, low symmetry triphenylene discotic liquid crystals were synthesized and characterized.

Columnar phases from semi-discoid molecules. Phase induction via hydrogen bonding and charge transfer interactions

Abstract To investigate the non-linear optical properties of nitrophenylhydrazones, a series of 4-nitro- and 2,4-dinitrophenylhydrazones of substituted aromatic aldehydes were synthesized. It was found that many of the dinitrophenythydrazone derivatives are liquid-crystalline and X-ray investigations show that the mesophase corresponds to a hexagonal columnar structure. To explain this unusual behaviour it is necessary to assume that a mesogenic structure is formed by intramolecular hydrogen bonding of the dinitrophenylhydrazones. Charge transfer induced antiparallel alignment of these moleculer dipoles leads to discoid structures, forming the columnar phases.

Improved stability of black lipid membranes by coating with polysaccharide derivatives bearing hydrophobic anchor groups

Abstract Black lipid membranes were coated with modified polysaccharides bearing hydrophobic palmitoyl and cholesteryl moieties. The changes in membrane structure were investigated using dipicrylamine, a lipophilic ion, as membrane probe. The kinetics of ion transport through the black lipid membranes were studied using the charge pulse relaxation technique. With this technique it was found that it is possible to detect the insertion of the hydrophobic anchor groups of the polysaccharides into the membrane bilayer. As a result of the surface coating, these membranes exhibit a drastically increased long-term stability.

Specific Protein Binding to Functionalized Interfaces

We report on the characterization of specific binding reactions between streptavidin and biotinylated model membrane surfaces. Self-assembly techniques as well as the Langmuir-Blodgett-Kuhn method were employed to prepare reactive, functionalized surfaces on various solid supports in contact with the aqueous protein solution. Plasmon surface polaritons optical measurements as well as atomic force microscopy and studies with the surface forces apparatus give rather detailed information as to the streptavidin monolayer formation, the kinetics of this process (either binding site- or diffusion limited), the selectivity of the reaction at laterally heterogeneous membranes, and the involved inte…

Ellipsometric and fluorescence microscopic investigations of a cyclam derivative at the air/water interface

Synthesis, structure and properties of liquid crystalline polymers

The following is an extended abstract of a paper presented at the conference on Liquid Crystalline Polymers in Leeds, 1980, summarising the principles of the synthesis of thermotropic liquid crystalline polymers, their structure dependant phase behaviour and their orientation in electric and magnetic fields.

Studies on the interaction of C1q,a subcomponent of the first component of complement, with porins fromSalmonella minnesotaincorporated into artificial membranes

AbstractPurified outer membrane proteins (OMP) of Salmonella minnesota, Re-form, were incorporated into liposomes. These induced in macrophages a chemiluminescence signal identical to that of the intact Re-form. This signal was abolished by preincubation of porin-containing liposomes with purified C1q. Incorporation of isolated OMP into black lipid membranes (BLM) resulted in channel-formation which could not be inhibited by isolated C1q. Additionally, incubation of OMP-containing liposomes with BLM resulted in pore-formation within the BLM. This was amplified when lipid A was present within the liposomes. Preincubation of OMP-containing liposomes with purified C1q abolished pore-formation …

Hermann Staudinger and the Future of Polymer Research Jubilees—Beloved Occasions for Cultural Piety

Liquid crystal polymers from swallow-tailed mesogens

Abstract Swallow-tailed compounds containing an acetylenic unit have been synthesized. Only those compounds with a three ring structure exhibited liquid-crystalline phases. The platinum catalysed addition of these monomers to compounds containing Si-H groups was used to synthesize polymeric materials. Only those polymers with the tetramethyldisiloxane unit showed mesophases. The synthesis, characterization, and phase behaviour are described.

