Dichroism Spectra Research Articles

Deeply Reduced Chiral MoIV6-Polyoxometalates with Highly Enhanced Electronic Conductivity.

A series of deeply reduced MoIV6-polyoxometalates (POMs), [MoIV6(bpy)6MoVI2O16S2]·10H2O (1) (bpy = 2,2'-bipyridine), [MoIV6(bpy)4(L-TrA)2MoV4(bpy)2O14S4]2·36.5H2O (2), and [MoIV6(bpy)4(D-TrA)2MoV4(bpy)2O14S4]2 (3) (TrA = tartaric acid), were obtained from one-pot hydrothermal syntheses. They feature the bioxo-bridged [MoIV3O3S]4+ incomplete cuboidal cores stabilized by strong triangular metal-metal bonds and datively chelated bpy π-ligands. The two apical MoVIO4 in 12e-Mo8 (1) and two [MoV2O3STrAbpy] in 16e-Mo10 (2, 3) complete the octahedral coordination geometry of the deeply reduced MoIV, not counting the MoIV-MoIV d2-d2 bonds. The aromatic planar bpy π ligands form a two-dimensional face-to-face π stacking supramolecular structure, which are further strengthened by point-to-face C-H···π interactions in the π stacked layers. 16e-Mo10 (2, 3) has stronger intramolecular face-to-face π stacking interactions, which are interconnected by intermolecular C-H···π into a three-dimensional framework structure. These structural features account for their highly enhanced electronic conductivities (1, 6.19 × 10-8 S cm-1; 2, 2.18 × 10-7 S cm-1), providing a new way of thinking to improve electronic conductivity of POMs. 1-3 have been described by first-principles density function theory (DFT) calculations and also characterized by elemental analyses, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), solid UV-visible spectra, and circular dichroic (CD) spectra.

Orientational effects in the polarized absorption spectra of molecular aggregates.

We present a detailed theoretical analysis of polarized absorption spectra and linear dichroism of cyanine dye aggregates whose unit cells contain two molecules. The studied threadlike ordered system with a molecular exciton delocalized along its axis can be treated as two chains of conventional molecular aggregates, rotated relative to each other at a certain angle around the aggregate axis. Our approach is based on the general formulas for the effective cross section of light absorption by a molecular aggregate and key points of the molecular exciton theory. We have developed a self-consistent theory for describing the orientational effects in the absorption and dichroic spectra of such supramolecular structures with nonplanar unit cell. It is shown that the spectral behavior of such systems exhibits considerable distinctions from that of conventional cyanine dye aggregates. They consist in the strong dependence of the relative intensities of the J- and H-type spectral bands of the aggregate with a nonplanar unit cell on the angles determining the mutual orientations of the transition dipole moments of constituting molecules and the aggregate axis as well as on the polarization direction of incident light. The derived formulas are reduced to the well-known analytical expressions in the particular case of aggregates with one molecule in the unit cell. The calculations performed within the framework of our excitonic theory combined with available vibronic theory allow us to quite reasonably explain the experimental data for the pseudoisocyanine bromide dye aggregate.

Two new alkaloids from the endophytic fungus Aspergillus fumigatus SAS10 isolated from the mangrove tree Sonneratia apetala

Two new alkaloids designated aspernigrin E (1) and pyranonigrin L (2) were isolated from mangrove endophytic fungus Aspergillus fumigatus SAS10, together with the known alkaloid compounds pyranonigrin A (3), asperazine (4), (+)-iso-pestalazine A (5), pestalazine A (6), and pestalazine B (7). The planar structures of the new compounds were elucidated by HR-MS and NMR spectroscopic data analyses. The absolute configurations of compounds 1 and 2 were determined by comparison of the electronic circular dichroic (ECD) spectra with the calculated ECD spectra. All these compounds were tested for anti-bacterial activity.

