Linear dichroism (LD) spectroscopy is an important technique in the study of the orientation and organization of pigments in the photosynthetic membrane complexes in vivo and in vitro . In this work, the orient...Linear dichroism (LD) spectroscopy is an important technique in the study of the orientation and organization of pigments in the photosynthetic membrane complexes in vivo and in vitro . In this work, the orientation of the pigments in the isolated photosystem Ⅱ (PSⅡ) sub_core reaction center complexes was analyzed and characterized by means of low temperature absorption and LD spectroscopy. The preparations containing different amounts of CP47 isolated from spinach (Spinacia oleracea L.) chloroplast were used in order to investigate the orientation of pigments in the PSⅡ sub_core CP47/D1/D2/Cyt b_559 (CP47/D1/D2) complexes. Chlorophyll a (Chl a) absorbing at 680 nm in CP47/D1/D2/Cyt b_559 complex showed an orientation of the Q y transition parallel to the membrane plane. It is proposed that there are two forms of β_carotene (β_Car) in CP47/D1/D2/Cyt b_559 complex, denoted as β_Car (Ⅰ) and β_Car (Ⅱ), with different orientations, β_Car (Ⅰ) at 470 and 505 nm is roughly parallel to the membrane plane, and β_Car (Ⅱ) at 460 and 490 nm seems to be perpendicular orientation. Upon the photoinhibitory experiment β_Car (Ⅱ) was found to be photosensitive and easily photodamaged. It also showed that the positive LD signal observed at 680 nm was quite complicated. This signal is tentatively attributed to P680 and some Chl a of antenna in CP47 protein based upon our measurements.展开更多
The second-harmonic generation （SHG） circular dichroism in the light of reflection from chiral films of tripod-like chiral molecules is investigated. The expressions of the second-harmonic generation circular dichro...The second-harmonic generation （SHG） circular dichroism in the light of reflection from chiral films of tripod-like chiral molecules is investigated. The expressions of the second-harmonic generation circular dichroism are derived from our presented three-coupled-oscillator model for the tripod-like chiral molecules. Spectral dependence of the circular dichroism of SHG from film surface composed of tripod-like chiral molecules is simulated numerically and analysed. Influence of ehiral parameters on the second-harmonic generation circular dichroism spectrum in chiral films is studied. The result shows that the second-harmonic generation circular dichroism is a sensitive method of detecting chirality compared with the ordinary circular dichroism in linear optics. All of our work indicates that the classical molecular models are very effective to explain the second-harmonic generation circular dichroism of chiral molecular system. The classical molecular model theory can give us a clear physical picture and brings us very instructive information about the link between the molecular configuration and the nonlinear processes.展开更多
The stereochemistry of two 6, 9-oxygen bridge dibenzocyclooctadiene lignans from Kadsura coccinea, are difficult to separate and very unstable. The present study was designed to develop a high-performance liquid chrom...The stereochemistry of two 6, 9-oxygen bridge dibenzocyclooctadiene lignans from Kadsura coccinea, are difficult to separate and very unstable. The present study was designed to develop a high-performance liquid chromatography using circular dichroism detection for the analysis of the stereochemistry. A new 6, 9-oxygen bridge dibenzocyclooctadiene lignans named Kadsulignan Q was firstly found with an S-biphenyl configuration. The other compound was identified as Kadsulignan L with an R- biphenyl configuration. In order to obtain kinetic data on their reversible interconversion, the stability was measured at different deuterated solvents such as deuterated methanol, deuterated chloroform and deuterated dimethylsulfoxide. The lignans were more unstable and converted more easily in deuterated methanol than in deuterated chloroform and deuterated dimethylsulfoxide.展开更多
Selective detection of multiple analytes in a compact design with dual-modality and theranostic features presents great challenges. Herein, we wish to report a coumarin-thiazolidine masked D-penicillamine based dual-m...Selective detection of multiple analytes in a compact design with dual-modality and theranostic features presents great challenges. Herein, we wish to report a coumarin-thiazolidine masked D-penicillamine based dual-modality fluorescent probe COU-DPA-1 for selective detection, differentiation, and detoxification of multiple heavy metal ions(Ag^(+), Hg^(2+), Cu^(2+)). The probe shows divergent fluorescence(FL)/circular dichroism(CD) responses via divergent bond-cleavage cascade reactions(metal ion promoted C-S cleavage and hydrolysis at two distinctive cleavage sites): FL “turn-off” and CD “turn-on” for Ag+(no hydrolysis), FL “turn-on” and CD “turn-off” for Hg^(+)(imine hydrolysis), and FL “self-threshold ratiometric” and CD “turn-off” for excess Cu^(2+)(lactone and imine hydrolysis), providing the first example of a fluorescence/CD dual-modality probe for multiple species with complimentary responses. Moreover, the bond-cleavage cascade reactions also lead to the formation of D-penicillamine heavy metal ion complexes for potential detoxification treatments.展开更多