Different polymeric transport systems for biologically active substances are presented. In the past, most of the reviews on polymeric drugs dealt with pharmaca, fixed to conventional water-soluble polymers. Naturally occuring transport proteins with their complex features have recently been imitated by micellar solubilized polymers. Polymerized liposomes from polymerizable lipids can be regarded as vesicular solubilized polymers and are discussed as stable models for biomembranes. By insertion of glycolipids, these liposomes are rendered susceptible to specific recognition by proteins. When natural or cleavable synthetic lipids are incorporated into polymerizable membranes, phase-separation…

Pharmakologisch aktive polymere, 5. Modellreaktionen zur umsetzung von pharmaka und enzymen mit monomeren und polymeren reaktiven estern

Die Darstellung reaktiver Ester der Acryl-, Methacryl- und N-Vinylcarbaminsaure wird beschrieben. Die Verbindungen sind im Gegensatz zu anderen reaktiven Saurederivaten wie Saurechloriden, -anhydriden und Isocyanaten kristalline Monomere, die gut zu handhaben sind. Sie lassen sich leicht zu unvernetzten, loslichen Polymeren homo- und copolymerisieren. Die Copolymerisationsparameter wurden bestimmt. Entsprechend wie die aus der Peptidchemie bekannten reaktiven Ester reagieren sie in monomerer wie in polymerer Form bei niedriger Temperatur selektiv und schonend mit Nucleophilen in guten Ausbeuten, z. B. mit Aminen in wasriger Losung. Dies eroffnet die Moglichkeit zur nebenreaktionsfreien Bind…

Polyreaktionen in orientierten systemen, 6.Mizellare assoziationen in 4-vinylpyridiniumsalzlösungen

Kritische Mizellkonzentrationen (cmc) aus Oberflachenspannungsmessungen und durch Farbstoffsolubilisierung werden von 4-Vinylpyridinium- bzw. 4-Athylpyridinium-Salzlosungen bestimmt. Erhohung der Gegenionen-Konzentration erniedrigt die cmc; gleichzeitig damit andert sich auch die Zusammensetzung der Polymerisationsprodukte der spontanen Polymerisation in Wasser. Mogliche Erklarungen hierfur werden diskutiert. Critical micell concentrations (cmc) of 4-vinylpyridinium or 4-ethylpyridinium salt solutions are determined from surface tension measurements and solubilisation of a dyestuff. Increase of the concentration of the gegenions decreases the cmc; at the same time, the composition of the po…

Specific dye adsorption at oriented monolayers

We studied the adsorption of water soluble cyanine dyes (pseudoiso-cyanine and “stains-all”) to monomolecular layers of arachidic acid at the water-air interface in a Langmuir trough. Fluorescence microscopy was employed to on-line monitor the formation of J-aggregates upon adsorption. Large two-dimensional monodomain single crystals could be grown by this self-assembly process with optical properties reminiscent of those found and extensively studied for amphiphilic derivatives of the same chromophors [12]. In addition to the necessary Coulombic interaction between subphasedye and target monolayer, we found that details of the crystal morphology also crucially depend on substrate parameter…

Chemically driven phase separation in black lipid membranes and its coupling to membrane functions

Abstract We analysed the single-channel current fluctuations of gramicidin in bimolecular lipid membranes in order to demonstrate (i) the influence of protein binding to the lateral organisation of a mixed membrane, and (ii) how this couples to the function of the ionophore. Examples of phase separations induced by synthetic polyelectrolytes, as models for peripheral membrane proteins, and specific ligand-receptor interactions are presented and discussed in view of the important lateral order-function relationship in biomembranes.

