Inherent Chirality Research Articles

Asymmetric Synthesis of Chiral Calix[4]arenes with Both Inherent and Axial Chirality via Cobalt‐Catalyzed Enantioselective Intermolecular C−H Annulation

AbstractInherently chiral calixarenes have garnered significant attention due to their distinctive properties, yet the development of efficient catalytic asymmetric synthesis methods remains a critical challenge. Herein, we report the asymmetric synthesis of calix[4]arenes featuring inherent or both inherent and axial chirality via a cobalt‐catalyzed C−H activation/annulation strategy in high yield with excellent enantio‐ and diastereoselectivity (up to >99 % ee and >20 : 1 dr). Electrooxidation was also suitable for this transformation to obviate the sacrificial metal oxidants, underscoring the environmentally friendly potential of this approach. A key octahedral cobaltacycle intermediate was synthesized and characterized, providing valuable insights into the mode of enantio‐ and diastereocontrol of this protocol. Noteworthy photoluminescence quantum yields of up to 0.94 were measured, underscoring the potential of these compounds in the domain of organic fluorescent materials.

Chiral Metal-Organic Framework Films with Ordered Macropores for Enantioselective Analysis of Proteins.

Chiral film-based sensors show great promise for discriminating between enantiomers due to their miniaturization and low power consumption. However, their practical use is hindered by the trade-off between enantioselectivity and mass transfer capability, especially concerning biomacromolecules such as proteins. In this work, we present an effective and straightforward method for creating highly organized macropores within crystalline chiral metal-organic framework (CMOF) films. This approach harnesses the shaping influence of a polystyrene nanosphere template and the crystallization induced by the liquid dielectric barrier discharge plasma. The resultant highly ordered macro-microporous structures improve mass diffusion and access to chiral active sites in the hierarchical CMOF films. Coupled with their inherent chirality, strong fluorescence emission, high crystallinity, and exceptional stability, these attributes endow these CMOF films with enhanced sensing capabilities for chiral molecules. Particularly, the macro-microporous structure facilitates efficient protein recognition, overcoming a significant challenge encountered by MOFs due to protein dimensions surpassing MOF pore sizes. These films exhibit increased enantioselectivity, better limits of detection, and wider linear ranges compared with purely microporous CMOF films. This study thus provides a powerful synthetic approach for hierarchical CMOF films, addressing the limitations of traditional thin film sensors and opening an avenue for efficient chiral sensing of large biomacromolecules.

Enantioselective synthesis of saddle-shaped eight-membered lactones with inherent chirality via organocatalytic high-order annulation

Inherently chiral medium-ring derivatives have important applications in many research fields, such as materials science, molecular recognition, and asymmetric catalysis. However, the enantioselective assembly of these molecules, especially by organocatalytic strategies, remains a formidable challenge, and few methods are available. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) formal high-order (5 + 3) annulation of 1-(2-indolyl)naphthalen-2-ols with ynals. In the presence of an NHC pre-catalyst, base, Lewis acid and oxidant, this protocol enables the catalytic formation of C–C and C-O bonds, providing practical and facile access to an array of inherently chiral saddle-shaped eight-membered lactones featuring an oxocin-2-one scaffold with structural diversity in good efficiency and excellent enantiocontrol. Moreover, the scale-up preparation and representative late-stage transformations of the eight-membered lactones further demonstrate the application potential of this synthetic technology.

Asymmetric Synthesis of Chiral Calix[4]arenes with Both Inherent and Axial Chirality via Cobalt-Catalyzed Enantioselective Intermolecular C-H Annulation.

Inherently chiral calixarenes have garnered significant attention due to their distinctive properties, yet the development of efficient catalytic asymmetric synthesis methods remains a critical challenge. Herein, we report the asymmetric synthesis of calix[4]arenes featuring inherent or both inherent and axial chirality via a cobalt-catalyzed C-H activation/annulation strategy in high yield with excellent enantio- and diastereoselectivity (up to > 99% ee and > 20:1 dr). Electrooxidation was also suitable for this transformation to obviate the sacrificial metal oxidants, underscoring the environmentally friendly potential of this approach. A key octahedral cobaltacycle intermediate was synthesized and characterized, providing valuable insights into the mode of enantio- and diastereocontrol of this protocol. Noteworthy photoluminescence quantum yields of up to 0.94 were measured, underscoring the potential of these compounds in the domain of organic fluorescent materials.

