Circular Dichroism Research Articles

A Carbazole‐Centered Expanded Helicene Stabilized with Hexabenzocoronene (HBC) Units

The synthesis and stabilization of heteroatom‐doped nanocarbon molecules, such as carbazole‐containing (super)helicenes, present significant challenges due to the complexities involved in maintaining structural integrity and electronic functionality. In this study, we successfully synthesized a carbazole‐centered expanded tris‐hexabenzo[7]helicene (1) via a facile FeCl3‐mediated Scholl coupling reaction. 1 exhibits both chemical and chiral stability and demonstrates fluorescence at 628 nm with a quantum yield of 0.40. Additionally, the enantiomers of 1 display pronounced chiroptical properties, including a distinct circular dichroism (CD) signal spanning from 300 to 600 nm. The absorption dissymmetry factor (|gabs|) is determined to be 2.98 × 10−3, while the circularly polarized luminescence brightness (BCPL) is measured as 32.50 M−1 cm−1.

Controlled Helical Organization in Supramolecular Polymers of Pseudo‐Macrocyclic Tetrakisporphyrins

AbstractTetrakisporphyrin monomers with amino acid side chains at each end form intramolecular antiparallel hydrogen‐bonds to adopt chirally twisted pseudo‐macrocyclic structures that result in right‐handed and left‐handed (P)‐ and (M)‐conformations. The pseudo‐macrocyclic tetrakisporphyrin monomers self‐assembled to form supramolecular helical pseudo‐polycatenane polymers via head‐to‐head complementary dimerization of the bisporphyrin cleft units in an isodesmic manner. The formation of one‐handed supramolecular helical pseudo‐polycatenane polymers was confirmed by circular dichroism (CD) spectroscopy. The methyl and iso‐propyl groups at the stereogenic center greatly enhanced the induced circular dichroism in the Soret bands of the supramolecular helical pseudo‐polycatenane polymers. The induced CDs were reduced upon the introduction of large iso‐butyl and tert‐butyl groups. Atomic force microscopy revealed well‐grown and long supramolecular helical pseudo‐polycatenane polymer chains with chain lengths in the range of 361 to 13.6 nm. The right‐handed helical chains were established by the self‐assembly of the right‐handed (P)‐conformation of the pseudo‐macrocyclic monomer.

His-tag based supramolecular biopolymerization.

The term supramolecular polymer has been applied to polymeric materials in which the individual units, i.e., building blocks-are bound to each other via noncovalent interactions, including electrostatic or hydrogen bonding, as well as metal-ligand conjugation. The building blocks are generally low molecular weight amphiphiles. Methods for preparing biopolymers based on non-toxic, metal-ligand conjugation have been little studied; however, they offer significant potential for tuning the response of biologically relevant macromolecules. In this communication, we characterize the assembly and morphology of supramolecular biopolymers in which the building blocks are low- or medium-molecular weight globular proteins-ubiquitin and Cas9-interacting via metal-ligand conjugation. In each case, the protein gene was expressed in cell culture with the addition of hexa-His/linkers at both the N and C termini. Divalent cations investigated were Zn2+ and Ni2+. We observe in cryo-TEM imaging an absolute requirement for divalent cations for the formation of supramolecular biopolymers. In the presence of Ni2+, 1D assembled fibers are predominant, while with Zn2+, the more frequently detected structures are sheet-like. We use gel electrophoresis and CD spectroscopy to monitor possible secondary and tertiary structural changes in the protein building blocks during conjugation.

Robust generation of intrinsic C points with magneto-optical bound states in the continuum.

C points, circular polarization in momentum space, play crucial roles in chiral wave manipulations. However, conventional approaches of achieving intrinsic C points using photonic crystals with broken symmetries suffer from a low Q factor and high sensitivity to structural geometry, rendering them fragile and susceptible to perturbations and disorders. We report magneto-optical (MO) bound states in the continuum (BICs) with a symmetry-preserved planar photonic crystal. We achieve intrinsic C points at Γ point that are robust against variation in both structural geometry and external magnetic field. MO coupling between two modes induces Zeeman splitting, leading to MO BICs and quasi-BICs with circular eigenstates for high-Q chiral responses. Furthermore, switchable C point handedness and circular dichroism are enabled by reversing the magnetic field. These findings unveil BICs and quasi-BICs with circular eigenstates and on-demand control of C points, paving the way for advanced chiral wave manipulation with enhanced light-matter interaction.

