Rational Design and in-Situ FTIR Analyses of Colorimetrically Reversibe Polydiacetylene Supramolecules

Kim, Jong Man; Lee, Jiseok; Choi, Hyun Ju; Sohn, Daewon; Ahn, Dong June

doi:10.1021/ma051551i

Cited by 198 publications

(181 citation statements)

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“…Since molecular packing in crystals is determined by the intermolecular interactions between monomers, the selection of substituents attached to the butadiyne moiety is quite important in the preparation of PDAs. On the other hand, much research on the physical properties of PDAs, such as electrical, 3,4 chromic [5][6][7] and nonlinear optical (NLO) [8][9][10] properties, which originate from the p-conjugated backbone structure, have been undertaken. In particular, the third-order NLO properties of PDAs have attracted interest.…”

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confidence: 99%

Solid-state polymerization of conjugated hexayne derivatives with different end groups

Inayama

Tatewaki

Okada

2009

Polym J

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Three hexayne derivatives with different end groups-that is, 10,12,14,16,18,20-triacontahexayne-1,30-diol (1) and its diphenylurethane (2) and diphenylester (3)-were synthesized, and their solid-state polymerization behaviors were investigated. All three monomers were thermally polymerizable. Polymers from 1 and 2 showed an absorption maximum at about 730 nm, indicating that linear polydiacetylenes (PDAs) with octatetraynyl substituents were synthesized. However, broad absorption bands in the near-infrared region were only observed for 2 at 980 and 860 nm, indicating that regular polymerization occurred in 2 to give ladder-type PDA. On the other hand, a polymer from 3 showed a visible absorption increase but no clear absorption maximum. It was estimated that intermolecular hydrogen bonding between hexayne monomers helps to form polymerizable stacks in 1 and 2. In particular, urethane groups are more effective, and 2 showed the highest reactivity in this study with an ordered interlayer structure even after a two-step solid-state polymerization to give ladder-type PDA. Keywords: ladder polymer; polydiacetylene; solid-state polymerization; p-conjugated polymer Some butadiyne compounds are polymerized in the solid state by ultraviolet irradiation or by thermal treatment. This solid-state polymerization was clarified by Wegner 1 as a single-crystal-to-singlecrystal topochemical transition to yield polydiacetylene (PDA), which is classified as a one-dimensional p-conjugated polymer. Since the reaction is topochemically controlled, the reactivity of butadiyne monomers is greatly affected by their packing in crystals. 2 In fact, when the butadiyne monomers in crystals have a stacking distance d of about 5 Å between adjacent molecules in the array and an angle y of about 45 1 between the butadiyne rod and stacking axis, 1,4-addition polymerization occurs. Since molecular packing in crystals is determined by the intermolecular interactions between monomers, the selection of substituents attached to the butadiyne moiety is quite important in the preparation of PDAs. On the other hand, much research on the physical properties of PDAs, such as electrical, 3,4 chromic 5-7 and nonlinear optical (NLO) [8][9][10] properties, which originate from the p-conjugated backbone structure, have been undertaken. In particular, the third-order NLO properties of PDAs have attracted interest. To achieve larger NLO susceptibility (w (3) ) in PDA, it is necessary to increase the density of the p-conjugated polymer backbone and the p-electron number in a repeating unit. In this connection, we have synthesized ladder-type PDAs, in which two polymer backbones were introduced in a repeating unit. 11,12 In addition, several PDAs with p-conjugated substituents, such as aromatic rings and C-C multiple bonds, directly bound to the polymer backbone [13][14][15][16][17][18][19][20][21][22] have been synthesized to obtain PDAs with absorption maxima at longer wavelengths, resulting in larger w (3) -values. In particular, oligoyne derivatives with five...

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confidence: 99%

Solid-state polymerization of conjugated hexayne derivatives with different end groups

Inayama

Tatewaki

Okada

2009

Polym J

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“…[43][44][45][46][47] In addition, all the vesicles had in common a peak around 1690 cm −1 , which was due to the carbonyl groups involving hydrogen bonds. 30 The results suggested that the five polymerized vesicles had enough cohesiveness among the PCDA molecules to form hydrogen bonds between headgroups and self-assemblies between alkyl groups.…”

Section: Resultsmentioning

confidence: 95%

“…[36][37][38][39] Regarding factors affecting conformation change in the π-bond, head group interactions, arising from hydrogen bonds/lateral stacking between aromatic rings or the flexibility of head groups, were suggested to play important roles. 30,[33][34][35]40 Meanwhile, melting of the unreacted monomers was also suggested to be a factor for the conformation change of the backbone. 41 On the other hand, it is little known how deeply the characteristics of selfassembled bilayers (in case of vesicles) or films of the polydiacetylenes connected with the conformation change of the backbone, affecting the colorimetric transitions.…”

Section: -35mentioning

confidence: 99%

Role of Gel to Fluid Transition Temperatures of Polydiacetylene Vesicles with 10,12-Pentacosadiynoic Acid and Cholesterol in Their Thermochromisms

Kwon

Song

Yoon

et al. 2014

Bulletin of the Korean Chemical Society

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This study demonstrates gel-to-fluid transition temperatures of polydiacetylene bilayer vesicles could play important roles in their colorimetric transition temperatures. We prepared five types of polydiaceylene vesicles with 10,12-pentacosadiynoic acid (PCDA) and cholesterol (0-40 mol % of total content). From temperaturedependent observations of the optical signals (colors and UV-vis spectra), the blue-to-red colorimetric transition temperatures of polydiacetylene vesicles were decreased with the cholesterol contents. A further study with microcalorimetry and dynamic light scattering revealed that the polydiacetylene vesicles first underwent gel-to-fluid transitions, which were followed by event(s) responsible for the colorimetric transitions. Energies required for each event were quantified from analysis of the peaks in the microcalorimetry thermograms. The inclusion of cholesterol in the vesicles decreased both the gel-to-fluid and the colorimetric transition temperatures, suggesting that the colorimetric transition of the polydiacetylene vesicles was mediated by the former event although the event was not the direct reason for the color change.

