干涉滤光片双稳器件的热光动力学分析

基于ZnSe全电介质干涉滤光片光双稳器件结构的模型,采用数值方法分析了介质层具有线性吸收与热光效应时,干涉滤光片受到纳秒量级脉宽的光脉冲作用后,其介质内部吸收层吸收光能引起的介质层的光学性质变化,导致滤光片透过率变化的动力学过程.其结果对提高器件的开关速度,降低阈值功率都具有积极意义.

Temperature-feedback two-photon-responsive metal-organic frameworks for efficient photothermal therapy

The realization of real-time thermal feedback for monitoring photothermal therapy(PTT)under near-infrared(NIR)light irradiation is of great interest and challenge for antitumor therapy.Herein,by assembling highly efficient photothermal conversion gold nanorods and a temperature-responsive probe((E)-4-(4-(diethylamino)styryl)-1-methylpyridin-1-ium,PyS)within MOF-199,an intelligent nanoplatform(AMPP)was fabricated for simultaneous chemodynamic therapy and NIR light-induced temperature-feedback PTT.The fluorescence intensity and temperature of the PyS probe are linearly related due to the restriction of the rotation of the characteristic monomethine bridge.Moreover,the copper ions resulting from the degradation of MOF-199 in an acidic microenvironment can convert H_(2)O_(2)into•OH,resulting in tumor ablation through a Fenton-like reaction,and this process can be accelerated by increasing the temperature.This study establishes a feasible platform for fabricating highly sensitive temperature sensors for efficient temperature-feedback PTT.

Effects of Fluorescent Pair on the Kinetics of DNA Strand Displacement Reaction

Fluorescent labels are widely used in the characterizations of DNA-based reaction network operations.We systematically studied the effects of commonly used fluorescent pairs on thermal stabilities of signal-substrate duplex and the strand displacement kinetics.It is demonstrated that the modifications of duplex with fluorescent pairs stabilize DNA duplex by up to 3.5°C,and the kinetics of DNA strand displacement circuit is also evidently slowed down.These results highlight the importance of fluorescent pairs towards the kinetic modulation in designing nucleic acid probes and complex DNA dynamic circuits.

Temperature-Induced Unfolding Pathway of Staphylococcal Enterotoxin B:Insights from Circular Dichroism and Molecular Dynamics Simulation

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.

Effect of Heat Stress on Photosynthetic Characteristics of Different Green Organs of Winter Wheat During Grain-filling Stage

Four winter wheat (Triticum aestivum L.) varieties ('JD 8', 'Jing 411','Centurk' and 'Tam 202') were used to study the effect of heat stress on photosynthetic characteristics of flag leaf blade, nag leaf sheath, peduncle, glume, lemma and awn during grain-filling stage. The results showed that heat acclimation during grain-filling stage increased thermotolerance of wheat with significant differences among different green organs. During heat stress, the decreases of the efficiency of primary light energy conversion (F-v/F-m) of PS II and pigment (chlorophyll and carotenoid) content were much slower in peduncle, flag leaf sheath and glume than in nag leaf blade, lemma and ann; and the percentage of decrease in net photosynthetic rate (P-n) of ear was lower than that of the nag leaf blade. The measured photosynthetic parameters (F-v/F-m, P-n and pigment content) of 'JD 8', a relatively heat tolerant variety, declined more slowly than those of the other three varieties during the whole heat stress period.

Adsorption kinetics and thermodynamics of sodium butyl xanthate onto bornite in flotation

In this paper,the effect of sodium butyl xanthate(NaBX)adsorption on the surface of bornite at different pH on flotation was studied by adsorption kinetic and thermodynamic.The flotation results demonstrated that the recovery was the highest when pH was 9 in NaBX solution(4×10^?5 mol/L).The adsorption kinetics showed the reaction of NaBX on the bornite conformed to the second order kinetic equation;it belonged to the multimolecular layer adsorption of Freundlich model;the maximum adsorption rate constant was 0.30 g/(10^?6 mol·min),and the equilibrium adsorption capacity was 2.70×10^?6 mol/g.Thermodynamic calculation results indicated that the adsorption process was spontaneous chemisorption,and the adsorption products of NaBX on bornite surface were cupric butyl xanthate,ferric butyl xanthate and dixanthogen,which were confirmed by infrared spectrum measurements.

