In this article,a steady-state mathematical model was developed and experimentally evaluated to inves- tigate the effect of influent flow distribution and volume ratios of anoxic and aerobic zones in each stage on the...In this article,a steady-state mathematical model was developed and experimentally evaluated to inves- tigate the effect of influent flow distribution and volume ratios of anoxic and aerobic zones in each stage on the to- tal nitrogen concentration of the effluent in the step-feed biological nitrogen removal process.Unlike the previous modeling methods,this model can be used to calculate the removal rates of ammonia and nitrate in each stage and thereby predict the concentrations of ammonia,nitrate,and total nitrogen in the effluent.To verify the simulation results,pilot-scale experimental studies were carried out in a four-stage step feed process.Good correlations were achieved between the measured data and the simulation results,which proved the validity of the developed model. The sensitivity of the model predictions was analyzed.After verification of the validity,the step feed process was optimally operated for five months using the model and the criteria developed for the design and operation.During the pilot-scale experimental period,the effluent total nitrogen concentrations were all below 5mg·L -1 ,with more than 90%removal efficiency.展开更多
In this work,a series of self-activated KYb(MoO_(4))_(2) phosphors with various x at% Er^(3+) doping concentrations(x=0.5,1,3,5,8,10,15) was synthesized by the solid-state reaction method.The phase structure of the as...In this work,a series of self-activated KYb(MoO_(4))_(2) phosphors with various x at% Er^(3+) doping concentrations(x=0.5,1,3,5,8,10,15) was synthesized by the solid-state reaction method.The phase structure of the as-prepared samples was analyzed by X-ray diffraction(XRD),XRD Rietveld refinement and Fourier transform infrared(FT-IR) spectroscopy.The as-prepared samples retain the orthorhombic structure with space group of Pbcn even Er^(3+) doping concentration up to 15 at%.High-purity upconversion(UC) green emission with green to red intensity ratio of 55 is observed from the as-prepared samples upon the excitation of 980 nm semiconductor laser and the optimum doping concentration of Er^(3+) ions in the self-activated KYb(MoO_(4))_(2) host is revealed as 3 at%.The strong green UC emission is confirmed as a two-photon process based on the power-dependent UC spectra.In addition,the fluorescence intensity ratios(FIRs) of the two thermally-coupled energy levels,namely ^(2)H_(11/2) and ^(4)S_(3/2).of Er^(3+) ions were investigated in the temperature region 300-570 K to evaluate the optical temperature sensor behavior of the sample.The maximum relative sensitivity(S_(R)) is determined to be 0.0069 K^(-1) at300 K and the absolute sensitivity(S_(A)) is determined to be 0.0126 K^(-1) at 300 K.The S_(A) of self-activated KYb(MoO_(4))2:Er^(3+)is almost twice that of traditional KY(MoO_(4))2:Er^(3+)/Yb^(3+)codoping phosphor.The results demonstrate that Er^(3+) ions doped self-activated KYb(MoO_(4))2 phosphor has promising application in visible display,trademark security and optical temperature sensors.展开更多
The conventional symmetry numbers σ_≠~' of activated complexes may lead to error in the rate constant expression of transition state theory, whereas the statistical factor ι~≠ or ι may violate the principle o...The conventional symmetry numbers σ_≠~' of activated complexes may lead to error in the rate constant expression of transition state theory, whereas the statistical factor ι~≠ or ι may violate the principle of detailed balance. A mathematically precise definition of the symmetry number σ_≠ of activated complex is given, i.e. σ_≠=_iN_4(?)/m, m is the number of physically distinct configurations of labelled transition state and N_i is the identical atoms in the activated complex. The identical atoms must belong to the same molecule of reactants and products. The present symmetry numbers σ_≠ of activated complexes assure not only obtaining correct rate constant expressions but also obeying the principle of detailed balance. It can be used with the statistical factor ι to construct the structures of transition states for unimolecular and bimolecular exchange reactions.展开更多