Spectromicroscopic study of the transformation with low energy ions of a hematite thin film into a magnetite/hematite epitaxial bilayer

The search of new properties in novel oxide heterostructures requires the exploration of new fabrication methods and the study, at the microscopic level, of the processes involved during the synthesis. We present a synchrotron-based spectromicroscopic investigation of a magnetite/hematite bilayer on Pt(111) grown in a two-step process by thermal evaporation and Low Energy Ion Bombardment (LEIB). The characterization includes the study of structural, electronic, chemical, and magnetic properties using X-ray Absorption Spectroscopy (XAS), Low Energy Electron Microscopy (LEEM), Photoemission Electron Microscopy (PEEM), or X-ray Magnetic Circular Dichroism (XMCD). The aim is to obtain microscopic information of the thin film before, during, and after the ion bombardment. Ion bombardment gradually transforms the topmost layers of the hematite thin film into a defective sub-oxide, where magnetite nuclei grow and coalesce with increasing ion doses. Two rotational domains of magnetite coexist, which are typically a few tens of nanometres large and do not grow significantly with temperature annealings. The incoherent growth of the magnetite nuclei favours the formation of stable twin boundaries (TBs) and antiphase boundaries (APBs). Dichroic spectra show the characteristics of the ferrimagnetic (FiM) order of magnetite, and the spatial distribution of magnetic domains shows no apparent correlation with the structural image, displaying smooth domains separated by diffuse frontiers. These findings illustrate the importance of a spectromicroscopic characterization of novel oxide heterostructures for potential future applications.

Effect of Heat Treatment on Yellow Field Pea (Pisum sativum) Protein Concentrate Coupled with Membrane Ultrafiltration on Emulsification Properties of the Isolated >50 kDa Proteins.

The aim of this paper was to determine the emulsification properties of protein aggregates obtained from heat pretreated yellow field pea protein concentrate (PPC). PPC dispersions were prepared in distilled water (adjusted to pH 3.0, 5.0, 7.0, or 9.0), heated in a water bath (100 °C) for 30 min, centrifuged and the supernatant passed first through a 30 kDa membrane and, then, the first retentate (>30 kDa) through a 50 kDa membrane. The 50 kDa membrane separation yielded a second retentate (>50 kDa proteins), which was isolated for emulsification studies. The near UV circular dichroic spectra of the protein samples showed more unfolded structures at pH 3.0 and 5.0 than at pH 7.0 and 9.0. The presence of small and spherical oil droplets of emulsions stabilized by the >50 kDa proteins at pH 3.0, 7.0, and 9.0 was confirmed by confocal laser scanning microscopy images. Emulsions stabilized at pH 7.0 and 9.0 had a narrower size distribution range than at pH 3.0 and 5.0. A narrow oil droplet size distribution range and lower interfacial protein concentrations of the emulsions stabilized by the >50 kDa proteins were observed at the corresponding pH of the heat treatment when compared to other pH values. Emulsions stabilized by the >50 kDa proteins exhibited a relatively low flocculation and coalescence index, which infers relative stability. The results from this work suggest that heat pretreatment of the PPC led to the formation of new protein aggregates, especially FT9 with enhanced emulsification properties, at some of the test conditions when compared to the unheated PPC.

Lignans from the seed shells of Cerasus humilis (Bge.) Sok and their bioactivities

The exploration of Cerasus humilis (Bge.) Sok seed shells yielded the identification of six previously uncharacterized compounds, in addition to twelve known compounds. Structure elucidation of these compounds relied on spectroscopic data analysis, and their absolute configurations were established by comparing calculated and experimental electronic circular dichroic (ECD) spectra, supplemented by interpretation of optical rotation data. Notably, none of these compounds exhibited cytotoxicity against HepG2 and A549 cell lines. Remarkably, a majority of the compounds displayed potent antioxidant activity.

Wavelength scaling of photoionization circular dichroism of atomic electron ring currents and its effect on photoelectron spin polarization

Circularly polarized orbitals in atoms are referred to as electron ring currents with a helical angular phase and thus manifest circular dichroism in photoionization by circularly polarized light fields. Opposite circular dichroism has been revealed in single-photon and nonadiabatic tunneling ionization regimes. The transition of the circular dichroism and its underlying mechanism are still not clear. Here, we systematically study the wavelength scaling of photoionization circular dichroism of electron ring currents. We present a universal description of the dichroic photoelectron energy spectra and the spin polarization from the infrared to the extreme ultraviolet regions. We reveal that the channel interference and competition via the intermediate states with different angular quantum numbers in a few-photon ionization regime give rise to the transition of the circular dichroism and the spin polarization of photoelectrons.

