Liquid-liquid phase separation(LLPS)of proteins and nucleic acids is a common phenomenon in cells that underlies the formation of membraneless organelles.Although the macroscopic behavior of biomolecular coacervates h...Liquid-liquid phase separation(LLPS)of proteins and nucleic acids is a common phenomenon in cells that underlies the formation of membraneless organelles.Although the macroscopic behavior of biomolecular coacervates has been elucidated by microscopy,the detailed dynamic properties of proteins/peptides during the LLPS process remain poorly characterized.Here,site-directed spin labeling-electron paramagnetic resonance(SDSL-EPR)spectroscopy was employed to characterize the dynamic properties of a minimal model LLPS system consisting of positively charged peptides and RNA.The degree of phase separation,indicated by broadening of the EPR spectrum of the spin-labeled peptide due to slow molecular tumbling,was monitored by EPR.In addition,three distinct populations with varying molecular motion during LLPS,featuring different spectral lineshapes,were identified.These populations included a fast motion component(Ⅰ),a slower motion component(Ⅱ)associated with peptides in the dispersed phase and an immobile component(Ⅲ)observed in the dense phase.With gradual titration of the peptides to RNA,the EPR spectrum gradually shifted,refiecting changes in the populations of the components.Together,SDSL-EPR method not only provides new insights into the dynamic behavior of biomolecules during LLPS,but also offers a sensitive method for biomolecular phase separation processes at the molecular level.展开更多
Perturbation theory on optical ac stark effect is applied to study the NMR spectroscopy in paramagnetic systems. Application of the circularly or linearly polarized optical field would lead to shifts in the NMR line, ...Perturbation theory on optical ac stark effect is applied to study the NMR spectroscopy in paramagnetic systems. Application of the circularly or linearly polarized optical field would lead to shifts in the NMR line, which is proportional to the laser intensity and the induced polarizability tensors by hyperfine interaction.展开更多
This work revisits the temperature dependence of^(1)H paramagnetic shift in nickelocene as a potential nuclear magnetic resonance(NMR)thermometer under fast magic angle spinning(MAS)rate.Surprisingly,an abnormal tempe...This work revisits the temperature dependence of^(1)H paramagnetic shift in nickelocene as a potential nuclear magnetic resonance(NMR)thermometer under fast magic angle spinning(MAS)rate.Surprisingly,an abnormal temperature dependence of^(1)H paramagnetic shift has been observed.In addition to a 1/T dependence term,a 1/T^(2)dependence term must be included to correctly describe the curvature behavior of the δ^(1)H-T correlation under fast MAS rate.展开更多
The effects of Fe2O3 content on the microstructure and mechanical properties of the CaO-Al2O3-SiO2 system were investigated by differential thermal analysis（DTA）, X-ray diffraction（XRD）, scanning electron microsc...The effects of Fe2O3 content on the microstructure and mechanical properties of the CaO-Al2O3-SiO2 system were investigated by differential thermal analysis（DTA）, X-ray diffraction（XRD）, scanning electron microscopy（SEM）, electron spin resonance（ESR）, and Mssbauer spectroscopy. The results show that the addition of Fe2O3 does not affect the main crystalline phase in the prepared glasses, but it reduces the crystallisation peak temperature, increases the crystallisation activation energy, and reduces the crystal granularity. The ESR results indicate that Fe2O3 can promote crystallization, as it leads to the phase separation of the CaO-Al2O3-SiO2 system due to axial distortion. Moreover, Fe2O3 alters the network structure of the CaO-Al2O3-SiO2 system, allowing Fe3＋ to enter octahedral sites that exhibit higher symmetry than tetrahedral sites. All of these factors are favourable to increasing the bending strength. The Mssbauer results reveal that there are two types of coordination for both Fe3＋ and Fe2＋ and the bending strength of the CaO-Al2O3-SiO2 system increases with the amount of six-coordinate Fe3＋. The increasing interaction between Fe3＋ and Fe2＋ can also enhance the bending strength of the CaO-Al2O3-SiO2 system. The microhardness of the CaO-Al2O3-SiO2 system was determined to be HV 896.9 and the bending strength to be 217 MPa under the heat treatment conditions of nucleation temperature of 700 °C and nucleation time of 2 h, crystallization temperature of 910 °C and crystallization time of 3 h.展开更多
The development of organic frameworks with radical skeletons is desired.In this study,we report the development of a novel two-dimensional radical halogen-bonded organic framework(XOF).The radical monomer,benzimidazol...The development of organic frameworks with radical skeletons is desired.In this study,we report the development of a novel two-dimensional radical halogen-bonded organic framework(XOF).The radical monomer,benzimidazole triphenylmethyl(BTTM),was synthesized through the coupling of TTM radicals with benzimidazole.Initially,the benzimidazole units were coordinated with Ag^(+)ions to create a[N···Ag···N]^(+)framework.Subsequently,the addition of iodine led to the in situ replacement of Ag^(+)with I^(+)ions,forming[N···I···N]^(+)linkers and resulting in the creation of the XOF structure.The resulting XOF-HBTTM and XOF-BTTM structures demonstrated good-crystallinity,confirmed by PXRD,HR-TEM,SEAD,and SAXS analyses.EPR measurements confirmed the preservation of radical characteristics within the XOF framework.Furthermore,SQUID