Rotatory Dispersion Research Articles

Isolation and characterization of antioxidative monoterpenes from Cynanchum atratum roots.

One novel monoterpene rhamnoside (1) and 7 known monoterpenes (2-8) were isolated from the ethanol extract of Cynanchum atratum for the first time. Their structures were identified by comprehensive spectroscopic data analysis such as nuclear magnetic resonance, high-resolution electrospray ionization mass spectra, optical rotatory dispersion, and acid hydrolysis. In the subsequent antioxidant assay, compound 8 exhibited obvious 2,2-diphenyl-2-picrylhydrazyl hydrate radical scavenging activity.

At What Mass Are Stars Braked? The Implication from the Turnoff Morphology of NGC 6819

Abstract Extended main-sequence turnoffs (eMSTOs) apparent in most young and intermediate-age clusters (younger than ∼2 Gyr) are known features caused by fast rotating early-type (earlier than F-type) stars. Late-type stars are not fast rotators because their initial angular momenta have been quickly dispersed due to magnetic braking. However, the mass limit below which stars have been magnetically braked has not been well constrained by observation. In this paper, we present an analysis of the eMSTO of NGC 6819, an open cluster of an intermediate-age (∼2.5 Gyr), believed to be comparable to the lifetime of stars near the mass limit for magnetic braking. By comparing the observation with synthetic color–magnitude diagrams, we find that NGC 6819 does not harbor an obvious eMSTO. The morphology of its turnoff region can be readily explained by a simple stellar population considering the observational uncertainties as well as the differential reddening. In addition, the MSTO stars in NGC 6819 have very small values of average rotational velocity and dispersion, indicating that they have undergone significant magnetic braking. Combining with results in the literature for clusters of younger ages, our current work suggests that the critical age for the disappearance of eMSTO in star clusters must be shorter but very close to the age of NGC 6819, and this in turn implies a critical stellar mass for magnetic braking at solar metallicity above but close to 1.54 M ⊙ based on the PARSEC model. We emphasize that the phenomenon of eMSTO could provide an unique way to constrain the onset mass of magnetic braking.

The present-day globular cluster kinematics of lenticular galaxies from the E-MOSAICS simulations and their relation to the galaxy assembly histories

ABSTRACT We study the present-day rotational velocity (Vrot) and velocity dispersion (σ) profiles of the globular cluster (GC) systems in a sample of 50 lenticular (S0) galaxies from the E-MOSAICS galaxy formation simulations. We find that $82{{\ \rm per\ cent}}$ of the galaxies have GCs that are rotating along the photometric major axis of the galaxy (aligned), while the remaining $18{{\ \rm per\ cent}}$ of the galaxies do not (misaligned). This is generally consistent with the observations from the SLUGGS survey. For the aligned galaxies, classified as peaked and outwardly decreasing ($49{{\ \rm per\ cent}}$), flat ($24{{\ \rm per\ cent}}$), and increasing ($27{{\ \rm per\ cent}}$) based on the Vrot/σ profiles out to large radii, we do not find any clear correlation between these present-day Vrot/σ profiles of the GCs and the past merger histories of the S0 galaxies, unlike in previous simulations of galaxy stars. For just over half of the misaligned galaxies, we find that the GC misalignment is the result of a major merger within the last $10\, \mathrm{Gyr}$ so that the ex-situ GCs are misaligned by an angle between 0° (co-rotation) and 180° (counter-rotation), with respect to the in situ GCs, depending on the orbital configuration of the merging galaxies. For the remaining misaligned galaxies, we suggest that the in situ metal-poor GCs, formed at early times, have undergone more frequent kinematic perturbations than the in situ metal-rich GCs. We also find that the GCs accreted early and the in situ GCs are predominantly located within 0.2 virial radii (R200) from the centre of galaxies in 3D phase-space diagrams.

