The mass-and field-shift parameters of the two 2s^(2)S_(1/2)→ 2p^(2)P_(1/2,3/2) transitions in the Li-like Ca ions are calculated by using multi-configuration Dirac-Hartree-Fock(MCDHF) and the relativistic configurat...The mass-and field-shift parameters of the two 2s^(2)S_(1/2)→ 2p^(2)P_(1/2,3/2) transitions in the Li-like Ca ions are calculated by using multi-configuration Dirac-Hartree-Fock(MCDHF) and the relativistic configuration interaction(RCI) methods with the inclusion of the transverse photon(Breit) interaction,vacuum polarization and self-energy corrections.In addition,the mass shift and field shift of these two transitions are calculated,where the field shift is calculated by using the evaluated value δ(r^(2)) obtained by [Atomic Data and Nuclear Data Tables 99 69(2013)].It is found that the mass shift of Li-like Ca ions is greater than the field shift.展开更多
The electron-impact single ionization cross section for W8+ion has been calculated using flexible atomic code,employing the level-to-level distorted-wave approximation.This calculations takes into account contribution...The electron-impact single ionization cross section for W8+ion has been calculated using flexible atomic code,employing the level-to-level distorted-wave approximation.This calculations takes into account contributions form both direct ionization(DI)and excitation autoionization(EA).However,the theoretical predictions,based solely on the ground state,tends to underestimate the experimental values.This discrepancy can be mitigated by incorporation contributions from excited states.We extended the theoretical analysis,including the contributions from the long-lived metastable states with lifetimes exceeding 1.5×10-5 s.We employed two statistical models to predict the fraction of ground state ions in the parent ion beam.Assuming a 79%fraction of parent ions in ground configuration,the experiment measurements align with the predictions.Furthermore we derived the theoretical cross-section for the ground state as correlated plasma rate coefficients,and compared it with existing data.Despite the uncertainty in our calculations,our results are still acceptable.展开更多
The direct construction of functionalized diphosphine ligands from P_(4)is a highly valuable but challenging transformation.In this work,a simple method has been developed for the direct formation of an amidofunctiona...The direct construction of functionalized diphosphine ligands from P_(4)is a highly valuable but challenging transformation.In this work,a simple method has been developed for the direct formation of an amidofunctionalized diphosphanato ligand from a silyl-bridged amido/methylene yttrium complex and white phosphorus.The resulting amido-functionalized diphosphanato yttrium complex 2 has proved to be a useful intermediate for further diversification of the diphosphine ligand through the metal template procedure,for which no evident limitations are enforced by initially present substituents and ancillary ligands,and some unprecedented reactivity patterns of the RPPR unit are revealed.The results described here demonstrate that appending a strongly coordinative substituent to the alkyl ligand together with a coordination to rare earth ions is an efficient strategy for controlling the cleavage modes of P_(4)during alkylation and the reactivity of the resulting diphosphanato complex.展开更多
The treatment of rare-earth metal dialkyl complexes Tp^(Me2)YBn_(2)(THF)(Bn=CH_(2)Ph,1^(Y))with P4 in toluene at ambient temperature formed yttrium norbornane-BnP_(7)^(4-)(2^(Y))and chain Bn_(4)P_(6)^(4-)(3^(Y))comple...The treatment of rare-earth metal dialkyl complexes Tp^(Me2)YBn_(2)(THF)(Bn=CH_(2)Ph,1^(Y))with P4 in toluene at ambient temperature formed yttrium norbornane-BnP_(7)^(4-)(2^(Y))and chain Bn_(4)P_(6)^(4-)(3^(Y))complexes,accompanied by the formation of PBn_(3)(I).However,only lutetium norbornane-BnP_(7)^(4-)complex 2^(Lu) and I were obtained from the reaction of 1^(Lu) with P_(4) under the same conditions.Moreover,an atom-economic conversion of P_(4) to PBn_(3) and norbornane-BnP_(7)(Me_(3)Si)_(4)(Ⅱ)was also realized by the treatment of Tp^(Me2)LuCl_(2)(THF)with KBn,followed by a sequential reaction with P_(4) and Me_(3)SiCl.These results indicated that P_(4) functionalization using rare-earth dialkyl complexes can form not only novel rare-earth polyphosphorus complexes,but also organophosphorus compounds.All new compounds have been characterized by NMR spectroscopy and single-crystal X-ray diffraction studies.展开更多
The hypoxic nature of solid tumors has severely negative effects on oxygen-based photodynamic therapy.In this study,we used porous Pt nanoparticles as a catalase(CAT)nanozyme,the second near-infrared(NIR-Ⅱ)region pho...The hypoxic nature of solid tumors has severely negative effects on oxygen-based photodynamic therapy.In this study,we used porous Pt nanoparticles as a catalase(CAT)nanozyme,the second near-infrared(NIR-Ⅱ)region photothermal transition agents(PTAs),and carriers of photosensitizer chlorin e6(Ce6)to synthesize a composite nanosystem Pt-Ce6.In this system,Pt-Ce6 can continuously and stably decompose H2O2 into oxygen,thereby alleviating tumor hypoxia and improving the effect of photodynamic therapy(PDT).With 650 nm illumination,the reactive oxygen species(ROS)produced by Ce6 will decrease the mitochondrial membrane potential(MMP,ΔΨm)to release cytochrome c(Cyt-c)from the mitochondria into the cytoplasm,eventually leading to mitochondrial-mediated cellular apoptosis during the PDT process.In addition,Pt-Ce6 has good photothermal stability and high photothermal conversion efficiency(52.62%)in the NIR-II region.In U14 tumor-bearing mice,Pt-Ce6 completely suppressed tumor growth and recurrence under laser irradiation.Thus the nanocomposite shows excellent PDT/photothermal therapy(PTT)synergistic performance in vitro and in vivo.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant No.11864036)the Funds for Creative Research Groups of Gansu Province,China(Grant No.20JR5RA541)。
文摘The mass-and field-shift parameters of the two 2s^(2)S_(1/2)→ 2p^(2)P_(1/2,3/2) transitions in the Li-like Ca ions are calculated by using multi-configuration Dirac-Hartree-Fock(MCDHF) and the relativistic configuration interaction(RCI) methods with the inclusion of the transverse photon(Breit) interaction,vacuum polarization and self-energy corrections.In addition,the mass shift and field shift of these two transitions are calculated,where the field shift is calculated by using the evaluated value δ(r^(2)) obtained by [Atomic Data and Nuclear Data Tables 99 69(2013)].It is found that the mass shift of Li-like Ca ions is greater than the field shift.