measurements indicated that XOF-BTTM exhibits spin moments of S=1/2 at 2 K,with a saturated magnetization strength peaking at 4.10 emu/g,a notable enhancement compared to 1.87 emu/g for the BTTM monomer.This improvement in magnetism is attributed to the extended spin density distribution and the presence of[N···I···N]^(+)interactions,as suggested by DFT calculations.Additionally,the radical XOF-BTTM exhibited significantly enhanced electrical conductivity,reaching up to 1.30×10^(-4)S/cm,which is two orders of magnitude higher than that of XOF-HBTTM.This increased conductivity is linked to a reduced HOMO-LUMO gap,higher carrier density,and the incorporation of triphenylmethyl radicals within the framework.This research highlights the potential of benzimidazolyl motifs in constructing functional XOFs and advances our understanding of radical organic frameworks.展开更多
The formation and qualification of redox sites in transition metal oxides are always the active fields related to electronics, catalysis, sensors, and energy-storage units. In the present study, the temperature depend...The formation and qualification of redox sites in transition metal oxides are always the active fields related to electronics, catalysis, sensors, and energy-storage units. In the present study, the temperature dependence of thermal reduction of MoO3 was surveyed at the range of 350℃ to 750℃. Upon reduction, the formed redox species characterized by EPR spectroscopy are the MoVion and superoxide anion radical (O2-) when the reduction was induced at the optimal temperature of 300-350℃. When heating-up from 350℃, the EPR signals started to decline in amplitude. The signals in the range of 400-450℃ decreased to half of that at 350℃, and then to zero at ~600℃. Further treatment at even higher temperature or prolonged heating time at 500℃ caused more reduction and more free electrons were released to the MoO3 bulk, which results in a delocalized means similar to the antiferromagnetic coupling. These data herein are helpful to prepare and study the metal-oxide catalysts.展开更多
On account of excellent thermal physical properties, molten nitrates/nitrites salt has been widely employed in heat transfer and thermal storage industry, especially in concentrated solar power system. The thermal sta...On account of excellent thermal physical properties, molten nitrates/nitrites salt has been widely employed in heat transfer and thermal storage industry, especially in concentrated solar power system. The thermal stability study of molten nitrate/nitrite salt is of great importance for this system, and the decomposition mechanism is the most complicated part of it. The oxide species O2^2- and O2^- were considered as intermediates in molten KNO3-NaNO3 while hard to been detected in high temperature molten salt due to their trace concentration and low stability. In this work, the homemade in situ high temperature UV- Vis instrument and a commercial electron paramagnetic resonance were utilized to supply evidence for the formation of superoxide during a slow decomposition process of heat transfer salt （HTS, 53 wt% KNO3/40 wt% NaNO2/7 wt% NaNO3）. It is found that the superoxide is more easily generated from molten NaNO2 compared to NaNO3, and it has an absorption band at 420-440 nm in HTS which red shifts as temperature increases. The band is assigned to charge-transfer transition in NaO2 or KO2, responsible for the yellow color of the molten nitrate/nitrite salt. Furthermore, the UV absorption bands of molten NaNO2 and NANO3 are also obtained and compared with that of HTS.展开更多
Paramagnetic polymer microspheres were synthesized by the inverse suspension polymerizationmethod through polymerization of glycidyl methacrylate,ally glycidyl ether and methacrylamide onthe surface of silica‐coated ...Paramagnetic polymer microspheres were synthesized by the inverse suspension polymerizationmethod through polymerization of glycidyl methacrylate,ally glycidyl ether and methacrylamide onthe surface of silica‐coated Fe3O4nanoparticles using N,N’‐methylene‐bis(acrylamide)as across‐linking agent.Penicillin G acylase(PGA)was covalently immobilized on the surface of theparamagnetic microspheres by reacting the amino groups of the PGA molecules with the epoxygroups of the paramagnetic polymer microspheres.The effect of the SiO2coating and the amount ofparamagnetic Fe3O4nanoparticles on the initial activity and the operational stability of the immobilizedPGA was investigated.The results indicated that SiO2played an important role in the polymerization process and paramagnetic polymer microspheres with a SiO2‐coated Fe3O4nanoparticles mass content of7.5%are an optimal support material for PGA immobilization.Immobilized PGA on the paramagnetic polymer microspheres shows a high initial activity of430U/g(wet)and retains99%of its initial activity after recycling10times.Furthermore,immobilized PGA exhibits high thermal stability,pH stability and excellent reusability,which can be rapidly recycled by the aid of magnet.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of am...Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance （EPR） spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorurn was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly,from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses.展开更多
