A pressure-induced ratiometric signalling chemosensor: a case of helical anthracenes

Kinoshita, Tomokazu; Fujise, Kei; Tsurumaki, Eiji; Toyota, Shinji; Fukuhara, Gaku

doi:10.1039/d2cc00428c

Cited by 8 publications

(4 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The former behavior originates from the pressure-induced solvent polarizability (density) changes that cause the stabilization of the π* orbital, , and the latter phenomenon occurs because of the increasing effective concentration during solution compression. Considering that the hydrostatic pressure effect on the bathochromic shift is generally observed at approximately 1 cm –1 MPa –1 for common π-conjugated organic molecules (such as anthracene, pyrene, and perylene), ,− the resulting shifts of 0 ∼ −0.39 cm –1 MPa –1 for 1Zn and −0.11 ∼ −0.25 cm –1 MPa –1 for 1Zn 2 were relatively small (Figures S6 and S9 in SI, respectively). This remarkable pressure effect was likely responsible for the characteristic Q-band obtained for the Pc chromophore, which revealed that the hydrostatic pressure responses in the Q-band were considerably different from those obtained for the regular π–π* transition.…”

Section: Results and Discussionmentioning

confidence: 99%

Multidimensional Dynamic Control of Supramolecular Phthalocyanine Gear: A Self-Assembly System Responding to Solvent, Temperature, and Hydrostatic Pressure

Kinoshita,

Sakamaki,

Fukuhara

2024

ACS Omega

Self Cite

View full text Add to dashboard Cite

Smart supramolecular materials that respond toward various external stimuli hold great promise for various applications in molecular memories, logic gates, and drug delivery systems. In this study, the active control over the self-assembly of phathalocyanine gear was achieved by combining temperature and hydrostatic pressure stimuli with a dynamic solvent. Eventually, we found that the supramolecular gear can behave as a logic gate; "engaged" (+1) or "not" (0) state is switchable by solvent, temperature, and hydrostatic pressure. This paper describes not only new aspects for the rational design of smart stimuli-responsive supramolecular materials but also the significance of multidimensional dynamic control.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Multidimensional Dynamic Control of Supramolecular Phthalocyanine Gear: A Self-Assembly System Responding to Solvent, Temperature, and Hydrostatic Pressure

Kinoshita,

Sakamaki,

Fukuhara

2024

ACS Omega

Self Cite

View full text Add to dashboard Cite

show abstract

“…Many other applications are outside this Review because of its limited space and inability to cover all of them by a single author. Among them are the λ-ratiometric sensors for viscosity [139], temperature [140] and pressure [141] on a molecular scale. Detection of pathogenic bacteria [142], checking their drug resistance [143] and identifying the spores [144] benefit from using ratiometric fluorescence sensing.…”

Section: Fluorescentmentioning

confidence: 99%

Dual emission and its λ-ratiometric detection in analytical fluorimetry Pt. II. Exploration in sensing and imaging

Demchenko

2023

Methods Appl. Fluoresc.

View full text Add to dashboard Cite

The wavelength-ratiometric techniques demonstrate strong advantages in fluorescence sensing and imaging over techniques employing variations of intensity at single wavelength. We present different possibilities for realization of these advantages in different simplified, miniaturized and multiplexing devices. They include the smartphone-based detection systems and strips, in which the color changes are observed with naked eye. The array-based techniques and different immunoassays with λ-ratiometric detection demonstrate strongly increased stability and sensitivity. The application areas extend from on-site monitoring of environment and point-of-care diagnostics to testing in personal need. Selected examples of sensing different analytes in chemical and biological systems demonstrate multiple possibilities of coupling the analyte-sensor interaction with the generation of λ-ratiometric output signal. Among them, simultaneous detection of several analytes and performing logical operations that can be useful in analysis. Finally, the benefits of multicolor ratiometric fluorescence imaging are demonstrated by visualization the functionally important parameters of biological membranes.

show abstract

“…In anthraquinone analog [3]HAq , we identified unusually short distances between the inner carbonyl oxygen atoms [12] . Additionally, we recently reported that [4]HA exhibits a ratiometric fluorescence response upon intramolecular [4+4] cycloaddition under high hydrostatic pressure [13] . Previous studies reveal that modifications to helical structures, particularly deformations along the helical axis akin to a mechanical spring, can significantly impact their properties and reactivity [6,14] .…”

Section: Introductionmentioning

confidence: 98%

“…[12] Additionally, we recently reported that [4]HA exhibits a ratiometric fluorescence response upon intramolecular [4 + 4] cycloaddition under high hydrostatic pressure. [13] Previous studies reveal that modifications to helical structures, particularly deformations along the helical axis akin to a mechanical spring, can significantly impact their properties and reactivity. [6,14] Cyclization of both ends of the helical moiety via a covalent bond offers a dependable method to compress the helical structure.…”

Section: Introductionmentioning

confidence: 99%

Unusually Short H⋅⋅⋅H Contacts in Intramolecularly Cyclized Helically Fused Anthracenes

Fukuda,

Tsurumaki,

Wakamatsu

et al. 2024

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

The intramolecular coupling of dichloro‐substituted helically fused anthracenes using the Yamamoto coupling yielded cyclized products with sterically congested molecular structures. The X‐ray analysis and DFT calculations showed that the aromatic framework adopted a nonplanar structure with a twisted conformation about the newly formed single bond, which acts as a chiral axis. Interestingly, the X‐ray structure obtained through the Hirshfeld atom refinement revealed short interatomic distances between the inner hydrogen atoms (1.648–1.692 Å), much shorter than the sum of their van der Waals radii. Owing to these unusually short contacts, the 1H NMR spectrum exhibited a significant deshielding (12.5 ppm) and a large nuclear Overhauser effect (44%). Additionally, the IR spectrum displayed a high‐frequency shift of the C–H stretching vibration. These observations, along with the noncovalent interaction plot indicative of a characteristic steric environment, strongly support the presence of steric hindrance. Moreover, dynamic NMR measurement of the mesityl‐substituted derivative yielded a barrier to helical inversion of 84 kJ mol−1. The optical properties and crystal packing of the cyclized products are also reported.

show abstract

A pressure-induced ratiometric signalling chemosensor: a case of helical anthracenes

Abstract: One of the helical anthracenes, [4]HA in which two fused anthracene ends are spatially arranged upper and lower, exhibits a ratiometric fluorescence response due to the hydrostatic pressure-dependent intramolecular [4+4]...

Cited by 8 publications

References 52 publications

Multidimensional Dynamic Control of Supramolecular Phthalocyanine Gear: A Self-Assembly System Responding to Solvent, Temperature, and Hydrostatic Pressure

Multidimensional Dynamic Control of Supramolecular Phthalocyanine Gear: A Self-Assembly System Responding to Solvent, Temperature, and Hydrostatic Pressure

Dual emission and its λ-ratiometric detection in analytical fluorimetry Pt. II. Exploration in sensing and imaging

Unusually Short H⋅⋅⋅H Contacts in Intramolecularly Cyclized Helically Fused Anthracenes

Contact Info

Product

Resources

About