Solar-heating boosted catalytic reduction of CO_(2） under full-solar spectrum

Catalytic converting CO2 into fuels with the help of solar energy is regarded as‘dream reaction’,as both energy crisis and environmental issue can be mitigated simultaneously.However,it is still suffering from low efficiency due to narrow solar-spectrum utilization and sluggish heterogeneous reaction kinetics.In this work,we demonstrate that catalytic reduction of CO2 can be achieved over Au nanoparticles(NPs)deposited rutile under full solar-spectrum irradiation,boosted by solar-heating effect.We found that UV and visible light can initiate the reaction,and the heat from IR light and local surface-plasmon resonance relaxation of Au NPs can boost the reaction kinetically.The apparent activation energy is determined experimentally and is used to explain the superior catalytic activity of Au/rutile to rutile in a kinetic way.We also find the photo-thermal synergy in the Au/rutile system.We envision that this work may facilitate understanding the kinetics of CO2 reduction and developing feasible catalytic systems with full solar spectrum utilization for practical artificial photosynthesis.

Effect of a Novel Nucleating Agent on Isothermal Crystallization of Poly（L-lactic acid）

The effect of a novel active nucleating agent(TBC8-eb) on the isothermal crystallization of poly(L-lactic acid) (PLLA) was studied by differential scanning calorimetry(DSC) and Fourier transform infrared spectroscopy(FTIR) . The analysis on kinetics demonstrates that TBC8-eb can not only accelerate the crystallization rate but also transform most of the original spherulite crystals of PLLA into sheaf-like crystals. Furthermore,the free energy of folding(σe) of PLLA and PLLA with TBC8-eb is 0.15 and 0.06 J·m-2,respectively,which suggests that the addition of TBC8-eb favors the regular folding of molecule chains in the crystallization of PLLA,improv-ing its crystallization rate. The FTIR results show that TBC8-eb can accelerate the conformational ordering of PLLA in the isothermal crystallization. The conformational ordering of PLLA nucleated with TBC8-eb begins with the interchain interaction of CH3,and then a short helix emerges where a couple of CH3 groups interact.

EOM-CCSD-Based Neural Network Diabatic Potential Energy Matrix for ^(1)πσ^(*)-Mediated Photodissociation of Thiophenol

A new diabatic potential energy matrix(PEM)of the coupled~^(1)ππ^(*)and~1πσ*states for the~1πσ*-mediated photodissociation of thiophenol was constructed using a neural network(NN)approach.The diabatization of the PEM was specifically achieved by our recent method[Chin.J.Chem.Phys.34,825(2021)],which was based on adiabatic energies without the associated costly derivative couplings.The equation of motion coupled cluster with single and double excitations(EOM-CCSD)method was employed to compute adiabatic energies of two excited states in this work due to its high accuracy,simplicity,and efficiency.The PEM includes three dimensionalities,namely the S-H stretch,C-S-H bend,and C-C-S-H torsional coordinates.The root mean square errors of the NN fitting for the S1 and S2 states are 0.89 and 1.33 me V,respectively,suggesting the high accuracy of the NN method as expected.The calculated lifetimes of the S1 vibronic 00 and31 states are found to be in reasonably good agreement with available theoretical and experimental results,which validates the new EOM-CCSD-based PEM fitted by the NN approach.The combination of the diabatization scheme solely based on the adiabatic energies and the use of EOM-CCSD method makes the construction of reliable diabatic PEM quite simple and efficient.