The transport properties in the mixed state of high-quality Ca_(0.8)La_(0.2)Fe_(0.98)Co_(0.02)As_2single crystal,a newly discovered 112-type iron pnictide superconductor,are comprehensively studied by magneto-resistiv...The transport properties in the mixed state of high-quality Ca_(0.8)La_(0.2)Fe_(0.98)Co_(0.02)As_2single crystal,a newly discovered 112-type iron pnictide superconductor,are comprehensively studied by magneto-resistivity measurement.The field-dependent activation energy,U_0,is derived in the framework of thermally activated flux flow(TAFF)theory,yielding a power law dependence U_0～H~αwith a crossover at a magnetic field around 2 T in both H⊥ab and H//ab,which is ascribed to the different pinning mechanisms.Moreover,we have clearly observed the vortex phase transition from vortex-glass to vortex-liquid according to the vortex-glass model,and vortex phase diagrams are constructed for both H⊥ab and H//ab.Finally,the results of mixed-state Hall effect show that no sign reversal of transverse resistivityρ_(xy)(H)is detected,indicating that the Hall component arising from the vortex flow is in theories or experiments previously reported on some high-T_ccuprates.展开更多
Improving the utilization of excitons has always been an important topic for the development of electroluminescence devices.In this work,we designed and synthesized three red TADF emitters TPA-DBT12,TPA-DBT3 and DTPA-...Improving the utilization of excitons has always been an important topic for the development of electroluminescence devices.In this work,we designed and synthesized three red TADF emitters TPA-DBT12,TPA-DBT3 and DTPA-DBT by employing dibenzothioxanthone(DBT)acceptor framework to stabilize the locally excited triplet state to participate in the reverse intersystem crossing(RISC)process.The fast RISC process and singlet radiation decay process gave rise to evidently enhanced exciton utilization.All of the red OLEDs based on these materials showed maximum EQE over 11% and high exciton utilization close to 100%.This work not only extend the acceptor framework for red materials but also provide a new perspective for the design of highly efficient red TADF materials with 100% exciton utilization by managing locally excited triplet state.展开更多
A reversible dual-responsive luminescent material was introduced by our group to show the simultaneous color and lifetime switching in response to external stimuli.Pristine crystalline powder of(E)-2-(benzo[d]thiazol-...A reversible dual-responsive luminescent material was introduced by our group to show the simultaneous color and lifetime switching in response to external stimuli.Pristine crystalline powder of(E)-2-(benzo[d]thiazol-2-yl)-3-(pyren-1-yl)acrylonitrile(Py-BZTCN)shows the orderedπ–πstacking with only near-monomer-normal orange-yellow fluorescence,but it exhibits red emission with thermally activated delayed fluorescence(TADF)after grinding,which can be reversibly recovered by heating or fuming treatment.Grinding disturbs the orderedπ–πstacking of pristine powder,leading to the formation of small aggregates with compressed distance and increased overlap ofπ–πstacking between adjacent molecules.The cause of switching was verified by single-crystal X-ray diffraction experiments of two corresponding crystals.This strongπ–πinteraction effectively promotes the excited-state energy splitting and substantially decreases the singlet–triplet energy gap(ΔEST)of aggregates,resulting in the red TADF emission of aggregates through reverse intersystem crossing.This finding proposes a new route to realizing the TADF emission of aggregates through strong intermolecular interactions based on non-TADF monomer,thereby enabling a novel high-contrast dualresponsive luminescence switching.展开更多
The solid stale C13-NMR spectra of different ACFs from various precursor fiberswere recorded in this paper. The effects of activation conditions on chemical structuresOf ACFs, as well as the changes of chemical struct...The solid stale C13-NMR spectra of different ACFs from various precursor fiberswere recorded in this paper. The effects of activation conditions on chemical structuresOf ACFs, as well as the changes of chemical structures during carbonization and redoxreaction were investigated by NMR technique. At same time, the solid state P31-NMRspectra of ACFs are studied The C13-NMR spectra of ACFs can be divided into sixbands that are assigned to methyl and methylene groups, hydroxyl and ether groups,acetal (or methylenedioxy carbon, graphite-like aromatic carbon structure, phenol,and quinone groups, respectively. Only phosphorous pentoxide exists on ACFs andCFs. Moreover, most of them are stuck over the crystal face but not at the edge ofgraphite-like micro-crystaL The carbonization and activation conditions affect theC13-NMR spectra of ACFs. The experimental results indicate that the redox reactionof ACFs with oxidants greatly consumes C-H group.展开更多
