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
Objective This work examines the impact of external electric fields at terahertz(THz)frequencies on doublestranded deoxyribonucleic acid(dsDNA)systems adsorbed on Au(111)surfaces in aqueous environments.Methods The in...Objective This work examines the impact of external electric fields at terahertz(THz)frequencies on doublestranded deoxyribonucleic acid(dsDNA)systems adsorbed on Au(111)surfaces in aqueous environments.Methods The investigation utilizes a molecular dynamics(MD)approach at the atomic level and vibrational dynamics calculations using the GolDNA-Amber force field.Results The results reveal that the sugar-phosphate backbone of the DNA exhibits reduced adherence to the gold surface,while the side chains display a stronger affinity.When subjecting the hydrated DNA strands to an electric field with frequencies up to 10 THz,peak intensities of vibrational dynamic density(VDoS)are observed at five different frequencies.Moreover,the strong electric field causes hydrogen bonds in the DNA within the slit to break.The sensitivity to the electric field is particularly pronounced at 8.8 THz and 9.6 THz,with different vibrational modes observed at varying electric field strengths.Conclusion These findings contribute to an enhanced understanding of the molecular organization of gold-plated charged biological interfaces.展开更多
A recently released XMM-Newton note revealed a significant calibration issue between nuclear spectroscopic telescope array(NuSTAR)and XMM-Newton European Photon Imaging Camera(EPIC)and provided an empirical correction...A recently released XMM-Newton note revealed a significant calibration issue between nuclear spectroscopic telescope array(NuSTAR)and XMM-Newton European Photon Imaging Camera(EPIC)and provided an empirical correction to the EPIC effective area.To quantify the bias caused by the calibration issue in the joint analysis of XMM-NuSTAR spectra and verify the effectiveness of the correction,in this work,we perform joint-fitting of the NuSTAR and EPIC-pn spectra for a large sample of 104 observation pairs of 44 X-ray bright active galactic nuclei(AGN).The spectra were extracted after requiring perfect simultaneity between the XMM-Newton and NuSTAR exposures(merging good time intervals(GTIs)from two missions)to avoid bias due to the rapid spectral variability of the AGN.Before the correction,the EPIC-pn spectra are systematically harder than the corresponding NuSTAR spectra by■subsequently yielding significantly underestimated cutoff energy E_(cut)and the strength of reflection component R when performing joint-fitting.We confirm that the correction is highly effective and can commendably erase the discrepancy in best-fitΓ,E_(cut),and R.We thus urge the community to apply the correction when joint-fitting XMM-NuSTAR spectra,but note that the correction is limited to 3–12 keV and therefore not applicable when the soft X-ray band data are included.Besides,we show that as merging GTIs from two missions would cause severe loss of NuSTAR net exposure time,in many cases,joint-fitting yields no advantage compared with utilizing NuSTAR data alone.Finally,We present a technical note on filtering periods of high background flares for XMM-Newton EPIC-pn exposures in the small window(SW)mode.展开更多
Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as ...Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.展开更多
Two kinds of UV curable polyurethane acrylate oligomers （PUPA and PUCA） were synthesized via the addition reaction between isophorone diisocyanate （IPDI） and polyethylene glycol monoacrylate （PEA6） or polycaprol...Two kinds of UV curable polyurethane acrylate oligomers （PUPA and PUCA） were synthesized via the addition reaction between isophorone diisocyanate （IPDI） and polyethylene glycol monoacrylate （PEA6） or polycaprolactone modified hydroxyethyl acrylate （PCLA2）. The structures of PUPA and PUCA were characterized by Fourier transform infrared spectroscopy （FT-IR）, IH nuclear magnetic resonance （^H NMR）, gel permeation chromatography （GPC） and differential scanning calorimeter （DSC）, and the thermal stability and dynamic mechanical thermal properties of their cured films were measured by thermogravimetric analysis （TGA） and dynamic mechanical analysis （DMA）, respectively. The viscosity of the oligomers and mechanical properties of the cured films were also studied. The results show that both oligomers have narrow molecular weight distribution. The viscosity of PUPA is 2.310 Pa.s at 25 ℃, while that of PUCA is： up to 3.980 Pa-s. The UV cured PUPA and PUCA films have homogeneous phase structure, and the PUCA film shows higher glass transition temperature and storage modulus. Furthermore, the PUCA film possesses better mechanical properties than PUPA, while the latter shows better alkali resistance.展开更多