New glucosidated indole-quinazoline alkaloids from mangrove endophytic fungus Aspergillus fumigatus SAl12

Two new glucosidated indole-containing quinazoline alkaloids designated fumigatosides G (1) and H (2) were isolated from mangrove-derived fungus Aspergillus fumigatus SAl12, together with the known analogues fumigatoside B (3) and fumiquinazoline J (4). The planar structures of the new compounds were elucidated by HR-MS and NMR spectroscopic data analyses. The absolute configurations were determined by comparison of electronic circular dichroic (ECD) spectra with that of the known compound fumigatoside B and with the calculated ECD spectrum. All these indole-quinazoline compounds were tested for anti-bacterial and cytotoxic activities.

Probing magnetic orbitals and Berry curvature with circular dichroism in resonant inelastic X-ray scattering

Resonant inelastic X-ray scattering (RIXS) can probe localized excitations at selected atoms in materials, including particle-hole transitions between the valence and conduction bands. These transitions are governed by fundamental properties of the corresponding Bloch wave functions, including orbital and magnetic degrees of freedom, and quantum geometric properties such as the Berry curvature. In particular, orbital angular momentum (OAM), which is closely linked to the Berry curvature, can exhibit a nontrivial momentum dependence. We demonstrate how information on such OAM textures can be extracted from the circular dichroism in RIXS. Based on accurate modeling with a first-principles treatment of the key ingredient—the light–matter interaction—we simulate dichroic RIXS spectra for the prototypical transition-metal dichalcogenide MoSe2 and the two-dimensional topological insulator 1T{}^{{prime}}-MoS2. Guided by an intuitive picture of the optical selection rules, we discuss how the momentum-dependent OAM manifests itself in the dichroic RIXS signal if one controls the momentum transfer. Our calculations are performed for typical experimental geometries and parameter regimes, and demonstrate the possibility of observing the predicted circular dichroism in forthcoming experiments. Thus, our work establishes a new avenue for observing Berry curvature and topological states in quantum materials.

Effect of Steam Flash-Explosion on Physicochemical Properties and Structure of High-Temperature Denatured Defatted Rice Bran Protein Isolate.

The effects of Steam Flash-Explosion (SFE) on the physicochemical properties and molecular structure of high-temperature denatured defatted rice bran protein isolate (RBPI) were investigated. The mechanism of SFE treatment on high-temperature denatured defatted RBPI was revealed. The analysis of the physical and chemical properties of RBPI showed that the surface hydrophobicity, characteristic viscosity, and thermal stability of rice bran protein isolate were significantly affected by the pressure of saturated steam and pressure holding time. Under the conditions of 2.1 MPa and 210 s, the surface hydrophobicity index decreased significantly from 137.5 to 17.5, and the characteristic viscosity increased significantly. The peak temperature of denaturation decreases from 114.2 to 106.7 °C, and the enthalpy of denaturation decreases from 356.3 to 231.4 J/g. The higher structure (circular dichroic spectrum and endogenous fluorescence spectrum) of rice bran protein isolate was analyzed by volume rejection chromatography (SEC). The results showed that steam flash treatment could depolymerize and aggregate RBPI, and the relative molecular weight distribution changed greatly. The decrease in small molecules with poor solubility was accompanied by the increase in macromolecules (>550 kDa) soluble aggregates, which were the products of a Maillard reaction. The contents of free sulfhydryl and disulfide bonds in high-temperature rice bran meal protein isolate were significantly increased, which resulted in the increase in soluble aggregates containing disulfide bonds. Circular dichroism (CD) analysis showed that the α-helix content of the isolated protein was significantly decreased, the random curl content was increased, and the secondary structure of the isolated protein changed from order to disorder. The results of endogenous fluorescence spectroscopy showed that the high-temperature rice bran meal protein isolate was more extended, tryptophan was in a more hydrophilic microenvironment, the fluorescence intensity was reduced, and the tertiary structure was changed. In addition, the mean particle size and net surface charge of protein isolate increased in the aqueous solution, which was conducive to the development of the functional properties of the protein.

Photo-Induced Anisotropy of Methyl Red Azo Dye in Polymer Film

A photo-induced anisotropy (PIA) of Methyl Red (MR) azo dye embedded in PMMA polymer solid films was investigated by studying dichroic spectra and photo-induced birefringence. The reversible PIA of MR dye was measured in situ during photoactive irradiation process. Photoinduced order increases with the rise of exposure power. It is shown that PIA dark relaxation slows down at higher exposure energy. The MR rotational diffusion was evaluated at different exposure modes. These data are useful for the characterization of Methyl Red azo dye as a liquid crystal photo-aligning material.