The electron paramagnetic resonance spectra of the chelate-based ionic liquid[C_(10)mim][Cu(F_6-acac)_3]in different solvents have been obtained at 120 K.It was found that the values of the^(63)Cu hyperfine coupling c...The electron paramagnetic resonance spectra of the chelate-based ionic liquid[C_(10)mim][Cu(F_6-acac)_3]in different solvents have been obtained at 120 K.It was found that the values of the^(63)Cu hyperfine coupling constants(A_(IL))of[C_(10)mim][Cu(F_6-acac)_3]in molecular solvents were from 116 to 180 Gauss.Moreover,the A_(IL)values in general ionic liquids are more complicated,and two sets of peaks can often be observed in their electron paramagnetic resonance spectra.Based on the Kamlet-Taft parameters,relative permittivity,the experimental results were discussed in terms of solvation effect and coordination of the solvents.展开更多
The compounds of iron substituted yttrium oxide systems have been prepared for the importance in the field of magneto electric materials.The polycrystalline samples of Y2–xFexO3–y(x=0.1,0.2) were prepared by solid-s...The compounds of iron substituted yttrium oxide systems have been prepared for the importance in the field of magneto electric materials.The polycrystalline samples of Y2–xFexO3–y(x=0.1,0.2) were prepared by solid-state reaction method.The single-phase formation of these compounds was confirmed by X-ray diffraction studies.It was found that the samples crystallized in tetragonal phase and the lattice parameters were calculated as a=1.0559(7) nm,c=1.0832(9) nm for Y1.9Fe0.1O3–y and a=1.0545(6) nm,c=1.0841(8)...展开更多
Deep-level defects in silicon carbide(SiC)are critical to the control of the performance of SiC electron devices.In this paper,deep-level defects in aluminumion-implanted 4H-SiC after high-temperature annealingwere st...Deep-level defects in silicon carbide(SiC)are critical to the control of the performance of SiC electron devices.In this paper,deep-level defects in aluminumion-implanted 4H-SiC after high-temperature annealingwere studied using electron paramagnetic resonance(EPR)spectroscopy at temperatures of 77 K and 123 K under different illumination conditions.Results showed that the main defect in aluminum ion-implanted 4H-SiC was the positively charged carbon vacancy(VC+),and the higher the doping concentration was,the higher was the concentration of VC+.Itwas found that the type of material defectwas independent of the doping concentration,although more VC+defects were detected during photoexcitation and at lower temperatures.These results should be helpful in the fundamental research of p-type 4H-SiC fabrication in accordance with functional device development.展开更多
The finite-temperature Pauli paramagnetic susceptibility of a three-dimensional ideal anyon gas obeying Haldane fractional exclusion statistics is studied analytically.Different from the result of an ideal Fermi gas,t...The finite-temperature Pauli paramagnetic susceptibility of a three-dimensional ideal anyon gas obeying Haldane fractional exclusion statistics is studied analytically.Different from the result of an ideal Fermi gas,the susceptibility of an ideal anyon gas depends on a statistical factor g in Haldane statistics model.The low-temperature and high-temperature behaviors of the susceptibility are investigated in detail.The Pauli paramagnetic susceptibility of the two-dimensional ideal anyons is also derived.It is found that the reciprocal of the susceptibility has the similar factorizable property which is exhibited in some thermodynamic quantities in two dimensions.展开更多
CdGd2 （WO4）4 -δ single crystal was grown using the Czochralski＇s method. The crystal structure was tetragonal seheelite with lattice parameters a = b = 0.5203 nm and c = 1. 1359 nm. There were vacancies of （WO4）...CdGd2 （WO4）4 -δ single crystal was grown using the Czochralski＇s method. The crystal structure was tetragonal seheelite with lattice parameters a = b = 0.5203 nm and c = 1. 1359 nm. There were vacancies of （WO4）^2- , therefore, there were some Gd^2＋ ions. Langevin paramagnetism and anisotropy were observed from the δ-T curves at room temperature. The susceptibility X//was 3.5018×10^-3, and X⊥ was 3.4403× 10^-2. The anisotropy was also observed in the electron spin resonance （ESR） experiments. The anisotropic Land6 factors were g//= 2. 1333 and g~ = 2. 8411. The direction of easy magnetization was in the α-b plane. Anisotropic paramagnetic Curie constants C//and C⊥ were not only related to macroscopic a that was observed through the experiment, but were also related to J⊥ and J//, which were the microscopic quantum numbers of the Gd^2＋ and Gd^3｜ ions. Based on the detailed analyses, the proportion of 36.8% of Gd^3＋ ions to 63.2% of Gd^2＋ ions in the Gd ions of the CdGd2（WO4）4-δ crystal was calculated, and δ was 0.638 in the single crystal.展开更多
The bauxite mineral obtained from Araku, Vishakapatnam district of Andhra Pradesh, India is used in the present work. Structural characterization was performed by X-ray diffraction (XRD). The mineral was found to be g...The bauxite mineral obtained from Araku, Vishakapatnam district of Andhra Pradesh, India is used in the present work. Structural characterization was performed by X-ray diffraction (XRD). The mineral was found to be gibbsite in phase. The transitional metal ions present were investigated using electron paramagnetic resonance (EPR) and optical absorption spectra. The EPR results suggest that Fe3+ has replaced Al3+ in the unit cell of bauxite. The optical absorption spectrum is due to Fe3+ which indicates that it is in distorted octahedral environment. The near-infrared (NIR) spectrum is due to water fundamentals and combination overtones, which confirm the formula of the compound. The impurities in the mineral are identified using spectroscopic techniques.展开更多