Buagafuran is a novel drug candidate derived from natural product.Its absolute configuration has been confirmed by electronic circular dichroism combined with modern quantum-chemical calculation using time-dependent d...Buagafuran is a novel drug candidate derived from natural product.Its absolute configuration has been confirmed by electronic circular dichroism combined with modern quantum-chemical calculation using time-dependent density functional theory.The predicted UV absorbance peak is underestimated by several nanometers compared with the experimental data.The applicability of empirical rule for the C=C-C-O system in Buagafuran has also been discussed.Our results show that electronic circular dichroism could be a useful tool for the absolute configuration assignment of chiral drugs,especially for the oily or semisolid substances,whose crystal structures are impossible to obtain.展开更多
The obvious circular dichroism（CD） and optical activity can be obtained based on the chiral metamaterial due to the plasmon-enhanced effect, which is very attractive for future compact devices with enhanced capabili...The obvious circular dichroism（CD） and optical activity can be obtained based on the chiral metamaterial due to the plasmon-enhanced effect, which is very attractive for future compact devices with enhanced capabilities of light manipulation. In this paper, we propose a dual-chiral metamaterial composed of bilayer asymmetric split ring resonators（ASRR）that are in mirror-symmetry shape. It is demonstrated that the CD can get enhancement in the terahertz regime. Moreover,the CD can be further improved by modulating the asymmetry of ASRR. The enhanced CD effect in the terahertz regime has great potential applications in sensing, biomedical imaging, and molecular recognition.展开更多
Interaction of procainamide hydrochloride（PAH） with human serum albumin（HSA） is of great significance in understanding the pharmacokinetic and pharmacodynamic mechanisms of the drug. Multi-spectroscopic techniques...Interaction of procainamide hydrochloride（PAH） with human serum albumin（HSA） is of great significance in understanding the pharmacokinetic and pharmacodynamic mechanisms of the drug. Multi-spectroscopic techniques were used to investigate the binding mode of PAH to HSA and results revealed the presence of static type of quenching mechanism. The number of binding sites, binding constants and thermodynamic parameters were calculated. The results showed a spontaneous binding of PAH to HSA and hydrophobic interactions played a major role. In addition, the distance between PAH and the Trp–214 was estimated employing the F？rster＇s theory. Site marker competitive experiments indicated that the binding of PAH to HSA primarily took place in subdomain IIA（Sudlow＇s site I）. The influence of interference of some common metal ions on the binding of PAH to HSA was studied. Synchronous fluorescence spectra（SFS）, 3D fluorescence spectra and circular dichroism（CD） results indicated the conformational changes in the structure of HSA.展开更多
The interconnection of polarization and phase in electromagnetic scattering process has attracted both fundamental and practical interest.Here we propose the principle and experimental demonstration of a scatteringcon...The interconnection of polarization and phase in electromagnetic scattering process has attracted both fundamental and practical interest.Here we propose the principle and experimental demonstration of a scatteringcontrol mechanism based on the simultaneous control of polarization and phase via a continuously shaped planar metasurface.Under circularly polarized illumination,the scattering is redirected to off-specular direction,leading to significant reduction of the scattering cross section.Theoretical investigation shows that the underlying physical mechanism is the spin-dependent phase modulation in the anisotropic scattering process.Our approach would provide valuable guidance for the full control of electromagnetic wave for diverse applications.展开更多
Circular dichroism(CD)has shown very interesting possibilities as a means to characterize the chiral signal of a chiral structure.Here,we theoretically demonstrated enhanced and tunable CD in the visible light regime ...Circular dichroism(CD)has shown very interesting possibilities as a means to characterize the chiral signal of a chiral structure.Here,we theoretically demonstrated enhanced and tunable CD in the visible light regime using a composite structure consisting of a double-layer metal grating gaped by a dielectric waveguide layer.Based on the coupling of the waveguide modes and the localized plasmonic resonances,the CD could reach a maximum value as high as 0.52 at635 nm,which is four times higher than the CD value obtained in a conventional double-layer grating without the waveguide coupling effect.Furthermore,the spectral positions of the enhanced CD bands could be easily tuned by controlling the structural parameters.The proposed hybrid double-grating and waveguide structures could have potential applications in chiral selective imaging,sensing and spectroscopy,especially where the transmission measurement is required.展开更多
