Langmuir Monolayers of Polyion Complexes of Soluble Quaternary Ammonium-Functionalized Azobenzene Chromophores

Panambur, Gangadhar; Robert, C.; Zhang, Yubao; Bazuin, C. Géraldine; Ritcey, Anna M.

doi:10.1021/la030206o

Cited by 10 publications

(8 citation statements)

References 39 publications

(64 reference statements)

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“…We previously investigated these same complexes at the air–water interface, where the complexation takes place by spreading the surfactomesogen on the water subphase containing the polyelectrolyte 20. This led to monolayers that could be transferred repeatedly to solid substrates, giving Z‐type multilayers.…”

Section: Resultsmentioning

confidence: 99%

“…The synthesis and characterization of the azo10Q surfactomesogen are described elsewhere 20, 21. One batch of sodium poly(4‐styrene sulfonate) (PSS45) was supplied by Aldrich, and two other batches (PSS20 and PSS60), prepared by controlled free radical polymerization and therefore having lower polydispersities, were obtained from Dr. Michael Georges at the Xerox Research Center Canada, Mississauga; all were in the form of powders.…”

Section: Methodsmentioning

confidence: 99%

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Liquid crystalline complexes of an azo‐containing surfactomesogen with oppositely charged polyelectrolytes

Tibirna

Bazuin

2005

J Polym Sci B Polym Phys

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A triethyl-ammonium functionalized 4-nitro-4 0 -alkoxy azobenzene mesogen with a 10-carbon spacer (azo10Q, a ' 'surfactomesogen' ') was complexed in equimolar proportions to a variety of oppositely charged polyelectrolytes, and studied by differential scanning calorimetry (DSC), polarizing optical microscopy, and X-ray diffraction. The complexation generates a single-layer smectic A mesophase over a very wide temperature range from a surfactomesogen that, alone, melts directly to the isotropic phase. The clearing temperatures, ranging from 130 to 190 8C and generally higher than the melting point of azo10Q, are dependent on the nature of the polyelectrolyte as well as its molecular weight. In contrast, a prominent glass transition near ambient temperature appears to be independent of molecular weight, but varies somewhat with the type of polyelectrolyte. A second T g -like transition of much lower intensity is detectable at higher temperatures (generally above 100 8C), and, with literature support, is tentatively attributed to nanophase separation involving sublayer planes in the lamellar packing structure. A series of nonequimolar complexes was also investigated, and it was found that, with decreasing azo10Q content, the clearing temperature viewed by DSC decreases rapidly in intensity (and somewhat in temperature) and then disappears although birefringence remains, whereas the lower glass transition increases rapidly in temperature to finally merge with the upper one.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Liquid crystalline complexes of an azo‐containing surfactomesogen with oppositely charged polyelectrolytes

Tibirna

Bazuin

2005

J Polym Sci B Polym Phys

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“…Materials. The synthesis of the amphiphiles, n Q, has been described previously . Docosanyl triethylammonium bromide, DS-Q, was obtained by quaternization of 1-bromodocosane (Aldrich), similar to the procedure used for the n Q amphiphiles.…”

Section: Methodsmentioning

confidence: 99%

Preparation and Characterization of Polyion-Complexed Langmuir−Blodgett Films Containing an NLO Chromophore

et al. 2004

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Polyion complexes formed by monolayers of quaternary ammonium amphiphiles containing the 4-nitro-4'-alkoxy azobenzene chromophore spread at the surface of aqueous solutions of a number of anionic polyelectrolytes were investigated. In general, pi-A isotherms were found to depend on the nature of the polyion present in the subphase, with monolayers of complexes involving polycarboxylates tending to exhibit larger limiting areas than those formed with polysulfonates or polysulfates. Monolayers of the polyion complexes can be transferred to hydrophilic solid substrates to yield Z-type LB films, although some peeling off for more than 10 layers is an impediment. X-ray reflectivity measurements indicate that relatively smooth and uniform films are obtained up to about 10 layers. Average layer thicknesses are, however, significantly smaller than extended molecular lengths, implying that the amphiphiles are strongly inclined from the surface normal. Polarized FT-IR measurements also indicate poor molecular orientation perpendicular to the surface. Preliminary SHG measurements for LB films of two systems, 12Q/CMC-Na and 12Q/PAA, confirm the presence of noncentrosymmetric out-of-plane chromophore ordering. Stable signals are observed for elevated temperatures up to 130 degrees C and for a period of 4 months at room temperature. To the best of our knowledge, this represents the first report of stable SHG in LB films of polyion complexes.

