Redox-Regulated and Guest-Driven Transformations of Aromatic Oligoamide Foldamers in Advanced Structures.

In this study, we demonstrate that an aromatic oligoamide sequence assembles into a trimeric helix-turn-helix architecture with a disulfide linkage, and upon cleavage of this linkage, it reconstructs into an antiparallel double helix. The antiparallel double helix is accessible to encapsulate a diacid guest within its cavity, forming a 2:1 host-guest complex. In contrast, hydrogen-bonding interactions between the trimeric-assembled structure and guests induce a conformational shift in the trimeric helix, resulting in a cross-shaped double-helix complex at a 2:2 host-guest ratio. Interconversions between the trimeric helix and the antiparallel double helix, along with their respective host-guest complexes, can be initiated through thiol/disulfide redox-mediated regulation.

Chirality Interplay between the Interior and Exterior of Metal-Organic Cages.

A series of metal-organic cages featuring two stereogenic elements, in terms of the twisting of amide moieties within the ligand backbones and the rotation of diazaanthracene segments along the ligand ridges, were exploited. These two chiral components are correlative and serve as relays for transmitting chirality information between the internal and external cages. The chirality information induced by a chiral guest inside the cage cavity can pass through the cage framework and influence the orientation of the diazaanthracene segments on the periphery of the cage. In turn, the chirality of a stereogenic center within the diazaanthracene segments can transfer back into the cavity, enabling discrimination of enantiomeric guests.

Foldaxane-Based Switchable [c2]Daisy Chains.

Artificial molecular muscles are highly attractive in the field of molecular machinery due to their unique properties of contraction and stretching motion. However, the synthesis of molecular muscles poses formidable challenges as it is hindered by undesirable yields and poor selectivity. Herein, we present a procedure for the dynamic assembly of foldaxane-based [c2]daisy chains, wherein the hermaphroditic sequences consisting of aromatic helices and peptide rods are interlocked through inter-strand hydrogen-bonding interactions. The binding complementarity facilitates a selective and efficient assembly of [c2]daisy chain structures, inhibiting the creation of by-products. Introducing multiple recognition sites confers the system with contraction and stretching motion actuated by chemical stimuli. The rate of this muscle-like motion is calculated to be 0.8 s-1, which is 107 times faster than that of complex dissociation.

Crystal Structure and NMR of an α,δ-Peptide Foldamer Helix Shows Side-Chains are Well Placed for Bifunctional Catalysis: Application as a Minimalist Aldolase Mimic.

We report the first NMR and X-ray diffraction (XRD) structures of an unusual 13/11-helix (alternating i, i+1 {NH-O=C} and i, i+3 {C=O-H-N} H-bonds) formed by a heteromeric 1 : 1 sequence of α- and δ-amino acids, and demonstrate the application of this framework towards catalysis. Whilst intramolecular hydrogen bonds (IMHBs) are the clear driver of helix formation in this system, we also observe an apolar interaction between the ethyl residue of one δ-amino acid and the cyclohexyl group of the next δ-residue in the sequence that seems to stabilize one type of helix over another. To the best of our knowledge this type of additional stabilization leading to a specific helical preference has not been observed before. Critically, the helix type realized places the α-residue functionalities in positions proximal enough to engage in bifunctional catalysis as demonstrated in the application of our system as a minimalist aldolase mimic.

Optimization of an Asymmetric Reaction.

Invited for the cover of this issue are Quan Gan and co-workers at the Huazhong University of Science and Technology. The image depicts aromatic oligoamide sequences winding around a substrate with conformational control. Read the full text of the article at 10.1002/chem.202200834.

Optimization of an Asymmetric Reaction in the Cavity of Chiral Aromatic Oligoamide Foldamers.

An asymmetric reaction can be implemented and refined in the helical cavity of aromatic oligoamide sequences. These sequences, which bear a chiral inducer, can fold into helical structures with absolute control of the helical sense, whereby a ketone substrate covalently linked in the cavity can be asymmetrically reduced to diastereomers. The diastereoselectivity of the reduction is highly dependent on the shielding efficiency of the helical cavity. Iterative modifications of the sequence, such as addition and replacement of monomers, can fine-tune the cavity to realize the asymmetric reaction, thereby progressively increasing the diastereomeric excess up to 90 %.

A Disulfide Switch Providing Absolute Handedness Control in Double Helices via Conversion from the Antiparallel to Parallel Helical Pattern.

