Programming Peptide Liquid Crystal Media to Acquire Independent Sets of Residual Dipolar Couplings and Enantiodiscrimination in Multiple Solvent Systems

Qin, Si-Yong; He, Jin-Hao; Zhao, You; Yang, Yan-Ling; Zhang, Ai-Qing; Lei, Xinxiang

doi:10.1021/acs.analchem.3c03777

Cited by 5 publications

(3 citation statements)

References 29 publications

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“…In our previous study, we explored the utility of self-assembled amphiphilic peptides as robust alignment media for the measurement of RDCs. − By redesigning the peptide backbones or adjusting the length of hydrophobic tails, multiple peptide-based alignment media were established and applied for acquiring independent sets of RDCs. To ensure the formation of a homogeneous LLC medium for RDC measurement, the sample-containing NMR tube was generally turned up and down several times before recording the NMR spectra.…”

Section: Resultsmentioning

confidence: 99%

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Tandem “One-Shot” Measurement of Residual Chemical Shift Anisotropy and Residual Dipolar Coupling using Biphasic Supramolecular Peptide Liquid Crystals

He,

Cheng,

Zhang

et al. 2024

Anal. Chem.

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Both solitary and tandem applications of residual chemical shift anisotropy (RCSA) and residual dipolar coupling (RDC) show great potential for the structural and configurational determination of organic molecules. A critical component of both RDC and RCSA methodologies is the alignment medium, whose availability is limited, especially for RCSA measurement. Moreover, reported RDC and RCSA acquisitions mainly rely on two experiments conducted under two different conditions, which are relatively time-consuming and easily cause experimental errors. Herein, a biphasic supramolecular lyotropic liquid crystalline (LLC) system was developed through the self-assembly of C 21 H 43 − CONH-V 4 K 3 −CONH 2 , which could act as an alignment medium for not only RDC but also RCSA extraction in DMSO-d 6 . Notably, the RCSA extraction was easily achieved via one-shot measurement from a single one-dimensional 13 C NMR experiment, with no need for special instruments, devices, and correction. Relying on the biphasic LLC medium, meanwhile, RDC data were simply extracted from a single F1-coupled HSQC experiment, different from the standard protocol that requires two spectral acquisitions corresponding to the isotropic and anisotropic conditions. Collectively, the biphasic LLC medium is applicable for tandem RCSA and RDC measurements in one single sample, advancing the stereochemical elucidation of molecules of interest.

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Section: Resultsmentioning

confidence: 99%

“…As an initial proof of concept, the self-assembled biphasic LLC was first applied as an alignment medium for RCSA collection of estrone, which was extensively employed as a model molecule to establish RCSA , and RDC − , measurements as a viable tool for the determination of constitution and/or configuration.…”

Section: Resultsmentioning

confidence: 99%

Tandem “One-Shot” Measurement of Residual Chemical Shift Anisotropy and Residual Dipolar Coupling using Biphasic Supramolecular Peptide Liquid Crystals

He,

Cheng,

Zhang

et al. 2024

Anal. Chem.

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“…The information about the solvent type, sample preparation process, aligning ability, concentration, stability, background signal feature, and advantage/disadvantage was provided (see Supplementary Table S1). Very recently, we programmed the hydrophobic tails of oligopeptide amphiphiles instead of de novo design on peptide sequence to construct multiple independent LC media …”

Section: Self-assembled Oligopeptide Lcmentioning

confidence: 99%

Weak Alignment Liquid Crystal Media from Colloidal Dispersion and Self-assembled Oligopeptide for Anisotropic NMR

Qin,

Zhao,

et al. 2024

Acc. Mater. Res.

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS: Acquiring anisotropic NMR parameters such as residual dipolar couplings (RDCs) and residual chemical shift anisotropies (RCSAs) has been demonstrated as a powerful route to elucidate the three-dimensional structure of organic molecules in organic and medicinal chemistry. However, this methodology is somewhat compromised by the limited availability of alignment media, which are indispensable to induce the partial orientation of analytes for anisotropic data acquisition. Given the feature of inherent anisotropy, lyotropic liquid crystals (LLCs) have been documented as excellent candidates to act as alignment media. This Account aims to review the research progress of developing LLCs to obtain anisotropic NMR data. We mainly focus on two complementary LC media, i.e., two-dimensional (2D) colloidal dispersions and self-assembled peptides, that are generated by a "top-down" approach and "bottom-up" approach, respectively. Our laboratory has been at the forefront of developing 2D colloidal dispersions as alignment media. We first demonstrated the applicability of graphene oxide (GO) LLCs in the RDC-based structural elucidation of small molecules. When used as alignment media, GO LLCs showed a striking feature of no background signals. Clean NMR spectra enable accurate data assignment without disturbances and even effective RDC measurements of rare natural products. To circumvent the limitation that preparing GO LLC media needs tedious solvent exchange to remove nondeuterated solvents for NMR experiments, we subsequently developed MXene LLCs. Different from GO media whose anisotropy would be destroyed after direct freeze-drying, MXene can self-align in the redispersed solution to recover LC behavior. This feature provides great convenience for sample preservation and rapid medium preparation. Another advantage of MXene LLCs over GO media is the applicability to directly measure RDCs of aromatic solutes with no need for chemical modification on MXenes.To complement the 2D colloidal media that are only compatible with strong polar solvents, we further develop supramolecular LLCs. Oligopeptides, due to their mature synthesis strategy, structural designability, and robust self-assembly ability, have been exploited to create supramolecular alignment media in different solvents. We first reported CH 3 OH-, DMSO-, and multiple solventcompatible peptide media, which show the broad applicability of their corresponding analytes. Meanwhile, the chiral amino acids confer oligopeptide LLCs with potential chirality, and we have demonstrated their relative application of enantiodiscrimination.Arising from the structural diversity of oligopeptides, several distinct LLC media are constructed and applied to measure independent sets of RDCs. This offers an opportunity for de novo structural determination of organic molecules.In light of the good fluidity of these media, analytes can rapidly penetrate the LLC phases for self-alignment, facilitating simple and fas...

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Increase of chiral sensing ability in host-guest chemistry by magnetic anisotropy

Chen,

Li,

Yang

et al. 2024

Sci. China Chem.

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Programming Peptide Liquid Crystal Media to Acquire Independent Sets of Residual Dipolar Couplings and Enantiodiscrimination in Multiple Solvent Systems

Cited by 5 publications

References 29 publications

Tandem “One-Shot” Measurement of Residual Chemical Shift Anisotropy and Residual Dipolar Coupling using Biphasic Supramolecular Peptide Liquid Crystals

Tandem “One-Shot” Measurement of Residual Chemical Shift Anisotropy and Residual Dipolar Coupling using Biphasic Supramolecular Peptide Liquid Crystals

Weak Alignment Liquid Crystal Media from Colloidal Dispersion and Self-assembled Oligopeptide for Anisotropic NMR

Increase of chiral sensing ability in host-guest chemistry by magnetic anisotropy

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