Quartz grains in contact with uranium-bearing minerals or fluids are characterized by natural radiation-induced paramagnetic defects （e. g. , oxygen vacancy centers, silicon vacancy centers, and peroxy radicals）, wh...Quartz grains in contact with uranium-bearing minerals or fluids are characterized by natural radiation-induced paramagnetic defects （e. g. , oxygen vacancy centers, silicon vacancy centers, and peroxy radicals）, which are amenable to study by electron paramagnetic resonance （EPR） spectroscopy. These natural radiation-induced paramagnetic defects, except for the oxygen vacancy centers, in quartz are concentrated in narrow bands penetrated by α particles： （1） in halos around U- and Th-bearing mineral inclusions and （2） in outer rims or along fractures. The second type of occurrence provides information about uranium mineralization or remobilization （i. e. , sources of uranium, timing of mineralization or remobilization, pathways of uranium-bearing fluids）. It can also be used to evaluate sedimentary basins for potential of uranium mineralization. In particular, the peroxy radicals are stable up to 800℃ and, therefore, are useful for evaluating metasedimentary rocks （e. g. , Paleoproterozoic metasedimentary sequences in the central zone of the North China craton）. EPR study of the Changcheng Series can focus on quartz from the sediment-basement unconformity and faults to determine the presence and types of natural radiation-induced paramagnetic defects, with which to identify and prioritize uranium anomalies. Other potential applications of natural radiation-induced paramagnetic defects in quartz include uranium-bearing hydrocarbon deposits in sedimentary basins. For example, the Junggar, Ordos, and Tarim basins in northwestern China all contain important oil and natural gas fields and are well known for elevated uranium concentrations, including economic sandstone-hosted uranium deposits. Therefore, systematic studies on the distribution of natural radiation-induced paramagnetic defects in quartz from host sedimentary sequences are expected to provide information about the migration of oil and natural gas in those basins.展开更多
FAMn:PbI<sub>3</sub> perovskite films were synthesized and probed mainly through electron spin resonance (ESR) spectroscopy. FAMn:PbI<sub>3</sub> with low (~1%) Mn concentration showed a hyperf...FAMn:PbI<sub>3</sub> perovskite films were synthesized and probed mainly through electron spin resonance (ESR) spectroscopy. FAMn:PbI<sub>3</sub> with low (~1%) Mn concentration showed a hyperfine sextet line originated from Mn<sup>++</sup> ions. FAMn:PbI<sub>3</sub> with high (10%) Mn concentration showed broad resonance (~500 G peak-to-peak linewidth). However, after bombardment of FAMn:PbI<sub>3</sub> with high Mn concentration by focused ion beams (FIB), a sharp ESR peak appeared. The peak-to-peak linewidth (ΔH<sub>pp</sub>) was ~8 G regardless of the temperature. The FIB-induced defect showed Curie behavior at low temperatures (5 K - 50 K), which indicates the presence of localized electrons at the defect sites at low temperatures. The g-value increased from g = 2.0002 to 2.0016 as the temperature increased from 5 K to 50 K. Together with the ongoing search for electron spin echo (ESE), this could potentially provide a platform for realizing magnetic bits, information storage, and increased manipulation speed.展开更多
The electron paramagnetic resonance (EPR) parameters (zero-Geld splitting Dand g factors g_‖, g_⊥) of Cr~(4+) ions in Ca_2 GeO_4 crystals have been calculated from thecomplete high-order perturbation formulas of EPR...The electron paramagnetic resonance (EPR) parameters (zero-Geld splitting Dand g factors g_‖, g_⊥) of Cr~(4+) ions in Ca_2 GeO_4 crystals have been calculated from thecomplete high-order perturbation formulas of EPR parameters for a 3d~2 ion in trigonal MX_4clusters. In these formulas, in addition to the contributions to EPR parameters from the widely usedcrystal-field (CF) mechanism, the contributions from the charge-transfer (CT) mechanism (which areoften neglected) are included. From the calculations, it is found that for the high valence state3d~n ions in crystals, the reasonable explanation of EPR parameters (in particular, the g factors)should take both the CF and CT mechanisms into account.展开更多
We report a new design of microwave source for X-band electron paramagnetic resonance spectrometer.The microwave source is equipped with a digital automatic frequency control circuit.The parameters of the digital auto...We report a new design of microwave source for X-band electron paramagnetic resonance spectrometer.The microwave source is equipped with a digital automatic frequency control circuit.The parameters of the digital automatic frequency control circuit can be flexibly configured for different experimental conditions,such as the input powers or the quality factors of the resonator.The configurability makes the microwave source universally compatible and greatly extends its application.To demonstrate the ability of adapting to various experimental conditions,the microwave source is tested by varying the input powers and the quality factors of the resonator.A satisfactory phase noise as low as-135 d Bc/Hz at 100-k Hz offset from the center frequency is achieved,due to the use of a phase-locked dielectric resonator oscillator and a direct digital synthesizer.Continuous-wave electron paramagnetic resonance experiments are conducted to examine the performance of the microwave source.The outstanding performance shows a prospect of wide applications of the microwave source in numerous fields of science.展开更多
