Self-Assembly in Sensor Nanotechnology

Anees, Palapuravan; Praveen, Vakayil K.; Kartha, Kalathil K.; Ajayaghosh, Ayyappanpillai

doi:10.1016/b978-0-12-409547-2.12644-7

Cited by 6 publications

(6 citation statements)

References 103 publications

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“…9,25 This particular class of materials have generated interest because of their widespread applications in the area of sensing, 46,47 imaging, 47,48 organic electronics, 9,49 photonics 9,50,51 etc. There are a few reports in the literature on Bodipy derivatives as gelators.…”

Section: Bodipy-derived Supramolecular Gelatorsmentioning

confidence: 99%

“…46,47 For instance, self-assembly of block copolymers with multi-color fluorophores is considered to be an emerging strategy to construct multifunctional structures with a high degree of spatial control. 7,18 In particular, crystallization-driven self-assembly of block copolymers is a useful synthetic tool to prepare complex nanoscale architectures.…”

Section: Self-assembly Of Bodipy-linked Polymersmentioning

confidence: 99%

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Self-Assembly of Bodipy-Derived Extended π-Systems

Cherumukkil

Vedhanarayanan

Das

et al. 2017

Bulletin of the Chemical Society of Japan

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Self-assembly is a viable approach to create soft functional materials with architectural diversity and property variations. Among the large number of different chromophores used, borondipyrromethene (Bodipy) dyes find a unique space because of their promising photophysical properties such as high molar absorptivity, fluorescent quantum yield and excellent photostability along with the associated synthetic ease. Recently, research on Bodipy dyes has experienced a surge of activities in view of favorable self-assembling properties. In this review, recent developments in self-assembled Bodipy dyes and their significance in various applications are discussed.

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Section: Bodipy-derived Supramolecular Gelatorsmentioning

confidence: 99%

Section: Self-assembly Of Bodipy-linked Polymersmentioning

confidence: 99%

Self-Assembly of Bodipy-Derived Extended π-Systems

Cherumukkil

Vedhanarayanan

Das

et al. 2017

Bulletin of the Chemical Society of Japan

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“…An extended molecular assembly of π-systems is known to facilitate several excited-state phenomena such as exciton migration, , energy and electron transfer, aggregation-induced emission (AIE), , triplet–triplet energy-migration-assisted photon upconversion, and so on. Any perturbation in the molecular arrangements of chromophores can bring substantial color and intensity changes to the optical properties of π-system assemblies. ,, Thus, being a sensitive system, the optical properties of molecular assemblies have been extensively used in the development of sensors, diagnostic probes, and stimuli-responsive smart materials. − …”

Section: Introductionmentioning

confidence: 93%

Self-Assembled Extended π-Systems for Sensing and Security Applications

et al. 2020

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Metrics & MoreArticle RecommendationsCONSPECTUS: Molecules and materials derived from selfassembled extended π-systems have strong and reversible optical properties, which can be modulated with external stimuli such as temperature, mechanical stress, ions, the polarity of the medium, and so on. In many cases, absorption and emission responses of self-assembled supramolecular π-systems are manifested several times higher when compared with the individual molecular building blocks. These properties of molecular assemblies encourage scientists to have a deeper understanding of their design to explore them for suitable optoelectronic applications. Therefore, it is important to bring in highly responsive optical features in π-systems, for which it is necessary to modify their structures by varying the conjugation length and by introducing donor−acceptor functional groups. Using noncovalent forces, πsystems can be put together to form assemblies of different shapes and sizes with varied optical band gaps through controlling intermolecular electronic interactions. In addition, using directional forces, it is possible to bring anisotropy to the self-assembled nanostructures, facilitating efficient exciton migration, resulting in the modulation of optical and electron-transport properties.In this Account, we mainly summarize our findings with optically tunable self-assemblies of extended π-systems such as pphenylenevinylenes (PVs), p-phenyleneethynylenes (PEs), and diketopyrrolopyrroles (DPPs) as different stimuli-responsive platforms to develop sensors and security materials. We start with how PV self-assemblies and their coassemblies with appropriate electron-deficient systems can be used for the sensing of analytes in contact mode or in the vapor phase. For example, whereas the PV having electron-deficient terminal groups has high sensitivity toward trinitrotoluene (TNT) in contact mode, the supercoiled fibers formed by the coassembly of self-sorted stacks of C 3 -symmetrical PV and C 3 -symmetrical electron-deficient perylene bisimide are capable of sensing vapors of nitrobenzene and o-toluidine. The power of different functional groups in combination with PVs has been further illustrated by attaching CO 2 -sensitive tertiary amine moieties to a cyano-substituted PV, which allowed the bimodal detection of CO 2 using fluorescence and Raman spectroscopy. Interestingly, the functionalization of PVs with terminal amide groups and chiral alkoxy side chains provided a mechanochromic system that allows self-erasable imaging. Whereas PVs exhibit quenching of fluorescence in most cases during self-assembly, PE derivatives exhibit aggregation-induced emission. This property of PEs has been exploited for the development of stimuli-responsive security materials, especially for currency and documents. For instance, the blue fluorescence of a PE attached to hydrophilic oxyethylene side chains coated on a filter paper upon contact with water changes to cyan emission due to the change in the molecular packing. Interestingly, the mole...