基金Project supported by the National Natural Science Foundation of China(Grant No.12364034)the National Key Research and Development Program of China(Grant No.2022YFA1602501)the Science and Technology Project of Gansu Province,China(Grant No.23YFFA0074).
文摘The electron-impact single ionization cross section for W8+ion has been calculated using flexible atomic code,employing the level-to-level distorted-wave approximation.This calculations takes into account contributions form both direct ionization(DI)and excitation autoionization(EA).However,the theoretical predictions,based solely on the ground state,tends to underestimate the experimental values.This discrepancy can be mitigated by incorporation contributions from excited states.We extended the theoretical analysis,including the contributions from the long-lived metastable states with lifetimes exceeding 1.5×10-5 s.We employed two statistical models to predict the fraction of ground state ions in the parent ion beam.Assuming a 79%fraction of parent ions in ground configuration,the experiment measurements align with the predictions.Furthermore we derived the theoretical cross-section for the ground state as correlated plasma rate coefficients,and compared it with existing data.Despite the uncertainty in our calculations,our results are still acceptable.
基金National Natural Science Foundation of China(grant no.21871058,22271051,and 22371049)973 program(2015CB856600)。
文摘The direct construction of functionalized diphosphine ligands from P_(4)is a highly valuable but challenging transformation.In this work,a simple method has been developed for the direct formation of an amidofunctionalized diphosphanato ligand from a silyl-bridged amido/methylene yttrium complex and white phosphorus.The resulting amido-functionalized diphosphanato yttrium complex 2 has proved to be a useful intermediate for further diversification of the diphosphine ligand through the metal template procedure,for which no evident limitations are enforced by initially present substituents and ancillary ligands,and some unprecedented reactivity patterns of the RPPR unit are revealed.The results described here demonstrate that appending a strongly coordinative substituent to the alkyl ligand together with a coordination to rare earth ions is an efficient strategy for controlling the cleavage modes of P_(4)during alkylation and the reactivity of the resulting diphosphanato complex.
基金the National Natural Science Foundation of China(Grant No.21472020,21732007,21871058,22371049)for financial support.
文摘The treatment of rare-earth metal dialkyl complexes Tp^(Me2)YBn_(2)(THF)(Bn=CH_(2)Ph,1^(Y))with P4 in toluene at ambient temperature formed yttrium norbornane-BnP_(7)^(4-)(2^(Y))and chain Bn_(4)P_(6)^(4-)(3^(Y))complexes,accompanied by the formation of PBn_(3)(I).However,only lutetium norbornane-BnP_(7)^(4-)complex 2^(Lu) and I were obtained from the reaction of 1^(Lu) with P_(4) under the same conditions.Moreover,an atom-economic conversion of P_(4) to PBn_(3) and norbornane-BnP_(7)(Me_(3)Si)_(4)(Ⅱ)was also realized by the treatment of Tp^(Me2)LuCl_(2)(THF)with KBn,followed by a sequential reaction with P_(4) and Me_(3)SiCl.These results indicated that P_(4) functionalization using rare-earth dialkyl complexes can form not only novel rare-earth polyphosphorus complexes,but also organophosphorus compounds.All new compounds have been characterized by NMR spectroscopy and single-crystal X-ray diffraction studies.
基金the National Natural Science Foundation of China(51872263 and 31970755)Zhejiang Provincial Natural Science Foundation(LZ19E020001 and LQ18B010002)。
文摘The hypoxic nature of solid tumors has severely negative effects on oxygen-based photodynamic therapy.In this study,we used porous Pt nanoparticles as a catalase(CAT)nanozyme,the second near-infrared(NIR-Ⅱ)region photothermal transition agents(PTAs),and carriers of photosensitizer chlorin e6(Ce6)to synthesize a composite nanosystem Pt-Ce6.In this system,Pt-Ce6 can continuously and stably decompose H2O2 into oxygen,thereby alleviating tumor hypoxia and improving the effect of photodynamic therapy(PDT).With 650 nm illumination,the reactive oxygen species(ROS)produced by Ce6 will decrease the mitochondrial membrane potential(MMP,ΔΨm)to release cytochrome c(Cyt-c)from the mitochondria into the cytoplasm,eventually leading to mitochondrial-mediated cellular apoptosis during the PDT process.In addition,Pt-Ce6 has good photothermal stability and high photothermal conversion efficiency(52.62%)in the NIR-II region.In U14 tumor-bearing mice,Pt-Ce6 completely suppressed tumor growth and recurrence under laser irradiation.Thus the nanocomposite shows excellent PDT/photothermal therapy(PTT)synergistic performance in vitro and in vivo.
