Electric Dichroism Research Articles

Structurally Diverse Stilbenoids as Potent α-Glucosidase Inhibitors with Antidiabetic Effect from Morus alba.

Fifteen stilbenoid derivatives, including five previously undescribed ones (albaphenols A-E, 1-5) with diverse scaffolds, were obtained from the well-known agricultural economic tree Morus alba. Their structures, including absolute stereochemistries, were fully characterized by detailed interpretation of spectroscopic data and quantum chemical computational analyses of nuclear magnetic resonance (NMR) and electric circular dichroism (ECD). Albaphenol A (1) features an unprecedented rearranged carbon skeleton incorporating a novel 2-oxaspiro[bicyclo[3.2.1]octane-6,3'-furan] motif; albaphenol C (3) is likely derived from a cometabolite through an interesting intramolecular transesterification reaction; and albaphenol E (5) bears a cleavage-reconnection scaffold via a dioxane ring. All of the compounds exhibited significant inhibition against the diabetic target α-glucosidase, with low to submicromole IC50 values (0.70-8.27 μM), and the binding modes of selected molecules with the enzyme were further investigated by fluorescence quenching, kinetics, and molecular docking experiments. The antidiabetic effect of the most active and abundant mulberrofuran G (6) was further assessed in vivo in diabetic mice, revealing potent antihyperglycemic activity and comparable antidiabetic efficacy to the clinical drug acarbose.

Positioning of functional group for tailoring absorption spectrum of carbon dots: Insights from density functional theory

This research provided a comprehensive theoretical investigation into the tailoring of absorption in carbon dots (CDs) through the positioning of functional groups (amino and carbonyl) on their surfaces, employing Density Functional Theory (DFT). This study not only unveils the underlying physical mechanisms governing the absorption properties of CDs but also provides valuable insights into the optimal positioning of functional groups to achieve redshift absorption. A detailed analysis of the electronic structure provided a profound understanding of the intricate relationship between the optical behaviors exhibited by the system's CDs. By strategically arranging these functional groups, the CDs' electric circular dichroism (ECD) spectra were unique, which might coherently indicate the molecular chirality behavior in the CDs system. This paves the way for exciting possibilities in their potential biomedical and optoelectronic applications.

Molecular dyad exhibiting strong multi‐resonance blue fluorescence

AbstractA multi‐resonance (MR) fluorophore exhibiting circularly polarized luminescence (CPL) holds a significant promise for enhancing the utility of organic light‐emitting devices. To meet this demand, we have devised molecular dyads having azaoxaborin MR emitters based on homochiral (R)‐ and (S)‐1,1′‐bi‐2‐naphthol. The synthesized 12,12′‐di‐tert‐butyl‐9,9′‐bi(8,8′‐dioxa‐4b,4′b‐diaza‐14b,14′b‐diborafluorantheno[1,2,3‐de]tetracene) products (TBNBOCz) exhibit strong blue fluorescence, with a remarkable 100% fluorescence quantum yield and an extremely narrow full width at half‐maximum of 22 nm. However, unexpectedly, TBNBOCz exhibits negligible electric circular dichroism and CPL activities. Chiroptical investigations into the reaction precursors reveals an occurrence of racemization in the borylation step. This result emphasizes the importance of understanding synthetic processes and their impact on the chiroptical properties.

Chiroptical Properties of Planar Benzobisthiazole-Bridged Squaraine Dimers.

Five chiral squaraine dimers were synthesized by fusing chiral indolenine semisquaraines with three different benzobisthiazole bridges. The thereby created squaraine dimers show a strong splitting of the lowest energy absorption bands caused by exciton coupling. The intensities of the two exciton transitions and the energetic splitting depend on the angle of the two squaraine moieties within the chromophore dimer. The electric circular dichroism spectra of the dimers show intense Cotton effects whose sign depends on the used squaraine chromophores. Sizable anisotropies gabs of up to 2.6 × 10-3 could be obtained. TD-DFT calculations were used to partition the rotational strength into the three Rosenfeld terms where the electric-magnetic coupling turned out to be the dominant contribution while the exciton chirality term is much smaller. This is because the chromophore dimers are essentially planar but the angle between the electric transition dipole moment of one squaraine and the magnetic transition dipole moment of the other squaraine strongly deviates from 90°, which makes the dot product between the two moment vectors and, thus, the rotational strength substantial.