Seven diterpenoids from the resin of Pinus yunnanensis Franch and their anti-inflammatory activity

Phytochemical investigation of the 95% ethanol extract from Pinus yunnanensis Franch resin induced the isolation of six previously unreported diterpenoids pinuyunnanacids K − N, P − Q, a nor-diterpenoid with a novel skeleton pinuyunnanacid O and six known analogues. Their structures were elucidated by spectroscopic analysis and computational methods, including nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, calculated NMR chemical shifts method and electronic circular dichroic (ECD) spectra. All the compounds were analyzed for anti-inflammatory activity through western blotting and cell viability, compounds 2, 10 and 12 significantly downregulated the protein expression of iNOS at the concentration of 40 μM. At the same time, compounds 10 and 12 decreased the expression of COX-2 in LPS-treated RAW264.7 (leukemia cells in mouse macrophage) cells at the concentration of 40 μM.

Seaweed Slurry Improved Gel Properties and Enhanced Protein Structure of Silver Carp (Hypophthalmichthys molitrix) Surimi.

In order to improve the gel quality of silver carp (Hypophthalmichthys molitrix) surimi, the texture and rheological properties and microstructure of silver carp surimi gel products were analyzed by adding Laminaria japonica (LJ), Undaria pinnatifida (UP) and Sargassum fusiforme (SF) slurries. After adding kelp slurry (KS), the gel strength reached the highest level of 1047.26 ± 85.04 (g·mm). The carbonyl content and surface hydrophobicity of surimi protein increased, while the free amino groups, total sulfhydryl groups, and fluorescence intensity decreased significantly. The results of transform infrared spectroscopy (FT-IR), circular dichroic (CD), and Raman spectra showed that the KS promoted the change of the secondary structure of protein. Scanning electron microscopy (SEM) images revealed that kelp slurry had a more compact gel microstructure. In conclusion, the kelp slurry could significantly increase the gel strength, improve the quality of surimi products, enrich the nutrition of silver carp surimi, and have great significance for expanding the application range of seaweed.

Ionones and lignans from the fresh roots of Rehmannia glutinosa

Nine undescribed compounds, together with 21 known components, were isolated from the fresh roots of Rehmannia glutinosa. Their structures were elucidated based on spectroscopic data analysis, and the absolute configurations of undescribed compounds were determined by comparison of their calculated and experimental electronic circular dichroic (ECD) spectra and interpretation of their optical rotation data. The α-glucosidase inhibitory effects of the isolated compounds were investigated and all of them exhibited slightly inhibitory activities.

Ionic liquid modified chloroperoxidase is immobilized on gold nanoparticles-reduced graphene oxide nanocomposites for efficient sensoring of nitrite by electroenzymatic catalysis

Electroenzymatic biosensors have wide applications due to its fastness and sensitivity. Here we propose a bio-nanocomposite to be dropped on glassy carbon electrode (GCE) for nitrite sensoring by electroenzymatic catalysis. The composite is constructed by ionic liquids (1-butyl-3-methylimidazolium bromide, ILBMB) modified chloroperoxidase (CPO) immobilized on gold nanoparticles (Au NPs) modified reduced graphene oxide (rGO). The ILBMB can facilitate the direct electron transfer (DET) of CPO on GCE without a redox mediator. The molecular docking indicates ILBMB is located at the opening of substrate channel rather than occupy the active site of CPO, which is beneficial to its DET. Circular dichroic spectrum (CD) verifies the α-helix content of CPO is increased, and ultraviolet-visible spectrum (UV–vis) demonstrates the heme prosthetic group become more exposed by ILBMB. These changes result in the enhancement of CPO activity. The rGO-Au NPs plays two roles enhancing the detection signal and improving the loading of CPO on GCE. The sensor (CPO-ILBMB/rGO-Au NPs/GCE) provides two models for nitrite detection as cyclic voltammetry and amperometry. The detection limit is 0.25 μmol·L−1 and 0.049 μmol·L−1, respectively with corresponding detection range of 2.0−2500 μmol·L−1 and 0.5–300 μmol·L−1. The high sensitivity, stability, and selectivity of this electroenzymatic biosensor ensure its potential practical application.