Eu3+-activated Gd2(MoO4)3 pseudo-pompon-like red-emitting phosphors were prepared by solid-state method. The structure, morphology, and luminescent properties of these powder samples were investigated by X-ray diffrac...Eu3+-activated Gd2(MoO4)3 pseudo-pompon-like red-emitting phosphors were prepared by solid-state method. The structure, morphology, and luminescent properties of these powder samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and fluorescent spectrophotometry, respectively. The as-obtained phosphors were single crystalline phase with orthorhombic unit cell. The particles of the powder samples had the length of 5-12 m and width of 3-7 m with flake shape and large surface area, which is suitable for manufacture of white LEDs. The phosphor could be efficiently excited by the incident light of 348-425 nm, well matched with the output wavelength of near-UV (In,Ga)N chip, and re-emitted an intense red light peaking at 615 nm. By combing this phosphor with a ~395 nm-emitting (In,Ga)N chip, a red LED was fabricated, so that the applicability of this novel phosphor to white LEDs was confirmed. It is considered to be an efficient red-emitting conversion phosphor for solid-state lighting based on (In,Ga)N LEDs.展开更多
Phototheranostics is an emerging field in synergistic antitumor therapy in which irradiation and sensitizers are combined to produce reactive oxygen species(ROS),bio-images,and high temperatures.All of these are arriv...Phototheranostics is an emerging field in synergistic antitumor therapy in which irradiation and sensitizers are combined to produce reactive oxygen species(ROS),bio-images,and high temperatures.All of these are arrived from the energy of sensitizers,which located in excited single state(S_(1)).Undeniably,the decentralization of the S_(1)population indirectly decreases the effect of each individual treatment.In this study,a strategy was proposed for enhancing the S_(1)population,and a sensitizer with mitochondrial targeting property,1,4-indolyl iodinated pyrrolo[3,2-b]pyrrole derivative(2I-TPIS),was assembled into adenosine triphosphate(ATP)-responsive nanoparticles(DPA-2I NPs)to achieve dual responses to irradiation and ultrasonication(US)for application to photo-sonodynamic therapy(PSDT).Compared with monotherapies,2I-TPIS generated more ROS in PSDT,inducing mitochondrial autophagy and apoptosis,which in turn triggered immunogenic cell death(ICD).Subsequently,DPA-2I NPs were constructed and self-assembled with the chemotherapeutic agents DPA-Cd and 2I-TPIS to achieve a triple synergistic strategy involving chemotherapy(CT)and PSDT.DPA-2I NPs exhibited absolute sensitization,intra-tumoral overexpression of ATP,and disassembly.Importantly,the biosafety and potent antitumor efficiency of the DPA-2I NP-based“PSDT+CT”therapy were revealed using a 4T1 tumor model.The study results provide insights into the design of sensitizers possessing a sufficient S_(1)population and a highly efficient tumor ablation capacity derived from molecular structural modulation,further enabling triple synergistic antitumor therapies,and expanding the clinical application of sensitizers.展开更多
As a type of chemical adsorption working pair, the physical adsorption occurs first for CaCl2-NH3 because the effective reaction distance for van der Waals force is longer than that for chemical reaction force, and th...As a type of chemical adsorption working pair, the physical adsorption occurs first for CaCl2-NH3 because the effective reaction distance for van der Waals force is longer than that for chemical reaction force, and this physical adsorption state is named the precursor state of chemical adsorption. In order to get the different precursor states of CaCl2-NH3, the different distances between NH3 gas and Ca2+ are realized by the control of different phenomena of swelling and agglomeration in the process of adsorption. When the serious swelling exists while the agglomeration does not exist in the process of adsorption, experimental results show that the activated energy consumed by adsorption reaction increases for the reason of longer distance between Ca2+ and NH3, and at the same time the performance attenuation occurs in the repeated adsorption cycles. When the agglomeration occurs in the process of adsorption, the activated energy for the transition from precursor state to chemical adsorption decreases because the distance between NH3 gas and Ca2+ is shortened by the limited expansion space of adsorbent, and at the same time the performance attenuation does not occur. The adsorption refrigeration isobars are researched by the precursor state of chemical adsorption; results also show that the precursor state is a key factor for isobaric adsorption performance while the distribution of Ca2+ does not influence the permeation of NH3 gas in adsorbent.展开更多
基金supported by grants from National Basic Research Development Program of China(973 ProgramNo.2011CBA00400)+2 种基金the Strategic Priority Research Program(No.XDB02040300)Hundred Talents Program from the Chinese Academy of SciencesChina
基金Supported by the National Natural Science Foundation Key International Cooperation Project of China （No.50521140075）, the 863 Attached Financial Supporting Item of Beijing Municipal Science and Technology Commission （No.Z0005186040421） and the Doctor Subject Soecial Financial Supporfing Item of High College （No.20060005002）.