Based on the starch hydrolysis reaction accelerated by microwave irradiation with α-amylase, the circular dichroism （CD） and secondary structure changes of α-amylase under the condition of microwave irradiation an...Based on the starch hydrolysis reaction accelerated by microwave irradiation with α-amylase, the circular dichroism （CD） and secondary structure changes of α-amylase under the condition of microwave irradiation and water bath were studied by circular dichroism spectra. The results showed that, both the peak heights （at 2=193 nm） of the CD spectra of the samples treated by microwave irradiation and water bath reduced. The reduced rate by microwave irradiation ranged from 140% to 220%, while the reduced rate by water bath ranged from 60% to 140%. The peak of the sample treated by microwave irradiation for 60 min disappeared at λ=193 nm, while the sample showed a wake peak by water bath. The peak position by microwave irradiation emerged a blue shift in the range of 5-8 nm at λ=204 nm and λ=220 nm, while it emerged in the range of 3-5 nm by water bath. With time going on, the microwave irradiation and water bath have prompted the secondary structure of α-helix, β-sheet, β-turn and the mutual transformations of random coil, but the trends were different.展开更多
Researchers have long studied circular dichroism(CD) for its enormous prospects in life sciences. Many biomolecules have vibration modes in the terahertz region, and terahertz CD spectra are robust to detect biomolecu...Researchers have long studied circular dichroism(CD) for its enormous prospects in life sciences. Many biomolecules have vibration modes in the terahertz region, and terahertz CD spectra are robust to detect biomolecular structures. However,few studies explore the terahertz CD spectra on even natural materials due to technical challenges in both fields. Here, we report a setup of home-built terahertz time-domain spectroscopy to measure the polarization states of terahertz waves.By carefully measuring the transmission Jones matrix, we obtain terahertz CD spectra of α-lactose tablets and D-glucose tablets. Our results show that the terahertz CD spectra are sensitive to vibrational motions in biochemical compounds,which will find wide applications in biosensing and biomedical diagnostics.展开更多
In this study,circular dichroism(CD)and molecular dynamics(MD)simulation were used to investigate the thermal unfolding pathway of staphylococcal enterotoxin B(SEB)at temperatures of 298–371 and 298–500 K,and the re...In this study,circular dichroism(CD)and molecular dynamics(MD)simulation were used to investigate the thermal unfolding pathway of staphylococcal enterotoxin B(SEB)at temperatures of 298–371 and 298–500 K,and the relationship between the experimental and simulation results were explored.Our computational findings on the secondary structure of SEB showed that at room temperature,the CD spectroscopic results were highly consistent with the MD results.Moreover,under heating conditions,the changing trends of helix,sheet and random coil obtained by CD spectral fitting were highly consistent with those obtained by MD.In order to gain a deeper understanding of the thermal stability mechanism of SEB,the MD trajectories were analyzed in terms of root mean square deviation(RMSD),secondary structure assignment(SSA),radius of gyration(R_(g)),free energy surfaces(FES),solvent-accessible surface area(SASA),hydrogen bonds and salt bridges.The results showed that at low heating temperature,domain Ⅰ without loops(omitting the mobile loop region)mainly relied on hydrophobic interaction to maintain its thermal stability,whereas the thermal stability of domain Ⅱ was mainly controlled by salt bridges and hydrogen bonds.Under high heating temperature conditions,the hydrophobic interactions in domain Ⅰ without loops were destroyed and the secondary structure was almost completely lost,while domain Ⅱ could still rely on salt bridges as molecular staples to barely maintain the stability of the secondary structure.These results help us to understand the thermodynamic and kinetic mechanisms that maintain the thermal stability of SEB at the molecular level,and provide a direction for establishing safer and more effective food sterilization processes.展开更多
The effects of temperature,pH and long-term storage on the secondary structure and conformation changes of bovine haemoglobin（bHb） were studied using circular dichroism（CD） and ultraviolet-visible（UV-vis） spectr...The effects of temperature,pH and long-term storage on the secondary structure and conformation changes of bovine haemoglobin（bHb） were studied using circular dichroism（CD） and ultraviolet-visible（UV-vis） spectroscopies.Neural network software was used to deconvolute the CD data to obtain the fractional content of the five secondary structures.The storage stability of bHb solutions in pH 6,7 and8 buffers was significantly higher at 4 ℃ than at 23 ℃ for the first 3 days.A complete denaturation of bHb was observed after 40 days irrespective of storage temperature or pH.The bHb solutions were also exposed to heating and cooling cycles between 25 and 65 ℃ and structural changes were followed by UVvis and CD spectroscopies.These experiments demonstrated that α-helix content of bHb decreased steadily with the increasing temperature above 35 ℃ at all pH values.The loss in a-helicity and gain in random coil conformations was pH-dependent and the greatest under alkaline conditions.Furthermore,there was minimal recovery of the secondary structure content upon cooling to 25 ℃.The use of bHb as a model drug is very common and this study elucidates the significance of storage and processing conditions on its stability.展开更多