Diterpenes from Pinus kesiya var. langbianensis (A.Chev.) Gaussen ex Bui (Pinaceae) and their protective effects in LPS-treated BEAS-2B cells

Eight previously undescribed diterpenoids, rosins A−H, and nine known diterpenoids were isolated from the resin from Pinus kesiya var. langbianensis (A.Chev.) Gaussen ex Bui (Pinaceae) extracted with 95% ethanol. Their structures were determined by nuclear magnetic resonance spectroscopy, mass spectrometry, J−based configuration analysis (JBCA), NOESY spectra, calculated NMR chemical shifts and electronic circular dichroic (ECD) spectra. All compounds were evaluated for their protective effects in LPS-treated human normal lung epithelial cells (BEAS-2B), and the cell viability was significantly increased after treatment with compounds 5, 10, 12, or 15 at a concentration of 10 μM.

SPECTRAL DEPENDENCIES OF MAGNETOOPTICAL EFFECTS IN MAGNETIC FLUIDS

The spectral dependences of the transmittance and optical anisotropy effects in magnetic fluid have been investigated. It is shown that the refractive index spectra of bulk magnetite known are of little use for the quantitativeand qualitative interpretation of optical effects in magnetic fluids. The transmission, birefringence, and dichroism spectra are calculated using the known refractive index spectra of magnetite. The best agreement with the experiment was obtained using the experimental spectra of the complex refractive index of the powder of magnetite nanoparticles. It is concluded that there is a significant difference in the spectra of the complex refractive index for bulk and nanosized magnetite.

Exploring the intercalation binding of tiamulin with DNA using multispectroscopy and a molecular modelling approach.

The binding of tiamulin with calf thymus DNA was systematically investigated using multispectroscopy and molecular modelling techniques. For DNA, once tiamulin was added, viscosity (η) and melting temperature (Tm ) both exhibited an uptrend. The fluorescence performance of the tiamulin-DNA complex did not change with the ionic strength changes. The binding constant (Ka ) of tiamulin for single-stranded DNA (ssDNA, 1.48 × 104 M-1 ) was obviously higher than that for double-stranded DNA (dsDNA, 9.51 × 103 M-1 ) at 291 K. The helix structure became looser and the base stack force became stronger for DNA due to the presence of tiamulin as seen from circular dichroic (CD) spectra. The intercalation binding mode of tiamulin with DNA was disclosed. Molecular modelling also revealed tiamulin inserting into the base pairs with the lowest binding free energy of -18.73 kJ mol-1 using van der Waals forces as well as hydrogen bonds.

Rapid nanomolar detection of methamphetamine in biofluids via a reagentless electrochemical aptamer-based biosensor

The availability of sensing platforms able to rapidly measure abused drugs directly in biological fluids in a single step would allow performing drugged driving screening on the site. The achievement of this goal is extremely important for preventing and controlling drug abuse and crime incidence. Motived by this, we constructed a simple, cost-effective and reagentless electrochemical aptamer-based (EAB) sensor with methamphetamine (MAMP) as the target molecule. This EAB sensor produced a nanomolar level of detection accuracy in unprocessed or minimally processed bio-samples. Specifically, circular dichroic spectrum was used to confirm that the truncated aptamer from the original sequence would undergo large binding-induced conformational changes. We then engineered the aptamer to work in the EAB platform and the resulting sensor enabled sensitive and specific detection of MAMP with the detection limit of 30 nM in undiluted serum, 50 nM in undiluted urine and 20 nM in 50% saliva. The sensor has good recovery rate, implying this method has good reliability and repeatability. The detection limit is far below the clinical detection threshold, it would be hopefully used for preliminary screening of drugged driving in real world.

Computational Approaches and Use of Chiroptical Probes in the Absolute Configuration Assignment to Natural Products by ECD Spectroscopy: A 1,2,3-Trihydroxy-p-menthane as a Case Study.

In this study, the computational analysis of electronic circular dichroism (ECD) spectra and the employment of biphenyl chiroptical probes were compared in the absolute configuration assignment of (-)-1α,2α,3β-trihydroxy-p-menthane (1), taken as a representative example of a UV-transparent chiral natural product. The usefulness of chiroptical probes in the configurational assignments of natural products and their complementarity to the computational protocols is herein highlighted. The biphenyl probe approach proves to be straightforward, reliable, and suitable for conformationally mobile and ECD silent compounds, not treatable by computational analysis of chiroptical data.