RESUMEN

Chirality plays a pivotal role in both the origin of life and the self-assembly of materials. However, the governing principles behind chirality transfer in hierarchical self-assembly across multiple length scales remain elusive. Here, we propose a concise and versatile simulation strategy using the patchy particle chain model to investigate the self-assembly of rods interacting through chiral and aggregation interactions. We reveal that chiral interaction possessing an entropic nature, amplifies the fluctuations and twists in the alignment of rods, while aggregation interaction serves as a foundational platform for aggregation and assembly. When both interactions exhibit moderate absolute and relative values, their synergistic interplay facilitates the chirality transfer from rods to assemblies, resulting in the formation of chiral mesoscale ordered structures. Furthermore, we observe a two-step chirality transfer process by monitoring the formation kinetics of the twisted assemblies. This work not only provides a comprehensive insight into chirality transfer mechanisms, but also introduces a versatile mesoscale simulation framework for exploring the role of chirality in hierarchical self-assembly.

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The chirality transfer phenomenon is attractive for enhancing the optical functionality of nanomaterials by inducing sensitivity to the circular polarization states of photons. An underexplored aspect is how material properties of the achiral semiconductor impact the induced chiroptical signatures. Here we apply atomistic time-dependent density functional theory simulations to investigate the material properties that influence the chiroptical signatures of a lead halide perovskite nanocrystal with a chiral molecule bound to the surface. First, we find that both lattice disorder created by surface strain and halide substitution can increase the chiroptical response of the perovskite quantum dots by an order of magnitude. Both phenomena are attributed to a broadening of the density of the electronically excited states. Second, the intensity of the anisotropy spectra decreases with increasing dot size with a power law decay. Overall, these insights can be used to help guide experimental realization of highly resolvable polarized optical features in semiconducting nanomaterials.

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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.

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In biological systems, nucleosides play crucial roles in various physiological processes. In this study, we designed and synthesized four achiral anthracene-based tetracationic nanotubes (1-4) as artificial hosts and chiroptical sensors for nucleosides in aqueous media. Notably, different nanotubes exhibit varied chirality sensing on circular dichroism (CD)/circularly polarized luminescence (CPL) spectra through the host-guest complexation, which prompted us to explore the factors influencing their chiroptical responses. Through systematic host-guest experiments, the structure-chirality sensing relationship between achiral anthracene-based tetracationic nanotubes and nucleosides in the host-guest complexation was unraveled. Firstly, the CD response originates from the anthracene rings situated at the side-wall position, resulting from the right-handed (P)- or left-handed (M)-twisted conformation of the macrocyclic structure. Secondly, the CPL signal is influenced by the presence of anthracene rings at the linking-wall position, which results from intermolecular chiral twisted stacking between these anthracene rings. Therefore, these nanotubes can serve as chiroptical sensor arrays to enhance the accuracy of nucleotide recognition through principal component analysis (PCA) analysis based on the diversified CD spectra. This study provides insights for the construction of adaptive chirality from achiral nanotubes with dynamic conformational nature and might facilitate further design of chiral functional materials for several applications.

Asunto(s)

RESUMEN

In nature, chirality transfer refines biomolecules across all size scales, bestowing them with a myriad of sophisticated functions. Despite recent advances in replicating chirality transfer with biotic or abiotic building blocks, a molecular understanding of the underlying mechanism of chirality transfer remains a daunting challenge. In this paper, the coassembly of two types of glycopeptide molecules differing in capability of forming intermolecular hydrogen bonds enabled the involvement of discontinuous hydrogen bond, which allowed for a nanoscale chirality transfer from glycopeptide molecules to chiral micelles, yet inhibited the micrometer scale chirality transfer toward helix formation, leading to an achiral transfer from chiral micelles to planar monolayer. Upon stacking the monolayer into a bilayer, the nonsuperimposable front and back faces of the chiral micelles involved in the monolayer ribbons lead to the opposite rotation of two layers toward increasing the continuity of H-bonds. The resultant continuity triggered the symmetry breaking of stacked bilayers and thus reactivated the micrometer-scale chirality transfer toward the final helix. This work delineates a promising step toward a better understanding and replicating the naturally occurring chirality transfer events and will be instructive to future chiral material design.

