In this paper,we study quantum dynamics of entanglement and single excitation transfer(SET) in an LH1-RC-type trimer which can describe a basic unit cell in the LH1-RC complex in the photosynthetic process.It is shown...In this paper,we study quantum dynamics of entanglement and single excitation transfer(SET) in an LH1-RC-type trimer which can describe a basic unit cell in the LH1-RC complex in the photosynthetic process.It is shown that there exists a sudden change of entanglement at the critic point of quantum phase transition(QPT) of the system at low temperatures,the entanglement sudden change caused by the QPT is suppressed at higher temperatures.We investigate the influence of environment on entanglement and SET.We show the generation of the dephasing-assisted entanglement between a donor and an acceptor and the existence of the steady-state entanglement,and demonstrate the entanglement transfer from donor-donor entanglement to donor-acceptor entanglement in the dynamic evolution.We reveal the close relation between the SET probability and donor-acceptor entanglement.Especially,we find that the SET probability is proportional to the amount of donor-acceptor entanglement under certain conditions.展开更多
We investigate the dynamics of entanglement in the excitation transfer through a model consisting of three interacting molecules coupled to environments. It is shown that the entanglement can be further enhanced if th...We investigate the dynamics of entanglement in the excitation transfer through a model consisting of three interacting molecules coupled to environments. It is shown that the entanglement can be further enhanced if the distance between the molecules is oscillating. Our results demonstrate that the motional effect plays a constructive role on quantum entanglement in the dynamics of excitation transfer. This mechanism might provide a useful guideline for designing artificial systems to battle against decoherence.展开更多
Light absorption and energy transfer were studied in a bionic system with donors and an acceptor.In the optimal case of uniform couplings,this seemingly complicated system was reduced to a three-level L-type system.Wi...Light absorption and energy transfer were studied in a bionic system with donors and an acceptor.In the optimal case of uniform couplings,this seemingly complicated system was reduced to a three-level L-type system.With this observation,we showed that the efficiency of energy transfer through a dark-state channel,which is free of the spontaneous decay of the donors,was dramatically improved.After the overall average transfer time was evaluated,it was revealed that the time required for transfer through this channel was not optimal.To find the optimal parameters for the present system,we defined a new quantity,output power,which characterizes the average mean output of the whole transfer process.We estimated the optimal parameters of the system to achieve the maximum output power.The splitting behaviour of the maximum power may be used to explain the phenomenon of photosynthetic systems primarily absorbing two colours of light.展开更多
Triplet-triplet energy transfer in fluorene dimer with electronic structure calculations. The two is investigated by combining rate theories key parameters for the control of energy transfer, electronic coupling and r...Triplet-triplet energy transfer in fluorene dimer with electronic structure calculations. The two is investigated by combining rate theories key parameters for the control of energy transfer, electronic coupling and reorganization energy, are calculated based on the diabatic states constructed by the constrained density functional theory. The fluctuation of the electronic coupling is further revealed by molecular dynamics simulation. Succeedingly, the diagonal and off-diagonal fluctuations of the Hamiltonian are mapped from the correlation functions of those parameters, and the rate is then estimated both from the perturbation theory and wavepacket diffusion method. The results manifest that both the static and dynamic fluctuations enhance the rate significantly, but the rate from the dynamic fluctuation is smaller than that from the static fluctuation.展开更多
The relativistic configuration interaction method is employed to calculate the dielectronic recombination（DR） cross sections of helium-like krypton via the 1s2lnl ＇（n = 2,3,...,15） resonances.Then,the resonant tr...The relativistic configuration interaction method is employed to calculate the dielectronic recombination（DR） cross sections of helium-like krypton via the 1s2lnl ＇（n = 2,3,...,15） resonances.Then,the resonant transfer excitation（RTE） processes of Kr 34＋ colliding with H,He,H 2,and CH x（x = 0-4） targets are investigated under the impulse approximation.The needed Compton profiles of targets are obtained from the Hartree-Fock wave functions.The RTE cross sections are strongly dependent on DR resonant energies and strengths,and the electron momentum distributions of the target.For H 2 and H targets,the ratio of their RTE cross sections changes from 1.85 for the 1s2l2l ＇ to 1.88 for other resonances,which demonstrates the weak molecular effects on the Compton profiles of H 2.For CH x（x = 0-4） targets,the main contribution to the RTE cross section comes from the carbon atom since carbon carries 6 electrons;as the number of hydrogen increases in CH x,the RTE cross section almost increases by the same value,displaying the strong separate atom character for the hydrogen.However,further comparison of the individual orbital contributions of C（2p,2s,1s） and CH 4（1t 2,2a 1,1a 1） to the RTE cross sections shows that the molecular effects induce differences of about 25.1%,19.9%,and 0.2% between 2p-1t 2,2s-2a 1,and 1s-1a 1 orbitals,respectively.展开更多