In this text,we use inexpensive and natural amino acid,successfully obtained the asymmetric crystallization of three PTCs,[Ti6(OiPr)14(μ2-O)(μ3-O)2(D/L-pGlu)2](D-PTC-53;L-PTC-53;H2 pGlu=pyroglutamic acid)and[Ti6(OiP...In this text,we use inexpensive and natural amino acid,successfully obtained the asymmetric crystallization of three PTCs,[Ti6(OiPr)14(μ2-O)(μ3-O)2(D/L-pGlu)2](D-PTC-53;L-PTC-53;H2 pGlu=pyroglutamic acid)and[Ti6(OiPr)14(μ2-O)(μ3-O)2(D-pGlu)2][Ti6(OiPr)14((μ2-O)(μ3-O)2(L-pGlu)2](D,L-PTC-53).Interestingly,in situ lactamide reaction starting from glutamic acid to pyroglutamic acid was observed.In addition,the chirality features of these PTCs have been thoroughly discussed.The two enantiomers crys tallize in chiral P21 space group.The optically pure pGlu ligands transform its chirality to the inorganic titanium oxo clusters.As a result,the stack of these inorganic clusters generates homochiral helical chains along the characteristic axial direction.Apart from the microscopic structural analysis,the macroscopic solid-state samples exhibit unusual strong circular dichroism(CD)signals,further verified the homochiral feature of the enantiomers.展开更多
Chiral mesoporous silica ribbons and rods with inversed handedness have been synthesized with the same enantio pure N-acylaminoacidat temperatures of 0℃and 20℃ respectively. With involving Cu^(2+)and meso-tetra(4-su...Chiral mesoporous silica ribbons and rods with inversed handedness have been synthesized with the same enantio pure N-acylaminoacidat temperatures of 0℃and 20℃ respectively. With involving Cu^(2+)and meso-tetra(4-sulfonatophenyl)porphyrin(TPPS) as probes, ribbons and rods revealed opposite signals in diffuse-reflectance circular dichroism(DRCD) spectra, indicating the existence of inversed supramolecular chiral imprintings through helical stacking of amphiphiles. The structural evolution was systematically studied by the freeze-dried products sampled at different time after the addition of silica precursors. The H-bonding-depended molecular orientation probably controls the chiral sense upon forming chiral molecular stacking, which would be the origin of such handedness inversion展开更多
Magnetic field-induced orientation of a chiral side chain liquid crystalline polyacrylate(P-11) was studied by using IR dichroism. For the investigated P-11, it has been shown thatthe magnetic alignment takes place ov...Magnetic field-induced orientation of a chiral side chain liquid crystalline polyacrylate(P-11) was studied by using IR dichroism. For the investigated P-11, it has been shown thatthe magnetic alignment takes place over the entire temperature range between its meltingpoint and clearing point and the orientation level is strongly temperature-dependent, thedevelopment with time of the magnetic orieatation follows an exponeotial-type relation,and the smectic phase state influences the thermal relaxation process in the absence of themagnetic field.展开更多
Perpendicular optical reversal of the linear dichroism transition has promising applications in polarization-sensitive optoelectronic devices. We perform a systematical study on the in-plane optical anisotropy of quas...Perpendicular optical reversal of the linear dichroism transition has promising applications in polarization-sensitive optoelectronic devices. We perform a systematical study on the in-plane optical anisotropy of quasi-one-dimensional PdBr_(2) by using combined measurements of the angle-resolved polarized Raman spectroscopy(ARPRS) and anisotropic optical absorption spectrum. The analyses of ARPRS data validate the anisotropic Raman properties of the PdBr_(2) flake.And anisotropic optical absorption spectrum of PdBr_(2) nanoflake demonstrates distinct optical linear dichroism reversal. Photodetector constructed by PdBr_(2) nanowire exhibits high responsivity of 747 A·W^(-1) and specific detectivity of 5.8×10^(12) Jones. And the photodetector demonstrates prominent polarization-sensitive photoresponsivity under 405-nm light irradiation with large photocurrent anisotropy ratio of 1.56, which is superior to those of most of previously reported quasi-one-dimensional counterparts. Our study offers fundamental insights into the strong optical anisotropy exhibited by PdBr_(2), establishing it as a promising candidate for miniaturization and integration trends of polarization-related applications.展开更多
The circular dichroism(CD) signal of a molecule is usually weak,however,a strong CD signal in optical spectrum is desirable because of its wide range of applications in biosensing,chiral photo detection,and chiral cat...The circular dichroism(CD) signal of a molecule is usually weak,however,a strong CD signal in optical spectrum is desirable because of its wide range of applications in biosensing,chiral photo detection,and chiral catalysis.In this work,we show that a strong chiral response can be obtained in a hybridized system consisting of an artificial chiral molecule and a nanorod in the strong coupling regime.The artificial chiral molecule is composed of six quantum dots in a helix assembly,and its CD signal arises from internal Coulomb interactions between quantum dots.The CD signal of the hybridized system is highly dependent on the Coulomb interactions and the strong coupling progress through the electromagnetic interactions.We use the coupled oscillator model to analyze strong coupling phenomenon and address that the strong coupling progress can amplify the CD signal.This work provides a scenario for designing new plasmonic nanostructures with a strong chiral optical response.展开更多