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Chirality transfer from chiral molecules to chiral nanomaterials represents an important topic for exploring the origin of chirality in many natural and artificial systems. Moreover, developing a promising class of chiral nanomaterials holds great significance for various applications, including sensing, photonics, catalysis, and biomedicine. Here we demonstrate the geometric control and tunable optical chirality of chiral pentatwinned Au nanoparticles with 5-fold rotational symmetry using the seed-mediated chiral growth method. A distinctive growth pathway and optical chirality are observed using pentatwinned decahedra as seeds, in comparison with the single-crystal Au seeds. By employing different peptides as chiral inducers, pentatwinned Au nanoparticles with two distinct geometric chirality (pentagonal nanostars and pentagonal prisms) are obtained. The intriguing formation and evolution of geometric chirality with the twinned structure are analyzed from a crystallographic perspective upon maneuvering the interplay of chiral molecules, surfactants, and reducing agents. Moreover, the interesting effects of the molecular structure of peptides on tuning the geometric chirality of pentatwinned Au nanoparticles are also explored. Finally, we theoretically and experimentally investigate the far-field and near-field optical properties of chiral pentatwinned Au nanoparticles through numerical simulations and single-particle chiroptical measurements. The ability to tune the geometric chirality in a controlled manner represents an important step toward the development of chiral nanomaterials with increasing architectural complexity for chiroptical applications.

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Supramolecular chirality-mediated selective interaction among native assemblies is essential for precise disease diagnosis and treatment. Herein, to fully understand the supramolecular chiral binding affinity-achieved therapeutic efficiency, supramolecular chiral nanoparticles (WP5⊃D/L-Arg+DOX+ICG) with the chirality transfer from chiral arginine (D/L-Arg) to water-soluble pillar[5]arene (WP5) are developed through non-covalent interactions, in which an anticancer drug (DOX, doxorubicin hydrochloride) and a photothermal agent (ICG, indocyanine green) are successfully loaded. Interestingly, the WP5⊃D-Arg nanoparticles show 107 folds stronger binding capability toward phospholipid-composed liposomes compared with WP5⊃L-Arg. The enantioselective interaction further triggers the supramolecular chirality-specific drug accumulation in cancer cells. As a consequence, WP5⊃D-Arg+DOX+ICG exhibits extremely enhanced chemo-photothermal synergistic therapeutic efficacy (tumor inhibition rate of 99.4%) than that of WP5⊃L-Arg+DOX+ICG (tumor inhibition rate of 56.4%) under the same condition. This work reveals the breakthrough that supramolecular chiral assemblies can induce surprisingly large difference in cancer therapy, providing strong support for the significance of supramolecular chirality in bio-application.

Asunto(s)

RESUMEN

Chiroptical activities arising in nanoclusters (NCs) are emerging as one of the most dynamic areas of modern science. However, devising an overarching strategy that is capable of concurrently enhancing the photoluminescence (PL) and circularly polarized luminescence (CPL) of metal NCs remains a formidable challenge. Herein, gold and silver nanoclusters (AuNCs, AgNCs) are endowed with CPL, for the first time, through a universal host-guest approach─centered around perturbing a chiral microenvironment within chiral hosts, simultaneously enhancing emissions. Remarkably, the photoluminescence quantum yield (PLQY) of AuNCs has undergone an increase of over 200 times upon confinement, escalating from 0.05% to 12%, and demonstrates a CPL response. Moreover, a three-dimensional (3D) model termed "NCs@CMOF" featuring CPL activity is created using metal cluster-based assembly inks through the process of 3D printing. This work introduces a potentially straightforward and versatile approach for achieving both PL enhancement and CPL activities in metal clusters.

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Electromagnetic chirality transfer represents an effective means of the nanoscale manipulation of optical chirality. While most of the previous reports have exclusively focused on the circular dichroism (CD) transfer from UV-responsive chiral molecules toward visible-resonant achiral colloidal nanoparticles, here we demonstrate a reverse process in which plasmonic chirality can be transferred to achiral molecules, either upward from visible to UV or downward from visible to near infrared (NIR). By hybridizing achiral UV- or NIR-responsive dye molecules with chiral metal nanoparticles in solution, we observe a chiral-plasmon-induced CD (CPICD) signal at the intrinsically achiral molecular absorption bands. Full-wave electromagnetic modeling reveals that both near-field Coulomb interaction and far-field radiative coupling contribute to the observed CPICD, indicating that the mechanism considered here is universal for different material systems and types of optical resonances. Our study provides a set of design guidelines for broadband nanophotonic chiral sensing from the UV to NIR spectral regime.