The important role of high-energy intramolecular vibrational modes for excitation energy transfer in the detuned photosynthetic systems is studied. Based on a basic dimer model which consists of two two-level systems ...The important role of high-energy intramolecular vibrational modes for excitation energy transfer in the detuned photosynthetic systems is studied. Based on a basic dimer model which consists of two two-level systems （pigments） coupled to high-energy vibrational modes, we find that the high-energy intramolecular vibrational modes can enhance the energy transfer with new coherent transfer channels being opened when the phonon energy matches the detuning between the two pigments. As a result, the energy can be effectively transferred into the acceptor. The effective Hamiltonian is obtained to reveal the strong coherent energy exchange among the donor, the acceptor, and the high-energy intramolecular. A semi-classical explanation of the phonon-assisted mechanism is also shown.展开更多
The phonon-assisted process of energy transfer aiming at exploring the newly emerging frontier between biology and physics is an issue of central interest.This article shows the important role of the intramolecular vi...The phonon-assisted process of energy transfer aiming at exploring the newly emerging frontier between biology and physics is an issue of central interest.This article shows the important role of the intramolecular vibrational modes for excitation energy transfer in the photosynthetic systems.Based on a dimer system consisting of a donor and an acceptor modeled by two two-level systems,in which one of them is coupled to a high-energy vibrational mode,we derive an effective Hamiltonian describing the vibration-assisted coherent energy transfer process in the polaron frame.The effective Hamiltonian reveals in the case that the vibrational mode dynamically matches the energy detuning between the donor and the acceptor,the original detuned energy transfer becomes resonant energy transfer.In addition,the population dynamics and coherence dynamics of the dimer system with and without vibration-assistance are investigated numerically.It is found that,the energy transfer efficiency and the transfer time depend heavily on the interaction strength of the donor and the high-energy vibrational mode,as well as the vibrational frequency.The numerical results also indicate that the initial state and dissipation rate of the vibrational mode have little influence on the dynamics of the dimer system.Results obtained in this article are not only helpful to understand the natural photosynthesis,but also offer an optimal design principle for artificial photosynthesis.展开更多
We study the photo-oxidation of bacteriochlorophylls （BChls） in peripheral light harvesting complexes （LH2） from rhodobacter sphaeroides by using the steady absorption and the femtosecond pump-probe measurement, t...We study the photo-oxidation of bacteriochlorophylls （BChls） in peripheral light harvesting complexes （LH2） from rhodobacter sphaeroides by using the steady absorption and the femtosecond pump-probe measurement, to realize the detailed dynamics of LH2 in the presence of photo-oxidation. The experimental results reveal that BChl-B850 radical cations may act as an additional channel to compete with the unoxidized BChl-B850 molecules for rapidly releasing the excitation energy, while the B800→B850 energy transfer rate is almost unaffected in the oxidation process.展开更多
Objective To observe the clinical efficacy of excitement transfer therapy for insomnia. Methods According to the inclusion criteria, 32 patients, selected from Guoyitang, affiliated Zhongshan Hospital Yanwu Branch of ...Objective To observe the clinical efficacy of excitement transfer therapy for insomnia. Methods According to the inclusion criteria, 32 patients, selected from Guoyitang, affiliated Zhongshan Hospital Yanwu Branch of Xiamen University from May to October, 2016, were diagnosed with insomnia and included in this study. All the patients were treated by adopting the excitement transfer therapy, i.e. cluster needling was carried out at the acupoints of wrist and ankle in the manner of penetration needling, and combined with sliding- cupping at governor vessel and bladder meridian on the back. All the subjects were treated for 3 times per week, and treatment for 6 times was considered as I course of treatment. The curative effect was observed after treatment for 2 courses, and follow-up visit was performed for two months after treatment. Efficacy evaluation criteria were established by reference to Guidelines of Clinical Research on Chinese New Herbal Medicine （Trial） Results Cured： 11 cases （34%4 markedly effective： 16 cases （50%）, effective： 4 cases （13%4 ineffective： 1 case. The total effective rate was up to 97%. There was no relapse during two months after the treatment. Conclusion The efficacy of excitement transfer therapy for insomnia was significant, which was worthy of clinical promotion and application.展开更多
Herein we have employed high-level multi-reference CASSCF and MS-CASPT2 electronic structure methods to systematically study the photochemical mechanism of intramolecularly hydrogen-bonded 2-（2＇-hydroxyphenyl）-4-me...Herein we have employed high-level multi-reference CASSCF and MS-CASPT2 electronic structure methods to systematically study the photochemical mechanism of intramolecularly hydrogen-bonded 2-（2＇-hydroxyphenyl）-4-methyloxazole. At the CASSCF level, we have optimized minima, conical intersections, minimum-energy reaction paths relevant to the excited-state intramolecular proton transfer （ESIPT）, rotation, photoisomerization, and the excited-state deactivation pathways. The energies of all structures and paths are refined by the MS-CASPT2 method. On the basis of the present results, we found that the ESIPT process in a conformer with the OH... N hydrogen bond is essentially barrierless process; whereas, the ESIPT process is inhibited in the other conformer with the OH... O hydrogen bond. The central single-bond rotation of the S1 enol species is energetically unfavorable due to a large barrier. In addition, the excited-state deactivation of the S1 keto species, as a result of the ultrafast ESIPT, is very efficient because of the existence of two easily-approached keto S1/S0 conical intersections. In stark contrast to the S1 keto species, the decay of the S1 enol species is almostly blocked. The present theoretical study contributes valuable knowledge to the understanding of photochemistry of similar intramolecularly hydrogen-bonded molecular and biological systems.展开更多
