Piezoelectric semiconductors bear the bifunctional photocatalysis and piezocatalysis,while the absent or weak internal charge driving force severely restricts its catalytic activity.Developing polarization strategy is...Piezoelectric semiconductors bear the bifunctional photocatalysis and piezocatalysis,while the absent or weak internal charge driving force severely restricts its catalytic activity.Developing polarization strategy is desirable,and particularly understanding its mechanism from a microscopic perspective remains scanty.Herein,we report a secondary recrystallization approach to achieving the simultaneous micro-and macroscopic polarization enhancement on Bi2WO6 nanosheets for boosting piezo-photocatalytic oxygen activation,and unravel the mechanism at an atom-level.The secondary recrystallization process not only results in a strengthened distortion of[WO6]octahedra with distortion index enhancement by~20%for a single octahedron,but also enables lateral crystal growth of nanosheets along the ab plane(av.50 to 180 nm),which separately allows the rise in dipole moment of unit cell(e.g.,1.63 D increase along a axis)and the stacking of the distorted[WO6]octahedron to accumulate the unit cell dipole,collectively contributing to the considerably strengthened spontaneous polarization and piezoelectricity.Besides,exposure of large-area{001}front facet enables more efficient capture and conversion of stress into piezo-potential.Therefore,the well-recrystallized Bi2WO6 nanosheets exhibit considerably promoted piezo-photocatalytic reactive oxygen species generation,given the decreased specific surface area.This work presents a feasible methodology to regulate inside-out polarization for guiding carriers transfer behavior,and may advance the solid understanding on the intrinsic mechanism.展开更多
Inclusion bodies(IBs)of respiratory syncytial virus(RSV)are formed by liquid-liquid phase separation(LLPS)and contain internal structures termed“IB-associated granules”(IBAGs),where anti-termination factor M2-1 and ...Inclusion bodies(IBs)of respiratory syncytial virus(RSV)are formed by liquid-liquid phase separation(LLPS)and contain internal structures termed“IB-associated granules”(IBAGs),where anti-termination factor M2-1 and viral mRNAs are concentrated.However,the mechanism of IBAG formation and the physiological function of IBAGs are unclear.Here,we found that the internal structures of RSV IBs are actual M2-1-free viral messenger ribonucleoprotein(mRNP)condensates formed by secondary LLPS.Mechanistically,the RSV nucleoprotein(N)and M2-1 interact with and recruit PABP to IBs,promoting PABP to bind viral mRNAs transcribed in IBs by RNArecognition motif and drive secondary phase separation.Furthermore,PABP-eIF4G1 interaction regulates viral mRNP condensate composition,thereby recruiting specific translation initiation factors(eIF4G1,eIF4E,eIF4A,eIF4B and eIF4H)into the secondary condensed phase to activate viral mRNAs for ribosomal recruitment.Our study proposes a novel LLPS-regulated translation mechanism during viral infection and a novel antiviral strategy via targeting on secondary condensed phase.展开更多
The direct partial reduction of highly stable secondary amides to more reactive aldimines and aldehydes is a challenging yet highly demanding transformation. In this context, only three methods have been reported. We ...The direct partial reduction of highly stable secondary amides to more reactive aldimines and aldehydes is a challenging yet highly demanding transformation. In this context, only three methods have been reported. We report herein an improved version of the Charette's method. Our protocol consists of activation of secondary amides with triflic anhydride/2-fluoropyridine,and partial reduction of the resulting intermediates with 1,1,3,3-tetramethyldisiloxane(TMDS), which delivered aldimines or aldehydes upon acidic hydrolysis. Aromatic amides were reduced to the corresponding aldimines in 85%–100% NMR yields,and yields(NMR) from aliphatic amides were 72%–86%. Acidic hydrolysis of the aldimine intermediates afforded, in one-pot,the corresponding aldehydes in 80%–96% yields. A simple protocol was established to isolate labile aldimines in pure form in92%–96% yields. The improved method gave generally higher yields as compared to the known ones, and features the use of cheaper and more atom-economical TMDS as a chemoselective reducing agent. In addition, a convenient extraction protocol has been established to allow the isolation of amines, which constitutes a mild method for the N-deacylation of amides, another highly desirable transformation. The extended method retains the advantages of the original method of Charette in terms of mild conditions, good functional group tolerance, and excellent chemoselectivity.展开更多