A strategy to reversibly switch the parallel/antiparallel helical conformation of aromatic double helices through the formation/breakage of a disulfide bond is presented. Single-crystal X-ray structures, NMR, and circular dichroism spectroscopy demonstrate that the double helices with terminal thiol groups favor an antiparallel helical arrangement both in the solid state and in solution, while the P/M bias of helicity induced by chiral segments from another extremity of the sequence is weak in this structural motif. The antiparallel helices can be rearranged to parallel helices through the disulfide connection of the sequences. This change enhances the bias of helical handedness and results in absolute chirality control of the double helices. The handedness-mediated process can be governed by the oxidation-reduction cycle, thereby switching the structural arrangement and the enhancement of chiral bias. In addition, we find that the sequences can dimerize into an intermolecular double helix with the disulfide connection. And the helical handedness is also fully controlled due to the head-to-head structural motif.

Absolute handedness control of oligoamide double helices by chiral oxazolylaniline induction.

Aromatic oligoamide double helices bearing a chiral oxazolylaniline moiety at the C-terminus were synthesized and their helix handedness was completely controlled (de > 99%). The absolute helix sense and the de values were evaluated by using 1H NMR, X-ray crystallography, and circular dichroism (CD). Using crystal structure analysis, the high efficiency of helix handedness induction was attributed to the close location of the asymmetric carbon center to the helix orbits via intramolecular hydrogen bonding. The CD experiments also showed that there is no loss of chiral induction either in the interconversion of single and double helices or by elongation of the sequences.

Quantum plasmonics pushes chiral sensing limit to single molecules: a paradigm for chiral biodetections.

Chiral sensing of single molecules is vital for the understanding of chirality and their applications in biomedicine. However, current technologies face severe limitations in achieving single-molecule sensitivity. Here we overcome these limitations by designing a tunable chiral supramolecular plasmonic system made of helical oligoamide sequences (OS) and nanoparticle-on-mirror (NPoM) resonator, which works across the classical and quantum regimes. Our design enhances the chiral sensitivity in the quantum tunnelling regime despite of the reduced local E-field, which is due to the strong Coulomb interactions between the chiral OSs and the achiral NPoMs and the additional enhancement from tunnelling electrons. A minimum of four molecules per single-Au particle can be detected, which allows for the detection of an enantiomeric excess within a monolayer, manifesting great potential for the chiral sensing of single molecules.

Difference in Step-Wise Production Rules of SP Binary Flooding for Conglomerate Reservoirs with Different Lithologies.

The purpose of this study is to clarify the difference in oil production rules of conglomerate reservoirs with different pore structures during surfactant-polymer (SP) binary flooding and to ensure the efficient development of conglomerate reservoirs. In this paper, the full-diameter natural cores from the conglomerate reservoir of the Triassic Kexia Formation in the seventh middle block of the Karamay Oilfield (Xinjiang, China) are selected as the research objects. Two schemes of single constant viscosity (SCV) and echelon viscosity reducing (EVR) are designed to displace oil from three main oil-bearing lithologies, namely fine conglomerate, glutenite, and sandstone. Through comprehensive analysis of parameters, such as oil recovery rate, water content, and injection pressure difference, the influence of lithology on the enhanced oil recovery (EOR) of the EVR scheme is determined, which in turn reveals the differences in the step-wise oil production rules of the three lithologies. The experimental results show that for the three lithological reservoirs, the oil displacement effect of the EVR scheme is better than that of the SCV scheme, and the differences in recovery rates between the two schemes are 9.91% for the fine conglomerate, 6.77% for glutenite, and 6.69% for sandstone. By reducing the molecular weight and viscosity of the SP binary system, the SCV scheme achieves the reconstruction of the pressure field and the redistribution of seepage paths of chemical micelles with different sizes, thus, achieving the step-wise production of crude oil in different scale pore throats and enhancing the overall recovery of the reservoir. The sedimentary environment and diagenesis of the three types of lithologies differ greatly, resulting in diverse microscopic pore structures and differential seepage paths and displace rules of SP binary solutions, ultimately leading to large differences in the enhanced oil recoveries of different lithologies. The fine conglomerate reservoir has the strongest anisotropy, the worst pore throat connectivity, and the lowest water flooding recovery rate. Since the fine conglomerate reservoir has the strongest anisotropy, the worst pore throats connectivity, and the lowest water flooding recovery, the EVR scheme shows a good "water control and oil enhancement" development feature and the best step-wise oil production effect. The oil recovery rate of the two schemes for fine conglomerate shows a difference of 10.14%, followed by 6.36% for glutenite and 5.10% for sandstone. In addition, the EOR of fine conglomerate maintains a high upward trend throughout the chemical flooding, indicating that the swept volume of small pore throats gradually expands and the producing degree of the remaining oil in it gradually increases. Therefore, the fine conglomerate is the most suitable lithology for the SCV scheme among the three lithologies of the conglomerate reservoirs.

Study on the Difference in CO2 and Air Injection in the Fracture/Matrix Dual Medium of Continental Shale Reservoirs.