RESUMEN

We synthesized cyclic chiral compounds [(R)/(S)-D2s] by linking a photoresponsive bisbenzothienylethene (BTE) moiety with an axially chiral binaphthyl moiety. Chiral nematic liquid crystals (N*-LCs) were prepared by adding chiral compounds as dopants to host N-LCs. These N*-LCs exhibited reversible chirality inversion upon photoisomerization between the open and closed forms of the BTE moiety. Here, the mechanism underlying chirality inversion in photoresponsive N*-LCs was investigated by comparing the helical twisting powers (HTPs) of (R)-D2s with those of analogous compounds. It was found that the helical inversion of N*-LCs containing (R)-D2s is governed by a delicate balance between two types of opposite helicity, i.e., the right-handed helicity of the inherently chiral binaphthyl moiety and the left-handed helicity of the BTE moiety bearing intramolecularly induced chirality. Namely, (R)-D2s induced chirality of the BTE moiety, which is attributed to intramolecular chirality transfer from the axially chiral binaphthyl moiety to the BTE moiety. Thus, (R)-D2s are chiral compounds with double chirality consisting of an intrinsically chiral moiety and an intramolecularly induced chiral moiety. Photocontrol of the helical senses and reversible photoinversion of the N*-LCs are achieved by utilizing UV and visible light irradiation and the steric effects of the substituents at the binaphthyl rings in (R)-D2s. In addition, photocontrol of the induced circularly polarized luminescence (CPL) was achieved using the photoinvertible N*-LC. The achiral aromatic conjugated copolymers that exhibited red, green, and blue fluorescence were dissolved and mixed in the present N*-LC, and they exhibited left- and right-handed white CPL with large dissymmetry factors (|glum|) ranging from 0.2 to 1.0. The CPLs were reversibly photoswitched due to photoisomerization between the open and PSS forms of the chiral compounds through UV and visible light irradiation.

RESUMEN

The development of ultraviolet circularly polarized light (UVCPL) sources has the potential to benefit plenty of practical applications but remains a challenge due to limitations in available material systems and a limited understanding of the excited state chirality transfer. Herein, by constructing hybrid structures of the chiral perovskite CsPbBr3 nanoplatelets and organic molecules, excited state chirality transfer is achieved, either via direct binding or triplet energy transfer, leading to efficient UVCPL emission. The underlying photophysical mechanisms of these two scenarios are clarified by comprehensive optical studies. Intriguingly, UVCPL realized via the triple energy transfer, followed by the triplet-triplet annihilation upconversion processes, demonstrates a 50-fold enhanced dissymmetry factor glum. Furthermore, stereoselective photopolymerization of diacetylene monomer is demonstrated by using such efficient UVCPL. This study provides both novel insights and a practical approach for realizing UVCPL, which can also be extended to other material systems and spectral regions, such as visible and near-infrared.

RESUMEN

Constructing full-color circularly polarized luminescence (CPL) materials with switchable handedness in the solid state is an appealing yet considerably challenging task, especially for supramolecular polymer films assembled from homochiral monomers. Herein, supramolecular polymers with full-color CPL and inverted handedness are realized through the coassembly of a homochiral cholesterol derivative (PVPCC), metal ions (Zn2+), and achiral fluorescent dyes. The obtained coassembled systems show anion-directed supramolecular chirality inversion by exchanging the anions of NO3-, ClO4-, BF4-, and Cl-. For instance, the negative CD and right-handed CPL are detected in the PVPCC/Zn(NO3)2 aggregates, which convert into positive CD and left-handed CPL after introducing Cl-, corresponding to the transformation from nanorods to nanofibers. Furthermore, the tunable CPL color and handedness inversion of the coassembly system of PVPCC/Zn(NO3)2 and achiral fluorescent dyes can be established by alternately changing the assembling temperature of 298 and 273 K. Importantly, the full-color CPL polymeric materials are then constructed by doping the PVPCC/Zn(NO3)2/dyes complexes into poly(methyl methacrylate) (PMMA) film, which maintains the handedness inversion and shows the enhanced CPL performance. The work not only deepens the understanding of chirality inversion in supramolecular chemistry but also helps to construct full-color CPL materials with switchable handedness from homochiral building blocks in materials science.

