Polymerization of diacetylenes in multilayers

Tieke, Bernd; Lieser, Günter; Wegner, Gerhard

doi:10.1002/pol.1979.170170607

Cited by 257 publications

(145 citation statements)

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“…Although there is still discussion as to whether such long-wavelength absorption depends on a solid-state effect, 30 the observed rapid polymerization and formation of blue-state polydiacetylene in this study was due at least in part to the one-dimensional organization of the diacetylene moieties guided by the formation of b-sheet peptides and the two-dimensional organization at the air-water interface (Figure 4b). In fact, the distance between parallel b-sheets (B5 Å ) is consistent with the preferred distance between diacetylene monomers (4.7B5.2 Å ) 3,30 for efficient topochemical polymerization.…”

Section: Resultssupporting

confidence: 49%

“…The efficient polymerization of diacetylene yielding highly conjugated backbones requires the positioning of atoms in a crystalline lattice, and there is little displacement before and after polymerization; such a reaction is known as a topochemical reaction. [1][2][3] When properly aligned, diacetylene groups undergo ultraviolet (UV)-induced photopolymerization to form an ene-yne alternating polymer backbone, resulting in organized structures. In aqueous environments, these materials often appear blue or red, with the blue color indicating greater order in the conjugated p-system.…”

Section: Introductionmentioning

confidence: 99%

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β-Sheet peptide-assisted polymerization of diacetylene at the air–water interface and thermochromic property

Koga

Taguchi

Higashi

2011

Polym J

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A peptide-diacetylene hybrid (PDH), in which 5,7-dodecadiynedioic acid was conjugated to the amphiphilic penta-peptide Leu-Lys-Leu-Lys-Leu, which can form b-sheets on both ends of the diacetylene moiety, was prepared through solid-phase peptide synthesis using fluorenylmethoxycarbonyl chemistry. Spreading experiments and spectroscopic observations showed that the PDH formed a stable Langmuir monolayer, primarily in the parallel b-sheet conformation at the air-water interface. When the PDH monolayer was exposed to ultraviolet radiation and a single-layer Langmuir-Blodgett (LB) film of the treated monolayer was deposited on a CaF 2 plate, the polymerization proceeded successfully and provided highly p-conjugated, blue-colored polydiacetylenes with absorption maxima at 653 and 640 nm, respectively. The polymerized PDH LB film displayed almost completely reversible thermochromism between blue and red (less conjugated) states upon heating and cooling. Polymer Journal (2012) 44, 195-199; doi:10.1038/pj.2011.105; published online 9 November 2011Keywords: b-Sheet; diacetylene; peptide; surface monolayer; thermochromism; topochemical polymerization INTRODUCTION Polydiacetylenes are conjugated polymeric materials with unique optical properties. The efficient polymerization of diacetylene yielding highly conjugated backbones requires the positioning of atoms in a crystalline lattice, and there is little displacement before and after polymerization; such a reaction is known as a topochemical reaction. 1-3 When properly aligned, diacetylene groups undergo ultraviolet (UV)-induced photopolymerization to form an ene-yne alternating polymer backbone, resulting in organized structures. In aqueous environments, these materials often appear blue or red, with the blue color indicating greater order in the conjugated p-system. 4 As the conjugated p-system becomes less ordered, the observed color shifts from blue to red. This unique chromatic property has made polydiacetylenes applicable to colorimetric biosensors. [5][6][7][8][9][10][11] We describe herein the thermoreversible color change of polydiacetylene prepared through b-sheet peptide-templated polymerization at the air-water interface. b-Sheet peptides are promising candidates for such a template or scaffold because they are often present in natural fibers as a structural element. Langmuir monolayers of b-sheet peptides were, for example, reported to function as templates and serve as nuclei for the formation of inorganic nanocrystallites at the air-water interface. 12 Recently, numerous research groups have demonstrated that amphiphilic peptides self-assemble into b-sheet nanofiber architectures, 13-20 the surface of which has potential as a novel nanotemplate. [21][22][23] Several groups 24-27 have separately used b-sheet peptide nanofibers as templates to organize diacetylenes or dienes and promote their topochemical polymerization. In this study,