Isolation and characterization of bioactive phenolic compounds from Cinnamomum camphora barks

Abstract Two new phenolic rhamnosides (1–2) and 12 known phenolic compounds (3–14) were isolated from the ethanolic extract of Cinnamomum camphora barks by repeated column chromatography. The structures of all isolated compounds were identified by comprehensive spectroscopic data analysis such as high-resolution electrospray ionization mass spectra, nuclear magnetic resonance, optical rotatory dispersion and chemical method. In vitro assay revealed that compound 8 showed strong inhibitory activity against tyrosinase, and compounds 1, 3–7, 8–9, 13 showed obvious acetylcholinesterase inhibitory activity.

Rapid Optical Rotatory Dispersion Polarimetry Over Wide Continuous Spectrum Based on Pixelated-Polarization

Rapid Optical Rotatory Dispersion Polarimetry Over Wide Continuous Spectrum Based on Pixelated-Polarization

Absolute Configuration Determination of Two Diastereomeric Neovasifuranones A and B from Fusarium oxysporum R1 by a Combination of Mosher's Method and Chiroptical Approach.

Endophytic fungi are one of prolific sources of bioactive natural products with potential application in biomedicine and agriculture. In our continuous search for antimicrobial secondary metabolites from Fusarium oxysporum R1 associated with traditional Chinese medicinal plant Rumex madaio Makino using one strain many compounds (OSMAC) strategy, two diastereomeric polyketides neovasifuranones A (3) and B (4) were obtained from its solid rice medium together with N-(2-phenylethyl)acetamide (1), 1-(3-hydroxy-2-methoxyphenyl)-ethanone (2) and 1,2-seco-trypacidin (5). Their planar structures were unambiguously determined using 1D NMR and MS spectroscopy techniques as well as comparison with the literature data. By a combination of the modified Mosher’s reactions and chiroptical methods using time-dependent density functional theory-electronic circular dichroism (TDDFT-ECD) and optical rotatory dispersion (ORD), the absolute configurations of compounds 3 and 4 are firstly confirmed and, respectively, characterized as (4S,7S,8R), (4S,7S,8S). Bioassay results indicate that these metabolites 1–5 exhibit weak inhibitory effect on Helicobacter pylori 159 with MIC values of ≥16 μg/mL. An in-depth discussion for enhancement of fungal metabolite diversity is also proposed in this work.

Sir Dai Rees (28 April 1936 to 10 June 2021)

Sir Dai Rees (28 April 1936 to 10 June 2021)

Quantum Fisher information bounds on precision limits of circular dichroism

Circular dichroism (CD) is a widely used technique for investigating optically chiral molecules, especially for biomolecules. It is thus of great importance that these parameters be estimated precisely so that the molecules with desired functionalities can be designed. In order to surpass the limits of classical measurements, we need to probe the system with quantum light. We develop quantum Fisher information matrix (QFIM) for precision estimates of the circular dichroism and the optical rotary dispersion for a variety of input quantum states of light. The Cramer-Rao bounds, for all four chirality parameters are obtained, from QFIM for (a) single photon input states with a specific linear polarization and for (b) NOON states having two photons with both either left polarized or right polarized. The QFIM bounds, using quantum light, are compared with bounds obtained for classical light beams i.e., beams in coherent states. Quite generally, both the single photon state and the NOON state exhibit superior precision in the estimation of absorption and phase shift in relation to a coherent source of comparable intensity, especially in the weak absorption regime. In particular, the NOON state naturally offers the best precision among the three. We compare QFIM bounds with the error sensitivity bounds, as the latter are relatively easier to measure whereas the QFIM bounds require full state tomography. We also outline an empirical scheme for estimating the measurement sensitivities by projective measurements with single-photon detectors.