Monolayer Polymerization of Diacetylene Monocarbonic Acids at the Gas-Water-Interface

Synthesis and phase behaviour of liquid-crystalline side group polyesters

Abstract Several series of liquid-crystalline side group polymers with a polyester backbone structure have been synthesized using mesogenic diethylmalonate and 1,3-propanediol derivatives. The structures of the polymer backbone and the mesogenic units have been varied systematically. As shown by differential scanning calorimetry, polarizing microscopy and X-ray diffraction, the side group polyesters exhibit nematic and/or smectic mesophases. Polyesters synthesized from mesogenic diethylmalonate derivatives can tolerate long non-mesogenic segments in the polymer main chain without losing their liquid crystal properties. X-ray studies suggest that some of the smectic polymers exhibit interdig…

Preparation of large unilamellar vesicles

Single (unilamellar) and oligolamellar lipid bilayer vesicles of large diameter have great potential in membrane research. In particular, large unilamellar bilayer vesicles (diam. >50 m) would permit the insertion of microelectrodes for the measurement of the electrical properties of lipid bilayer membranes of different compositions. Furthermore, vesicles large enough to be observed by light microscopy could be fused with cells with the aid of the electric field method [l-4]. Since vesicles (liposomes) can be loaded with macromolecules, this might be an elegant means of transferring proteins or plasmids into cells. Large vesicles with different lipid compositions and only one unit membrane …

Influence de la structure de chaine sur le type de phase et relation entre la masse moleculaire et les temperatures de transition

Cast multibilayer films from polymerizable lipids

Discotic liquid crystals at the air water interface

The monolayer properties of two types of discotic liquid crystals, hexasubstituted triphenylenes 1 and azo derivatives of phloroglucinol 5, were examined. First investigations show that these discotic liquid crystals form stable monolayers. It could be shown that electron acceptors insert into the monolayer of 1. Azo discs display a packing behaviour at the monolayer that is ascribed to a side-on packing of the molecules.

Electric field-induced fusion of large liposomes from natural and polymerizable lipids

Orientation, recognition, and photoreaction of nucleolipids in model membranes

Amphiphiles with nucleobases and nucleosides as headgroups have been synthesized. Their surface behavior was investigated in monolayers at the air/water interface. The double chain nucleolipids form stable monolayers with nearly identical surface pressure-area diagrams, whereas the spreading behavior of the mono chain amphiphiles is dominated by the various nucleobase-headgroups. When measuring the interactions between nucleolipid monolayers and nucleobases (monomeric and polymeric ones), specific base-base effects could be observed: the complementary nucleobases solubilized in the subphase expand the monolayer more than the non-complementary ones. Photodimerization reactions of thymine-amp…

Optical data storage in Langmuir-Blodgett-Kuhn multilayer assemblies of azo-dye side chain LC-polymers

We describe the preparation of LB-films of novel polymers containing azobenzene dye side chains. X-ray refection measurements, surface-plasmon experiments were used to determine the structure of LB-films which had been transferred onto a substrate. Illumination with UV-light causes trans-cis isomerisation of the azobenzene side groups. This effect can be used for optical data storage and will be discussed in detail.

Functionalized lipid tubules as tools for helical crystallization of proteins

The development of functional supramolecular devices built by self-assembly of elementary molecules and with bioactive properties arouses considerable interest in the field of nanotechnology and new materials. We report here the formation of a new class of lipid tubules exhibiting both properties of molecular recognition and crystal formation for the protein streptavidin. These lipid tubules, made of biotin-containing dioctadecylamine molecules, are straight hollow cylinders with a constant diameter of 27 nm and variable length up to several micrometers. They are unilamellar with an inner diameter of about 16 nm, as shown by cryoelectron microscopy. Streptavidin binds to the biotinylated tu…

Electronic Properties of Discotic LC-Materials

Abstract We have made extensive studies of the charge-carrier mobilities in the discotic hexagonal mesophases of triphenylene-based discotic liquid crystals. Using the time-of-flight technique, transient photocurrents were measured yielding charge-carrier mobilities for various electric fields and temperatures. Starting from promising results obtained with the monomeric discotic liquid crystalline model compound hexapentyloxytriphenylene (H5T), we synthesized a “discotic twin” with two triphenylene units linked together by a suitable spacer. Additionally, we synthesized a discotic liquid crystalline oligomer consisting of four triphenylene units which are bound to a flexible cyclosiloxane r…