The excited state intramolecular proton transfer （ESIPT） coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the ...The excited state intramolecular proton transfer （ESIPT） coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the absorption peak from S1 excited state both in the experi-mental and calculated absorption spectra indicates that S1 is a dark state. The dark excited state S1 results in the very weak fluorescence of solid baicalein in the experiment. The fron- tier molecular orbital and the charge difference densities of baicalein show clearly that the S1 state is a charge-transfer state whereas the S2 state is a locally excited state. The only one stationary point on the potential energy profile of excited state suggests that the ESIPT reaction of baicalein is a barrierless process.展开更多
Time-dependent density functional theory(TDDFT)method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT)process and the mechanism for temperature effect on the Enol^(*)/Keto^...Time-dependent density functional theory(TDDFT)method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT)process and the mechanism for temperature effect on the Enol^(*)/Keto^(*)emission ratio for the Me_(2)N-substited flavonoid(MNF)compound.The geometric structures of the S_(0) and S_(1) states are denoted as the Enol,Enol^(*),and Keto*.In addition,the absorption and fluorescence peaks are also calculated.It is noted that the calculated large Stokes shift is in good agreement with the experimental result.Furthermore,our results confirm that the ESIPT process happens upon photoexcitation,which is distinctly monitored by the formation and disappearance of the characteristic peaks of infrared(IR)spectra involved in the proton transfer and in the potential energy curves.Besides,the calculations of highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)reveal that the electronegativity change of proton acceptor due to the intramolecular charge redistribution in the S_(1) state induces the ESIPT.Moreover,the thermodynamic calculation for the MNF shows that the Enol^(*)/Keto^(*)emission ratio decreasing with temperature increasing arises from the barrier lowering of ESIPT.展开更多
The excited-state double-proton transfer （ESDPT） mechanism of 2-amino-3-methoxypyridine and acetic acid com- plex is studied by the density functional theory （DFT） and time-dependent DFT with CAM-B3LYP functional....The excited-state double-proton transfer （ESDPT） mechanism of 2-amino-3-methoxypyridine and acetic acid com- plex is studied by the density functional theory （DFT） and time-dependent DFT with CAM-B3LYP functional. The complex is connected through two different types of inter-molecular hydrogen bonds. After photo-excitation, both hydrogen bonds get strengthened, which can facilitate the ESDPT reaction. The scanned potential energy curve along the proton transfer coordinate indicates that the ESDPT reaction proceeds in a stepwise pattern.展开更多
Excited-state double proton transfer(ESDPT)in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol(HYDRAVH_(2))ligand was studied by the density functional theory and time-dependent density functi...Excited-state double proton transfer(ESDPT)in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol(HYDRAVH_(2))ligand was studied by the density functional theory and time-dependent density functional theory method.The analysis of frontier molecular orbitals,infrared spectra,and non-covalent interactions have crossvalidated that the asymmetric structure has an influence on the proton transfer,which makes the proton transfer ability of the two hydrogen protons different.The potential energy surfaces in both S_(0)and S_1 states were scanned with varying O-H bond lengths.The results of potential energy surface analysis adequately proved that the HYDRAVH_(2)can undergo the ESDPT process in the S_1 state and the double proton transfer process is a stepwise proton transfer mechanism.Our work can pave the way towards the design and synthesis of new molecules.展开更多
Thylakoid membrane preparations of super high-yield hybrid rice (Oryza sativa L.), Liangyoupeijiu (P9) and Shanyou 63 (SH 63) were used for investigating its spectral and time properties by using picosecond time-resol...Thylakoid membrane preparations of super high-yield hybrid rice (Oryza sativa L.), Liangyoupeijiu (P9) and Shanyou 63 (SH 63) were used for investigating its spectral and time properties by using picosecond time-resolved fluorescence spectrum measuring system. The thylakoid membrane preparations of P9 and SH 63 were excited by an Ar+ laser with a pulse width of 120 ps, repetition rate of 4 MHz and wavelength of 514 nm. The time constants of the excited energy transfer in these two varieties at flowering stage and grain filling stage were calculated from the experimental data. Based on the comparative studies of the time and spectral properties of the excited fluorescence in these ultrafast dynamic experiments the following was found: at both the flowering stage and grain filling stage, the speed of the excitation energy transfer, in photosystem was faster than that in photosystem II in P9 variety; and the speed of the excitation energy transfer at grain filling stage was faster than those at flowering stage for both rice varieties; the experiments also implied that the components and assembly of pigments in SH 63, but not in P9, changed during the process from flowering stage to grain filling stage for in these two rice varieties.展开更多