Electron magnetic circular dichroism opens a new door to explore magnetic properties by transmitted electrons in the transmission electron microscope. However, obtaining quantitative magnetic parameters, such as spin ...Electron magnetic circular dichroism opens a new door to explore magnetic properties by transmitted electrons in the transmission electron microscope. However, obtaining quantitative magnetic parameters, such as spin and orbital magnetic moment with element-specificity, goes a long way along with the development and improvement of this technique both in theoretical and experimental aspects. In this review, we will give a detailed description of the quantitative electron magnetic circular dichroism（EMCD） technique to measure magnetic parameters with spin-specificity, element-specificity,site-specificity, and orbital-spin-specificity. The discussion completely contains the procedures from raw experimental data acquisition to final magnetic parameters, together with the related custom code we have developed.展开更多
基金Commissaire Energie de Atomique de Francethe 9th Five-Year Major Program of the National Natural Science Foundation of China(39890390)+1 种基金the State Key Basic Research Development Plan of China(973)(G1998010100)Innovation of Laboratory of Photosynthests Basic Research,Institute of Botany,The Chinese Acadeny of Sciences
文摘Linear dichroism (LD) spectroscopy is an important technique in the study of the orientation and organization of pigments in the photosynthetic membrane complexes in vivo and in vitro . In this work, the orientation of the pigments in the isolated photosystem Ⅱ (PSⅡ) sub_core reaction center complexes was analyzed and characterized by means of low temperature absorption and LD spectroscopy. The preparations containing different amounts of CP47 isolated from spinach (Spinacia oleracea L.) chloroplast were used in order to investigate the orientation of pigments in the PSⅡ sub_core CP47/D1/D2/Cyt b_559 (CP47/D1/D2) complexes. Chlorophyll a (Chl a) absorbing at 680 nm in CP47/D1/D2/Cyt b_559 complex showed an orientation of the Q y transition parallel to the membrane plane. It is proposed that there are two forms of β_carotene (β_Car) in CP47/D1/D2/Cyt b_559 complex, denoted as β_Car (Ⅰ) and β_Car (Ⅱ), with different orientations, β_Car (Ⅰ) at 470 and 505 nm is roughly parallel to the membrane plane, and β_Car (Ⅱ) at 460 and 490 nm seems to be perpendicular orientation. Upon the photoinhibitory experiment β_Car (Ⅱ) was found to be photosensitive and easily photodamaged. It also showed that the positive LD signal observed at 680 nm was quite complicated. This signal is tentatively attributed to P680 and some Chl a of antenna in CP47 protein based upon our measurements.
基金Project supported by the excellent Team in Harbin Institute of Technology,Chinathe Natural Science Foundation of Heilongjiang Province,China (Grant No. A200406)
文摘The second-harmonic generation （SHG） circular dichroism in the light of reflection from chiral films of tripod-like chiral molecules is investigated. The expressions of the second-harmonic generation circular dichroism are derived from our presented three-coupled-oscillator model for the tripod-like chiral molecules. Spectral dependence of the circular dichroism of SHG from film surface composed of tripod-like chiral molecules is simulated numerically and analysed. Influence of ehiral parameters on the second-harmonic generation circular dichroism spectrum in chiral films is studied. The result shows that the second-harmonic generation circular dichroism is a sensitive method of detecting chirality compared with the ordinary circular dichroism in linear optics. All of our work indicates that the classical molecular models are very effective to explain the second-harmonic generation circular dichroism of chiral molecular system. The classical molecular model theory can give us a clear physical picture and brings us very instructive information about the link between the molecular configuration and the nonlinear processes.
基金supported by the PAPD(Priority Academic Program Development)of Jiangsu Higher Education Institutions,University Science Research Project of Jiangsu Province(No.09KJB350002)National Key Technology R&D Program(No.2012BAI30B02),National Natural Science Foundation of China(No.30901853)Hepatic Fibrosis Innovative Medicine-Research and Development of Fructus Schisandrae capsule(No.F12-157-9-00)
文摘The stereochemistry of two 6, 9-oxygen bridge dibenzocyclooctadiene lignans from Kadsura coccinea, are difficult to separate and very unstable. The present study was designed to develop a high-performance liquid chromatography using circular dichroism detection for the analysis of the stereochemistry. A new 6, 9-oxygen bridge dibenzocyclooctadiene lignans named Kadsulignan Q was firstly found with an S-biphenyl configuration. The other compound was identified as Kadsulignan L with an R- biphenyl configuration. In order to obtain kinetic data on their reversible interconversion, the stability was measured at different deuterated solvents such as deuterated methanol, deuterated chloroform and deuterated dimethylsulfoxide. The lignans were more unstable and converted more easily in deuterated methanol than in deuterated chloroform and deuterated dimethylsulfoxide.