Suadimins D—J, Monoterpenoid Indole‐Quinoline and Bisindole Alkaloids from Melodinus suaveolens

Comprehensive SummaryCompounds 1—12, including seven complex monoterpenoid indole‐quinoline and bisindole alkaloids, suadimins D—J (1—7) with previously unreported carbon‐carbon linkages, were isolated and identified from the twigs and leaves of Melodinus suaveolens. Their structures were elucidated by a combination of diverse methods, especially the extensive spectroscopic data analysis and electric circular dichroism (ECD) calculations. The cytotoxicity of these compounds against three cancer cell lines was evaluated, some of which showed moderate activities with IC50 values ranging from 2.4 to 8.0 μM.

Monoterpenoid indole alkaloid adducts and dimers from Melodinus fusiformis

Eight unprecedented monoterpenoid indole alkaloid (MIA) adducts and dimers, melofusinines A–H (1–8), and three undescribed melodinus-type MIA monomers, melofusinines I–K (9–11), together with six putative biogenetic precursors were isolated from the twigs and leaves of Melodinus fusiformis Champ. ex Benth. Compounds 1 and 2 are unusual hybrid indole alkaloids incorporating an aspidospermatan-type MIA with a monoterpenoid alkaloid unit via C–C coupling. Compounds 3–8 feature the first MIA dimers constructed through an aspidospermatan-type monomer and a rearranged melodinus-type monomer with two different types of couplings. Their structures were elucidated by spectroscopic data, single crystal X-ray diffraction, and calculated electric circular dichroism spectra analysis. In addition, dimers 5 and 8 showed significant neuroprotection effects on MPP +-injured primary cortical neurons.

Phytochemical investigation of Scutellaria scordiifolia and its trypanocidal activity

Scutellaria scordiifolia Fisch. ex Schrank is used to treat various inflammatory diseases and other ailments in traditional and contemporary medicine. In this study, 10 undescribed compounds, including a flavanone (1), four chrysin C-glycosides (2–5), a phenanthrene glucoside (6), four iridoid glucosides (7–10) and 31 known compounds were identified from an extract of the aerial parts of S. scordiifolia. The absolute configurations of sugars in C-glycosides were determined by comparing electric circular dichroism spectra with calculated data. The flavanones (1 and 17), flavonols (11–13), flavone (14), and some of the flavone glucuronides (15, 16) exhibited trypanocidal activities against Trypanosoma congolense. The activity data and quantitative HPLC analysis of flavonoids from the aerial parts of S. scordiifolia suggest that they may effectively treat diseases caused by the aforementioned trypanosomes. Other compounds such as novel iridoids and phenanthrene glycosides, which may be useful for chemophenetic and chemoecological discussions, were also identified.

Isolation and Identification of Novel Antioxidant Polyketides from an Endophytic Fungus Ophiobolus cirsii LZU-1509

Sixteen new polyketides, ophicirsins A-P (1-16), including four novel carbon skeletons (5-9, 14, 15, and 16), were isolated from the extract of an endophytic fungus Ophiobolus cirsii LZU-1509. The unique frameworks of ophicirsin N (14) and O (15) feature a different cyclic ether connected with an aromatic ring system. Ophicirsin P (16) is characterized by the unprecedented heterozygote of a polyketide and an alkaloid. The absolute stereochemistries of those polyketides were characterized via single-crystal X-ray diffraction analysis and the experimental and computational electric circular dichroism spectra comparison. Theoretical reaction pathways in the fermentation to generate different novel skeletons starting from acetyl CoA and malonyl CoA helped to assign their structures. Compounds 1-16 appear almost nontoxic in HepG2 and HT-1080 tumor cells. Their antioxidant effects were further evaluated, and 15 exhibits an excellent protection activity in hydrogen peroxide-stimulated oxidative damage in neuron-like PC12 cells via screening all compounds. Moreover, 15 displays a greater ability to scavenge the 2,2-diphenyl-1-picrylhydrazyl free radicals than resveratrol. Taken together, these findings suggest that the novel polyketides could serve as potential antioxidant agents for neuroprotection.