Self-organization of amphiphilic N-acylated linear polyethyleneimines: investigation of a reversible monolayer collapse

Abstract Poly-N-4-decyloxybenzoylethyleneimine, highly crystalline in bulk, forms a stable monolayer at the air-water interface which undergoes a reversible collapse into a probable bilayer structure at higher surface pressures. We achieved transfer both from the monolayer and “bilayer” region of the polymer film at the water surface onto hydrophilic and hydrophobized quartz supports. Based on X-ray investigations on the deposited Langmuir-Blodgett films, a possible mechanism for the reversible collapse is proposed.

Untersuchungen von Polymeren im Massenspektrometer. II. Abbaureaktionen von Poly-β-alaninen

Die Abbaureaktionen von Poly-β-alaninen bei der direkten Pyrolyse im Massenspektrometer wurden untersucht. Die thermischen Abbaureaktionen und die Fragmentierung in der Ionenquelle waren unterscheidbar. Die pyrolytische Spaltung verlauft unter den angewendeten Bedingungen fast ausschlieslich zwischen Amidstickstoff und β-Kohlenstoff und fuhrt unter Disproportionierung zu oligomeren β-Alaninen. Die entstehenden Pyrolysebruchstucke werden nach uberwiegender Ionisation an den Heteroatomen unter αN-, αO-, βO- und Keten-Spaltung fragmentiert. The degradation reactions of poly-β-alanines by direct pyrolysis in the mass spectrometer was investigated. The thermal degradation step and the fragmentat…

Quenching of fluorescein-conjugated lipids by antibodies. Quantitative recognition and binding of lipid-bound haptens in biomembrane models, formation of two-dimensional protein domains and molecular dynamics simulations

Three model biomembrane systems, monolayers, micelles, and vesicles, have been used to study the influence of chemical and physical variables of hapten presentation at membrane interfaces on antibody binding. Hapten recognition and binding were monitored for the anti-fluorescein monoclonal antibody 4–4-20 generated against the hapten, fluorescein, in these membrane models as a function of fluorescein-conjugated lipid architecture. Specific recognition and binding in this system are conveniently monitored by quenching of fluorescein emission upon penetration of fluorescein into the antibody's active site. Lipid structure was shown to play a large role in affecting antibody quenching. Interes…

A block copolymer (6) with both hydrophilic and hydrophobic regions was synthesized, in order to examine its interaction with model membranes and its uptake by living cells. The copolymer comprised poly(ethylene oxide) and poly(L-lysine) with 50 mol-% substitution of the e-amino groups with palmitoyl groups. To permit 125I-labelling, p-methoxyphenyl residues (1–4 mol-%) were incorporated into the block copolymer and into a poly(ethylene oxide) used for comparison. Sudan Red 7 B solubilization studies indicated that the block copolymer, but not the homopolymer, forms micelles. Differential scanning calorimetry of dipalmitoyl-phosphatidylcholine liposomes indicated that the block copolymer in…

The sanidic polyamide [NM-Ph(CO 2 R) 3 (CO 2 Me)-NMCO-Ph(OR) 2 CO] n (R=C 12 H 25 ) is studied. It is shown that this polymer has a biaxial structure with quasi 2-D long range translational correlations. The correlations in one direction are limited by the length of the molecule. The oriented regions are separated by regions in which the molecules are less oriented

Coupling of proton translocation through ATPase incorporated into supported lipid bilayers to an electrochemical process

Abstract H+-ATPase is incorporated into solid-supported lipid bilayers separated from the gold support by a peptide spacer. The translocation of protons across the lipid film to the inner side is coupled to the discharge of protons at the gold surface. The overall process is investigated by square wave voltammetry (SWV) and double potential-pulse chronoamperometry (CA). As a result, the formation of a proton gradient is monitored by SWV whereas currents measured by CA monitor the stationary state when the enzyme activity is directly coupled to the charge transfer at the electrode. These currents markedly depend on the number of ATPases present in the bilayer.