Electron paramagnetic resonance （EPR） and optical absorption studies were carried out at room temperature on copper doped mixed alkali cadmium phosphate （LiNaCdP） glasses to understand the nature and symmetry of d...Electron paramagnetic resonance （EPR） and optical absorption studies were carried out at room temperature on copper doped mixed alkali cadmium phosphate （LiNaCdP） glasses to understand the nature and symmetry of dopant. Three samples with varying concentrations of alkali ions have been prepared. The spin Harniltonian parameters obtained from room temperature EPR spectra are： gli=2.437, 9⊥=2.096, A‖=117×10-4 cm-1, A⊥=26×10-4 cm-1 for LiNaCdP1, g‖=2.441, g⊥=2.088, A‖=121×10-4 cm-1, A⊥=25×10-4 cm-1 for LiNaCdP2and g‖=2.433,g⊥=2.096, A‖=125×10 4cm-1, A⊥=32×10-4cm-1 for LiNaCdP3. TheseEPR results indicate that the dopant Cu2＋ ion enters the glass matrix into a tetragonally elongated octahedral site. The bonding parameters evaluated by correlating optical and EPR data suggest that bonding between the central metal ion and ligands is partially covalent. The mixed alkali effect in cadmium phosphate glasses was reported.展开更多
基金supported by the National Natural Science Foundation of China(No.21927814)the National Key Research and Development Program of China(Nos.2019YFA0405600,2019YFA0706900,2021YFA1200104,2022YFC3400500)+2 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(Nos.XDB0540200,XDB37040201)Plans for Major Provincial Science&Technology Projects(No.202303a07020004)the Youth Innovation Promotion Association,CAS(No.2022455)。
文摘Liquid-liquid phase separation(LLPS)of proteins and nucleic acids is a common phenomenon in cells that underlies the formation of membraneless organelles.Although the macroscopic behavior of biomolecular coacervates has been elucidated by microscopy,the detailed dynamic properties of proteins/peptides during the LLPS process remain poorly characterized.Here,site-directed spin labeling-electron paramagnetic resonance(SDSL-EPR)spectroscopy was employed to characterize the dynamic properties of a minimal model LLPS system consisting of positively charged peptides and RNA.The degree of phase separation,indicated by broadening of the EPR spectrum of the spin-labeled peptide due to slow molecular tumbling,was monitored by EPR.In addition,three distinct populations with varying molecular motion during LLPS,featuring different spectral lineshapes,were identified.These populations included a fast motion component(Ⅰ),a slower motion component(Ⅱ)associated with peptides in the dispersed phase and an immobile component(Ⅲ)observed in the dense phase.With gradual titration of the peptides to RNA,the EPR spectrum gradually shifted,refiecting changes in the populations of the components.Together,SDSL-EPR method not only provides new insights into the dynamic behavior of biomolecules during LLPS,but also offers a sensitive method for biomolecular phase separation processes at the molecular level.
基金Project supported by the National Natural Science Foundation of China (No. 29873043)the Ph. D. Foundation of Education ministry of China
文摘Perturbation theory on optical ac stark effect is applied to study the NMR spectroscopy in paramagnetic systems. Application of the circularly or linearly polarized optical field would lead to shifts in the NMR line, which is proportional to the laser intensity and the induced polarizability tensors by hyperfine interaction.
基金supported by grants from the National Natural Science Foundation of China(Nos.22172049,22272055).
文摘This work revisits the temperature dependence of^(1)H paramagnetic shift in nickelocene as a potential nuclear magnetic resonance(NMR)thermometer under fast magic angle spinning(MAS)rate.Surprisingly,an abnormal temperature dependence of^(1)H paramagnetic shift has been observed.In addition to a 1/T dependence term,a 1/T^(2)dependence term must be included to correctly describe the curvature behavior of the δ^(1)H-T correlation under fast MAS rate.
基金Project(50974090)supported by the National Natural Science Foundation of ChinaProjects(JCYJ20140418182819155,JCYJ20130329113849606)supported by the Shenzhen Dedicated Funding of Strategic Emerging Industry Development Program,China
文摘The effects of Fe2O3 content on the microstructure and mechanical properties of the CaO-Al2O3-SiO2 system were investigated by differential thermal analysis（DTA）, X-ray diffraction（XRD）, scanning electron microscopy（SEM）, electron spin resonance（ESR）, and Mssbauer spectroscopy. The results show that the addition of Fe2O3 does not affect the main crystalline phase in the prepared glasses, but it reduces the crystallisation peak temperature, increases the crystallisation activation energy, and reduces the crystal granularity. The ESR results indicate that Fe2O3 can promote crystallization, as it leads to the phase separation of the CaO-Al2O3-SiO2 system due to axial distortion. Moreover, Fe2O3 alters the network structure of the CaO-Al2O3-SiO2 system, allowing Fe3＋ to enter octahedral sites that exhibit higher symmetry than tetrahedral sites. All of these factors are favourable to increasing the bending strength. The Mssbauer results reveal that there are two types of coordination for both Fe3＋ and Fe2＋ and the bending strength of the CaO-Al2O3-SiO2 system increases with the amount of six-coordinate Fe3＋. The increasing interaction between Fe3＋ and Fe2＋ can also enhance the bending strength of the CaO-Al2O3-SiO2 system. The microhardness of the CaO-Al2O3-SiO2 system was determined to be HV 896.9 and the bending strength to be 217 MPa under the heat treatment conditions of nucleation temperature of 700 °C and nucleation time of 2 h, crystallization temperature of 910 °C and crystallization time of 3 h.