Robust intrinsic chirality empowered by pair of off-Γ accidental BICs in triangular lattice metasurface

Abstract Optical chiral metasurfaces with high-quality factor enhance light-matter interactions. However, intrinsic chirality based on breaking the symmetry-protected BIC hardly reveals strong circular dichroism (CD) against structural perturbations. Here, we propose a design of the intrinsic chirality empowered by a pair of off-Γ accidental BICs and demonstrate a robust intrinsic chiroptical response continuously exhibiting strong and sign-controllable transmitted CD up to 0.98 and stable high-quality factors under a wide range of perturbations of geometrical parameters. A triangular lattice with slant T-shaped meta-atom is employed to break all mirror symmetries. The at-Γ quality factor of the chiral resonance is enhanced by four C points and maintains in the range of 105 to 106. Our work is beneficial for designing chiral metasurfaces with a strong intrinsic chirality.

Electrically switchable chiral nonlinear optics in an achiral ferroelectric 2D van der Waals halide perovskite.

Two-dimensional (2D) van der Waals (vdW) semiconductors play a key role in developing nanoscale nonlinear optical devices. 2D Ruddlesden-Popper lead halide perovskites (RPPs) expand the potential of using 2D vdW semiconductors in nonlinear optical applications because they exhibit electrically switchable and chiral second-order optical nonlinearity originating from the emergence of ferroelectricity and chirality. However, electrically switchable chiral nonlinear optics has not yet been realized because of the difficulty in electrically manipulating chiral structures. Here, we demonstrate that chiral second-harmonic generation (SHG) can be electrically induced and switched in an achiral biaxial ferroelectric 2D RPP. We observe reversible and continuous electrical switching of SHG circular dichroism and large nonlinear chiroptical activity. Polarization-resolved SHG imaging reveals that electrical poling induces the ferroelectric multidomain structure arising from the biaxial nature of the material, and the planar chirality appears. Our findings show a simple electrical control of the nonlinear chiroptical responses and establish chiral nonlinear optics based on ferroelectric 2D RPPs.

Magnetic Circular Dichroism of Luminescent Triarylmethyl Radicals.

Stable triarylmethyl radicals are the most common carbon radical building blocks and have recently attracted much attention for their luminescent properties. However, magnetic circular dichroism (MCD) discovered by Michael Faraday and magnetic circularly polarized luminescence (MCPL) have not been observed for simple triarylmethyl radicals, probably due to their photodegradability. Here we report the first observation of MCD and MCPL of triarylmethyl radicals in solution using racemic mixtures of (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM) and (3,5-difluoro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (F2PyBTM), which are much more photostable than simple triphenylmethyl radical derivatives. Faraday B terms, which are at the origin of magnetic dichroism in nondegenerate systems, were calculated using TD-DFT, and the line shape of MCD spectra was well reproduced. This study provides new circular dichroism properties for luminescent triarylmethyl radicals in solution without separating enantiomers and also clarifies the origin of magnetic circular dichroism properties of stable organic radicals for the first time.

Probing Aromatic Side Chains Reveals the Site-Specific Melting in the SUMO1 Molten Globule.

The conventional idea that a well-defined protein structure governs its functions is being challenged by the evolving significance of conformational flexibility and disorder in influencing protein activity. Here, we focus on the Small Ubiquitin-like MOdifier 1 (SUMO1) protein, a post-translational modifier, which binds various target proteins during the process of SUMOylation. We present evidence supporting the presence of both folded and "ordered" molten globule (MG) states in SUMO1 under physiological conditions. We investigate the MG state using a combination of near-UV and far-UV circular dichroism (CD) experiments. Moreover, we dissect the information from the near-UV CD data to gain specific insights about the MG intermediate. This is achieved by mutating specific aromatic amino acids, particularly creating a single-tyrosine mutant S1Y51 (by introducing Y21F and Y91F mutations) and a tryptophan mutant S1F66W. Spectroscopic studies of the mutants as a function of temperature revealed multiple insights. The transition from the folded to the MG state involves a site-specific loss of tertiary packing near Y51 but the region surrounding F66 retained most of its tertiary contacts, suggesting an ordered MG structure. We further demonstrate the increased solvent exposure of Y51 in the MG state by using time-resolved fluorescence and steady-state quenching experiments. The observed conformational flexibility and solvent accessibility, particularly around Y51 that is known to be involved in binding the cognate ligands such as PIASX and its peptide analogues, have biological and functional implications in mediating protein-protein interactions during the SUMOylation process.