文摘In this article,a steady-state mathematical model was developed and experimentally evaluated to inves- tigate the effect of influent flow distribution and volume ratios of anoxic and aerobic zones in each stage on the to- tal nitrogen concentration of the effluent in the step-feed biological nitrogen removal process.Unlike the previous modeling methods,this model can be used to calculate the removal rates of ammonia and nitrate in each stage and thereby predict the concentrations of ammonia,nitrate,and total nitrogen in the effluent.To verify the simulation results,pilot-scale experimental studies were carried out in a four-stage step feed process.Good correlations were achieved between the measured data and the simulation results,which proved the validity of the developed model. The sensitivity of the model predictions was analyzed.After verification of the validity,the step feed process was optimally operated for five months using the model and the criteria developed for the design and operation.During the pilot-scale experimental period,the effluent total nitrogen concentrations were all below 5mg·L -1 ,with more than 90%removal efficiency.
基金supported by the National Natural Science Foundation of China (52202001)Open Project of Advanced Laser Technology Laboratory of Anhui Province (AHL2021KF07)+1 种基金Major Science and Technology of Anhui Province(202203a05020002)University Natural Science Research Project of Anhui Province (KJ2021A0388)。
文摘In this work,a series of self-activated KYb(MoO_(4))_(2) phosphors with various x at% Er^(3+) doping concentrations(x=0.5,1,3,5,8,10,15) was synthesized by the solid-state reaction method.The phase structure of the as-prepared samples was analyzed by X-ray diffraction(XRD),XRD Rietveld refinement and Fourier transform infrared(FT-IR) spectroscopy.The as-prepared samples retain the orthorhombic structure with space group of Pbcn even Er^(3+) doping concentration up to 15 at%.High-purity upconversion(UC) green emission with green to red intensity ratio of 55 is observed from the as-prepared samples upon the excitation of 980 nm semiconductor laser and the optimum doping concentration of Er^(3+) ions in the self-activated KYb(MoO_(4))_(2) host is revealed as 3 at%.The strong green UC emission is confirmed as a two-photon process based on the power-dependent UC spectra.In addition,the fluorescence intensity ratios(FIRs) of the two thermally-coupled energy levels,namely ^(2)H_(11/2) and ^(4)S_(3/2).of Er^(3+) ions were investigated in the temperature region 300-570 K to evaluate the optical temperature sensor behavior of the sample.The maximum relative sensitivity(S_(R)) is determined to be 0.0069 K^(-1) at300 K and the absolute sensitivity(S_(A)) is determined to be 0.0126 K^(-1) at 300 K.The S_(A) of self-activated KYb(MoO_(4))2:Er^(3+)is almost twice that of traditional KY(MoO_(4))2:Er^(3+)/Yb^(3+)codoping phosphor.The results demonstrate that Er^(3+) ions doped self-activated KYb(MoO_(4))2 phosphor has promising application in visible display,trademark security and optical temperature sensors.
文摘The conventional symmetry numbers σ_≠~' of activated complexes may lead to error in the rate constant expression of transition state theory, whereas the statistical factor ι~≠ or ι may violate the principle of detailed balance. A mathematically precise definition of the symmetry number σ_≠ of activated complex is given, i.e. σ_≠=_iN_4(?)/m, m is the number of physically distinct configurations of labelled transition state and N_i is the identical atoms in the activated complex. The identical atoms must belong to the same molecule of reactants and products. The present symmetry numbers σ_≠ of activated complexes assure not only obtaining correct rate constant expressions but also obeying the principle of detailed balance. It can be used with the statistical factor ι to construct the structures of transition states for unimolecular and bimolecular exchange reactions.