基金supported by National Natural Science Foundation of China(Nos.22371218,21702153,52270070 and21801194)Natural Science Foundation of Zhejiang Province(No.LR22B020001)+1 种基金Wuhan Science and Technology Bureau(No.whkxjsj009)the support of the Core Facility of Wuhan University and the Large-scale Instrument and Equipment Sharing Foundation of Wuhan University。
文摘The development of organic frameworks with radical skeletons is desired.In this study,we report the development of a novel two-dimensional radical halogen-bonded organic framework(XOF).The radical monomer,benzimidazole triphenylmethyl(BTTM),was synthesized through the coupling of TTM radicals with benzimidazole.Initially,the benzimidazole units were coordinated with Ag^(+)ions to create a[N···Ag···N]^(+)framework.Subsequently,the addition of iodine led to the in situ replacement of Ag^(+)with I^(+)ions,forming[N···I···N]^(+)linkers and resulting in the creation of the XOF structure.The resulting XOF-HBTTM and XOF-BTTM structures demonstrated good-crystallinity,confirmed by PXRD,HR-TEM,SEAD,and SAXS analyses.EPR measurements confirmed the preservation of radical characteristics within the XOF framework.Furthermore,SQUID measurements indicated that XOF-BTTM exhibits spin moments of S=1/2 at 2 K,with a saturated magnetization strength peaking at 4.10 emu/g,a notable enhancement compared to 1.87 emu/g for the BTTM monomer.This improvement in magnetism is attributed to the extended spin density distribution and the presence of[N···I···N]^(+)interactions,as suggested by DFT calculations.Additionally,the radical XOF-BTTM exhibited significantly enhanced electrical conductivity,reaching up to 1.30×10^(-4)S/cm,which is two orders of magnitude higher than that of XOF-HBTTM.This increased conductivity is linked to a reduced HOMO-LUMO gap,higher carrier density,and the incorporation of triphenylmethyl radicals within the framework.This research highlights the potential of benzimidazolyl motifs in constructing functional XOFs and advances our understanding of radical organic frameworks.
基金supported by the National Key R&D Program of China(No.2018YFA0306600)AnHui Initiative in Quantum Information Technologies(No.AHY050000)
文摘The formation and qualification of redox sites in transition metal oxides are always the active fields related to electronics, catalysis, sensors, and energy-storage units. In the present study, the temperature dependence of thermal reduction of MoO3 was surveyed at the range of 350℃ to 750℃. Upon reduction, the formed redox species characterized by EPR spectroscopy are the MoVion and superoxide anion radical (O2-) when the reduction was induced at the optimal temperature of 300-350℃. When heating-up from 350℃, the EPR signals started to decline in amplitude. The signals in the range of 400-450℃ decreased to half of that at 350℃, and then to zero at ~600℃. Further treatment at even higher temperature or prolonged heating time at 500℃ caused more reduction and more free electrons were released to the MoO3 bulk, which results in a delocalized means similar to the antiferromagnetic coupling. These data herein are helpful to prepare and study the metal-oxide catalysts.
基金This work was supported by the ＂Strategic Priority Research Program, TMSR＂ of the Chinese Academy of Sciences （No.XD02002400）, the National Natural Science Foundation of China （No.51506214）, the Hundred Talents Program, CAS and Shanghai Pujiang Program.
文摘On account of excellent thermal physical properties, molten nitrates/nitrites salt has been widely employed in heat transfer and thermal storage industry, especially in concentrated solar power system. The thermal stability study of molten nitrate/nitrite salt is of great importance for this system, and the decomposition mechanism is the most complicated part of it. The oxide species O2^2- and O2^- were considered as intermediates in molten KNO3-NaNO3 while hard to been detected in high temperature molten salt due to their trace concentration and low stability. In this work, the homemade in situ high temperature UV- Vis instrument and a commercial electron paramagnetic resonance were utilized to supply evidence for the formation of superoxide during a slow decomposition process of heat transfer salt （HTS, 53 wt% KNO3/40 wt% NaNO2/7 wt% NaNO3）. It is found that the superoxide is more easily generated from molten NaNO2 compared to NaNO3, and it has an absorption band at 420-440 nm in HTS which red shifts as temperature increases. The band is assigned to charge-transfer transition in NaO2 or KO2, responsible for the yellow color of the molten nitrate/nitrite salt. Furthermore, the UV absorption bands of molten NaNO2 and NANO3 are also obtained and compared with that of HTS.
基金This work was supported by the National Natural Science Foundation of China(91545103)Shu Guang Project of Shanghai Municipal Education Commission and Shanghai Education Development Foundation(10SG30)the Fundamental Research Funds for the Central Universities(222201717003)~~
文摘Paramagnetic polymer microspheres were synthesized by the inverse suspension polymerizationmethod through polymerization of glycidyl methacrylate,ally glycidyl ether and methacrylamide onthe surface of silica‐coated Fe3O4nanoparticles using N,N’‐methylene‐bis(acrylamide)as across‐linking agent.Penicillin G acylase(PGA)was covalently immobilized on the surface of theparamagnetic microspheres by reacting the amino groups of the PGA molecules with the epoxygroups of the paramagnetic polymer microspheres.The effect of the SiO2coating and the amount ofparamagnetic Fe3O4nanoparticles on the initial activity and the operational stability of the immobilizedPGA was investigated.The results indicated that SiO2played an important role in the polymerization process and paramagnetic polymer microspheres with a SiO2‐coated Fe3O4nanoparticles mass content of7.5%are an optimal support material for PGA immobilization.Immobilized PGA on the paramagnetic polymer microspheres shows a high initial activity of430U/g(wet)and retains99%of its initial activity after recycling10times.Furthermore,immobilized PGA exhibits high thermal stability,pH stability and excellent reusability,which can be rapidly recycled by the aid of magnet.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
基金the National Natural Science Foundation of China （No.30371002）.
文摘Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance （EPR） spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorurn was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly,from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses.