Stellar Dynamical Models for 797 z ∼ 0.8 Galaxies from LEGA-C

Abstract We present spatially resolved stellar kinematics for 797 z = 0.6–1 galaxies selected from the LEGA-C survey and construct axisymmetric Jeans models to quantify their dynamical mass and degree of rotational support. The survey is K s -band selected, irrespective of color or morphological type, and allows for a first assessment of the stellar dynamical structure of the general L* galaxy population at large look-back time. Using light profiles from Hubble Space Telescope imaging as a tracer, our approach corrects for observational effects (seeing convolution and slit geometry), and uses well-informed priors on inclination, anisotropy, and a non-luminous mass component. Tabulated data include total mass estimates in a series of spherical apertures (1, 5, and 10 kpc; 1 × and 2 × R e), as well as rotational velocities, velocity dispersions, and anisotropy. We show that almost all star-forming galaxies and ∼50% of quiescent galaxies are rotation dominated, with deprojected V/σ ∼ 1–2. Revealing the complexity in galaxy evolution, we find that the most massive star-forming galaxies are among the most rotation dominated, and the most massive quiescent galaxies among the least rotation-dominated galaxies. These measurements set a new benchmark for studying galaxy evolution, using stellar dynamical structure for galaxies at large look-back time. Together with the additional information on stellar population properties from the LEGA-C spectra, the dynamical mass and V/σ measurements presented here create new avenues for studying galaxy evolution at large look-back time.

A femtosecond magnetic circular dichroism spectrometer.

We describe the development of a broadband magneto-optical spectrometer with femtosecond temporal resolution. The absorption spectrometer is based on a white-light supercontinuum (∼320 to 750 nm) using shot-to-shot temporal and spectral referencing at 1 kHz. Static and transient absorption spectra using circularly polarized light are collected in a magnetic field. The difference spectra with respect to the external field direction give the static and transient magneto-optical Faraday rotation (magnetic optical rotary dispersion) and ellipticity (magnetic circular dichroism) spectra. An achromatic quarter-wave plate is used, and the impact of the deviation from ideal retardance on the spectra is discussed. Results from solution-based and thin-film samples are used to demonstrate the performance and wide applicability of the instrument. The sensitivities for the static and time-resolved data were found to be 5 and 0.4 mdeg, respectively. The method presents a simple way to measure magneto-optical spectra using a transient absorption spectrometer and an electromagnet.

Engineering of inorganic nanostructures with hierarchy of chiral geometries at multiple scales

Engineering of inorganic nanostructures with hierarchy of chiral geometries at multiple scales

Optical rotation dispersion of cholesteric-nematic mixture

The dispersion of the specific rotation constant of a cholesteric-nematic mixture of 5CB and Ch17 at a low concentration was studied by optical spectroscopy. The dispersion of the anisotropy of the refractive index as a function of the wavelength is studied, and the helical pitch of the cholesteric-nematic mixture is calculated.

Magnetic optical rotary dispersion and magnetic circular dichroism in methylammonium lead halide perovskites.

Large magnetic optical rotary dispersion (Faraday rotation) has been demonstrated recently in methylammonium lead bromide. Here, we investigate the prospect of extending the active spectral range by altering the halogen. We also investigate the origins of large Faraday rotation in these diamagnetic materials using magnetic circular dichroism (MCD) spectroscopy and the Kramers-Kronig relations. We find that, while MAPbCl3 (MA = methylammonium) single crystals exhibit a large Verdet constant in the blue, no appreciable Faraday rotation is observed in the red/near infra-red for MAPbI3 single crystals. However, in all film samples, we find clear evidence of large MCD resulting from the Zeeman splitting of the highly resonant 1s exciton state. Our Kramers-Kronig calculations of Faraday rotation based on MCD data matches well with the dispersion of our experimental data for MAPbCl3 and MAPbBr3 , with some deviation in magnitude-demonstrating the excitonic nature of Faraday rotation in these materials. However, our calculations predict significant Faraday rotation in MAPbI3 , contrary to our experimental results, indicating a potential discrepancy between the properties of the thin film and single crystal.