Excessive mercury ions(Hg^(2+)) in the environment can accumulate in human body along with the food chain to cause serious physiological reactions.The fluorescence probes were considered as convenient tool with great ...Excessive mercury ions(Hg^(2+)) in the environment can accumulate in human body along with the food chain to cause serious physiological reactions.The fluorescence probes were considered as convenient tool with great potential for Hg^(2+) detection.Most existing probes suffer from aggregation-induced quenching(ACQ) effects and insufficient sensitivity.Herein,a novel type of fluorophore was developed by combining the aggregation-induced emission(AIE) and excited state intramolecular proton transfer(ESIPT) characteristics.Subsequently,a phenyl thioformate group with photoinduced electron transfer(PET)effect was connected to give an efficient "turn-on" probe(HTM),which exhibited good selectivity toward Hg^(2+),short response time(30 min),coupled with extremely low detection limit(LOD=1.68 nmol/L).In addition,HTM was used successfully in real samples,cells and drug evaluation,underlying the superiority of HTM to detect Hg^(2+) in practical applications.展开更多
It is of great significance to study the relationship between the excited state intramolecular proton transfer(ESIPT)properties and antioxidant activities of compounds in the field of life sciences.In this work,two no...It is of great significance to study the relationship between the excited state intramolecular proton transfer(ESIPT)properties and antioxidant activities of compounds in the field of life sciences.In this work,two novel compounds 5HF-OMe and 5HF-NH2 are designed through introducing a methoxy-and amino-group into the structure of 5-hydroxyflavone(5HF)respectively.The relationship between the ESIPT reaction and antioxidant activities of the three compounds is studied via the density functional theory(DFT)and time-dependent DFT(TD-DFT)methods.The calculated potential energy curves suggest that the rate of ESIPT reaction will gradually slow down from 5HF to 5HF-OMe and 5HF-NH2.In addition,the antioxidant activities of the three compounds gradually enhance from 5HF to 5HF-OMe and 5HF-NH2,which can be seen from the calculated energy gaps and ionization potential values.Interestingly,the above results imply that the rate of ESIPT reaction has a negative relationship with the antioxidant activities of the compounds,i.e.,the slower rate of ESIPT reaction will reflect the higher antioxidant activity of the compound,which will provide valuable reference for detecting the antioxidant activity of compound via the photophysical method.展开更多
The hierarchical stochastic Schrodinger equations(HSSE)are a kind of numerically exact wavefunction-based approaches suitable for the quantum dynamics simulations in a relatively large system coupled to a bosonic bath...The hierarchical stochastic Schrodinger equations(HSSE)are a kind of numerically exact wavefunction-based approaches suitable for the quantum dynamics simulations in a relatively large system coupled to a bosonic bath.Starting from the influence-functional description of open quantum systems,this review outlines the general theoretical framework of HSSEs and their concrete forms in different situations.The applicability and efficiency of HSSEs are exemplified by the simulations of ultrafast excitation energy transfer processes in large-scale systems.展开更多
In this work,we study environment-assisted excitation energy transfer(EET) through calculating energy transfer efficiency(ETE) in LH1-RC-type and LH2-type trimers,which can be used to mimic energy transfer behaviors i...In this work,we study environment-assisted excitation energy transfer(EET) through calculating energy transfer efficiency(ETE) in LH1-RC-type and LH2-type trimers,which can be used to mimic energy transfer behaviors in the basic unit cells of LH1-RC and LH2 light-harvesting complexes.Quantum state evolution of the trimers is described by a non-Hermitian quantum master equation.ETE in these trimer systems is investigated by the use of numerical solutions at finite temperatures for the non-Hermitian master equation.We theoretically reveal the temperature-assisted ETE enhancement.It is found that highly efficient EET with nearly unit efficiency may occur in the nearby regime of the critical point of quantum phase transition.展开更多
Exosomes play significant roles in physiological and tumorigenic processes and it is desirable to visualize and track the exosomes.Herein,a novel amphiphilic fluorescent probe HBT-Exo based on excited-state intramolec...Exosomes play significant roles in physiological and tumorigenic processes and it is desirable to visualize and track the exosomes.Herein,a novel amphiphilic fluorescent probe HBT-Exo based on excited-state intramolecular proton transfer(ESIPT)mechanism is reported for exosome-labeling.Its ESIPT characteristics were confirmed by both theory calculation and experimental observation,which enable the probe to show a large Stokes shift as well as near-infrared(NIR)keto-form emission.HBT-Exo displayed excellent biocompatibility and remarkable efficiency for exosome-labeling in gastric cancer cells.Furthermore,the labeled exosomes were successfully applied for the real-time in situ imaging in mouse models.展开更多