Synthesis of Inherently Chiral Homo-heteracalixaromatics.

There is a resurgence of research interest in inherently chiral calixarenes and heteracalixaromatics. However, the examples of macrocyclic ring-expanded homocalixarenes and heterocalixaromatics of inherent chirality are not known. Here we report an efficient method to construct inherently chiral N2,O2-linked homo-heteracalixaromatics from reductive amination reactions between bis-aldehydes and aliphatic diamines. Examples of post-macrocyclization derivatization were also demonstrated. Enantiomers were obtained from resolution and did not undergo racemization at an elevated temperature. This study provides a new strategy to design novel and functional inherently chiral macrocycles that have potential applications in supramolecular chemistry.

Simultaneous construction of inherent and axial chirality by cobalt-catalyzed enantioselective C-H activation of calix[4]arenes

The simultaneous construction of multiple stereogenic elements in a single step is highly appealing and desirable in the field of asymmetric synthesis. Furthermore, the catalytic enantioselective synthesis of inherently chiral calix[n]arenes with high enantiopurity has long been a challenging endeavor. Herein, we report an enantioselective cobalt-catalyzed C–H activation/annulation for the efficient construction of inherently chiral calix[4]arenes bearing multiple C–N axially chiral element. By employing the benzamide tethered calix[4]arene as the substrate, the C–H annulation with alkynes can be successfully accomplished, leading to the generation of multiple stereogenic elements. A wide range of calix[4]arenes and alkynes are found to be well compatible, and exhibit good yields, high enantioselectivity and excellent diastereoselectivity. Notably, the gram-scale reaction, catalytic application, synthetic transformations, and chiral recognition further showcase the potential applications of this protocol.

Enhancing Biocatalysis through Chiral Supramolecular Scaffolds: Insights into the Structural Adaptability of Lipase.

How to maintain high catalytic activity and stability in the process of biocatalysis is crucial, inspiring strategies to construct an appropriate catalytic microenvironment. Considering the lipase's inherent chirality and the necessity for a delicate hydrophilic-hydrophobic equilibrium, we crafted a chiral, nonaqueous catalytic microenvironment via the in situ coassembly of Boc-FLFL-NHNH2 (Bfl) and lipase. Benefiting from the chirality and distinct Bfl-lipase interactions, the lipase@Bfl supramolecular hybrid amplifies biological functionalities and can serve as a versatile and highly efficient catalyst. Kinetic investigations and molecular docking simulations uncover the strong lipase-substrate affinity and lipase-Bfl interactions, explaining the enhanced biological effects, catalytic activity, and stability. Our study establishes a suitable microenvironment to address the chirality and hydrophobicity during catalysis and highlights the potential of artificial chiral scaffolds and catalytic medium for enhancing lipase activity.

Chirality and self-assembly of structures derived from optically active 1,2-diaminocyclohexane and catecholamines

Abstract Chiral biomimetic nanostructures were successfully synthesized through the oxidative polymerization of chiral and achiral catecholamines in the presence of optically active 1,2-diaminocyclohexane (DACH). Analysis of these nanostructures using circular dichroism confirmed their chiral nature, demonstrating the feasibility of inducing chirality in achiral polycatecholamine materials. Furthermore, the chiral nanostructures exhibited self-assembly behaviour, forming distinctive patterns or curly carpets-like structures on silicon surfaces. The arrangement and morphology of these structures were closely linked to the amount of DACH and its inherent chirality. Additionally, the self-assembly process was shown to be significantly influenced by the pH of the reaction and the choice of supporting materials. These findings are particularly relevant in the context of molecular self-assembly of nanoaggregates/particles generated during dopamine polymerization, suggesting a promising avenue for the development of novel chiral polycatechols-based materials.

Electric Field-Manipulated Optical Chirality in Ferroelectric Vortex Domains.