Mobile supported monolayers of ionic amphiphiles: variation of domain morphology via preadsorbed polyelectrolytes

Hydrolytic action of phospholipase A2 in monolayers in the phase transition region: direct observation of enzyme domain formation using fluorescence microscopy.

Phospholipase A2, a ubiquitous lipolytic enzyme highly active in the hydrolysis of organized phospholipid substrates, has been characterized optically in its action against a variety of phospholipid monolayers using fluorescence microscopy. By labeling the enzyme with a fluorescent marker and introducing it into the subphase of a Langmuir film balance, the hydrolysis of lipid monolayers in their liquid-solid phase transition region could be directly observed with the assistance of an epifluorescence microscope. Visual observation of hydrolysis of different phospholipid monolayers in the phase transition region in real-time could differentiate various mechanisms of hydrolytic action against …

Untersuchungen von polymeren im massenspektrometer, 3. Fragmentierungsreaktionen oligomerer benzyle

Beim thermischen Abbau von Polybenzylen im Massenspektrometer werden oligomere Benzylbruchstucke mit gesattigten (Phenyl-, Alkyl-) und ungesattigten (Chinonmethid)-Endgruppen gebildet. Zur Differenzierung der thermischen und elektronenstosinduzierten Abbaureaktionen wurden die Fragmentierungsreaktionen oligomere Benzyle vom Typ 1a, b im Massenspektrometer untersucht. Bei Anwendung niedriger Elektronenstosenergien wurden als Hauptfragmentierungsreaktionen Alkyl-, α-Benzyl- und β-Benzylspaltung sowie die fur 1,2-disubstituierte Benzyle strukturspezifische ortho-Umalgerung gefunden, die eine Differenzierung stellungsisomerer Oligobenzyle ermoglicht. Die genannten Reaktionen wurden durch Hochau…

Discotic Twin and Triple Molecules with Charge-Transfer Interactions in Langmuir−Blodgett Films

X-ray and atomic force microscopy observations reveal features of the surface morphology of Langmuir-Blodgett (LB) films from discotic donor-acceptor molecules with strong core-to-core interactions caused by a charge-transfer (CT) complexation. The compounds are designed to be twin and triple molecules composed of chemically connected donor (triphenylene) and acceptor (trinitrofluorenone) fragments which display liquid crystalline structure in the bulk state. The LB films from these compounds possess edge-on orientation of molecules within monolayers with a smooth surface on a submicron scale but with substantial macroscopic imperfections. These imperfections are represented by the micron s…

The synthesis and the results of the structural study of two copolysiloxanes with laterally fixed trinitrofluorenone (TNF) units is reported. The two copolysiloxanes having 2,4 (1a) and 5,3 (1b) dimethylsiloxane comonomer units per TNF side group differ significantly in their phase behaviour as evident from optical microscopy, differential scanning calorimetry and X-ray scattering: 1b shows a nematic mesophase whereas 1a is an amorphous material. The different phase behaviour is discussed in terms of microphase separation between the siloxane backbone and TNF side groups.

Interactions of liposomes and hydrophobically-modified poly-(N-isopropylacrylamides): an attempt to model the cytoskeleton

The interactions of small unilamellar vesicles (SUV) and water-soluble copolymers were studied by fluorescence spectroscopy, differential scanning calorimetry (DSC) and quasi-elastic light scattering (QELS). The anchoring onto liposomal bilayer membranes of copolymers of N-isopropylacrylamide, N-(2-(1-naphthyl)ethyl)-N-n-octadecylacrylamide and or N-[4-(1-pyrenyl)butyl]-N-n-octadecylacrylamide (0.5 mol% of the octadecylacrylamide comonomer) was monitored by non-radiative energy transfer between excited naphthalene and pyrene. The anchoring process occurred on zwitterionic lecithin liposomes and on negatively charged phosphatidic acid liposomes, whether the bilayer was in the crystalline or …

Pharmakologisch aktive Polymere, 12. Depotformen von Chlorambucil durch kovalente Bindung an Polymere

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.