基金Supported by the National Fundamental Research Program under Grant No.2007CB925204the National Natural Science Foundation under Grant Nos.10775048 and 11075050+1 种基金the Program for Changjiang Scholars and Innovative Research Team in University under Grant No.IRT0964Hunan Provincial Natural Science Foundation under Grant No.11JJ7001
文摘In this paper,we study quantum dynamics of entanglement and single excitation transfer(SET) in an LH1-RC-type trimer which can describe a basic unit cell in the LH1-RC complex in the photosynthetic process.It is shown that there exists a sudden change of entanglement at the critic point of quantum phase transition(QPT) of the system at low temperatures,the entanglement sudden change caused by the QPT is suppressed at higher temperatures.We investigate the influence of environment on entanglement and SET.We show the generation of the dephasing-assisted entanglement between a donor and an acceptor and the existence of the steady-state entanglement,and demonstrate the entanglement transfer from donor-donor entanglement to donor-acceptor entanglement in the dynamic evolution.We reveal the close relation between the SET probability and donor-acceptor entanglement.Especially,we find that the SET probability is proportional to the amount of donor-acceptor entanglement under certain conditions.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11374085,61073048 and 11274010the Specialized Research Fund for the Doctoral Program of Higher Education under Grant No 20113401110002+3 种基金the 211 Project of Anhui Universitythe Anhui Provincial Natural Science Foundation under Grant No 1408085MA20the Personnel Department of Anhui Provincethe 136 Foundation of Hefei Normal University under Grant No 2014136KJB04
文摘We investigate the dynamics of entanglement in the excitation transfer through a model consisting of three interacting molecules coupled to environments. It is shown that the entanglement can be further enhanced if the distance between the molecules is oscillating. Our results demonstrate that the motional effect plays a constructive role on quantum entanglement in the dynamics of excitation transfer. This mechanism might provide a useful guideline for designing artificial systems to battle against decoherence.
基金This work is supported by the Natural Science Foundation of China through Grant nos.10935010 and 11074261.
文摘Light absorption and energy transfer were studied in a bionic system with donors and an acceptor.In the optimal case of uniform couplings,this seemingly complicated system was reduced to a three-level L-type system.With this observation,we showed that the efficiency of energy transfer through a dark-state channel,which is free of the spontaneous decay of the donors,was dramatically improved.After the overall average transfer time was evaluated,it was revealed that the time required for transfer through this channel was not optimal.To find the optimal parameters for the present system,we defined a new quantity,output power,which characterizes the average mean output of the whole transfer process.We estimated the optimal parameters of the system to achieve the maximum output power.The splitting behaviour of the maximum power may be used to explain the phenomenon of photosynthetic systems primarily absorbing two colours of light.
基金This work was supported by the National Natural Science Foundation of China （No.20833004 and No.21073146） and the Research Fund for the Doctoral Program of Higher Education of China （No.200803840009）.
文摘Triplet-triplet energy transfer in fluorene dimer with electronic structure calculations. The two is investigated by combining rate theories key parameters for the control of energy transfer, electronic coupling and reorganization energy, are calculated based on the diabatic states constructed by the constrained density functional theory. The fluctuation of the electronic coupling is further revealed by molecular dynamics simulation. Succeedingly, the diagonal and off-diagonal fluctuations of the Hamiltonian are mapped from the correlation functions of those parameters, and the rate is then estimated both from the perturbation theory and wavepacket diffusion method. The results manifest that both the static and dynamic fluctuations enhance the rate significantly, but the rate from the dynamic fluctuation is smaller than that from the static fluctuation.
基金Project supported by the National Natural Science Foundation of China （Grant Nos. 1179041,11025417,and 10979007） the NSAF （Grant No. 10876043）
文摘The relativistic configuration interaction method is employed to calculate the dielectronic recombination（DR） cross sections of helium-like krypton via the 1s2lnl ＇（n = 2,3,...,15） resonances.Then,the resonant transfer excitation（RTE） processes of Kr 34＋ colliding with H,He,H 2,and CH x（x = 0-4） targets are investigated under the impulse approximation.The needed Compton profiles of targets are obtained from the Hartree-Fock wave functions.The RTE cross sections are strongly dependent on DR resonant energies and strengths,and the electron momentum distributions of the target.For H 2 and H targets,the ratio of their RTE cross sections changes from 1.85 for the 1s2l2l ＇ to 1.88 for other resonances,which demonstrates the weak molecular effects on the Compton profiles of H 2.For CH x（x = 0-4） targets,the main contribution to the RTE cross section comes from the carbon atom since carbon carries 6 electrons;as the number of hydrogen increases in CH x,the RTE cross section almost increases by the same value,displaying the strong separate atom character for the hydrogen.However,further comparison of the individual orbital contributions of C（2p,2s,1s） and CH 4（1t 2,2a 1,1a 1） to the RTE cross sections shows that the molecular effects induce differences of about 25.1%,19.9%,and 0.2% between 2p-1t 2,2s-2a 1,and 1s-1a 1 orbitals,respectively.