Manipulating optical chirality via electric fields has garnered considerable attention in the realm of both fundamental physics and practical applications. Chiral ferroelectrics, characterized by their inherent optical chirality and switchable spontaneous polarization, are emerging as a promising platform for electronic-photonic integrated circuits applications. Unlike organics with chiral carbon centers, integrating chirality into technologically mature inorganic ferroelectrics has posed a long-standing challenge. Here, the successful introduction of chirality is reported into self-assembly La-doped BiFeO3 nanoislands, which exhibit ferroelectric vortex domains. By employing synergistic experimental techniques with piezoresponse force microscopy and nonlinear optical second-harmonic generation probes, a clear correlation between chirality and polarization configuration within these ferroelectric nanoislands is established. Furthermore, the deterministic control of ferroelectric vortex domains and chirality is demonstrated by applying electric fields, enabling reversible and nonvolatile generation and elimination of optically chiral signals. These findings significantly expand the repertoire of field-controllable chiral systems and lay the groundwork for the development of innovative ferroelectric optoelectronic devices.

Molecular Materials Based on Subphthalocyanines

Subphthalocyanines (SubPcs) are well-known cone-shaped chromophores consisting on three 1,3-diiminoisoindole units assembled around a boron atom. As a result of their 14 pi-electron aromatic core and their tetrahedral geometry, SubPcs exhibit outstanding physical and optoelectronic properties (e.g., strong dipole moment, excellent light absorption in the 550-650 nm, rich redox features, and excellent charge transport capabilities), that have been skilfully used in variety of applied fields, such as molecular photovoltaics, among others. SubPcs were used by us as non-fullerene acceptors in bulk heterojunctions (BHJ) solar cells. On the other hand as part of our systematic investigation in the preparation and study of novel SubPc-based D–A systems, we have used 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) as partner for SubPcs. Moreover, in the case of unsymmetrically substituted SubPcs (i.e., prepared by cyclotrimerization of a phthalonitrile with no C2v symmetry), they present inherent chirality and the corresponding couple of enantiomers can be isolated Columnar aggregates based on chiral SubPcs have been also prepared, giving rise to ferroelectric self-assembled molecular materials showing both rectifying and switchable

Sedimentation dynamics of triply twisted Möbius bands: Geometry versus topology

We explore the sedimentation dynamics of triply twisted Möbius bands, each characterized by threefold rotational symmetry but distinguished by its construction and intrinsic geometrical properties. Three types of bands are considered: one with vanishing Gaussian curvature, constructed by isometrically deforming flat rectangular strips through bending without stretching; and two with negative Gaussian curvature, one being constructed by isometrically deforming helicoids. Experiment on these three types of bands, with a focus on varying aspect ratios, reveals a singular phenomenon: while the spin directions of bands not derived from helicoids spin in directions consistent with their inherent chirality, bands derived from helicoids exhibit an aspect-ratio-dependent spin, pointing to the existence of a critical aspect ratio at which geometric factors dominate over chiral influences. Supported by numerical simulations and a detailed analysis of the resistance tensors, we propose the unique response of bands derived from helicoids originates from a complex interaction among geometry, topology, and hydrodynamics. Two explanations are offered for the chiral transition observed in bands derived from helicoid. First, this transition may parallel the dynamics of superhelices, for which competing chiralities influence rotational behavior. Second, the unique geometrical properties of bands derived from helicoids, coupled with deviations between the rotation axis and the local symmetry axis, may underlie the observed aspect-ratio-dependent chiral transition. Our study underscores the significant role of geometrical and topological nuances in determining the behavior of chiral objects suspended in fluids. In addition to offering transformative potential across diverse fields, it promises advancements in mixing, separation processes, and innovative passive swimmers. Published by the American Physical Society 2024

Maltodextrin-modified graphene oxide composite membrane applied to the enantioseparation of amino acids

The separation of enantiomers using chiral membranes has garnered much research interest. In this study, the enantioseparation of amino acids using chiral membranes, namely graphene oxide-ethylenediamine-maltodextrin (GO-EDA-MD) and GO-EDA-hydroxypropyl-MD (GO-EDA-HP-MD), was evaluated. HP-MD and MD were investigated as chiral selectors due to their inherent chirality. Various characterization techniques, including atomic force microscopy, Fourier transform infrared spectrometry, field emission scanning electron microscopy, water contact angle analysis, tensile properties, and thermal gravimetric analysis were employed to analyze the membrane structures. The evaluation of enantioseparation performance was conducted by employing tryptophan, phenylalanine, and tyrosine enantiomers. Optimal conditions for enantiomer separation were achived using a GO-EDA-HP-MD chiral composite (1.75 wt%), a feed concentration of 10 mg/L for each enantiomer, a separation time of 15 min, and a membrane effective surface area of 1.0 cm2. Also, the bovine serum albumin rejection was 90.0 %, and the water flux reached 37.1 L m−2 h−1. The highest enantiomeric excess (ee.%) values were 46.33 %, 76.97 %, and 73.04 % for tryptophan, phenylalanine, and tyrosine, respectively. The impact of voltage on ee.% and substance flux was also explored. This membrane was able to separate enantiomers successfully.