Negatively charged lipid molecules were converted into polymerizable lipids by introduction of polymerizable mono- or bifunctional counterions. As an attempt to mimic the cytoskeleton of biomembranes, unsymmetrical polymeric vesicles were prepared, where the polyelectrolyte is attached either only to the inner or to the outer bilayer surfaces. Polymerizable cations were introduced to the outer surface of preformed small unilamellar vesicles via ion-exchange. The outer counterions of vesicles bearing polymerizable counterions at both sides of the membrane were replaced by Na+. Polymerization of these systems leads to unsymmetrical vesicles. The introduction, separation and polymerization of …

Photoconductivity in Discotic Liquid Crystals: A New Class of High-Mobility Materials

Abstract Using a time-of-flight technique, different transport mechanisms, deep trapping, multiple shallow trapping and Gaussian transport, can be observed in the different temperature and phase regions of the liquidcrystalline (LC) photoconductor hexapentyloxytriphenylene (HPT). Transient photocurrents and carrier mobilities for various temperatures, electric fields, and sample histories were examined. The ideal intrinsic Gaussian transport, observed for holes in the mesophase, puts HPT into a new class of highmobility materials with both hole mobilities on the order of 1.10−3cm2/Vs and a steplike current decay. These features result from the fact that there is obviously neither a position…

The comparative spreading behavior of enantiomeric and racemic tyrosine amphiphiles

Several derivatives of tyrosine or its methyl ester have been synthesized in which the para hydroxyl group on the aromatic side chain has been converted to a long chain alkyl ether or urethane. The surface behavior of these compounds is discussed. Enantiomeric discrimination, the ability of a chiral molecule to distinguish between mirror-image stereoisomers, has been investigated for the urethane derivates by comparing the surface pressure-area isotherms of the enantiomer with that of the racemic compound. Enantiomeric discrimination was demonstrated for the methyl ester analog, but was not conclusively observed for the zwitterionic compounds. Possible structural requirements for enantiomer…

Photoreactive Langmuir–Blodgett–Kuhn multilayer assemblies from functionalized liquid-crystalline side chain polymers, I. Homopolymers containing azobenzene chromophores

Stable monomolecular layers of a liquid-crystalline homopolymer bearing azobenzene chromophores in the mesogenic side groups could be prepared at the water–air interface by slow compression at room temperature. From the area per monomer unit of A0≈0.25 nm2 a structural model with tightly packed azobenzene groups oriented nearly parallel to the surface normal was deduced. After transfer to a solid support in a Y-type mode the obtained Langmuir–Blodgett–Kuhn (LBK) multilayer assemblies of varying thicknesses (from a double layer to a thick film of d = 238 nm, capable of guiding optical modes) were prepared and analyzed by X-ray reflection and optical evanescent wave techniques. A monolayer th…

Mesophase behaviour of 2,5-dibenzoyloxy-p-benzoquinone derivatives and tetrahydrobenzene tetraesters

Abstract The synthesis of 2,5-dibenzoyloxy-p-benzoquinone derivatives, their products after reduction and tetraesters from tetrahydroxybenzene prepared from those products is described. Their phase behaviour was investigated by differential scanning calorimetry and polarizing microscopy and is discussed in terms of their detailed structure.

The synthesis of a new type of combined polymers containing both disc- and rod-like mesogens is reported. The polyesters, having a triphenylene derivative as a discotic mesogen in the side group and azobenzene or biphenyl derivatives as rod-like mesogens in the main chain were characterized by polarizing microscopy, differential scanning calorimetry, and X-ray scattering studies. The homopolymer 7 is highly crystalline, while the copolymer 8 is amorphous, both, however, do not form liquid-crystalline phases.