Understanding Photolysis of CH_(3)ONO_(2) with on-the-fly Nonadiabatic Dynamics Simulation at the ADC(2) Level

The nonadiabatic dynamics of methyl nitrate(CH_(3)ONO_(2))is studied with the on-the-fy trajectory surface hopping dynamics at the ADC(2)level.The results confirmed the existence of the ultrafast nonadiabatic decay to the electronic ground state.When the dynamics starts from S_(1) and S_(2),the photoproducts are CH_(3)O+NO_(2),consistent with previous results obtained from the experimental studies and theoretical dynamics simulations at more accurate XMS-CASPT2 level.The photolysis products are CH_(3)O+NO_(2) at the ADC(2)level when the dynamics starts from S3,while different photolysis products were obtained in previous experimental and theoretical works.These results demonstrate that the ADC(2)method may still be useful for treating the photolysis mechanism of CH_(3)ONO_(2) at the long-wavelength UV excitation,while great caution should be paid due to its inaccurate performance in the description of the photolysis dynamics at the short-wavelength UV excitation.This gives valuable information to access the accuracy when other alkyl nitrates are treated at the ADC(2)level.

GW/BSE Nonadiabatic Dynamics Simulations on Excited-State Relaxation Processes of Zinc Phthalocyanine-Fullerene Dyads:Roles of Bridging Chemical Bonds

In this work,we employ electronic structure calculations and nonadiabatic dynamics simulations based on many-body Green function and BetheSalpeter equation(GW/BSE)methods to study excited-state properties of a zinc phthalocyanine-fullerene(ZnPcC_(60))dyad with 6-6 and 5-6 configurations.In the former,the initially populated locally excited(LE)state of ZnPc is the lowest S1 state and thus,its subsequent charge separation is relatively slow.In contrast,in the latter,the S1 state is the LE state of C_(60)while the LE state of ZnPc is much higher in energy.There also exist several charge-transfer(CT)states between the LE states of ZnPc and C_(60).Thus,one can see apparent charge separation dynamics during excited-state relaxation dynamics from the LE state of ZnPc to that of C_(60).These points are verified in dynamics simulations.In the first 200 fs,there is a rapid excitation energy transfer from ZnPc to C_(60),followed by an ultrafast charge separation to form a CT intermediate state.This process is mainly driven by hole transfer from C_(60)to ZnPc.The present work demonstrates that different bonding patterns(i.e.5-6 and 6-6)of the C−N linker can be used to tune excited-state properties and thereto optoelectronic properties of covalently bonded ZnPc-C_(60)dyads.Methodologically,it is proven that combined GW/BSE nonadiabatic dynamics method is a practical and reliable tool for exploring photoinduced dynamics of nonperiodic dyads,organometallic molecules,quantum dots,nanoclusters,etc.

Photodissociation Exploration for Near-Visible UV Absorption of Molecular Bromine

The photodissociation of Br2 was investigated within the near-visible UV absorption band. Based on the potential curves for the ground and low-lying excited states, the optical cross-sections for the discrete transitions of C1^Пu,B^3Пou^＋, A^3П1u←X^1∑g＋ and their total energy absorption spectrum are derived, and the quantum yield of （Br＋Br6＊） channel are determined correspondingly. The one-dimensional Landau-Zener model is used to evaluate the behavior of curve crossing during photodissociation. The results indicate that the influence of nonadiabatic mechanism, which may be caused by the electronic-vibrational interplay between the 13 and C states, is negligibly small for the （Br＋Br^＊） channel. From the Landau-Zener modeling of the observed product recoil parameter β（Br＋Br）, the best-fit value of the coupling matrix elenment or coupling strength between the diabatic B and C state potentials is obtained.

Solvent Effects on Excited-State Relaxation Dynamics of Paddle-Wheel BODIPY-Hexaoxatriphenylene Conjugates:Insights from Non-adiabatic Dynamics Simulations

Understanding the excited state dynamics of donor-acceptor(D-A)complexes is of fundamental importance both experimentally and theoretically.Herein,we have first explored the photoinduced dynamics of a recently synthesized paddle-wheel BODIPY-hexaoxatriphenylene(BODIPY is the abbreviation for BF_(2)-chelated dipyrromethenes)conjugates D-A complexes with the combination of both electronic structure calculations and nonadiabatic dynamics simulations.On the basis of computational results,we concluded that the BODIPY-hexaoxatriphenylene(BH)conjugates will be promoted to the local excited(LE)states of the BODIPY fragments upon excitation,which is followed by the ultrafast exciton transfer from LE state to charge transfer(CT).Instead of the photoinduced electron transfer process proposed in previous experimental work,such a exciton transfer process is accompanied with the photoinduced hole transfer from BODIPY to hexaoxatriphenylene.Additionally,solvent effects are found to play an important role in the photoinduced dynamics.Specifically,the hole transfer dynamics is accelerated by the acetonitrile solvent,which can be ascribed to significant influences of the solvents on the charge transfer states,i.e.the energy gaps between LE and CT excitons are reduced greatly and the non-adiabatic couplings are increased in the meantime.Our present work not only provides valuable insights into the underlying photoinduced mechanism of BH,but also can be helpful for the future design of novel donor-acceptor conjugates with better optoelectronic performance.