基金supported by the National Natural Science Foundation,China(No.21573196)the Fundamental Research Funds for the Central Universities,Chinathe National High Technology Research and the National Natural Science Foundation,China(No.22073081)。
文摘The electron paramagnetic resonance spectra of the chelate-based ionic liquid[C_(10)mim][Cu(F_6-acac)_3]in different solvents have been obtained at 120 K.It was found that the values of the^(63)Cu hyperfine coupling constants(A_(IL))of[C_(10)mim][Cu(F_6-acac)_3]in molecular solvents were from 116 to 180 Gauss.Moreover,the A_(IL)values in general ionic liquids are more complicated,and two sets of peaks can often be observed in their electron paramagnetic resonance spectra.Based on the Kamlet-Taft parameters,relative permittivity,the experimental results were discussed in terms of solvation effect and coordination of the solvents.
文摘The compounds of iron substituted yttrium oxide systems have been prepared for the importance in the field of magneto electric materials.The polycrystalline samples of Y2–xFexO3–y(x=0.1,0.2) were prepared by solid-state reaction method.The single-phase formation of these compounds was confirmed by X-ray diffraction studies.It was found that the samples crystallized in tetragonal phase and the lattice parameters were calculated as a=1.0559(7) nm,c=1.0832(9) nm for Y1.9Fe0.1O3–y and a=1.0545(6) nm,c=1.0841(8)...
基金supported by the National Natural Science Foundation of China (No. 51575389, 51761135106)the National Key Research and Development Program of China (2016YFB1102203)+2 种基金the State Key Laboratory of Precision Measurement Technology and Instruments (Pilt1705)the ‘111’ Project by the State Administration of Foreign Experts Affairsthe Ministry of Education of China (Grant No. B07014)
文摘Deep-level defects in silicon carbide(SiC)are critical to the control of the performance of SiC electron devices.In this paper,deep-level defects in aluminumion-implanted 4H-SiC after high-temperature annealingwere studied using electron paramagnetic resonance(EPR)spectroscopy at temperatures of 77 K and 123 K under different illumination conditions.Results showed that the main defect in aluminum ion-implanted 4H-SiC was the positively charged carbon vacancy(VC+),and the higher the doping concentration was,the higher was the concentration of VC+.Itwas found that the type of material defectwas independent of the doping concentration,although more VC+defects were detected during photoexcitation and at lower temperatures.These results should be helpful in the fundamental research of p-type 4H-SiC fabrication in accordance with functional device development.
基金Supported by the National Natural Science Foundation of China under Grant Nos. 11275082 and 11178001
文摘The finite-temperature Pauli paramagnetic susceptibility of a three-dimensional ideal anyon gas obeying Haldane fractional exclusion statistics is studied analytically.Different from the result of an ideal Fermi gas,the susceptibility of an ideal anyon gas depends on a statistical factor g in Haldane statistics model.The low-temperature and high-temperature behaviors of the susceptibility are investigated in detail.The Pauli paramagnetic susceptibility of the two-dimensional ideal anyons is also derived.It is found that the reciprocal of the susceptibility has the similar factorizable property which is exhibited in some thermodynamic quantities in two dimensions.
基金Project supported by the National Natural Science Foundation of China (69977005)
文摘CdGd2 （WO4）4 -δ single crystal was grown using the Czochralski＇s method. The crystal structure was tetragonal seheelite with lattice parameters a = b = 0.5203 nm and c = 1. 1359 nm. There were vacancies of （WO4）^2- , therefore, there were some Gd^2＋ ions. Langevin paramagnetism and anisotropy were observed from the δ-T curves at room temperature. The susceptibility X//was 3.5018×10^-3, and X⊥ was 3.4403× 10^-2. The anisotropy was also observed in the electron spin resonance （ESR） experiments. The anisotropic Land6 factors were g//= 2. 1333 and g~ = 2. 8411. The direction of easy magnetization was in the α-b plane. Anisotropic paramagnetic Curie constants C//and C⊥ were not only related to macroscopic a that was observed through the experiment, but were also related to J⊥ and J//, which were the microscopic quantum numbers of the Gd^2＋ and Gd^3｜ ions. Based on the detailed analyses, the proportion of 36.8% of Gd^3＋ ions to 63.2% of Gd^2＋ ions in the Gd ions of the CdGd2（WO4）4-δ crystal was calculated, and δ was 0.638 in the single crystal.
文摘The bauxite mineral obtained from Araku, Vishakapatnam district of Andhra Pradesh, India is used in the present work. Structural characterization was performed by X-ray diffraction (XRD). The mineral was found to be gibbsite in phase. The transitional metal ions present were investigated using electron paramagnetic resonance (EPR) and optical absorption spectra. The EPR results suggest that Fe3+ has replaced Al3+ in the unit cell of bauxite. The optical absorption spectrum is due to Fe3+ which indicates that it is in distorted octahedral environment. The near-infrared (NIR) spectrum is due to water fundamentals and combination overtones, which confirm the formula of the compound. The impurities in the mineral are identified using spectroscopic techniques.
基金This paper is supported by the Natural Science and Engineering Re-search Council (NSERC) of Canada and the Cameco Corporation .