RESUMEN

Due to their broken symmetry, chiral plasmonic nanostructures have unique optical properties and numerous applications. However, there is still a lack of comprehension regarding how chirality transfer occurs between circularly polarized light (CPL) and these structures. Here, we thoroughly investigate the plasmon-assisted growth of chiral nanoparticles from achiral Au nanocubes (AuNCs) via CPL without the involvement of any chiral molecule stimulators. We identify the structural chirality of our synthesized chiral plasmonic nanostructures using circular differential scattering (CDS) spectroscopy, which is correlated with scanning electron microscopy imaging at both the single-particle and ensemble levels. Theoretical simulations, including hot-electron surface maps, reveal that the plasmon-induced chirality transfer is mediated by the asymmetric distribution of hot electrons on achiral AuNCs under CPL excitation. Furthermore, we shed light on how this plasmon-induced chirality transfer can also be utilized for chiral growth in bimetallic systems, such as Ag or Pd on AuNCs. The results presented here uncover fundamental aspects of chiral light-matter interaction and have implications for the future design and optimization of chiral sensors and chiral catalysis, among others.

RESUMEN

The development of chiral nanostructures-based supramolecular catalysts with satisfied enantioselectivity remains a significantly more challenging task. Herein, the synthesis and self-assembly of various amino acid amphiphiles as chiral supramolecular catalysts after metal ion coordination is reported and systematically investigate their enantioselectivity in asymmetric Diels-Alder reactions. In particular, the self-assembly of l/d-phenylglycine-based amphiphiles (l/d-PhgC16) and Cu(II) into chiral supramolecular catalysts in the methanol/water solution mixture is described, which features the interesting M/P nanohelices (diameter ≈8 nm) and mostly well-aligned M/P nanoribbons (NRs). The M/P supramolecular catalysts show both high but inverse enantioselectivity (>90% ee) in Diels-Alder reactions, while their monomeric counterparts display nearly racemic products. Analysis of the catalytic results suggests the outstanding enantioselectivities are closely related to the specific stereochemical microenvironment provided by the arrangement of the amphiphiles in the supramolecular assembly. Based on the experimental evidence of chirality transfer from supramolecular nanohelices to coordinated Cu(II) and substrate aza-chalcone and the molecular dynamics simulations, the enantioselective catalytic mechanisms are proposed. Moreover, the relationships between molecular structures of amino acid amphiphiles (the hydrophilic head group and hydrophobic alkyl chain length) in supramolecular catalysts and enantioselectivity in Diels-Alder reactions are elaborated.

RESUMEN

Chirality transfer is essential to acquire helical hierarchical superstructures from the self-assembly of supramolecular materials. By taking advantage of chirality transfers at different length scales through intra-chain and inter-chain chiral interactions, helical phase (H*) can be formed from the self-assembly of chiral block copolymers (BCPs*). In this study, chiral triblock terpolymers, polystyrene-b-poly(ethylene oxide)-b-poly(L-lactide) (PS-PEO-PLLA), and polystyrene-b-poly(4-vinylpyridine)-b-poly(L-lactide) (PS-P4VP-PLLA) are synthesized for self-assembly. For PS-PEO-PLLA with an achiral PEO mid-block that is compatible with PLLA (chiral end-block), H* can be formed while the block length is below a critical value. By contrast, for the one with achiral P4VP mid-block that is incompatible with PLLA, the formation of H* phase would be suppressed regardless of the length of the mid-block, giving cylinder phase. Those results elucidate a new type of chirality transfer across the phase domain that is referred as cross-domain chirality transfer, providing complementary understanding of the chirality transfer at the interface of phase-separated domains.

RESUMEN

Spin-polarized lasers, arising from stimulated emission of imbalanced spin populations, play a vital role in spin-optoelectronics. It is usually tackled by external spin injection, inevitably suffering from additional losses across the barriers from injection sources to gain materials. Herein, spin-polarized coherent light emission is self-triggered from the 1D-anchoring-3D perovskites, where the imbalanced populations in achiral 3D perovskites are endowed with the spin selectivity of exciton chirality (EC) underpinned by chiral 1D perovskites. Efficient transfer of EC is enabled by rapid energy transfer, thereby creating an imbalance of the spin population of excited states. Stimulated emission of such populations brings self-triggered spin-polarized amplified spontaneous emission in the composite perovskites, yielding a higher degree of polarization (DOP) than that based on optical spin injection into bare achiral 3D perovskites. Chemical diversity of composite perovskites not only enables to adjust band gap for broadband output of spin-polarized light signals but also promises to manipulate radiative decay and spin relaxation toward remarkably increased DOP. These results highlight the importance of EC transfer mechanism for spin-polarized lasing and represent a crucial step toward the development of chiral-spintronics.