基金supported by the National Natural Science Foundation of China (Nos. 21577037 and 21738002)the State Key Laboratory of Bioreactor Engineering, Shanghai Natural Science Fund (No. 20ZR1414700)+2 种基金Shanghai Sailing Program (No. 19YF1412500)Natural Science Basic Research Program of Shaanxi (No. 2019JQ-924)Key Breeding Program by Collaborative Innovation Center of Green Manufacturing Technology for Traditional Chinese Medicine in Shaanxi Province (No. 2019XT-1-03)。
文摘Selective detection of multiple analytes in a compact design with dual-modality and theranostic features presents great challenges. Herein, we wish to report a coumarin-thiazolidine masked D-penicillamine based dual-modality fluorescent probe COU-DPA-1 for selective detection, differentiation, and detoxification of multiple heavy metal ions(Ag^(+), Hg^(2+), Cu^(2+)). The probe shows divergent fluorescence(FL)/circular dichroism(CD) responses via divergent bond-cleavage cascade reactions(metal ion promoted C-S cleavage and hydrolysis at two distinctive cleavage sites): FL “turn-off” and CD “turn-on” for Ag+(no hydrolysis), FL “turn-on” and CD “turn-off” for Hg^(+)(imine hydrolysis), and FL “self-threshold ratiometric” and CD “turn-off” for excess Cu^(2+)(lactone and imine hydrolysis), providing the first example of a fluorescence/CD dual-modality probe for multiple species with complimentary responses. Moreover, the bond-cleavage cascade reactions also lead to the formation of D-penicillamine heavy metal ion complexes for potential detoxification treatments.
基金supported by the Fundamental Research Funds for the Central Institutes(No.2012ZD03)
文摘Buagafuran is a novel drug candidate derived from natural product.Its absolute configuration has been confirmed by electronic circular dichroism combined with modern quantum-chemical calculation using time-dependent density functional theory.The predicted UV absorbance peak is underestimated by several nanometers compared with the experimental data.The applicability of empirical rule for the C=C-C-O system in Buagafuran has also been discussed.Our results show that electronic circular dichroism could be a useful tool for the absolute configuration assignment of chiral drugs,especially for the oily or semisolid substances,whose crystal structures are impossible to obtain.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11174051,11374049,and 11204139)the Natural Science Foundation of Jiangsu Province of China(Grant No.BK20131283)the Fundamental Research Funds for the Central Universities,China
文摘The obvious circular dichroism（CD） and optical activity can be obtained based on the chiral metamaterial due to the plasmon-enhanced effect, which is very attractive for future compact devices with enhanced capabilities of light manipulation. In this paper, we propose a dual-chiral metamaterial composed of bilayer asymmetric split ring resonators（ASRR）that are in mirror-symmetry shape. It is demonstrated that the CD can get enhancement in the terahertz regime. Moreover,the CD can be further improved by modulating the asymmetry of ASRR. The enhanced CD effect in the terahertz regime has great potential applications in sensing, biomedical imaging, and molecular recognition.
文摘Interaction of procainamide hydrochloride（PAH） with human serum albumin（HSA） is of great significance in understanding the pharmacokinetic and pharmacodynamic mechanisms of the drug. Multi-spectroscopic techniques were used to investigate the binding mode of PAH to HSA and results revealed the presence of static type of quenching mechanism. The number of binding sites, binding constants and thermodynamic parameters were calculated. The results showed a spontaneous binding of PAH to HSA and hydrophobic interactions played a major role. In addition, the distance between PAH and the Trp–214 was estimated employing the F？rster＇s theory. Site marker competitive experiments indicated that the binding of PAH to HSA primarily took place in subdomain IIA（Sudlow＇s site I）. The influence of interference of some common metal ions on the binding of PAH to HSA was studied. Synchronous fluorescence spectra（SFS）, 3D fluorescence spectra and circular dichroism（CD） results indicated the conformational changes in the structure of HSA.
基金the China Triumph International Engineering Co. Ltd.(CTIEC),Shanghai,China,which offers generous financial support for this work
文摘The interconnection of polarization and phase in electromagnetic scattering process has attracted both fundamental and practical interest.Here we propose the principle and experimental demonstration of a scatteringcontrol mechanism based on the simultaneous control of polarization and phase via a continuously shaped planar metasurface.Under circularly polarized illumination,the scattering is redirected to off-specular direction,leading to significant reduction of the scattering cross section.Theoretical investigation shows that the underlying physical mechanism is the spin-dependent phase modulation in the anisotropic scattering process.Our approach would provide valuable guidance for the full control of electromagnetic wave for diverse applications.
基金Project supported by the National Natural Science Foundation of China(Grant No.11474215)。
文摘Circular dichroism(CD)has shown very interesting possibilities as a means to characterize the chiral signal of a chiral structure.Here,we theoretically demonstrated enhanced and tunable CD in the visible light regime using a composite structure consisting of a double-layer metal grating gaped by a dielectric waveguide layer.Based on the coupling of the waveguide modes and the localized plasmonic resonances,the CD could reach a maximum value as high as 0.52 at635 nm,which is four times higher than the CD value obtained in a conventional double-layer grating without the waveguide coupling effect.Furthermore,the spectral positions of the enhanced CD bands could be easily tuned by controlling the structural parameters.The proposed hybrid double-grating and waveguide structures could have potential applications in chiral selective imaging,sensing and spectroscopy,especially where the transmission measurement is required.