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“…On the other hand, the obtained compounds, like some other natural and biocompatible compounds, have potential applications as the Langmuir–Blodgett films in the different fields and have been appreciated 21–27. The Langmuir–Blodgett films in comparison with the common films have some advantages such as high degree of molecular orientation, precise control of film thickness at the molecular level, control of layer architecture, high optical stability for optical processes, and building up noncentrosymmetric structures for second‐order nonlinear optics 28–30. Based on hairy‐rod concept, several types of macromolecules namely rigid‐rod‐like polymers, could decorate with flexible alkyl side chains, has been used to construct stable and homogeneous ultrathin films by the Langmuir–Blodgett technique.…”

Section: Introductionmentioning

confidence: 99%

“…[21][22][23][24][25][26][27] The Langmuir-Blodgett films in comparison with the common films have some advantages such as high degree of molecular orientation, precise control of film thickness at the molecular level, control of layer architecture, high optical stability for optical processes, and building up noncentrosymmetric structures for second-order nonlinear optics. [28][29][30] Based on hairy-rod concept, several types of macromolecules namely rigid-rodlike polymers, could decorate with flexible alkyl side chains, has been used to construct stable and homogeneous ultrathin films by the Langmuir-Blodgett technique. Among these macromolecules, the incompletely alkylated cellulose derivatives, which contain free hydroxyl functions, are one of the most suitable candidates to construct regular ultrathin multilayers by Langmuir-Blodgett technique with respect to their practical applications.…”

Section: Introductionmentioning

confidence: 99%

Preparation of the new derivatives of cellulose and oligomeric species of cellulose containing magneson II chromophore

Namazi

Jafarirad

2008

J of Applied Polymer Sci

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Fully acetylated cellulose triacetate (CTA) was hydrolyzed in the presence of hydronium ions in a solution of acetic acid and concentrated sulfuric acid to give a hydroxyl-terminated cellulose triacetate oligomers (HCTA). By using gel permeation chromatography (GPC) analysis, the molecular weight of the isolated oligomeric product was calculated to be 3748 Da. HCTA was converted to their new derivatives having 4-(4-nitrophenylazo)-1-naphthol (magneson II) as a chromophore. Then 4 0 -bromobutoxy-4-(4-nitrophenylazo) naphthalene was synthesized from the reaction of 4-(4-nitrophenylazo)-1-naphthol with 1,4-dibromobutane. The synthesized alkylated chromophore was reacted with oligomeric cellulose and cellulose itself in the solution of dimethyl sulfoxide to produce cellulose ethers containing the desired chromophore. In the last step, the isolated compounds were used for the preparation of new polymers and oligomers, which contain both of dodecane and butoxy-4-(4-nitrophenylazo)naphthalene as the alkyl side chains in their backbone.

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Langmuir Monolayers of Polyion Complexes of Soluble Quaternary Ammonium-Functionalized Azobenzene Chromophores

Abstract: sciences et inge ´nie ´rie des macromole ´cules (CERSIM), De ´partement de chimie, Universite ´Laval, Que ´bec (QC), Canada G1K 7P4

Cited by 10 publications

References 39 publications

Liquid crystalline complexes of an azo‐containing surfactomesogen with oppositely charged polyelectrolytes

Liquid crystalline complexes of an azo‐containing surfactomesogen with oppositely charged polyelectrolytes

Preparation and Characterization of Polyion-Complexed Langmuir−Blodgett Films Containing an NLO Chromophore

Preparation of the new derivatives of cellulose and oligomeric species of cellulose containing magneson II chromophore

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