Dataset Information

Stretching the Bisalkyne Raman Spectral Palette Reveals a New Electrophilic Covalent Motif.

ABSTRACT: Small heteroaryl-diyne (Het-DY) tags with distinct vibrational frequencies, and physiologically relevant cLog P were designed for multiplexed bioorthogonal Raman imaging. Pd-Cu catalyzed coupling, combined with the use of Lei ligand, was shown to improve overall yields of the desired heterocoupled Het-DY tags, minimizing the production of homocoupled side-products. Spectral data were in agreement with the trends predicted by DFT calculations and systematic introduction of electron- rich/poor rings stretched the frequency limit of aryl-capped diynes (2209-2243 cm^-1 ). The improved Log P of these Het-DY tags was evident from their diffuse distribution in cellular uptake studies and functionalizing tags with organelle markers allowed the acquisition of location-specific biological images. LC-MS- and NMR-based assays showed that some heteroaryl-capped internal alkynes are potential nucleophile traps with structure-dependent reactivity. These biocompatible Het-DY tags, equipped with covalent reactivity, open up new avenues for Raman bioorthogonal imaging.

SUBMITTER: Ravindra MP

PROVIDER: S-EPMC10946950 | biostudies-literature | 2023 Jul

REPOSITORIES: biostudies-literature

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Stretching the Bisalkyne Raman Spectral Palette Reveals a New Electrophilic Covalent Motif.

Ravindra Manasa Punaha MP Lee Martin M Dimova Silviya S Steven Craig F CF Bluntzer Marie T J MTJ Brunton Valerie G VG Hulme Alison N AN

Chemistry (Weinheim an der Bergstrasse, Germany) 20230515 38

Small heteroaryl-diyne (Het-DY) tags with distinct vibrational frequencies, and physiologically relevant cLog P were designed for multiplexed bioorthogonal Raman imaging. Pd-Cu catalyzed coupling, combined with the use of Lei ligand, was shown to improve overall yields of the desired heterocoupled Het-DY tags, minimizing the production of homocoupled side-products. Spectral data were in agreement with the trends predicted by DFT calculations and systematic introduction of electron- rich/poor rin ...[more]

PMID: 37014262

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Project description:The introduction of dynamic covalent bonds into cross-linked polymer networks enables the development of strong and tough materials that can still be recycled or repurposed in a sustainable manner. To achieve the full potential of these covalent adaptable networks (CANs), it is essential to understand-and control-the underlying chemistry and physics of the dynamic covalent bonds that undergo bond exchange reactions in the network. In particular, understanding the structure of the network architecture that is assembled dynamically in a CAN is crucial, as exchange processes within this network will dictate the dynamic-mechanical material properties. In this context, the introduction of phase separation in different network hierarchies has been proposed as a useful handle to control or improve the material properties of CANs. Here we report-for the first time-how Raman confocal microscopy can be used to visualize phase separation in imine-based CANs on the scale of several micrometers. Independently, atomic force microscopy (AFM) confirmed the phase-separated domains inside the polymer. Remarkably, the materials were found to undergo phase separation despite being built up from miscible monomers, which arguably should yield homogeneous materials. We found that the phase separation not only affected the appearance of the material but-more notably-also had a noticeable effect on the thermal-mechanical properties of the material: CANs (of equal aliphatic/aromatic monomer composition) that displayed phase separation had both a higher crossover temperature (T cross, where tan(δ) = 1, and where the material transits from a rubbery to a viscous state) and an increased elastic modulus (G'). By modifying the CAN architecture, we were able to either suppress or enhance the phase separation, and we propose that the phase separation is driven by favorable π-π interactions between the aromatic components. Our work further shows the importance of phase separation in CANs, including in networks built from miscible components, and provides a handle to control the dynamic material properties. Moreover, our work underlines the suitability of Raman imaging as a method to visualize phase separation in CANs.

Dataset Information

Stretching the Bisalkyne Raman Spectral Palette Reveals a New Electrophilic Covalent Motif.

Publications

Stretching the Bisalkyne Raman Spectral Palette Reveals a New Electrophilic Covalent Motif.

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