To clarify the impact of different displacement media on the enhanced oil recovery of continental shale and realize the efficient and reasonable development of shale reservoirs, this paper takes the continental shale of the Lucaogou Formation in the Jimusar Sag in the Junggar Basin (China, Xinjiang) as the research object and uses real cores to build the fracture/matrix dual-medium model. Computerized tomography (CT) scanning is used to visually compare and analyze the influence of fracture/matrix dual-medium and single-matrix medium seepage systems on oil production characteristics and clarify the difference between air and CO2 in enhancing the oil recovery of continental shale reservoirs. Through a comprehensive analysis of the production parameters, the whole oil displacement process can be divided into three stages: the oil-rich and gas-poor stage, oil and gas coproduction stage, and gas-rich and oil-poor stage. Shale oil production follows the rule of fractures first and matrix second. However, for CO2 injection, after the crude oil in the fractures is recovered, the oil in the matrix migrates to the fractures under the action of CO2 dissolution and extraction. Overall, the oil displacement effect of CO2 is better than that of air, resulting in a 5.42% higher final recovery factor. Additionally, fractures can increase the permeability of the reservoir, which can greatly enhance oil recovery in the early oil displacement process. However, as the amount of injected gas increases, its impact gradually decreases, and ultimately, it is consistent with the recovery of nonfractured shale, which can achieve nearly the same development effect.

Crystal Structure and NMR of an α,δ-Peptide Foldamer Helix Shows Side-Chains are Well Placed for Bifunctional Catalysis: Application as a Minimalist Aldolase Mimic.

We report the first NMR and X-ray diffraction (XRD) structures of an unusual 13/11-helix (alternating i, i+1 {NH-O=C} and i, i+3 {C=O-H-N} H-bonds) formed by a heteromeric 1 : 1 sequence of α- and δ-amino acids, and demonstrate the application of this framework towards catalysis. Whilst intramolecular hydrogen bonds (IMHBs) are the clear driver of helix formation in this system, we also observe an apolar interaction between the ethyl residue of one δ-amino acid and the cyclohexyl group of the next δ-residue in the sequence that seems to stabilize one type of helix over another. To the best of our knowledge this type of additional stabilization leading to a specific helical preference has not been observed before. Critically, the helix type realized places the α-residue functionalities in positions proximal enough to engage in bifunctional catalysis as demonstrated in the application of our system as a minimalist aldolase mimic.

Hierarchical communication of chirality for aromatic oligoamide sequences.

The communication of chirality at a molecular and supramolecular level is the fundamental feature capable of transmitting and amplifying chirality information. Yet, the limitation of one-step communication mode in many artificial systems has precluded the ability of further processing the chirality information. Here, we report the chirality communication of aromatic oligoamide sequences within the interpenetrated helicate architecture in a hierarchical manner, specifically, the communication is manipulated by three sequential steps: (i) coordination, (ii) concentration, and (iii) ion stimulus. Such approach enables the information to be implemented progressively and reversibly to different levels. Furthermore, the chiral information on the side chains can be accumulated and transferred to the helical backbones of the sequences, resulting in that one of ten possible diastereoisomers of the interpenetrated helicate is finally selected. The circular dichroism experiments with a mixture of chiral and achiral ligands demonstrate a cooperative behavior of these communications, leading to amplification of chiral information.

Macrocyclic Aromatic Amide Foldamer: Synthesis, Twisted-to-Boxlike Conformational Switching, and Molecular Recognition.

In this study, a twisted macrocycle was synthesized via ring closure of a double-helical aromatic oligoamide foldamer with two disulfide bridges. Single-crystal X-ray structure and NMR spectroscopy demonstrate the twisted conformation of macrocycle both in the solid state and in solution. As a result of the rearrangement of hydrogen bonding preference, the twisted conformation could be transformed to boxlike through protonation of the pyridine segments of macrocycle. In addition, the NMR titration experiments revealed that flat aromatic guests (e. g., coronene and perylene) could bind to the boxlike macrocycle with a 1 : 1 binding stoichiometry. The addition of base to the host-guest complexes resulted in conformational reversal of the macrocycle from boxlike to twisted as well as the release of guest.

Quadruple hybridization of quinoline-triazole oligomers.

A series of quinoline-triazole oligomers and their quadruple helical structures are demonstrated. The helical folding is mainly induced by the intramolecular hydrogen bonds, and solvophobic effects impel the aggregation, causing the quadruplex to be more stable in DMSO than in CDCl3 by four orders of magnitude. As a proof of concept, our studies reveal a tetramerization mechanism in which the single sequences first hybridize to dimers, and then two such dimers further aggregate into a quadruplex.

Helicity adaptation within a quadruply stranded helicate by encapsulation.

The helicity of a quadruply stranded M2L4 helicate consisting of an aromatic amide bidendate ligand is flexible due to the twisting of the amide moieties and can be tuned by the encapsulated anions. This study reveals the multiple interplays and complementarities between the anions as well as between the anions and the helicate, which are synthetically responsive to the ultimate conformation of the helicate.