The large consumption and discharge of diclofenac(DCF) lead to its frequent detection in surface water and groundwater, posing great threats to humans and ecosystems. This study explored the oxidation kinetics of DCF ...The large consumption and discharge of diclofenac(DCF) lead to its frequent detection in surface water and groundwater, posing great threats to humans and ecosystems. This study explored the oxidation kinetics of DCF by permanganate(Mn(Ⅶ)), and expounded the underlying reason for the unusual p Hdependency that was unclear in previous studies. The kinetics of DCF analogues(i.e., aromatic secondary amines) by Mn(Ⅶ) oxidation were comparatively investigated. Then, a tentative kinetic model involving the formation of an intermediate between Mn(Ⅶ) and DCF or its analogues was proposed to fit the p H-rate profile. Since DCF contained two chloro groups, and a carboxyl group which could be ionized by negative electrospray ionization, a precursor ionization scanning approach was used for the first time for detection of N-containing chlorinated oxidation products. New degradation pathways of DCF containing ring opening, carboxylation, carbonylation, electrophilic addition, hydroxylation and dehydrogenation were proposed based on the identified oxidation products. Moreover, it was demonstrated that the introduction of various reducing agents such as Mn(Ⅱ), Fe(Ⅱ) and bisulfite significantly improved the oxidation kinetics of DCF by Mn(Ⅶ). The positive effects of Mn(Ⅱ) and Fe(Ⅱ) were mainly attributed to the accelerated formation of MnO_(2)that acted as a catalyst or co-oxidizer contributing to DCF degradation. The presence of bisulfite caused two-stage kinetics, where a sharp drop of DCF concentration followed by a slowdown of DCF removal. In the first stage, potent reactive manganese species(e.g., Mn(Ⅲ), Mn(V), and Mn(VI)) and sulfate radical were generated during reaction of bisulfite with Mn(Ⅶ), whereas bisulfite was depleted fast due to excess Mn(Ⅶ) concentrations and the system became the Mn(Ⅶ)/MnO_(2)system in the second stage. These results provide new insight into reaction mechanism of DCF with Mn(Ⅶ)as well as propose a feasible strategy for enhancing the treatment of DCF contaminated water 展开更多
The effect of the improvement of commercial activated carbon(AC) on its specific capacitance and high rate capability of double layer(dl) charging/discharging process has been studied. The improvement of AC was carrie...The effect of the improvement of commercial activated carbon(AC) on its specific capacitance and high rate capability of double layer(dl) charging/discharging process has been studied. The improvement of AC was carried out \%via\% a secondary activation under steam in the presence of catalyst NiCl\-2, and the suitable condition was found to be a heat treatment at about 875 ℃ for 1 h. Under those conditions, the discharge specific capacitance of the improved AC increases up to 53.67 F/g, showing an increase of about 25% as compared with that of as-received AC. The good rectangular-shaped voltammograms and A.C. impedance spectra prove that the high rate capability of the capacitor made of the improved AC is enhanced significantly. The capacitance resistance(RC) time constant of the capacitor containing the improved AC is 1\^74 s, which is much lower than that of the one containing as-received AC(an RC value of 4.73 s). It is noted that both kinds of AC samples show a similar specific surface area and pore size distribution, but some changes have taken place in the carbon surface groups, especially a decrease in the concentration of surface carbonyl groups after the improvement, which have been verified by means of X-photoelectron spectroscopy. Accordingly, it is suggested that the decrease in the concentration of surface carbonyl groups for the improved AC is beneficial to the organic electrolyte ion penetrating into the pores, thus leading to the increase in both the specific capacitance and high rate capability of the supercapacitor.展开更多