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“…9 Chemoselective responsive hydrogels 6 and organogels 10,11 often incorporate molecular recognition groups within the polymer networks. The molecular recognition event actuates selective chemical responses such as volume changes, 12 fluorescence, 13 or that trigger catalysis. 8,14 We developed multiple hydrogel chemical sensors by attaching molecular recognition groups that induce hydrogel volume phase transitions (VPTs) upon analyte binding.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Chemoselective responsive hydrogels and organogels , often incorporate molecular recognition groups within the polymer networks. The molecular recognition event actuates selective chemical responses such as volume changes, fluorescence, or that trigger catalysis. , We developed multiple hydrogel chemical sensors by attaching molecular recognition groups that induce hydrogel volume phase transitions (VPTs) upon analyte binding. , This VPT response is understood in the context of the Flory polymer theory. − Chemical binding processes that induce Gibbs free-energy changes in the system generate osmotic pressures that swell or shrink the hydrogel or organogel. Small perturbations in the chemical environment can lead to remarkably large VPT .…”

Section: Introductionmentioning

confidence: 99%

Stimuli-Responsive Pure Protein Organogel Sensors and Biocatalytic Materials

Smith

Coukouma

Wilson

et al. 2019

ACS Appl. Mater. Interfaces

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Utilizing protein chemistry in organic solvents has important biotechnology applications. Typically, organic solvents negatively impact protein structure and function. Immobilizing proteins via cross-links to a support matrix or to other proteins is a common strategy to preserve the native protein function. Recently, we developed methods to fabricate macroscopic responsive pure protein hydrogels by lightly cross-linking the proteins with glutaraldehyde for chemical sensing and enzymatic catalysis applications. The water in the resulting protein hydrogel can be exchanged for organic solvents. The resulting organogel contains pure organic solvents as their mobile phases. The organogel proteins retain much of their native protein function, i.e., protein−ligand binding and enzymatic activity. A stepwise ethylene glycol (EG) solvent exchange was performed to transform these hydrogels into organogels with a very low vapor pressure mobile phase. These responsive organogels are not limited by solvent/mobile phase evaporation. The solvent exchange to pure EG is accompanied by a volume phase transition (VPT) that decreases the organogel volume compared to that of the hydrogel. Our organogel sensor systems utilize shifts in the particle spacing of an attached two-dimensional photonic crystal (2DPC) to report on the volume changes induced by protein−ligand binding. Our 2DPC bovine serum albumin (BSA) organogels exhibit VPT that swell the organogels in response to the BSA binding of charged ligands like ibuprofen and fatty acids. To our knowledge, this is the first report of a pure protein organogel VPT induced by protein−ligand binding. Catalytic protein organogels were also fabricated that utilize the enzyme organophosphorus hydrolase (OPH) to hydrolyze toxic organophosphate (OP) nerve agents. Our OPH organogels retain significant enzymatic activity. The OPH organogel rate of OP hydrolysis is ∼160 times higher than that of un-cross-linked OPH monomers in a 1:1 ethylene glycol/water mixture.

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Self-Assembly in Sensor Nanotechnology

Cited by 6 publications

References 103 publications

Self-Assembly of Bodipy-Derived Extended π-Systems

Self-Assembly of Bodipy-Derived Extended π-Systems

Self-Assembled Extended π-Systems for Sensing and Security Applications

Stimuli-Responsive Pure Protein Organogel Sensors and Biocatalytic Materials

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