基金Project(08A080) supported by the Scientific Research Fund of Hunan Provincial Education Department,China
文摘Based on the starch hydrolysis reaction accelerated by microwave irradiation with α-amylase, the circular dichroism （CD） and secondary structure changes of α-amylase under the condition of microwave irradiation and water bath were studied by circular dichroism spectra. The results showed that, both the peak heights （at 2=193 nm） of the CD spectra of the samples treated by microwave irradiation and water bath reduced. The reduced rate by microwave irradiation ranged from 140% to 220%, while the reduced rate by water bath ranged from 60% to 140%. The peak of the sample treated by microwave irradiation for 60 min disappeared at λ=193 nm, while the sample showed a wake peak by water bath. The peak position by microwave irradiation emerged a blue shift in the range of 5-8 nm at λ=204 nm and λ=220 nm, while it emerged in the range of 3-5 nm by water bath. With time going on, the microwave irradiation and water bath have prompted the secondary structure of α-helix, β-sheet, β-turn and the mutual transformations of random coil, but the trends were different.
基金Project supported by the National Natural Science Foundation of China (Grant No. 61775233)。
文摘Researchers have long studied circular dichroism(CD) for its enormous prospects in life sciences. Many biomolecules have vibration modes in the terahertz region, and terahertz CD spectra are robust to detect biomolecular structures. However,few studies explore the terahertz CD spectra on even natural materials due to technical challenges in both fields. Here, we report a setup of home-built terahertz time-domain spectroscopy to measure the polarization states of terahertz waves.By carefully measuring the transmission Jones matrix, we obtain terahertz CD spectra of α-lactose tablets and D-glucose tablets. Our results show that the terahertz CD spectra are sensitive to vibrational motions in biochemical compounds,which will find wide applications in biosensing and biomedical diagnostics.
文摘In this study,circular dichroism(CD)and molecular dynamics(MD)simulation were used to investigate the thermal unfolding pathway of staphylococcal enterotoxin B(SEB)at temperatures of 298–371 and 298–500 K,and the relationship between the experimental and simulation results were explored.Our computational findings on the secondary structure of SEB showed that at room temperature,the CD spectroscopic results were highly consistent with the MD results.Moreover,under heating conditions,the changing trends of helix,sheet and random coil obtained by CD spectral fitting were highly consistent with those obtained by MD.In order to gain a deeper understanding of the thermal stability mechanism of SEB,the MD trajectories were analyzed in terms of root mean square deviation(RMSD),secondary structure assignment(SSA),radius of gyration(R_(g)),free energy surfaces(FES),solvent-accessible surface area(SASA),hydrogen bonds and salt bridges.The results showed that at low heating temperature,domain Ⅰ without loops(omitting the mobile loop region)mainly relied on hydrophobic interaction to maintain its thermal stability,whereas the thermal stability of domain Ⅱ was mainly controlled by salt bridges and hydrogen bonds.Under high heating temperature conditions,the hydrophobic interactions in domain Ⅰ without loops were destroyed and the secondary structure was almost completely lost,while domain Ⅱ could still rely on salt bridges as molecular staples to barely maintain the stability of the secondary structure.These results help us to understand the thermodynamic and kinetic mechanisms that maintain the thermal stability of SEB at the molecular level,and provide a direction for establishing safer and more effective food sterilization processes.
基金the University of Greenwich for financial support
文摘The effects of temperature,pH and long-term storage on the secondary structure and conformation changes of bovine haemoglobin（bHb） were studied using circular dichroism（CD） and ultraviolet-visible（UV-vis） spectroscopies.Neural network software was used to deconvolute the CD data to obtain the fractional content of the five secondary structures.The storage stability of bHb solutions in pH 6,7 and8 buffers was significantly higher at 4 ℃ than at 23 ℃ for the first 3 days.A complete denaturation of bHb was observed after 40 days irrespective of storage temperature or pH.The bHb solutions were also exposed to heating and cooling cycles between 25 and 65 ℃ and structural changes were followed by UVvis and CD spectroscopies.These experiments demonstrated that α-helix content of bHb decreased steadily with the increasing temperature above 35 ℃ at all pH values.The loss in a-helicity and gain in random coil conformations was pH-dependent and the greatest under alkaline conditions.Furthermore,there was minimal recovery of the secondary structure content upon cooling to 25 ℃.The use of bHb as a model drug is very common and this study elucidates the significance of storage and processing conditions on its stability.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.21673238 and 21771181)Youth Innovation Promotion Association CAS(No.2017345)Natural Science Foundation of Fujian Province(Nos.2017J06009 and2017J05036)
文摘In this text,we use inexpensive and natural amino acid,successfully obtained the asymmetric crystallization of three PTCs,[Ti6(OiPr)14(μ2-O)(μ3-O)2(D/L-pGlu)2](D-PTC-53;L-PTC-53;H2 pGlu=pyroglutamic acid)and[Ti6(OiPr)14(μ2-O)(μ3-O)2(D-pGlu)2][Ti6(OiPr)14((μ2-O)(μ3-O)2(L-pGlu)2](D,L-PTC-53).Interestingly,in situ lactamide reaction starting from glutamic acid to pyroglutamic acid was observed.In addition,the chirality features of these PTCs have been thoroughly discussed.The two enantiomers crys tallize in chiral P21 space group.The optically pure pGlu ligands transform its chirality to the inorganic titanium oxo clusters.As a result,the stack of these inorganic clusters generates homochiral helical chains along the characteristic axial direction.Apart from the microscopic structural analysis,the macroscopic solid-state samples exhibit unusual strong circular dichroism(CD)signals,further verified the homochiral feature of the enantiomers.