Glass forming materials are characterized by a complex relaxation pattern, which evolves over several time decades. Dielectric spectroscopy has proven particularly useful for studying such scenario as it is able to mo...Glass forming materials are characterized by a complex relaxation pattern, which evolves over several time decades. Dielectric spectroscopy has proven particularly useful for studying such scenario as it is able to monitor the dielectric dynamics of a system over a range up to 16 time decades. In this work we study effect of thermodynamic history on activation volume of secondary relaxation inside the glassy forming systems, Poly[(phenyl glycidyl ether)-co-formaldehyde], (PPGE) and 1,18-bis (p methoxyphenyl) cyclohexane (BMPC), with two different type of secondary relaxation. Our results show that at bout systems, activation volume of secondary depends to the thermodynamic history.展开更多
Thermal analyses on squeeze cast aluminum alloy A380(SC A380) solidified under 90MPa were carried out to study the microstructure development of the alloy, in which a differential scanning calorimeter(DSC) was employe...Thermal analyses on squeeze cast aluminum alloy A380(SC A380) solidified under 90MPa were carried out to study the microstructure development of the alloy, in which a differential scanning calorimeter(DSC) was employed. During the DSC runs, heating and cooling rates of 1, 3, 10, and 20 °C·min^(-1) were applied to investigate the heating and cooling effects on dissolution of secondary eutectic phases and microstructure evolution. Various reactions corresponding to troughs and peaks of the DSC curves were identified as corresponding to phase transformations taking place during dissolution or precipitation suggested by the principles of thermodynamics and kinetics. The comparison of the identified characteristic temperatures in the measured heating and cooling curves are generally in good agreement with the computed equilibrium temperatures. The microstructure analyses by scanning electron microscopy(SEM) with energy dispersive X-ray spectroscopy(EDS) indicate that the distribution and morphology of secondary phases present in the microstructure of the annealed sample are similar to the as-cast A380, i.e., strip β(Si), buck bone like or dot distributed θ(Al_2Cu), β(Al_5Fe Si) and Al_(15)(FeMn)_3Si_2. Two kinetic methods are employed to calculate the activation energies of the three common troughs and three common peaks in DSC curves of SC A380. The activation energies of the identified reaction θ_(CuAl_2) = α(Al)+β(Si) is 188.7 and 187.1 k J?mol^(-1) when the activation energies of reaction α(Al)+β(Si)→θCu Al_2 is^(-1)22.7 and^(-1)21.8 k J?mol^(-1), by the Kissinger and Starink methods, respectively.展开更多
基金the National Key Research and Development Program of China(No.2022YFB3803600)the National Natural Science Foundation of China(Nos.52272244 and 51972288)+1 种基金the Fundamental Research Funds for the Central Universities(No.2652022202)2021 Graduate Innovation Fund Project of China University of Geosciences,Beijing(No.ZY2021YC006).
文摘Piezoelectric semiconductors bear the bifunctional photocatalysis and piezocatalysis,while the absent or weak internal charge driving force severely restricts its catalytic activity.Developing polarization strategy is desirable,and particularly understanding its mechanism from a microscopic perspective remains scanty.Herein,we report a secondary recrystallization approach to achieving the simultaneous micro-and macroscopic polarization enhancement on Bi2WO6 nanosheets for boosting piezo-photocatalytic oxygen activation,and unravel the mechanism at an atom-level.The secondary recrystallization process not only results in a strengthened distortion of[WO6]octahedra with distortion index enhancement by~20%for a single octahedron,but also enables lateral crystal growth of nanosheets along the ab plane(av.50 to 180 nm),which separately allows the rise in dipole moment of unit cell(e.g.,1.63 D increase along a axis)and the stacking of the distorted[WO6]octahedron to accumulate the unit cell dipole,collectively contributing to the considerably strengthened spontaneous polarization and piezoelectricity.Besides,exposure of large-area{001}front facet enables more efficient capture and conversion of stress into piezo-potential.Therefore,the well-recrystallized Bi2WO6 nanosheets exhibit considerably promoted piezo-photocatalytic reactive oxygen species generation,given the decreased specific surface area.This work presents a feasible methodology to regulate inside-out polarization for guiding carriers transfer behavior,and may advance the solid understanding on the intrinsic mechanism.
基金supported by the grants from National Key R&D Program of China(2021YFC2300702 and 2021YFC2300200)the Hubei Provincial Natural Science Foundation of China(2021CFB364)+1 种基金the National Natural Science Foundation of China(82130064,81825015,U22A20337 and 32000119)the Key Biosafety Science and Technology Program of Hubei Jiangxia Laboratory(JXBS001).