Electric field tuning of the optical absorbance of topological insulator thin films

In view of electro-optic modulators and switches operating in the terahertz frequency range, we study the absorbance of a topological insulator (TI) thin film subjected to a static electric field. Adopting the Hamiltonian for the three-dimensional ${\mathrm{Bi}}_{2}{\mathrm{Se}}_{3}$ class of TIs including terms to second order in the electron wave vector and to first order in the electric field, we present an effective model for a TI thin film. We demonstrate the distinct influences of in-plane and out-of-plane external electric fields, the in-plane electric field-induced dichroism, and the electric field and chemical potential tuning of the absorbance edge. Under the influence of an out-of-plane electric field, a TI film with a thickness of about 2 nm exhibits a considerable absorbance at the absorbance edge. Of prime practical importance, the absorbance edge can be shifted about $0.3\phantom{\rule{0.28em}{0ex}}\mathrm{eV}$ with the application of moderate electric fields about $0.4\phantom{\rule{0.28em}{0ex}}\mathrm{V}{\mathrm{nm}}^{\ensuremath{-}1}$ or with chemical potential variations about $0.3\phantom{\rule{0.28em}{0ex}}\mathrm{eV}$.

Three Pairs of Novel Enantiomeric 8-O-4' Type Neolignans from Saussurea medusa and Their Anti-inflammatory Effects In Vitro.

Three pairs of novel enantiomeric 8-O-4' type neolignans (1a/1b-3a/3b), together with seven known analogues (4-10), were isolated from the whole plants of Saussurea medusa. Their structures were elucidated by extensive spectroscopic data analysis and electric circular dichroism (ECD) calculations after chiral separations. All compounds were obtained from S. medusa for the first time, and compounds 1-3 and 5-10 had never been obtained from the genus Saussurea previously. The anti-inflammatory activities of the compounds were evaluated by determining their inhibitory activities on the production of NO and inducible nitric oxide synthase (iNOS) expression in LPS-stimulated RAW 264.7 cells. Compounds (+)-1a, (-)-1b and 5-7 inhibited NO production and had IC50 values ranging from 14.3 ± 1.6 to 41.4 ± 3.1 μM. Compound 7 induced a dose-dependent reduction in the expression of iNOS in LPS-treated RAW 264.7 cells. Molecular docking experiments showed that all active compounds exhibited excellent docking scores (<-7.0 kcal/mol) with iNOS. Therefore, compounds (+)-1a, (-)-1b and 5-7 isolated from the whole plants of S. medusa may have therapeutic potential in inflammatory diseases.

Observation of antiferromagnetic domains in Cr2O3 using nonreciprocal optical effects

The archetypal magnetoelectric (ME) antiferromagnet ${\mathrm{Cr}}_{2}{\mathrm{O}}_{3}$, which has the diagonal components of linear ME tensor, exhibits several different types of nonreciprocal optical effects: the electric field-induced $(E\text{\ensuremath{-}}\mathrm{induced})$ Faraday effect, the electric field-induced magnetic circular dichroism ($E\text{\ensuremath{-}}\mathrm{induced}$ MCD), and the spontaneous nonreciprocal rotation of reflected light (NRR). In principle, antiferromagnetic (AFM) domains of ${\mathrm{Cr}}_{2}{\mathrm{O}}_{3}$ are expected to be distinguished by using these effects. However, such domain observations have never been reported mainly due to the smallness of the effects studied to date. In this study, we demonstrate that all these nonreciprocal optical effects allow the observation of AFM domains in ${\mathrm{Cr}}_{2}{\mathrm{O}}_{3}$. We first measured spectra of the $E\text{\ensuremath{-}}\mathrm{induced}$ Faraday effect and $E\text{\ensuremath{-}}\mathrm{induced}$ MCD, and found that relatively large effects appear in the visible light region. Then, by imaging spatial distributions of the three nonreciprocal effects via field and light-polarization modulation imaging techniques, we succeeded in visualizing AFM domains. Intriguingly, the domain patterns obtained via the bulk sensitive $E\text{\ensuremath{-}}\mathrm{induced}$ Faraday effect and MCD and those via the surface-sensitive NRR are identical to each other, revealing that the AFM domains in ${\mathrm{Cr}}_{2}{\mathrm{O}}_{3}$ are uniform in the thickness direction. The domain observation methods provided here will be widely applied to various ME antiferromagnets, not only insulators but also metals, with the diagonal components of linear ME tensor.