A novel chelating resin with sulfonic group was synthesized by chemical modification of D401 resin with sulphonation reaction and characterized by FT-IR spectrometry. The adsorption properties of the novel chelating r...A novel chelating resin with sulfonic group was synthesized by chemical modification of D401 resin with sulphonation reaction and characterized by FT-IR spectrometry. The adsorption properties of the novel chelating resin for Pb2+ were studied by batch adsorption, and the adsorption process was analyzed from thermodynamics and kinetics aspects. The adsorption mechanism of Pb2+ on the modified D401 chelating resin was discussed by FT-IR spectrometry. Experimental results show that in the Pb2+ concentration range of 200-400 mg/L, the adsorption capacities of the modified D401 chelating resin for Pb2+ increase by 77%-129%, and Langmuir isothermal adsorption model is more suitable for the equilibrium adsorption data. Adsorption is an endothermic process that runs spontaneously. Kinetic analysis shows that the adsorption rate is mainly governed by liquid film diffusion. The best pH value under adsorption condition is 4-5. The saturated resin can be regenerated by 3 mol/L nitric acid, and the adsorption capacity remains stable after five consecutive adsorption-desorption cycles. The maximal static saturated adsorption capacity of the resin is 206 mg/g at 333 K in the Pb2+ concentration range of 200-400 mg/L. The modified D401 chelating resin is an efficient adsorbent for the removal of Pb2+ from its single-metal ion solution.展开更多
The precipitation performance and kinetics of gibbsite from sodium aluminate solution with different sodium oxalate concentrations as well as the corresponding influence mechanism of oxalate during the seed precipitat...The precipitation performance and kinetics of gibbsite from sodium aluminate solution with different sodium oxalate concentrations as well as the corresponding influence mechanism of oxalate during the seed precipitation process were systematically investigated by physicochemical properties test,using SEM and Raman spectra.As the concentration of sodium oxalate increases,both the precipitation rate and particle size of gibbsite decrease.The presence of sodium oxalate not only increases the viscosity of sodium aluminate solution,but also promotes the transformation of Al(OH)4^? to Al2O(OH)6^2?.The overall reaction rate constant decreases and the apparent activation energy of gibbsite increases with the increasing sodium oxalate concentration,the rate controlling step of which is chemical reaction.The needle-like sodium oxalate precipitates on the gibbsite crystals and covers the active Al(OH)3 seed sites,which leads to the lower precipitation rate and the finer particle size of gibbsite during the seed precipitation process.展开更多
Thin films of PrCoO3 were deposited on LaAlO3 substrates by pulsed laser deposition technique.X-ray diffraction result indicates that films are single phase and c-axis textured.To investigate the spin state transition...Thin films of PrCoO3 were deposited on LaAlO3 substrates by pulsed laser deposition technique.X-ray diffraction result indicates that films are single phase and c-axis textured.To investigate the spin state transition,Raman spectroscopy measurements were performed at different temperatures.The position of the Raman modes is found to increase while full width at half maximum(FWHM) of these modes is found to decrease with the decrease of temperature across spin state transition temperature(220 K) of PrCoO3.展开更多
Four types of common seaweeds(Laminaria japonica,Undaria pinnatifida,Porphyra haitanensis,and Gracilaria lemaneiformis) were examined to remove Cr(Ⅵ) ions from aqueous solution.The experimental parameters that affect...Four types of common seaweeds(Laminaria japonica,Undaria pinnatifida,Porphyra haitanensis,and Gracilaria lemaneiformis) were examined to remove Cr(Ⅵ) ions from aqueous solution.The experimental parameters that affected the biosorption process including pH,biomass dosage,contact time and temperature were investigated via batch experiments.The surface characteristics of seaweeds before and after Cr(Ⅵ) adsorption were studied with scanning electron microscopy and Fourier transform infrared spectroscopy.The results show that an initial solution with the pH of 1.0 is most favorable for Cr(Ⅵ) adsorption.Rapid adsorption is observed in the initial stage and adsorption equilibrium state is reached within 1 h.The adsorption efficiency by Porphyra haitanensis is the maximum among four types of seaweed powders,followed by Laminaria japonica and Undaria pinnatifida with biosorption efficiency up to 90%.The removal rate of Gracilaria lemaneiformis is less than 60%.The kinetic data obtained using the seaweeds are found to follow pseudo-second order kinetic model.Experimental sorption data adequately correlate with the Langmuir model.FTIR indicates that amino and carboxyl groups play an important role in the process of Cr(Ⅵ) adsorption and a large percentage of Cr(Ⅵ) ions are reduced by reductive groups on the surface of seaweeds.展开更多
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supported by a grant from National Defense Science and Technology Innovation Special Zone of China(02-ZT-008).
