Kinetic study of diacetylene polymerization in mono- and multilayers of the Langmuir-Blodgett type

Кручинин, В. Н.; Repinsky, S.M.; Sveshnikova, L. L.; Koshkina, I. M.; Auvinen, E.M; Domnin, I. N.

doi:10.1016/0040-6090(94)90709-9

Cited by 18 publications

(4 citation statements)

References 10 publications

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“…Furthermore, as polymerization may transform the crystal lattice, a certain degree of mobility of the lipids is deemed necessary. , Hence, PD films are often prepared as well ordered films at the air/water interface where lipid packing and mobility can be controlled, polymerized, and then transferred to solid substrates via the Langmuir−Blodgett (LB) or Langmuir−Schaefer (LS) methods . Attempts at a direct polymerization of single monolayers of diacetylenes on solid substrates are often unsuccessful, result in a reduced polymerization rate, or yield films whose properties differ from those of the counterparts polymerized at the air/water interface …”

Section: Introductionmentioning

confidence: 99%

Influence of Substrate Properties on the Topochemical Polymerization of Diacetylene Monolayers

et al. 2001

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The influence of the underlying substrate on the UV initiated polymerization of diacetylene lipid monolayers was investigated using absorption spectroscopy and Brewster angle microscopy (BAM). The lipid/substrate affinity was tuned through choice of lipid headgroup as well as substrate properties. Lipids with positively charged headgroups, which readily polymerized in both blue (6 °C) and red (16 °C) polymer forms at the air/water interface, failed to polymerize when transferred to glass or hydrophobic glass (headgroups facing ambient) at either temperature. BAM analysis revealed that the diacetylene film was disordered on hydrophobic glass, which likely impeded the topochemical polymerization. On glass, however, BAM showed a highly crystalline film identical to that seen at the air/water interface, suggesting that strong interactions between the positively charged lipid headgroups and the glass inhibited polymerization in this case. In agreement, when the lipid/substrate interactions were reduced, either by introducing a cadmium arachidate bilayer between the diacetylene film and the glass or by substituting mica for glass, a limited polymerization occurred, forming the red film exclusively. As a further test, monolayers of acidic diacetylene lipids were deposited on glass. In this case polymerization was possible in both blue and red forms but diminished as the transferred film was aged. These results suggest that a strong lipid/substrate affinity may impede the topochemical polymerization, possibly by restricting the mobility of the lipids. By investigating polymerization as a function of substrate and headgroup chemistry, several factors influencing the lability of diacetylene films toward topochemical polymerization are presented.

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Section: Introductionmentioning

confidence: 99%

Influence of Substrate Properties on the Topochemical Polymerization of Diacetylene Monolayers

et al. 2001

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“…The topochemical polymerization of diacetylenes by irradiation or thermal annealing has been widely used for preparing ordered macromolecules. , Most topochemical polymerization of diacetylenes has been carried out in the solid state. Monomers with molecular arrangements suitable for polymerization are prepared as single crystals, Langmuir−Blodgett films, − self-assembling monolayers, , and vesicles. , Recently the liquid crystalline (LC) state polymerization of diacetylenes was also found to proceed by a 1,4-polymerization pathway as the solid-state polymerization. − In an LC state, molecules are self-organized into ordered arrays comparable to those in Langmuir−Blodgett or self-assembling processes. Several mesogenic linear diacetylenes have been polymerized in nematic or smetic phases. − …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Mesogenic Disklike Benzenetricarboxylates Containing Diacetylenic Groups and Their Polymerization

et al. 2000

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Polymerizable disklike compounds that have a benzene ring core and three rigid diacetylenic units were prepared. The diacetylenic units were attached to the benzene ring via ester linkages. By varying number of alkoxy tail carbons and benzene rings of the disk, the morphological change of the compounds and their polymerization were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy, infrared spectroscopy (IR), and powder X-ray diffraction (XRD). Compound 7 with no alkoxy tail was glassy or small crystals at room temperature and showed crystal-to-crystal phase transition when heated. Compounds 8 with butyloxy tails, 9 with hexyloxy tails, and 10 with octyloxy tails showed monotropic transitions. When the compounds were cooled from the isotropic liquid states, birefringent phases with mosaic textures were observed. XRD study showed that compounds 9 and 10 had hexagonal columnar structures in their liquid crystalline (LC) states. The diacetylene compounds were polymerized by irradiation with UV in solid states or LC states. IR and UV−vis studies showed that the polymerization proceeded by 1,4-addition.

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“…In this respect, the use of Langmuir-Blodgett procedure is attractive. We were the first to perform the studies, by means of the in situ automatic ellipsometry and IR -ATR, of the topochemical UV-initiated polymerization of long-chain alkyl-substitutcd acetylenes as Y-type layers obtained from C 21 H 43 C=CCH 2 OH monomers according to the Langmuir-Blodgett procedure [30]. The orientation of monomer molecules governed by the preparation procedure helps to obtain trans-configuration of polyacetylene layers.…”

Section: Organized Molecular Assemblies Of Unidimensional Topologymentioning

confidence: 99%

Organized Molecular Assemblies: Creation and Investigation of Their Functional Properties

Repinsky

2003

e-J. Surf. Sci. Nanotechnol.

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It has been discussed the notion of an organized molecular assemblies as the key problem of the low-dimension systems physics and the supramolecular chemistry. An organized molecular assembly is a group of atoms or molecules built in a solid matrix due to chemical or intermolecular interactions and possessing, in total, the ability to produce a definite response to the given perturbation. The effectiveness of this approach has been shown on examples the search for systems that evolve to the formation of two dimensional organized molecular assemblies at the boundary between a semiconductor crystal and a dielectric and also creating quantum dots and chemical sensors.

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Kinetic study of diacetylene polymerization in mono- and multilayers of the Langmuir-Blodgett type

Cited by 18 publications

References 10 publications

Influence of Substrate Properties on the Topochemical Polymerization of Diacetylene Monolayers

Influence of Substrate Properties on the Topochemical Polymerization of Diacetylene Monolayers

Synthesis and Characterization of Mesogenic Disklike Benzenetricarboxylates Containing Diacetylenic Groups and Their Polymerization

Organized Molecular Assemblies: Creation and Investigation of Their Functional Properties

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