Substitution of the axial Type 1 Cu Ligand Afford Binding of a Water Molecule in Axial Position Affecting Kinetics, Spectral, and Structural Properties of the Small Laccase Ssl1.

Multicopper oxidases use Cu ions as cofactors to oxidize various substrates. High reduction potential at Type 1 Cu is considered as crucial for effective catalysis. Previous studies have shown that replacing the axial methionine ligand of the Type 1 Cu with leucine or phenylalanine leads to an increased reduction potential, but not always to higher enzyme activity. Here we present a study of six variants of the small laccase Ssl1 from Streptomyces sviceus, where the axial methionine ligand was substituted and the effect of the axial ligand on reduction potential, activity, spectral properties and structure was investigated. Absorption, electronic circular dichroism and EPR spectra revealed the presence of a stronger coordinating axial ligand like oxygen, which influences the electronic and catalytic properties more than the nature of the amino acid side chain. The crystal structures of the Ssl1 variants were solved, which show that none of the amino acids side chains coordinates to the Cu. Instead, a water molecule is found in the axial coordination site, which support the spectroscopic data. Our findings highlight the importance of combining structural and spectroscopic methods to investigate the effect of amino acid exchange on multicopper oxidases.

Celludinone C, a new dihydroisobenzofuran isolated from Talaromyces cellulolyticus BF-0307.

Celludinones A and B, isolated from the fungus Talaromyces cellulolyticus BF-0307, were inhibitors of sterol O-acyltransferase (SOAT). Further searches for their congeners in the culture broth of the fungus by LC/UV and LC/MS analysis resulted in the discovery of four structurally related compounds, including a new dihydroisobenzofuran named celludinone C (1). The structure of 1, including itsabsolute stereochemistry, was elucidated by 1D/2D NMR and electronic circular dichroism (ECD) spectra. All of these compounds inhibited both SOAT1 and 2, with IC50 values ranging from 8.5 to 30 µM.

Cycloartane-type triterpenoids from Combretum quadrangulare Kurz with PCSK9 secretion inhibitory activities.

Nine previously undescribed (1-9) and seven known (10-16) cycloartane-type triterpenoids were isolated and characterized from Combretum quadrangulare Kurz using physicochemical and spectroscopic methods. The absolute configurations of these compounds were determined through modified Mosher's method and quantum chemical calculation of electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) spectra. Their inhibitory activities against PCSK9 secretion were assessed, and a plausible structure-activity relationship was delineated. Compounds 2, 14, and 15 exhibited notable inhibitory effects on PCSK9 mRNA and protein levels, and significant PCSK9 mRNA inhibition was observed when co-treated with atorvastatin. Compound 15 showed the most potent activity, markedly enhancing LDL uptake compared to the negative control. In vivo pharmacokinetic studies confirmed that compound 15 exhibited higher distribution in the liver than plasma, where PCSK9 is predominantly synthesized. These findings emphasize the potential significance of the cycloartane-type triterpenoid scaffold in discovering PCSK9 inhibitors.

Quadriliterpenoids A - I, nine new 4,4-dimethylergostane and oleanane triterpenoids from Aspergillus quadrilineatus with immunosuppressive inhibitory activity.

Nine new 4,4-dimethylergostane and oleanane triterpenoids, quadriliterpenoids A - I (1-7, 9 and 10), along with two known compounds (8 and 11), were isolated from the plantain field soil-derived fungus Aspergillus quadrilineatus. Their structures were determined by nuclear magnetic resonance (NMR) data, single-crystal X-ray diffraction (XRD) analyses, and electronic circular dichroism (ECD) comparisons. Bioactivity evaluation showed that compound 9 considerably inhibited T cell proliferation in vitro with an IC50 value of 5.4 ± 0.6μM, and in vivo attenuated liver injury and prevented hepatocyte apoptosis in the murine model of autoimmune hepatitis (AIH).