基金Project supported by the National Natural Science Foundation of China(Grant No.11174233)
文摘The important role of high-energy intramolecular vibrational modes for excitation energy transfer in the detuned photosynthetic systems is studied. Based on a basic dimer model which consists of two two-level systems （pigments） coupled to high-energy vibrational modes, we find that the high-energy intramolecular vibrational modes can enhance the energy transfer with new coherent transfer channels being opened when the phonon energy matches the detuning between the two pigments. As a result, the energy can be effectively transferred into the acceptor. The effective Hamiltonian is obtained to reveal the strong coherent energy exchange among the donor, the acceptor, and the high-energy intramolecular. A semi-classical explanation of the phonon-assisted mechanism is also shown.
基金Project supported by the National Natural Science Foundation of China(Grant No.11174233)
文摘The phonon-assisted process of energy transfer aiming at exploring the newly emerging frontier between biology and physics is an issue of central interest.This article shows the important role of the intramolecular vibrational modes for excitation energy transfer in the photosynthetic systems.Based on a dimer system consisting of a donor and an acceptor modeled by two two-level systems,in which one of them is coupled to a high-energy vibrational mode,we derive an effective Hamiltonian describing the vibration-assisted coherent energy transfer process in the polaron frame.The effective Hamiltonian reveals in the case that the vibrational mode dynamically matches the energy detuning between the donor and the acceptor,the original detuned energy transfer becomes resonant energy transfer.In addition,the population dynamics and coherence dynamics of the dimer system with and without vibration-assistance are investigated numerically.It is found that,the energy transfer efficiency and the transfer time depend heavily on the interaction strength of the donor and the high-energy vibrational mode,as well as the vibrational frequency.The numerical results also indicate that the initial state and dissipation rate of the vibrational mode have little influence on the dynamics of the dimer system.Results obtained in this article are not only helpful to understand the natural photosynthesis,but also offer an optimal design principle for artificial photosynthesis.
基金Supported by the National Natural Science Foundation of China under Grant Nos 10274013 and 10374020.
文摘We study the photo-oxidation of bacteriochlorophylls （BChls） in peripheral light harvesting complexes （LH2） from rhodobacter sphaeroides by using the steady absorption and the femtosecond pump-probe measurement, to realize the detailed dynamics of LH2 in the presence of photo-oxidation. The experimental results reveal that BChl-B850 radical cations may act as an additional channel to compete with the unoxidized BChl-B850 molecules for rapidly releasing the excitation energy, while the B800→B850 energy transfer rate is almost unaffected in the oxidation process.
文摘Objective To observe the clinical efficacy of excitement transfer therapy for insomnia. Methods According to the inclusion criteria, 32 patients, selected from Guoyitang, affiliated Zhongshan Hospital Yanwu Branch of Xiamen University from May to October, 2016, were diagnosed with insomnia and included in this study. All the patients were treated by adopting the excitement transfer therapy, i.e. cluster needling was carried out at the acupoints of wrist and ankle in the manner of penetration needling, and combined with sliding- cupping at governor vessel and bladder meridian on the back. All the subjects were treated for 3 times per week, and treatment for 6 times was considered as I course of treatment. The curative effect was observed after treatment for 2 courses, and follow-up visit was performed for two months after treatment. Efficacy evaluation criteria were established by reference to Guidelines of Clinical Research on Chinese New Herbal Medicine （Trial） Results Cured： 11 cases （34%4 markedly effective： 16 cases （50%）, effective： 4 cases （13%4 ineffective： 1 case. The total effective rate was up to 97%. There was no relapse during two months after the treatment. Conclusion The efficacy of excitement transfer therapy for insomnia was significant, which was worthy of clinical promotion and application.
文摘Herein we have employed high-level multi-reference CASSCF and MS-CASPT2 electronic structure methods to systematically study the photochemical mechanism of intramolecularly hydrogen-bonded 2-（2＇-hydroxyphenyl）-4-methyloxazole. At the CASSCF level, we have optimized minima, conical intersections, minimum-energy reaction paths relevant to the excited-state intramolecular proton transfer （ESIPT）, rotation, photoisomerization, and the excited-state deactivation pathways. The energies of all structures and paths are refined by the MS-CASPT2 method. On the basis of the present results, we found that the ESIPT process in a conformer with the OH... N hydrogen bond is essentially barrierless process; whereas, the ESIPT process is inhibited in the other conformer with the OH... O hydrogen bond. The central single-bond rotation of the S1 enol species is energetically unfavorable due to a large barrier. In addition, the excited-state deactivation of the S1 keto species, as a result of the ultrafast ESIPT, is very efficient because of the existence of two easily-approached keto S1/S0 conical intersections. In stark contrast to the S1 keto species, the decay of the S1 enol species is almostly blocked. The present theoretical study contributes valuable knowledge to the understanding of photochemistry of similar intramolecularly hydrogen-bonded molecular and biological systems.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.61137005 and No.10974023）, the Program for Liaoning Excellent Talents in University （No.LJQ2012002）, and the Program for New Century Excellent Talents in University （No.NCET-12-0077）.