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Section: Resultssupporting

confidence: 49%

Section: Introductionmentioning

confidence: 99%

β-Sheet peptide-assisted polymerization of diacetylene at the air–water interface and thermochromic property

Koga

Taguchi

Higashi

2011

Polym J

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“…6 It was purified by column chromatography (silica gel, benzene) and recrystallized twice from hexane-ether mixture in the dark place. Chloroform of spectroscopic quality was used as a solvent for spreading.…”

Section: Methodsmentioning

confidence: 99%

New Phase Formation in Hetero-Structured Multilayers of Tricosa-2,4-diynoic Acid and Arachidic Acid

Okada

Nakanishi

Matsuda

et al. 1988

Polym J

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ABSTRACT:Four different types of hetero-structured multilayers of tricosa-2,4-diynoic acid (18-0ADA) and arachidic acid (C20CA) in cadmium salts were prepared, and the structures and polymerization behavior of 18-0ADA in such hetero-multilayers were compared with those in the multilayers of pure 18-0ADA. A new phase of 18-0ADA was found in the multilayers having hydrophilic interactions with C20CA, whereas in the multilayers having hydrophilic interactions by themselves new and original phases were mixed up. To clarify these phenomena, the structures of the same types of hetero-multilayers of fatty acids were also investigated, and no new phases were found for the fatty acids. From these results, it was concluded that large differences in surface area per molecule of two components must be important for the new phase formation in heteromultilayers.KEY WORDS Hetero-Structured Multilayer / Amphiphilic Diacetylene Compound / Fatty Acid / New Phase Formation / Recently fabrication of polar LangmuirBlodgett (LB) films 1 • 2 has been investigated with particular references to their physical properties such as piezoelectricity, pyroelectricity3 and even-order nonlinear optical effects. 4 In previous paper we studied the alternately deposited multilayers of amphiphilic diacetylenes (CH3-f-CH2-k-=-r-C = C-C = C-f-CH 2 +,.cO 2 H: m -nADA) and arachidic acid (CH3-f-CHd11::2 CO2H: C"CA, n = 20), and found that in the case of tricosa-2,4-diynoic acid (18-0ADA) in which a diacetylene group is conjugated with a carboxyl group, the structure and photopolymerization behavior of 18-0ADA in such alternately deposited multilayers were different from those of multilayer of pure 18-0ADA. 5 To clarify the reason for this new phase formation, four different types of multilayers with different interlayer interaction between monolayers were prepared by changing the deposition-order, and structural differences of these multilayers were investigated by Xray diffraction. In addition hetero-structured multilayers of fatty acids which have alkyl groups of different chain lengths were also prepared, and the possibility of new phase formation was investigated. EXPERIMENTAL

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“…Since the theoretical molecular length of our diacetylene is about 3.5 nm, this can only correspond to a bilayer repeat. The less than theoretical repeat distance is common for LB films, and is typically explained by molecular tilting [34,35]. An interdigitation mechanism has also been proposed [36].…”

Section: X-ray Diffractionmentioning

confidence: 99%

The use of the Langmuir-Blodgett technique to obtain ultra-thin polar films

Biddle

Rickert

Lando

et al. 1989

Sensors and Actuators

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The piezoelectric and pyroelectric properties of oriented films possessing dipole moments are increasingly being used in pressure, acoustic, thermal and optical devices. The performance of these devices in many applications may be enhanced by thin-film technology. The developing LangmuirBlodgett thin-film deposition technique offers the opportunity to obtain highly oriented and uniform organic-based films in the 10-5000 nm thickness range. Special techniques must be used, however, to assemble these molecules in such a way as to result in polar multilayer films. Several possible deposition techniques are investigated, with one resulting in a polar and pyroelectric film about 50 nm thick.

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Polymerization of diacetylenes in multilayers

Cited by 257 publications

References 21 publications

β-Sheet peptide-assisted polymerization of diacetylene at the air–water interface and thermochromic property

β-Sheet peptide-assisted polymerization of diacetylene at the air–water interface and thermochromic property

New Phase Formation in Hetero-Structured Multilayers of Tricosa-2,4-diynoic Acid and Arachidic Acid

The use of the Langmuir-Blodgett technique to obtain ultra-thin polar films

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