文摘Objective This work examines the impact of external electric fields at terahertz(THz)frequencies on doublestranded deoxyribonucleic acid(dsDNA)systems adsorbed on Au(111)surfaces in aqueous environments.Methods The investigation utilizes a molecular dynamics(MD)approach at the atomic level and vibrational dynamics calculations using the GolDNA-Amber force field.Results The results reveal that the sugar-phosphate backbone of the DNA exhibits reduced adherence to the gold surface,while the side chains display a stronger affinity.When subjecting the hydrated DNA strands to an electric field with frequencies up to 10 THz,peak intensities of vibrational dynamic density(VDoS)are observed at five different frequencies.Moreover,the strong electric field causes hydrogen bonds in the DNA within the slit to break.The sensitivity to the electric field is particularly pronounced at 8.8 THz and 9.6 THz,with different vibrational modes observed at varying electric field strengths.Conclusion These findings contribute to an enhanced understanding of the molecular organization of gold-plated charged biological interfaces.
基金supported by the National Natural Science Foundation of China(12033006,12192221,123B2042).
文摘A recently released XMM-Newton note revealed a significant calibration issue between nuclear spectroscopic telescope array(NuSTAR)and XMM-Newton European Photon Imaging Camera(EPIC)and provided an empirical correction to the EPIC effective area.To quantify the bias caused by the calibration issue in the joint analysis of XMM-NuSTAR spectra and verify the effectiveness of the correction,in this work,we perform joint-fitting of the NuSTAR and EPIC-pn spectra for a large sample of 104 observation pairs of 44 X-ray bright active galactic nuclei(AGN).The spectra were extracted after requiring perfect simultaneity between the XMM-Newton and NuSTAR exposures(merging good time intervals(GTIs)from two missions)to avoid bias due to the rapid spectral variability of the AGN.Before the correction,the EPIC-pn spectra are systematically harder than the corresponding NuSTAR spectra by■subsequently yielding significantly underestimated cutoff energy E_(cut)and the strength of reflection component R when performing joint-fitting.We confirm that the correction is highly effective and can commendably erase the discrepancy in best-fitΓ,E_(cut),and R.We thus urge the community to apply the correction when joint-fitting XMM-NuSTAR spectra,but note that the correction is limited to 3–12 keV and therefore not applicable when the soft X-ray band data are included.Besides,we show that as merging GTIs from two missions would cause severe loss of NuSTAR net exposure time,in many cases,joint-fitting yields no advantage compared with utilizing NuSTAR data alone.Finally,We present a technical note on filtering periods of high background flares for XMM-Newton EPIC-pn exposures in the small window(SW)mode.
基金the National Basic Research Development of China(2011CB936003)the National Natural Science Foundation of China(50971116)。
文摘Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.
基金Project(2007168303) supported by Guangdong-Hong Kong Technology Cooperation Funding
文摘Two kinds of UV curable polyurethane acrylate oligomers （PUPA and PUCA） were synthesized via the addition reaction between isophorone diisocyanate （IPDI） and polyethylene glycol monoacrylate （PEA6） or polycaprolactone modified hydroxyethyl acrylate （PCLA2）. The structures of PUPA and PUCA were characterized by Fourier transform infrared spectroscopy （FT-IR）, IH nuclear magnetic resonance （^H NMR）, gel permeation chromatography （GPC） and differential scanning calorimeter （DSC）, and the thermal stability and dynamic mechanical thermal properties of their cured films were measured by thermogravimetric analysis （TGA） and dynamic mechanical analysis （DMA）, respectively. The viscosity of the oligomers and mechanical properties of the cured films were also studied. The results show that both oligomers have narrow molecular weight distribution. The viscosity of PUPA is 2.310 Pa.s at 25 ℃, while that of PUCA is： up to 3.980 Pa-s. The UV cured PUPA and PUCA films have homogeneous phase structure, and the PUCA film shows higher glass transition temperature and storage modulus. Furthermore, the PUCA film possesses better mechanical properties than PUPA, while the latter shows better alkali resistance.