A supernova remnant association for the fast-moving pulsar PSR J0908–4913

ABSTRACT A recent measurement of the proper motion of PSR J0908–4913 shows that it is a fast-moving object at a distance of some 3 kpc. Here, we present evidence that the pulsar is located at the edge of a previously unknown, filled-centre supernova remnant (SNR), G270.4–1.0. The velocity vector of the pulsar points directly away from the centre of the remnant. The putative association of the pulsar with SNR G270.4–1.0 implies the pulsar is ∼12 kyr old, significantly less than its characteristic age of 110 kyr. We show that the rotation axis of the pulsar points in the direction of the proper motion. Rotation measure and dispersion measure variations are seen over time, likely indicating the pulsar is passing behind a filament of the remnant.

High-Precise Measurement of Optical Rotatory Dispersion Based on Weak Value Amplification

Chiroptical signals (generally very weak) play significant roles in chiral discrimination that bring great benefits in biochemistry, pharmacy, chemical, and so on. But, high-precise chiroptical detection is still a challenge. In this paper, a high-precise measurement of optical rotatory dispersion (ORD) based on weak value amplification (WVA) is presented. We proposed ORD detection method with parameter separation: by introducing complex coupling strength and dimensionless parameter “intensitiy contrast ratio” pointer, the ORD is only associated with the imaginary part of the weak value while circular dichroism (CD) is only associated with the real part. By designing a suitable WVA scheme, the ORD and CD can be measured separately. In the experiment, the reliability of the parameter separation method for ORD measurement is verified, and the precision reach the order of $10^{-6}$ rad. This method has a broad application prospect in biomedical sensing, medicine, chemical analysis and other fields.

Broadband Optical Activity Spectroscopy with Interferometric Fourier-Transform Balanced Detection.

Spectrally resolved measurements of optical activity, such as circular dichroism (CD) and optical rotatory dispersion (ORD), are powerful tools to study chiroptical properties of (bio)molecular and nanoplasmonic systems. The wider utilization of these techniques, however, has been impeded by the bulky and slow design of conventional spectropolarimeters, which have been limited to a narrowband scanning approach for more than 50 years. In this work, we demonstrate broadband measurements of optical activity by combining a balanced detection scheme with interferometric Fourier-transform spectroscopy. The setup utilizes a linearly polarized light field that creates an orthogonally polarized weak chiral free-induction-decay field, along with a phase-locked achiral transmitted signal, which serves as the local oscillator for heterodyne amplification. By scanning the delay between the two fields with a birefringent common-path interferometer and recording their interferogram with a balanced detector that measures polarization rotation, broadband CD and ORD spectra are retrieved simultaneously with a Fourier transform. Using an incoherent thermal light source, we achieve state-of-the-art sensitivity for CD and ORD across a broad wavelength range in a remarkably simple setup. We further demonstrate the potential of our technique for highly sensitive measurements of glucose concentration and the real-time monitoring of ground-state chemical reactions. The setup also accepts broadband pulses and will be suitable for broadband transient optical activity spectroscopy and broadband optical activity imaging.

The role of gas kinematics in setting metallicity gradients at high redshift

ABSTRACT In this work, we explore the diversity of ionized gas kinematics (rotational velocity vϕ and velocity dispersion σg) and gas-phase metallicity gradients at 0.1 ≤ z ≤ 2.5 using a compiled data set of 74 galaxies resolved with ground-based integral field spectroscopy. We find that galaxies with the highest and the lowest σg have preferentially flat metallicity gradients, whereas those with intermediate values of σg show a large scatter in the metallicity gradients. Additionally, steep negative gradients appear almost only in rotation-dominated galaxies (vϕ/σg > 1), whereas most dispersion-dominated galaxies show flat gradients. We use our recently developed analytical model of metallicity gradients to provide a physical explanation for the shape and scatter of these observed trends. In the case of high σg, the inward radial advection of gas dominates over metal production and causes efficient metal mixing, thus giving rise to flat gradients. For low σg, it is the cosmic accretion of metal-poor gas diluting the metallicity that gives rise to flat gradients. Finally, the reason for intermediate σg showing the steepest negative gradients is that both inward radial advection and cosmic accretion are weak as compared to metal production, which leads to the creation of steeper gradients. The larger scatter at intermediate σg may be due in part to preferential ejection of metals in galactic winds, which can decrease the strength of the production term. Our analysis shows how gas kinematics play a critical role in setting metallicity gradients in high-redshift galaxies.