Synthesis and characterization of polymeric derivatives of the folic acid antagonist, Methotrexate, N-[4-(N-methyl-2,4-diamino-6-pteridinylmethylamino)benzoyl] glutamic acid (1a), a widely used antitumor agent, are described. Derivatives of poly(L-lysine), poly(iminoethylene), poly(vinyl alcohol), and carboxymethylcellulose with various contents (3–15 mole-%) of substituted repeating units were prepared by polymer-analogous amidation and transesterification of the dimethyl ester of 1a and with N-[2-(N-methylmorpholinio)ethyl]carbodiimide p-toluenesulfonate as coupling reagent. By nucleophilic addition reactions of the pteridinyl amino groups under mild conditions, 1a was bound without cross…

Structure and morphology of liquid-crystalline polymers

Liquid-crystalline phases are characterized by structures intermediate between a three-dimensionally ordered crystal and a disordered fluid. Polymers with liquid-crystalline structures can be obtained from specific monomers containing mesogenic groups with a tendency to form liquid-crystalline phases. These mesogenic groups are either incorporated into the main chain or attached to a chain as side groups. In both cases liquid-crystalline structures, and also enantiotropic liquid-crystalline phases, have been reported. Smectic polymers are characterized by layered structures with long-range order in the direction of the layer normal and two-dimensional short-range order within the layers. Th…

Herstellung und Charakterisierung flüssig-kristalliner Polymere mit cholesterischer Phase

Formation and behaviour of radiation induced free radicals in statistical copolymers from vinyl hydrosulfide and styrene (1:1, 1:4, and 1:10) were investigated by means of ESR spectroscopy. The corresponding homopolymers were also included in these studies. After γ-irradiation of the copolymers at 77 K and subsequent annealing to 293 K it was possible to detect thio radicals. Their relative yields were found to increase with increasing styrene content. Investigations regarding the thermal behaviour of the radiation induced radicals in the copolymers allowed the assumption of two mechanisms responsible for the formation of the thio radicals: First, the formation takes place via ion radicals …

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

Structure and Dilution of Mesogenic Side Chains in Liquid Crystalline Polysiloxanes

Abstract The structure of the smectic phases in four series of homo- and copolymers based on dimethylsiloxane chains with a definite variation of the concentration of the paired mesogenic side chains has been investigated by means of X-ray methods. The dilution of the mesogenic moiety was achieved by insertion of additional dimethylsiloxane segments. A nearly linear dependence of the layer spacings on the dilution has been found. A model of the structure is proposed which consists of two sublayers one of which contains the irregularly arranged main chain whereas the other one is formed by the side chains.

Freely-Suspended and Transferred Freely-Suspended Films of Polymeric Liquid Crystals

Freely-suspended (FS) liquid-crystal (LC) films of a polymethylsiloxane homo- and a copolymer with different mesogenic side groups have been prepared and investigated. For both substances the preparation of the films succeeded only in the isotropic phase but the higher ordered phases were reached after cooling. The films of the homopolymer have only been obtained with thicknesses estimated to be in the pm-range and with an unusual “Book-Shelf” orientation of the smectic layers. In contrast, the films of the copolymer were thinner and showed a homeotropic orientation of the mesogens in the smectic A phase. Interestingly, this material exhibited a different layer spacing in film and bulk, alt…

It is shown that the acceptor polyesters [(CH 2 ) x OCOC(=R) COO(CH 2 ) x ] n (R=9-[2,4,7-trinitrofluorenylidene]) x=3, 6, 8) influence the chain behaviour of the discotic hexapentyloxytriphenylene without changing the phase type (D ho ). The clearing temperature of the complexes has a maximum value when x=G. Both intra- and intercolumnar distance are smaller than in the pure discotic compound and independant of the spacer

Photoinduced electron transfer in molecular organizates at the gas-water interface