基金Project(708049) supported by the Important Item Cultivation Foundation of Scientific Innovation Project of Colleges and Universities of China
文摘A novel chelating resin with sulfonic group was synthesized by chemical modification of D401 resin with sulphonation reaction and characterized by FT-IR spectrometry. The adsorption properties of the novel chelating resin for Pb2+ were studied by batch adsorption, and the adsorption process was analyzed from thermodynamics and kinetics aspects. The adsorption mechanism of Pb2+ on the modified D401 chelating resin was discussed by FT-IR spectrometry. Experimental results show that in the Pb2+ concentration range of 200-400 mg/L, the adsorption capacities of the modified D401 chelating resin for Pb2+ increase by 77%-129%, and Langmuir isothermal adsorption model is more suitable for the equilibrium adsorption data. Adsorption is an endothermic process that runs spontaneously. Kinetic analysis shows that the adsorption rate is mainly governed by liquid film diffusion. The best pH value under adsorption condition is 4-5. The saturated resin can be regenerated by 3 mol/L nitric acid, and the adsorption capacity remains stable after five consecutive adsorption-desorption cycles. The maximal static saturated adsorption capacity of the resin is 206 mg/g at 333 K in the Pb2+ concentration range of 200-400 mg/L. The modified D401 chelating resin is an efficient adsorbent for the removal of Pb2+ from its single-metal ion solution.
基金Projects(51774079,51674075)supported by the National Natural Science Foundation of ChinaProject(N182508026)supported by the Fundamental Research Funds for the Central Universities,China。
文摘The precipitation performance and kinetics of gibbsite from sodium aluminate solution with different sodium oxalate concentrations as well as the corresponding influence mechanism of oxalate during the seed precipitation process were systematically investigated by physicochemical properties test,using SEM and Raman spectra.As the concentration of sodium oxalate increases,both the precipitation rate and particle size of gibbsite decrease.The presence of sodium oxalate not only increases the viscosity of sodium aluminate solution,but also promotes the transformation of Al(OH)4^? to Al2O(OH)6^2?.The overall reaction rate constant decreases and the apparent activation energy of gibbsite increases with the increasing sodium oxalate concentration,the rate controlling step of which is chemical reaction.The needle-like sodium oxalate precipitates on the gibbsite crystals and covers the active Al(OH)3 seed sites,which leads to the lower precipitation rate and the finer particle size of gibbsite during the seed precipitation process.
基金Project supported by the Second Stage of Brain Korea 21 Project
文摘Thin films of PrCoO3 were deposited on LaAlO3 substrates by pulsed laser deposition technique.X-ray diffraction result indicates that films are single phase and c-axis textured.To investigate the spin state transition,Raman spectroscopy measurements were performed at different temperatures.The position of the Raman modes is found to increase while full width at half maximum(FWHM) of these modes is found to decrease with the decrease of temperature across spin state transition temperature(220 K) of PrCoO3.
基金Project(KLUEH201302) supported by Funded by the Key Laboratory of Urban Environment and Health,Institute of Urban Environment,Chinese Academy of SciencesProject(51004053) supported by the National Natural Science Foundation of China+2 种基金Project(3502Z20116008) supported by the Science and Technology Research Project of Xiamen City,ChinaProject(JA11146) supported by the Program for Fostering Distinguished Young Scholars in University of Fujian Province,ChinaProject(2011B003) supported by the Foundation for Young Professors of Jimei University,China
文摘Four types of common seaweeds(Laminaria japonica,Undaria pinnatifida,Porphyra haitanensis,and Gracilaria lemaneiformis) were examined to remove Cr(Ⅵ) ions from aqueous solution.The experimental parameters that affected the biosorption process including pH,biomass dosage,contact time and temperature were investigated via batch experiments.The surface characteristics of seaweeds before and after Cr(Ⅵ) adsorption were studied with scanning electron microscopy and Fourier transform infrared spectroscopy.The results show that an initial solution with the pH of 1.0 is most favorable for Cr(Ⅵ) adsorption.Rapid adsorption is observed in the initial stage and adsorption equilibrium state is reached within 1 h.The adsorption efficiency by Porphyra haitanensis is the maximum among four types of seaweed powders,followed by Laminaria japonica and Undaria pinnatifida with biosorption efficiency up to 90%.The removal rate of Gracilaria lemaneiformis is less than 60%.The kinetic data obtained using the seaweeds are found to follow pseudo-second order kinetic model.Experimental sorption data adequately correlate with the Langmuir model.FTIR indicates that amino and carboxyl groups play an important role in the process of Cr(Ⅵ) adsorption and a large percentage of Cr(Ⅵ) ions are reduced by reductive groups on the surface of seaweeds.