Optical Activity in Saturated Cyclic Amines: Untangling the Roles of Nitrogen-Inversion and Ring-Puckering Dynamics.

The dispersive optical activity of two saturated cyclic amines, (R)-2-methylpyrrolidine (R-2MPY) and (S)-2-methylpiperidine (S-2MPI), has been interrogated under isolated and solvated conditions to elucidate the roles of large-amplitude motion associated with nitrogen-center inversion and ring-puckering dynamics. Experimental optical rotatory dispersion profiles were almost mirror images of one another and displayed parallel solvent dependencies. Quantum-chemical analyses built on density-functional and coupled-cluster methods revealed four low-lying conformers for each molecule, which are distinguished by axial/equatorial orientations of their amino hydrogens and methyl substituents. Chiroptical signatures predicted for these species were combined through an independent-conformer ansatz to simulate the ensemble-averaged response, with a polarizable continuum model (PCM) being used to treat implicit solute-solvent interactions. The intrinsic behavior observed for isolated (gaseous) R-2MPY and S-2MPI was reproduced best by merging coupled-cluster (CCSD) estimates of rotatory powers with thermal population fractions deduced from complete basis set (CBS-APNO) free-energy calculations. Although prior claims of sizable chiroptical contributions arising from helically twisted (chiral) heterocyclic frameworks could be discounted, less satisfactory agreement between experiment and theory was realized for solution phases. Response properties sustained modest isomer-dependent changes in the presence of PCM solvation, but the corresponding energy metrics showed systematic trends, whereby structures having larger electric-dipole moments were stabilized preferentially in media of high polarity. Despite the fact that R-2MPY conformations were predicted to undergo a progressive reordering of their relative energies across the six solvents of interest, S-2MPI was found to exhibit more pronounced solvent-induced perturbations at long wavelengths (viz., in regions far removed from electronic resonances). Experimental results are discussed in terms of the distinct ring-puckering mechanisms for R-2MPY and S-2MPI, which are expected to be dominated by hindered pseudorotation among envelope/twist motifs and semi-inversion between chairlike antipodes, respectively.

Constraints for Use of Ultraviolet Spectropolarimetry to Detect Chiral Amino Acids from Comets.

Life is pervasive on planet Earth, but whether life is ubiquitous in the Galaxy and sustainable over timescales comparable to stellar evolution is unknown. Evidence suggests that life first appeared on Earth more than 3.77 Gyr ago, during a period of heavy meteoric bombardment. Amino acids, the building blocks of proteins, have been demonstrated to exist in interstellar ice. As such, the contribution of space-generated amino acids to those existing on Earth should be considered. However, detection of space amino acids is challenging. In this study, we used analytical data from several meteorites and in situ measurements of the comet 67P/Churyumov-Gerasimenko collected by the Rosetta probe to evaluate the detectability of alanine by ultraviolet spectropolarimetry. Alanine is the second-most abundant amino acid after glycine and is optically active. This chirality produces a unique signature that enables reliable identification of this amino acid using the imprint of optical rotatory dispersion (ORD) and circular dichroism (CD) in the ultraviolet spectrum (130–230 nm). Here, we show that the ORD signature could be detected in comets by using ultraviolet spectropolarimetric observations conducted at middle size space observatories. These observations can also provide crucial information for the study of sources of enantiomeric imbalance on Earth.