Abstract The influence of the molecular geometry is of fundamental importance for a better understanding of the photoinduced electron transfer mechanism. Because of their typical molecular structures, cyclophane rings have proved to be suitable for this purpose as electron acceptor molecules adsorbed under an amphiphile monolayer. We used a pyrene-labelled phospholipid derivative both as molecular anchor for the cyclophane ring and electron donor molecule. The co-spreading technique was used to prepare the complex monolayers. Surface pressure and surface potential measurements have indicated similar monolayer behaviour as with dimyristoylphosphatidic acid as anchor molecule, leading to the …

α, ω-Dipolar amphiphiles: Influence of rigid and flexible units on aggregation behavior

Mono- and α,ω-dipolar amphiphiles with hydrophilic pyridinium head groups, and flexible and rigid hydrophobic parts have been synthesized. Surface tension and conductivity measurements proved that micellar aggregates for amphiphiles 1–4 are formed. The incorporation of rigid units leads to a decrease in the critical micellar concentration (CMC): the rigid monopolar amphiphile 2 aggregates at lower concentration than the flexible monopolar amphiphile 1. A similar decrease was observed when chain ends were connected: the flexible α,ω-dipolar amphiphile 3 has a lower CMC than the flexible monopolar amphiphile 1. The more flexible amphiphiles 1–3 allow the formation of micelles of different sha…

Homogeneous Langmuir-Blodgett Film of Double-Chain Ammonium Amphiphile Complexed with Anionic Polymer

Heterogeneous textures suggesting the coexistence of a fluid and a solid phase were found both in a surface monolayer and in a deposited Langmuir-Blodgett (LB) film of double-chain ammonium amphiphiles by fluorescence microscopy. Although an annealing of the surface monolayer at 40°C allowed crystal growth, the heterogeneous phase separation remained in the LB film. A drastic change of the fluorescence image shows that the recrystallization of the complexed monolayer with anionic polymers conducted the homogeneous monolayer.

Optical measurements of an acylated azacrown at the air-water interface

In this study, a cyclame derivative bearing four aliphatic chain substituents shows, like many amphiphiles, solid-condensed as well as liquid-expanded phases. In contrast to the classical amphiphiles, the onset of its phase transition is characterized by a bump-like shape whose amplitude is a function of the compression speed. Ellipsometry which is very sensitive to the monolayer physical state changes, and fluorescence microscopy which has contributed significantly to the understanding of the phenomena occurring in the phase transition region have been used to investigate the monolayer behavior of this compound. This study shows that in the liquid-expanded state, the film is homogeneous an…

Structures, properties and miscibility behaviour of liquid crystalline polycatenar tetrone derivatives

Abstract The tetrones represent an interesting new mesogenic building block. The results of this study show that they can be incorporated into a variety of mesophases. A smectic phase was observed in the polycatenar compound with four terminal chains as expected. The phase exhibits a tilted structure (Sc phase) to prevent void formation. The compound with six pendant chains forms a columnar phase. In spite of their structural similarity, the tetrones studied tended not to be completely miscible. However, complete miscibility with a semi-discoid phenylhydrazone was observed. When this hydrazone, which forms a columnar ‘Dho phase’, was mixed with tetrone which forms a columnar ‘Dhd phase’ a c…

A series of combined main-chain side-group liquid-crystalline polymers was synthesized by melt polycondensation from trans-1,4-cyclohexanedicarboxylic acid, chloro-1,4-phenylene diacetate and 6-(4-methoxy-4′-biphenylyloxy)hexyl-1,4-phenylene diacetate. These polyesters combine the features of rigid-rod main-chain LC-polymers and of side-group LC-polymers. Polymers with small fractions of mesogenic side-groups (5 and 10 mol-%) have lower melting points than the parent polymer poly(chloro-1,4-phenylene 1,4-cyclohexanedicarboxylate) but are still liquid crystalline up to their decomposition at T ≥ 400°C. In polymers with larger fractions of mesogenic side-groups (50 and 100 mol-%) partial isom…