Molecular sensors producing circularly polarized luminescence responses

Circularly polarized luminescence (CPL) refers to spontaneous emission with the oscillation axis of the emission's electric dipole rotating either right handedly or left handedly along the propagation axis. CPL provides a unique principle in luminescence visualization of target analytes: both the direction and magnitude of light polarization are sensitive to an asymmetric environment around a luminophore, which enables chirality sensing. In addition, CPL spectra are usually less complex than electric circular dichroism spectra because they emerge only from the lowest excited state. To exploit these benefits, researchers have vigorously developed CPL probes. This minireview provides the basic principles for creating molecular CPL activity, including asymmetric exciton coupling and helical intramolecular charge transfer. Emphasis is placed on molecular design. Analyte interactions can perturb the magnitude, reverse the polarization direction, or shift the peak wavelength of CPL, thereby enabling tractable strategies for creating CPL sensors. This minireview outlines selected examples of CPL sensors for physical stimuli, including changes in external magnetic fields, solvent polarity, and temperature. Probes capable of detecting chemical species, such as protons, metal ions, anions, amino acids, nucleosides and DNA, reactive oxygen species, and humidity, are also highlighted. These examples demonstrate the unique sensing utility of CPL sensors. We hope that this minireview will stimulate future research interest toward developing advanced CPL sensors with applications in bioimaging.

Comparison of Length, Velocity, and Symmetric Gauges for the Calculation of Absorption and Electric Circular Dichroism Spectra with Real-Time Time-Dependent Density Functional Theory.

A velocity and symmetric gauge implementation for real-time time-dependent density functional theory (RT-TDDFT) in the CP2K package using a Gaussian and plane wave approach is presented, including the explicit gauge-transformed contributions due to the nonlocal part of pseudopotentials. Absorption spectra of gas-phase α-pinene are calculated in length and velocity gauges in the long-wavelength approximation for the application of a δ pulse in linear and full order. The velocity gauge implementation is also applied to a solvated uracil molecule to showcase its use within periodic boundary conditions (PBC). For the calculation of the expectation value of the electric dipole moment in PBC, both the velocity representation and the modern theory of polarization give equivalent absorption spectra if a distributed reference point is used for the nonlocal term of the velocity operator. The discussion of linear response theory takes place in a unified framework in terms of linear response functions in propagator notation, distinguishing the parts of the linear response functions associated with perturbation and response. To further investigate gauge dependence, electric circular dichroism (ECD) spectra of α-pinene were calculated either as magnetic response to an electric field perturbation, in length or velocity gauge, or as electric response to a magnetic field perturbation in the symmetric gauge. Both approaches, electric and magnetic perturbations, have been found to yield equivalent ECD spectra.

Saussurenoids A–G, seven new sesquiterpenoids from Saussurea medusa Maxim.

Seven new sesquiterpenoids (1–7), including two rare botryane-type sesquiterpenoids (1 and 2), and five megastigmane sesquiterpenoids and its glycoside (3–7) were isolated from the whole plants of Saussurea medusa Maxim. Their structures were elucidated based on extensive spectroscopic methods, electric circular dichroism (ECD) calculations and the single-crystal X-ray diffraction analysis. The absolute configuration of the 10,11-diol moiety in compound 6 was determined by observing the circular dichroism induced after addition of dimolybdenum tetracetate [Mo2(OAc)4] in DMSO solution. Compound 2 displayed modest cytotoxic effects against A549 and HL-60 cell lines with IC50 values of 5.6 ± 1.0 and 7.4 ± 1.2 μM, respectively.

Recent Progress in the Simulation of Chiral Systems with Real Time Propagation Methods

AbstractIn this brief review, an overview about recent efforts to simulate the spectroscopic signatures of chiral molecules is given with focus on real time propagation approaches to solve the time‐dependentSchrödingerequation. In particular the simulation of electric circular dichroism spectra and vibrationalRamanoptical activity is discussed. In comparison to linear absorption spectra, where only the response of the electric dipole moment is necessary, the response of the magnetic dipole moment and electric quadrupole moment is more intricate. Issues such as gauge origin dependence, basis set dependence, non‐local potentials and the dipole approximation are addressed.