Chiral Charge Carriers Chiralions for Polyaniline Examined with Optical Rotation Spectroelectrochemistry

In this study, the optical active polyaniline film was examined with optical rotatory dispersion (ORD) through change in potential with spectroelectrochemical method. Polyaniline is one of the representative conducting polymers. Preparation of polyaniline is convenient because synthesis of polyaniline can perform in water medium. Conducting polymers shows electrochromism via change in the electronic state upon electrochemical redox process. Polyaniline forms various electronic states such as emeraldine base, emeraldine salt, and pernigraniline. This change allows to color tuning through electrochemical method. Further, optically active polyanilines have been synthesized in the presence of (+) or (-)-camphorsulfonic acid (CSA) by electrochemical polymerization or chemical polymerization with ammonium persulfate (oxidizing agent). Both electrochemical method and chemical method produce polyaniline through radical polymerization process. Polyaniline emeraldine salt as prepared form of polyaniline is doped with CSA, showing optical activity in the circular dichroism. In this research, we carried out to synthesis of polyaniline in the presence of optically active CSA, according to previously reported method (by Wallace et al). Here, we have found that the polyaniline thus prepared showed optically active electrochromism via electrochemical redox process in circular dichroism spectroscopy measurements. In our previous study, we calculated the ORD spectra for the polymer by Kramars - Kronich (K-K) conversion from circular dichromism. In the present research, we successfully obtained experimental data of optical rotation-spectroelectrochemical result, as a first example of optical rotation control of natural optical activity for conjugated polymers based on electrochemical method. In the case of low potential for the polymer in the electrochemical redox process, the polymer shows intense optical rotation at visible wavelength range. On the other hands, higher potential at around 1 V affords to give doping process for the polymer, resulting generation of polaron as charge carrier, which shows optical activity at near infrared region. We referred this optical charge carrier as “chiral charge carrier chiralions”. The electrochemical oxidation equivalents to electrochemical doping from the polymer. In other words, electrochemical oxidation gives electrochemical doping which results change in degree of optical rotation for the polymer. The control of optical ration for materials can be driven by magnetic field (Faraday rotation), and electric field (Kerr rotation). We propose a new phenomenon as ‘‘electrochemical optical rotation’’. The electro-conductivity of the polymer is measured with four-probe method. The polymer which is electronic doped state with (+)-CSA as electric dopant for production of radical cation (polarons) or dication (bipolarons) as charge carriers and chiral inducer for twisting main-chain. The polymer film was synthesized as followed. First, electrochemical polymerization of aniline as a monomer was carried out in excessive optically active (+)-CSA with three electrode system consisting of working electrode (indium-tin oxide coated glass), counter electrode (platinum wire), and reference electrode (SCE) in water. The polymerization reaction is rapidly progressed with formation of polymer thin film onto the counter electrode. The polymer was washed with excess amount of water, acetone. The electroactive polymer film was thus deposited on the electrode was used for optical activity measurements. Cyclic voltammetry (CV) measurements were carried out for the resultant polymer (monomer free) deposited on to the ITO coated glass electrode. The CV results with change in scan rate from 10-100 mV/s indicates electroactive. Increase of scan rate increases current density for the polymer due to increase of diffusion of ion in the electrolyte solution. Oxidation signals of the polymer are observed due to change in electronic state of the polymer. Corresponding reduction signals against oxidation process are observed, indicating reversible redox activity for the polymer. ORD measurement reveled that the polymer film thus obtained is optically active. The polyaniline can be formed helical structure due to doping of optically active CSA. We carried out in-situ ORD measurement with potential change, evaluating electrochemical driven change in optical rotation. Chemical structure of the double layer polymer is examined with Fourie transform infrared optical absorption spectroscopy measurements which reveled this polymer is polyaniline, and CSA as a dopant. Ultra-violet optical absorption measurements for the polymer film indicates intense and wide range absorptions from invisible to infrared range as charge carriers the delocalized along the main-chain, indicating the polymers are conductive materials. The advantages of the polymer film are formation of self-standing redox activity, tuning of optical activity and color coordination. This paper reports novel function of control optical rotation with electrochemical method examined with spectroelectrochemistry. This concept can be a first example as optical rotation effect of electro-optically active conducting polymers. This paper reports the charge carries of helical polyaniline as chiralions can tune via electrochemical method.