RESUMEN

Herein, chiral deep eutectic solvents (DES) are prepared by lauric acid as hydrogen bond donors (HBD) and chiral menthol as hydrogen bond acceptors (HBA). When achiral fluorescent molecules are dopedin the menthol-based chiral DES, they emit circularly polarized luminescence (CPL) with handedness controlled by the molecular chirality (l or d) of menthol. Remarkably, the strategy is universal and a series of achiral fluorescent molecules can be endowed with CPL activity, showing a full-color and white CPL upon appropriate mixing, which paves the way to prepare white CPL materials. Interestingly, CPL appears only in a certain temperature range in the DES. Variable-temperature spectra and other characterization methods reveal that the H-bond network in the chiral DES plays an important role in inducing CPL. This work unveils how the interior structure as well as the hydrogen-bond network of a chiral DES can transfer its chirality to achiral luminophores for the first time and realizes a full-color and white CPL in a DES.

RESUMEN

Tetraphenylethylene (TPE) helicates with single helical handedness not only owe high fluorescence quantum yield but also possess good helical chirality, showing an excellent circularly polarized luminescence active material. In this work, a new method for directly obtaining single-handed TPE helicates has been developed. By using chiral p-phenylenediamine derivatives as an intramolecular cyclization reagent of TPE, the single-handed propeller-like conformation and stable helical chirality of the TPE unit were obtained, avoiding complicated and expensive HPLC chiral column separation. The as-prepared chiral TPE helicates displayed strong emission with an almost quantitative fluorescence quantum yield (Φf) and strong circularly polarized luminescence (CPL). In addition, the chirality and CPL signals of the TPE helicates could be significantly magnified by the helical arrangement together with 4'-pentyl-4-biphenylcarbonitrile (5CB) liquid crystal molecules. Moreover, full-color CPL emissions with both a high absolute CPL dissymmetrical factor up to 0.43 and high Φf were afforded.

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Chirality transfer from the chiral molecule (R)-1,2-propylene oxide to the achiral anion of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid is observed. The chiral probe selectively affects one part of the binary ionic liquid, i. e., it has previously been shown experimentally and theoretically that this particular imidazolium cation can be affected by chirality transfer, but in the present system chirality is almost exclusively transferred to the anion and not to both parts of the solvent (anion and cation). This observation is of high relevance because of its selectivity and because anion effects are usually much more important in ionic liquid research than cation effects. From ab initio molecular dynamics simulations, a conformational analysis and dissected vibrational circular dichroism spectra are obtained to study the chirality transfer. While in the neat ionic liquid two mirror imaged trans conformers of the anion occur almost equally, we observe an excess of one of these conformers in the presence of the chiral solute, causing optical activity of the anion. Although the cis conformers are not tremendously affected by the chirality transfer, they gain in total population when (R)-1,2-propylene oxide is dissolved in the ionic liquid.

RESUMEN

Molecules stereogenic only at tetrahedral boron atoms show great promise for applications, for example as chiroptical materials, but are scarcely investigated due to their synthetic challenge. Hence, this study reports a two-step synthesis of enantioenriched boron C,N-chelates. First, the diastereoselective complexation of alkyl/aryl borinates with chiral aminoalcohols furnished boron stereogenic heterocycles in up to 86 % yield and d.r. >98 : 2. Treatment of these O,N-complexes with chelate nucleophiles was surmised to transfer the stereoinformation via the ate-complex into the C,N-products. This chirality transfer succeeded by substitution of the O,N-chelates with lithiated phenyl pyridine to give boron stereogenic C,N-chelates in up to 84 % yield and e.r. up to 97 : 3. The chiral aminoalcohol ligands could be recovered after isolation of the C,N-chelates. The chirality transfer tolerated alkyl, alkynyl and (hetero-)aryl moieties at boron and could be further extended by post-modification: transformations such as catalytic hydrogenations or sequential deprotonation/electrophilic trapping were feasible while maintaining the stereochemical integrity of the C,N-chelates. Structural aspects of the boron chelates were studied by variable temperature NMR and X-ray diffraction.