文摘Quartz grains in contact with uranium-bearing minerals or fluids are characterized by natural radiation-induced paramagnetic defects （e. g. , oxygen vacancy centers, silicon vacancy centers, and peroxy radicals）, which are amenable to study by electron paramagnetic resonance （EPR） spectroscopy. These natural radiation-induced paramagnetic defects, except for the oxygen vacancy centers, in quartz are concentrated in narrow bands penetrated by α particles： （1） in halos around U- and Th-bearing mineral inclusions and （2） in outer rims or along fractures. The second type of occurrence provides information about uranium mineralization or remobilization （i. e. , sources of uranium, timing of mineralization or remobilization, pathways of uranium-bearing fluids）. It can also be used to evaluate sedimentary basins for potential of uranium mineralization. In particular, the peroxy radicals are stable up to 800℃ and, therefore, are useful for evaluating metasedimentary rocks （e. g. , Paleoproterozoic metasedimentary sequences in the central zone of the North China craton）. EPR study of the Changcheng Series can focus on quartz from the sediment-basement unconformity and faults to determine the presence and types of natural radiation-induced paramagnetic defects, with which to identify and prioritize uranium anomalies. Other potential applications of natural radiation-induced paramagnetic defects in quartz include uranium-bearing hydrocarbon deposits in sedimentary basins. For example, the Junggar, Ordos, and Tarim basins in northwestern China all contain important oil and natural gas fields and are well known for elevated uranium concentrations, including economic sandstone-hosted uranium deposits. Therefore, systematic studies on the distribution of natural radiation-induced paramagnetic defects in quartz from host sedimentary sequences are expected to provide information about the migration of oil and natural gas in those basins.
文摘FAMn:PbI<sub>3</sub> perovskite films were synthesized and probed mainly through electron spin resonance (ESR) spectroscopy. FAMn:PbI<sub>3</sub> with low (~1%) Mn concentration showed a hyperfine sextet line originated from Mn<sup>++</sup> ions. FAMn:PbI<sub>3</sub> with high (10%) Mn concentration showed broad resonance (~500 G peak-to-peak linewidth). However, after bombardment of FAMn:PbI<sub>3</sub> with high Mn concentration by focused ion beams (FIB), a sharp ESR peak appeared. The peak-to-peak linewidth (ΔH<sub>pp</sub>) was ~8 G regardless of the temperature. The FIB-induced defect showed Curie behavior at low temperatures (5 K - 50 K), which indicates the presence of localized electrons at the defect sites at low temperatures. The g-value increased from g = 2.0002 to 2.0016 as the temperature increased from 5 K to 50 K. Together with the ongoing search for electron spin echo (ESE), this could potentially provide a platform for realizing magnetic bits, information storage, and increased manipulation speed.
文摘The electron paramagnetic resonance (EPR) parameters (zero-Geld splitting Dand g factors g_‖, g_⊥) of Cr~(4+) ions in Ca_2 GeO_4 crystals have been calculated from thecomplete high-order perturbation formulas of EPR parameters for a 3d~2 ion in trigonal MX_4clusters. In these formulas, in addition to the contributions to EPR parameters from the widely usedcrystal-field (CF) mechanism, the contributions from the charge-transfer (CT) mechanism (which areoften neglected) are included. From the calculations, it is found that for the high valence state3d~n ions in crystals, the reasonable explanation of EPR parameters (in particular, the g factors)should take both the CF and CT mechanisms into account.
基金Project supported by the Chinese Academy of Sciences(Grant Nos.XDC07000000 and GJJSTD20200001)Hefei Comprehensive National Science CenterYouth Innovation Promotion Association of Chinese Academy of Sciences for the support。
文摘We report a new design of microwave source for X-band electron paramagnetic resonance spectrometer.The microwave source is equipped with a digital automatic frequency control circuit.The parameters of the digital automatic frequency control circuit can be flexibly configured for different experimental conditions,such as the input powers or the quality factors of the resonator.The configurability makes the microwave source universally compatible and greatly extends its application.To demonstrate the ability of adapting to various experimental conditions,the microwave source is tested by varying the input powers and the quality factors of the resonator.A satisfactory phase noise as low as-135 d Bc/Hz at 100-k Hz offset from the center frequency is achieved,due to the use of a phase-locked dielectric resonator oscillator and a direct digital synthesizer.Continuous-wave electron paramagnetic resonance experiments are conducted to examine the performance of the microwave source.The outstanding performance shows a prospect of wide applications of the microwave source in numerous fields of science.
文摘Electron paramagnetic resonance （EPR） and optical absorption studies were carried out at room temperature on copper doped mixed alkali cadmium phosphate （LiNaCdP） glasses to understand the nature and symmetry of dopant. Three samples with varying concentrations of alkali ions have been prepared. The spin Harniltonian parameters obtained from room temperature EPR spectra are： gli=2.437, 9⊥=2.096, A‖=117×10-4 cm-1, A⊥=26×10-4 cm-1 for LiNaCdP1, g‖=2.441, g⊥=2.088, A‖=121×10-4 cm-1, A⊥=25×10-4 cm-1 for LiNaCdP2and g‖=2.433,g⊥=2.096, A‖=125×10 4cm-1, A⊥=32×10-4cm-1 for LiNaCdP3. TheseEPR results indicate that the dopant Cu2＋ ion enters the glass matrix into a tetragonally elongated octahedral site. The bonding parameters evaluated by correlating optical and EPR data suggest that bonding between the central metal ion and ligands is partially covalent. The mixed alkali effect in cadmium phosphate glasses was reported.