文摘Inclusion bodies(IBs)of respiratory syncytial virus(RSV)are formed by liquid-liquid phase separation(LLPS)and contain internal structures termed“IB-associated granules”(IBAGs),where anti-termination factor M2-1 and viral mRNAs are concentrated.However,the mechanism of IBAG formation and the physiological function of IBAGs are unclear.Here,we found that the internal structures of RSV IBs are actual M2-1-free viral messenger ribonucleoprotein(mRNP)condensates formed by secondary LLPS.Mechanistically,the RSV nucleoprotein(N)and M2-1 interact with and recruit PABP to IBs,promoting PABP to bind viral mRNAs transcribed in IBs by RNArecognition motif and drive secondary phase separation.Furthermore,PABP-eIF4G1 interaction regulates viral mRNP condensate composition,thereby recruiting specific translation initiation factors(eIF4G1,eIF4E,eIF4A,eIF4B and eIF4H)into the secondary condensed phase to activate viral mRNAs for ribosomal recruitment.Our study proposes a novel LLPS-regulated translation mechanism during viral infection and a novel antiviral strategy via targeting on secondary condensed phase.
基金supported by the National Natural Science Foundation of China(21332007)Xiamen University
文摘The direct partial reduction of highly stable secondary amides to more reactive aldimines and aldehydes is a challenging yet highly demanding transformation. In this context, only three methods have been reported. We report herein an improved version of the Charette's method. Our protocol consists of activation of secondary amides with triflic anhydride/2-fluoropyridine,and partial reduction of the resulting intermediates with 1,1,3,3-tetramethyldisiloxane(TMDS), which delivered aldimines or aldehydes upon acidic hydrolysis. Aromatic amides were reduced to the corresponding aldimines in 85%–100% NMR yields,and yields(NMR) from aliphatic amides were 72%–86%. Acidic hydrolysis of the aldimine intermediates afforded, in one-pot,the corresponding aldehydes in 80%–96% yields. A simple protocol was established to isolate labile aldimines in pure form in92%–96% yields. The improved method gave generally higher yields as compared to the known ones, and features the use of cheaper and more atom-economical TMDS as a chemoselective reducing agent. In addition, a convenient extraction protocol has been established to allow the isolation of amines, which constitutes a mild method for the N-deacylation of amides, another highly desirable transformation. The extended method retains the advantages of the original method of Charette in terms of mild conditions, good functional group tolerance, and excellent chemoselectivity.
基金financially supported by the program for the National Natural Science Foundation of China (Nos. 51979044,42177045 and 42107053)the Guangdong Natural Science Funds for Distinguished Young Scholar (No. 2019B151502023)+2 种基金Guangdong International Training Program for Outstanding Young Talentsthe China Postdoctoral Science Foundation (No. 2021M700878)Guangdong-Hong Kong-Macao Joint Laboratory for Contaminants Exposure and Health (No. 2020B1212030008)。
文摘The large consumption and discharge of diclofenac(DCF) lead to its frequent detection in surface water and groundwater, posing great threats to humans and ecosystems. This study explored the oxidation kinetics of DCF by permanganate(Mn(Ⅶ)), and expounded the underlying reason for the unusual p Hdependency that was unclear in previous studies. The kinetics of DCF analogues(i.e., aromatic secondary amines) by Mn(Ⅶ) oxidation were comparatively investigated. Then, a tentative kinetic model involving the formation of an intermediate between Mn(Ⅶ) and DCF or its analogues was proposed to fit the p H-rate profile. Since DCF contained two chloro groups, and a carboxyl group which could be ionized by negative electrospray ionization, a precursor ionization scanning approach was used for the first time for detection of N-containing chlorinated oxidation products. New degradation pathways of DCF containing ring opening, carboxylation, carbonylation, electrophilic addition, hydroxylation and dehydrogenation were proposed based on the identified oxidation products. Moreover, it was demonstrated that the introduction of various reducing agents such as Mn(Ⅱ), Fe(Ⅱ) and bisulfite significantly improved the oxidation kinetics of DCF by Mn(Ⅶ). The positive effects of Mn(Ⅱ) and Fe(Ⅱ) were mainly attributed to the accelerated formation of MnO_(2)that acted as a catalyst or co-oxidizer contributing to DCF degradation. The presence of bisulfite caused two-stage kinetics, where a sharp drop of DCF concentration followed by a slowdown of DCF removal. In the first stage, potent reactive manganese species(e.g., Mn(Ⅲ), Mn(V), and Mn(VI)) and sulfate radical were generated during reaction of bisulfite with Mn(Ⅶ), whereas bisulfite was depleted fast due to excess Mn(Ⅶ) concentrations and the system became the Mn(Ⅶ)/MnO_(2)system in the second stage. These results provide new insight into reaction mechanism of DCF with Mn(Ⅶ)as well as propose a feasible strategy for enhancing the treatment of DCF contaminated water