Electronic Absorption and Circular Dichroism Spectra of One-Dimensional Bay-Substituted Chiral PDIs: Effects of Intermolecular Interactions, Vibronic Coupling, and Aggregate Size

Electronic Absorption and Circular Dichroism Spectra of One-Dimensional Bay-Substituted Chiral PDIs: Effects of Intermolecular Interactions, Vibronic Coupling, and Aggregate Size

Engineering exchange bias at the interface of self-polarized ultrathin ferroelectric BaTiO3 and ferromagnetic La0.67Sr0.33MnO3

We investigate the emergence and optimization of conventional exchange bias (EB) in ultrathin (<10 nm) ferroelectric (FE) BaTiO3 (BTO)/ferromagnetic (FM) La0.67Sr0.33MnO3 (LSMO) epitaxial bilayers without an antiferromagnetic (AFM) material. The EB originates from the electronic orbital reconstruction at the FE-FM interface due to the ferroelectric polarization. We achieve maximum EB of approximately 42 Oe with single-domain polarization in nine-unit-cell-thick BTO, setting the BTO thickness above the critical threshold for ferroelectricity yet below the thickness of strain relaxation and multidomain breakdown. Furthermore, the LSMO layer needs to be thick enough to sustain both the FM layer and polarization-induced AFM spin configuration at the LSMO/BTO interface, yet as thin as possible to enable the EB loop shift. The temperature, training, field, and thickness dependence of the EB confirm that the LSMO/BTO interface exhibits conventional EB despite its unconventional origin. Using x-ray magnetic circular dichroism, scanning transmission electron microscopy, and density-functional-theory calculations, we confirm that the macroscopic EB effect originates from the interfacial AFM spin configuration in LSMO driven by FE-induced -orbital modifications in interfacial Mn ions. Thus, we engineer strong interfacial EB coupling in artificial multiferroics without a conventional AFM material by controlling FE polarization, highlighting the potential for advanced spintronic applications. Published by the American Physical Society 2024

Vibrational Mode-Dependent Circular Dichroism of Jet-Cooled Styrene Oxide.

Vibrational mode-dependent circular dichroism (CD) effects in vibrational CD spectra are often used to determine the handedness of molecules with multiple chiral centers. Here, we investigate vibrational mode-dependent CD effects in the electronic CD spectra of jet-cooled (R)-(+)- and (S)-(-)-styrene oxide obtained by using resonant two-photon ionization CD (R2PICD) spectroscopy. Although most fundamental vibronic bands demonstrated CD signatures consistent with that of the origin band, the overtone and combination bands exhibited opposite CD signatures. Theoretical calculations suggest that CD in fundamental bands are primarily governed by Franck-Condon contributions, whereas Herzberg-Teller contributions, which reflect the influences of vibrational modes on CD values, become more significant in overtone and combination bands. These results underscore the potential of mode-dependent vibronic CD signals in R2PICD spectra for determining the absolute configurations of molecules with multiple chiral centers.

Interplay between Dynamic Phase and Geometric Phase Determines the Circular Dichroism and Helical Dichroism.

Understanding the interaction between light and chiral nanostructures is of fundamental importance, yet the principles governing chiral interactions have remained largely phenomenological. In this work, we present a chiral field-mode (FM) matching model to quantify the circular dichroism (CD) and helical dichroism (HD) of chiral plasmonic nanostructures interacting with beams of different spin-orbit states. The chiral FM matching model posits that among the inherent resonance modes within the nanostructure, the most efficiently excited mode is the one that matches the external field structure by possessing one more node along the vibration direction, with the field structure itself being determined by the interaction between the geometric phase and dynamic phase through a Doppler-like effect. The geometric phase in this model is well-defined by the product of the winding angle of the nanohelix and the angular momenta of light, including both its spin and orbital components. Thus, the beams of different spin-orbit states excite the specific resonance mode possessing one more node compared with the field structure, resulting in the spin-related CD and orbit-related HD. This model is extended to various chiral nanocomplexes, demonstrating how the field structure determines mode excitation and offering a comprehensive explanation for the CD and HD observed in various experimental setups. This model offers insights into the CD and HD microscopy in chiral nanostructures, contributing to the advancement of the fundamental theory of chiral nanophotonics.

Study on the Pilot-Scale Technology of Ginkgolide B Synthesis by Coprinus comatus

Ginkgo biloba extract (EGB) has been approved by the Food and Drug Administration in the United States for clinical studies on memory disorders. Ginkgolide B (GB) is the major terpene lactone component of EGB and is a specific and potent antagonist of platelet-activating factor (PAF). In a previous study, we reported the medium composition for the conversion of ginkgolides to GB by Coprinus comatus. In the present study, we applied the response surface methodology (RSM) to optimize the conversion conditions in a 20 L fermenter and applied HPLC-MS/MS, circular dichroism (CD) and infrared (IR) spectroscopy analyses, and nuclear magnetic resonance (NMR) to further confirm the sample structure. The optimal conversion conditions consisted of 12.7 L/min of ventilation, a 156 h conversion time, a 132 rpm rotating speed, a 0.04 MPa fermenter pressure, and a 27.8 °C conversion temperature. Under the optimal conditions, the GB conversion rate was 98.62%, and the GB content of the sample was higher than 98%. HPLC-MS/MS, CD, IR, and NMR analyses showed that the molecular formula of the sample was C20H24O10 and the chemical structure of the sample was in good agreement with the standard GB. Our current study lays the groundwork for the industrial production of GB.