Ultrafast Electron Diffraction with Spatiotemporal Resolution of Atomic Motion

Ultrafast electron diffraction （UED） is a rapidly advancing technique capable of recording the atomic-detail structural dynamics in real time. We report the establishment of the first UED system in China. Employing this UED apparatus, both the coherent and the concurrent thermal lattice motions in an aluminium thin-film, trigged by ultrafast laser heating, have been observed. These results demonstrate its ability to directly measure a sub-milli-angstrom lattice spacing change on a sub-picosecond time scale.

Adsorption behavior of uranium on polyvinyl alcohol-g-amidoxime:Physicochemical properties, kinetic and thermodynamic aspects

Amidoxime-based adsorbents are widely studied as the main adsorbent in the recovery of uranium from seawater. However, the adsorption rate and loading capacity of such adsorbents should be further improved due to the economic viability consider- ation. In this paper, polyvinyl alcohol functionalized with amidoxime （PVA-g-AO） has been prepared as a new adsorbent for uranium （VI） adsorption from aqueous solution. The physicochemical properties of PVA-g-AO were investigated using infra- red spectroscopy （IR）, scanning electron microscope （SEM）, X-ray diffraction （XRD）, and X-ray photoelectron spectroscopy （XPS）. Results showed that the ligand monomers were successfully grafted onto the matrixes. The XRD and XPS analysis showed that uranium was adsorbed in metal ionic form rather than in crystal form. Uranyl （U （VI）） adsorption properties onto PVA-g-AO were evaluated. The adsorption of U （VI） by PVA-g-AO was fast, with an equilibrium time of less than 50 rnin. Additionally the maximum adsorption capacity reached 42.84 mg/g at pH 4.0.

Exploration of uniform heat flux on the flow and heat transportation of ferrofluids along a smooth plate： Comparative investigation

The paper is devoted to a new extension in Gegenbauer wavelet method （GWM） to investigate the transfer of heat and MHD boundary-layer flow of ferrofluids beside a flat plate with velocity slip. A homogenous model study is conducted in which we assumed the heat transfer and forced convective flow of ferrofluids along a flat plate with a uniform wall heat flux. In the direction of transverse to plate, a magnetic field is imposed. Three various magnetic nanoparticle types including Mn-ZnFe204, CoFe204, Fe3O4 are incorporated inside the base fluid. Two types of base fluids （water and kerosene） with bad thermal conductivity as compared to nanoparticles of solid magnetic have been assumed. The mathematical model is tackled via modified Gegenbauer wavelet method （MGWM）. A simulation is accomplished for individual ferrofluid mixture by assuming the prevailing impacts of uniform and slip heat fluxes. The variation of heat transfers and skin friction were also observed at the surface of the plate and we analyzed the better heat transfer for every mixture. Kerosene-based magnetite （Fe304） delivers the better rate of heat transfer at wall due to its association with the kerosene-based Mn-Zn and cobalt ferrites. The slip velocity and magnetic field effects on the temperature, dimensionless velocity, rate of heat transfer and skin friction are examined for various magnetic nanoparticles inside the kerosene oil and water. We observed that the primary influence of magnetic field reduces the dimensionless surface temperature and accelerates the dimensionless velocity as compared to the hydrodynamic case, thus enhancing the rate of heat transfer and skin friction ferrofluids. Moreover, a detailed evaluation of outcomes obtained by MGWM, already published work and numerical RK-4 were found to be in excellent agreement. The error and convergence analysis are presented. Comparison of results,graphical plots, error and convergence analysis reveal the appropriateness of proposed method. The proposed algorithm can be extended for other nonlinear problems.