基金Supported by the National Natural Science Foundation of China(No.2 0 0 0 30 0 5 ) and the Natural Science Foundation ofJiangsu Province(No.BQ2 0 0 0 0 0 9)
文摘The effect of the improvement of commercial activated carbon(AC) on its specific capacitance and high rate capability of double layer(dl) charging/discharging process has been studied. The improvement of AC was carried out \%via\% a secondary activation under steam in the presence of catalyst NiCl\-2, and the suitable condition was found to be a heat treatment at about 875 ℃ for 1 h. Under those conditions, the discharge specific capacitance of the improved AC increases up to 53.67 F/g, showing an increase of about 25% as compared with that of as-received AC. The good rectangular-shaped voltammograms and A.C. impedance spectra prove that the high rate capability of the capacitor made of the improved AC is enhanced significantly. The capacitance resistance(RC) time constant of the capacitor containing the improved AC is 1\^74 s, which is much lower than that of the one containing as-received AC(an RC value of 4.73 s). It is noted that both kinds of AC samples show a similar specific surface area and pore size distribution, but some changes have taken place in the carbon surface groups, especially a decrease in the concentration of surface carbonyl groups after the improvement, which have been verified by means of X-photoelectron spectroscopy. Accordingly, it is suggested that the decrease in the concentration of surface carbonyl groups for the improved AC is beneficial to the organic electrolyte ion penetrating into the pores, thus leading to the increase in both the specific capacitance and high rate capability of the supercapacitor.
文摘Glass forming materials are characterized by a complex relaxation pattern, which evolves over several time decades. Dielectric spectroscopy has proven particularly useful for studying such scenario as it is able to monitor the dielectric dynamics of a system over a range up to 16 time decades. In this work we study effect of thermodynamic history on activation volume of secondary relaxation inside the glassy forming systems, Poly[(phenyl glycidyl ether)-co-formaldehyde], (PPGE) and 1,18-bis (p methoxyphenyl) cyclohexane (BMPC), with two different type of secondary relaxation. Our results show that at bout systems, activation volume of secondary depends to the thermodynamic history.
基金supported by the Natural Sciences and Engineering Research Council of Canada(NSERC)Discovery(No239080-2010)the project of Shandong science and technology development plan(No2014GGX103035),China
文摘Thermal analyses on squeeze cast aluminum alloy A380(SC A380) solidified under 90MPa were carried out to study the microstructure development of the alloy, in which a differential scanning calorimeter(DSC) was employed. During the DSC runs, heating and cooling rates of 1, 3, 10, and 20 °C·min^(-1) were applied to investigate the heating and cooling effects on dissolution of secondary eutectic phases and microstructure evolution. Various reactions corresponding to troughs and peaks of the DSC curves were identified as corresponding to phase transformations taking place during dissolution or precipitation suggested by the principles of thermodynamics and kinetics. The comparison of the identified characteristic temperatures in the measured heating and cooling curves are generally in good agreement with the computed equilibrium temperatures. The microstructure analyses by scanning electron microscopy(SEM) with energy dispersive X-ray spectroscopy(EDS) indicate that the distribution and morphology of secondary phases present in the microstructure of the annealed sample are similar to the as-cast A380, i.e., strip β(Si), buck bone like or dot distributed θ(Al_2Cu), β(Al_5Fe Si) and Al_(15)(FeMn)_3Si_2. Two kinetic methods are employed to calculate the activation energies of the three common troughs and three common peaks in DSC curves of SC A380. The activation energies of the identified reaction θ_(CuAl_2) = α(Al)+β(Si) is 188.7 and 187.1 k J?mol^(-1) when the activation energies of reaction α(Al)+β(Si)→θCu Al_2 is^(-1)22.7 and^(-1)21.8 k J?mol^(-1), by the Kissinger and Starink methods, respectively.