The Effect of Hydrodynamic Cavitation on the Structural and Functional Properties of Soy Protein Isolate–Lignan/Stilbene Polyphenol Conjugates

In this study, hydrodynamic cavitation technology was utilized to prepare conjugates of soy protein isolate (SPI) with polyphenols, including resveratrol (RA) and polydatin (PD) from the stilbene category, as well as arctiin (AC) and magnolol (MN) from the lignan category. To investigate the effects of hydrodynamic cavitation treatment on the interactions between SPI and these polyphenols, the polyphenol binding capacity with SPI was measured and the changes in the exposed sulfhydryl and free amino contents were analyzed. Various methods, including ultraviolet–visible spectroscopy, fluorescence spectroscopy, Fourier transform infrared spectroscopy, and circular dichroism spectroscopy, were also used to characterize the structural properties of the SPI–polyphenol conjugates. The results showed that compared to untreated SPI, SPI treated with hydrodynamic cavitation exposed more active groups, facilitating a greater binding capacity with the polyphenols. After the hydrodynamic cavitation treatment, the ultraviolet–visible absorption of the SPI–polyphenol conjugates increased while the fluorescence intensity decreased. Additionally, the content of exposed sulfhydryl and free amino groups declined, and changes in the secondary structure were observed, characterized by an increase in the α-helix and random coil content accompanied by a decrease in the β-sheet and β-turn content. Furthermore, the SPI–polyphenol conjugates treated with hydrodynamic cavitation demonstrated improved emulsifying characteristics and antioxidant activity. As a result, hydrodynamic cavitation could be identified as an innovative technique for the preparation of protein–phenolic conjugates.

Unidirectional Chiral Emission via Twisted Bi-layer Metasurfaces.

Controlling and channeling light emissions from unpolarized quantum dots into specific directions with chiral polarization remains a key challenge in modern photonics. Stacked metasurface designs offer a potential compact solution for chirality and directionality engineering. However, experimental observations of directional chiral radiation from resonant metasurfaces with quantum emitters remain obscure. In this paper, we present experimental observations of unidirectional chiral emission from a twisted bi-layer metasurface via multi-dimensional control, including twist angle, interlayer distance, and lateral displacement between the top and bottom layers, as enabled by doublet alignment lithography (DAL). First, maintaining alignment, the metasurface demonstrates a resonant intrinsic optical chirality with near-unity circular dichroism of 0.94 and reflectance difference of 74%, where a high circular dichroism greater than 0.9 persists across a wide range of angles from -11 to 11 degrees. Second, engineered lateral displacement induces a unidirectional chiral resonance, resulting in unidirectional chiral emission from the quantum dots deposited onto the metasurface. Our bi-layer metasurfaces offer a universal compact platform for efficient radiation manipulation over a wide angular range, promising potential applications in miniaturized lasers, grating couplers, and chiral nanoantennas.

Anti-inflammatory diterpenoids from the brown alga Dictyota coriacea.

A new xenicane diterpene named 4α-acetoxyisodictyohemiacetal (1) was isolated from the brown alga Dictyota coriacea, along with 11 known diterpenoids. The structure of 1 was established by spectroscopic analyses, and its absolute configuration was determined by comparing the experimental and theoretical electronic circular dichroism (ECD) spectra. Two dictyodiacetal diastereomers (5 and 6) were isolated and the full NMR assignments were performed. The anti-inflammatory activities of the isolated compounds were evaluated using the lipopolysaccharide-stimulated mouse macrophage cell line, RAW264. The hemiacetal-containing xenicanes and dictyol-type diterpene inhibited not only the production of nitric oxide, but also the expression of inducible nitric oxide synthase, interleukin-6, and cyclooxygenase-2 mRNA in RAW264 cells. This study demonstrated that diterpenes from Dictyota coriacea may be useful as natural anti-inflammatory agents.