Circularly polarized lasing from chiral metal-organic frameworks

Circularly polarized lasers play a pivotal role in classical optics, nanophotonics, and quantum optical information processing, while their fabrication remains complex. This article begins with examining the interactions between stimulated emission and chiral matter, outlining a simple strategy for producing circularly polarized lasing from chiral metal-organic frameworks (MOFs), such as the zeolitic imidazolate framework (ZIF), embedded with achiral laser dyes (L/D-ZIF⊃dyes). It is found that the stimulated emission threshold and intensity are influenced by the interplay between the chiral polarization of the pump light and the inherent chirality of the MOF nanoparticles. We further present the design of a chiral vertical-cavity surface-emitting laser (VCSEL), comprising an L/D-ZIF⊃dyes solid-state film sandwiched between a high-reflectivity distributed Bragg reflector (DBR) mirror and a silver film. The cavity-based lasing exhibits higher asymmetry between emitting left-handed and right-handed polarized light compared to chiral spontaneous emission (SE) and amplified spontaneous emission (ASE), with an asymmetry value g lum of approximately ±0.31. This value is nearly four-fold greater than that of SE and twice that of ASE. Our findings reveal a new approach to amplify chiral signals, promoting the comprehension and application of chiral–matter interactions, and offering a simple yet effective strategy to fabricate chiral lasers.

A Double Twisted Nanographene with a Contorted Pyrene Core

AbstractThe mature synthetic methodologies enable us to rationally design and produce chiral nanographenes (NGs), most of which consist of multiple helical motifs. However, inherent chirality originating from twisted geometry has just emerged to be employed in chiral NGs. Herein, we report a red‐emissive chiral NG constituted of orthogonally arranged two‐fold twisted π‐skeletons at a contorted pyrene core which contributes to optical transitions of S0→S1 and vice versa. The thus‐obtained NG exhibited a robustness on its redox properties through 2e− uptake/release. The chemical oxidation generated stable radical cation whose absorption covers near‐infrared I and II regions. Overall, the contorted pyrene core governs electronic nature of the chiral NG. The twist operation on NGs would be, therefore, a design strategy to alter conventional chirality induction on NGs.

A Double Twisted Nanographene with a Contorted Pyrene Core.

The mature synthetic methodologies enable us to rationally design and produce chiral nanographenes (NGs), most of which consist of multiple helical motifs. However, inherent chirality originating from twisted geometry has just emerged to be employed in chiral NGs. Herein, we report a red-emissive chiral NG constituted of orthogonally arranged two-fold twisted π-skeletons at a contorted pyrene core which contributes to optical transitions of S0→S1 and vice versa. The thus-obtained NG exhibited a robustness on its redox properties through 2e- uptake/release. The chemical oxidation generated stable radical cation whose absorption covers near-infrared I and II regions. Overall, the contorted pyrene core governs electronic nature of the chiral NG. The twist operation on NGs would be, therefore, a design strategy to alter conventional chirality induction on NGs.

Enantiomerically Resolvable Inherent Chirality Induced by Strong Para-Steric Hindrance in Cycloparaphenylene-Based Carbon Nanohoops.

The chemical modification of the achiral carbon nanohoops to break the symmetry will result in inherently chiral structures with interesting optical properties. Herein, we report two novel π-extended chiral macrocycles, cyclo[10]paraphenylene-pyrene ([10]CPP-2Pyrene) and cyclo[10]paraphenylene-hexa-peri-hexabenzocoronene ([10]CPP-2HBC). The large substituents on the nanohoop peripheries effectively prevented free rotation and the racemization process. The conformation of each enantiomer is stable enough to be resolved by recycling HPLC.

