Quantification of energy of activation to supramolecular nanofibre formation reveals enthalpic and entropic effects and morphological consequence

Samperi, Mario; Pérez-García, Lluïsa; Amabilino, David B.

doi:10.1039/c9sc03280k

Cited by 12 publications

(10 citation statements)

References 61 publications

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“…3) and consistent with incorporation of the organic anions between the layers of cationic amphiphile (Fig. 1) as we reported previously for Gel@TCPP, 11 although some of the organic anions may reside on the outer surface of the fibres. The rheological properties of these multicomponent gels also reflect the morphological changes.…”

Section: Multicomponent Gel Preparation and Characterisationsupporting

confidence: 90%

“…26 The reorganization of the fibres in certain solvent conditions is facilitated here as a result of similar effects, where the movement of the traveller is accompanied by path change. The possibilities of changing the supramolecular fibre nature through controlled mixing in these systems 11,27 and others opens a myriad of possibilities to modulate the dynamic nature of the systems.…”

Section: Discussionmentioning

confidence: 99%

“…The path is made of a gemini imidazolium-based amphiphile (1•2Br, Fig. 1A) that self-assembles in mixtures of water and ethanol leading to supramolecular gels, 11 and incorporates the 5,10,15,20tetrakis(4-carboxyphenyl)porphyrin tetra-anion (TCPP). 12 This hybrid gel has TCPP-containing fibres that are robust and not dynamic when irradiated (under identical conditions to those we describe below), 12 because of the electrostatic interaction between the components and high degree of order in the fibres.…”

Section: Main Article Textmentioning

confidence: 99%

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Light-controlled micron-scale molecular motion

et al. 2021

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The micron-scale movement of biomolecules along supramolecular pathways -mastered by nature -is a remarkable system requiring strong yet reversible interactions between components under action of a suitable stimulus. Responsive microscopic systems using a variety of stimuli have demonstrated impressive relative molecular motion. However, locating the position of a movable object that travels along selfassembled fibres under an irresistible force has yet to be achieved. Here, we describe a purely supramolecular system where a molecular "traveller" moves along a "path" over several microns when irradiated with visible light. Real time imaging of the motion in the solvated state using total internal reflection fluorescence microscopy shows that anionic porphyrin molecules move along the fibres of a bis-imidazolium gel upon irradiation. Slight solvent changes mean movement and restructuring of the fibres giving microtoroids, indicating control of motion by fibre mechanics with solvent composition. 'The insight provided here may lead to the development of artificial travellers that can perform catalytic and other functions.

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Section: Multicomponent Gel Preparation and Characterisationsupporting

confidence: 90%

Section: Discussionmentioning

confidence: 99%

Section: Main Article Textmentioning

confidence: 99%

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Light-controlled micron-scale molecular motion

et al. 2021

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“…These kinds of supramolecular assemblies are generally formed closer to equilibrium conditions than larger crystals, although nucleation and growth mechanisms can be similar. [80][81][82] A particularly interesting case of twisted fibers are those formed from a synthetic amphiphilic peptide (Figure 9) that evolves from one kind of morphology to another over time. [83] When dissolved in ultrapure water at 25 °C twisted ribbons form quickly.…”

Section: Twisted Aggregates Crystals and Stereochemistrymentioning

confidence: 99%

Stereochemistry and Twisted Crystals

Killalea

Amabilino

2021

Israel Journal of Chemistry

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“…Herein, we have demonstrated how the solvent ratio affects the self-assembly and the properties of final aggregates of double chain cationic gemini imidazolium-based surfactant (1,3-bis[(3-octadecyl-1-imidazolio)methyl]benzene dibromide (GBIB) and a double chain anionic surfactant diaoctyl sodium sulfosuccinate or Aerosol OT (AOT). Our previous study found that solvent ratios played an important role in aggregation behavior of pure gemini GBIB surfactant. , This cationic GBIB and anionic double chain AOT were mixed in different molar ratios in various E/W solvent ratios (30:70, 50:50, and 70:30). These CaSs were then characterized using dynamic light scattering (DLS) and field emission gun scanning electron microscopy (FEG-SEM).…”

Section: Introductionmentioning

confidence: 98%

Gemini Surfactant Mediated Catansomes for Enhanced Singlet Oxygen Generation of Rose Bengal and Their Phototoxicity against Cancer Cells

Sharma

Samperi

Jain

et al. 2022

ACS Biomater. Sci. Eng.

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Photodynamic therapy (PDT) is an innovative technique for cancer treatment with minimal side effects, based on the use of a photosensitizer, oxygen, and light. Photosensitizers (PSs) have several limitations, that may limit their clinical use, like poor solubilization, self-aggregation, and lack of specific targeting, which can be addressed with the use of nanomaterials. Herein, a unique type of catansomes (CaSs) was prepared using a gemini imidazolium-based surfactant (1,3-bis[(3-octadecyl-1-imidazolio)methyl]benzene dibromide (GBIB) and a double chain surfactant, diaoctyl sodium sulfosuccinate or Aerosol OT (AOT). The formation of CaS GBIB/AOT was optimized in various ethanol/ water (E/W) solvent ratios by employing a facile, quick, and most reliable solution−solution mixing method. The CaS was characterized by dynamic light scattering (DLS) and field emission gun scanning electron microscopy (FEG-SEM) techniques. The experimental results reveal that stable CaSs with a spherical shape were obtained at lower concentration (100 μM). Rose Bengal (RB), a PS of the xanthene family, was incorporated into these prepared CaSs, as proven by fluorescence spectroscopy, UV−visible absorption spectroscopy, and confocal laser scanning microscopy. Singlet oxygen ( 1 O 2 ) generation studies revealed the relevant role of the E/W solvent ratio as there was a 4-fold boost in the 1 O 2 production for GBIB/AOT in E/W = 50:50 and around 3-fold in E/ W = 30:70. Also, the GBIB-rich 80:20 fraction was more efficient in increasing the 1 O 2 generation as compared to the AOT rich fraction (20:80). Further, their phototoxicity was tested in a water-rich solvent ratio (E/W = 30:70) against MCF-7 cells. Upon irradiation with a 532 nm laser (50 mW) for 5 min, RB@GBIB/AOT(20:80) fraction caused 50% decrease in the metabolic activity of MCF-7 cells, and RB@GBIB/AOT(80:20) fraction produced a maximum 85% decrease in cell viability. Furthermore, the enhancement in intracellular 1 O 2 generation by RB@GBIB/AOT, as compared to pure RB, was confirmed with singlet oxygen sensor green (SOSG). This new type of CaS based on gemini surfactants exhibiting a large amount of 1 O 2 generation, holds great interest for several applications, such as use in photomedicine in future.

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Quantification of energy of activation to supramolecular nanofibre formation reveals enthalpic and entropic effects and morphological consequence

Abstract: The dimensions of supramolecular fibres formed from a system that starts far from equilibrium because of fast solvent – anti-solvent mixing is determined by the balance between enthalpy and entropy in different solvent mixtures.

Cited by 12 publications

References 61 publications

Light-controlled micron-scale molecular motion

Light-controlled micron-scale molecular motion

Stereochemistry and Twisted Crystals

Gemini Surfactant Mediated Catansomes for Enhanced Singlet Oxygen Generation of Rose Bengal and Their Phototoxicity against Cancer Cells

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