基金Foundation of China (Grant Nos. 11674054, and 11611140101)XiangZhou Xing was also sponsored by the Scientific Research Foundation of Graduate School of Southeast University (Grant No. YBJJ1621)
文摘The transport properties in the mixed state of high-quality Ca_(0.8)La_(0.2)Fe_(0.98)Co_(0.02)As_2single crystal,a newly discovered 112-type iron pnictide superconductor,are comprehensively studied by magneto-resistivity measurement.The field-dependent activation energy,U_0,is derived in the framework of thermally activated flux flow(TAFF)theory,yielding a power law dependence U_0～H~αwith a crossover at a magnetic field around 2 T in both H⊥ab and H//ab,which is ascribed to the different pinning mechanisms.Moreover,we have clearly observed the vortex phase transition from vortex-glass to vortex-liquid according to the vortex-glass model,and vortex phase diagrams are constructed for both H⊥ab and H//ab.Finally,the results of mixed-state Hall effect show that no sign reversal of transverse resistivityρ_(xy)(H)is detected,indicating that the Hall component arising from the vortex flow is in theories or experiments previously reported on some high-T_ccuprates.
基金financially supported by the National Natural Science Foundation of China(No.21772209)the National Program for Support of Top-notch Young Professionals.
文摘Improving the utilization of excitons has always been an important topic for the development of electroluminescence devices.In this work,we designed and synthesized three red TADF emitters TPA-DBT12,TPA-DBT3 and DTPA-DBT by employing dibenzothioxanthone(DBT)acceptor framework to stabilize the locally excited triplet state to participate in the reverse intersystem crossing(RISC)process.The fast RISC process and singlet radiation decay process gave rise to evidently enhanced exciton utilization.All of the red OLEDs based on these materials showed maximum EQE over 11% and high exciton utilization close to 100%.This work not only extend the acceptor framework for red materials but also provide a new perspective for the design of highly efficient red TADF materials with 100% exciton utilization by managing locally excited triplet state.
基金supported by the National Natural Science Foundation of China(nos.52073117,91833304,51873077,and 51803071)the National Basic Research Program of China(no.2016YFB0401001)+1 种基金the Postdoctoral Innovation Talent Support Project(no.BX20180121)the China Postdoctoral Science Foundation(nos.2018M641767 and 2019TQ0198).
文摘A reversible dual-responsive luminescent material was introduced by our group to show the simultaneous color and lifetime switching in response to external stimuli.Pristine crystalline powder of(E)-2-(benzo[d]thiazol-2-yl)-3-(pyren-1-yl)acrylonitrile(Py-BZTCN)shows the orderedπ–πstacking with only near-monomer-normal orange-yellow fluorescence,but it exhibits red emission with thermally activated delayed fluorescence(TADF)after grinding,which can be reversibly recovered by heating or fuming treatment.Grinding disturbs the orderedπ–πstacking of pristine powder,leading to the formation of small aggregates with compressed distance and increased overlap ofπ–πstacking between adjacent molecules.The cause of switching was verified by single-crystal X-ray diffraction experiments of two corresponding crystals.This strongπ–πinteraction effectively promotes the excited-state energy splitting and substantially decreases the singlet–triplet energy gap(ΔEST)of aggregates,resulting in the red TADF emission of aggregates through reverse intersystem crossing.This finding proposes a new route to realizing the TADF emission of aggregates through strong intermolecular interactions based on non-TADF monomer,thereby enabling a novel high-contrast dualresponsive luminescence switching.
文摘The solid stale C13-NMR spectra of different ACFs from various precursor fiberswere recorded in this paper. The effects of activation conditions on chemical structuresOf ACFs, as well as the changes of chemical structures during carbonization and redoxreaction were investigated by NMR technique. At same time, the solid state P31-NMRspectra of ACFs are studied The C13-NMR spectra of ACFs can be divided into sixbands that are assigned to methyl and methylene groups, hydroxyl and ether groups,acetal (or methylenedioxy carbon, graphite-like aromatic carbon structure, phenol,and quinone groups, respectively. Only phosphorous pentoxide exists on ACFs andCFs. Moreover, most of them are stuck over the crystal face but not at the edge ofgraphite-like micro-crystaL The carbonization and activation conditions affect theC13-NMR spectra of ACFs. The experimental results indicate that the redox reactionof ACFs with oxidants greatly consumes C-H group.