文摘The excited state intramolecular proton transfer （ESIPT） coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the absorption peak from S1 excited state both in the experi-mental and calculated absorption spectra indicates that S1 is a dark state. The dark excited state S1 results in the very weak fluorescence of solid baicalein in the experiment. The fron- tier molecular orbital and the charge difference densities of baicalein show clearly that the S1 state is a charge-transfer state whereas the S2 state is a locally excited state. The only one stationary point on the potential energy profile of excited state suggests that the ESIPT reaction of baicalein is a barrierless process.
基金Project supported by the National Basic Research Program of China(Grant No.2013CB922204)the National Natural Science Foundation of China(Grant Nos.11574115 and 11704146)the Natural Science Foundation of Jilin Province,China(Grant No.20150101063JC)
文摘Time-dependent density functional theory(TDDFT)method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT)process and the mechanism for temperature effect on the Enol^(*)/Keto^(*)emission ratio for the Me_(2)N-substited flavonoid(MNF)compound.The geometric structures of the S_(0) and S_(1) states are denoted as the Enol,Enol^(*),and Keto*.In addition,the absorption and fluorescence peaks are also calculated.It is noted that the calculated large Stokes shift is in good agreement with the experimental result.Furthermore,our results confirm that the ESIPT process happens upon photoexcitation,which is distinctly monitored by the formation and disappearance of the characteristic peaks of infrared(IR)spectra involved in the proton transfer and in the potential energy curves.Besides,the calculations of highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)reveal that the electronegativity change of proton acceptor due to the intramolecular charge redistribution in the S_(1) state induces the ESIPT.Moreover,the thermodynamic calculation for the MNF shows that the Enol^(*)/Keto^(*)emission ratio decreasing with temperature increasing arises from the barrier lowering of ESIPT.
文摘The excited-state double-proton transfer （ESDPT） mechanism of 2-amino-3-methoxypyridine and acetic acid com- plex is studied by the density functional theory （DFT） and time-dependent DFT with CAM-B3LYP functional. The complex is connected through two different types of inter-molecular hydrogen bonds. After photo-excitation, both hydrogen bonds get strengthened, which can facilitate the ESDPT reaction. The scanned potential energy curve along the proton transfer coordinate indicates that the ESDPT reaction proceeds in a stepwise pattern.
基金Project supported by the National Basic Research Program of China(Grant No.2019YFA0307701)the National Natural Science Foundation of China(Grant No.11874180)the Young and Middle-aged Scientific and Technological Innovation leaders and Team Projects in Jilin Province,China(Grant No.20200301020RQ)。
文摘Excited-state double proton transfer(ESDPT)in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol(HYDRAVH_(2))ligand was studied by the density functional theory and time-dependent density functional theory method.The analysis of frontier molecular orbitals,infrared spectra,and non-covalent interactions have crossvalidated that the asymmetric structure has an influence on the proton transfer,which makes the proton transfer ability of the two hydrogen protons different.The potential energy surfaces in both S_(0)and S_1 states were scanned with varying O-H bond lengths.The results of potential energy surface analysis adequately proved that the HYDRAVH_(2)can undergo the ESDPT process in the S_1 state and the double proton transfer process is a stepwise proton transfer mechanism.Our work can pave the way towards the design and synthesis of new molecules.
文摘Thylakoid membrane preparations of super high-yield hybrid rice (Oryza sativa L.), Liangyoupeijiu (P9) and Shanyou 63 (SH 63) were used for investigating its spectral and time properties by using picosecond time-resolved fluorescence spectrum measuring system. The thylakoid membrane preparations of P9 and SH 63 were excited by an Ar+ laser with a pulse width of 120 ps, repetition rate of 4 MHz and wavelength of 514 nm. The time constants of the excited energy transfer in these two varieties at flowering stage and grain filling stage were calculated from the experimental data. Based on the comparative studies of the time and spectral properties of the excited fluorescence in these ultrafast dynamic experiments the following was found: at both the flowering stage and grain filling stage, the speed of the excitation energy transfer, in photosystem was faster than that in photosystem II in P9 variety; and the speed of the excitation energy transfer at grain filling stage was faster than those at flowering stage for both rice varieties; the experiments also implied that the components and assembly of pigments in SH 63, but not in P9, changed during the process from flowering stage to grain filling stage for in these two rice varieties.