基金supported by the National Natural Science Foundation of China (Nos. 21471099, 21601123)
文摘Chiral mesoporous silica ribbons and rods with inversed handedness have been synthesized with the same enantio pure N-acylaminoacidat temperatures of 0℃and 20℃ respectively. With involving Cu^(2+)and meso-tetra(4-sulfonatophenyl)porphyrin(TPPS) as probes, ribbons and rods revealed opposite signals in diffuse-reflectance circular dichroism(DRCD) spectra, indicating the existence of inversed supramolecular chiral imprintings through helical stacking of amphiphiles. The structural evolution was systematically studied by the freeze-dried products sampled at different time after the addition of silica precursors. The H-bonding-depended molecular orientation probably controls the chiral sense upon forming chiral molecular stacking, which would be the origin of such handedness inversion
文摘Magnetic field-induced orientation of a chiral side chain liquid crystalline polyacrylate(P-11) was studied by using IR dichroism. For the investigated P-11, it has been shown thatthe magnetic alignment takes place over the entire temperature range between its meltingpoint and clearing point and the orientation level is strongly temperature-dependent, thedevelopment with time of the magnetic orieatation follows an exponeotial-type relation,and the smectic phase state influences the thermal relaxation process in the absence of themagnetic field.
基金Project supported by the National Key Research and Development Program of China (Grant Nos. 2022YFA1403203 and 2021YFA1600201)the National Natural Science Foundation of China (Grant No. 12274414)the Basic Research Program of the Chinese Academy of Sciences Based on Major Scientific Infrastructures (Contract No. JZHKYPT-2021-08)。
文摘Perpendicular optical reversal of the linear dichroism transition has promising applications in polarization-sensitive optoelectronic devices. We perform a systematical study on the in-plane optical anisotropy of quasi-one-dimensional PdBr_(2) by using combined measurements of the angle-resolved polarized Raman spectroscopy(ARPRS) and anisotropic optical absorption spectrum. The analyses of ARPRS data validate the anisotropic Raman properties of the PdBr_(2) flake.And anisotropic optical absorption spectrum of PdBr_(2) nanoflake demonstrates distinct optical linear dichroism reversal. Photodetector constructed by PdBr_(2) nanowire exhibits high responsivity of 747 A·W^(-1) and specific detectivity of 5.8×10^(12) Jones. And the photodetector demonstrates prominent polarization-sensitive photoresponsivity under 405-nm light irradiation with large photocurrent anisotropy ratio of 1.56, which is superior to those of most of previously reported quasi-one-dimensional counterparts. Our study offers fundamental insights into the strong optical anisotropy exhibited by PdBr_(2), establishing it as a promising candidate for miniaturization and integration trends of polarization-related applications.
基金Project supported by the National Key R&D Program of China(Grant No.2016YFA0301300)the Fundamental Research Funds for the Central Universities,China(Grant No.2019XD-A09)the National Natural Science Foundation of China(Grant No.11574035)。
文摘The circular dichroism(CD) signal of a molecule is usually weak,however,a strong CD signal in optical spectrum is desirable because of its wide range of applications in biosensing,chiral photo detection,and chiral catalysis.In this work,we show that a strong chiral response can be obtained in a hybridized system consisting of an artificial chiral molecule and a nanorod in the strong coupling regime.The artificial chiral molecule is composed of six quantum dots in a helix assembly,and its CD signal arises from internal Coulomb interactions between quantum dots.The CD signal of the hybridized system is highly dependent on the Coulomb interactions and the strong coupling progress through the electromagnetic interactions.We use the coupled oscillator model to analyze strong coupling phenomenon and address that the strong coupling progress can amplify the CD signal.This work provides a scenario for designing new plasmonic nanostructures with a strong chiral optical response.
文摘Electron magnetic circular dichroism opens a new door to explore magnetic properties by transmitted electrons in the transmission electron microscope. However, obtaining quantitative magnetic parameters, such as spin and orbital magnetic moment with element-specificity, goes a long way along with the development and improvement of this technique both in theoretical and experimental aspects. In this review, we will give a detailed description of the quantitative electron magnetic circular dichroism（EMCD） technique to measure magnetic parameters with spin-specificity, element-specificity,site-specificity, and orbital-spin-specificity. The discussion completely contains the procedures from raw experimental data acquisition to final magnetic parameters, together with the related custom code we have developed.
基金the National Natural Science Foundation of China，the 'Chun Hui' Plan of Chinese Ministry Education，the Scientific Research Foundation of Education Department of Yunnan Province，the Youth Program of Yunnan Province，the Chemistry of Key Construction Disciplines for Master Degree Program in Yunnan，the Educational Reform Program of Honghe University，the General Program of Yunnan Provincial Education Departmen