Binding effect of tyrosine-based chiral carbon dots on human serum albumin and lysozyme

Recently, chiral carbon dots (CCDs) have generated significant interest in biological fields such as biosensing, bioimaging, and drug delivery, due to the combination of inherent chirality and nanoscale size. Here, spectroscopic methods have been used to monitor the interaction between human serum albumin (HSA) and lysozyme (LYZ) with CCDs. Long-wavelength emission CCDs (LWE-CCDs) were synthesized using L/D-tyrosine (L/D-Tyr) and o-phenylenediamine (o-PDA) through a facile and one-step solvothermal approach. Two mentioned proteins interacted with L- and D-CDs and the results of secondary structure studies revealed that proteins preserve their native structure while having a small increase in their compactness. Furthermore, studies on the tertiary structure indicated more flexibility and the possibility of disorder in the hydrophobic regions of HSA, while LYZ appeared to become more rigid. Generally, the L- and D-CDs have more effect on the secondary and tertiary structures of HSA and LYZ, respectively. In addition, the interaction of L/D-Tyr (chiral precursor) with proteins was studied using molecular docking to explain the different effects of the CCDs on HSA and LYZ, and the obtained results are almost consistent with the results of experimental tests. This research offers new perspectives on the synthesis of LWE-CCD and the impact of their chirality on protein-nanoparticle interactions. Studying the action of CCDs at the molecular level will help researchers to choose suitable isomers to apply in biological applications.

Fagopyrins from Buckwheat Flowers: Structural and Stereochemical Characterization Through Combined NMR/CD Spectroscopy and Theoretical Calculations.

Fagopyrins are phenantroperylenequinones present in the flowers of Fagopyrum esculentum (buckwheat) endowed with photodynamic activity. It has been reported that fagopyrin extracts actually contain a complex mixture of closely related compounds, differing only on the nature of the perylenequinone substituents. We report our systematic and detailed study on the chemical composition of fagopyrin extracts by a combination of preparative and analytical techniques. The combined use of 1H-NMR and CD spectroscopy was found to be particularly suited to fully characterize all stereochemical aspects of the extracted fagopyrins. For the first time nine isomers have been structurally characterized and their stereochemistry fully elucidated. The presence of two different heterocyclic ring substituents, two stereogenic centers and the inherent axial chirality of the aromatic system provides a complex stereochemical relationships among isomers, thus giving account of the high level of molecular multiplicity found in the extract.

Catalytic Asymmetric Synthesis of Inherently Chiral Saddle‐Shaped Dibenzo[b,f][1,5]diazocines†

Comprehensive SummaryDibenzo[b,f][1,5]diazocines are a class of eight‐membered heterocycles, which exhibit unique rigid saddle‐shaped structure and possess inherent chirality. In this study, we report a convenient and straightforward method for the catalytic enantioselective synthesis of these unique chiral molecules through chiral phosphoric acid‐catalyzed dimerization of 2‐acylbenzoisocyanates. Notably, the addition of corresponding 2‐acylaniline as the co‐catalyst significantly improved the efficiency of these reactions, and a simple phase separation operation resulted in products with excellent enantiopurity. Experimental studies were performed to elucidate the mechanism behind these reactions, leading to the proposal of a plausible reaction mechanism based on the study findings.

Exploring the potential of inherent chiral single-walled carbon nanotubes in enantioselective electrochemical sensing: A novel microsensor for discriminating DOPA enantiomers

A range of electrochemical sensors capable of enantiomer discrimination have been developed, but the creation of their electrochemical interfaces remains complex. This often entails combining externally introduced chiral centers with conductive materials. This study marks a significant departure from this approach by exploiting the inherent chirality of single-walled carbon nanotubes (SWCNTs) for enantiomer discrimination. We have crafted a miniaturized, enantioselective electrochemical microsensor by seamlessly integrating high-purity SWCNTs, possessing inherent chirality, with an ultra-sensitive carbon fiber microelectrode. Using differential pulse voltammetry, we observed a notable difference in peak current, highlighting the sensor's precise ability to distinguish between enantiomers of 3,4-dihydroxyphenylalanine (DOPA). Furthermore, we investigated the intricacies of the interplay between enantioselective interfaces and the molecules under discrimination, offering deeper insights into the mechanisms governing this phenomenon. This study provides substantial momentum into the realm of enantioselective electrochemical sensing and sheds light on the unique attributes of inherently chiral carbon nanotubes in such applications. This paves the way for a new breed of chiral sensors that are simpler, more efficient, and cost-effective.