基金financial supports from the National Natural Science Foundation of China (Nos. 81971678 and 81671756)the Innovation Fund for Post graduate Students of Central South University (No. 2020zzts827)。
文摘Excessive mercury ions(Hg^(2+)) in the environment can accumulate in human body along with the food chain to cause serious physiological reactions.The fluorescence probes were considered as convenient tool with great potential for Hg^(2+) detection.Most existing probes suffer from aggregation-induced quenching(ACQ) effects and insufficient sensitivity.Herein,a novel type of fluorophore was developed by combining the aggregation-induced emission(AIE) and excited state intramolecular proton transfer(ESIPT) characteristics.Subsequently,a phenyl thioformate group with photoinduced electron transfer(PET)effect was connected to give an efficient "turn-on" probe(HTM),which exhibited good selectivity toward Hg^(2+),short response time(30 min),coupled with extremely low detection limit(LOD=1.68 nmol/L).In addition,HTM was used successfully in real samples,cells and drug evaluation,underlying the superiority of HTM to detect Hg^(2+) in practical applications.
基金Project supported by the National Basic Research Program of China(Grant No.2019YFA0307701)the National Natural Science Foundation of China(Grant No.11874180)the Science and Technology Development Project of Jilin Province of China(Grant No.20190103101JH).
文摘It is of great significance to study the relationship between the excited state intramolecular proton transfer(ESIPT)properties and antioxidant activities of compounds in the field of life sciences.In this work,two novel compounds 5HF-OMe and 5HF-NH2 are designed through introducing a methoxy-and amino-group into the structure of 5-hydroxyflavone(5HF)respectively.The relationship between the ESIPT reaction and antioxidant activities of the three compounds is studied via the density functional theory(DFT)and time-dependent DFT(TD-DFT)methods.The calculated potential energy curves suggest that the rate of ESIPT reaction will gradually slow down from 5HF to 5HF-OMe and 5HF-NH2.In addition,the antioxidant activities of the three compounds gradually enhance from 5HF to 5HF-OMe and 5HF-NH2,which can be seen from the calculated energy gaps and ionization potential values.Interestingly,the above results imply that the rate of ESIPT reaction has a negative relationship with the antioxidant activities of the compounds,i.e.,the slower rate of ESIPT reaction will reflect the higher antioxidant activity of the compound,which will provide valuable reference for detecting the antioxidant activity of compound via the photophysical method.
基金supported by the National Natural Science Foundation of China(No.22033006,No.21833006,and No.21773191).
文摘The hierarchical stochastic Schrodinger equations(HSSE)are a kind of numerically exact wavefunction-based approaches suitable for the quantum dynamics simulations in a relatively large system coupled to a bosonic bath.Starting from the influence-functional description of open quantum systems,this review outlines the general theoretical framework of HSSEs and their concrete forms in different situations.The applicability and efficiency of HSSEs are exemplified by the simulations of ultrafast excitation energy transfer processes in large-scale systems.
基金supported by the National Fundamental Research Program (Grant No. 2007CB925204)the National Natural Science Foundation of China (Grant Nos. 11075050 and 10775048)+1 种基金the Program for Changjiang Scholars and Innovative Research Team in University (Grant No. IRT0964)the Hunan Provincial Natural Science Foundation (Grant No. 11JJ7001)
文摘In this work,we study environment-assisted excitation energy transfer(EET) through calculating energy transfer efficiency(ETE) in LH1-RC-type and LH2-type trimers,which can be used to mimic energy transfer behaviors in the basic unit cells of LH1-RC and LH2 light-harvesting complexes.Quantum state evolution of the trimers is described by a non-Hermitian quantum master equation.ETE in these trimer systems is investigated by the use of numerical solutions at finite temperatures for the non-Hermitian master equation.We theoretically reveal the temperature-assisted ETE enhancement.It is found that highly efficient EET with nearly unit efficiency may occur in the nearby regime of the critical point of quantum phase transition.
基金the financial support from the National Natural Science Foundation of China(Nos.82272067,81974386 and M-0696)Research and Development program in Key Areas of Hunan Province(No.2019SK2143)Natural Science Foundation of Hunan Province(Nos.2022JJ80052 and 2022JJ30920).
文摘Exosomes play significant roles in physiological and tumorigenic processes and it is desirable to visualize and track the exosomes.Herein,a novel amphiphilic fluorescent probe HBT-Exo based on excited-state intramolecular proton transfer(ESIPT)mechanism is reported for exosome-labeling.Its ESIPT characteristics were confirmed by both theory calculation and experimental observation,which enable the probe to show a large Stokes shift as well as near-infrared(NIR)keto-form emission.HBT-Exo displayed excellent biocompatibility and remarkable efficiency for exosome-labeling in gastric cancer cells.Furthermore,the labeled exosomes were successfully applied for the real-time in situ imaging in mouse models.