Four new diterpenoids from the twigs and leaves of Phyllanthus acidus

Abstract Four new ent-cleistanthane type diterpenoids, phyacioids A–D (1–4), along with two known analogues (5 and 6) were isolated from the powered twigs and leaves of Phyllanthus acidus. Compound 1 was characterized as the third reported structure that possesses a 4,5-seco-20(10 → 5)-abeo-(ent)-cleistanthane scaffold, and compounds 2 and 3 feature a rare alkynyl group. The structures of 1–4 were assigned by spectroscopic data, with their absolute structures being determined through electric circular dichroism (ECD) calculations. Compounds 3, 5 and 6 showed moderate cytotoxicity with IC50 values ranging from 13.8 to 36.0 μM.

Type B polycyclic polyprenylated acylphloroglucinols from the roots of Hypericum beanii.

Two new type B polycyclic polyprenylated acylphloroglucinols (PPAPs) (1 and 2) and a known biogenetic precursor hyperbeanol Q (3) were isolated from the root extract of Hypericum beanii, a medicinal plant widespread in southwest China. Their chemical structures were elucidated by 1D/2D NMR and HRESIMS data analysis, and absolute configurations were determined through detailed electric circular dichroism (ECD) analysis including ECD exciton chirality, Mo2(OAc)4-induced ECD, and ECD comparison. Of these compounds, hyperbeone A (1) is a typical [3.3.1]-type B PPAP with an unusual C-1 geranyl side chain, and hyperberin C (2) possesses a rare bicyclo[5.3.1]hendecane core. Taking compound 3 as a starting point, a plausible biosynthetic pathway to the bicyclic type B frameworks of 1 and 2 was proposed.

Electrogyration in Metamaterials: Chirality and Polarization Rotatory Power that Depend on Applied Electric Field

AbstractOne of the most fascinating properties of chiral molecules is their ability to rotate the polarization of light. Since Faraday's experiments in 1845, it has been known that nonreciprocal polarization rotatory power can be induced by a magnetic field. But can reciprocal polarization rotation in chiral molecules be influenced by an electric field? In the 1960s, Aizu and Zheludev introduced the phenomenon of electrogyration. While the linear (Pockels) and quadratic (Kerr) electro‐optical effects describe how an external electric field changes linear birefringence and dichroism, electrogyration describes how a field changes the circular birefringence and dichroism of a medium. Electrogyration is observed in dielectrics, semiconductors, and ferroelectrics, but the effect is small. This work demonstrates a nanostructured photonic metamaterial that exhibits quadratic electrogyration—proportional to the square of the applied electric field—six orders of magnitude stronger than in any natural medium. Giant quadratic electrogyration emerges as electrostatic forces acting against forces of elasticity change the chiral configuration of the metamaterial's nanoscale building blocks and consequently its polarization rotatory power. This observation of giant electrogyration alters the perception of the effect from that of an esoteric phenomenon into a functional part of the electro‐optic toolkit with application potential.

Cajuputones A-C, β-Triketone Flavanone Hybrids from the Branches and Leaves of Melaleuca cajuputi.

Three new β-triketone flavanone hybrids, cajuputones A-C were obtained from Melaleuca cajuputi (the Australian 'tea tree'). The structures of cajuputones A-C were elucidated by 1D/2D NMR spectroscopy and HR-ESI-MS analyses; and their absolute configurations were established by electric circular dichroism (ECD) calculations using TDDFT method. Structurally, cajuputones A-C feature a rare 6/6/6/6 oxatetracyclic ring system fused between an acylphloroglucinol-derived β-triketone and a pinocembrin or strobopinin moiety via an angle-type pyran-like motif. DFT-based conformational optimization in chloroform explained the similarity of the 1D NMR data of cajuputones B and C (C-2 epimers).

Structural Revision and Absolute Configuration of Burnettramic Acid A.

The recently discovered antibiotic burnettramic acid A (1) and three new congeners, burnettramic acids C-E (2-4), were identified from the co-cultures of two marine Aspergillus strains. The structure of burnettramic acid A was revised on the basis of reinterpretation of the nuclear magnetic resonance (NMR) data and chemical derivatization. The full absolute configurations of burnettramic acids were established using the Mosher ester method and Marfey's analysis, combined with density functional theory calculation of NMR and electric circular dichroism data.