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“…As a result, they can be readily generated in matrix formats for biosensing purposes. Finally, color (blue-to-red) and fluorescence (noneto-red) changes occur when PDAs are subjected to environmental perturbations, such as temperature and ligand-receptor interactions.[ [16][17][18][19][20][21][22][23][24] In general, PDA-based chemosensors are prepared as vesicles in aqueous solutions, [25] Langmuir-Blodgett (LB)/ Langmuir-Schaefer (LS) films, [6] or immobilized vesicles in/on solid supports. [26,27] Recently, we reported new methods for the fabrication of PDA-based microarray chips, [28] PDAembedded electrospun fiber sensors, [29] and flexible strip-type PDA sensors.…”

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confidence: 99%

“…3), derived from 10,12-pentacosadiynoic acid (PCDA) and 2,2 0 -(ethylenedioxy)bis (ethylamine) (EDEA), was subjected to the standard procedure for the formation of PDA vesicles in deionized water. [25] A typical deep-blue-colored solution was obtained when a sonicated suspension containing the monomeric diacetylene was irradiated with 254 nm UV light. Scanning electron microscopy (SEM) images reveal that the polymerized diacetylene vesicles are nearly spherical with sub-100 nm diameters (Fig.…”

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A Microfluidic Conjugated‐Polymer Sensor Chip

Eo¹,

Song²,

Yoon³

et al. 2008

Advanced Materials

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Owing to their extensively delocalized p-networks and conformational restrictions, conjugated polymers have gained enormous attention as novel functional materials.[1] Especially interesting are the stimulus-induced changes that take place in the electronic absorption and emission properties of conjugated polymers. These phenomena have been elegantly applied in the design of efficient chemo-/biosensors.[2]Among the conjugated polymers reported to date, polydiacetylenes (PDAs) are unique in several regards. [3][4][5][6][7][8][9][10][11][12][13][14][15] Firstly, these polymers can be prepared from supramoleculary assembled crystalline or semi-crystalline states of diacetylene monomers. Conventional solution-based chemical approaches that are typically employed for the preparation of conjugated polymers do not yield PDAs efficiently. Secondly, PDAs are produced by UV or g irradiation of self-assembled diacetylenes. Since chemical initiators or catalysts are not required to promote polymerization, the resulting polymers are not contaminated with unwanted byproducts. Thirdly, PDAs can be readily prepared in aqueous solutions in the form of nanostructured liposomes, vesicles, and wires. As a result, they can be readily generated in matrix formats for biosensing purposes. Finally, color (blue-to-red) and fluorescence (noneto-red) changes occur when PDAs are subjected to environmental perturbations, such as temperature and ligand-receptor interactions.[ [16][17][18][19][20][21][22][23][24] In general, PDA-based chemosensors are prepared as vesicles in aqueous solutions, [25] Langmuir-Blodgett (LB)/ Langmuir-Schaefer (LS) films, [6] or immobilized vesicles in/on solid supports. [26,27] Recently, we reported new methods for the fabrication of PDA-based microarray chips, [28] PDAembedded electrospun fiber sensors, [29] and flexible strip-type PDA sensors. [30] In the course of investigations aimed at the development of PDA-based sensor systems, we discovered a conceptually new and interesting PDA sensor system. Without exception, the PDA sensor systems described until now are created in batch-type processes and are designed for single use. More importantly, the majority of PDA sensors developed thus far rely heavily on the blue-to-red color change mechanism and, as such, require relatively large amounts of test samples. In order to overcome the limitations associated with batch-type and color-based PDA sensors, we have designed a continuously flowing microfluidic PDA sensor system that employs fluorescence microscopy for monitoring. We anticipated that the microfluidic PDA sensor would have several advantages, including the consumption of nascent samples and reagents, large interfacial area, and short molecular diffusion distance, [31] which would enable a fast nonfluorescent-to-fluorescent phase transition of PDA upon interaction with analyte molecules. In addition, monitoring of interactions between PDA and analyte solutions of different concentrations should be possible in a single microfluidic sensor chip since multiple...

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Rational Design and in-Situ FTIR Analyses of Colorimetrically Reversibe Polydiacetylene Supramolecules

Cited by 198 publications

References 50 publications

Solid-state polymerization of conjugated hexayne derivatives with different end groups

Solid-state polymerization of conjugated hexayne derivatives with different end groups

Role of Gel to Fluid Transition Temperatures of Polydiacetylene Vesicles with 10,12-Pentacosadiynoic Acid and Cholesterol in Their Thermochromisms

A Microfluidic Conjugated‐Polymer Sensor Chip

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