基金Project supported by the Natural Science Research Project of the Jiangsu Higher Education Institutions (08KJD150014)the QingLan Project of the Jiangsu Province (2008)the Basic Research Fund of Jiangsu Teachers University of Technology (KYY09031)
文摘Eu3+-activated Gd2(MoO4)3 pseudo-pompon-like red-emitting phosphors were prepared by solid-state method. The structure, morphology, and luminescent properties of these powder samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and fluorescent spectrophotometry, respectively. The as-obtained phosphors were single crystalline phase with orthorhombic unit cell. The particles of the powder samples had the length of 5-12 m and width of 3-7 m with flake shape and large surface area, which is suitable for manufacture of white LEDs. The phosphor could be efficiently excited by the incident light of 348-425 nm, well matched with the output wavelength of near-UV (In,Ga)N chip, and re-emitted an intense red light peaking at 615 nm. By combing this phosphor with a ~395 nm-emitting (In,Ga)N chip, a red LED was fabricated, so that the applicability of this novel phosphor to white LEDs was confirmed. It is considered to be an efficient red-emitting conversion phosphor for solid-state lighting based on (In,Ga)N LEDs.
基金the financial support from the National Natural Science Foundation of China(Nos.U23A2089,22205159,and 22103055)Natural Science Foundation of Tianjin(No.21JCQNJC01450)Science and Technology Plans of Tianjin(Nos.22ZYJDSS00070 and 21ZYJDJC00050).
文摘Phototheranostics is an emerging field in synergistic antitumor therapy in which irradiation and sensitizers are combined to produce reactive oxygen species(ROS),bio-images,and high temperatures.All of these are arrived from the energy of sensitizers,which located in excited single state(S_(1)).Undeniably,the decentralization of the S_(1)population indirectly decreases the effect of each individual treatment.In this study,a strategy was proposed for enhancing the S_(1)population,and a sensitizer with mitochondrial targeting property,1,4-indolyl iodinated pyrrolo[3,2-b]pyrrole derivative(2I-TPIS),was assembled into adenosine triphosphate(ATP)-responsive nanoparticles(DPA-2I NPs)to achieve dual responses to irradiation and ultrasonication(US)for application to photo-sonodynamic therapy(PSDT).Compared with monotherapies,2I-TPIS generated more ROS in PSDT,inducing mitochondrial autophagy and apoptosis,which in turn triggered immunogenic cell death(ICD).Subsequently,DPA-2I NPs were constructed and self-assembled with the chemotherapeutic agents DPA-Cd and 2I-TPIS to achieve a triple synergistic strategy involving chemotherapy(CT)and PSDT.DPA-2I NPs exhibited absolute sensitization,intra-tumoral overexpression of ATP,and disassembly.Importantly,the biosafety and potent antitumor efficiency of the DPA-2I NP-based“PSDT+CT”therapy were revealed using a 4T1 tumor model.The study results provide insights into the design of sensitizers possessing a sufficient S_(1)population and a highly efficient tumor ablation capacity derived from molecular structural modulation,further enabling triple synergistic antitumor therapies,and expanding the clinical application of sensitizers.
文摘As a type of chemical adsorption working pair, the physical adsorption occurs first for CaCl2-NH3 because the effective reaction distance for van der Waals force is longer than that for chemical reaction force, and this physical adsorption state is named the precursor state of chemical adsorption. In order to get the different precursor states of CaCl2-NH3, the different distances between NH3 gas and Ca2+ are realized by the control of different phenomena of swelling and agglomeration in the process of adsorption. When the serious swelling exists while the agglomeration does not exist in the process of adsorption, experimental results show that the activated energy consumed by adsorption reaction increases for the reason of longer distance between Ca2+ and NH3, and at the same time the performance attenuation occurs in the repeated adsorption cycles. When the agglomeration occurs in the process of adsorption, the activated energy for the transition from precursor state to chemical adsorption decreases because the distance between NH3 gas and Ca2+ is shortened by the limited expansion space of adsorbent, and at the same time the performance attenuation does not occur. The adsorption refrigeration isobars are researched by the precursor state of chemical adsorption; results also show that the precursor state is a key factor for isobaric adsorption performance while the distribution of Ca2+ does not influence the permeation of NH3 gas in adsorbent.
